JP2769319B2 - Complex - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to composites, and particularly to impact resistance and thermal shock resistance.
Excellent in processing, etc. and suitable for moldings and coating materials.
About coalescence. [Prior art] In general, ceramic molded articles, plastic
Molded articles and composite molded articles. Conventional ceramic moldings have high strength, high hardness and chemical resistance
It has excellent properties such as heat resistance and high heat resistance, but on the other hand,
There are the following disadvantages to be solved. (A) Ceramics are brittle and break with small strain
You. Therefore, there is a property that the post-process is difficult. (B)
Ceramic powder to be sintered melts only at high temperatures and
It is hard to tie. Temperature of 1000 ℃ or more for sintering ceramics
Therefore, a high-temperature furnace is required for molding.
As a result, manufacturing equipment and manufacturing costs increase,
As a result, the product becomes expensive. (C) Vulnerable to thermal shock, slight
Destruction occurs at a rapid temperature change of about 150 ° C. (D)
Due to the high sintering temperature of Lamix compacts, ceramics
The material undergoes phase transition during the cooling process, which makes it difficult to obtain dimensional accuracy.
No. (E) The sliding parts of the ceramic molded body
Hard to wear due to the high hardness of the box material. But phase
The hand material is worn out due to the excessive hardness of the ceramic material.
I will. (F) Difficulty in processing ceramic materials (high sintering temperature
Very expensive parts because of the
Become. Next, conventional plastic moldings have excellent processability and are inexpensive
But it has to be solved as follows
There is a drawback that must not be. (A) Precise processing is difficult. (B) Hardness as a part
And low mechanical strength and short durability life (creep resistance
, Abrasion resistance). (C) Low heat resistance. FRP, FRM, filler rubber
(Tires, etc.), etc., and are applied to a wide range of uses.
The composite molded body has low dimensional change due to temperature change of the molded body,
There are advantages such as improved mechanical strength (see Fig. 2
Gap 13 between the filler 11 and the matrix 12
Structure), it is difficult to process after molding
There are drawbacks. On the other hand, resin coatings and ceramics
There are thermal spray coatings and the like. Most of the coatings currently on the market are made of resin
It is based on resin-based paint.
To paint general paint called paint and fluororesin paint
So that it is processed by a specialized processing manufacturer
Functional paints. No solution for resin paint
Common drawbacks that must be noted are: (a) low hardness
(B) Low durability (wear resistance), (c) Heat resistance
Poor (low decomposition temperature, low high temperature hardness)
You. Next, ceramic spray coating is used for the purpose of improving surface hardness etc.
However, there are the following disadvantages to be solved. You
In other words, (a) ceramic spraying is a high-temperature fused ceramic
The surface temperature of the substrate is
Go up. Due to the rise in temperature, the surface of the
Since the substrate is heated, thermal distortion occurs in the substrate. (B) Ceramic
Cracks due to rapid temperature changes after processing
Is easy to enter. [Problems to be Solved by the Invention] As described above, ceramic moldings and plastic moldings
Body, composite molded body and resin coating, ceramic spray coating
Films and the like each have their own disadvantages. An object of the present invention is to overcome the above-mentioned disadvantages of the prior art.
The properties of both ceramics and plastics
Excellent properties of impact resistance and thermal shock resistance
Another object of the present invention is to provide a composite which can be easily processed. [Means for Solving the Problems] The composite of the present invention for achieving the above object has a melting property of
Heat resistant resin mesh excluding inorganic material mesh and fluororesin
One of the eyes intersects with the fluororesin mesh
Having a reciprocal intervention network structure, wherein the fusible inorganic material
Quality mesh and heat resistant resin mesh excluding the fluororesin
Has an average particle size of 0.1 to 50 μm,
Made of an alloy and having a higher melting point than the fusible inorganic substance.
Metal powder, and the average particle size is 0.1-20 μm,
And a ceramic having a higher melting point than the fusible inorganic substance
Characterized in that at least one of the powders is a nucleus
You. That is, in the present invention, the fluororesin is other than the fluororesin.
Even if mixed with substances, it will be mixed below the primary particles of fluororesin
Utilizing incompatible properties, metal powder and ceramic powder
A fusible inorganic substance that forms an inorganic substance such as a nucleus or
Heat-resistant resin mesh excluding fluororesin and fluororesin
To form solely inside the complex with the network formed by bonding
A complex with an intervening network resulting from it. [Effect of the Invention] The composite of the present invention comprises a fluororesin network, a metal powder and
Formed with inorganic substances such as ceramics and ceramic powder as nuclei
Complex with each other forming a highly interrelated network
It is a united product, and its structure can
Can compensate for many drawbacks that need to be solved
You. Hereinafter, the effects of the present invention will be listed. 1) Effect as molded body Low friction and non-adhesiveness due to containing fluororesin
It has the property of not easily adhering. It has water repellency and oil repellency. )etc
Has the property of the fluororesin. The porosity can be selected in the range of 0.5 to 50%. So dirty
A filter that is difficult to be manufactured can be manufactured. Because it contains ceramics and metallic materials,
Hardness is improved as compared to plastics or composites, and
Increases thermal conductivity. Fluororesin, inorganic powder and soluble inorganic compound or resistant
By changing the blending amount of thermal resin for each purpose,
Hardness and strength can be freely selected to some extent. Independence of both fluororesin meshes and other meshes
Highly absorbing structure absorbs external stress inside
Therefore, destruction of the whole compact is less likely to occur. Also, post-processing
Easy to do. Resistant to thermal shock, dimensions with rapid temperature change up to 300 ° C,
No change in physical properties such as strength. Therefore, sintering is completed
After that, cooling can be performed immediately outside the furnace without requiring slow cooling inside the furnace.
Therefore, the manufacturing cost is reduced. Since this molded body contains fluororesin, its surface
Further processing of fluororesin paint without primer
To give strong fluororesin properties to the surface of the composite
be able to. Inorganic substance powder (ceramic material, metal powder) itself
800 ° C or less instead of forming a network by melting
Sintering the network with inorganic compounds and resins that melt below
Processing at relatively low temperatures.
You. Therefore, high-temperature furnaces of 1000 ° C or higher are necessary for processing equipment.
In addition, a general electric furnace can be used, and the cost can be reduced. The firing atmosphere is air, nitrogen gas, hydrogen gas, or vacuum.
Processing is possible even with misalignment. Molding methods include injection molding, extrusion molding, hot pressing, etc.
Processing is possible even with misalignment. 2) Effect as a paint Low friction and non-adhesiveness due to the inclusion of fluororesin
It has the property of not easily adhering. It has water repellency and oil repellency. )etc
Has the property of the fluororesin. Hardness is improved due to the inclusion of ceramics and metal materials.
And thermal conductivity increases. Fluorine resin, inorganic powder and fusible inorganic compound or resistant
Hardness and strength can be improved by changing the blending amount of thermal resin.
With some freedom to choose from hard coatings to elastic coatings
Processing with film is possible. Resistant to thermal shock, cools down like a ceramic sprayed coating
It does not crack as much. After completion of sintering,
Does not require internal cooling. Sudden temperature change when using at the same time
And can be applied in a wide range of environments
it can. Since this paint contains fluororesin,
It can be used as a primer for ingredients. Hardness of fluororesin coating
Compared to ceramic sprayed coatings processed for the purpose of improving
It is possible to shorten the entire process and reduce the manufacturing cost. The firing atmosphere is air, nitrogen gas, hydrogen gas, or vacuum.
Processing is possible even with misalignment. The coating method is spray coating or powder coating
Is possible. Hereinafter, the present invention will be described in more detail. FIG. 1 shows an example of the structure of the composite of the present invention.
1 is an inorganic powder, 2 is a fluororesin, 3 is a fusible inorganic substance.
The heat-resistant resin 4 except the resin or the fluororesin is a void. No.
As is clear from FIG. 1, the bonding between the fluororesins 2
Inorganic material formed with the core and inorganic powder 1 as the core
Or is the mesh of heat-resistant resin excluding fluororesin highly
It has a network structure of inter-intervention. This composite consists of a network of fluororesin and a core of inorganic powder.
Excluding fusible inorganic substances or fluorocarbon resin
Interaction with thermal resin network
It combines quality. In addition, the complex
External stress is absorbed inside to form impact resistance,
Excellent thermal shock resistance. Furthermore, with fluorocarbon resin, melting
With heat-resistant resin excluding conductive inorganic substances or fluororesin
Because of the intervening network structure, ceramic powder
No need for expensive equipment required for heating and sintering
Manufacturing equipment is inexpensive and the price of the finished product decreases
Connect. In the present invention, the inorganic powder is a metal or alloy powder.
Alternatively, a powder made of ceramics can be used. Metal powder
Aluminum, iron, nickel, copper, zinc,
Gold, silver, tin, lead, platinum, palladium, magnesium,
Manganese, molybdenum or alloys containing these as main components
Can be used. Stainless steel is particularly important for alloys.
It is suitable. There are no particular restrictions on the ceramic material, but metallic acids
Or one or more of carbides, metal nitrides and metal carbides
It is effective to use, for example, alumina,
Zirconia, calcium oxide, zinc oxide, silica, nitride
Examples thereof include silicon and silicon carbide. Inorganic powder can be converted to ceramic or metal as required
More surface-treated ones are desirable. For surface treatment
Improved adhesion to fusible inorganic substances and conductive powder
To improve insulation performance by coating with insulating material.
can do. In addition, characteristics that cannot be obtained with a single substance
Property can be realized by a composite material. As a coating method
Is thermal spraying, chemical vapor deposition, spray bonding,
There is knocking. The cells used for this surface treatment
Examples of Lamix include silica.
You. The average particle size of the metal powder is preferably in the range of 0.1 to 50 μm.
New If the average particle size is smaller than 0.1 μm,
It is difficult to form an eye structure and the average particle size is
If it is larger than 50 μm, the composite of the present invention
Period characteristics cannot be exhibited. The maximum particle size of the metal powder
The diameter is preferably adjusted to 600 μm. On the other hand, the average particle size of the ceramic powder is 0.1 to 20 μm.
The range of m is desirable. Out of this average particle size range
And the same result as in the case of the metal powder described above. What
The average particle size of the ceramic powder is the average particle size of the metal powder.
The smaller is due to the poor plasticity of the ceramics.
You. The maximum particle size of the ceramic powder was adjusted to 500 μm.
It is preferred that they are arranged. As fluororesin, ethylene tetrafluoride resin (PTFE),
Ethylene tetrafluoride-perfluoroalkylvinyl copolymer
(PFA), ethylene tetrafluoride-hexafluoropropyl
Len copolymer (FEP), polyvinyl fluoride (PVF), poly
Vinylidene fluoride (PVDF), polychlorinated ethylene fluoride
(PCTFE), ethylene-tetrafluoroethylene copolymer (ETF
E), ethylene-chlorinated ethylene trifluoride copolymer (ECTF
E) Any one or a mixture of the above fluororesins
Can be mentioned. The fusible inorganic substance is above the melting temperature of the fluororesin and
Inorganic compounds that melt at temperatures below 800 ° C are preferred and have low melting points
Glass, metal halide, low melting point metal and thermosetting
One or more inorganic substances can be used.
Zinc, aluminum, indium,
Tin, strontium, selenium, tellurium, lead, bismuth
And boronium are preferred. Where metal halide
Antimony fluoride, silver fluoride, tin fluoride,
Niobium fluoride, beryllium fluoride, rhodium fluoride, salt
Zinc chloride, aluminum chloride, antimony chloride,
Thorium, indium chloride, erbium chloride, gallium chloride
, Calcium chloride, gold chloride, silver chloride, kobar chloride
G, tin chloride, tungsten chloride, iron chloride, copper chloride, salt
Niobium chloride, neptunium chloride, bismuth chloride, bery chloride
Lium, magnesium chloride, manganese chloride, molybdenum chloride
Den, zinc bromide, aluminum bromide, indium bromide,
Gallium bromide, calcium bromide, silver bromide, tin bromide, odor
Strontium bromide, tungsten bromide, tantalum bromide,
Titanium bromide, iron bromide, copper bromide, lead bromide, niobium bromide, odor
Bismuth bromide, beryllium bromide, magnesium bromide, bromide
Manganese, zinc iodide, aluminum iodide, iodide
Ndium, calcium iodide, silver iodide, kobar iodide
G, zirconium iodide, tin iodide, stron iodide
Titanium, titanium iodide, iron iodide, copper iodide, iodide
Lead, nickel iodide, barium iodide, beryllium iodide
, Magnesium iodide, etc.
These mixtures can be used. Next, as a heat-resistant resin excluding fluororesin, polyimide
, Polyamide imide, polyphenylene sulfide,
Polyether ether ketone, polyether sulfo
, Epoxy resin, phenolic resin
The above can be used. Next, each compounding ratio in the composite is their volume percentage
Inorganic powder 10-80%, fluororesin 10-80%, no meltability
Adjusted to 10-80% of heat-resistant resin excluding organic substances or fluororesin
Adjustment is desirable. A particularly desirable compounding ratio is volume
Inorganic powder 20-70%, fluororesin 20-70% in percentage, melting
20-70% of heat-resistant resin except conductive inorganic material or fluororesin
It is. This blending ratio depends on the use of the composite and coating film.
Slightly different, for sliding applications requiring wear resistance
, 40-65% of fluororesin, 15-50% of inorganic powder, meltability
About 15-40% of heat-resistant resin except inorganic substance or fluororesin
Degree of wear has the lowest abrasion coefficient and low abrasion resistance is required.
In the case of sliding elements, 40 to 70% of fluororesin, inorganic powder
20-60% powder, excluding fusible inorganic material or fluororesin
About 5 to 40% of thermal resin has the lowest abrasion coefficient
You. For applications where strength is required, fluororesin 15-40
%, Inorganic powder 15-50%, fusible inorganic material or fluorine tree
Desirably, the heat-resistant resin excluding fat is about 30 to 70%. Thermal shock
If required, fluororesin, inorganic powder, meltability
Mixing ratio of heat-resistant resin excluding inorganic substances or fluororesin
In general, the mixing ratio of the best conditions is the chemical of the compound,
Depends on physical and thermal properties, but about 30 ± 15% is the most
Shows stable thermal shock resistance. For requesting other physical properties
In some cases, the above tendency regarding the mixing ratio is not seen.
Not. In the composite of the present invention, the fluororesin and the meltability
Mixing ratio of heat-resistant resin excluding inorganic substances or fluororesin
When the amount is large, it is difficult to form a sintered body.
Or a small proportion of heat-resistant resin except fluoro resin
It is difficult to form an intervening network structure. did
Therefore, depending on the selection of each compounding material considering this characteristic
The compounding amount is determined individually among the above compounding ratios. Next, a method for producing the composite of the present invention will be described. The composite of the present invention is a fusible inorganic material having an inorganic powder as a core.
Heat-resistant resin mesh excluding the quality or fluororesin, and fluorine
The resin network has an intervening network structure
To the properties of the composite described in the effect of the invention
The key to withdraw. Simply inorganic powder, fluororesin and melt
Heat-resistant resin dispersed except fusible inorganic material or fluororesin
If they do not form a network of mutual intervention,
Complex hardness or strength forms an intervening network
Less than half of those in the complex. So in the present invention
Is most important to form an intervening network in the complex
In order to achieve this, higher order mesh (complex inside the complex)
To improve the entanglement of each mesh)
Eye stabilization (to prevent the formed mesh from collapsing)
Is an important technology in the production of composites. Ma
Fluoro resin and fusible inorganic material or fluoro resin
Manufacturing of composites by fully understanding the properties of heat-resistant resins excluding
If not, the low surface free energy of fluororesin
Due to heat resistance excluding fusible inorganic substances or fluororesin
The resin separates from the fluororesin and has no fusibility inside the composite.
The heat-resistant resin except for the organic substance or fluoroplastic becomes spherical.
And does not form a network of mutual intervention. So the melting
General use of heat-resistant resin excluding the conductive inorganic material and the fluororesin
When roughly classified according to the properties, the following five types are obtained. Type 1 Solid (powder) at normal temperature and melting temperature of fluororesin
Melting at a temperature (melting point) or higher. Crosslinks or sticks on melting
No change such as a rise in degree occurs. For example, low melting glass
Steel, metal and others. Type 2 Solid (powder) at normal temperature and melting temperature of fluororesin
Melting at a temperature (melting point) or higher. Crosslinks or sticks on melting
A change such as a degree rise occurs. For example, heat-resistant resin (PE
EK) and others. Type 3 Solid (powder) at normal temperature and melting temperature of fluororesin
Melting at a temperature (melting point) or higher. Crosslinks or sticks on melting
No change such as a rise in degree occurs. For example, low melting glass
Steel, metal and others. Type 4 Solid (powder) at normal temperature and melting temperature of fluororesin
Melting below the temperature (melting point). Crosslinks or sticks on melting
A change such as a degree rise occurs. For example, heat-resistant resin (P
I, PPS, etc.), metal halides, etc. Type 5 Before mixing, dry with liquid (solution) and cure
What causes a state change. For example, a crosslinkable inorganic compound
Objects, heat-resistant resin (epoxy resin etc.). Depending on the above properties, the production method may be appropriately
Use a fabrication method. The manufacturing method is roughly divided into the following three
The method is distinguished. However, the manufacturing method is strictly divided
It is not the best one,
Set conditions. Production method 1 This method comprises the steps of using a fluororesin, an inorganic powder and a fusible inorganic substance.
Once when mixing the heat-resistant resin except the quality or fluororesin.
To form a composite. Therefore, processing
Fewer processes and excellent productivity. But in the melting process
Except for fluororesins and fusible inorganic substances or fluororesins
Because both are melted between the thermal resins,
Binding becomes competitive and the desired mutual within the complex
There may be cases where the intervention network is not formed.
You. This is made of fluororesin and fusible inorganic material or fluorocarbon
Melting point and melt viscosity of heat-resistant resin excluding fat, surface tension of melt
Characteristics such as force, presence or absence of crosslinkability of the melt, and properties before mixing
Related to contact. This method is very useful for Type 4 and Type 5 materials.
It is a manufacturing method suitable for. Conversely, the structure such as cross-linking during melting
Stable fusible inorganic material that does not change or change state
Or heat-resistant resin excluding fluororesin (Type 1 or
Ip 3) is a strict temperature control in the manufacturing process, heating speed tube
Process, heating cycle, optical crosslinking, continuous rotation
Force treatment (stir the melt under pressure to prevent layer separation
It is necessary to take measures such as For example, fusible inorganic substances
Or low melting point glass as a heat-resistant resin excluding fluororesin
Use PFA for fluorine resin and alumina for inorganic powder
If the melt viscosity of PFA is smaller than that of low melting glass
Injection molding was carried out at a temperature of 20-100 rpm with stirring
Thereafter, cooling is performed at a cooling rate of 60 ° C./min to produce a composite.
In the case of heat-resistant resin except fluororesin, electron beam in molten state
Irradiation etc. to increase viscosity or crosslink to separate layers
Prevent that. Production method 2 This method uses an inorganic powder and a fusible inorganic substance or fluorine.
After mixing the heat-resistant resin excluding the resin first to form a mesh
Melt impregnated with fluororesin, and vacuum impregnation of dispersion
A composite is prepared by adding the composition by immersion or the like. This
Is inferior to the above-mentioned production method 1 in the point of higher order of the mesh.
In some cases, mutual intervention networks can be formed. This one
The method includes a heat-resistant tree excluding fusible inorganic substances or fluororesin.
Type 1, type 2, type 4, and type 5 as fats
Suitable, Type 3 does not allow the production of composites. Ma
If the higher order of the fluororesin mesh does not progress,
Heat-resistant tree excluding powder and fusible inorganic substances or fluororesin
When forming a grease network, foaming treatment or the like may be applied.
When adding the silicone resin, heat the composite by high-frequency induction heating, etc.
Is effective. Production method 3 This method is different from production method 2 in that fluorine resin and inorganic powder are used.
After pre-press molding and mixing,
Or heat-resistant resin excluding fluororesin by vacuum impregnation etc.
It is to be added to produce a composite. This method is
Inferior to the manufacturing method 1 in the point of higher order of the mesh like the manufacturing method 2.
In some cases, mutual intervention networks can be formed. This one
The method includes a heat-resistant tree excluding fusible inorganic substances or fluororesin.
Type 3, Type 4, and Type 5 are suitable as fats
In addition, composites cannot be produced with types 1 and 2.
In this method, the pressure at the time of pre-press molding,
Excluding fusible inorganic substances and fluororesin
The solution of the heat-resistant resin and the surface tension of the solution are problematic. In each of the above-mentioned production methods 1 to 3, the mixing of the compound is performed by a wet method.
Alternatively, dry mixing is performed, and the mixing method is ball mill type, V-type mixing.
Single shaft rotor type, rotating disk type, etc.
No. The raw materials mixed in this way are plastic and
Molding and heat sintering using common processing methods for ceramics and ceramics.
You. The composite of the present invention is manufactured by the above-described manufacturing methods 1 to 3.
When forming, as a fluororesin that can be used in the present invention
May be any of the fluororesins described above, but the melt viscosity
Fluoroplastics (PTFE) and Meltable Fluoroplastics (Others)
Processing method is different for (fluororesin). Complex of the present invention
In, the network of fusible inorganic material and fluororesin
Except for the heat-resistant resin network (these networks are based on inorganic powder
One of them) and the fluororesin mesh
It is necessary to form an intervening network that intervenes
Therefore, if it is a fusible fluororesin, it should be above the melting point of the fluororesin.
If heated sufficiently, the fluororesin network will grow and intervene
The mesh can be formed to some extent. But melting
In the case of PTFE, which is highly conductive fluororesin,
PTFE particles need to be in contact,
Press molding with a force of 50 to 200 kg per square centimeter
Need to be In addition, similarly as a molded body by the hot press method
It can be used, and the composite is granulated to form a coating film
It can also be used. Further, the composite of the present invention can be used as a molded article or paint.
Wear. Example Next, an example of the present invention will be described. Example
Tables 1 to 19 are summarized in the latter half. Also below
The ethyl silica solution in each of Examples is ethyl silica
(The term "ethyl silica" used here means Si (OC _Two H _Five ) ₄ In table
And ethyl silicate, tetraethoxysilane, silicic acid
It means ethyl and the like. ) With an acid hydrolyzed solution
Used. (Example 1) A composite having a compounding ratio shown in Table 1 produced by the above-mentioned production method 1 was used.
Complex with intervening networks and intervening networks
No differences in the physical properties of the complexes were investigated. Mixing is dry
This was performed by a mill-mill method. 50 kg of the mixture using a mold
/cm ^Two Rod-shaped test of 10mm square x 140mm length under the pressure forming conditions
A piece was prepared and hardened under the heating conditions shown in the manufacturing method in Table 1.
It has become. The mechanical strength,
The sliding characteristics were measured. Table 2 shows the results. As described above, the interaction network inside the complex is
Supports degree and hardness. From this, the mutual
It is practically necessary to form an intervention network. (Example 2) Representative samples shown in Table 3 produced by Production Method 1
(11 types) Sliding characteristics, mechanical characteristics, chemical characteristics
Tables 4 and 5 show the results of the evaluation of the above. Ma
Table 3 shows the composition of the composite and the production conditions. The size of the composite is 10 mm wide x 140 mm long x 5 mm thick.
Dimensional deformation after heat curing is less than 0.1%
Table 4 assumes that the physical properties of each sample are the same.
It describes in. As shown in Table 4, all samples had high sliding characteristics and low
High friction coefficient and high abrasion resistance.
It shows a value that surpasses even excellent fluororesin paints. Complex and general purpose
Sliding test results with fluororesin coatings and polyimide sliding materials
Are shown in Table 5. In addition, the physical properties of the composite depend on the chemical composition of the compound and the inorganic powder.
It depends on the presence or absence of surface treatment. Especially inorganic powder is silica
By coating, resistant to fusible inorganic substances or fluororesin
Improves the strength of composites with improved adhesion to thermal resin
Can be seen. Also, ceramic powder as inorganic powder
(Alumina, zirconia), hardness and creep resistance
Use metal as inorganic powder
Increases the rate of deformation at break or increases the thermal conductivity
You can see above. In addition, a fusible inorganic substance or fluororesin
Hardness when using fusible inorganic material as heat-resistant resin except
Rise and the use of heat-resistant resin except fluorocarbon
Product quality and weight reduction can be achieved. Therefore, the use of each complex is large.
Table 6 is roughly divided. As described above, the composite produced by the production method 1 is a sliding part.
Relationships are widely applicable. In addition, the multiple
Coalescence is a manufacturing cost because the ingredients are mixed at once.
Has the advantage of being cheap. (Example 3) Representative samples shown in Table 7 produced by Production Method 2
(9 types) sliding properties, mechanical properties, chemical properties
Table 8 shows the results of the evaluations. Table 7
The composition of the coalescence and the production conditions are shown. The size of the composite is 10 mm wide x 140 mm long x 5 mm thick.
Dimensional deformation after heat curing is less than 0.1%
Table 8 assumes that each physical property value of each sample is the same size.
It describes in. The existence of the mutual intervention network is described in Example 1.
Confirmation was performed by the method described above. As shown in Table 8, the physical properties of the composite were determined by the chemical composition of the compound.
Actually, it depends on whether
Similar to the tendency of the composite of Production Method 1 shown in Example 2
You. However, the composite produced by Production Method 2 is
Excellent strength and hardness for use under more severe conditions
Endure. Further, the use of the composite produced by the production method 2 is described below.
It is shown in Table 9. As described above, the composite produced by the production method 2 is a sliding part.
Widely applicable applications due to heat resistance of composites
You. The composite produced by Production Method 2 is
Although the manufacturing unit price increases due to the additional process,
Wider and some more than the composite made in Production Method 1
Has excellent physical properties. Especially because of the high thermal stability
Very useful as a material for processing fluororesin paint on composites
Fluorocarbon without primer processing as described above
Processing of fat top coat is possible. (Example 4) Representative samples shown in Table 10 produced by Production Method 3
(9 types) sliding properties, mechanical properties, chemical properties
Table 11 shows the results of evaluations of the above. Table 10
The composition of the coalescence and the production conditions are shown. The size of the composite is 10 mm wide x 140 mm long x 5 mm thick.
Dimensional deformation after heat curing is less than 0.1%
Table 11 assumes that the physical properties of each sample are the same.
It describes in. The existence of the mutual intervention network is described in Example 1.
Confirmation was performed by the method described above. As shown in Table 11, the physical properties of the composite were
What is different depending on the composition and the presence or absence of surface treatment of inorganic powder
Similar to the third embodiment, manufactured by the manufacturing method 1 shown in the second embodiment.
Is similar to the tendency of the complex. But with Manufacturing Method 3
The prepared composite has good physical properties such as strength and hardness under high temperature conditions.
It has excellent sliding characteristics, especially abrasion resistance. Manufacturing method 3
Table 12 shows uses of the composite prepared in the above. As shown in Table 12, the composite produced by the production method 3
The use of the body is similar to that of the composite made in Manufacturing Method 1.
doing. This is the heat resistance of the composite made by Manufacturing Method 3.
The heat resistance is almost equal to the heat resistance of the composite made by Production Method 1.
It is caused by that. However, in production method 3, the meltability
Add heat resistant resin excluding inorganic substances or fluororesin later.
Therefore, this method has the advantage that a composite can be produced.
There is a point. (Example 5) Alumina having an average particle diameter of 20 μm coated on the surface with silica was used.
Surface with a mixture of PTFE powder and low melting glass and silica
Alumina and PTFE powder with an average particle size of 20μm
For the mixture system of ethyl silica and ethyl silica
A coalescence was produced. The mixing ratio is alumina: PTFE: meltable inorganic material
Heat-resistant resin excluding quality or fluororesin = 5: 4: 2.
The size of the composite is 100 mm diameter x 5 mm thickness. In addition, the sample No. was as follows. Sample No.037 Alumina + PTFE + Low melting glass (Production method
Method 1) Sample No.038 Alumina + PTFE + Low melting glass (Production method
Method 2) Sample No.039 Alumina + PTFE + Low melting glass (Production method)
Method 3) Sample No.040 Alumina + PTFE + ethyl silica (Production method
Method 1) Sample No.041 Alumina + PTFE + ethyl silica (Production method
Method 2) Sample No.042 Alumina + PTFE + ethyl silica (Production method
Method 3) Sample No. 043 Alumina + ethyl silica (Production method 1) This complex was attached to a filter and contained tar-like substances.
Measure the time to filter the organic solvent from the organic solvent mixture.
Was. For comparison, a composite containing no fluororesin was prepared.
A similar test was performed. Table 13 shows the results. The filters made with the above composite are shown in Table 13.
Pitch except for the system containing no fluororesin of sample No.043
Almost no clogging due to adhesion of
It can be used as an effective filter. (Example 6) Alumina surface-coated with silica and FEP were mixed at a ratio of 2: 3.
Mixed with PPS in the range of 25 to 150 parts by volume.
A composite was prepared by the manufacturing methods 1 to 3 for the combined product.
Was. No. of each sample is as shown below. Sample No.046 Alumina + FEP + PPS (Production method 1) Sample No. 047 Alumina + FEP + PPS (Production method 2) Sample No. 048 Alumina + FEP + PPS (Production method 3) Pencil hardness test (JIS-5400) for these composites
Of hardness of composites due to composition change due to compression and compression elasticity
It was investigated. Table 14 shows the results. As shown in Table 14, the composites varied in the composition ratio of the blends.
The hardness of the composite can be controlled as intended
It is a material that can be rolled. (Example 7) The following four samples were tested for thermal shock.
Was. Sample No. 049: A silica-coated surface with an average particle size of 7 μm
Luconia and PTFE powder and low melting glass in a volume ratio of 4: 4:
400 ° C, 50 kg / cm ^Two Condition
10mmφ obtained by extrusion molding while applying rotational stress at
100 mm cylindrical composite (Production method 1). Sample No.051: Stainless steel powder coated with silica and PTFE
Mix at a volume ratio of 1: 1 and 10kg / cm ^Two 10mmφ × 100mm under the condition of
Molded into a cylindrical shape, impregnated with a polyamideimide solution
After drying at ℃, the temperature was raised to 380 ℃ at 5 ℃ / min.
Sample No. 052: Alumina plate (10 mm x 1 mm x 100 mm). The strength of these composites against thermal shock was measured. Trial
The thermal shock to the test piece was performed by the following two methods. A specimen heated sufficiently in an electric furnace at 300 ° C is placed in water at 20 ° C.
It was charged to produce a quenched sample. Press the ironing iron heated at 300 ° C on the side of the test piece.
A minute heating sample was prepared. These specimens were bent by a bending tester.
The strength change from the inorganic treated test piece.
Small ones were judged to be resistant to thermal shock. Note that the comparison
Therefore, the same applies to a 10 mm × 100 mm × 1 mm alumina sintered body.
The same tests were performed. Table 15 shows the results. As shown in Table 15, the composite was strong even when subjected to thermal shock.
The degree of change is extremely small, and it is strong against thermal shock. Therefore, sintering
Can be cooled rapidly after
And can be inexpensive. Also, is it resistant to thermal shock?
It can be applied to various environments. (Example 8) For the composites shown in Table 16, PTFE top coat (enamel
), PFA top coat (powder)
Examined. Table 16 shows the composition of the sample and the production method. EK-4300CRN as PTFE top coat on the above composite
(Daikin Industries, Ltd.) as MP
-10 (Mitsui Fluoro Dupont Chemical Co., Ltd.)
From cross-cut test and peel strength test,
The adhesion properties of the sheet were studied. The PTFE top coat is
Poor cohesive strength of coating film, 100% for peel strength test
The test was performed by welding a PFA sheet of μm. as a result
Are shown in Table 17. As shown in Table 17, the composite was
Adhesion strength when primer is applied and adheres strongly to primer
And no need for primer processing. (Example 9) Regarding the preparation of a composite prepared by the methods of Production Methods 1 to 3,
I will describe. The composition and production method of these paints are shown in the table.
As shown in FIG. For the above sample, one coat was used to evaluate the properties of the coating film.
And sliding properties, chemical properties (contact angle), hardness of coating film, adhesion
Investigation of the properties, coating film made of composite as two coats
Of the primer and the hardness of the coating film in two coats were examined.
Note that PFA was used as the top coat. Also substrate
Used aluminum. Table 19 shows the results. As shown in Table 19, the composite was
Good adhesion to minium. No coating hardness
Machine powder used ceramic powder but metal powder used
The result was higher than the one. Pencils shown in Table 19
Hardness is 1-3 times higher than that of commercially available fluororesin paint.
High rank, excellent in hardness. In addition, wear resistance
The thrust type has good abrasion resistance of 10 to 1000 times.
The abrasion method also showed about twice the abrasion resistance of the commercial paint. heat
As for conductivity, since the coating film thickness is thin, it has
No clear difference appeared due to the difference in the composition. Also,
Table 19 also shows its applicability as a primer.
Adhesion with top coat is good and does not cause practical problems
No. In addition, the pencil hardness of the two-coat paint film is
Again, an improvement of about one or two ranks was observed.
The composite made in this way has several excellent properties.
It becomes a highly functional paint having characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing one embodiment of the composite of the present invention, FIG.
The figure is a schematic diagram of a conventional composite. 1 ... inorganic powder, 2 ... fluororesin, 3 ... heat-resistant resin excluding fusible inorganic substance or fluororesin.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 63/00 C08L 63/00 A 71/00 71/00 79/08 79/08 Z 81/00 81/00 C09D 127/12 C09D 127/12 (56) Reference JP-A-60-58467 (JP, A) JP-A-56-501566 (JP, A) JP-A-56-90862 (JP, A) JP-A-61-266451 (JP) JP-A-60-229947 (JP, A) JP-A-58-217543 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/12 C08K 3/00

Claims (1)

(57) [Claims] Either the network of the fusible inorganic material and the network of the heat-resistant resin except for the fluororesin, and the network of the fluororesin have an intervening network structure intervening with each other, The mesh of the heat-resistant resin excluding the fluororesin has an average particle size of 0.1 to 50 μm, is made of a metal simple substance or an alloy, and has a melting point higher than that of the fusible inorganic substance, and an average particle size of 0.1. ~ 20μ
m, wherein at least one of ceramic powders having a melting point higher than that of the fusible inorganic substance is used as a core. 2. The composite according to claim 1, wherein the fusible inorganic substance comprises an inorganic compound that melts at 800 ° C or lower. 3. The fluororesin is an ethylene tetrafluoride resin, an ethylene tetrafluoride-perfluoroalkylvinyl copolymer, an ethylene tetrafluoride-hexafluoropropylene copolymer,
At least one member selected from the group consisting of polyvinyl fluoride, polyvinylidene fluoride, polychlorinated ethylene, ethylene-tetrafluoroethylene copolymer and ethylene-ethylene trifluoride ethylene copolymer; The composite according to claim 1, wherein the composite is a resin. 4. The heat resistant resin is one or two selected from the group consisting of polyimide, polyamide imide, polyphenylene sulfide, polyether ether ketone, polyether sulfone, epoxy resin and phenol resin.
The composite according to claim 1, wherein the composite is at least one kind of resin. 5. Each of the above-mentioned blends comprises, by volume percentage, 10 to 80% of the metal powder and / or ceramic powder, 10 to 80% of the fluororesin, and 10 to 80% of the heat-resistant resin excluding the fusible inorganic substance or the fluororesin. The composite according to claim 1, wherein: 6. The metal powder is aluminum, iron, nickel,
The composite according to claim 1, wherein the composite is copper, zinc, gold, silver, tin, lead, platinum, palladium, magnesium, manganese, molybdenum, or an alloy containing these as main components. . 7. The composite according to claim 1, wherein the ceramic powder is a single or a mixture of a metal oxide, a metal nitride, and a metal carbide. 8. 2. The method according to claim 1, wherein said metal powder is surface-treated with ceramics or metal.
The conjugate according to the paragraph. 9. The composite according to claim 1, wherein said ceramic powder is surface-treated with ceramic or metal. 10. The method according to claim 1, wherein the fusible inorganic material comprises one or more of a low-melting glass, a metal halide, a low-melting metal, and a thermosetting inorganic material. Complex.