JP2011079261A - Low adhesion material, antifouling material, molding mold, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low adhesion material having low adhesiveness with respect to an object comprising a substance having basicity, thermoplastic resin or water, a molding mold having high mold releasability in the case of using the object, and to provide an antifouling material having antifouling property relating to smudge including the object. <P>SOLUTION: A mold release layer 4 is formed on the surface 8 of a substrate 5 made of ZrO<SB>2</SB>group ceramic in an upper mold 1 as the molding mold used for resin molding. The mold release layer 4 is composed of a low adhesion material having low adhesiveness with respect to the object comprising the substance having basicity, the thermoplastic resin or the substance containing water. In the mold release layer 4, Zr<SP>4+</SP>as a cation of a 4A group element and nitrogen are introduced onto at least the surface of Y<SB>2</SB>O<SB>3</SB>. In at least the surface of the low adhesion material, the amount of the cation of 4A the group element is preferably more than 0 and 20 mol% or less, and the amount of nitrogen is 0.01 to 10 mol%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Conventionally, in various fields, there is a need for a low adhesion material 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 related to antifouling materials having antifouling properties with respect to dirt containing such objects, materials used for molding dies used when molding molded products, 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. This means that the adhesiveness is low when compared to the adhesiveness between the target and the target substance made of a substance containing the substance. The term “basic” refers to the property of donating an electron pair, that is, 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 needs described above, the applicant of the present application firstly proposed the following low adhesion material and resin mold. The surface of a low adhesion material having low adhesion with respect to the adhesion between the thermosetting resin is constituted by a rare earth oxide, and the valence and ionic radius of each metal cation contained in the rare earth oxide are determined. This is a low-adhesion material having a field strength having a value calculated based on the predetermined range, and a resin mold in which a mold surface is constituted by the low-adhesion material described above (see Patent Document 1).

  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 an object composed of a basic substance or a thermosetting resin, and is provided with a base material containing at least a rare earth oxide, and nitrogen provided near the surface of the base material. It is a low-adhesion material provided with the functional layer to contain, and its manufacturing method. Moreover, it is a shaping | molding die provided with the respectively same base material and a functional layer, and its manufacturing method. Moreover, it is an antifouling material provided with the same base material and a functional layer, respectively, and its manufacturing method (Japanese Patent Application No. 2008-075781).

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

  However, according to the above-described low adhesion material or the like, there is a problem that the adhesion to an object made of a basic substance or a thermosetting resin cannot be said to be sufficiently low. Moreover, according to the low adhesion material provided with a base material containing at least 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. In some cases, it was found that there was a difference in the degree of low adhesion.

  In view of the problems described above, the present invention has the following objects. 1stly, the low adhesion material which has the lower and stable low adhesiveness with respect to the target object which consists of at least any one of the substance which has basicity, a thermosetting resin, or a water | moisture content is provided. That is. Second, it is to provide an antifouling material having a higher and more stable antifouling property with respect to dirt containing such objects. Third, it is to provide a mold having higher and more stable releasability when using at least one of such objects. 4th is providing the manufacturing method of the low-adhesion material mentioned above, antifouling | stain-proof material, or a shaping | molding die.

  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. In this case, at least the surface of the low adhesion material contains yttrium oxide and nitrogen.

  Further, 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 has low adhesion. At least the surface of the material is characterized by containing yttrium oxide and a cation of a group 4A element.

  Further, 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 has low adhesion. At least the surface of the material is characterized by containing yttrium oxide, nitrogen, and a cation of a group 4A element.

  In the low adhesion material according to the present invention, in the above low adhesion material, the amount of nitrogen contained in at least the surface of the low adhesion material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms. It is characterized by.

  Further, the low adhesion material according to the present invention is the above low adhesion material, wherein the amount of the cation of the group 4A element contained at least on the surface of the low adhesion material is more than 0 mol% and not more than 20 mol%. Features.

The low adhesion material according to the present invention is characterized in that, in the above low adhesion material, the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ .

  Further, the low adhesion material according to the present invention is the above-mentioned low adhesion material, the low adhesion material has a base material, the base material contains zirconium oxide as a main component, and yttrium oxide and nitrogen are: The yttrium oxide and the cation of the group 4A element, or the yttrium oxide, nitrogen, and the cation of the group 4A element are included in a layered portion provided on the surface of the base material.

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

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

  In addition, the antifouling material according to the present invention is an antifouling material having antifouling properties related to dirt including an object composed of a basic substance, a thermosetting resin, or a substance containing moisture, At least the surface of the antifouling material contains yttrium oxide, nitrogen, and a cation of a group 4A element.

  The antifouling material according to the present invention is the above antifouling material, wherein the amount of nitrogen contained in at least the surface of the antifouling material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms. It is characterized by.

  Further, the antifouling material according to the present invention is the above antifouling material, wherein the amount of the cation of the group 4A element contained in at least the surface of the antifouling material is more than 0 mol% and not more than 20 mol%. Features.

The antifouling material according to the present invention is characterized in that, in the above antifouling material, the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ .

  Further, the antifouling material according to the present invention is the above-mentioned antifouling material, the antifouling material has a base material, the base material contains zirconium oxide as a main component, and yttrium oxide and nitrogen are: The yttrium oxide and the cation of the group 4A element, or the yttrium oxide, nitrogen, and the cation of the group 4A element are included in a layered portion provided on the surface of the base material.

  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 of the molding die contains yttrium oxide and nitrogen.

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

  In addition, the mold according to the present invention is a mold used when molding a molded product, and at least the surface of the mold includes yttrium oxide, nitrogen, and a cation of a 4A group element. It is characterized by.

  Further, the mold according to the present invention is characterized in that, in the above-mentioned mold, 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.

  The mold according to the present invention is characterized in that, in the mold described above, the amount of a cation of the group 4A element contained in at least the surface of the mold exceeds 0 mol% and is 20 mol% or less.

Further, the mold according to the present invention is characterized in that, in the above-mentioned mold, the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ .

  Further, the molding die according to the present invention is the above-described molding die, wherein the molding die has a base material, and the base material contains zirconium oxide as a main component, and yttrium oxide and nitrogen are yttrium oxide and a group 4A element. The cation of yttrium oxide, nitrogen, and the cation of the group 4A element are contained in a layered portion provided on the surface of the base material.

  Further, according to the present invention, 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 antifouling related to dirt containing the object A method for producing an antifouling material having a property or a method for producing a mold used for molding a molded product is a method for producing a low-adhesion material having low adhesion to such an object. A method for producing an antifouling material having an antifouling property related to dirt containing a product, or a method for producing a mold used for molding a molded article, wherein a basic substance, a thermosetting resin, Alternatively, a method for producing a low-adhesion material having low adhesion to an object composed of a substance containing moisture, a method for producing an antifouling material having antifouling properties relating to dirt containing the object, or a molded product is formed. Method of forming mold used in the process A step of preparing a first raw material containing yttrium oxide and a group 4A element, and using the first raw material, at least one of a low adhesion material, an antifouling material, and a mold And a step of bringing the surface into a state containing yttrium oxide and a cation of a group 4A element.

  Further, according to the present invention, 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 antifouling related to dirt containing the object The method for producing an antifouling material having a property or the method for producing a molding die used for molding a molded product includes the step of preparing a base material containing zirconium oxide as a main component in the above-described production method. And at least a surface of any one of the low adhesion material, the antifouling material, or the molding die containing yttrium oxide and a cation of a group 4A element, provided on the surface of the base material. The layered portion is made to contain yttrium oxide and a cation of a group 4A element.

  Further, according to the present invention, 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 antifouling related to dirt containing the object The method for producing an antifouling material having a property or the method for producing a molding die used for molding a molded article is a low adhesion material, an antifouling material, or a molding die in the above production method. A step of further including nitrogen on at least the surface of any of the above.

  Further, according to the present invention, 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 antifouling related to dirt containing the object The method for producing an antifouling material having a property or the method for producing a molding die used for molding a molded article is the low adhesion material, the antifouling material, or the molding die in the above production method. The amount of the cation of the group 4A element contained in at least the surface of any of the above is more than 0 mol% and not more than 20 mol%.

Further, according to the present invention, 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 antifouling related to dirt containing the object The method for producing the antifouling material having the property or the method for producing the mold used for molding the molded article is the above-described production method, wherein the cation of the group 4A element is Zr ⁴⁺ or Hf ⁴⁺ It is characterized by being at least one.

  Further, according to the present invention, 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 antifouling related to dirt containing the object A method for producing an antifouling material having a property or a method for producing a mold used for molding a molded product is a method for producing a low-adhesion material having low adhesion to such an object. A method for producing an antifouling material having an antifouling property related to dirt containing a product, or a method for producing a mold used for molding a molded article, wherein a basic substance, a thermosetting resin, Alternatively, a method for producing a low-adhesion material having low adhesion to an object composed of a substance containing moisture, a method for producing an antifouling material having antifouling properties relating to dirt containing the object, or a molded product is formed. Method of forming mold used in the process There are, characterized in that it comprises a step of preparing a second feedstock comprising a yttrium oxide as a main component, a process to include nitrogen in the surface of the second raw material.

  Further, according to the present invention, 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 antifouling related to dirt containing the object The method for producing an antifouling material having a property or the method for producing a molding die used for molding a molded article is a low adhesion material, an antifouling material, or a molding die in the above production method. The amount of nitrogen contained in at least the surface of any of the above or the surface of the second raw material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms.

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 low adhesion materials for such objects, antifouling materials for soils containing such objects, or molds when using such objects. Can be used.

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. 3 (1) and 3 (2) are partial cross-sectional views showing the outline of a coated mold and a mold made of a bulk material, respectively, according to the present invention.

  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 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 of FIG. 1 is a value measured using a SIMS (Secondary Ion-microprobe Mass Spectrometer). 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 a 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. The nitrogen ion concentration shown here is considered to be the concentration of nitrogen ions contained in the Y ₂ O ₃ bulk material itself.

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

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, among the first low adhesion materials, the material indicated by the 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, regarding the material indicated by the black square (■) in FIG. 1 among the first low adhesion materials, the nitrogen ion concentration is 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 material indicated by white squares (□) in FIG. 1 has 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. Note that the nitrogen ion concentrations of the four types of first low adhesion materials described above are considered to be largely governed by the concentration of nitrogen ions implanted into 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 manufactured by implanting nitrogen ions into a bulk material of Y ₂ O ₃ has a low adhesion with low adhesion to an object made of a basic substance, a thermosetting resin, or a substance containing moisture. It can be used as an adhesive material.

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.

When the contact angle with respect to water was measured for each of the Y ₂ O ₃ bulk material 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 an object made of a substance 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, has been described is larger than the contact angle to water of Y ₂ O _3. As a result, “the first 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, or 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 thereof 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. And “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, or a substance containing moisture. It can be said that a material having the same is usable.

  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 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 not only a thermosetting resin but also 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, or a substance containing moisture, and at least the 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. As a result, 5 mol% of ZrO ₂ is present 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%. And it is the same also in each of the following Examples that the amount of the cation of the group 4A element contained on 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). In addition, 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 adhesion strength between the rare earth oxide Y ₂ O ₃ (material A) and the epoxy resin Y is 0.54 MPa, whereas the second low adhesion The adhesive strength between the conductive material (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, it was 90 ° in the case of the second low adhesion material, compared with 65 ° in the case of Y ₂ O ₃ . 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, or 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, or a substance containing moisture, and has at least a surface. 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). As a result, 5 mol% of ZrO ₂ is present on the surface of the material C which is the third low adhesion material.

Further, as shown in FIG. 2, the bonding strength between Y ₂ O ₃ (material A) and the epoxy resin Y is 0.54 MPa, whereas the third low adhesion material and The adhesive strength between the epoxy resin Y 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.

Furthermore, when the contact angle with respect to water was measured, it was 107 ° in the case of the third low adhesion material, compared with 65 ° in the case of Y ₂ O ₃ . 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 . In addition, this result shows that the third low-adhesion material has a lower adhesion to an object made of a substance containing moisture than Y ₂ O ₃ (adhesion lower than that of the second low-adhesion material). ).

  As a result, the third 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, or a substance containing moisture. It can be used. "

By the way, the inventors of the present invention are as follows about the mechanism in 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 lowered. I guessed. 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. Also, the inventors of the present invention inferred as follows.

When Y ₂ O _{3 is} simply nitrogen-substituted (0 ² →→ N ³⁻ ), the cause of the decrease in adhesion strength is that the covalent bond is increased and the polarization is relaxed compared to the Y—O bond. This is considered to be because the adsorption of organic substances is suppressed. 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 nitrogen substitution (0 ^2- > N ^3- ) is simply performed on Y ₂ O ₃ , anion vacancies (anionic vacancies; anion vacancies; Lattice defects) are formed. And when an anion vacancy exists, it is thought that the acidic point which accelerates | stimulates organic substance adsorption | suction through this vacancy newly develops.

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 larger than Y ³⁺ and fixed to Y ₂ O ₃ in order to cancel N ^3, which is one valence larger than 0 ^2−. cations group 4A elements soluble may be added to _Y 2 _{O 3.} One or more of Zr ⁴⁺ (ion radius: 0.83 Å = 83 pm) and Hf ⁴⁺ (ion radius: 0.83 Å = 83 pm) can be used as the cation of the group 4A element. 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, so that a composite oxide (consisting of yttrium oxide and zirconium oxide) or hafnium oxide is used. 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, if it is less than 0.01 mol%, the substitution amount of 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 made of 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, a suitable base material is prepared. The substrate is preferably a material having excellent mechanical properties, that is, high toughness and wear resistance. For example, zirconium-based ceramics (ZrO ₂ -based ceramics) can be used as the base material.

  Next, the liquid containing the salt containing Y and the salt containing a 4A group element is stirred. Thereby, the coating material containing an organic-inorganic precursor can be produced | generated 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 functions are low adhesion to certain substances, high releasability when used as a mold, and antifouling properties for certain substances. 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.

  As the nitriding treatment, the following method can be used. These include nitrogen atmosphere treatment, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), sol-gel method and the like. 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. . And according to these manufacturing methods, when manufacturing a low-adhesion material, the usage-amount of Y which is a rare element can be reduced. Further, the price of the low adhesion material can be suppressed.

  Moreover, according to the manufacturing method which concerns on a present Example, a diffusion solid solution layer (composition gradient layer) is formed in the interface of a base material and a 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, it is a first low-adhesion material in which nitrogen ions are implanted into the surface of a Y ₂ O ₃ bulk material. Next, it is a second low-adhesion material in which Y ₂ O ₃ and a cation of a 4A group element are contained at least in a layered portion provided on the surface of the substrate. Next, it is a third low adhesion material in which Y ₂ O ₃ , a cation of a 4A group element and nitrogen are contained in at least a layered portion provided on the surface of the substrate. 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. The low adhesion material may be a material (so-called bulk material) containing Y ₂ O ₃ and 4A group element cations 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. Thereby, the liquid material containing an organic-inorganic precursor is produced | 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, or 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 a layered material or a bulk material. 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. Moreover, 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 building outer walls and the like. In addition, as materials for pipes and tanks that come into contact with an object consisting of at least one of a basic substance, a thermosetting resin, or a substance containing moisture, first to third low Any of the adhesive materials can be used. Furthermore, any of the first to third low adhesion materials may be used as a material for coating the surface of a member used for these applications.

  Hereinafter, as Example 6, a mold according to the present invention will be described with reference to FIG. 3 (1) and 3 (2) are partial cross-sectional views showing the outline of a coated mold and a mold made of a bulk material, respectively, according to the present invention.

  Example 6 is the first low adhesion material described in Example 1, the second low adhesion material described in Example 2, or the third low adhesion material described in Example 3. Any of the materials is used as a mold. As shown in FIG. 3A, 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 mold 1 corresponds to the mold according to the present 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 (1) is made 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 (1), 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 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 (1) is used will be described. This mold is used when resin-sealing chip-shaped parts such as semiconductor chips.

  As shown in FIG. 3A, 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 13 is continuously 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 resin-sealed 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.

  As shown in FIG. 3 (2), the entire upper mold 12, which is a mold, may be constituted by the bulk material 13. In this case, first, the powdered material is molded according to the shape of the mold. Thereafter, 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, of the mold, a part of the mold surface 3 with which the fluid resin 13 contacts, for example, the inner bottom surface (upper surface in FIG. 3) of the cavity 7 is made 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. The present invention is not limited to this and can be applied to a mold used in general compression molding, injection molding, and the like. In other words, the present invention can be applied to a mold used when a molded body is manufactured by curing the fluid resin in a state where the cavity 7 is filled with the fluid resin.

  Further, the mold described in this embodiment includes a punching mold. That is, it is a mold used when manufacturing a molded product by punching a material, and is in contact with at least one of a basic substance, a thermosetting resin, or a substance containing moisture. The low adhesion material according to the present invention can be used for a mold having a possibility.

  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%.

  Further, the low adhesion material produced by the method for producing a low adhesion material described in Example 4 is also 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.

  In addition, the present invention is not limited to the above-described embodiments, and may be arbitrarily combined, changed, or selected as necessary without departing from the spirit of the present invention. It can be done.

DESCRIPTION OF SYMBOLS 1, 12 Upper mold | type 2 Lower mold | type 3 Mold surface 4 Release layer 5 Base material 6 Resin passage 7 Cavity 8 Surface 9 Substrate 10 Chip 11 Wire 13 Bulk material

Claims (28)

A low-adhesion material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture,
A low adhesion material, wherein at least a surface of the low adhesion material contains yttrium oxide and nitrogen. A low-adhesion material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture,
A low-adhesion material comprising at least a surface of the low-adhesion material containing yttrium oxide and a cation of a group 4A element. A low-adhesion material having low adhesion to an object composed of a basic substance, a thermosetting resin, or a substance containing moisture,
A low-adhesion material comprising at least a surface of the low-adhesion material containing yttrium oxide, nitrogen, and a cation of a group 4A element. In the low adhesion material according to claim 1 or 3,
The low adhesion material characterized in that the amount of nitrogen contained in at least the surface of the low adhesion material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atom. In the low adhesion material according to claim 2 or 3,
The low adhesion material, wherein the amount of the cation of the group 4A element contained in at least the surface of the low adhesion material is more than 0 mol% and 20 mol% or less. In the low adhesion material according to any one of claims 2, 3, or 5,
The low adhesion material, wherein the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ . In the low adhesion material according to any one of claims 1 to 6,
The low adhesion material has a base material;
The base material contains zirconium oxide as a main component,
Yttrium oxide and nitrogen are yttrium oxide and the cation of the group 4A element, or yttrium oxide, nitrogen and cation of the group 4A element are included in the layered portion provided on the surface of the base material. Low adhesion material characterized by An antifouling material having antifouling properties with respect to dirt containing an object composed of a substance having basicity, a thermosetting resin, or a substance containing moisture,
An antifouling material characterized in that at least the surface of the antifouling material contains yttrium oxide and nitrogen. An antifouling material having antifouling properties with respect to 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 of the antifouling material containing yttrium oxide and a cation of a group 4A element. An antifouling material having antifouling properties with respect to 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 of the antifouling material containing yttrium oxide, nitrogen, and a cation of a group 4A element. In the antifouling material according to claim 8 or 10,
The antifouling material, wherein the amount of nitrogen contained in at least the surface of the antifouling material is 0.01 mol% or more and 10 mol% or less in terms of nitrogen atoms. In the antifouling material according to claim 9 or 10,
The antifouling material, wherein the amount of the cation of the group 4A element contained in at least the surface of the antifouling material is more than 0 mol% and not more than 20 mol%. In the antifouling material according to any one of claims 9, 10, or 12,
The antifouling material, wherein the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ . In the antifouling material according to any one of claims 8 to 13,
The antifouling material has a base material,
The base material contains zirconium oxide as a main component,
Yttrium oxide and nitrogen are yttrium oxide and the cation of the group 4A element, or yttrium oxide, nitrogen and cation of the group 4A element are included in the layered portion provided on the surface of the base material. Antifouling material characterized by A mold used when molding a molded article,
A molding die characterized in that at least the surface of the molding die contains yttrium oxide and nitrogen. A mold used when molding a molded article,
A molding die characterized in that at least the surface of the molding die contains yttrium oxide and a cation of a group 4A element. A mold used when molding a molded article,
The mold according to claim 1, wherein at least a surface of the mold contains yttrium oxide, nitrogen, and a cation of a group 4A element. The mold according to claim 15 or 17,
The mold according to claim 1, wherein 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. The mold according to claim 16 or 17,
The mold according to claim 1, wherein the amount of the cation of the group 4A element contained in at least the surface of the mold exceeds 0 mol% and is 20 mol% or less. The mold according to any one of claims 16, 17 or 19,
The mold according to claim 4, wherein the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ . In the shaping | molding die described in any one of Claims 15-20,
The mold has a base material,
The base material contains zirconium oxide as a main component,
Yttrium oxide and nitrogen are yttrium oxide and the cation of the group 4A element, or yttrium oxide, nitrogen and cation of the group 4A element are included in the layered portion provided on the surface of the base material. Mold that is characterized by being. 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 an antifouling property having antifouling properties related to dirt containing the object A method for manufacturing a material, or a method for manufacturing 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, or the mold contains yttrium oxide and a cation of the group 4A element. The manufacturing method characterized by including the process to do. The manufacturing method according to claim 22, wherein
While preparing a step of preparing a base material containing zirconium oxide as a main component,
In the step of setting at least the surface of any one of the low adhesion material, the antifouling material, or the mold to contain yttrium oxide and a cation of the group 4A element, the surface of the base material A layered portion provided in the substrate is in a state containing yttrium oxide and a cation of the group 4A element. The manufacturing method according to claim 22 or 23,
A manufacturing method comprising the step of further including nitrogen on at least the surface of any of the low adhesion material, the antifouling material, or the mold. In the manufacturing method as described in Claim 22-24,
The amount of the cation of the group 4A element included in at least the surface of any of the low adhesion material, the antifouling material, or the mold is more than 0 mol% and not more than 20 mol%. Production method. In the manufacturing method as described in any one of Claims 22-25,
4. The production method according to claim 1, wherein the cation of the group 4A element is at least one of Zr ⁴⁺ or Hf ⁴⁺ . 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 an antifouling property having antifouling properties related to dirt containing the object A method for manufacturing a material, or a method for manufacturing a mold used when molding a molded article,
Preparing a second raw material containing yttrium oxide as a main component;
A manufacturing method comprising the step of including nitrogen in the surface of the second raw material. The manufacturing method according to claim 24 or 27,
The amount of nitrogen contained in at least the surface of any of the low adhesion material, the antifouling material, or the molding die or the surface of the second raw material is 0.01 mol% or more in terms of nitrogen atoms. And the manufacturing method characterized by being 10 mol% or less.

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