WO2017195448A1

WO2017195448A1 - Release agent, method for producing same, release agent product, release agent aerosol, and component provided with release agent

Info

Publication number: WO2017195448A1
Application number: PCT/JP2017/009112
Authority: WO
Inventors: 本多　祐二; 由佳利三上
Original assignee: 株式会社ユーテック
Priority date: 2016-05-12
Filing date: 2017-03-01
Publication date: 2017-11-16
Also published as: JPWO2017195448A1

Abstract

Provided is a release agent that can adhere easily to the surface of a component. An aspect of the invention is a release agent comprising particles 53, and an oil and/or a solvent, wherein: the particles, the oil, and the solvent each have a heat resistance of 250°C or higher; each particle includes a grain 51, and a first film 52 or a substance covering the grain; and the first film or the substance has a friction coefficient of 0.4 or less (preferably 0.3 or less, more preferably 0.2 or less).

Description

Release agent and manufacturing method thereof, release agent article, release agent aerosol, and member with release agent

The present invention relates to a release agent and a production method thereof, a release agent article, a release agent aerosol, and a member with a release agent.

There is a technique for forming a DLC film on the surface of a mold so that the mold can be used for a long period of time or improving the releasability of a molded product.
In order to form a DLC film on the surface of the mold, there is a method of introducing a mold into a vacuum chamber of a plasma CVD apparatus and performing a process of forming the DLC film on the mold in the vacuum chamber. (For example, refer to Patent Document 1).
However, when the mold as the film formation object is very large (when a DLC film is formed on a very large mold), the mold cannot be introduced into the vacuum chamber of the plasma CVD apparatus. A DLC film may not be formed on the surface of the mold.
In addition, even if the deposition target is small, the industry also demands that a release agent be attached to the surface of the mold by a simpler method of forming a DLC film using a plasma CVD apparatus.
Moreover, if oil is contained in the mold release agent to be attached to the surface of the mold, the oil will fly as a mist, so that it cannot be used in a clean room such as a semiconductor factory or a food factory. In addition, when molding parts for electrodes or parts that require electrical conductivity with copper, brass, etc., if a mold release agent containing oil is used, the electrical conductivity will decrease, so the oil attached to the molded product The process of degreasing is required. Therefore, there is a demand for a release agent that does not contain oil in various fields.

JP 2008-38217 A

An object of one embodiment of the present invention is to provide a release agent that can be easily attached to the surface of a member, a manufacturing method thereof, a release agent article, and a release agent aerosol.
Another object of one embodiment of the present invention is to provide a member with a release agent in which a release agent is attached to the surface.

Hereinafter, various aspects of the present invention will be described.
[1] A release agent having fine particles,
The fine particles have particles and a first film or substance that covers the particles,
The mold release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
[2] A release agent having fine particles,
The fine particles include particles, a second film that covers the particles, and a first film or substance that covers the second film,
The mold release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
[3] In the above [2],
The mold release agent, wherein the second film has a friction coefficient of 0.4 or less.
[4] In any one of [1] to [3] above,
The first film or substance has a friction coefficient of 0.05 or more and 0.3 or less (preferably 0.05 or more and 0.2 or less).
[4-1] In the above [3],
The mold release agent, wherein the second film or substance has a friction coefficient of 0.05 to 0.3 (preferably 0.05 to 0.2).
[5] In any one of [1] to [4] and [4-1] above,
A mold release agent, wherein a contact angle of water on the surface of the fine particles is 60 ° or more.
[6] In any one of the above [1] to [4], [4-1], and [5]
The mold release agent, wherein the particles include at least one selected from the group consisting of metals, ceramics, resins, and minerals.
[7] In any one of the above [1] to [4], [4-1], [5], and [6]
A mold release agent, wherein at least one of the particles and the first film has a heat resistance of 250 ° C. or higher.
[8] In the above [2] or [3],
A release agent, wherein at least one of the particles, the first film, and the second film has a heat resistance of 250 ° C. or higher.
[9] In any one of the above [1] to [4], [4-1], [5] to [8]
The release agent characterized in that the particles contain a substance having a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less).
[10] In any one of the above [1] to [4], [4-1], [5] to [8]
The mold release agent, wherein the particles include at least one selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, graphite, mica, talc, clay, apatite, kaolin, and silica.
[11] In any one of the above [1] to [4], [4-1], [5] to [10]
The first film or material is at least selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN, CrN, TiN, molybdenum disulfide and tungsten disulfide. A mold release agent characterized by comprising one.
[12] In any one of the above [2], [3] and [8],
The second film is selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN, CrN, TiN, molybdenum disulfide, tungsten disulfide, and Si. A mold release agent comprising at least one of the first film and a film different from the first film.
[13] In any one of the above [1] to [4], [4-1], [5] to [12],
A mold release agent, wherein the fine particles have a particle size of 100 μm or less.
[14] In any one of the above [1] to [4], [4-1], [5] to [13],
The mold release agent contains at least one of oil and a solvent.
[15] The mold release agent according to any one of [1] to [4], [4-1], [5] to [14],
A container containing the release agent;
A release agent product characterized by comprising:
[16] A release agent according to any one of [1] to [4], [4-1], [5] to [14], and a spray container filled with a propellant. Release agent aerosol.
[17] A mold,
A release agent attached to the surface of the mold;
Comprising
The release agent has fine particles,
The fine particles have particles and a first film or substance that covers the particles,
The first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Attached member.
[18] A mold,
A release agent attached to the surface of the mold;
Comprising
The release agent has fine particles,
The fine particles include particles, a second film that covers the particles, and a first film or substance that covers the second film,
The first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Attached member.
[19] In the above [18],
The second film has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). .
[19-1]
In any one of the above [17] to [19],
A member with a release agent, wherein a contact angle of water on the surface of the fine particles is 60 ° or more.
[19-2]
In any one of [17] to [19] and [19-1] above,
The particle includes a substance having a friction coefficient of 0.4 or less, and a member with a release agent.
[19-3]
In any one of the above [17] to [19], [19-1], [19-2]
A member with a release agent, wherein the fine particles adhering to the surface of the mold are crushed.
[20] The particles are accommodated in a chamber whose cross-sectional internal shape is circular or polygonal,
A counter electrode facing the inner surface of the chamber is disposed in the chamber;
Connect a ground to the chamber,
The chamber is evacuated,
The chamber is rotated or pendulum operated with a direction substantially perpendicular to the cross section as a rotation axis,
Introducing a source gas into the chamber;
Release to produce fine particles by coating the first film or substance on the surface of the particles by plasma CVD while stirring or rotating the particles in the chamber by supplying high frequency power to the counter electrode A method for producing the agent,
Release agent characterized in that the first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0 or 3 or less, more preferably 0.05 or more and 0.2 or less). Manufacturing method.
[21] The particles are accommodated in a chamber having a circular or polygonal cross-sectional shape,
A counter electrode facing the inner surface of the chamber is disposed in the chamber;
Connect a ground to the chamber,
The chamber is evacuated,
The chamber is rotated or pendulum operated with a direction substantially perpendicular to the cross section as a rotation axis,
Introducing a first source gas into the chamber;
By supplying high-frequency power to the counter electrode, the particles in the chamber are agitated or rotated, and the surface of the particles is coated with a second film by a plasma CVD method.
Stopping the introduction of the first source gas into the chamber;
Introducing a second source gas into the chamber;
By supplying high frequency power to the counter electrode, the surface of the second film of the particles is coated with the first film or substance by the plasma CVD method while stirring or rotating the particles in the chamber. A method for producing a release agent for producing fine particles with
The first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Manufacturing method.
[22] The particles are accommodated in a vacuum vessel having a polygonal internal shape of a cross section substantially parallel to the direction of gravity,
By performing sputtering while stirring or rotating the particles in the vacuum container by rotating the vacuum container about a direction substantially perpendicular to the cross section, the first film or substance is applied to the surface of the particles. It is a method for producing a release agent that produces fine particles by coating,
The first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Manufacturing method.
[23] The particles are accommodated in a vacuum vessel having a polygonal internal shape of a cross section substantially parallel to the direction of gravity,
The surface of the particles is coated with the second film by performing sputtering while rotating or rotating the vacuum vessel about the direction perpendicular to the cross section as the rotation axis. ,
Sputtering is performed while stirring or rotating the particles in the vacuum container by rotating the vacuum container about a direction substantially perpendicular to the cross section as a rotation axis, so that a first surface is formed on the surface of the second film. A method for producing a release agent for producing fine particles by coating a film or a substance,
The first film or substance has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Manufacturing method.
[24] In the above [21] or [23],
The second film has a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Method.
[25] In any one of [20] to [24] above,
A method for producing a release agent, wherein the contact angle of water on the surface of the fine particles is 60 ° or more.
[26] In any one of [20] to [25] above,
The particle contains a substance having a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Method.
[27] In any one of [20] to [26] above,
The said particle | grain contains at least 1 selected from the group which consists of a metal, ceramics, resin, and a mineral, The manufacturing method of the mold release agent characterized by the above-mentioned.
[28] In any one of [20] to [27] above,
A method for producing a release agent, wherein at least one of the particles and the first film has a heat resistance of 250 ° C. or higher.
[29] In any one of the above [21], [23] and [24]
A method for producing a release agent, wherein at least one of the particles, the first film, and the second film has a heat resistance of 250 ° C. or higher.
[30] In any one of [20] to [29] above,
After producing the said microparticles | fine-particles, the said microparticles | fine-particles and at least one of oil and a solvent are mixed, The manufacturing method of the mold release agent characterized by the above-mentioned.
According to one embodiment of the present invention, it is possible to provide a release agent that can be easily attached to the surface of a member, a manufacturing method thereof, a release agent article, or a release agent aerosol.
In addition, according to one embodiment of the present invention, a member with a release agent in which a release agent is attached to the surface can be provided.

1A is a cross-sectional view showing fine particles used in the release agent according to one embodiment of the present invention, and FIG. 1B is a cross-section showing fine particles used in the release agent according to another embodiment of the present invention. FIG.
2A to 2D are diagrams showing particles of various shapes.
FIG. 3 is a cross-sectional view illustrating a release agent aerosol according to one embodiment of the present invention.
4A is a cross-sectional view illustrating a plasma CVD apparatus used when manufacturing a release agent according to one embodiment of the present invention, and FIG. 4B is along a line 200-200 illustrated in FIG. It is sectional drawing.
FIG. 5 is a configuration diagram showing an outline of a polygonal barrel sputtering apparatus used when a film is coated on particles.
6A is a cross-sectional view illustrating a part of a member with a release agent according to one embodiment of the present invention, and FIG. 6B illustrates a part of the member with a release agent according to another embodiment of the present invention. It is sectional drawing shown.
FIG. 7 is an SEM (Scanning Electron Microscope) image of the fine particles of Example 1.
FIG. 8 is an SEM image obtained by covering the fine particles shown in FIG. 7 with a processing protective film and imaging the cut surface of the fine particles.
FIG. 9 is a photograph of the sample of Example 4.
FIG. 10 is a photograph of the sample of Example 4.
FIGS. 11A to 11D are photographs of Example 5. FIG.
FIG. 12 is a photograph of Example 5.
FIG. 13A is a photograph in which a release agent is applied to a glass substrate according to Example 6, and FIG. 13B is a photograph showing a state in which the contact angle of water in Example 6 is measured.
FIG. 14A is a photograph showing a glass substrate, and FIG. 14B is a photograph showing a state in which the contact angle of water in the comparative example was measured.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following description, and it will be easily understood by those skilled in the art that modes and details can be variously changed without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments below.
<Release agent>
FIG. 1A is a cross-sectional view illustrating fine particles used for a release agent according to one embodiment of the present invention. 2A to 2D are diagrams showing particles of various shapes.
A fine particle 53 illustrated in FIG. 1A is obtained by covering a particle 51 with a first film 52 or a substance. The first film 52 or the substance may have a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). Thereby, the fine particles 53 can have a function as a release agent. The lower the coefficient of friction of the first film 52 or substance, the higher the function as a release agent. The contact angle of water on the surface of the fine particles 53 is preferably 60 ° or more. Thereby, the function as a mold release agent of the microparticles | fine-particles 53 can be improved. The particles may contain a substance having a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). The particle size L1 of the fine particles 53 is preferably 100 μm or less, and may be 70 μm or less. In the present specification, the “particle diameter” means the longest diameter among the outer diameters of the fine particles 53.
As the particles 51, particles having various shapes can be used. For example, the particles having an indefinite shape shown in FIG. 2 (A), the particles having a spherical shape shown in FIG. 2 (B), and FIGS. The projection-shaped particles shown in FIG.
The film thickness of the first film 52 is preferably 1/20 or less of the particle diameter L1 of the fine particles 53. This is because if the thickness of the first film 52 is larger than 1/20 of the particle diameter of the fine particles 53, the first film 52 is easily peeled off from the fine particles 53.
The particles 51 may be particles containing at least one selected from the group consisting of metals, ceramics, resins, and minerals. In general, when a resin or metal molded product is manufactured using a mold, a material having heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher) may be used for the particles 51. When the material of the molded product is a resin that melts at a high temperature, a material having heat resistance close to 400 ° C. may be used for the particles 51, and when the material is a metal, a material having heat resistance close to 1000 ° C. may be used. Thereby, it becomes possible to use the release agent in a high temperature environment. Examples of metals that can be used for the particles 51 include silver, indium, tin, tellurium, antimony, and bismuth. As an example other than metal, a material having high heat resistance and heat insulation properties such as graphite, mica, talc, clay, and apatite is desirable. Further, kaolin, silica or the like may be used for the particles 51.
The first film 52 or material is at least selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN, CrN, TiN, molybdenum disulfide and tungsten disulfide. One should be included. The first film 52 or the substance may be a material having heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher). Note that the first film 52 or the substance may be made of a material different from that of the particles 51 or the same material. As described above, when any one of the particles 51, the first film 52, and the substance has a heat resistance of 250 ° C. or higher, it is possible to achieve releasability.
A DLC film having a friction coefficient of 0.1 to 0.4 may be used, and a DLC film having a friction coefficient of 0.1 or less may be used. The surface of the DLC film has a low roughness and a low friction coefficient like a mirror surface. A DLC film having a water contact angle of 65 ° to 98 ° may be used. When fluorine is contained in the DLC film, the friction coefficient can be lowered as compared with a DLC film not containing fluorine. In addition, when a mold release agent is applied to the mold, the DLC film containing fluorine has higher mold release properties than the DLC film containing no fluorine, and therefore it is desirable to select the material according to the raw material of the molded product. Further, since DLC has a heat resistance of 550 ° C., fine particles using silver for the particles 51 and DLC for the first film 52 have a heat resistance of 500 ° C. Such fine particles can be used as a release agent that requires high heat resistance.
The hydrogen content of the DLC film may be 30 atomic% or less (preferably 20 atomic% or less, more preferably 10 atomic% or less). Thus, by reducing the hydrogen content of the DLC film, the friction coefficient of the DLC film can be lowered. By setting the hydrogen content of the DLC film to 20 atomic% or less, the friction coefficient of the DLC film can be set to 0.15 or less.
FIG. 1B is a cross-sectional view showing fine particles used in the release agent according to another embodiment of the present invention.
A fine particle 57 illustrated in FIG. 1B is obtained by covering a particle 54 with a second film 55 and covering the second film 55 with a third film 56 or a substance. The third film 56 or substance may be the same as the first film 52 or substance shown in FIG. 1A, and is 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably Preferably has a friction coefficient of 0.05 or more and 0.2 or less. Thereby, the fine particles 57 can have a function as a release agent. The lower the coefficient of friction of the third film 56 or substance, the higher the function as a release agent. The contact angle of water on the surface of the fine particles 57 is preferably 60 ° or more. Thereby, the function as a mold release agent of the microparticles | fine-particles 53 can be improved. The second film 55 may have a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less). The particle diameter L2 of the fine particles 57 is preferably 100 μm or less, and may be 70 μm or less.
For the second film 55, the same material as that of the particles 51 shown in FIG. 1A may be used. For example, silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN , CrN, TiN, molybdenum disulfide, tungsten disulfide, and a material containing at least one selected from the group consisting of Si can be used. However, the second film 55 is preferably a film using a material different from that of the third film 56 or the substance, but the second film 55 is made of the same material as the third film 56 or the substance. It may be a membrane. For the second film 55, a material having heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher) may be used.
The second film 55 preferably has a function as an intermediate film for improving the adhesion between the third film 56 and the particles 54. For example, when the third film 56 is a DLC film, the second film 55 is a second film. The film may be a film containing Si. This film is a film formed by a CVD method using a source gas containing Si. By using a film containing Si as an intermediate film, adhesion between an organic material and an inorganic material can be improved by Si like a silane coupling agent.
The film thickness of each of the second film 55 and the third film 56 is preferably 1/20 or less of the particle diameter L2 of the fine particles 57. This is because if the thickness of each of the second film 55 and the third film 56 is larger than 1/20 of the particle diameter of the fine particles 57, the second film 55 and the third film 56 are easily peeled off from the fine particles 53. .
A resin having heat resistance of 250 ° C. or higher is used for the particles 54, the same material as the particles 51 shown in FIG. 1A is used for the second film 55, and the third film 56 is shown in FIG. By using the same material as that of the first film 52, the material cost can be reduced as compared with the fine particles 53 shown in FIG. 1A while exhibiting the release performance close to the fine particles 53 shown in FIG. be able to.
Further, the particles 54 may be particles containing at least one selected from the group consisting of metals, ceramics, and minerals.
The release agent may be composed of the fine particles 53 or the fine particles 57 described above, but the fine particles 53 or the fine particles 57 may contain at least one of oil and a solvent. The oil may have a heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher). This oil or the like should be easy to adhere the mold release agent to the mold, and even after the mold is heated to produce a molded product, the oil is difficult to evaporate from the mold surface. Good. By setting it as such, it can make it easy to release a molded article from a metal mold | die, and can make it hard to lose | release a mold release agent from a metal mold | die. In addition to oil, a solvent having heat resistance may be used to impart releasability, and a highly volatile organic solvent is used to apply or adhere the

fine particles

53 or 57 to the mold. May be used.
Said oil is good to contain at least one selected from the group of polymer compounds, such as silicone oil, mineral oil, fats and oils, synthetic esters, and waxes.
The solvent is at least one selected from the group consisting of hydrogen carbonate, alcohol, ketone, ester, ether, glycol, glycol ester, glycoether, glyme, halogen, and special solvents. It is good to include.
Although said mold release agent is demonstrated as a mold release agent, it is not limited to a mold, You may use as a mold release agent of things other than a metal mold | die.
<Release agent supplies and release agent aerosol>
A mold release product can be produced by housing the mold release agent in a container. In the present specification, the “container” is a concept including a syringe.
The release agent aerosol has the above release agent and an injection container filled with a propellant. Specifically, the release agent aerosol can be produced by filling the above-mentioned release agent together with the propellant in the injection container.
The particle size of the fine particles may be any size that can be sprayed without clogging when an aerosol product is used, and it is generally preferable that the average particle size is 20 μm or less.
For the release agent aerosol, it is preferable to shake the container to make the fine particles uniformly dispersed during use. In addition, in order to increase the stirring efficiency when the container is shaken, if a stirring ball is placed in the container, the stirring can be performed more easily and easily.
In particular, by using an aerosol container equipped with a metering valve that can inject a certain amount, it is possible to inject and apply only a necessary amount, and to prevent wasteful consumption of fine particles. The metering valve is a valve that is generally used for perfume, medicine, etc. with a small amount of use, and is designed to inject a certain volume for each operation.
For example, as schematically shown in FIG. 3, as an example, in the metering injection type container 1 having the metering valve 2, when the actuator 3 is pushed down, the metering chamber 2a and the dip tube 4 are first shut off, and further, When pressed down, the metering chamber 2a is opened and the contents are jetted from the nozzle port 5 into the atmosphere. Thereafter, when the actuator 3 is opened, the path from the metering chamber 2a to the atmosphere is first blocked, and then the contents are supplied to the metering chamber 2a through the dip tube 4.
Further, in the container 1, a release agent mainly composed of a solvent or oil having heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher), a highly volatile organic solvent, and liquefied hydrocarbon gas, A liquid phase 6 containing a propellant such as dimethyl ether is contained. A plurality of fine particles are dispersed in the liquid phase 6, and the

fine particles

53 or 57 are settled in the liquid phase 6. The container 1 also contains a gas phase 8 made of a propellant such as liquefied hydrocarbon gas, and a stirring ball 9 for increasing the stirring efficiency.
<Manufacturing method of release agent>
4A is a cross-sectional view illustrating a plasma CVD apparatus used for manufacturing a release agent according to one embodiment of the present invention, and FIG. 4B is a cross-sectional view of 200-200 illustrated in FIG. It is sectional drawing along a line. This plasma CVD apparatus is an apparatus for coating the surface of the particles 51 with a DLC film.
In the present embodiment, a description will be given of a plasma CVD apparatus in which particles 51 are accommodated in a container having an internal cross-sectional shape that is a polygon, and the particles 51 are covered with a DLC film. However, the internal cross-sectional shape of the container is not limited to a polygon. The internal cross-sectional shape of the container can be circular or elliptical. The difference between a container having a polygonal internal cross-sectional shape and a container having a circular or elliptical shape is that the polygonal container can coat the DLC film with a smaller particle diameter more uniformly than the circular or elliptical container. Is a point.
As shown in FIGS. 4A and 4B, the plasma CVD apparatus has a cylindrical chamber 13. One end of the chamber 13 is closed by a chamber lid 21a, and the other end of the chamber 13 is closed by a chamber lid 21b. Each of the chamber 13 and the

chamber lids

21a and 21b is connected to ground (ground potential).
Inside the chamber 13, a conductive container that accommodates the particles 51 is disposed. This container has a cylindrical first container member 29, a second container member 29a, a first ring-shaped member 29b, and a second ring-shaped member 29c. Each of the first container member 29, the second container member 29a, and the first and second ring-shaped members 29b and 29c has conductivity.
One end of the first container member 29 is closed, and an extension portion 29 d extending to the outside of the chamber 13 is formed on one end side of the first container member 29. The other end of the first container member 29 is opened. The extending portion 29d is connected to the ground.
A second container member 29a is arranged inside the first container member 29, and the second container member 29a has a barrel shape with a hexagonal cross section as shown in FIG. The cross section shown in FIG. 4B is a cross section substantially parallel to the gravity direction 11. In addition, in this specification, “substantially parallel” means to include those that are shifted by ± 3 ° with respect to perfect parallelism. Moreover, in this Embodiment, although the hexagonal barrel-shaped 2nd container member 29a is used, it is not limited to this, The polygonal 2nd container member other than a hexagon is used. It is also possible.
One end of the second container member 29a is attached to the inside of the first container member 29 by a first ring-shaped member 29b, and the other end of the second container member 29a is a first container by a second ring-shaped member 29c. It is attached inside the member 29. In other words, the first ring-shaped member 29b is located on one side of the second container member 29a, and the second ring-shaped member 29c is located on the other side of the second container member 29a. The outer periphery of each of the first and second ring-shaped members 29b and 29c is connected to the inner surface of the first container member 29, and the inner periphery of each of the first and second ring-shaped members 29b and 29c is the second container member. It is located on the gas shower electrode (counter electrode) 21 side from the inner surface of 29a.
The distance between the first ring-shaped member 29b and the second ring-shaped member 29c (that is, the distance between one end and the other end of the second container member 29a) is the distance between the one end and the other end of the first container member 29. Small compared to distance. Each of the first and second ring-shaped members 29 b and 29 c is disposed inside the first container member 29. And the powder (particle) 51 as a coating target object is accommodated in the space enclosed by the inner surface of the 2nd container member 29a and the 1st and 2nd ring-shaped members 29b and 29c. In other words, the inner surface 129a constituting the polygon of the second container member 29a and the first and second ring-shaped members 29b and 29c surrounding the inner surface 129a are respectively the

surfaces

129b and 129c (first and second ring-shaped members). , And the particles 51 are positioned on the accommodation surface.
In addition, the surface of the container other than the housing surface composed of the inner surface 129a forming the polygon in the second container member 29a and the

surfaces

129b and 129c of the first and second ring-shaped members surrounding the inner surface 129a is connected to the ground shielding member. (Not shown). The first container member 29, the first and second ring-shaped members 29b and 29c, and the ground shielding member may have a distance of 5 mm or less (preferably 3 mm or less). The earth shielding member is connected to a ground potential.
Further, the plasma CVD apparatus includes a source gas introduction mechanism that introduces a source gas into the chamber 13. This source gas introduction mechanism has a cylindrical gas shower electrode (counter electrode) 21. The gas shower electrode 21 is disposed in the second container member 29a. That is, an opening is formed on the other side of the second container member 29a, and the gas shower electrode 21 is inserted from this opening.
The gas shower electrode 21 is electrically connected to a power source 23, and high frequency power is supplied to the gas shower electrode 21 by the power source 23. The power source 23 is preferably a high frequency power source having a frequency of 10 kHz to 1 MHz, and more preferably a high frequency power source having a frequency of 50 kHz to 500 kHz. By using a power source having a low frequency in this way, it is possible to suppress the dispersion of plasma outside the space between the gas shower electrode 21 and the second container member 29a as compared with the case where a power source having a frequency higher than 1 MHz is used. be able to. In other words, the plasma can be confined between the gas shower electrode 21 and the second container member 29a. When RF plasma of 10 kHz to 1 MHz is used, induction heating is difficult to occur in such a closed plasma space, that is, in the barrel (second container member 29a), and a sufficient V at the time of film formation. _DC Therefore, it is easy to form a DLC film having a low coefficient of friction. On the other hand, when RF plasma such as 13.56 MHz is used, in a closed plasma space, V is applied to the particles 51. _DC Therefore, it is difficult to form a DLC film having a low friction coefficient.
The surface of the gas shower electrode (counter electrode) 21 other than the facing surface facing the particles 51 accommodated in the container is shielded by a ground shielding member 27a. The ground shielding member 27a and the gas shower electrode 21 have an interval of 5 mm or less (preferably 3 mm or less).
By covering the gas shower electrode 21 to which high-frequency power is supplied with the ground shielding member 27a, the high-frequency output can be concentrated inside the second container member 29a, and as a result, concentrated on the particles 51 accommodated in the container. High frequency power can be supplied.
A plurality of gas outlets for blowing out one or a plurality of source gases in a shower shape are formed on the facing surface on one side of the gas shower electrode 21. This gas outlet is disposed at the bottom (the facing surface) of the gas shower electrode 21 and is disposed so as to face the particles 51 accommodated in the second container member 29a. That is, the gas outlet is disposed so as to face the inner surface of the second container member 29a.
Further, as shown in FIG. 4B, the gas shower electrode 21 has a surface opposite to the gravity direction 11 having a convex shape on the opposite side. In other words, the cross-sectional shape of the gas shower electrode 21 is circular or elliptical except for the bottom. Thereby, even when the fine particles are placed on a circular or elliptical portion (convex shape portion) when the second container member 29a is rotated, the fine particles can be dropped from the gas shower electrode 21.
The other side of the gas shower electrode 21 is connected to one side of a mass flow controller (MFC) 22 via a vacuum valve 26a. The other side of the mass flow controller 22 is connected to the source gas generation source 20a via a vacuum valve 26b and a filter (not shown).
The other side of the gas shower electrode 21 is connected to one side of a mass flow controller (MFC) (not shown) via a vacuum valve (not shown). The other side of the mass flow controller is connected to an argon gas cylinder (not shown).
The first container member 29 is provided with a rotation mechanism (not shown). By this rotation mechanism, the first container member 29 and the second container member 29a are shown in FIG. The coating process is performed while stirring or rotating the particles 51 in the second container member 29a by rotating or pendulum-operating as shown by the arrows. A rotation axis when rotating the first container member 29 and the second container member 29a by the rotation mechanism is an axis parallel to a substantially horizontal direction (a direction perpendicular to the gravity direction 11). In the present specification, the “substantially horizontal direction” means including a deviation of ± 3 ° from the complete horizontal direction. Further, the airtightness in the chamber 13 is maintained even when the first container member 29 is rotated.
In addition, the plasma CVD apparatus includes a vacuum exhaust mechanism that exhausts the inside of the chamber 13. For example, the chamber 13 is provided with a plurality of exhaust ports (not shown), and the exhaust ports are connected to a vacuum pump (not shown).
Further, the inside of the chamber 13 is not shown so that the minimum diameter or the minimum gap in the path through which the gas is exhausted from the first container member 29 to the outside of the chamber 13 by the vacuum exhaust mechanism is 5 mm or less (preferably 3 mm or less). A grounding member is arranged. The source gas introduced into the second container member 29a from the gas shower electrode 21 is exhausted from the exhaust port through the minimum diameter or the minimum gap. At this time, by setting the minimum diameter or the minimum gap to 5 mm or less, it is possible to prevent the plasma from being confined in the vicinity of the particles 51 accommodated in the second container member 29a. That is, if the minimum diameter or the minimum gap is larger than 5 mm, the plasma may be dispersed or abnormal discharge may occur. In other words, by setting the minimum diameter or the minimum gap to 5 mm or less, it is possible to suppress the DLC film from being formed on the exhaust port side.
The gas shower electrode 21 has a heater (not shown). Further, the plasma CVD apparatus may have a grounding rod (not shown) as a striking member for applying vibration to the particles 51 accommodated on the inner surface of the second container member 29a. That is, it is preferable that the tip of the grounding rod can be hit against the first container member 29 or the ground shielding member through an opening provided in the chamber 13 by a drive mechanism (not shown). By continuously hitting the grounding rod against the ground shielding member rotating together with the first container member 29, it is possible to apply vibration to the particles 51 accommodated in the second container member 29a. Thereby, aggregation of the particles 51 can be prevented, and stirring and mixing of the particles 51 can be promoted. The ground shielding member and the first container member 29 are connected by an insulating member (not shown), and vibration from the ground shielding member may be transmitted to the first container member 29 through the insulating member. .
Next, the manufacturing method of a mold release agent is demonstrated in detail.
In this release agent manufacturing method, particles 51 are coated with a DLC film using the plasma CVD apparatus.
First, the plurality of particles 51 are accommodated in the second container member 29a. The average particle diameter of the particles 51 is, for example, about 20 μm. The particles 51 may contain a substance having a friction coefficient of 0.4 or less (preferably 0.05 or more and 0.3 or less, more preferably 0.05 or more and 0.2 or less).
Thereafter, a predetermined pressure (for example, 5 × 10 5) is generated in the chamber 13 by operating the vacuum pump. ^-5 The pressure is reduced to about Torr). At the same time, the first container member 29 and the second container member 29a are rotated by the rotating mechanism, whereby the particles 51 accommodated in the second container member 29a are stirred or rotated on the inner surface of the container. Here, although the first container member 29 and the second container member 29a are rotated, the first container member 29 and the second container member 29a can be operated in a pendulum manner by a rotation mechanism.
Next, a source gas is generated in the source gas generation source 20 a, the source gas is controlled to a predetermined flow rate by the mass flow controller 22, and the source gas whose flow rate is controlled is introduced inside the gas shower electrode 21. Then, the source gas is blown out from the gas outlet of the gas shower electrode 21. As a result, the source gas is sprayed onto the particles 51 moving while stirring or rotating in the second container member 29a, and the pressure suitable for film formation by the CVD method is maintained by the balance between the controlled gas flow rate and the exhaust capability. Be drunk.
Further, the grounding rod is continuously driven by the driving mechanism to the ground shielding member 27 rotating together with the first container member 29. Thereby, it is possible to vibrate the particles 51 accommodated in the second container member 29a, prevent the particles 51 from aggregating, and promote the stirring and mixing of the particles 51.
Thereafter, an RF output of 250 kHz at 150 W, for example, is supplied to the gas shower electrode 21 from the power source 23. At this time, the first container member 29, the first and second ring-shaped members 29b and 29c, the second container member 29a, and the particles 51 are connected to the ground. Thereby, plasma is ignited between the gas shower electrode 21 and the second container member 29 a, plasma is generated in the second container member 29 a, and the surface of the particle 51 is covered with the DLC film. That is, since the particles 51 are stirred and rotated by rotating the second container member 29a, it is possible to easily produce fine particles in which the entire surface of the particles 51 is uniformly coated with the DLC film. As described above, the entire surface of the particle 51 may be coated with a DLC film, but the surface of the particle 51 may be coated with DLC that does not become a film. The DLC film coated in this way has a coefficient of friction of 0.4 or less. Further, the contact angle of water on the surface of the fine particles thus produced is preferably 60 ° or more.
Next, a mold release agent is manufactured by mixing the fine particles produced as described above, at least one of a solvent and oil, and a highly volatile organic solvent. Each of the fine particles, the solvent, and the oil may have heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher).
In this embodiment, a release agent is produced by mixing fine particles, at least one of a solvent and oil, and a highly volatile organic solvent. However, the fine particles and at least one of solvent and oil are mixed. A mold release agent may be produced, or a mold release agent composed of fine particles may be produced.
According to the above embodiment, the first film 52 or the substance covering the particles 51 has a friction coefficient of 0.4 or less (or 0.05 or more and 0.3 or less, or 0.05 or more and 0.2 or less). By having it, the fine particles 53 shown in FIG. 1A can function as a release agent. Moreover, the function as a mold release agent of the microparticles | fine-particles 53 can be improved because the contact angle of the water of the surface of the microparticles | fine-particles 53 shall be 60 degrees or more. Further, when the particles 51 contain a substance having a friction coefficient of 0.4 or less, even if the fine particles 53 after adhering to the surface of the mold are crushed, they can function as a release agent.
In the present embodiment, the third film 56 or the material covering the particles 54 has a friction coefficient of 0.4 or less (or 0.05 or more and 0.3 or less, or 0.05 or more and 0.2 or less). Thus, the fine particles 57 shown in FIG. 1B can function as a release agent. Moreover, the function as a mold release agent of the microparticles | fine-particles 57 can be improved because the contact angle of the water of the surface of the microparticles | fine-particles 57 shall be 60 degrees or more. In addition, since the second film 55 covering the particles 54 has a friction coefficient of 0.4 or less (or 0.05 or more and 0.3 or less, or 0.05 or more and 0.2 or less), the surface of the mold Even if the fine particles 57 adhered to the surface are crushed, they can function as a release agent.
Moreover, in this Embodiment, a mold release agent can be easily apply | coated to the said metal mold | die irrespective of the magnitude | size of the object mold | die which applies a mold release agent.
Moreover, the release agent which does not contain oil can be manufactured by using the release agent which mixed the solvent with the fine particle instead of oil. As a result, it can be used in a clean room such as a semiconductor factory or a food factory.
Moreover, in this Embodiment, since it is set as the apparatus structure which connects a ground to the container which accommodates the particle | grains 51 by applying a high frequency power to the gas shower electrode 21, a ground is connected to the gas shower electrode 21, and a high frequency power is connected to the container Compared with the case of applying, the mechanical structure of the plasma CVD apparatus can be simplified, and the apparatus cost can be reduced. Further, since the mechanical structure of the plasma CVD apparatus can be simplified, the maintainability is improved.
Moreover, in this Embodiment, since it is set as the apparatus structure which applies high frequency power to the gas shower electrode 21, compared with the case where high frequency power is applied to a container, matching can be taken easily and it can make it difficult to remove | tune. The reason for this is that, if the configuration is such that high-frequency power is applied to the container, the impedance always changes due to the rotational movement of the container, making it difficult to achieve matching and make it difficult to tune.
In the present embodiment, the particles 51 themselves can be rotated and stirred by rotating the hexagonal barrel-shaped second container member 29a itself, and the particles 51 are periodically formed by gravity by making the barrel hexagonal. Can be dropped. For this reason, the stirring efficiency can be dramatically improved, and aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling powder (fine particles), can be prevented. That is, by rotation, stirring and pulverization of the aggregated particles 51 can be performed simultaneously and effectively. Therefore, the DLC film can be coated on the particles 51 having a very small particle diameter. Specifically, it becomes possible to coat the DLC film on particles having a particle size of 10 μm or less.
In the present embodiment, the surface of the gas shower electrode 21 other than the facing surface facing the particles 51 accommodated in the container is shielded by the ground shielding member 27a. For this reason, plasma can be generated between the inner surface of the second container member 29a and the gas shower electrode 21 opposed thereto. That is, the high frequency output can be concentrated inside the second container member 29a, and as a result, concentrated on the particles 51 accommodated on the inner surface of the second container member 29a (that is, the particles 51 positioned on the accommodation surface). Therefore, it is possible to supply high-frequency power to the particles 51 effectively. Therefore, the DLC film is formed on a portion other than the space for accommodating the particles 51 surrounded by the inner surface of the second container member 29a and the first and second ring-shaped members 29b and 29c (the surface of the container other than the accommodation surface). It can suppress adhering. In addition, the amount of high-frequency power can be reduced as compared with a conventional plasma CVD apparatus.
Moreover, in this Embodiment, stirring and mixing of the particle | grains 51 accommodated in the 2nd container member 29a can be accelerated | stimulated by hit | damaging an earth | ground stick | rod continuously to a container or an earth shielding member. Therefore, the DLC film can be coated evenly on the particles 51 having a smaller particle diameter.
Moreover, when making the internal cross-sectional shape of a container circular in the said embodiment, by changing into the apparatus which eliminated the 2nd container member 29a from the plasma CVD apparatus shown to FIG. 4 (A), (B), for example. It becomes possible to carry out.
In the above embodiment, when the inner cross-sectional shape of the container is elliptical, for example, the second container member 29a is eliminated from the plasma CVD apparatus shown in FIGS. 4A and 4B, and the first container member is further removed. This can be implemented by changing the internal cross-sectional shape of 29 to an ellipse.
In the above embodiment, the plasma power source 23 is connected to the first container member 29 and the ground potential is connected to the gas shower electrode 21. However, the present invention is not limited to this, and the following changes are made. It is also possible to carry out. For example, it is possible to connect the plasma power source 23 to the first container member 29 and connect the second plasma power source to the gas shower electrode 21.
In this embodiment, the DLC film is coated on the particles 51 using the plasma CVD apparatus. However, a second film such as silver is formed on the particles 54 shown in FIG. 1B using the plasma CVD apparatus. It is also possible to cover the second film 55 with a DLC film using the plasma CVD apparatus. Specifically, a second source material having a friction coefficient of 0.4 or less on the surface of the particles is introduced into the chamber 13 by plasma CVD while stirring or rotating the particles in the chamber 13. The film 55 is coated, and then the introduction of the first source gas into the chamber 13 is stopped, the second source gas is introduced into the chamber 13, and plasma CVD is performed while stirring or rotating the particles in the chamber 13. By coating the surface of the second film 55 of the particles with a DLC film, fine particles can be produced. Each of the second film 55 and the DLC film thus coated has a friction coefficient of 0.4 or less. Further, the contact angle of water on the surface of the fine particles thus produced is preferably 60 ° or more.
In this embodiment, the DLC film is coated on the particles 51 using the plasma CVD apparatus. However, the particles 51 are coated with a film containing the above-described material as the first film 52 shown in FIG. It is also possible to do.
In this embodiment, the plasma CVD apparatus is used to coat the particles 51 with a film. However, the present invention is not limited to this, and other dry film forming apparatuses such as a sputtering apparatus can also be used. It is.
Below, the example which coat | covers the film | membrane on the particle | grains 51 using the polygon barrel sputtering apparatus shown in FIG. 5 is demonstrated.
First, a polygon barrel sputtering apparatus will be described.
The polygonal barrel sputtering apparatus has a vacuum vessel 31 for coating particles 51 with ultrafine particles or a thin film. The vacuum vessel 31 has a cylindrical portion 31a having a diameter of 200 mm and a hexagonal barrel ( Hexagonal barrel) 31b. The cross section shown here is a cross section substantially parallel to the direction of gravity. In the present embodiment, the hexagonal barrel 31b is used. However, the present invention is not limited to this, and a polygonal barrel other than the hexagon (for example, 4 to 12 squares) can also be used. .
The vacuum vessel 31 is provided with a rotation mechanism (not shown). By this rotation mechanism, the hexagonal barrel 31b is rotated or reversed as indicated by an arrow, or shaken like a pendulum. The coating process is performed while stirring or rotating the inner particles 51. A rotation axis when the hexagonal barrel is rotated by the rotation mechanism is an axis substantially parallel to the horizontal direction (perpendicular to the gravity direction). Further, a sputtering target 32 is disposed on the central axis of the cylinder in the vacuum vessel 31, and the target 32 is configured so that the angle can be freely changed. Accordingly, when the coating process is performed while rotating or reversing the hexagonal barrel 31b or shaking like a pendulum, the target 32 can be directed in the direction in which the particles 51 are located, thereby increasing the sputtering efficiency. It becomes possible. The substance constituting the target 32 is a film substance covering the particles 51.
One end of a pipe 34 is connected to the vacuum vessel 31, and one side of the first valve 42 is connected to the other end of the pipe 34. One end of the pipe 35 is connected to the other side of the first valve 42, and the other end of the pipe 35 is connected to the intake side of the turbo molecular pump (TMP) 40. The exhaust side of the turbo molecular pump 40 is connected to one end of the pipe 36, and the other end of the pipe 36 is connected to one side of the second valve 43. The other side of the second valve 43 is connected to one end of a pipe 37, and the other end of the pipe 37 is connected to a pump (RP) 41. The pipe 34 is connected to one end of the pipe 38, and the other end of the pipe 38 is connected to one side of the third valve 44. The other side of the third valve 44 is connected to one end of the pipe 39, and the other end of the pipe 39 is connected to the pipe 37.
This apparatus includes a heater 47a for directly heating the particles 51 in the vacuum vessel 31, and a heater 47b for indirectly heating. In addition, the apparatus includes a vibrator 48 for applying vibration to the particles 51 in the vacuum container 31. In addition, the apparatus includes a pressure gauge 49 that measures the internal pressure of the vacuum vessel 3. The apparatus also includes a nitrogen gas introduction mechanism 45 that introduces nitrogen gas into the vacuum container 31 and an argon gas introduction mechanism 46 that introduces argon gas into the vacuum container 31. Moreover, the gas introduction mechanism 50 which can introduce | transduce oxygen etc. is also provided so that reactive sputtering can be performed. In addition, this apparatus includes a high frequency application mechanism (not shown) that applies a high frequency between the target 32 and the hexagonal barrel 31b. A direct current can also be applied between the target 32 and the hexagonal barrel 31b.
Next, a method for coating the surface of the particles 51 with the first film or substance using the polygon barrel sputtering apparatus will be described.
First, the particles 51 are introduced into the hexagonal barrel 31b. Next, a high vacuum state is created in the hexagonal barrel 31b using the turbo molecular pump 40, and the pressure in the hexagonal barrel is reduced. Thereafter, an inert gas such as argon or nitrogen is introduced into the hexagonal barrel 31b by the argon gas introduction mechanism 46 or the nitrogen gas introduction mechanism 45. Then, the hexagonal barrel 31b is rotated by the rotation mechanism, whereby the particles 51 in the hexagonal barrel 31b are rotated and agitated. At that time, the sputtering target 32 is directed in the direction in which the particles 51 are located.
Thereafter, sputtering is performed by applying a high frequency between the target 32 and the hexagonal barrel 31b by a high frequency application mechanism. Thereby, the surface of the particle 51 is coated with the first film or substance.
Next, a mold release agent is manufactured by mixing the fine particles produced as described above, at least one of a solvent and oil, and a highly volatile organic solvent. Each of the fine particles, the solvent, and the oil may have heat resistance of 250 ° C. or higher (preferably 500 ° C. or higher).
In this embodiment, a release agent is produced by mixing fine particles, at least one of a solvent and oil, and a high-species organic solvent. However, the fine particles and at least one of solvent and oil are mixed. A mold release agent composed of fine particles may be manufactured.
In the above example, the first film is coated on the particles 51 using the barrel sputtering apparatus. However, the second film 55 is formed on the particles 54 shown in FIG. 1B using the barrel sputtering apparatus. It is also possible to coat the second film 55 with the third film 56 or the substance using the barrel sputtering apparatus.
<Member with release agent>
FIG. 6A is a cross-sectional view illustrating part of a member with a release agent according to one embodiment of the present invention. In the member with a release agent shown in FIG. 6 (A), fine particles 53 have entered and adhered to the gaps of minute irregularities on the surface of the mold 58 by supplying the release agent described above to the surface of the mold 58. Is. The fine particle 53 includes a particle 51 and a first film 52 or a substance that covers the particle 51. The first film 52 or the substance is 0.4 or less (preferably 0.05 or more and 0.3 or less, more The friction coefficient is preferably 0.05 or more and 0.2 or less.
According to the member with the release agent, the wear of the surface of the mold 58 can be reduced by attaching the fine particles 53 to the surface.
FIG. 6B is a cross-sectional view illustrating a part of a member with a release agent according to another embodiment of the present invention. 6B supplies the release agent described above to the surface of the mold 59, and after the fine particles 53a adhere to the surface of the mold 59, the fine particles 53a are formed on the mold 59. It is crushed on the surface. The fine particle 53a includes a particle 51a and a first film 52a or a substance covering the particle 51a, and the first film 52a or the substance is 0.4 or less (preferably 0.05 or more and 0.3 or less, more The friction coefficient is preferably 0.05 or more and 0.2 or less. Since the fine particles 53a are crushed, the particles 51a and the first film 52a or the substance are deformed as shown in FIG. 6B.
Although FIG. 6B shows a portion where the particles 51a are not exposed even if the fine particles 53a are deformed, the particles 51a may be partially exposed.
In the member with a release agent, even if the fine particles 53a are adhered to the surface and then the fine particles 53a are crushed, the wear on the surface of the mold 59 can be reduced. In other words, by producing a molded product using the mold 59, the fine particles 53a on the surface of the mold 59 may be crushed. Even in that case, the wear of the surface of the mold 59 can be reduced.
6 (A) and 6 (B), the fine particles 53 shown in FIG. 1 (A) are attached to the surface of the mold, but the present invention is not limited to this, and FIG. 1 (B) shows. The fine particles 57 may be attached to the surface of the mold.

FIG. 7 is an SEM (Scanning Electron Microscope) image of the fine particles of Example 1. FIG. 8 is an SEM image obtained by covering the fine particles shown in FIG. 7 with a processing protective film and imaging the cut surface of the fine particles.
These fine particles have the structure shown in FIG. Specifically, in the fine particles, silver particles having a particle diameter of 5 μm (corresponding to the particles 54 in FIG. 1B) are covered with an adhesion film (corresponding to the second film 55), and the adhesion film is covered with a DLC film ( Equivalent to the third film 56). The adhesion film is a film containing a substance containing Si, and is an intermediate film for improving adhesion between the silver particles and the DLC film.
The deposition conditions for the adhesion film are as follows.
Film forming apparatus: plasma CVD apparatus shown in FIG. 4 Particle base material: Ag particles (φ5 μm)
Source gas: Gas containing Si and C Film type: Carbon film containing Si Film thickness: 0.2 μm
The conditions for forming the DLC film are as follows.
Film forming apparatus: plasma CVD apparatus shown in FIG. 4 Particle base material: Fine particles obtained by coating an Ag particle (φ5 μm) with an adhesion film Raw material gas and its ratio: C ₇ H ₈ / Ar = 7/20 cc
Film type: DLC
Film thickness: 0.3 μm
Since both the DLC film and the adhesion film are insulating materials, the DLC film and the adhesion film could not be observed separately in the SEM image shown in FIG. The total thickness of the DLC film and the adhesion film was about 240 nm.

In this example, the contact angle of water on the surface of fine particles in which the particles were coated with a DLC film was measured. However, since the water contact angle on the surface of the fine particles cannot be directly measured, a DLC film is formed on the glass substrate, the water contact angle of the DLC film is measured, and the measured value is measured on the surface of the fine particles. It was set as the measured value of the contact angle of water.
In the present specification, the “contact angle of water on the surface of fine particles” means a value obtained by measuring a contact angle of water on a film formed on a glass substrate with a film coated on the surface of the fine particles. Shall.
The sample of this example was formed under the following film formation conditions.
Film forming apparatus: Plasma CVD apparatus shown in FIG. 4 Base material: Glass substrate Film type: DLC = 2.4 μm
Deposition time: 30 minutes Stirring condition: No stirring Frequency of high frequency power supply: 250 kHz
Source gas and its ratio: C ₇ H ₈ / Ar = 7/20 cc
Deposition pressure: 10Pa
High frequency output: 250W
In addition, since the suitable film formation time and stirring conditions are different between the case where the substrate is a particle and the glass substrate, the film formation time and the stirring condition described above are different from the case where the substrate is a particle, Film formation conditions other than the film formation time and stirring conditions are the same as those used when the substrate is fine particles.
Next, the contact angle of the sample was measured by the following method. For comparison, the contact angle of the glass substrate was also measured by the same method. The contact angle measurement device is shown in Table 1, the sample is shown in Table 2, the measurement conditions are shown in Table 3, and the measurement results are shown in Table 4.

According to the measurement results in Table 4, it was confirmed that the contact angle of water on the surface of the fine particles can be 60 ° or more.

In this example, the friction coefficient of the DLC film in the fine particles obtained by coating the particles with the DLC film was measured. However, since the coefficient of friction of the fine DLC film cannot be directly measured, a DLC film is formed on the substrate of SUS304, the coefficient of friction of the DLC film is measured, and the measured value is measured on the fine DLC film. The measured coefficient of friction was used.
In this specification, “the friction coefficient of the film covering the particles” means a value obtained by forming a film coated with the particles on a SUS304 substrate and measuring the friction coefficient of the film. To do.
The sample of this example was formed under the following film formation conditions.
Film forming apparatus: Plasma CVD apparatus shown in FIG. 4 Base material: SUS304
Film type: DLC = 2.0 μm
Deposition time: 30 min
Stirring conditions: No stirring Frequency of high frequency power supply: 250 kHz
High frequency output: 300W
In addition, since the suitable film formation time and stirring conditions differ between the case where the substrate is particles and SUS304, the above film formation time and stirring conditions are different from the case where the substrate is particles, Film formation conditions other than the film formation time and stirring conditions are the same as those used when the substrate is fine particles.
Two samples formed under the above film forming conditions are shown in FIGS.
Next, the friction coefficient of the above two samples was measured by the following method.
The friction / wear characteristics of the DLC film formed on the SUS304 substrate were measured using a ball-on-disk type friction / wear tester with a measurement load of 5 N, a ball SUJ2, and no lubrication. As a result, the friction coefficients of the two samples were in the range of 0.17 to 0.2.
In addition, the friction coefficient of the other material described in the following literature is described below as a comparative example.
Reference: The Lubrication Society of Japan (1987) “Revised Lubrication Handbook” Yokendo P28
Silicon (silicon): 0.58
Aluminum: 0.82
Titanium: 0.58

FIG. 11 (A) is a photograph showing a spray sample of a release agent containing fine particles in which mica particles are coated with a DLC film.
The conditions for forming the DLC film are as follows.
Film forming apparatus: plasma CVD apparatus shown in FIG. 4 Particle base material: Mica particles (φ4.0 μm)
Film type: DLC = 0.1 μm
Frequency of high frequency power supply: 250 kHz
Source gas and its ratio: C ₇ H ₈ / Ar = 7/20 cc
Deposition time: 1 hour Deposition pressure: 10 Pa
High frequency output: 250W
Barrel swing: ± 75 °, 3rpm
This release agent is prepared by mixing volatile organic solvent as a main component and mixing the above fine particles by 10 wt% or less.
FIG. 11B is a photograph showing a state where the release agent shown in FIG. 11A is about to be applied to a copy sheet, and FIG. 11C is an enlarged view of the copy sheet shown in FIG. 11B. FIG. 11D is a photograph showing the state after the release agent is applied to the copy paper by spraying from the state shown in FIG. 11B.
FIG. 12 is a photograph showing a state in which a release agent containing fine particles in which a DLC film is coated on apatite particles having a particle size of 3.0 μm is applied to copy paper by spraying. The film formation conditions for the DLC film are the same as the film formation conditions for the mica particles.

FIG. 13 (A) is a photograph showing the release agent (DLC-coated mica fine particles) of Example 4 shown in FIG. 11 (A) after being applied to the glass substrate shown in FIG. 14 (A) by spraying. FIG. 13B is a photograph showing a state in which the contact angle of water on the surface of the release agent applied to the glass substrate shown in FIG. The method for measuring the contact angle is the same as in Example 2.
FIG. 14A is a photograph showing a glass substrate, and FIG. 14B is a photograph showing a state in which the contact angle of water on the surface of the glass substrate of FIG. 14A is measured as a comparative example. The method for measuring the contact angle is the same as in Example 2.
The measurement results of the contact angle are as shown in Table 5.

DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Metering valve 2a ... Metering chamber 3 ... Actuator 4 ... Dip tube 5 ... Nozzle port 6 ... Liquid phase 8 ... Gas phase 9 ... Stirring ball 11 ... Gravity direction 13 ... Chamber 20a ... Source gas generation source 21 ...

Gas Shower electrodes

21a, 21b ... Chamber lid 22 ... Mass flow controller (MFC)
DESCRIPTION OF SYMBOLS 23 ...

Power supply

26a, 26b ... Vacuum valve 27a ... Ground shielding member 29 ... 1st container member 29a ... 2nd container member 29b ... 1st ring-shaped member 29c ... 2nd ring-shaped member 29d ... Extension part 31 ... Vacuum Container 31a ... Cylindrical part 31b ... Hexagonal barrel 32 ... Target 34-39 ... Piping 40 ... Turbo molecular pump (TMP)
41 ... Pump (RP)
42 to 44 ... 1st to 3rd valve 45 ... Nitrogen gas introduction mechanism 46 ... Argon

gas introduction mechanism

47a, 47b ... Heater 48 ... Vibrator 49 ... Pressure gauge 50 ...

Gas introduction mechanism

51, 51a ...

Particles

52, 52a ...

First Films

53, 53a ... Fine particles 54 ... Particles 55 ... Second film 56 ... Third film 57 ...

Fine particles

58, 59 ... Mold 129a ... Inner surface 129b constituting the polygon in the second container member ... First ring Surface 129c ... surface of the second ring-shaped member

Claims

A release agent having fine particles,
The fine particles have particles and a first film or substance that covers the particles,
The mold release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
A release agent having fine particles,
The fine particles include particles, a second film that covers the particles, and a first film or substance that covers the second film,
The mold release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
In claim 2,
The mold release agent, wherein the second film has a friction coefficient of 0.4 or less.
In any one of Claims 1 thru | or 3,
The mold release agent, wherein the first film or substance has a friction coefficient of 0.05 or more and 0.3 or less.
In any one of Claims 1 thru | or 4,
A mold release agent, wherein a contact angle of water on the surface of the fine particles is 60 ° or more.
In any one of Claims 1 thru | or 5,
The mold release agent, wherein the particles include at least one selected from the group consisting of metals, ceramics, resins, and minerals.
In any one of Claims 1 thru | or 6,
A mold release agent, wherein at least one of the particles and the first film has a heat resistance of 250 ° C. or higher.
In claim 2 or 3,
A release agent, wherein at least one of the particles, the first film, and the second film has a heat resistance of 250 ° C. or higher.
In any one of Claims 1 thru | or 8,
The release agent, wherein the particles include a substance having a friction coefficient of 0.4 or less.
In any one of Claims 1 thru | or 8,
The mold release agent, wherein the particles include at least one selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, graphite, mica, talc, clay, apatite, kaolin, and silica.
In any one of Claims 1 thru | or 10,
The first film or material is at least selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN, CrN, TiN, molybdenum disulfide and tungsten disulfide. A mold release agent characterized by comprising one.
In any one of claims 2, 3 and 8,
The second film is selected from the group consisting of silver, indium, tin, tellurium, antimony, bismuth, DLC, graphite, BN, BC, WBN, CrN, TiN, molybdenum disulfide, tungsten disulfide, and Si. A mold release agent comprising at least one of the first film and a film different from the first film.
In any one of Claims 1 thru | or 12,
A mold release agent, wherein the fine particles have a particle size of 100 μm or less.
In any one of Claims 1 thru | or 13,
The mold release agent contains at least one of oil and a solvent.
A mold release agent according to any one of claims 1 to 14,
A container containing the release agent;
A release agent product characterized by comprising:
A release agent aerosol comprising the release agent according to any one of claims 1 to 14 and an injection container filled with a propellant.
Mold,
A release agent attached to the surface of the mold;
Comprising
The release agent has fine particles,
The fine particles have particles and a first film or substance that covers the particles,
The member with a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
Mold,
A release agent attached to the surface of the mold;
Comprising
The release agent has fine particles,
The fine particles include particles, a second film that covers the particles, and a first film or substance that covers the second film,
The member with a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
In claim 18,
The member with a release agent, wherein the second film has a friction coefficient of 0.4 or less.
Contain particles in a chamber whose cross-section is circular or polygonal,
A counter electrode facing the inner surface of the chamber is disposed in the chamber;
Connect a ground to the chamber,
The chamber is evacuated,
The chamber is rotated or pendulum operated with a direction substantially perpendicular to the cross section as a rotation axis,
Introducing a source gas into the chamber;
Release to produce fine particles by coating the first film or substance on the surface of the particles by plasma CVD while stirring or rotating the particles in the chamber by supplying high frequency power to the counter electrode A method for producing the agent,
The method for manufacturing a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
Contain particles in a chamber whose cross-section is circular or polygonal,
A counter electrode facing the inner surface of the chamber is disposed in the chamber;
Connect a ground to the chamber,
The chamber is evacuated,
The chamber is rotated or pendulum operated with a direction substantially perpendicular to the cross section as a rotation axis,
Introducing a first source gas into the chamber;
By supplying high-frequency power to the counter electrode, the particles in the chamber are agitated or rotated, and the surface of the particles is coated with a second film by a plasma CVD method.
Stopping the introduction of the first source gas into the chamber;
Introducing a second source gas into the chamber;
By supplying high frequency power to the counter electrode, the surface of the second film of the particles is coated with the first film or substance by the plasma CVD method while stirring or rotating the particles in the chamber. A method for producing a release agent for producing fine particles with
The method for manufacturing a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
The particles are housed in a vacuum vessel whose internal shape of the cross section substantially parallel to the direction of gravity is a polygon,
By performing sputtering while stirring or rotating the particles in the vacuum container by rotating the vacuum container about a direction substantially perpendicular to the cross section, the first film or substance is applied to the surface of the particles. It is a method for producing a release agent that produces fine particles by coating,
The method for manufacturing a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
The particles are housed in a vacuum vessel whose internal shape of the cross section substantially parallel to the direction of gravity is a polygon,
The surface of the particles is coated with the second film by performing sputtering while rotating or rotating the vacuum vessel about the direction perpendicular to the cross section as the rotation axis. ,
Sputtering is performed while stirring or rotating the particles in the vacuum container by rotating the vacuum container about a direction substantially perpendicular to the cross section as a rotation axis, so that a first surface is formed on the surface of the second film. A method for producing a release agent for producing fine particles by coating a film or a substance,
The method for manufacturing a release agent, wherein the first film or substance has a friction coefficient of 0.4 or less.
In claim 21 or 23,
The method for manufacturing a release agent, wherein the second film has a friction coefficient of 0.4 or less.
In any one of claims 20 to 24,
A method for producing a release agent, wherein the contact angle of water on the surface of the fine particles is 60 ° or more.
In any one of claims 20 to 25,
The said particle | grain contains the substance which has a friction coefficient of 0.4 or less, The manufacturing method of the mold release agent characterized by the above-mentioned.
In any one of claims 20 to 26,
The said particle | grain contains at least 1 selected from the group which consists of a metal, ceramics, resin, and a mineral, The manufacturing method of the mold release agent characterized by the above-mentioned.
In any one of claims 20 to 27,
A method for producing a release agent, wherein at least one of the particles and the first film has a heat resistance of 250 ° C. or higher.
25. In any one of claims 21, 23 and 24.
A method for producing a release agent, wherein at least one of the particles, the first film, and the second film has a heat resistance of 250 ° C. or higher.