JP2003306551A - Ptfe granular gel powder, ptfe granular semigel powder, ptfe powder, method for producing ptfe granular gel powder, and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PTFE (polytetrafluoroethylene) material powder excellent in fluidity at normal and high temperatures and having a high apparent density, a relatively small average particle size, and an improved handleability; a method for producing the same; and a molded article obtained from the same. <P>SOLUTION: The PTFE granular gel powder comprises unmodified PTFE and/or modified PTFE and has an apparent density higher than 1.05 g/cm<SP>3</SP>. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a PTFE granulated and pulverized product having a high apparent density and excellent powder flowability,
PTFE granulated semi-gelled pulverized product and PTFE powder, molded product obtained from these, and PTFE granulated semi-gelated pulverized product and PTFE granulated semi-gelated pulverized product for producing the above-mentioned PTFE granulated semi-gelated pulverized product The present invention relates to a crushed product manufacturing method.

[0002]

2. Description of the Related Art Polytetrafluoroethylene [PTF
E] has a highly symmetrical molecular structure, and therefore has excellent properties such as heat resistance, chemical resistance, weather resistance, electrical insulation, and non-adhesiveness among the fluororesins, and thus has a wide range of applications. is there.

Although PTFE is a thermoplastic resin, it has a very high melt viscosity, and therefore, it is a conventional plastic molding method used for general thermoplastic resins having a lower melt viscosity, such as general extrusion molding. It has been said that injection molding cannot be applied.

For this reason, a sinter molding method is generally used for molding PTFE instead of the usual plastic molding method. In the sinter molding method, raw material powder of PTFE is preformed, and the obtained preform is heated to a temperature equal to or higher than the melting point of PTFE to sinter the resin particles.

Examples of the sintering and molding method of PTFE include compression molding and ram extrusion molding. Compression molding is generally
A preform obtained by filling a mold with PTFE raw material powder and compressing the mixture is placed in a furnace for sintering, and then cooled to complete the forming. During this step, automatic compression molding is also used in which the steps from filling the raw material powder to obtaining a preform are automatically performed.

In the ram extrusion molding method, PTFE raw material powder intermittently supplied from one end in a cylinder is
Each supply amount is press-fitted using a piston (ram), and each press-fitting body is lowered to join the press-fitting body for the previous charge, and the continuous body fused by firing is cooled and cooled from the other end of the cylinder. Push it out.

Since PTFE powder has a low apparent density,
The volume per unit weight becomes bulky. Further, generally, even if the powdery resin has good powder fluidity, it tends to aggregate with an increase in temperature. However, the PTFE powder obtained by finely pulverizing the powder after polymerization has poor powder fluidity,
Easy to aggregate even at room temperature.

Therefore, when PTFE powder is used as the raw material powder in the automatic compression molding, ram extrusion molding method, etc., in the molding machine, the raw material powder causes a bridge in the hopper which is the raw material supply port, There are problems such as non-uniform filling and difficulty in downsizing of a mold or the like due to its bulkiness.

It is conceivable to granulate the PTFE powder for the purpose of improving the apparent density and powder fluidity of the raw material powder of PTFE. The obtained granulated product can be used for automatic compression molding in which the temperature rise of the hopper and the mold does not usually occur.

However, in this granulated product, the powder fluidity is remarkably deteriorated at a temperature of room temperature or higher, and a part of the granulated product is agglomerated, so that the raw material powder filling portion and the firing portion are in the same cylinder, There is a problem that it cannot be used in the ram extrusion molding method in which the temperature of the filling portion is likely to rise due to heat conduction from the firing portion.

For the purpose of improving the powder fluidity of the raw material powder of PTFE at a temperature above room temperature, PTF
It is considered that the E powder is gelled and then pulverized. The resulting pulverized product has improved powder fluidity at high temperatures and can be used in the ram extrusion molding method.

However, this pulverized product has extremely low sphericity of particles and has a fluffy appearance, and has poor powder fluidity at room temperature and poor shapeability at room temperature. There was a problem that it could not be used for.

In WO99 / 65659, PTF is disclosed.
A raw material powder obtained by heating the granulated product of E to gel and then crushing is disclosed. Apparent density 1.05g / cm ³
However, the average particle size in this example is 1 mm.
The average particle diameter is 5 mm or less, for example, 1 to 3 mm, which is a relatively large value for the entire technique, and the particles are not divided into individual particles before gelation and crushing.

[0014]

SUMMARY OF THE INVENTION In view of the above situation, the object of the present invention is to provide excellent powder fluidity, high apparent density, and a relatively small average particle size in both temperature ranges of normal temperature and high temperature. The raw material powder of PTFE having improved handleability, the method for producing the raw material powder, and the molded body obtained from the raw material powder are provided.

[0015]

SUMMARY OF THE INVENTION The present invention is a PTFE granulated gelled and pulverized product comprising unmodified polytetrafluoroethylene [unmodified PTFE] and / or modified polytetrafluoroethylene [modified PTFE]. A PTFE granulated and pulverized product having a density of more than 1.05 g / cm ³ .

The present invention is also a PTFE granulated gel pulverized product composed of non-modified PTFE and / or modified PTFE, characterized in that the average particle size is 1 μm or more and the length is less than 1 mm. This is a PTFE granulated gelled pulverized product. The present invention is also a PTFE granulated and pulverized product comprising unmodified PTFE and / or modified PTFE, and having an apparent density of 0.7 to 1.05 g / cm ³ .
A PTFE granulated and pulverized product characterized by having an average particle size of more than 600 μm and less than 1 mm.

The present invention is also a PTFE granulated gelled and pulverized product comprising unmodified PTFE and / or modified PTFE, characterized in that the angle of repose is less than 40 °.
It is a FE granulated, gelled and crushed product. The present invention is also a PTFE granulated gel pulverized product comprising unmodified PTFE and / or modified PTFE, wherein particles having an aspect ratio of 1 to 1.5 are separated from each other. This is a PTFE granulated gelled pulverized product.

The present invention is a PTFE granulated semi-gelled pulverized product comprising unmodified PTFE and / or modified PTFE, which has a heat of fusion of 30 to 60 J / g and two melting peaks at 320 to 350 ° C. It is a PTFE granulated semi-gelled pulverized product characterized by being some.

The present invention has an apparent density of 1.05 g / cm.
It is a PTFE powder characterized in that it exceeds ³ . The present invention also has an apparent density of 0.7 to 1.05.
g / cm ³ , the average particle size exceeds 600 μm, and 1
A PTFE powder having a length of less than mm. The present invention also has a heat of fusion of 30 to 60 J /
g, there are two melting peaks at 320 to 350 ° C.,
The PTFE powder has an apparent density of 0.4 g / cm ³ or more.

The present invention comprises a PTFE granulated gelled pulverized product for producing a PTFE granulated gelled pulverized product, which comprises gelling a PTFE granulated product comprising unmodified PTFE and / or modified PTFE and then pulverizing the product. A method for producing a PTFE granulated gelled and pulverized product, characterized in that the pulverization is performed so as to separate the individual particles of the PTFE granulated product. The present invention also provides a non-denaturing P
A method for producing a PTFE granulated gelled and pulverized product, comprising the steps of gelling a PTFE granulated product comprising TFE and / or modified PTFE, and pulverizing the resulting product. Has a particle size smaller than the average particle size of the PTFE granulated product and has an aspect ratio of 1 to 2 such that 60% by weight or more of the whole PTFE granulated gelled and ground product is present. The method is a method for producing a PTFE granulated gelled pulverized product, which is characterized in that it is carried out. The present invention will be described in detail below.

The PTFE granulated and pulverized product of the present invention comprises non-modified PTFE and / or modified PTFE. The PTFE granulated and pulverized product of the present invention is a non-modified PT.
It may consist of only FE or modified PTFE.
It may be composed of only one, non-modified PTFE or modified PTFE, or a mixture containing other thermoplastic resin, additives, etc. in addition to these. May be.

In the present specification, the above-mentioned "modified PTFE"
Means tetrafluoroethylene [TF
E] and a small amount of other comonomer, and means a copolymer obtained by copolymerization. In the present specification, the “non-modified PTFE” means a homopolymer of TFE obtained by polymerizing without containing the other comonomer as a monomer component.

The above-mentioned other comonomer is not particularly limited as long as it can be copolymerized with TFE.
Perfluoroolefins such as hexafluoropropene [HFP]; chlorotrifluoroethylene [CTFE];
Trifluoroethylene; perfluorovinyl ether and the like can be mentioned.

The above perfluorovinyl ether is not particularly limited and is represented by, for example, the following general formula (I) CF ₂ ═CF—ORf (I) (wherein Rf represents a perfluoroaliphatic hydrocarbon group). The perfluoro unsaturated compound etc. which are mentioned are mentioned. In the present specification, the “perfluoroaliphatic hydrocarbon group” means an aliphatic hydrocarbon group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The perfluoroaliphatic hydrocarbon group may have ether oxygen.

The above-mentioned perfluorovinyl ether is, for example, a perfluoro (alkyl vinyl ether) in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms in the general formula (I). PFVE].

Examples of the perfluoroalkyl group in the above PFVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group and a perfluorohexyl group. A fluoropropyl group is preferred.

Examples of the perfluorovinyl ether include perfluoro (alkoxyalkyl vinyl ether) in which Rf in the general formula (I) is a perfluoro (alkoxyalkyl) group. In this case, the perfluoroalkoxyl group in Rf is
The carbon chain may be a linear or branched chain carbon chain, or may have a cyclic ether structure having 1 to 3 oxygen atoms. Such Rf
Is not particularly limited, and includes, for example, a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms and the following general formula:

[0028]

[Chemical 1]

(Wherein m represents 0 or an integer of 1 to 4) or an organic group represented by the following general formula:

[0030]

[Chemical 2]

(In the formula, n represents an integer of 1 to 4) and the like.

The ratio (% by weight) of the above-mentioned other comonomer to the entire monomer components depends on the kind, but is preferably 2% by weight or less, more preferably 0.01 to 1% by weight.

The above unmodified PTFE and the above modified PTFE
It is preferable that the number average molecular weight is 2,000,000 to 20,000,000. When the number average molecular weight is within the above range,
The physical properties such as mechanical strength of the molded product obtained by using the PTFE granulated and pulverized product of the present invention are improved. Preferably,
It is 4-10 million.

As the above-mentioned modified PTFE, for example, one kind or two or more kinds having different average molecular weights, copolymer compositions and the like may be used, and as the non-modified PTFE, for example, one kind or two kinds having different average molecular weights are used. The above may be used. In the present specification, the non-modified PTFE and / or the modified PTFE may be referred to as “PTFE”.

In the present specification, the above-mentioned "PTFE granulated gelled and pulverized product" means that after gelling the PTFE granulated product comprising the above-mentioned non-modified PTFE and / or the above-mentioned modified PTFE,
It means the one obtained by crushing. The PTFE granulated and gelled product of the present invention can be suitably used as a raw material powder in various molding methods such as compression molding and extrusion molding.

The method for producing a PTFE granulated gelled and pulverized product for obtaining the above-mentioned PTFE granulated and gelled pulverized product is one aspect of the present invention. The method for producing a PTFE granulated and pulverized product according to the present invention comprises a P containing unmodified PTFE and / or modified PTFE.
After the TFE granulated product is gelled, it is pulverized to form P
It is for producing a TFE granulated gelled and ground product.

In the present specification, the "PTFE granulated product" means a granulated PTFE powder. In the present specification, the “PTFE powder” is obtained by finely pulverizing the unmodified PTFE and / or the modified virgin polymer of the modified PTFE obtained by various polymerization methods into powder, which will be described later. It means that neither granulation nor gelation has been performed.

The above-mentioned various polymerization methods are not particularly limited, and conventionally known polymerization methods such as suspension polymerization, emulsion polymerization and bulk polymerization can be used, but the suspension method is industrially widely used. Preference is given to using polymerization or emulsion polymerization. The conditions of the above various polymerization methods are not particularly limited.

The above-mentioned PTFE powder is generally obtained by subjecting the raw powder just after polymerization to a uniform particle size and generally pulverized to facilitate shaping. If necessary, the PTFE powder may be one that has been classified after the above general pulverization, or one that has been subjected to coarse pulverization, washing, drying, etc. of the virgin polymer taken out from the polymerization tank. .

Drying in the process of obtaining the above-mentioned PTFE powder is usually carried out by a method such as heating, if necessary, in order to remove washing water, water derived from a medium for carrying out the polymerization, a liquid consisting of an organic solvent and the like. It is something to do. The heating for drying is performed at a temperature lower than the melting point of PTFE.

The average particle size of the above PTFE powder is not particularly limited, and is, for example, less than 100 μm, preferably
It may be 20 to 50 μm. In the present specification, the average particle diameter of the PTFE powder is a value obtained according to the wet sheave method described in WO99 / 06475.

The PTFE powder thus obtained is then granulated to obtain the PTFE granulated product. In the present specification, the “granulation” means a treatment for making individual particles of the PTFE powder into a spherical shape or a spherical approximate shape. The granulation may be similar to what is commonly referred to as granulation or granulation.

The above granulation method is not particularly limited,
For example, an underwater granulation method in which the above PTFE powder is agitated and granulated in water in the presence of an organic liquid, and an emulsion in which the above PTFE powder is agitated and granulated in water in the presence of an organic liquid and a surfactant. A conventionally known method such as a dispersion granulation method can be used.

When the PTFE granulated gelled and pulverized product of the present invention is used in combination with the below-mentioned filler, the method of mixing the filler is not particularly limited, and examples thereof include a dry mixing method, a pulverization mixing method and a slurry. A mixed granulation method or the like can be used.

The above-mentioned slurry-mixing granulation method is the same as the above-mentioned PTFE.
The powder and the filler are made into a slurry state, and agitated and granulated in the presence of an organic liquid. The compounding method of the filler is that the PTFE powder and the filler are separately mixed without previously mixing. A method in which the mixture is poured into water and stirred in the presence of a surfactant to be mixed to form a slurry, or the above PTFE
There is a method in which only the powder is made into a slurry state and then the filler is added before being stirred with the organic liquid.

The individual particles of the PTFE powder before the granulation usually have a molecular chain terminal projecting from the surface in many cases, and there is no tightening as exemplified by the relatively large surface area. It is usually amorphous. Such individual particles have a spherical shape or a shape close to a spherical shape to reduce the surface area by performing the above-mentioned granulation, and the protruding molecular chain ends are contained in this particle shape and are in a tight state. Become.

In the above granulation, making the individual particles of the PTFE powder into a spherical shape or an approximate shape of a spherical shape means that the aspect ratio is as large as 2 to 4 before the granulation. Can be represented by decreasing to 1 or an approximate value of 1 like 1 to 2.

In the present specification, the aspect ratio is the longest diameter (d _L ) which is the longest of the straight lines connecting any two points on the surface of any one particle, and
It means the ratio (d _L / d _S ) to the shortest diameter (d _S ) which is the shortest of the straight lines perpendicular to this longest straight line. In this specification, the aspect ratio is a value obtained by image processing.

The change caused in the PTFE powder by the granulation is also caused mainly by the fact that the individual particles of the PTFE powder are in a tight state as described above, and thus the apparent density of the PTFE powder becomes, for example, It can be also represented by the fact that it was about 0.1 to 0.6 g / cm ³ before the above granulation, but increased to about 0.6 to 1 g / cm ³ after the above granulation. This change in apparent density can change depending on the shape and average particle size of individual particles before the above granulation, the above granulation conditions, and the like. In this specification, the apparent density is JIS K
It is a value obtained by measuring according to 6891-5.3.

Due to the above-mentioned granulation, the average particle size of the above-mentioned PTFE powder usually tends to increase. For example, the particle size of about 20 to 40 μm before the granulation increases to about 200 to 700 μm after the granulation.
However, since the average particle diameter can be widely controlled if desired, the above granulation does not always increase the average particle diameter.

In the present specification, the average particle size of the above-mentioned PTFE granulated product and the above-mentioned PTFE granulated pulverized product is the value obtained by the method for measuring the average particle size of the granular powder described in WO99 / 06475. Is. That is, 10, 20, 32, 48, 60 and 80 mesh (inch mesh) standard sieves are stacked in this order from the top, and the PTFE granular powder is placed on the 10-mesh sieve, and the sieve is vibrated to obtain fine PTFE granular powder in order. After dropping the particles and determining the percentage of the PTFE granular powder remaining on each sieve in%, the cumulative percentage of residual ratio (vertical axis) is plotted on the log probability paper for each sieve opening (horizontal axis). The scale and these points are connected by a straight line, the particle size at which the ratio is 50% is determined on this straight line, and this value is taken as the average particle size.

Of the above-mentioned PTFE powder and the above-mentioned PTFE granulated product, those obtained by suspension polymerization may be collectively referred to as "molding powder", and those obtained by emulsion polymerization may be collectively referred to as "fine powder". Sometimes.

In the present specification, the above "gelling" means
Heat treatment of the PTFE means that the heat treatment here does not include the above-mentioned heating for drying in the process of obtaining the PTFE powder.

Unlike the above PTFE powder, the above-mentioned PTFE granulated product has individual particles each maintaining the particle shape. Therefore, with respect to the above-mentioned PTFE granulated product,
When the heat treatment in the gelation is performed, the individual particles of the PTFE granulated product maintain their particle shape, but the particles are mainly fused by point contact, and the particles are integrally bonded with a weak bonding force as a whole. To be in a state of being When such gelling is performed, the PTF of the present invention, which has a high apparent density and is excellent in powder fluidity, is obtained through subsequent pulverization.
An E-granulated gelled pulverized product can be obtained. Above PTFE
The fusion between the particles of the granulated product does not necessarily have to be completely performed for all the particles, and may be in a semi-gelled state, so to speak.

In the present specification, the above "gelling" means "complete gelling" in which the heat treatment of each particle of the PTFE granulated product is completely carried out for all the particles, and a part of the particles. Alternatively, it is a concept including both "semi-gelling" which is a state of being performed on a part of one particle. That is, in the present specification, in particular, "complete gelation" or "semi-gelation"
When simply saying “gelling” without being limited to, it is possible to include both “complete gelling” and “semi-gelling”, and when the term is limited to “complete gelling”,
It refers to "complete gelation" and does not refer to "semi-gelling", but when the term is limited to "semi-gelling", it refers to "semi-gelling" and means "complete gelling". Gelling "
Does not mean Therefore, the “PTFE granulated gelled product” of the present invention and the “PTFE granulated gelled product” described later are
The gelation may include both a completely gelled one and a half gelled one. The "granulated semi-gelated pulverized product" of the present invention described below is a gelled product that is semi-gelled, and does not include a product that is completely gelled.

The above-mentioned gels that have undergone complete gelation have a heat of fusion of 20 to 40 J / g and / or a melting point peak of 320 to 330 ° C. as described later. The above semi-gelled product has two melting peaks at 320 to 350 ° C. as described later, and
It has a heat of fusion of 30 to 60 J / g and two melting peaks at 320 to 350 ° C. In the present specification, the above-mentioned “one having a melting point peak at 320 to 330 ° C.” means the above “melting point peak at 320 to 350 ° C. 2”.
"Things that exist" are not included. The heat of fusion and the melting peak are measured by the measuring method described below.

The heat treatment in the gelation is, for example, 100 ° C. or higher, and the PTF is
It is preferable to heat at a temperature equal to or lower than the decomposition start temperature of E for 1 minute to 5 hours. More preferably, 300-
It is 10 minutes to 3 hours at 390 ° C, and more preferably 1 to 2 hours at 350 to 380 ° C.

The above heat treatment is preferably carried out in an inert atmosphere or in air. The gelation may include a step of cooling to a temperature equal to or lower than the melting temperature of PTFE after the heat treatment, and in this case, slow cooling is preferable.

In the above-mentioned PTFE granulated product, it is considered that the polymer chains of PTFE in each particle have a certain degree of crystallinity before the above gelation. The individual particles of the above PTFE granulated product are heated by the above heat treatment, the polymer chains in the particles increase in momentum and are entangled with each other, and the content ratio of the crystalline part in the particle decreases to contain the amorphous part. The rate is expected to increase. As a result, the above-mentioned PTFE granulated product was
It is considered that the energy required for melting or softening is lower after the gelation than before.

Therefore, due to the gelation, the PTFE
The heat of fusion of the granulated product was, for example, 50 to 70 J / g, for example, about 60 J / g before the gelation, but 20 to 40 J / g, for example 30 J / g after the complete gelation. Decrease to a degree. When the gelling is performed in a semi-gelled state, the heat of fusion after the gelling is 20 J
/ G and less than 70 J / g, preferably more than 30 J / g and less than 60 J / g. In the present specification, the heat of fusion is a value obtained by using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation).

By the gelation, for example, the PT
The melting point peak of the FE granulated product was, for example, about 340 to 350 ° C. before the gelation but 320 to 330 ° C., preferably 323 to after the complete gelation.
It drops to about 327 ° C. When the gelation is performed in a semi-gelled state, the melting point peak after the gelation is usually
In the range of 320 to 350 ° C, two peaks will appear.

By the gelation, as described above, the PT
As a result of the polymer chains increasing in momentum and entangled with each other in the individual particles of the FE granulated product, the individual particles tend to shrink with a small size and a dense structure.
It is considered that the apparent density of the granulated product is increased. In the present specification, the gelled PTFE granulated product is
Sometimes referred to as "PTFE granulated gel product".

In the present specification, the term "pulverization" means that the PTFE granulated gelled product is a lump formed by fusing individual particles mainly by point contact and fusing to form a lump. It means crushing to a desired size. A product obtained by subjecting the above-mentioned PTFE granulated gelled product to the above pulverization is the PTFE granulated gelled pulverized product of the present invention.

In the method for producing a PTFE granulated gelled pulverized product of the present invention, it is preferable that the pulverization is carried out so as to separate the individual particles of the PTFE granulated product. In the pulverization, since the individual particles in the PTFE granulated gelled product are mainly fused to each other only at the contact portion, the individual particles originally constituting the PTFE granulated product are reduced to one by one. Can be crushed.

In the present specification, "dividing into individual particles of the above PTFE granulated product" means that the particles obtained by the above pulverization are the same as the individual particles of the above PTFE granulated product.
This means that the particles are separated from each other. Each particle separated into individual particles of the above-mentioned PTFE granulated product by the above-mentioned pulverization has the adhesion portion between the particles, which has been obtained by melting with other particles by the above-mentioned gelation, being mechanically cut by the above-mentioned pulverization. It was obtained.

Each particle separated into individual particles of the above-mentioned PTFE granulated product by the above-mentioned pulverization is usually separated from other particles under the environment where there is no restriction such as pressurization and at least no excess of moisture and heat. The relative position can be changed, and preferably the movement can be unique. Therefore, the PTFE of the present invention comprising such particles
The granulated gelled and pulverized product has excellent powder fluidity.

As described above, the PTFE granulated gel product has a small particle size in the gelation step. Therefore, the particles of the PTFE granulated gelled and pulverized product of the present invention obtained by pulverizing so as to be separated into individual particles of the above PTFE granulated product usually have the above-mentioned P content.
It has a particle size smaller than the average particle size of the TFE granulated product.

In the pulverization, particles having an aspect ratio of 1 to 2 are 60 to 10 of the whole PTFE granulated gel pulverized product.
It is performed so as to be 0% by weight. The above-mentioned pulverization is preferably carried out finely so as to be divided into individual particles of the above-mentioned PTFE granulated product as described above, but it is necessary to carry out pulverization too finely to produce the above-mentioned PT
If the individual particles of the FE granulated product are further divided, the obtained particles do not approximate a spherical shape, and the powder fluidity deteriorates, so the above-mentioned aspect ratio characteristics are used.

The PTFE of the present invention obtained by the above pulverization
The fact that the particles of the granulated gelled and pulverized product have an aspect ratio of 1 to 2 means that, as described above, the individual particles have a spherical shape or an approximate shape of a spherical shape due to the above-mentioned granulation, and the gelation causes point contact. This is because adjacent particles that have come into close contact are separated into individual particles of the PTFE granulated product by the pulverization.

It is not always necessary to carry out the pulverization so that all the particles of the PTFE granulated gelled product are separated into individual particles of the PTFE granulated product, and the particles are separated into individual particles of the PTFE granulated product. It suffices that the content of the particles is 50% by weight or more of the total amount of the particles constituting the PTFE granulated and pulverized product. Within the above range, the above P
The TFE granulated and gelled pulverized product has excellent powder fluidity and high apparent density as the whole particles.

In the method for producing a PTFE granulated gelled pulverized product according to the present invention, the pulverization has a particle size smaller than the average particle size of the PTFE granulated product and has an aspect ratio of 1 to 2. Is preferably 60 to 100% by weight of the entire PTFE granulated and pulverized product.

Of these, the PTFE granulated product has a particle size smaller than the average particle size and an aspect ratio of 1
As described above, the particles of ~ 2 are divided into individual particles of the above-mentioned PTFE granulated gelled product by the above-mentioned pulverization, and further finely pulverized to further divide the individual particles of the above-mentioned PTFE granulated product. Is not something. Therefore, such particles have a high apparent density and excellent powder flowability. By containing the particles capable of exhibiting such a high apparent density and excellent powder fluidity in the ratio within the above range, the PTFE granulated gelled and pulverized product has very excellent powder fluidity. Become.

The method of crushing is not particularly limited,
For example, a crusher used for general crushing can be used, and examples thereof include a rotary blade crusher commonly used for crushing general molten resin products and the like. As the method of pulverization, a method of pulverizing with a single-edged blade or a centrifugal force is preferable from the viewpoint that it is possible to suppress further division of individual particles of the PTFE granulated product.

After the pulverization, if necessary, the particle diameters may be made uniform by a method such as sieving. Particles having a uniform particle size can be appropriately selected and used for molding depending on the molding method used, the desired compactness of the molded body, the characteristics such as surface smoothness, and the like.

The PTFE of the present invention thus obtained
The granulated, gelled and pulverized product is appropriately determined according to the conditions of the molded product, the molding machine, etc., but the average particle diameter is usually 1 μm or more and less than 1 mm. Within the above range, the handleability during molding is good, and a compact compact having a good surface condition can be obtained. Heretofore, as a product obtained by subjecting the above-mentioned PTFE powder to the above-mentioned granulation, the above-mentioned gelation and the above-mentioned pulverization, no one having a small particle size within the above range has been obtained. The average particle size of the above PTFE granulated and pulverized product is
The thickness can be 1 μm to 3 mm depending on the purpose, but the preferable lower limit is 1 from the viewpoint of obtaining excellent powder fluidity.
μm, the preferred upper limit is 800 μm, the more preferred lower limit is 10 μm, the more preferred upper limit is 600 μm, the still more preferred lower limit is 100 μm, and the still more preferred upper limit is 400 μm.

The average particle diameter of the PTFE granulated and pulverized product is smaller in each step of the gelation and pulverization as described above. Above PTF
The E-granulated gelled and pulverized product can have a small average particle size and generally has a very small particle size distribution. From this point as well, a bridge is generated in the hopper when it is supplied to the molding machine. Hard to do.

The PTFE granulated and pulverized product of the present invention has an apparent density of 0.7 g / cm ³ or more. Within the above range, the volume per unit weight is reduced, so that the mold and cylinder of the molding machine can be downsized, and the powder fluidity is improved, enabling uniform filling of the mold and cylinder. Therefore, the particles are less likely to aggregate and cause a bridge in the hopper, so that the handleability can be improved. Above PT
Since the apparent density of the FE-granulated gelled and pulverized product is increased in each of the steps of granulation and gelation as described above, it is possible to obtain such a high value.

The apparent density of the PTFE granulated and pulverized product of the present invention is preferably more than 1.05 g / cm ³ . The PTFE granulated and pulverized product of the present invention has an apparent density of more than 1.05 g / cm ³ . A raw material powder of PTFE having such a high apparent density has not been obtained in the past. When the apparent density is within the above range, it is possible to reduce the size of the mold and the cylinder, to uniformly fill them, the powder fluidity, the bridge prevention property in the hopper, and the like. The apparent density is, for example, 1.05
It can be 1.5 g / cm ³ . The apparent density within such a range is such that the average particle diameter is 1 μm or more, and
It can be easily obtained when the length is less than mm, particularly when it is 1 to 600 μm.

Therefore, the PTFE granulated gelled and pulverized product of the present invention preferably has a length of more than 1.05 g / cm ³ and an average particle diameter of 1 μm or more and less than 1 mm. If the conditions are satisfied, a powder compact having excellent powder fluidity, a dense surface condition, and a good surface condition can be obtained.

The PTFE granulated gelled product of the present invention has a mean particle size of more than 1.05 g / cm ³ and an average particle size of 1
It is more preferably about 600 μm. If the conditions are satisfied, a molded product having excellent powder fluidity, high density and excellent surface condition can be obtained.

The PTFE granulated gelled and pulverized product of the present invention has an apparent density of 0.7 to 1.05 g / cm ³ .
The average particle size may be more than 600 μm and less than 1 mm. If such conditions are satisfied, powder fluidity will be good, and a compact compact having a good surface condition can be obtained.

As described above, the apparent density of the PTFE granulated and pulverized product of the present invention is 0. 0 even when the average particle size exceeds 600 μm and the length is less than 1 mm.
It can have a high value, such as 7 to 1.05 g / cm ³ . Conventionally, it has been generally said that the larger the average particle size, the lower the apparent density, but in the present invention, even if the average particle size is relatively large as in the above range, the apparent density may still be high. it can.

The PTFE granulated and pulverized product of the present invention preferably has an angle of repose of less than 40 °. The angle of repose is an index of powder fluidity and handleability, and the smaller the value, the better the powder fluidity and handleability.

In the present specification, the "angle of repose" means
It means the angle between the generatrix of the cone and the horizontal plane when the powdery resin is gently dropped from the funnel onto a flat surface and deposited in a conical shape. In the present specification, the angle of repose is
It is a value measured using a powder tester (manufactured by Hosokawa Micron).

The angle of repose within the above range can be easily obtained particularly when the average particle size is 1 to 800 μm. Conventionally, the angle of repose has been considered to increase as the particle size decreases, because the adhesive force of the particles increases. However, the PTFE granulated and pulverized product of the present invention overturns such common sense, and in the particle size within the above range, the smaller the particle size, the smaller the angle of repose, and the powder fluidity can be improved. The preferable lower limit is 200 μm and the preferable upper limit is 600 μm.

The average particle diameter, apparent density and / or angle of repose of each of the above-mentioned PTFE granulated and pulverized products are within the above ranges.
E granulated gelled pulverized product can be easily obtained when it is 60% by weight or more, preferably 90% by weight or more.
With such characteristics of the aspect ratio, the abundance ratio of particles that are relatively spherical or a spherical approximate shape increases. As a result, the particle shapes are relatively uniform, and the average particle size tends to be small. In addition, when the particles are spherical or approximate to a spherical shape, the individual particles are tight, and the packing rate of particles per unit volume is high, so that the apparent density is likely to be improved. Further, since the friction between the particles is small due to the shape of the particles, the powder fluidity is easily improved.

The PTFE granulated gelled and pulverized product of the present invention is one in which particles having an aspect ratio of 1 to 2, and preferably 1 to 1.5 are separated from each other. The above-mentioned PTFE granulated and gelled pulverized product is preferably the above-mentioned PTFE as described above.
The granulated product is pulverized so as to be divided into individual particles, and particles having an aspect ratio of 1 to 2, preferably 1 to 1.5 are obtained by the pulverization. The particles having the ratio will be separated from each other. Since the above-mentioned PTFE granulated gelled and pulverized product is in such a state, it has excellent powder fluidity, high apparent density, and excellent handleability.

The PTFE granulated semi-gelled pulverized product of the present invention is
It is composed of non-modified PTFE and / or modified PTFE.

In the present specification, the above-mentioned "PTFE granulated semi-gelated pulverized product" is obtained by semi-gelating and then pulverizing the non-modified PTFE and / or the PTFE granulated product comprising the modified PTFE. Means something that can be done. The non-modified PTFE, the modified PTFE, the PTFE granulated product and the pulverization are the same as those in the PTFE granulated gelled and pulverized product, and the semi-gelation is the gelation of the PTFE granulated product. Is.

The PTFE granulated semi-gelled pulverized product of the present invention is
There are two melting peaks at 320-350 ° C,
Usually, it has a heat of fusion of 30 to 60 J / g and two melting peaks at 320 to 350 ° C. As the method for measuring the heat of fusion and the melting peak, the same methods as those described above for the PTFE granulated gelled and pulverized product of the present invention can be used.

The PTFE granulated semi-gelled pulverized product of the present invention is
Those having two melting peaks at 320 to 350 ° C. and having an average particle diameter of 1 μm or more are preferable. The more preferable lower limit of the average particle diameter is 0.1 mm, the still more preferable lower limit thereof is 300 μm, the more preferable upper limit thereof is 3 mm, and the still more preferable upper limit thereof is 1 mm.

The PTFE granulated semi-gelled pulverized product of the present invention is
If there are two melting peaks at 320-350 ° C
Together, or two melting peaks at 320-350 ° C.
The average particle size is within the above range.
Has an apparent density of 0.7 g / cm ^ThreeIs better
Good Within the above range, the powder fluidity is good.
Therefore, it is possible to obtain a compact compact body with a good surface condition.
It A more preferable lower limit is 0.8 g / cm^Three, More preferred
The upper limit is 1.5 g / cm^ThreeIs.

The present invention also relates to PTFE powder. The PTFE powder of the present invention can be suitably used as a raw material powder in various molding methods such as compression molding and extrusion molding.

In the present specification, the above "PTFE powder"
And the above-mentioned non-modified PTFE and / or the above-mentioned modified PTFE
Means a powdery solid consisting of The PTFE powder is not particularly limited and is a concept that may include, for example, the PTFE powder, the PTFE granulated product, and the PTFE granulated gelled and ground product, but obtains excellent powder fluidity and high apparent density. From the viewpoint, the above-mentioned PTFE granulated gelled and pulverized product is preferable. This PTFE granulated gelled and pulverized product may include the above-mentioned PTFE granulated semi-gelated and pulverized product.

The PTFE powder of the present invention can have an average particle diameter of a length of 1 μm or more and less than 1 mm, which is appropriately determined depending on the intended molded product, the conditions of the molding machine and the like. Within the above range, a compact compact having a good surface condition can be easily obtained. The average particle diameter of the PTFE powder can be 1 μm to 3 mm depending on the purpose, but from the viewpoint of obtaining excellent powder fluidity, the preferable lower limit is 1 μm, the more preferable lower limit is 10 μm, and the still more preferable lower limit. Is 100 μm, and the preferable upper limit is 800 μm,
A more preferable upper limit is 600 μm, and a still more preferable upper limit is 4
It is 00 μm.

The PTFE powder of the present invention is 0.7 g / cm.
It can have an apparent density of ³ or more. Within the above range, it becomes possible to downsize the mold and cylinder of the molding machine, improve the powder fluidity, uniformly fill the mold and cylinder, and prevent bridges in the hopper. When the above PTFE powder is the above-mentioned PTFE granulated and gelled pulverized product,
A high apparent density within the above range can be easily obtained.

The apparent density of the PTFE powder of the present invention is
It is preferably more than 1.05 g / cm ³ . The PTFE powder of the present invention has an apparent density of more than 1.05 g / cm ³ . P having such a high apparent density
Although no TFE powder has hitherto been obtained, according to the present invention, an apparent density within the above range can be easily obtained, particularly when the above PTFE powder is the above PTFE granulated gelled and pulverized product. . When the apparent density is within the above range, it is possible to reduce the size of the mold and the cylinder, to uniformly fill them, the powder fluidity, the bridge prevention property in the hopper, and the like. The apparent density is, for example, 1.05
It may be 1.5 g / cm ³ . Such a high apparent density can be easily obtained when the average particle size is 1 μm or more and the length is less than 1 mm.

The PTFE powder of the present invention has an apparent density of more than 1.05 g / cm ³ and an average particle size of 1 to 600 μm.
More preferably m. When the average particle diameter is within the above range, such a high apparent density can be obtained particularly easily.

The PTFE powder of the present invention has an apparent density of 0.7 to 1.05 g / cm ³ and an average particle size of 60.
The length may be more than 0 μm and less than 1 mm.
Conventionally, when the average particle diameter is generally large, the apparent density tends to decrease, but in the present invention, the apparent density is still high even if the average particle diameter is relatively large as in the above range. Can have.

The PTFE powder of the present invention has an apparent density of more than 1.05 g / cm ³ and a heat of fusion of 20-4.
0 J / g or apparent density of 1.05 g /
cm ³ and one melting peak at 320 to 330 ° C., or an apparent density of 1.05 g / cm ³
It is more preferable that the amount of heat of fusion exceeds 20 to 40 J / g, and the melting peak is one at 320 to 330 ° C. Within the above range, it is possible to easily reduce the size of molds and cylinders and to uniformly fill them, powder flowability, bridge prevention in a hopper, and the energy required for melting or softening. Since it is not expensive, it is easy to apply to various molding methods.

The PTFE powder of the present invention has an apparent density of more than 1.05 g / cm ³ and an average particle size of 1 to 6.
Those having a melting heat of 20 to 40 J / g, or having an apparent density of more than 1.05 g / cm ³ and an average particle diameter of 1 to 600 μm, and a melting peak of 320 to 330. There is one at 0 ° C, or the apparent density exceeds 1.05 g / cm ³ and the average particle size is 1 to 6
00 μm, the heat of fusion is 20 to 40 J / g,
Further, it is more preferable that the melting peak is one at 320 to 330 ° C. Within the above range, it is possible to considerably reduce the size of molds and cylinders and evenly fill them, the powder fluidity, the bridge prevention property in the hopper, and the energy required for melting or softening. Since it is not expensive, it is easy to apply to various molding methods.

The PTFE powder of the present invention has an apparent density of 0.7 to 1.05 g / cm ³ and an average particle size of 60.
The length is more than 0 μm and less than 1 mm, the heat of fusion is 20 to 40 J / g, or the apparent density is 0.7 to 1.05 g / cm ³ , and the average particle diameter is 60.
The length is more than 0 μm and less than 1 mm, and the melting peak is one at 320 to 330 ° C., or the apparent density is 0.7 to 1.05 g / cm ³ , and the average particle diameter is 600 μm. The length is more than 1 mm and the heat of fusion is 20 to 40 J / g, and the melting peak is 3
More preferably, there is one at 20 to 330 ° C. Within the above range, molds and cylinders can be miniaturized and evenly filled therein, powder flowability, bridge prevention in a hopper, etc. are good, and the energy required for melting or softening is not high. Easy to apply to various molding methods.

The heat of fusion of these is 20 to 40 J / g, and / or the melting peak is 320 to 33.
The PTFE powder of the present invention, which has the characteristic of having one at 0 ° C., is usually a completely gelled product.

The PTFE powder of the present invention also has a heat of fusion of 30 to 60 J / g and a melting peak of 320 to 35.
There may be two at 0 ° C. and an apparent density of 0.4 g / cm ³ or more. Within the above range, it is possible to easily reduce the size of molds and cylinders and evenly fill them, powder flowability, bridge prevention property in a hopper, and the energy required for melting or softening. Since it is not expensive, it is easy to apply to various molding methods. The preferable lower limit of the apparent density is 0.6 g / cm ³ , and the preferable upper limit thereof is 1.3 g / cm ³ .

The PTFE powder of the present invention has a heat of fusion of 30.
˜60 J / g, two melting peaks at 320 to 350 ° C., and an apparent density of 0.4 g / cm ³ or more,
It is preferable that the average particle diameter is 1 μm or more. Within the above range, it is possible to reduce the size of molds and cylinders and to uniformly fill them, powder fluidity, bridge prevention in a hopper, and the like, and the energy required for melting or softening can be improved. Since it is not expensive, it is easy to apply to various molding methods. The more preferable lower limit of the apparent density is 0.6 g / cm ³ , and the more preferable upper limit thereof is 1.3 g.
/ Cm ³ , and more preferably, for example, 0.6 to 1.3 g / cm ³ . The more preferable lower limit of the average particle diameter is 0.1 m.
m, the more preferable lower limit is 0.3 mm, the more preferable upper limit is 3 mm, and the still more preferable upper limit is 1 mm.

The characteristic that these melting peaks are two at 320 to 350 ° C., or the melting peaks are 320 to 35 ° C.
The PTFE powder of the present invention having two characteristics at 0 ° C. and a heat of fusion of 30 to 60 J / g is usually a semi-gelled product.

The PTFE granulated and pulverized product of the present invention and the PTFE powder of the present invention may optionally contain other components such as other thermoplastic resins and additives in appropriate amounts. In this case, from the viewpoint of uniformly dispersing the above-mentioned additives in the obtained PTFE molded body, it is usually preferable to mix them in the step of performing the granulation or the gelation.

The above-mentioned other thermoplastic resin is not particularly limited, and for example, when the obtained PTFE molded article is used at high temperature, a heat resistant resin is preferable. The heat-resistant thermoplastic resin is not particularly limited, and examples thereof include polyester resin, polyamide resin, acrylic resin, acetal resin, polysulfone resin, polyimide resin, polyphenylene oxide resin, and the like.

As the above-mentioned additive, a filler such as a reinforcing material;
Examples include catalysts, support materials, colorants, and the like. The filler is not particularly limited, and examples thereof include glass fiber, graphite powder, bronze powder, gold powder, silver powder, copper powder, stainless steel powder, stainless steel fiber, nickel powder, metal fibers such as nickel fiber, or metal powder. Inorganic powders or powders of molybdenum disulfide powder, mica fluoride powder, coke powder, carbon fiber, boron nitride powder, carbon black and the like; aromatic heat resistant resin powder such as polyoxybenzoyl polyester; polyimide powder; Examples thereof include organic powders such as tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer [PFA] powder and polyphenylene sulfide powder. These can use 1 type (s) or 2 or more types.

The PTFE granulated and pulverized product of the present invention is obtained by subjecting the above-mentioned PTFE granulated product obtained by granulating the above-mentioned PTFE powder to gelation and subsequent pulverization. It has excellent powder flowability and high apparent density. The mechanism by which the PTFE granulated and gelled product of the present invention exerts such advantageous effects is considered as follows.

Since the above-mentioned PTFE granulated product is obtained by subjecting the above-mentioned PTFE powder to the above-mentioned granulation, since each particle has a relatively hard surface compacted into a spherical shape or a spherical approximate shape, It is considered that the adhesive force on the surface is not high, the fluidity of the powder is improved and the apparent density is increased as compared with the above PTFE powder. In the above PTFE granulated product, the individual particles thus have a spherical shape or a shape close to this,
Since it has a hard surface, each particle is brought into close contact with an adjacent particle by point contact due to the heating in the gelation, and is easily separated into individual particles by pulverization in the subsequent step.

Therefore, the obtained PTFE granulated gelled and pulverized product maintains the spherical shape in which individual particles are tightened or a shape close to this, through the above-mentioned steps of granulation, gelation and pulverization. It is considered that it has a high apparent density. The individual particles after the pulverization are also hard to adhere to each other because the surface maintains hardness,
It is considered that the powder has excellent fluidity because it maintains a spherical shape or a shape close to it, and is divided into individual particles with a small average particle size and a narrow particle size distribution.

Since the PTFE granulated and pulverized product of the present invention is heated in the above gelation, it does not cause problems such as aggregation even at room temperature and has excellent powder fluidity. You can The mechanism by which the above-mentioned PTFE granulated and pulverized product exhibits such advantageous effects is considered as follows.

Conventionally, PTFE has a transition point at room temperature. Therefore, when the above PTFE powder is granulated, the particles are close to spherical due to granulation, and although the powder fluidity is good at a temperature below the transition point, the particles have softness at a temperature above the transition point. It is considered that the powder fluidity was deteriorated as a result of easy deformation of the shape and aggregation of the granulated particles.

However, the PTFE granulated and pulverized product of the present invention is considered to be one in which the transition point disappears and the transition does not occur when the PTFE powder is heated by the gelation, and is excellent even at room temperature. It is thought that the powder fluidity can be maintained.

[0116] Conventionally, it is considered that the PTFE powder obtained by subjecting the above-mentioned PTFE powder to the above gelation had a poor sphericity because the transition point disappeared by heating, but the powder fluidity was poor. To be The PTFE granulated gelled and pulverized product of the present invention is obtained by performing the above granulation and further pulverizing so as to be divided into individual particles in addition to causing no transition even at room temperature as described above. Since the particles have a spherical shape or an approximate shape of a spherical shape, it is considered that the powder fluidity is excellent at both normal temperature and high temperature.

As described above, the method for producing a PTFE granulated gelled pulverized product according to the present invention comprises subjecting the above PTFE granulated product to the above gelation and then the above pulverization to obtain the above-mentioned PTFE.
E Granulation Gelation It is possible to easily obtain a crushed product. For the method of obtaining the above-mentioned PTFE granulated product, each step of the above-mentioned gelation and the above-mentioned pulverization, for example, a conventionally known method can be used, and the present invention can be easily and economically performed without requiring a special device or means. Can be applied to.

The PTFE powder of the present invention has a high apparent density and excellent powder flowability as described above,
In particular, these characteristics can be easily obtained in the case of the above-mentioned PTFE granulated gelled and pulverized product.

The PTFE granulated and pulverized product of the present invention and the PTFE powder of the present invention have a high apparent density as described above, and are excellent in powder fluidity at both normal temperature and high temperature, and therefore, they are molded by a molding machine. It can be suitably used for various molding methods, regardless of whether the process in which the apparent density and the powder fluidity such as the supply to the preform and the preparation process of the preform are affected at normal temperature or high temperature. Such a molding method is not particularly limited, and for example, it can be suitably used for a ram extrusion molding method which has conventionally been problematic in terms of powder fluidity and the like.

Since the PTFE granulated and pulverized product of the present invention and the PTFE powder of the present invention have undergone heating due to the gelation, the energy required for softening or melting can be lowered as described above. Since it can be softened or melted comparatively easily, and a common plastic molding method used for general thermoplastic resins having a relatively low melt viscosity, for example, resins for injection molding, injection compression molding, extrusion molding, etc. It can be used for a molding method that requires fluidity during melting.

A molded product characterized by being obtained from the above-mentioned PTFE granulated gelled and pulverized product is one aspect of the present invention. A molded product obtained from the above-mentioned PTFE granulated semi-gelled pulverized product is also one aspect of the present invention. A molded body characterized by being obtained from the above PTFE powder is also one aspect of the present invention.

[0122]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Production of PTFE granulation gelled pulverized product of molding powder Granulated product of modified PTFE molding powder (average particle diameter 400 μm, apparent density 0.90 g / cm ³ , trade name: New Polyflon PTFE M139, Daikin Industries, Ltd. (Made by the company) was spread on a stainless steel vat with a thickness of 5 cm, placed in an oven and heated in air. The heating was performed by raising the oven temperature from room temperature to 370 ° C. over 3 hours and holding the temperature for 2 hours, and then cooling to room temperature over 3 hours. The obtained block was crushed with a crusher equipped with a 2 mmφ screen to obtain a PTFE granulated gelled crushed product. This PTF
The E granulated gelled and pulverized product had an average particle size of 646 μm, an apparent density of 0.985 g / cm ³ and an angle of repose of 38.9 °.

Example 2 A granulated gelled and pulverized product was collected in the same manner as in Example 1 except that a 1 mmφ screen was used instead of the 2 mmφ screen. The average particle size of this granulated and pulverized product is 491μ.
m, apparent density 1.082 g / cm ³ , repose angle 3
It was 7.6 °.

Example 3 A granulated gelled and pulverized product was collected in the same manner as in Example 1 except that a 0.5 mmφ screen was used instead of the 2 mmφ screen. The average particle size of this granulated gelled product is 37
0 μm, apparent density was 1.230 g / cm ³ , and repose angle was 35.5 °.

From the examples, the above-mentioned PTFE granulated product was prepared as follows.
The above-mentioned PT obtained by performing the above gelling and then the above pulverization
It was found that the FE granulated gelled and pulverized product has a high apparent density, is excellent in powder fluidity, and can reduce the average particle size.

[0126]

The PTFE granulated gelled and pulverized product of the present invention including the PTFE granulated semi-gelled and pulverized product of the present invention has the above-mentioned constitution and therefore has a small average particle diameter and a high apparent density. Since the powder has excellent fluidity, the handling property can be improved. Since the method for producing a PTFE granulated gelled pulverized product of the present invention has the above-mentioned constitution, the PTF containing the PTFE granulated semi-gelated pulverized product can be prepared by a simple method.
An E-granulated gelled pulverized product can be obtained. PT of the present invention
Since the FE powder has the above-mentioned structure, it has a high apparent density, is excellent in powder fluidity, and can be improved in handleability.

Continued front page    (72) Inventor Kazuo Ishiwari             Daiichi Nishiichitsuya 1-1, Settsu City, Osaka Prefecture             Yodogawa Manufacturing Co., Ltd. (72) Inventor Koji Fukuyama             Daiichi Nishiichitsuya 1-1, Settsu City, Osaka Prefecture             Yodogawa Manufacturing Co., Ltd. F-term (reference) 4F070 AA24 DA50 DB09 DC06 DC07                       DC08 DC09                 4F071 AA27 AD02 AD06 BB03 BB05                       BC07

Claims (31)

[Claims] 1. A PTF comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
E granulated gelled and crushed product with an apparent density of 1.05g
PTFE characterized by exceeding / cm ^3.
Granulated gelled crushed product. 2. A PTF comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
An E-granulated gelled and pulverized product having an average particle diameter of 1 μm or more and less than 1 mm. 3. Further, the average particle diameter is 1 μm or more,
The PTFE granulated gelled and pulverized product according to claim 1, which is less than 1 mm. 4. The PTFE granulated and pulverized product according to claim 1, which has an average particle size of 1 to 600 μm. 5. A PTF composed of unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
E granulated gelled and crushed product with an apparent density of 0.7 to
It is 1.05 g / cm ³ and the average particle diameter is more than 600 μm and less than 1 mm. 6. A PTF comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
An E-granulated gelled and crushed product having a repose angle of less than 40 °. 7. Particles having an aspect ratio of 1-2 are PT.
60% by weight or more of the whole FE granulated gelled pulverized product, The PTFE granulated gelled pulverized product according to claim 1, 2, 3, 4, 5 or 6. 8. A PTF comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
E granulated gelled pulverized product having an aspect ratio of 1 to 1.
A PTFE granulated and pulverized product characterized in that the particles of No. 5 are separated from each other. 9. A PTF comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene.
E granulated semi-gelled pulverized product having a heat of fusion of 30 to 60
It is J / g and has two melting peaks at 320 to 350 ° C. A PTFE granulated semi-gelled and pulverized product. 10. The PTFE granulated semi-gelled pulverized product according to claim 9, which has an average particle size of 1 μm or more. 11. The PTFE granulated semi-gelled pulverized product according to claim 9, which has an average particle size of 0.1 to 3 mm. 12. The PTFE granulated semi-gelled pulverized product according to claim 9, which has an average particle size of 0.3 to 1 mm. 13. The PTFE granulated semi-gelled pulverized product according to claim 9, 10, 11 or 12, which has an apparent density of 0.7 g / cm ³ or more. 14. The apparent density is 0.8 to 1.5 g / cm.
The PTFE according to claim 9, 10, 11, or 12 which is ^3.
Granulated semi-gelled crushed product. 15. A PTFE powder having an apparent density of more than 1.05 g / cm ³ . 16. The PTFE powder according to claim 15, which has an average particle diameter of 1 to 600 μm. 17. The apparent density is 0.7 to 1.05 g / c.
PTFE powder having a length of m ³ and an average particle diameter of more than 600 μm and less than 1 mm. 18. The PTF according to claim 15, 16 or 17, which has a heat of fusion of 20 to 40 J / g.
E powder. 19. A melting peak of 320 to 330 ° C.
15. The method according to claim 15, 16, 17 or 18
The described PTFE powder. 20. Further, the melting peak is 320 to 350 ° C.
18. The PTFE powder according to claim 15, 16 or 17, wherein there are two of them. 21. A heat of fusion of 30 to 60 J / g,
PTF having two melting peaks at 320 to 350 ° C. and an apparent density of 0.4 g / cm ³ or more
E powder. 22. The apparent density is 0.6 to 1.3 g / c.
22. The PTFE powder according to claim 21, which is m ³ . 23. The PTFE powder according to claim 21, further having an average particle size of 1 μm or more. 24. The PTFE powder according to claim 23, which has an average particle diameter of 0.1 to 3 mm. 25. The PTFE powder according to claim 23, which has an average particle diameter of 0.3 to 1 mm. 26. A PT comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene
PT consisting of FE granulated product after gelling and crushing
A method for producing a PTFE granulated gelled pulverized product for producing an FE granulated gelled pulverized product, wherein
A method for producing a PTFE granulated and pulverized product, which is carried out so as to be divided into individual particles of the E granulated product. 27. A PT comprising unmodified polytetrafluoroethylene and / or modified polytetrafluoroethylene
PT consisting of FE granulated product after gelling and crushing
A method for producing a PTFE granulated gelled pulverized product for producing an FE granulated gelled pulverized product, wherein
The particle size is smaller than the average particle size of the E-granulated product, and the particles having an aspect ratio of 1 to 2 account for 60% by weight or more of the whole PTFE-granulated gelled and crushed product. A method for producing a PTFE granulated gelled and pulverized product, characterized in that 28. A molded product obtained from the PTFE granulated gel pulverized product according to claim 1, 2, 3, 4, 5, 6, 7 or 8. 29. A molded article obtained from the PTFE granulated semi-gelled pulverized product according to claim 9, 10, 11, 12, 13 or 14. 30. The method according to claim 15, 16, 17, 18 or 1.
A molded product obtained from the PTFE powder according to item 9. 31. Claims 20, 21, 22, 23, 24
Alternatively, a molded product obtained from the PTFE powder according to item 25.