JP5288736B2 - Ceramic composite - Google Patents

Description

  The present invention relates to a ceramic composite containing a ceramic powder, a fiber, and a plate at a high concentration in a resin. The present invention also relates to a ceramic molded body that is formed into a different shape and sintered at high temperature.

Recently, ceramic composites and ceramic compacts have begun to be used in various applications. For example, in a composite of a resin and a ceramic material, it has begun to be used for applications such as a separator for a lithium ion secondary battery (LIB), a heat resistant material, an electromagnetic wave insulating material, and a heat conductive film. In addition, ceramic compacts made by sintering and molding composites of resins and ceramic materials at high temperatures are used for ceramic capacitors, electrolyte membranes for polymer electrolyte fuel cells and solid oxide fuel cells, various filter applications, etc. Expansion to various uses is expected.
In order to be widely applied to these applications, it is important to be able to economically provide not only flat plate and sheet shapes but also deformed shapes such as pipe shapes and corrugated shapes at a low price. In the present invention, such a non-planar shape is referred to as a heteromorphic shape.

  As a conventional technique for realizing such a requirement, a method using ceramic particles such as silica and alumina, a binder such as a thermoplastic resin such as polyethylene, and a solvent such as a plasticizer is known. Examples of such a method include a green sheet lamination method using ceramic powder, a binder, and a solvent, an injection molding method, a slip casting method, and a powder pressing method that does not use a solvent. Further, as a method for further processing the ceramic composite formed by these methods, for example, a hydrostatic press method for imparting a desired shape by pressing, a production processing method for degreasing and sintering after machining, For example, a machinable ceramic molding method for machining the formed ceramic body with higher accuracy can be used.

However, since these forming methods are basically a method of forming with a mold or the like, or a method of forming a sheet-like or block-like formed body by cutting or pressing, There were limits to shape and thickness. In the former method using a mold, only products having the same shape can be obtained. In the latter post-processing method, the shape that can be formed is limited due to the brittleness and high hardness of ceramics. It has been difficult to make a complex and thin film by forming a ceramic into a pipe shape.
As means for improving this, Patent Documents 1 to 3 disclose a method in which a ceramic material is first bonded with an organic binder to form a ceramic / organic binder composite.

JP-A-1994-212560 JP 2005-15580 A JP 2005-324990 A

However, these methods are similar to the above-described green sheet method. For example, although a ceramic composite that can be self-supported without a support film can be formed, it can be formed into a thin film by stretching or the like, or it can be deformed. It had the problem that it was very difficult to obtain a deformed ceramic compact by sintering it.
In addition, when another material is supported in the voids of the sintered ceramic molded body so as to have a composite function to achieve high functionality, for example, a porous ceramic molded body in which ceramic particles such as silica are sintered and molded. This is the case of a filter for water treatment in which a functional substance such as an organic substance adsorbent is supported in the pores of this, but in such applications, it is necessary to control the size of the pores in addition to the heterogeneous shape. was there. However, with the conventional method described above, it has been impossible to simultaneously control the dysplasia and the pore size.
The present invention uses a specific resin component, a ceramic component, and a plasticizer component, and more preferably, by using a specific molding method, a thin-film ceramic composite can be easily formed by extrusion molding and stretch molding. It is an object of the present invention to provide a novel ceramic composite that can be easily formed in a different shape such as a cylinder or a corrugated shape and can control the pore size when it is made porous.

In order to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a resin component, ceramic particles, and plasticizer having a specific composition, and have reached the present invention.
That is, the present invention
1. 1 to 30 parts by weight of resin component (A), 70 to 99 parts by weight of ceramic component (B) (however, the total of (A) and (B) is 100 parts by weight), plasticizer (C) of resin component (A) 50 to 300 parts by weight of the total weight of 100 parts by weight of (A) and (B), a step of forming a sheet after melt-kneading, a step of extracting and removing the plasticizer (C) from the sheet, and the plastic Agent (C) before and / or after extraction, a step of producing a ceramic composite by stretching at least in the axial direction at an area magnification of 3 to 200 times,
And the resulting molded into irregular the ceramic composite, it comprising the step of sinter molding at 800 ° C. or higher temperature process for producing a free Muse ceramic molded body, the resin component (A) is a viscosity average It contains a polyolefin having a molecular weight Mv of 600,000 or more, the content W (A) expressed in parts by weight of the resin component (A) and the viscosity average molecular weight Mv (A) of the resin component (A) are represented by the following formula (1 ), And the ceramic component (B) has an average particle size of 0.005 to 10 μm .
Formula (1) W (A) × Mv (A) / 1,000,000 ≧ 7
2. 2. The method for producing a ceramic molded body according to 1 above, wherein the deformed shape is selected from the group consisting of a cylinder, a pyramid, a honeycomb, and a corrugated shape.
3 . The resin component (A) contains polyethylene, and the polyethylene contains a resin having a viscosity average molecular weight Mv of 2 million or more in an amount of 10 wt% or more based on the total amount of the resin component (A), and in the resin component (A) In the above 1 or 2, wherein the component having a molecular weight Mw of 1000 or less in the GPC chart is 8 wt% or less, and the ceramic component (B) is composed of two or more kinds of particles having different average particle diameters. The manufacturing method of the ceramic molded object of description.
4 . The average particle diameter (ΦB1) of the largest particles (B1) of the ceramic component (B) is in the range of 0.05 to 10 μm, and the average particle diameter (ΦB2) of the smallest particles (B2) is 0.00. 005 to 0.1 μm, ΦB1> ΦB2, and the weight mixing ratio (B1 / (B2 + B1)) of both is in the range of 0.99 to 0.50 The manufacturing method of the ceramic molded body in any one of 1-3 .
5 . 5. The method for producing a ceramic molded body according to any one of 1 to 4 , wherein the ceramic component (B) is at least one selected from the group consisting of zirconia, silica, alumina, and titania.

The ceramic composite and ceramic molded body of the present invention can be economically formed into a different shape such as a cylinder, honeycomb, corrugated shape, etc., and when formed into a porous body, the size of the pores can be controlled. In addition, it has excellent characteristics such as being able to effectively carry a third functional substance and the like.

The present invention will be specifically described below.
In the present invention, not only ceramic components but also those containing resin components and plasticizers are called ceramic composites, and only ceramics are the main constituent material, and resin components and plasticizers are not substantially contained. For example, a ceramic composite body sintered at about 1200 ° C. is referred to as a ceramic molded body.
In the present invention, the resin component (A) and the ceramic component (B) are 1 to 30 parts by weight of the resin component (A) and the ceramic component (B) when the total of (A) and (B) is 100 parts by weight. ) 70 to 99 parts by weight. Within this range, when a ceramic composite is used, the ceramic particles do not slide down, and a ceramic molded body with good strength can be obtained during sintering molding. When the resin component (A) is less than 1 part by weight, the connection of the ceramic particles is insufficient, and the separation of the particles increases when a ceramic composite is obtained. Moreover, when it exceeds 30 weight part, the shrinkage | contraction at the time of sintering molding will become large, and sinterability will deteriorate. Preferably the resin component (A) is 2 to 25 parts by weight, more preferably 3 to 20 parts by weight.

Further, the plasticizer (C) when the total of the resin component (A) and the ceramic component (B) is 100 parts by weight needs to be in the range of 50 to 300 parts by weight. Within this range, both the moldability of the ceramic composite and the controllability of the pore size can be achieved. When the amount of the plasticizer is less than 50 parts by weight, the moldability of the ceramic composite deteriorates, and in particular, the extrusion moldability deteriorates. When the amount exceeds 300 parts by weight, the ceramics in the ceramic composite are too separated from each other, and the subsequent sinterability is poor. Preferably, it is in the range of 50 to 250 parts by weight of the plasticizer (C), more preferably in the range of 75 to 200 parts by weight.
The resin component (A) contains a polyolefin having a viscosity average molecular weight Mv of 600,000 or more, the content W (A) in parts by weight of the resin component (A) and the viscosity average molecular weight Mv of the resin component (A) ( It is necessary for A) to satisfy the following formula (1).
Formula (1) W (A) × Mv (A) / 1,000,000 ≧ 7

  For example, when the resin component (A) contains 10 parts by weight of ultra high molecular weight polyethylene having an Mv of 6 million (the ceramic component (B) is 90 parts by weight), the value on the left side of the above formula (1) is 60. . Within this range, the strength of the ceramic composite is improved, and the ceramic composite can be easily formed into an irregular shape such as a cylinder. The value of the above formula (1) is preferably 10 or more, particularly preferably in the range of 10 to 300, and more preferably in the range of 10 to 150. If it is less than 7, the binding property between the ceramics by polyolefin is insufficient, and the dysplasia is lowered. The upper limit is not particularly limited, but if it becomes too high, the strength tends to decrease and the deformed shape tends to be somewhat difficult, so the above range is preferred.

  Further, the resin component (A) needs to contain a polyolefin having a viscosity average molecular weight Mv of 600,000 or more. From the viewpoint of the strength and dysplasia of the ceramic composite, it is preferable to contain at least 30 wt% of polyolefin having a viscosity average molecular weight Mv of 600,000 or more when the entire resin component (A) is 100 wt%. More preferably, it is 50 wt% or more. If it is less than 30 wt%, the dysplasia is reduced. Furthermore, from the viewpoint of improving the strength, the resin component (A) preferably contains 10 wt% or more of a resin having a viscosity average molecular weight Mv of 1 million or more, more preferably 2 million or more. More preferably, it is 30 wt% or more. By using a resin having an Mv of 2 million or more, the strength of the ceramic composite is further strengthened, and the deformability is improved.

Moreover, it is preferable that the component of molecular weight Mw <= 1000 in GPC in a resin component (A) is 8 wt% or less. The component amount of Mw ≦ 1000 is obtained from the GPC chart of the entire resin component (A). When the content is 8 wt% or less, the strength of the ceramic composite is further strengthened, and the deformability is further improved.
The polyolefin resin that can be used is not particularly limited, and, for example, general polyethylene (PE), polypropylene (PP), and the like are used.
Examples of polyethylene that can be preferably used include low-pressure high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), high-pressure low-density polyethylene (LDPE), and ultrahigh molecular weight polyethylene (UHMWPE). These include copolymers of ethylene and α-olefins such as propylene, 1-butene, 1-hexene, 1-octene, 4-methylpentene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer. A polymer (EAA), an ethylene-ethyl acrylate copolymer (EEA), an ethylene-methyl acrylate copolymer (EMA), an ethylene-methyl methacrylate copolymer (EMMA), or the like may be used. Further, these resins may be mixed.

Examples of polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and the like. The crystallinity may be homo PP or ethylene and a random copolymer or block copolymer.
As the polyolefin catalyst, a general Ziegler catalyst, a chromium catalyst, a metallocene catalyst, or the like is preferably used. The polymerization may be single stage polymerization or multistage polymerization. In addition, different resins and elastomers such as polystyrene, polyester and polyamide may be blended within the range not impairing the gist of the present invention, and other fillers, heat stabilizers, slip agents, antistatic agents, pigments, etc. Additives may be mixed.

In the present invention, the ceramic component (B) needs to have an average particle size of 0.005 to 10 μm. Within this range, the moldability, deformability, and sinterability of the ceramic composite are satisfactorily satisfied. Moreover, it is preferable that a ceramic component (B) consists of 2 or more types of particle | grains from which an average particle diameter differs. Among these, the average particle diameter (ΦB1) of the largest particle (B1) is in the range of 0.05 to 10 μm, and the average particle diameter (ΦB2) of the smallest particle (B2) is 0.005 to 0.1 μm. Preferably, ΦB1 is in the range of 0.1 to 2 μm, and ΦB2 is in the range of 0.005 to 0.05 μm (more preferably 0.01 to 0.05 μm). Is preferred. Furthermore, the weight mixing ratio (B1 / (B2 + B1)) of both is preferably in the range of 0.99 to 0.50. Within the above range, it is possible to adopt a structure in which a small B2 enters a large B2 gap, and the strength of the ceramic composite and the formed body obtained by sintering it can be increased by B2.
Here, in the present invention, the largest particle (B1) and the smallest particle (B2) are defined as the particle material having the largest average particle diameter before mixing or the smallest average particle diameter. For example, when a silica particle material (B1) having an average particle size of 0.5 μm and a particle size distribution and a silica particle material (B2) having an average particle size of 0.05 μm and a particle size distribution are used, ΦB1 = 0. 5 μm, and ΦB2 = 0.05 μm. The particle size distribution after mixing depends on the particle diameter, mixing amount, particle type, and the like of the particles to be mixed, but there may be a single broad peak or a plurality of peaks.

Further, the particle system distribution of the ceramic component (B1) is preferably narrow, and 2 <D90 / D50 is preferable because a uniform ceramic composite and molded body can be obtained. As used herein, D50 is the number average particle size, and D90 is the particle size from 90% to the smallest particle size.
The ceramic component used in the present invention is not particularly limited, and zirconia, silica, alumina, titania, magnesia, calcium carbonate, barium sulfate, talc, clay, mica, zeolite and the like can be used. Particularly preferred are zirconia, silica, alumina, titania, and magnesia. In the case of zirconia, the one stabilized with yttria or the like is preferable because it improves the strength of the ceramic composite and improves the ionic conductivity for electrolyte applications. In the case of silica, more preferably, the silica surface is subjected to a hydrophobic treatment from the viewpoint of dispersibility of polyolefin in a plasticizer, and the oil absorption with respect to the plasticizer used is preferably 150 ml / 100 g or more. Furthermore, 150 ml / 100g or more and 1000ml / 100g or less are preferable. More preferably, they are 150 ml / 100g or more and 500 ml / 100g or less. When the oil absorption is 150 ml / 100 g or more, when the ceramic particles are melt-kneaded and formed into an extruded sheet, aggregates are not easily formed in the sheet, the film-forming property is good, and high strength and a thin film can be achieved. Moreover, in the case of 1000 ml / 100 g or less, since the bulk density of the ceramic particles is large, the handling at the time of production is easy, and in addition, aggregates are hardly generated.

As the plasticizer, an organic compound that is compatible at the melting point or higher when mixed with polyolefin is desirable. Examples of such plasticizers include hydrocarbons such as liquid paraffin and paraffin wax, phthalates such as diethylhexyl phthalate, diheptyl phthalate, and dibutyl phthalate, other sebacic acid esters, stearic acid esters, and adipic acid. Examples include esters and phosphate esters. These plasticizers may be used alone or in combination of two or more.
Further, the plastic composite extracted and removed from the ceramic composite of the present invention is also within the scope of the present invention. Particularly, the porous ceramic is characterized in that the shape is a sheet, the thickness is 5 μm to 3 mm, the porosity is 40% or more, and the relationship between the puncture strength (g) and the thickness (μm) satisfies the following formula (2). The composite has high strength and good dysplasia. If the piercing strength is weak, it tends to collapse when it is formed into a cylinder, for example, in the case of an irregular shape.
Formula (2) Puncture strength (g)> Thickness (μm) / 2

An example of a method for producing such a ceramic composite is shown below.
In the present invention, the method of melt-kneading polyolefin resin, ceramic particles and plasticizer is a method in which polyolefin resin, ceramic particles and plasticizer are previously kneaded at a predetermined ratio by a Henschel mixer or the like, put into an extruder, and heated and melted. For example, a plasticizer may be introduced at an arbitrary ratio and further kneaded. Specifically, a raw material obtained by pre-kneading a polyolefin resin, ceramic particles, and a total amount of a predetermined amount of plasticizer or a part of a plasticizer with a Henschel mixer or the like is put into a twin screw extruder, and a predetermined amount of plasticizer is added. A sheet with better dispersibility of the ceramic particles can be obtained by side-feeding the remaining amount in the extruder, for example, into the barrel, and for example, high-stretching can be performed without film breakage. it can. The raw material can be charged into the extruder by a known method using a normal feeder, but a belt feeder is preferable because it can cope with a wide raw material composition. The melt kneading includes a method using a single screw extruder or a twin screw extruder. The melt kneading temperature is preferably 160 ° C. or higher and 300 ° C. or lower.
Extrusion molding is performed by a method of cooling with an extrusion cast roll or the like from a sheet die such as a slit die or a T die, or by an inflation method, whereby a ceramic composite gel sheet is obtained. The extrusion may be single layer extrusion or multilayer extrusion. In the case of multiple layers, it can be produced by either coextrusion method or gel sheet extruding method, and superimposing them and heat-sealing them. However, using coextrusion method makes it easy to obtain high interlayer adhesion strength and productivity. It is preferable because it is excellent.

The ceramic composite gel sheet obtained by extrusion may be stretched for thinning or strength. As the stretching method, biaxial stretching that is excellent in the balance of physical and longitudinal properties is preferable. Preferred are simultaneous biaxial stretching and sequential biaxial stretching. The stretching temperature is preferably from 100 ° C to 135 ° C. The draw ratio is preferably 3 to 200 times in terms of area magnification. From the viewpoint of film strength, the draw ratio is preferably from 10 times to 60 times.
The plasticizer may be extracted. In the case of extraction, it is performed by immersing a stretched or unstretched gel sheet in an extraction solvent, and then the membrane is sufficiently dried. The extraction solvent is a poor solvent for the polyolefin and a good solvent for the plasticizer, and the boiling point is desirably lower than the melting point of the polyolefin. Examples of such extraction solvents include chlorine-based solvents such as methylene chloride, ketones such as methyl ethyl ketone and acetone, halogen-based organic solvents such as hydrofluorocarbon, hydrofluoroether, cyclic hydrofluorocarbon, perocarbon, and perfluoroether, diethyl ether. And ethers such as hexane, low-boiling hydrocarbons such as hexane, and alcohols such as methanol and isopropyl alcohol. Two or more of these extraction solvents may be used. Of these, methylene chloride is particularly preferred.

Further, before or after extraction, stretching may be added as necessary for adjusting film physical properties such as film thickness and air permeability. Examples of the stretching include uniaxial stretching, simultaneous biaxial stretching, and sequential biaxial stretching, preferably simultaneous biaxial stretching and sequential biaxial stretching. The stretching temperature is preferably from 100 ° C to 135 ° C. The draw ratio is preferably more than 1 time and 10 times or less in terms of area magnification.
In order to reduce film shrinkage in a high-temperature atmosphere, the heat treatment is performed in the width direction at a temperature range of 80 ° C. or higher, preferably 100 ° C. or higher and lower than the melting point of polyolefin using, for example, a tenter, a uniaxial stretching machine, or both. , By reducing the contraction stress in the length direction or in both directions.
The ceramic composite produced as described above preferably has a three-dimensional network structure in which holes are three-dimensionally complicated. The three-dimensional network structure is a structure in which the surface is vein-like and the film structure of a cross section from three directions is sponge-like. Leaf vein is a state in which fibrils form a network structure. These can be confirmed by observing the surface and cross section with a scanning electron microscope. The fibril diameter of the three-dimensional network structure is preferably 0.01 μm or more and 0.3 μm or less, and can be observed with a scanning electron microscope.

Further, the ceramic composite according to the present invention obtained as described above is formed into a deformed shape such as a cylinder, a pyramid, a honeycomb, or a corrugated shape, and is fired at a temperature of 800 ° C. or higher, preferably 1100 ° C. or higher. It becomes possible to manufacture a deformed ceramic molded body easily by forming.
The ceramic molded body thus obtained can carry a photocatalyst or a third substance having a water purification function in the pores.

Hereinafter, the present invention will be described with reference to examples.
[Measurement method]
1. Viscosity average molecular weight Based on ASTM D4020, the intrinsic viscosity [η] at 135 ° C. in a decalin solvent is determined. Mv of polyethylene was calculated by the following formula.
[Η] = 6.77 × 10 ⁻⁴ Mv ^0.67
2. Molecular weight by GPC Molecular weight gel permeation chromatography (trade name 150-GPC, manufactured by Nippon Waters Co., Ltd.) was used, and one SHODX AT-807S and two TOSO TSK-GEL GMH-6H were used as columns. . Further, measurement was performed at a column temperature of 140 ° C. using 1,2,4-trichlorobenzene as a solvent.

3. Ceramic particle size (μm)
The measurement was performed under the following conditions using a laser diffraction / scattering particle size distribution analyzer “SALD-3000” (trademark) manufactured by Shimadzu Corporation. As a measurement solvent, industrial alcohol (Echinen F-8 (trade name) manufactured by Nippon Alcohol Sales Co., Ltd., ethanol 86.4%, methanol 7.3%, moisture 6.3%) was used.
The dispersion condition was measured after irradiation with 40 W ultrasonic waves for 10 minutes while stirring at 200 rpm. The set value of the silica refractive index was measured at 1.40 for the real part, 0 for the imaginary part, and 25 ° C. for the temperature.
4). The porosity of the ceramic composite A 10 cm × 10 cm square sample was cut from the microporous membrane, its volume (cm ³ ) and mass (g) were determined, and from these and the membrane density (g / cm ³ ), the following equation was used: Calculated.
Porosity = (volume−mass / film density) / volume × 100
The film density was measured by a density gradient tube method (23 ° C.) in accordance with ASTM-D1505.

5. Puncture strength of ceramic composite
By using a Kato Tech KES-G5 handy compression tester and performing a piercing test under the conditions of a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mm / sec, the raw piercing strength (N) is obtained as the maximum piercing load. can get. By multiplying this by 20 (μm) / film thickness (μm), a 20 μm film thickness equivalent puncture strength (N / 20 μm) was calculated.
6). Atypical formability of ceramic composite The ceramic composite sheet after bending the ceramic composite sheet into a cylinder with a diameter of 10mm and a length of 100mm, and forming by sintering, is judged as follows according to strength. It was.
A: Strongly bonded after sintering.
○: After sintering, it does not collapse even by hand, and there is no practical problem.
Δ: After sintering, the apparent shape is maintained, but it does not collapse when held by hand.
X: After sintering, it is already broken even if it is not touched by hand. Or already collapsed before sintering
Yes.

[Example 1]
As a polyolefin resin, 10 parts by weight of ultra high molecular weight polyethylene UHMWPE1 having a viscosity average molecular weight Mv of 6 million (component of molecular weight Mw ≦ 1000 in the GPC chart is 0 wt%), yttria stabilized zirconia as ceramic particles 1 (TZ-8Y average manufactured by Tosoh Corporation) 90 parts by weight, 0.3 parts by weight of tetrakis- [methylene- (3 ′, 5′-di-t-butyl4′-hydroxyphenyl) propionate] methane as an antioxidant, metal inert After adding 0.2 parts by weight of calcium stearate as an agent and 50 parts by weight of liquid paraffin (kinematic viscosity at 37.78 ° C.) as a plasticizer, the mixture was stirred with a mixer to prepare a raw material. This raw material was charged into a twin screw extruder having a screw diameter of 25 mm and L / D = 48 via a belt feeder. Further, 50 parts by weight of liquid paraffin was injected by side feed in the extruder. The mixture was kneaded at an extrusion rate of 15 kg / hr and an extrusion temperature of 200 ° C., and then extruded from a T die attached to the tip of the extruder. Immediately, the sheet was cooled and solidified with a cast roll cooled to 25 ° C. to form a sheet having a thickness of 1 mm. This sheet was stretched 2.5 × 3 times at 124 ° C. with a simultaneous biaxial stretching machine, then this stretched film was immersed in methylene chloride, and liquid paraffin was extracted and dried, followed by tenter stretching to adjust the physical properties. The film was stretched 1.5 times in the horizontal direction under a condition of 125 ° C. using a machine, and then heat treated by relaxing in the width direction by 7% at 130 ° C. to obtain a flat sheet of a ceramic composite having a thickness of 100 μm. Even when the ceramic composite was rolled, the sheet was not torn and the ceramic particles did not slide down. Next, this ceramic composite sheet was bent into a cylinder having a diameter of 10 mm and a length of 100 mm, sintered and molded at 1200 ° C. in an electric furnace, and then cooled to obtain a cylindrical thin film ceramic molded body. This cylindrical thin film ceramic molded body did not break even when held by hand, and had sufficient handling properties. Table 1 shows the characteristics of the ceramic composite and the molded body.

[Example 2]
The same method as in Example 1 except that 80 parts by weight of yttria-modified zirconia used in Example 1 as ceramic particles 1 and 10 parts by weight of hydrophobic silica having an average particle size of 0.02 μm were used as ceramic particles 2. Thus, a ceramic composite and a molded body were obtained. This molded body had higher piercing strength and strength after sintering than those of Example 1.
[Example 3]
Except for using 6 parts by weight of the ultra-high molecular weight polyethylene used in Example 1 and 4 parts by weight of high-density polyethylene HDPE having a viscosity average molecular weight Mv of 300,000 (a component having a molecular weight of Mw ≦ 1000 on the GPC chart is 1 wt%) as used in Example 1. A ceramic composite and a molded body were obtained in the same manner as in Example 2. With this resin composition, the extrusion moldability was excellent.

[Example 4]
In the same manner as in Example 1 except that 12 parts by weight of ultrahigh molecular weight polyethylene UHMWPE2 having a viscosity average molecular weight Mv of 700,000 (component of molecular weight Mw ≦ 1000 on the GPC chart is 0 wt%) was used as the polyolefin resin. And a molded body was obtained. The results are shown in Table 1.
[Examples 5 to 9]
Ceramic composites and molded bodies having the compositions shown in Table 1 were obtained in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Examples 1-4]
Ceramic composites and molded bodies having the compositions shown in Table 1 were obtained in the same manner as in Example 1. The results are shown in Table 1. In either case, sintering molding was impossible, or even if sintered, it was very brittle and could not be put to practical use.
[Comparative Example 5]
As the polyolefin resin, 5 parts by weight of ultrahigh molecular weight polyethylene UHMWPE3 having a viscosity average molecular weight Mv of 2.4 million (components having a molecular weight Mw ≦ 1000 in the GPC chart are 0 wt%) and low density polyethylene LDPE having a viscosity average molecular weight of 50,000 (molecular weight Mw ≦ in the GPC chart) The composition shown in Table 1 was used in the same manner as in Example 1 except that 2 parts by weight of 1000 component (1 wt%) and 93 parts by weight of barium titanate (average particle size 0.5 μm) were used as ceramic particles 3. A ceramic composite and a molded body were obtained. The results are shown in Table 1. Although sintered, it was very brittle and could not be put to practical use.

Since the present invention can be easily formed with different shapes of ceramic, it can be used for various applications such as ceramic capacitor applications, electrolyte membrane applications of solid polymer fuel cells and solid oxide fuel cells, and various filter applications. Is possible.
For example, non-sintered ceramic composites can be used for LIB (lithium ion secondary battery) separators, thermal conductive films, glass green sheets, mounting substrates, abrasives, and so on. The body can be used for purification of water, exhaust gas, etc., all solid LIB, ceramic capacitor electrode, EDLC electrode, thermoelectric element, LED substrate, transparent panel material, and the like.

Claims (5)

1 to 30 parts by weight of resin component (A), 70 to 99 parts by weight of ceramic component (B) (however, the total of (A) and (B) is 100 parts by weight), plasticizer (C) of resin component (A) 50 to 300 parts by weight of the total weight of 100 parts by weight of (A) and (B), a step of forming a sheet after melt-kneading, a step of extracting and removing the plasticizer (C) from the sheet, and the plastic Agent (C) before and / or after extraction, a step of producing a ceramic composite by stretching at least in the axial direction at an area magnification of 3 to 200 times,
And the resulting molded into irregular the ceramic composite, it comprising the step of sinter molding at 800 ° C. or higher temperature process for producing a free Muse ceramic molded body, the resin component (A) is a viscosity average It contains a polyolefin having a molecular weight Mv of 600,000 or more, the content W (A) expressed in parts by weight of the resin component (A) and the viscosity average molecular weight Mv (A) of the resin component (A) are represented by the following formula (1 ), And the ceramic component (B) has an average particle size of 0.005 to 10 μm .
Formula (1) W (A) × Mv (A) / 1,000,000 ≧ 7   The method for producing a ceramic molded body according to claim 1, wherein the deformed shape is selected from the group consisting of a cylinder, a pyramid, a honeycomb, and a corrugated shape. The resin component (A) contains polyethylene, and the polyethylene contains a resin having a viscosity average molecular weight Mv of 2 million or more in an amount of 10 wt% or more based on the total amount of the resin component (A), and in the resin component (A) component molecular weight Mw of 1,000 or less in the GPC chart is not more than 8 wt%, and said ceramic component (B), according to claim 1 or 2, characterized in that it consists of two or more particles having different average particle size method of manufacturing the ceramic formed structure according to. The average particle diameter (ΦB1) of the largest particles (B1) of the ceramic component (B) is in the range of 0.05 to 10 μm, and the average particle diameter (ΦB2) of the smallest particles (B2) is 0.00. 005 to 0.1 μm, ΦB1> ΦB2, and the weight mixing ratio (B1 / (B2 + B1)) of both is in the range of 0.99 to 0.50. Item 4. A method for producing a ceramic molded body according to any one of Items 1 to 3 . The method for producing a ceramic molded body according to any one of claims 1 to 4 , wherein the ceramic component (B) is at least one selected from the group consisting of zirconia, silica, alumina, and titania.