JP2000072944A - Antistatic polytetrafluoroethylene composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can give an article having good antistatic properties and having a light color and excellent mechanical strengths by selecting a composition comprising polytetrafluoroethylene(PTFE) and spherical titanium oxide made from a starting material being a titanium oxide precursor and having a specified content of the spherical titanium oxide. SOLUTION: The content of the spherical titanium oxide is 10-99 wt.%. The titanium oxide precursor is selected from an aqueous solution of e.g. a titanium alkoxide compound (e.g. titanium tetramethoxide) or a titanium salt (e.g. titanium sulfate) and a dispersion of titanium-containing solid particles. The PTFE is mixed with the titanium oxide precursor, and the obtained mixture is converted into a solid or a gel by, for example, drying, the addition of a coagulating/gelling agent, or precipitation by a chemical reaction. The particle diameter of the formed spherical titanium oxide is desirably about 0.05-5.0 μm. Next, the obtained starting gel is dried at 100 deg.C and disintegrated into particles of at most about 1 mm, and the particles are packed into a mold and kept at 340-360 deg.C to obtain the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a light-colored antistatic polytetrafluoroethylene (hereinafter referred to as PTFE) composition having an antistatic effect and a method for producing the same.

[0002]

2. Description of the Related Art PTFE has excellent heat resistance, chemical resistance, non-adhesion and low coefficient of friction. On the other hand, because of its high electrical insulation, it is very easy to be charged. For example, when powder is transported using a pipe coated with PTFE, there is a risk of causing an electrostatic explosion. Therefore, for the purpose of imparting conductivity to prevent electrification, for example, a conductive filler such as carbon black or metal powder is added.

[0003] As an example of adding conductive carbon black to PTFE fine powder to impart conductivity,
JP-B-49-17856 and JP-B-52-34653 are known.
However, carbon is obtained because it is black
The PTFE composition also turns black and tends to be avoided in food and semiconductor related fields. Furthermore, since it is black, it hinders free coloring.

On the other hand, examples of solving the black problem of carbon black using a white conductive filler include JP-B-1-16854 using zinc oxide and tin oxide, and JP-B-1-16854 using mica. -20182, Tokuho 2-255 using titanium oxide
No. 751 and Japanese Patent Publication No. 4-309548, all of which have poor dispersibility of the conductive filler and require surface modification. For example, Japanese Patent Publication No. 2255751 and Japanese Patent Publication No. 4-309548 disclose a surface treatment of acicular titanium oxide with a silane coupling agent. However, there is a limit to the improvement of the dispersibility by this surface modification, and the cost is increased. In particular, the conductive PT described in Japanese Patent Publication No. 2255571 / JP-B No. 4-309548
In the FE composition, since titanium oxide is acicular, the effect of improving dispersibility by surface modification is small. In addition, when the conductive filler is unevenly distributed, the mechanical strength of the PTFE composition decreases, so that the content cannot be increased too much.
The effect of imparting conductivity to FE was not always sufficient.

[0005] Further, conductivity can be imparted by adding metal powder, but in this case, the effect of imparting conductivity to PTFE is small, and it is necessary to add a large amount in terms of weight. Therefore, there is a disadvantage that the mechanical strength of the PTFE composition is reduced.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and has a good antistatic property, a light-colored PTFE composition and excellent mechanical strength. The purpose is to provide.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a spherical titanium oxide produced from a specific titanium oxide precursor is used as a conductive filler. As a result, it has been found that the dispersibility of the titanium oxide particles is enhanced, high conductivity can be imparted to PTFE, and a decrease in mechanical strength can be reduced, and the present invention has been completed.

That is, in order to achieve the above-mentioned object, the present invention provides a PTFE and a spherical titanium oxide starting from a titanium oxide precursor, wherein the content of the spherical titanium oxide is 10 to 99% by weight. Antistatic property characterized by being
A PTFE composition is provided. To achieve a similar goal,
The present invention is characterized in that either one or both of polytetrafluoroethylene and a precursor of titanium oxide are in a liquid phase, and they are mixed, solidified by gelation, dried, and then crushed. Provided is a method for producing a raw material powder of an antistatic polytetrafluoroethylene composition. In addition, in order to achieve the same object, the present invention provides a method for producing a mixture of one or both of polytetrafluoroethylene and a precursor of titanium oxide which is in a liquid phase and mixed and solidified by gelation. A method for producing an antistatic polytetrafluoroethylene composition, comprising: forming a powder obtained by drying, crushing, and shaping into a predetermined shape, followed by firing at a firing temperature of polytetrafluoroethylene.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The antistatic PTFE composition of the present invention comprises PTFE and spherical titanium oxide starting from a titanium oxide precursor. The PTFE used in the present invention is obtained by copolymerizing a homopolymer of tetrafluoroethylene and an olefin (eg, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, etc.) of 2 wt% or less as a modifier. What can be used. The PTFE may be either a powder or a dispersion thereof. Preferably, the use of the dispersion improves the dispersibility of the precursor of the spherical titanium oxide particles.
Although the particle size of the PTFE powder is not particularly limited, the average particle size is 0.1%.
About 0.3 μm is preferred. When forming a dispersion, it is preferable that the PTFE powder is an aqueous dispersion of 5 to 70 wt%.

On the other hand, the titanium precursor of the present invention is selected from at least one of a titanium alkoxide compound, a titanium chelate compound, an aqueous solution of a titanium salt and a dispersion of solid particles containing titanium. Titanium alkoxide compounds include titanium tetramethoxide Ti (OCH ₃ ) ₄ , titanium tetraethoxide Ti (OC ₂ H ₅ ) ₄ , titanium tetra-i-propoxide Ti (OiC ₃ H ₇ ) ₄ , titanium tetra-n- Butoxide Ti (On
-C ₄ H ₉ ) ₄ , tetrastearyloxytitanium Ti (OC ₁₈ H ₃₇ ) ₄
Although it is possible to use titanium methoxide, it is necessary to dissolve it in a solvent having high compatibility with water, such as propyl alcohol, since titanium methoxide is a solid by itself. In addition, the titanium alkoxide compound, the reactivity with water decreases with an increase in the number of carbon atoms of the alkoxy group, PTFE
When mixed with the dispersion, a local reaction is suppressed and a uniform dispersion state is obtained. Also, the titanium alkoxide compound produces an alcohol in the reaction with water,
Although heat generation and foaming occur, the amount of heat generation and foaming amount per unit time tend to decrease as the number of carbon atoms of the alkoxy group increases. However, an increase in the carbon number of the generated alcohol causes a decrease in the vapor pressure of the alcohol, which makes it difficult to remove the solvent from the obtained gel. Also, as the number of carbon atoms increases, the amount of titanium oxide obtained from a unit weight of titanium alkoxide compound decreases. Therefore, among those listed above, in consideration of the heat generation, the amount of foaming, and the removal of the produced alcohol, titanium tetra-i-propoxide is preferable, and in order to further improve the handling property,
It is desirable to use as a mixture to which a titanium alkoxide having many carbon atoms is added.

As the titanium chelate compound, for example, titanium tetraacetylacetonate Ti (CH ₃ COCHCOCH ₃ ) ₄ ,
Titanium acetylacetonate di-i-propoxide Ti (CH ₃ C
OCHCOCH ₃ ) ₂ (OiC ₃ H ₇ ) _{2 and the} like can be used. At this time, the reaction stability of the titanium chelate compound against hydrolysis is higher than that of the alkoxide compound, and the handleability is good. Therefore, the titanium chelate compound is also effective as an additive for improving the handleability of the alkoxide compound.

Further, as for the titanium alkoxide compound and the titanium chelate compound, polymers thereof, for example, titanium tetra-n-butoxide tetramer C ₄ H ₉ O [Ti (O
C ₄ H ₉ ) ₂ O] ₄ C ₄ H ₉ , polytitanium acetylacetonate [Ti (C
H ₃ COCHCOCH ₃ ) ₂ O] _{n and the} like can be used, and in this case, the handling property is improved due to a decrease in the number of active functional groups.

As the aqueous solution of the titanium salt, titanium sulfate,
An aqueous solution of titanium chloride can be used. In addition, when an aqueous solution of these titanium salts is used, arbitrary mixing with the PTFE dispersion is possible, but since a gelling reaction does not occur, it is necessary to add an alkali such as ammonia to generate titanium oxide. It is. The diameter of the spherical titanium oxide particles is increased by increasing the pH value of the alkali added at this time.

As the titanium-containing solid particles, titanium nitrate, titanium sulfide and the like can be used.

Further, a part of the titanium oxide precursor can be replaced with a sol solution of titanium oxide particles. In that case, the titanium oxide particles preferably have an average particle size of about 0.2 to 0.3 μm, and have a content of 20 wt%
However, in order to obtain uniform dispersion, the content is desirably 10% by weight or less.

In producing the antistatic PTFE composition of the present invention, PTFE and a titanium oxide precursor, or a part of titanium oxide particles are mixed. At the time of this mixing, in order to achieve uniform dispersion, it is desirable that either one, preferably both, of the PTFE and the titanium oxide precursor are in a liquid phase. At that time, as described above, the PTFE is preferably a dispersion. On the other hand, the titanium oxide precursor has the best degree of dispersion in the case of a solution, followed by dispersion and particles. Therefore, when a combination of a PTFE dispersion and a titanium oxide precursor solution is used for mixing, the dispersibility of the spherical titanium oxide produced therefrom is most improved, and the performance stability of the product is obtained. The mixing ratio of the PTFE and the titanium oxide precursor is not particularly limited as long as a gel body described later can be formed, and the amount of the titanium oxide precursor is determined according to the intended conductivity of the antistatic PTFE composition. To adjust.

The obtained mixture is dried, and a coagulant
It is solidified or gelled by the addition of a gelling agent or precipitation by a chemical reaction. The spherical titanium oxide produced at this time preferably has a particle size of about 0.05 to 5.0 μm. Gels composed of fine particles are generally arranged in a dendritic manner,
Easy to make porous. Therefore, the spherical titanium oxide produced is 0.
The particle diameter is preferably about 05 to 5.0 μm, and more preferably 0.1 μm or more in order to prevent porosity during gelation. In addition, current may flow through the titanium oxide particles in contact or jump between distant particles by tunneling. When the content of titanium oxide is the same, as the particle diameter increases, the probability of physical contact between the particles decreases, and the spacing between the particles increases. When a current flows through the gap due to the tunnel effect, the resistance is an exponential function of the grain spacing. Therefore, as the grain spacing decreases, the resistivity decreases and the antistatic effect increases. Therefore, it is desirable that the particle diameter of the spherical titanium oxide is preferably 0.2 μm or less. In the titanium alkoxide compound or the titanium salt aqueous solution, the particles are aged by decreasing the gelation rate, and the particle diameter increases. In the case of a titanium alkoxide compound, a method of suppressing the gelation rate includes a method of adding an alkylamine, formamide, dimethylformamide, or the like to the titanium alkoxide compound, a method of diluting the titanium alkoxide compound with an alcohol, and a contact probability with hydrolysis water. And a method of partially hydrolyzing in the presence of a catalyst are effective.

Next, the obtained raw material gel is dried at 100 ° C. and crushed into particles having a size of, for example, 1 mm or less to obtain a raw material powder. Then, the raw material powder is filled in a mold having a predetermined shape, and is kept at, for example, 340-360 ° C. for several hours to obtain an antistatic PTFE composition. As a molding method, pressure molding, extrusion molding, and the like are possible, and for example, various shapes such as a sheet, a tube, a rod, and a block can be used. The above temperature is the general calcination temperature of PTFE, and at the same time, the titanium oxide precursor is converted to spherical anatase-type titanium oxide at 340-400 ° C. Maintains a dispersed state and is generated in situ and uniformly dispersed in the PTFE matrix. In the conventional conductive PTFE composition, the conductive filler is unevenly distributed, which adversely affects the conductivity and the mechanical strength.However, the conductive PTFE composition of the present invention is a spherical titanium oxide which is a conductive filler. Has a high dispersibility, and a higher conductivity than a conventional conductive PTFE composition can be obtained when compared at the same content, and at the same time, a decrease in mechanical strength can be suppressed.

Generally, the volume resistivity of the resin composition is 10 ¹¹ Ω
Cm or less, preferably 10 ¹⁰ Ωcm or less,
The resin composition is said to have an antistatic effect. The antistatic PTFE composition of the present invention has a volume resistivity of 10 ¹¹ Ω · cm when the content of spherical titanium oxide is 10 wt%.
When the content of the spherical titanium oxide is 20 wt%, the volume resistivity is 10 ¹⁰ Ω · cm or less.
Therefore, the lower limit of the content of the spherical titanium oxide in the antistatic PTFE composition of the present invention is 10% by weight. Regarding the upper limit, even if the concentration of the titanium oxide precursor is increased, the dispersion state in the gel body is maintained well, so that even when the antistatic PTFE composition is used, the spherical titanium oxide content can be increased, The content of spherical titanium oxide can be up to 99% by weight. However, since the mechanical strength decreases as the amount of the spherical titanium oxide increases, it is preferable to keep the content low especially in applications requiring mechanical strength. For example,
In order to obtain a sheet-like antistatic PTFE having sufficient handling strength when the molding surface pressure is 70 MPa, the content of the spherical titanium oxide is 10-80 wt%, and particularly, the volume resistivity is 10
^In order to make it ¹⁰ Ω · cm or less, the content is set to 20-80 wt%.

As an application of the antistatic PTFE composition of the present invention, an inner wall of a pipe has an antistatic effect at the time of powder transportation. It can also be applied to semiconductors such as ICs and LSIs, and electrical equipment. Further, the antistatic PTFE composition of the present invention becomes a light-colored composition by using titanium oxide,
Free coloring becomes possible by adding a pigment.

[0021]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

(Examples 1-21 and Comparative Examples 1-2) An aqueous dispersion of polytetrafluoroethylene having a solid content of 60% by weight was used as PTFE, and a titanium alkoxide compound and a titanium chelate compound were used as a titanium oxide precursor. Was. As titanium alkoxide compounds, titanium tetramethoxide Ti (OCH ₃ ) ₄ , titanium tetraethoxide Ti (OC ₂ H ₅ )
₄ , titanium tetra-i-propoxide Ti (OiC ₃ H ₇ ) ₄ , titanium tetra-n-butoxide Ti (OnC ₄ H ₉ ) ₄ , tetrastearyloxytitanium Ti (OC ₁₈ H ₃₇ ) ₄ 1, 2: Examples 1-12, 14). However, titanium tetramethoxide Ti (OCH
₃ ) ₄ was dissolved in propyl alcohol before use. As the titanium alkoxide polymer, titanium tetra-n-butoxide tetramer C ₄ H ₉ O [Ti (OC ₄ H ₉ ) ₂ O] ₄ C ₄ H ₉ was used (Table 2: Example 13). Further, a mixture of the above alkoxides having a mixing ratio as shown in Example 18-19 in Table 3 was used.

Titanium tetraacetylacetonate Ti (CH ₃ COCHCOCH ₃ ) ₄ and titanium acetylacetonate di-i-propoxide Ti (CH ₃ COCHCOCH ₃ ) ₂ as titanium chelate compounds
(OiC ₃ H ₇ ) ₂ was used, and a mixture thereof was used (Table 2: Examples 15, 16 and Table 3: Example 20). In addition, titanium acetylacetonate is used as a titanium chelate polymer.
[Ti (CH ₃ COCHCOCH ₃ ) ₂ O] _n was used (Table 2: Example 17).
Further, as a mixture of a titanium alkoxide compound and a titanium chelate compound, titanium tetra-i-propoxide Ti (O-
iC ₃ H ₇ ) ₄ and titanium tetraacetylacetonate Ti (CH ₃ CO
Table 3 in terms of titanium oxide for the mixture with CHCOCH ₃ ) ₄
The mixture was mixed so as to have a mixing ratio as shown in Example 21. The method for producing the composition is as follows.

First, the PTFE dispersion is collected in a stirring vessel, and the liquid is added to a place where the PTFE is gently stirred so as not to fibrillate, for example, in the case of Ti (OiC ₃ H ₇ ) _4. did. At this time, the amount added was such that the value converted to the solid content (W _T ) of titanium oxide obtained from Ti (OiC ₃ H ₇ ) ₄ was as shown in Table 1. When the stirring was started after the addition, the mixture gelled within 1 minute. This gel was dried at 100 ° C., and classified and pulverized to a mesh of 1 mm or less to obtain a raw material powder. Other titanium alkoxides, titanium chelate compounds, and mixtures thereof were also added in amounts calculated from the amount of titanium oxide obtained from each raw material. At this time, as the various mixtures, those in which a titanium oxide precursor was previously mixed were used.

The obtained raw material powder is pressure-formed into a shape of 120 mm × 120 mm × 2 mm (thickness).
At 50 ° C./h, firing was performed at 360 ° C. for 5 hours, and the volume resistivity was measured. Volume resistivity is resistivity cell Model.8009 (KEITHLEY)
A sample is mounted in the inside, and a high resistance measuring instrument Model.6517 (KEITHLEY
Was used for the measurement. Tables 1 to 3 show the measurement results.
In the case of a system using only Ti (OiC ₃ H ₇ ) ₄ , for example, generation of TiO ₂ particles of about 0.1 μm was confirmed.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

(Examples 22-24) As a titanium oxide precursor, an aqueous solution of titanium sulfate and an aqueous solution of titanium chloride (24 wt% and 20 wt% aqueous solutions, respectively) as a titanium salt aqueous solution, and a mixture thereof were used. When the aqueous solution of the titanium salt was mixed with the PTFE dispersion, a uniform dispersion was obtained.
A 28 wt% ammonia (NH ₄ OH) aqueous solution was gradually added to the mixture, and the mixture was gelled by standing. After removing sulfate groups and chloride ions by washing with water, the mixture was dried and crushed to obtain a raw material powder. And At this time, the amount of ammonia required 40% or more of the theoretical amount required to obtain titanium hydroxide. The obtained raw material was molded and fired. Table 4 shows the measurement results of the volume resistivity of the fired body.

[0030]

[Table 4]

Comparative Example 3-5 Spherical conductive titanium oxide powder (particle diameter: 0.2-0.3 μm) was used as titanium oxide. The conductive titanium oxide was dispersed under PTFE stirring. The obtained raw material was molded and fired. Regardless of the amount of titanium oxide, the dispersibility was poor and the appearance of the molded product was also poor. Table 5 shows the measurement results of the volume resistivity of the fired bodies obtained from these.

[0032]

[Table 5]

(Example 25-30) As a titanium oxide precursor, titanium nitrate Ti (N
O ₃ ) ₄ , prepare a dispersion of titanium sulfide TiS ₂ , PT
It was mixed with FE dispersion. These titanium oxide precursor dispersions, and various titanium oxide precursors and mixtures as shown in Example 1-23 were mixed with the PTFE dispersion. The medium of the dispersion of the titanium oxide precursor is mainly water (hereinafter, aqueous dispersions of titanium nitrate Ti (NO ₃ ) ₄ and titanium sulfide TiS ₂ are respectively T _N W33 and T _N W33.
And _S W33), the concentration is adjusted so that it would be 33 wt% in terms of titanium oxide was used as the raw material dispersion. Table 6 shows these dispersions and their mixtures.
After mixing with PTFE at the quantitative ratios shown in Table 2, the mixture was dried and crushed to obtain a raw material powder. The volume resistivity of the fired body obtained from this raw material powder was measured (Table 6: Examples 25 to 27). Also,
When used in combination with other precursors, the dispersion medium of the titanium oxide precursor was selected depending on the gelling method of the precursors to be mixed at the same time. That is, when a titanium alkoxide or a titanium chelate compound is used, i-
A dispersion was prepared using C ₃ H ₇ OH as a catalyst, and the concentration was 33 wt% in terms of titanium oxide (hereinafter, titanium nitrate Ti (NO
_{3) 4,} the iC ₃ H ₇ OH dispersion of titanium disulfide TiS ₂ and _{T N A P 33, T S} A P 33 , respectively).

The gelation method is as described in Example 1-24. When the precursor other than titanium oxide dispersion is titanium alkoxide or titanium chelate compound, PT
When mixing with FE dispersion, the reaction with water, which is the dispersion medium, is used, and when the precursor other than titanium oxide dispersion is a titanate aqueous solution, a titanium hydroxide gel is added by adding an ammonia aqueous solution. Was generated, and this was washed with water to remove residual ions. The obtained gel was dried and crushed to obtain a raw material powder. Table 6 shows the measurement results of the volume resistivity of the fired body obtained from this raw material powder (Table 6: Examples 28 to 30).

[0035]

[Table 6]

(Examples 31-34) As a titanium oxide precursor, a mixture of various titanium oxide precursors and a dispersion of titanium oxide (particle diameter: 0.2-0.3 μm) as shown in Example 1-29 was used. . Titanium alkoxide to gel, the iC ₃ H ₇ OH in the case of the titanium chelate compound as a medium titanium oxide precursor to be mixed simultaneously with hydrolysis, 33 wt% titanium oxide dispersion (hereinafter, referred to as TA _P 33) Preparation In the case of a titanate aqueous solution, a 33 wt% aqueous titanium oxide dispersion (CS-C, manufactured by Ishihara Techno Co., Ltd.) was used and mixed at a mixing ratio as shown in Table 6. And this is PTFE
And mixed. The method of gelation is as in Example 1-23,
When the precursor other than the titanium oxide dispersion is a titanium alkoxide or a titanium chelate compound, the precursor other than the titanium oxide dispersion is used by mixing with the PTFE dispersion and using a reaction with water as a dispersion medium. In the case where is a titanate aqueous solution, a titanium hydroxide gel was formed by the addition of the ammonia aqueous solution, and this was washed with water to remove residual ions. These were dried and crushed to obtain raw material powder. When mixing with the titanium oxide precursor dispersion, this mixture is used.
After mixing with the PTFE dispersion, it was dried and crushed to obtain a raw material powder. Table 6 shows the measurement results of the volume resistivity of the fired body obtained from this raw material powder (Table 6: Example 3
1-34).

Example 35 As a titanium oxide precursor, Ti (O
using -iC ₃ H _{7) 4,} was added a hydrolysis inhibitor to relieve the hydrolysis. Dimethylformamide was used as a hydrolysis inhibitor. The amount of dimethylformamide added to Ti (OiC ₃ H ₇ ) ₄ was 1-2 mol / Ti-mol, and they were mixed in advance. This mixture was added to the PTFE dispersion. This was dried and crushed to obtain a raw material powder. The amount of heat generated during hydrolysis and the amount of foaming were reduced, but the drying time was prolonged because dimethylformamide had a high boiling point. Table 7 shows the measurement results of the volume resistivity of the fired body obtained from the raw material powder (Table 7: Example 35).

[0038]

[Table 7]

Example 36 As a titanium oxide precursor, Ti (O
using -iC ₃ H _{7) 4,} was relaxed hydrolysis by diluting with a solvent such as an alcohol. Ti (OiC ₃ H ₇ ) ₄ with the same weight of i
Diluted with -C ₃ H ₇ OH solvent was added to the PTFE dispersion. This was dried and crushed to obtain a raw material powder. The heating time during the hydrolysis and the amount of foaming decreased, and the drying time was prolonged by increasing the amount of the solvent. Table 7 shows the measurement results of the volume resistivity of the fired body obtained from this raw material powder (Table 7:
Example 36).

Example 37 As a titanium oxide precursor, Ti (O
-iC ₃ H ₇ ) ₄ was used for partial hydrolysis to reduce the number of active groups. First, a C ₂ H ₅ OH solution of 15 wt% Ti (OiC ₃ H ₇ ) ₄ was prepared. After this was added to the PTFE dispersion and stirred, a hydrochloric acid solution as a catalyst was quickly added and stirred. At this time, the molar ratio of Ti, HCl, and H ₂ O was 1: 0.2: 4 in molar ratio.
This resulted in a uniform gel. This was dried and crushed to obtain a raw material powder. Table 7 shows the measurement results of the volume resistivity of the fired body obtained from the raw material powder (Table 7: Example 37).

[0041]

As described above, according to the present invention,
A PTFE composition having good antistatic properties, a bright color system, and excellent mechanical strength is provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F070 AA24 AC15 AC18 AC19 AC20 AC36 AC67 AC84 AD04 AE05 DA31 DA41 DB05 DC07 4F071 AA27 AB17 AD06 AF38 AG28 AG34 AH19 BA01 BB03 BB05 BC01 BC03 BC05 BC06 4J002 BD151 DE136 FD106 GQ02

Claims (9)

[Claims] 1. A polytetrafluoroethylene and spherical titanium oxide starting from a titanium oxide precursor, and the content of the spherical titanium oxide is 10 to 99% by weight.
An antistatic polytetrafluoroethylene composition, characterized in that: 2. The antistatic according to claim 1, wherein the titanium oxide precursor is selected from at least one of a titanium alkoxide compound, a titanium chelate compound, an aqueous solution of a titanium salt and a dispersion of solid particles containing titanium. Polytetrafluoroethylene composition. 3. Titanium oxide precursors are titanium tetramethoxide Ti (OCH ₃ ) ₄ , titanium tetraethoxide Ti (OC
₂ H _{5) 4,} titanium tetra -i- propoxide _{Ti (OiC 3 H 7) 4} ,
Titanium tetra-n-butoxide Ti (OnC ₄ H ₉ ) ₄ , tetrastearyloxytitanium Ti (OC ₁₈ H ₃₇ ) ₄ , titanium tetraacetylacetonate Ti (CH ₃ COCHCOCH ₃ ) ₄ , titanium acetylacetonate di-i- Propoxide Ti (CH ₃ COCHCOCH ₃ ) ₂ (OiC
₃ H _{7) 2,} titanium tetra -n- butoxide tetramer C ₄ H ₉ O [Ti
(OC ₄ H ₉ ) ₂ O] ₄ C ₄ H ₉ and polytitanium acetylacetonate
_{[Ti (CH 3 COCHCOCH 3)} 2 O] at least one titanium alkoxide compound is selected from or antistatic polytetrafluoroethylene composition of claim 2, wherein the titanium chelate compound of _n. 4. The antistatic polytetrafluoroethylene composition according to claim 2, wherein the titanium oxide precursor is an aqueous solution of titanium sulfate or titanium chloride. 5. A titanium oxide precursor comprising titanium nitrate Ti (N
O _{3) 4} or antistatic polytetrafluoroethylene composition according to claim 2 characterized in that it is a dispersion of solid particles consisting of titanium disulfide TiS _2. 6. The method according to claim 2, wherein a part of the titanium oxide precursor is replaced by titanium oxide particles.
6. The antistatic polytetrafluoroethylene composition according to any one of 5. 7. The spherical titanium oxide has an average diameter of 0.05 to 5.
The antistatic polytetrafluoroethylene composition according to any one of claims 1 to 6, wherein the composition has a thickness of 0 µm. 8. One or both of polytetrafluoroethylene and a precursor of titanium oxide are in a liquid phase,
A method for producing a raw material powder of an antistatic polytetrafluoroethylene composition, comprising mixing, solidifying by gelling, drying and crushing. 9. One or both of polytetrafluoroethylene and a precursor of titanium oxide are in a liquid phase,
These are mixed, solidified by gelling, dried and crushed to form a powder into a predetermined shape, and then fired at the firing temperature of polytetrafluoroethylene, characterized in that it is an antistatic polytetrafluoroethylene. A method for producing an ethylene composition.