WO2002102572A1

WO2002102572A1 - Method for producing polytetrafluoroethylene resin formed product and resin formed product

Info

Publication number: WO2002102572A1
Application number: PCT/JP2002/005316
Authority: WO
Inventors: Shinji Murakami; Kazuo Ishiwari
Original assignee: Daikin Industries, Ltd.
Priority date: 2001-05-30
Filing date: 2002-05-30
Publication date: 2002-12-27
Also published as: JPWO2002102572A1

Abstract

A novel method for producing a polytetrafluoroethylene resin formed product, characterized in that a material comprising a polytetrafluoroethylene resin to be formed is stretched through the application of a pressure difference to the material at a temperature not lower than the temperature at which a crystal of the polytetrafluoroethylene resin starts to melt and in a state wherein crystals are still present in the material, and then cooling the stretched material, while retaining the pressure difference, to a temperature lower than the above temperature of start of melting; and a formed product produced by the method. The method allows the production of a better PTFE formed product as compared to a conventional PTFE formed product, that is, a formed product which is not porous and has been stretched so as to have a uniform thickness.

Description

Specification

Method for producing polytetrafluoroethylene resin molded article and resin molded article

The present invention relates to a method for producing a molded article made of polytetrafluoroethylene resin by stretching a molded article made of polytetrafluoroethylene resin, particularly a production method utilizing a blow molding method, And a molded article obtained by the method. The present invention also relates to a resin molded product having a high degree of crystallinity and high transparency, and more particularly to a resin molded product excellent in barrier properties and surface smoothness, and comprising the resin molded product. The present invention relates to a packaging material for blocking atmospheric moisture, a packaging material for blocking chemicals, a packaging material for blocking gas, a belt material, and a package. Background art

Fluororesin, especially polytetrafluoroethylene resin [PTFE], has excellent heat resistance and can be used at high temperatures. Furthermore, chemical resistance, weather resistance, non-adhesion, electrical insulation, high frequency properties, etc. Since it has many excellent properties, it is used in many fields such as chemicals such as chemicals, semiconductors, automobiles and machinery.

PTFE has a high melt viscosity and does not show fluidity even at temperatures higher than its melting point.Therefore, in order to obtain a PTFE molded product, compression molding or pre-molding such as paste extrusion molding is generally used. After the preform is obtained, a method of firing it is used (Fluorine Resin Handbook (1990, Nikkan Kogyo Shimbun, edited by Takaomi Satokawa), No. 93-: L4 See page 7).

Japanese Unexamined Patent Publication No. Hei 6-520265 discloses a method for producing a bellows for a bellows pump by preforming a preform of a perfluoroalkylbutyl ether-modified polytetrafluoroethylene resin. Is disclosed. Bellows as molded articles obtained by the method disclosed in this publication are those obtained by performing the same operation except that blow molding is not performed, that is, those having a specific gravity lower than that of molded articles having the same heat history. Yes, it functions as a bellows, but the molded product itself is in a so-called porous state. Therefore, a molded article whose porous state is not desirable, for example, This pro-molding method is not suitable for obtaining molded articles used for containers and the like. In addition, Japanese Patent Application Laid-Open Nos. Hei 4-296332, Hei 4-34536 and Heisei 53-58579 disclose a blow molding method as a method for producing a PTFE heat-shrinkable tube. In these methods, tubes are manufactured at very high ambient temperatures, and it is presumed that PTFE is in a completely molten state during molding. It has been found that such a method tends to result in a bent molded product, a molded product having an uneven wall thickness, or a ruptured molded product, as described later.

In these patent publications, there is no clear and specific disclosure of detailed information on the temperature of the resin at the time of molding, and in particular, there is no description of the crystal state, crystallinity, etc. of the PTFE used. Also, information on the dimensions of molded articles is not always sufficient. Fluororesins, especially PTFE, are known to have high crystallinity due to their molecular structure. For example, a molded product obtained by compression molding or paste extrusion molding has a high degree of crystallinity. However, the degree of crystallization of the molded article obtained by these molding methods is not sufficiently high.

It is generally known that the higher the crystallinity of a molded product, the higher the barrier property. WO 0 OZl 0805 discloses that PTFE is improved in crystallinity to improve barrier properties.

As a method of increasing the crystallinity of a molded article of PTFE, there is a method of slowing the cooling rate after baking the preformed body in molding. (Q & A reading book for all fluororesins (1991, Fluoroplastics Industry Association, Committee · Q & A Readers' Editing Committee, pp. 107-109) However, with this method, the crystallinity usually rises only to about 75%, and resin molded products with higher crystallinity can be obtained. There was a problem that it could not be obtained.

The crystals formed by sintering the preformed body and then slowly cooling are randomly generated without any direction. When the amount of such disordered crystals increases, light scattering at the interface of the crystals increases. Therefore, there has been a problem that the higher the crystallinity, the lower the transparency.

The conventional molding of PTFE differs from the general molding of thermoplastics in that Since the powder particles are fused at the time of firing the form and then cooled, voids are easily generated, and the PTFE 'does not show fluidity even at the time of firing, so that the generated voids are hard to disappear. Poids are also generated in PTFE paste extrusion by drying out the necessary lubricating aids. There was a problem that the transparency of the molded article was also impaired by light scattering in the void.

As described above, conventionally, a PTFE molded article having improved crystallinity and transparency has not been obtained. Therefore, PTFE has conventionally been used for applications that require both high barrier properties and transparency, such as for use in electorum luminescent elements or protective films for solar cells, packaging materials for drugs, etc. There was a problem that it could not be used for the required applications such as chemical tubes. Summary of the Invention

A first object of the present invention is to provide a new PTFE molding method capable of obtaining a molded article better than the known PTFE molding method, that is, it is possible to stretch with a uniform thickness without making it porous. An object of the present invention is to provide a method for manufacturing a molded article and a molded article. The first invention is to form a P-shaped FE by stretching a PTFE molded body at a temperature higher than the crystal melting start temperature of PTFE and at a temperature at which a crystal part exists in PTFE constituting the molded body. A method for producing a product, comprising stretching a molded body by a differential pressure, and cooling to a temperature lower than a crystal melting start temperature while maintaining the differential pressure.

A second object of the present invention is to provide a resin molded article having a higher degree of crystallinity and excellent transparency, a resin molded article made of PTFE having excellent barrier properties, and a PTFE having excellent surface smoothness. To provide a resin molded product.

The second present invention is a resin molded product having a melting point peak of 250 ° C. or higher, a crystallinity of 78% or higher, and a haze value of 30% or lower. A third aspect of the present invention is a resin molded article made of a fluorine-containing resin, wherein the fluorine-containing resin is made of a tetrafluoroethylene-based polymer, and has a crystallinity of 78% or more, A resin molded product having a haze value of 30% or less. The fourth present invention relates to a tetrafluoroethylene homopolymer and / or a modified polyester. A resin molded article comprising the trough Ruo Russia ethylene, 25 ° water vapor permeability coefficient of 0. 02 (g · mm) at a relative humidity of difference of 90% in the C / (m ² · day), wherein Der Rukoto less It is a resin molded body to be described.

The fifth of the present invention is a resin molded article comprising tetrafluoropropoxy O b ethylene homopolymers and / or modified Porite trough Ruo Russia ethylene, 35 weight ^_0/0 in 25 ° C permeability coefficient of hydrochloric acid 1.8 a resin molded body characterized by X 10- ¹¹ (g · cm) Bruno (cm ² · sec) or less.

The sixth invention is a resin molded article comprising a tetrafluoroethylene homopolymer and / or a modified polytetrafluoroethylene, which has a nitrogen permeability coefficient of 0.2 MPa at 25 ° C. of 6.8 X ^{^{10- 8 (cm 3 · cm)}} / (cm 2 - sec - MP a) is a resin molding, which is a bottom.

A seventh aspect of the present invention is a resin molded product comprising a tetrafluoroethylene homopolymer and Ζ or modified polytetrafluoroethylene, having a specific gravity of 2.1 or more and an arithmetic average roughness of 0.03 μπι. It is a resin molding characterized by the following. An eighth aspect of the present invention is a packaging material for blocking moisture in the air, comprising the resin molded product of the second to seventh aspects of the present invention, which is used for covering an article to be packaged. A ninth aspect of the present invention is a drug blocking packaging material comprising the resin molded product of the second to seventh aspects of the present invention.

A tenth aspect of the present invention is a gas shielding packaging material comprising the resin molded product of the second to seventh aspects of the present invention.

The eleventh aspect of the present invention is a belt material comprising the resin molded product of the second to seventh aspects of the present invention, which is used for a photosensitive portion for forming an image in an electrophotographic apparatus. Belt material.

According to a twelfth aspect of the present invention, there is provided a belt material comprising the resin molded product according to the second to seventh aspects of the present invention, wherein the belt material is used for a fixing unit for forming an image in an electrophotographic apparatus. It is a belt material.

According to a thirteenth aspect of the present invention, there is provided a package comprising the packaged article and the resin molded article according to the second to seventh aspects of the present invention, wherein the resin molded article covers the packaged article. The contact between the above package and the atmospheric moisture, chemicals and / or gas must be suppressed. It is a package characterized by the above. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic cross-sectional view of a mold of a pottle-shaped blow-stretched product according to one embodiment of the present invention (used in Examples 1 to 5 and Comparative Examples 1 and 2).

FIG. 2 is a schematic cross-sectional view of a mold for a fusion bottle-shaped professional stretch-formed product according to one embodiment of the first invention (used in Embodiment 7).

FIG. 3 is a schematic sectional view of a mold of a cylindrical blow-stretched product according to one embodiment of the first invention (used in Example 5, Comparative Examples 3 and 4).

FIG. 4 is a schematic cross-sectional view of a blow-stretch-molded mold according to one embodiment of the first invention (used in Embodiment 6 and Comparative Example 5).

FIG. 5 is a schematic diagram of X-ray diffraction for obtaining crystallinity by an X-ray diffraction method. FIG. 6 is a schematic cross-sectional view of a measuring device for determining a chemical solution permeability coefficient.

FIG. 7 is a schematic cross-sectional view of the mold used in Examples 8 to 10.

FIG. 8 is a schematic sectional view of the mold used in Examples 11 to L3.

FIG. 9 is an X-ray diffraction chart of the molded body 1 obtained in Production Example 1.

Figure 10 is a _c Figure 1 1 is an X-ray diffraction Chiya one bets PTFE stretched molded article obtained in Example 11 is a TEM replica photograph of the cross section of the molded body 1 obtained in Production Example 1 _c Fig. 12 is a TEM replica photograph of a cross section of the stretched PTFE product obtained in Example 11; Explanation of reference numerals

1 1, 2 1, 3 1, 4 1, 72, 8 2 Mold head,

1 2, 22, 42 Mold body,

1 3, 23, 43, 73, 8 3 Mold bottom,

14, 25, 44 air vent holes,

1 5, 75, 85 air fitting

24 Splice sleeve installation part,

3 2 Head body connection, 3 3 Mold body, 34 Mold bottom 3 5 Angle for sandwiching the molded object,

6 1 Measurement sample

6 2a, 6 2b glass container

6 3 O—Ring

6 4 Sampling port

7 1, 8 1 Mold

7 4, 8 4 Movable angle Detailed disclosure of the invention

Hereinafter, the present invention will be described in detail.

The present inventors have conducted intensive studies to provide a new method of molding PTFE.As a result, when the molded body is stretched in a state in which the crystalline part and the amorphous part are mixed in the PTFE constituting the molded body, the stretching is performed. First, the amorphous portion having a lower elastic modulus than the crystalline portion tends to proceed preferentially, and then the stretching also proceeds in the crystalline portion.Also, the stretching of the crystalline portion of the PTFE constituting the molded body to some extent It has been found that the molded article becomes porous as it proceeds. This is because, when stretching is performed in a state where the crystal part and the amorphous part are mixed, the amorphous part having a small elastic modulus is easily stretched first, and the elasticity of the amorphous part is increased by the stretching. When the elastic modulus of the crystal part reaches the same as the elastic modulus of the crystal part, it is considered that the stretching also starts substantially in the crystal part. It is thought that when it becomes large, porosity occurs. In general, the decrease in the elastic modulus due to temperature rise is greater in the amorphous part than in the crystalline part.Therefore, in a state where the crystalline part and the amorphous part are mixed, the amorphous part has the same elasticity as the crystalline part at the higher temperature. The amount of deformation up to the rate increases. As a result, the amount by which the amorphous portion is stretched before the stretching of the crystalline portion substantially starts increases, and therefore, the stretching ratio of the PTFE until the portion becomes porous is increased. That is, when the stretching is performed at a higher temperature, the amount by which the amorphous portion is stretched before the stretching of the crystal portion substantially starts increases.

Naturally, the higher the proportion of the amorphous part, the greater the amount of deformation due to stretching until it becomes porous, that is, the larger the stretching ratio, and it is possible to stretch at a larger stretching ratio. The higher the ratio, the smaller the amount of deformation due to stretching until it becomes porous, that is, the smaller the draw ratio. In other words, the higher the proportion of the amorphous portion, the easier it is to stretch the PTFE at a higher stretching ratio without being porous, and conversely, the greater the proportion of the crystalline portion, the smaller the stretching ratio until it becomes porous. . In addition, the above-mentioned stretching ratio is an amount of deformation caused by stretching a heated molded body and then cooling it as defined below.

PTFE is known as a resin having high crystallinity. In addition, below the crystal melting onset temperature, the ratio of the crystalline part to the amorphous part does not change. Therefore, when the film is stretched at a temperature lower than the crystal melting onset temperature, the crystal portion starts to be stretched even at a relatively low stretching ratio, and is easily made porous.

Further, when the molded body is stretched by a blow method using a gas in a state in which the crystal part is substantially absent (completely melted state), the molded body is stretched without whitening. However, the molded body before stretching is not always uniform in thickness and strength, and usually has a thinner portion, a lower strength portion, and the like. Wake up. As a result, the uneven thickness of the molded product increases, and depending on the dimension Z of the molded product, the part is brought into contact with the mold first due to local elongation and then further stretched, so that the part that has not been stretched It was also found that the molded body was bent by pushing in, causing a portion to overlap with the molded product, and even more severe, bursting.

In this way, in the completely melted state, local elongation occurs. Therefore, regardless of the draw ratio, the larger the size of the molded product, that is, the larger the diameter or length of the obtained molded product, the greater the uneven thickness And the probability of rupture increases. This is because, even if the stretching ratio is the same, as the size increases, the absolute value of the amount of deformation of the molded body due to stretching increases. When local elongation occurs, only that part has a larger deformation amount than the other parts, and as the size of the molded article increases, the deformation amount of the locally expanded part, that is, the stretching ratio, increases. This is because, in that part, the drawable ratio exceeds the limit.

Based on the above findings, as a result of further studies, when a preformed article, which is a PTFE molded object, is drawn to produce a molded article, a specific elongation at a temperature equal to or higher than the PTFE crystal melting onset temperature At a temperature and in a state where crystals are present in PTFE, the molded article described in the section of the prior art is stretched at a specific stretching ratio. It has been found that an improved molded article can be obtained with regard to the porosity of the molded article and the problems of uneven thickness and rupture of the molded article.

This is because, when a crystal part exists in the PTFE constituting the molded body at the time of stretching, the force for stretching is transmitted to the entire molded body, and the molded body is prevented from being locally stretched. As a result, it is considered that this is based on the fact that elongation occurs uniformly without making the entire molded body porous. In other words, the presence of crystal parts in the molded body during stretching prevents local elongation, and as a result, the molded body is more uniformly stretched as a whole and has good unevenness with small thickness unevenness. A stretch molded product is obtained. In this way, local elongation was prevented, and uniform elongation made it possible to obtain a molded article having a large size.

The larger the size of the molded product, that is, the larger the diameter or length of the obtained molded product, the greater the amount of deformation of the molded body.However, even expansion can be achieved at the set stretching ratio even if the size changes. This is because the entire molded object is stretched. In contrast, in the completely melted state, local elongation occurs, and as the size of the molded product increases, the amount of deformation of the locally expanded portion, that is, the stretching ratio, increases, and as a result, the thickness deviation And eventually burst beyond the limit of the draw ratio. In fact, the complete melting disclosed in Japanese Patent Application Laid-Open Nos. Hei 4-29663-2, Hei 4-3495836, and Hei 5-3-5797, etc. In the method of manufacturing a PTFE heat-shrinkable tube in the state, a molded product having an outer diameter of up to 40 mm is merely described in the examples. However, in the first invention, satisfactory molded products having an outer diameter of, for example, 12 O mm or a length of 30 O mm can be obtained, and although these molded products are large in size, Small unevenness.

In the first aspect of the present invention, a molded article of PTFE (hereinafter referred to as “molded article (I)” in the first aspect of the present invention) is not less than the crystal melting start temperature of PTFE and constitutes the molded article (I). This is a method of manufacturing a PTFE molded article by stretching at a temperature at which crystal parts exist in PTFE, and stretching the molded object (I) by differential pressure, and starting crystal melting while maintaining the differential pressure A production method characterized by cooling to a temperature lower than the temperature.

In particular, in a preferred embodiment, the PTF constituting the molded article (I) according to the stretching ratio It has been found that by appropriately selecting the proportion of the crystal part contained in E, a molded article which is further improved with respect to the above problems can be obtained, and as a result, a non-porous molded article can be obtained. That is, the first aspect of the present invention relates to a method for forming a molded article (I) at a temperature not lower than the melting start temperature of the PTFE constituting the molded article (I), wherein the PTFE has both a crystalline part and an amorphous part. The molding (I) is stretched.

Specifically, at a temperature at which the crystal part of the PTFE constituting the material starts melting, that is, a temperature equal to or higher than the melting start temperature and at a preselected temperature at which both the crystal part and the amorphous part exist. Stretching is performed by applying a pressure difference to the molded body (I) at a stretch ratio selected in advance, and then cooled while maintaining the stretched state to obtain a molded product. The specific gravity (d _b ) of the article is compared with the specific gravity (d _c ) of the molded body (I) (also referred to as “reference body”) that has been subjected to the same thermal history except that stretching is not performed. _b > d. Or d _b = d. By obtaining the temperature (ie, the stretching temperature) and the stretching ratio at the time of, and then performing molding using the stretching temperature and the stretching ratio, it is possible to obtain a molded product that can achieve the above-mentioned objects. The stretching temperature and the stretching ratio are determined by selecting these conditions in advance, performing molding, and then comparing the specific gravities of the obtained molded article and the reference body. It can be easily determined whether or not the stretching ratio and the stretching temperature allow the method of the present invention to be carried out. That is, the stretching temperature and the stretching ratio required for the first method of the present invention can be determined by trial and error. In carrying out the method for producing a molded article of PTFE according to the first aspect of the present invention, the molded object (I) is placed in a mold, and the molded object (I) is pressed against a wall defining the mold cavity. In this case, the molded object (I) is stretched and formed into a desired shape, preferably by pressing with a gas. In this sense, the molded object (I) used in the first method of the present invention is a hollow body having a wall, and the first method of the present invention can be called a stretch molding method. Further, when pressure is applied using a gas as in a preferred embodiment, the method also has a side face of a blow molding method, and thus can be called a professional stretch molding method.

In the first method for producing a molded article of PTFE of the present invention, the specific gravity of the molded article is not reduced, that is, the specific gravity of the molded article is reduced due to the stretching, as compared with the conventional blow molding method. Never. In this sense, the term "non-porous" is used herein. 6

Ten

ing. This means that the molded article (I) receives the same heat history as the molded article (I) in the production method of the first invention (that is, is exposed to the same temperature conditions). a specific gravity (d _c) of), is compared with the first specific gravity of the molded article that is obtained by the production method of the present invention (d _b), the latter specific gravity of Ji substantially the same as the former gravity force , Which means that the specific gravity does not decrease. In this case, the specific gravity of the molded article to be produced can be changed due to the change in crystallinity (that is, the ratio of crystal parts after cooling) depending on the conditions of the cooling process after stretching. The thermal history of the non-stretched molded object (I) includes the thermal history of the process from cooling to removal of the molded product from the mold after molding.

In the method of the first aspect of the present invention, the crystal melting onset temperature of PTFE is determined by measuring using a differential scanning calorimeter [DSC] obtained for PTFE constituting the molded object (I), and the curve obtained by measuring the PTFE sample is as follows. In measurements with increasing temperature, it means the temperature at which the endothermic curve begins to fall away from the baseline, ie, the temperature at which the crystal begins to require heat of fusion to begin melting. Conversely, in the measurement when the temperature of the PT FE sample is lowered, it means the temperature at which the curve obtained by heat radiation descends and reaches the baseline and agrees with it, that is, the temperature at which heat release due to crystallization ends. . The crystal melting onset temperature varies slightly depending on the type of PTFE, but in general, it is within the range of about 270 to 290 ° C when increasing the temperature of the PTFE sample. In the case of measurement, it is within the range of about 260 to 280 ° C.

In the method of the first aspect of the present invention, at the time of stretching, that is, at the temperature at the time of stretching (hereinafter also referred to as “Te”), it is determined whether or not a crystal part exists in the PTFE constituting the molded body (I). The determination is made based on the curve obtained by subjecting the PTFE constituting the molded article (I) to differential scanning calorimetry. It is generally known that when measuring PTFE by DSC, the profiles of the obtained curves do not always match when the PTFE sample is subjected to the temperature rising condition as described above and when the PTFE sample is subjected to the temperature decreasing condition. You.

Therefore, even at the same temperature, the crystals are not always present at both the temperature increase condition and the temperature decrease condition. for that reason, The determination of whether or not a crystal part exists in the PTFE constituting the molded object (I) depends on the temperature process during which the PTFE reaches the stretching temperature during stretching, that is, a low temperature. The method of determination differs depending on whether it is the force to reach the stretching temperature only by heating from the beginning, or whether it is heated to a temperature higher than the stretching temperature and then cooled to reach the stretching temperature. In the former case (for convenience, also referred to as “Case Aj”), the latter case (also called “Case B” for convenience) is based on the curve obtained by applying the temperature rise condition. The presence or absence of a crystal part is determined based on the obtained curve.

Therefore, the presence or absence of a crystal part in the PTFE constituting the molded body (I) at the time of stretching is determined based on the DSC curve measured in accordance with the temperature condition in the molding method. In the measurement at the time of temperature rise, whether or not the crystal part exists is determined by whether or not heat is absorbed at the selected temperature Te (whether or not the measurement point at the temperature Te is located below the baseline). (If an endotherm is observed, the crystal part is still present.) Conversely, in the measurement at the time of temperature drop, whether or not the crystal part exists is determined by whether or not heat is generated at Te (whether or not the measurement point at temperature Te is located above the baseline). (If a fever is observed, the melted crystal part is still present).

In other words, the state in which the crystal part exists at or above the crystal melting onset temperature means that in case A, the curve obtained by the differential scanning calorimeter falls from the baseline due to crystal melting, and a peak occurs. This is a state at any temperature within the temperature range until it completely returns to the baseline.In case B, the curve obtained by the differential scanning calorimeter rises from the baseline due to crystallization, and a peak is generated. After that, the condition at any temperature within the temperature range until it completely returns to the baseline. ·

Note that this state differs between the case where the PTFE is heated and the case where the temperature is lowered as described above, and the case where the PTFE is a fired product and the case where the PTFE is not fired. As a result, the same temperature is obtained. However, if the heat history and the type of PTFE are different, the presence or absence of crystals in the molded body (I) does not always match, and the crystal melting ratio described later may differ depending on the heat history and the type of PTFE. . In the method of the first aspect of the present invention, the stretching can be performed at a large stretching ratio due to the state in which the crystal part is slightly present at the time of stretching. In this case, the dimensions of the obtained molded article (or Irrespective of the dimension) and the draw ratio, it is particularly preferable in that the film is drawn uniformly without substantially reducing the specific gravity described above.

In carrying out the method of the first aspect of the present invention, the molded object (I) may be heated after fixing the molded object (I) in the mold. In such a case, the molded article (I) is preferably restrained in the mold in a stretch-free state during stretching because the molded article may have a defective portion. This is the object (I

) Is thermally expanded and softened, that is, by fixing the molded body (I) by applying tension thereto at a temperature close to the stretch molding temperature. ·

In the first method of the present invention, the molded object (I) is an object to be stretched corresponding to the parison in the blow molding method, and may be formed by any appropriate method. Specific examples include paste extrusion molding, compression molding, ram extrusion molding, cutting, isostatic molding, and wrapping molding. The molded object (I) may be a fired product or an unfired product. The shape of the molded object (I) may be any suitable form if the airtight state for applying a differential pressure can be secured during stretching. Considering the molding efficiency of the molded object (I), etc. In general, it is preferably a tubular (or tubular) hollow material. .

In the present specification, the term “cylindrical” has a longitudinal axis, and a cross section perpendicular to the axial direction has substantially the same shape at any point of the longitudinal axis. Are substantially congruent. Such cross-sectional shapes include what is called an irregular shape (that is, a non-circular cross-sectional shape, such as an ellipse, a polygon, a shape with rounded corners of a polygon, a combination of these shapes, a more complex shape, etc.). ) Or a non-irregular shape, that is, a cross-sectional shape may be circular. The longitudinal axis of the cylinder is, for example, an axis passing through the center of the cylinder, and such an axis passes through the center of the circumscribed circle or the inscribed circle having the above-described vertical cross section. Good. Specifically, the longitudinal axis is its central axis in the case of a cylinder. "The term longitudinal J means the direction along the length (or height) of the cylinder, where the longitudinal dimension (or dimension) is longer than the dimension along the other direction. Does not mean Thus, for example, in the case of a cylindrical shape, the length (or height) of the cylinder may be smaller than the diameter of the circular cross section of the cylinder.

The cylindrical form of the molded article (I) is selected according to the form of the molded article, but is preferably cylindrical because of high versatility. Accordingly, paste extrusion molding is particularly preferable among the above-mentioned molding methods in that a tube-shaped molded product can be efficiently obtained. The molded object (I) may have a bottomed form, for example, a cylindrical shape with a bottom, in which case the force of obtaining such a molded object (I) by compression molding, isostatic molding, or cutting s. it can.

The PTFE used for molding such a molded article (I) is either a suspension (molding powder) obtained by suspension polymerization or an emulsification (fine powder) obtained by emulsion polymerization. However, it is more preferable to use a material (fine powder) obtained by emulsion polymerization because the film has better stretchability. In the first method of the present invention, either homopolymer or modified PTFE can be used as PTFE. Modifiers used for denaturation include hexafluoropropene, chlorotrinoleoethylene, ヽ⁰ —fluoro (anoreki / levininoleatenore) ロ perfluoro (anolecoxy alkynole vinyl ether), trifluoroethylene And polyfluoroanolealkyl ethylene.

In one preferred embodiment of the first present invention, at the time of stretching, that is, at the temperature Te at the time of stretching, PTFE constituting the molded article (I) contains a crystal part. Therefore, the PTFE constituting the molded object (I) has a certain percentage of crystals in the crystal parts originally contained (ie, the crystals contained in the PTFE at the time of producing the molded object (I)). Thawing. As used herein, the “crystal melting ratio j” (hereinafter, also referred to as “crystal melting ratio J”) can be obtained from the curve obtained by the above-mentioned DSC measurement. ) Is the ratio of the area in the temperature range from the melting start temperature to the stretching temperature Te with respect to the area surrounded by the curve.The crystal melting ratio can be obtained, for example, by weighing out a DSC measurement chart. As described above, the DSC curve generally differs between a temperature rise and a temperature drop, in which case the same stretching temperature T is used. However, the ratio of the crystal part differs between Case A and Case B. That is, in the case A, in the process of temperature rise, the crystal melting ratio is the amount of the crystal part already dissolved at the stretching temperature with respect to the total amount of the crystal part existing in the PTFE constituting the molded object (I). In case B, it can be said that in the course of the temperature drop, it is the ratio of the amount of crystal parts that are still molten at the stretching temperature to the total amount of crystal parts crystallized by cooling.

In the first method of the present invention, basically, a crystal part needs to be present at the stretching temperature Te, but the larger the crystal melting ratio, the more preferable. In particular, it is preferable that the higher the draw ratio, the higher the crystal melting ratio. Therefore, the upper limit of the crystal melting ratio can be defined as less than 100%. In other words, as long as precise measurement of the crystal melting onset temperature of PTFE constituting the molded object (I) and precise control of the stretching temperature are possible, the first embodiment of the present invention can be performed. It suffices if the film can be stretched at a temperature lower than the temperature at which the crystal part completely melts. Considering the accuracy of industrially practical temperature measurement and temperature control, stretching is usually performed at a crystal melting ratio of 99.8% or less, preferably 95 to 99.5%, for example, about 99%. It is possible.

As described above, the first aspect of the present invention stretches in a state where crystal parts are present in PTFE at a temperature equal to or higher than the crystal melting start temperature of PTFE constituting the molded object (I), and the specific gravity decreases substantially. Try not to happen. Substantially preventing this specific gravity reduction from occurring can be implemented, for example, by the following specific embodiments:

When the stretching ratio is about 3 times or less (of course, greater than 1 time), the crystal melting ratio is preferably at least 10%, more preferably at least 20%, still more preferably at least 25%, and particularly preferably. Is at least 30%, most preferably at least 50%;

When the stretching ratio is about 5 times or less (for example, about 3 to 5 times), the crystal melting ratio is preferably at least 20%, more preferably at least 25%, further preferably at least 30%, particularly Preferably at least 50%, most preferably at least 70%;

When the draw ratio is about 10 times or less (for example, about 5 to 10 times), the crystal melting ratio is preferably at least 50%, more preferably at least 80%, and most preferably at least 90%. And; When the stretching ratio is about 20 times or less (for example, about 10 to 20 times), the crystal melting ratio is preferably at least 80%, more preferably at least 90%, and most preferably at least 90%. 5% or more.

Specifically, when the stretching ratio is about 5 times, the crystal melting ratio at the stretching temperature Te is 30% or more; L 0% (excluding 100%), particularly 80 to 100%. L 00. / ₀ (伹, excluding 100%). When the stretching ratio is about 10 times, the crystal melting ratio at the stretching temperature Te is 50% to 100% (伹, excluding 100%), particularly 80 to 100%. (However, 100% is not included). When the stretching ratio is about 20 times, the crystal melting ratio at the stretching temperature Te is preferably 80 to 100% (however, 100% is not included).

Basically, it is particularly preferable that the crystal melting ratio is close to 100%, because the higher the crystal melting ratio, the higher the draw ratio. On the other hand, if the crystal melting ratio is 100%, local thickness deviation occurs due to local elongation, and it is not preferable to stretch at a temperature higher than 100%.

In this specification, the stretching ratio is defined as a one-dimensional dimension of a portion of the molded object (I).

It is the ratio of the one-dimensional dimension (length) of the stretched product corresponding to that part to (length). For example, when the object (I) has a cylindrical shape and the stretch-formed product has a cylindrical shape, the stretch ratio is a ratio of the diameter of the cylinder before stretching to the diameter of the cylinder before stretching. The ratio based on the length of the cylinder instead of the diameter is also a draw ratio. The above-mentioned stretch-formed product is a stretched product obtained by stretching a heated molded body and then cooling it.

In general, various portions of the molded article (I) are often stretched at different magnifications to form molded articles. In such a case, the largest magnification is the stretching magnification used in the present specification. When a cylindrical molded object (I) is stretched, the ratio of stretching in the circumferential direction (or diametric direction) is generally the largest, so the corresponding one-dimensional dimension of the molded object (I) and the molded product is The ratio of the length of the circumference is used as the stretching ratio. For example, when the object to be molded (I) is substantially cylindrical and the molded article is also substantially cylindrical and the stretching ratio in the circumferential direction is the largest, the ratio of the length of the circumference (or The ratio of the length of the diameter) is the stretching magnification of the first present invention. The crystal melting onset temperature, the presence or absence of crystals, the crystal melting ratio, and the draw ratio of PTFE described above are concepts that can be easily understood by those skilled in the field of PTFE molding.

In the method of the first aspect of the present invention, the stretching by the differential pressure is a result of a difference in pressure acting on the inside and outside of the molded object (I) in a state where the molded object (I) is arranged in a mold. Then, when the pressure substantially acts from the inside to the outside of the molded object (I) (that is, a differential pressure acts), the molded object (I) is pressed against the inner wall of the mold. Means to extend the PTFE constituting the molded object (I). Thus, the mold has an inner wall that forms a cavity corresponding to the outer shape of the molded article produced by stretching. Stretching by such a differential pressure is substantially the same as a molding method known as a blow molding method.

When a differential pressure acts on the molded object (I), any of the following methods may be used: only pressurization inside the molded object (I), reduced pressure only outside the molded object (I), or a combination thereof. It is not possible to cope with a thick body (I) with only the body. That is, when the wall thickness is large, the differential pressure required to start stretching is larger than 0.098 MPa, which is the upper limit of the differential pressure due to the reduced pressure. Also, in order to use reduced pressure, it is necessary to form a large number of holes required for reduced pressure in part or all of the mold, or to make the material of the mold porous, so that the pressure difference by means of only pressurization is required. Is efficient and preferred.

In the case of pressurization, the pressure is preferably applied using a fluid, particularly a gas. As the gas, any gas can be used as long as it is inert to the molded object (I) and the apparatus. However, from the viewpoint of handling and cost, air, nitrogen, helium, and carbon dioxide are used. Are preferred.

In the first method of the present invention, after stretching, a temperature lower than the crystal melting onset temperature from the stretching temperature while maintaining the differential pressure (for example, a temperature of about 200 to 250 ° C. or lower). Temperature), and then remove the molded product from the mold. In the first method of the present invention, the molded product is taken out after cooling while maintaining the differential pressure, but when the pressure is released at a temperature equal to or higher than the melting start temperature, the molded product shrinks due to residual stress. It is.

The molded product obtained by the production method of the first aspect of the present invention as described above usually has a size of about 2.1 or less. It has the above specific gravity (d _b ), and when heated to a temperature equal to or higher than the crystal melting onset temperature, it has a shrinkage property that tends to return to the original shape of the molded object (I). When heated in such a manner, the thickness of the molded article becomes close to the thickness of the molded object (I) before stretching. The molded article obtained by the method of the prior art (for example, the method described in JP-A-6-520265) is porous and has a specific gravity of about 1.7 (see the comparative example described later). See).

In the first method of the present invention, since the shape is formed not by melt flow but by stretching, it may not be easy to form a relatively fine shape. In particular, when the thickness of the molded object (I) is large, the shape that can be formed may be limited. Therefore, when it is necessary to impart a fine shape to a molded article, it may be preferable to incorporate, in the method of the first invention, fusion of another member to the molded object (I). This fusion may be performed at any time before, during, or after the stretching.However, it is possible to perform fusion with another member by heating during the stretching and a differential pressure acting thereon. Sometimes it is efficient and most preferred. The other members are not particularly limited as long as they provide a desired molded product, and may be, for example, a molded product of PPTFE having a predetermined shape, a cut product, or the like.

Specifically, another member having a predetermined shape is prepared in advance, this is placed in a mold, and this member is fused to the molded object (I) stretched at the time of stretching, and then cooled. Thus, a molded article can be obtained. In another aspect, a molded product having a desired shape can be obtained by cutting or the like the member fused to the molded product as necessary.

By fusing other members in this way, it is possible to reinforce a molded product or to increase the thickness of only a portion necessary for later processing. In the case of fusing at the time of stretching, the fusing includes a member for fusing another member to be fused (fused member) and a member to be molded (I) outside the member to be molded (I); The molded article (I) is stretched by a differential pressure so that the molded article (I) is stretched by a differential pressure so that a part of the stretched molded article (I) is fused to a predetermined portion of the molded article. This is carried out by holding in a state pressed against the fusion member.

In addition to the case where another member is fused so as to constitute a part of the molded article as described above, for example, another cylindrical fusion member is arranged outside the cylindrical body (I), After the molded article (I) and the fusion member come into contact by stretching, the fusion member is removed together with the molded article (I). Also, it is possible to perform overall fusion such that fusion is performed while stretching. In this case, regarding the fixing of the welding member, a method of fixing the upper and lower parts, a method of fixing only the upper part, a method of fixing only the lower part, or both ends to the mold together with the molded object (I). However, it is possible to adopt a method that does not fix it.

When performing fusion, it is preferable to increase the differential pressure during stretching, since the fusion state is improved. In addition, it is preferable to extend the time during which the temperature and pressure during stretching are maintained, or to raise the temperature while maintaining the differential pressure after stretching to bring the PTFE into a completely molten state, because the fusion state is improved, which is preferable. is there. The material of the fusion member may be any material that has heat resistance at the stretching temperature and that can be fused to PPTFE (including one containing a filler), but is preferably a fluorine-based resin from the viewpoint of heat resistance. It is particularly preferable that the fluororesin is a PTFE resin, a PTFE resin, or a FEP resin because of its heat resistance. The PTFE may be the same type of PTFE as that constituting the molded object (I), and in another preferred embodiment, may be a modified PTFE having good fusibility (for example, an alkylbutyl ether-modified PTFE). .

The molded article according to the first aspect of the present invention is based on the assumption that the longitudinal axis of the molded article (I) as described above remains as it is in the molded article obtained by stretching and molding the molded article (I). Can be specified as follows. That is, it is assumed that the molded article manufactured according to the first aspect of the present invention is the direction in the molded article corresponding to the longitudinal axis of the molded object (I) (that is, it remains in the molded article as it is). Cross-section of the molded product in a direction perpendicular to the direction of the longitudinal axis of the molded object (I) (a cross-section in which the thickness of the molded product is neglected, hereinafter simply referred to as “cross-sectional shape of the molded product”) ) Includes when:

(1) In one case, at least one molded product cross-sectional shape is an irregular cross-sectional shape. The cross-sectional shape may be, for example, an ellipse, a polygon, a shape obtained by rounding a corner of a polygon, or the like, and further, at least one other cross-sectional shape may be a circular cross-section. More specifically, a part or all of the molded article is a hollow three-dimensional form other than the cylindrical form, for example, a molded article having a rectangular cylindrical form, and a part of such a molded article has a cylindrical form and A molded product in the form of a truncated cone can be exemplified. In other words, the molded articles included in this case are not simple forms having a cylindrical shape as a whole, but include virtually all molded forms in which various forms are complicated or simply combined. . this Specific examples of such molded articles include containers of various forms (for example, so-called polycontainers), molded articles used for lining of different-diameter pipes or fuel tanks, molded articles used for casings of chemical pumps, and the like. Moldings (ie, pre-molded products), etc., which are used as materials for obtaining various molded products.

(2) In another case, the cross-sectional shape of the molded product is a non-irregular cross-sectional shape, that is, a circular shape. In this case, when the diameters of the circles are the same, the molded article is substantially cylindrical, and the cylindrical form may be substantially straight or bent. Further, when the diameters of the circles are different, for example, the shape is a conical or truncated cone shape, and a shape in which a bulging portion and a shrinking portion exist along the longitudinal axis direction.

In the method for producing a molded article according to the first aspect of the present invention, as described above, the molded object (I) is stretched more uniformly. As a result, unevenness in the thickness of the PTFE defining the molded product, that is, the thickness, is suppressed. As will be specifically shown in the examples described later, the thickness deviation of the cylindrical portion of the molded article having the same diameter and the same cross-sectional shape, therefore, the thickness unevenness is compared with the case of the conventional professional molding. , Greatly improved.

Specifically, the following formula (1) of the molded article of the first present invention:

Deflection degree (%) = (2 (maximum thickness-minimum thickness) / (maximum thickness + minimum thickness)) X100 formula (1)

(Where the maximum thickness is the maximum thickness measured at the relevant cylindrical part, and the minimum thickness is the minimum thickness measured at the relevant cylindrical part. Measure the location and calculate from the maximum and minimum values of the measured values.) Depth of wall thickness expressed as (%) 1S 120% or less, preferably 100% or less, more preferably 50% or less It is. Such improved thickness unevenness is observed not only in the cylindrical part but also in other parts of the molded article.

The method for producing a molded article according to the first aspect of the present invention is useful for forming a molded article having a large deformation amount, and therefore, a molded article having a large size, particularly a cylindrical molded article. The usefulness of the first invention is demonstrated by the fact that the cross-sectional shape of the molded article is circular (strictly, the cross-sectional shape is a narrow ring shape because the molded article is hollow). Those whose length is larger than those of conventional cylindrical products, for example, at least 5 mn! , Preferably at least 10 Omm, more preferably at least 15 Omm .

20

It is.

The resin molded product of the second aspect of the present invention is characterized in that the melting point peak is 250 ° C. or more, the crystallinity is 78% or more, and the haze value is 30% or less. In the present specification, the above-mentioned “second resin molded article of the present invention” is referred to as a resin molded article (1). In this specification, the term "resin molded body" without such a number refers to the resin molding of the second to seventh aspects of the present invention, which is not limited to the resin molded body represented by such a number. Mean body.

The resin molded article (1) is obtained by molding a resin. The resin is not particularly limited as long as a molded article having a crystallinity, a haze value, and a melting point peak within the above-described ranges can be obtained, but is preferably a fluororesin. . Molded articles made of fluorine-containing resin are heat-resistant, have a relatively high crystallinity, and have non-adhesive properties, electrical insulation properties, chemical resistance, weather resistance, water and oil repellency, etc. It has a wide range of applications because of its excellent properties.

The fluororesin used for the resin molded product (1) is not particularly limited as long as the obtained molded product can exhibit a crystallinity, a haze value and a melting point peak within the above ranges. In particular, a resin made of a polymer obtained from a monomer component containing tetrafluoroethylene [TFE] is preferable in that it has a relatively high molecular weight and is often excellent in the above-mentioned properties. In the present specification, a polymer obtained from such a monomer component containing TFE may be referred to as a “tetrafluoroethylene-based polymer [TFE-based polymer]”. .

The TFE polymer is not particularly limited, and examples thereof include tetrafluoroethylene homopolymer [PTFE homopolymer], modified polytetrafluoroethylene [modified PTFE], tetrafluoroethylene / perfluoro (alkyl vinyl ether). Ter) copolymer [PFA], tetrafluoroethylene / hexafluoropropylene copolymer [FEP], and the like. Among them, PTFE homopolymer and modified PTFE are more preferable in terms of good crystallinity and melting point peak characteristics.

Conventional molded articles made of PTFE homopolymer or modified PTFE have not sufficiently high crystallinity and have problems in properties such as barrier properties caused by the crystallinity. However, the above resin molded article (1) Has a high degree of crystallinity, even if it is made of fluororesin. Since it also has transparency, its use can be expanded.

The fluororesin used for the resin molded article (1) may be a polymer (a) containing a modifying agent. In the present specification, the “polymer (a) containing a modifier (hereinafter, referred to as“ polymer (a) ”)” means a polymer obtained from a monomer component and a modifier. The polymer (a) may be one in which a monomer component and a modifier are polymerized to form a polymer chain, or the polymer (a) may be used in a state in which the modifier is not polymerized. May be contained, or a mixture thereof.

When at least one of the monomer components is TFE, the polymer (a) is one of the above-mentioned TFE-based polymers. As such a polymer (a), for example, the above-mentioned modified PTFE And the like.

In the present specification, the “modified PTFE” means a polymer obtained from TFE and a modifying agent. The modified PTFE is different from the PTFE homopolymer in that the PTFE homopolymer is a TFE homopolymer obtained by polymerizing TFE alone and does not contain a modifier.

The modifier for the modified PTFE is not particularly limited as long as it can be copolymerized with TFE. Examples of the modifier include perfluorophenol such as hexafluoropropene [HFP]; chlorotrifluoroethylene [CTFE ]; Hydrofluoroolefins such as trifluoroethylene; perfluorobier ether and the like. The perfluorovinyl ether is not particularly limited, and may be, for example, the following general formula (I)

CF ₂ = CF—OR f (I)

(In the formula, R f represents a perfluoro group.) And the like. In the present specification, the perfluoro opening means that all hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms. The perfluoro group may have an ether oxygen.

Examples of the above perfluorovinyl ether include, for example, perfluoro (alkyl vinyl ether) [PAVE in which R f represents a perfluoroalkyl group having 1 to 10 carbon atoms in the above general formula (.1). ]. Perfolo above The alkyl group preferably has 1 to 5 carbon atoms.

Examples of the perfluoroalkyl group in the above PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoropropyl group, a perfluoropentyl group, and a perfluorohexyl group. However, a monofluoropropyl group is preferred.

Examples of the perfluorovinyl ether include a perfluoro (alkoxyalkyl) group having 4 to 9 carbon atoms in the general formula (I);

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

CF 3

CF ₃ CF ₂ CF ₂ — (-0—CF-CF ₂ †-(wherein, n represents an integer of 1 to 4). Butyl ether) or perfluoro (alkylpolyoxyalkylene biel ether).

As the modifying agent for the modified PTFE, perfluorovinyl ether and chlorotrifluoroethylene are preferred from the viewpoint that the resulting resin molded article (1) has good crystallinity, and perfluorovinyl ether is preferred. PAVE is preferred.

The ratio (% by weight) of the modified PTFE to the total amount of the modified agent and TFE in the modified PTFE depends on the type of the modified agent, but is not large enough to give the obtained modified PTFE melt flowability. Preferably, the amount is small. For example, when using the par full O b vinyl ether as the modifying agent, usually 1 weight ^_0/0 or less good Preferred, from 0.001 to 1 weight ^_0/0 is more preferable.

As the fluorinated resin used in the resin molded article (1), one or more kinds can be used.For example, one or more kinds of the TFE polymers can be used. One or more of the polymers (a) can be used. For example, as the modified PTFE, those having different average molecular weights, copolymer compositions, etc.

One or two or more kinds may be used. As the PTFE homopolymer, for example, one or more kinds having different average molecular weights may be used, or a mixture of modified PTFE and PTFE homopolymer may be used.

In the present specification, the above-mentioned “PTFE homopolymer one and modified or modified PTFE” in the second to thirteenth inventions may be referred to as “PTFE”. These "P

“TFE homopolymer” and “modified PTFE” are the same as those in the first present invention.

PTFE can be obtained by conventionally known polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization.However, since PTFE is widely used industrially, it is necessary to use suspension polymerization or emulsion polymerization. Emulsion polymerization is more preferred because moldability, particularly stretchability, when producing the resin molded article (1) is good.

In the present specification, a resin powder composed of PTFE obtained by suspension polymerization may be referred to as PTFE molding powder, and a resin powder composed of PT FE obtained by emulsion polymerization may be referred to as PTFE fine powder. As the resin powder for producing the resin molded article (1), PTFE fine powder is preferable. The resin molded product (1) has a crystallinity of 78% or more. Within the above range, the water vapor permeability, gas permeability and drug permeability of the resin molded article (1) can be reduced. When these permeability can be reduced, the amount of gas molecules such as water vapor and nitrogen in the atmosphere and chemicals such as acid permeate the resin molded article (1), that is, the resin molded article (1) ) Can be suppressed from passing through from one field to the other field. The above two fields are, for example, space, solution, etc. In this specification, the reduction in water vapor permeability, gas permeability and drug permeability may be referred to as “barrier property” or “improvement in barrier property”. In the present specification, the above “drug” means a substance having a chemical action. The above-mentioned drug may be composed of one or more compounds, and may be various drugs, drugs, drug solutions, acids, etc., regardless of whether it is solid, liquid or gas. The lower limit of the crystallinity is preferably 80%, and more preferably 81%. When the crystallinity is within the above range, the upper limit may be 98% from the viewpoint that the barrier property of the resin molded article (1) is not practically impaired, and 95 ° /. It may be.

The crystallinity can be made particularly high when the resin molded product (1) is made of the above-mentioned fluororesin, especially PTFE. Fluorine-containing resins, especially PTFE, have a rigid molecular chain and are easily arranged in an orderly manner, so that crystallization proceeds during the polymerization process, and is usually obtained as a polymer with high crystallinity. However, when molding using this polymer, the conventional molding method involves firing at a temperature equal to or higher than the melting point in order to fuse the particles. Although new crystals were formed, a sufficiently high crystallinity could not be obtained even if the cooling rate was reduced. Since the resin molded article (1) is obtained by a method for producing a resin molded article described later, it can have a high degree of crystallinity.

In the present specification, the “crystallinity” means a value obtained by using an X-ray diffraction method as follows. That is, as shown in the schematic diagram of X-ray diffraction shown in Fig. 5, a chart obtained by scanning the Bragg reflection angle and weighing the diffraction intensity with a gomometer has a peak at 2Θ = 16 °. The area [Ia] of the signal derived from the crystal part and the area [Ic] of the signal derived from the crystal part having a peak at 20 = 18 ° are calculated. The baseline is drawn between 20 = 10 ° and 20 = 20 ° and the boundary between the crystalline and amorphous parts is between 20 = 17 ° and 26 = 19 ° Pull. Using the area obtained in this way, calculate using the following formula (see Fluoroplastics Handbook (1990, Nikkan Kogyo Shimbun, edited by Takaomi Satokawa), pp. 45-46). RAD-RA type (trade name, manufactured by Rigaku Denki Co., Ltd.) is used as an X-ray diffractometer.

C = X 100

I c + KIa (Where C is the crystallinity (%), I c is the area of the crystal part, I a is the area of the amorphous part, and K is 0.66.)

The resin molded article (1) has a haze value of 30% or less. When it is within the above range, the resin molded article (1) can have transparency. With a conventional molded body having a melting point peak in the range described below, a molded product having a high crystallinity as in the above range and having a low haze value in the above range has not been obtained. However, the resin molded article (1) can achieve both high crystallinity and high transparency.

As the haze, a preferable upper limit is 20 ° / ₀ , a more preferable upper limit is 15%, a further preferable upper limit is 10%, and a particularly preferable upper limit is 8%. The haze value may be 0.5% or more, or 1% or more, as long as the haze value is within the above range, in that high transparency is maintained.

The haze value is easily reduced to 30% or less when the resin molded article (1) is made of a fluororesin and the fluororesin is made of a polymer (a) containing a modifier. be able to. As such a polymer (a), a TFE polymer containing a modifying agent is preferable, and modified PTFE is more preferable.

The polymer (a) differs from PTFE homopolymer in that atoms other than side chains and fluorine are bonded to the main chain, resulting in reduced crystallinity, less microcrystals that cause light scattering, and high transparency. Can be provided. As the haze value, when the resin molded article (1) is composed of the polymer (a), a preferable upper limit is 20%, a more preferable upper limit is 15%, and a further preferable upper limit is 10%. If it is within these ranges, it may be 0.5% or more, or 1% or more, in that high transparency is maintained.

In the present specification, the above-mentioned “haze value” means a value measured using a haze meter (manufactured by Toyo Seiki Seisaku-Sho, Ltd., direct-read haze meter) in accordance with JIS K 7136.

The resin molded product (1) has a melting point peak of 250 ° C. or higher. Having a melting point peak within the above range can be used not only for applications used at low and medium temperatures such as room temperature, but also for applications used at high temperatures because of its high heat resistance.

A preferred lower limit of the melting point peak is 260 ° C. With the above melting point peak Then, within the above range, the temperature may be 400 ° C or lower, or 350 ° C or lower, from the viewpoint of having sufficient heat resistance in ordinary use.

In the present specification, the “melting point peak” means a temperature at which a peak is observed in a melting curve measured using a differential scanning calorimeter [DSC].

As long as the resin molded product (1) has a melting point peak, a crystallinity and a haze value within the above-mentioned ranges, various additives such as a molding aid, a leveling agent, a heat stabilizer and the like may be used as required. It may be molded using.

The resin molded article according to the third aspect of the present invention is made of a fluorine-containing resin, wherein the fluorine-containing resin is made of a TFE polymer, and has a crystallinity of 78% or more, The haze value is 30% or less. In this specification, the above-mentioned “third resin molded article of the present invention” is referred to as a resin molded article (2).

Since such a resin molded article (2) is obtained by molding a fluororesin made of a TFE-based polymer, it can be used in a wide range of applications. Those satisfying both the degree of crystallinity and the haze value were not obtained.

The fluororesin, the TFE polymer, the crystallinity, the haze value, and the heat resistance of the resin molded product (2) are as described above for the resin molded product (1).

The resin molded article of the fourth invention is made of PTF E homopolymer and / or modified PTFE, and has a water vapor permeability coefficient of 0.02 (g (m ² ■ day) or less. In the present specification, the above-mentioned “fourth resin molded article of the present invention” is referred to as a resin molded article (3).

When the resin molded body (3) has a water vapor transmission coefficient within the above range, it can substantially block water vapor in the atmosphere under a normal use environment. Therefore, the resin molded body (3) can prevent contact with water vapor by, for example, covering an object that is not preferable to contact with water vapor.

As the water vapor permeability coefficient, the preferred upper limit is 0. 0 15 (g - mm) / (m 2 'day) in a more preferred upper limit is 0. 0 1 (g · mm) / (m 2 · da y). The water vapor permeability coefficient is within the above range, a point capable of retaining water vapor barrier properties in normal applications, even 0. 0 0 0 1 (g · mm) / (m 2 ■ day) or well, further 0. 0 0 1 (g · mm ) / (m 2 · day) or more der connexion may.

In the present specification, the “water vapor permeability coefficient” means a value obtained by measuring according to JISZ208. The unit of the water vapor transmission coefficient represents the amount (g) of water vapor that permeates a thickness l mm of the resin molded body (3) to be measured per day per lm ² of surface area.

The PTFE homopolymer and / or modified PTFE for the resin molded product (3) is as described above for the resin molded product (1).

The fifth resin molded article of the present invention is made of a PTFE homopolymer and / or a modified PTFE, and has a permeation coefficient of 35% by weight of hydrochloric acid at 25 ° C. (hereinafter, referred to as “a permeation coefficient of hydrochloric acid”). There is characterized in that 1. at ^{8 X 1 0- 1 1 (g} · cm) / (cm 2 ■ sec) or less. In the present specification, the “fifth resin molded article of the present invention” is referred to as a resin molded article (4).

When the resin molded product (4) has a hydrochloric acid permeability within the above range, it can substantially block hydrochloric acid under a normal use environment, and can effectively remove various chemicals such as other acids. It can have drug permeability to block. As described above, it is a resin molded product composed of PTFE homopolymer and / or modified PTFE, which has a chemical barrier property that is not limited to a hydrochloric acid barrier property, and is measured using 35% by weight hydrochloric acid at 25 ° C. The resin molded article (4) having a hydrochloric acid permeability coefficient in the above range in the above case. The resin molded body (4) can prevent contact with the above-mentioned chemicals, for example, by covering an object which is not preferably in contact with the chemicals such as hydrochloric acid and other acids.

As the hydrochloric acid permeability coefficient, the preferred upper limit is ^{1. 5 X 1 0- 1 1 (} g. Cm) / (cm 2 ' s), and more preferable upper limit is ^{1. 0 X 1 0- 1 1 (} g. Cm) / (cm ² · sec), still more preferred upper limit 9. is 0 X 1 0- ^12. The hydrochloric acid permeability coefficient may be at least 1 × ^10-15 (g-cm) / (cm ² ■), as long as it has a practically sufficient hydrochloric acid barrier property, as long as it is within the above range. ^{X 1 0- 14 (g · cm} ) / ( cm ² · second).

The 35% by weight hydrochloric acid is a 35% by weight aqueous hydrogen chloride solution.

In the present specification, the “hydrochloric acid permeability coefficient” means a value obtained by the following method for determining a chemical solution permeability coefficient. That is, using the measuring device shown in the schematic cross-sectional view of FIG. Pinch it. One glass container 62a is charged with hydrochloric acid having a concentration of 35% by weight, and the other glass container 62b is charged with 20 Om1 each, and placed in a thermostat at 25 ° C. The liquid contact surface of the measurement sample 61 is 70 mmmm. In this state, the sample was sampled from the sampling port 64 of the glass container 62b containing pure water, and the chlorine ion concentration in the pure water was measured using a liquid chromatograph (trade name: IC700-E, Yokogawa). (Made by Denki Co., Ltd.). The amount permeating the measurement sample 61 is calculated from the obtained hydrochloric acid ion concentration, and the obtained calculated value is plotted with respect to time. The same measurement is performed until the plotted values are aligned on a straight line, and the daily transmission amount per unit thickness is calculated from the slope of the straight line.

The PTFE homopolymer and Z or modified PTFE are as described above for the resin molded article (1), and are excellent in chemical resistance. It is considered that the chemical barrier property of the resin molded article (1) is physically caused by the high crystallinity obtained by the method for producing a resin molded article described later and the dense crystal structure composed of a multilayer structure described later. . The chemical barrier property of the resin molded article (1) is further characterized in that the chemical resistance of the PTFE homopolymer and / or the modified PTFE can prevent the resin molded article (1) from being deteriorated or deteriorated by the chemical. Which is chemically contributed.

The sixth resin molded product of the present invention is made of PTFE homopolymer and / or modified PTFE, and has a nitrogen permeability coefficient of 0.2 MPa at 25 ° C (hereinafter referred to as “nitrogen permeability coefficient”) of 6. ^{^{. 8 X 10- 8 (cm 3}} · cm) / - is characterized in that it is (cm ² sec ■ MP a) below. In this specification, the “resin molded article of the sixth aspect of the present invention” is referred to as a resin molded article (5).

When the resin molded article (5) has a nitrogen permeability coefficient within the above range, it can substantially block nitrogen molecules under a normal use environment, and usually effectively blocks other gas molecules. It can have a gas barrier property for blocking. Thus, the PTF EResin molded body made of homopolymer and / or modified PTF II.It has gas barrier properties that are not limited to nitrogen barrier properties and is measured using 0.2 MPa nitrogen at 25 ° C. The resin molded article having the nitrogen permeability coefficient in the above range is the resin molded article (5). The resin molded body (5) can prevent contact with gas by, for example, covering an object that is not preferable to contact with gas.

As the nitrogen permeability coefficient, the preferred upper limit is ^{^{6. 4 X 10- 8 (cm 3}} ■ cm) / (cm 2 · sec · MP a), a more preferred upper limit ^{^{6. OX 10- 8 (cm 3 ·}} cm) ^{/ (cm 2 - sec · MP} a), a still more preferred upper limit is 5. is ^{^{0 X 10- 8 (cm 3 ·}} cm) / (cm 2 · sec ■ MP a). In ^{- (sec · MP a cm 2} ) or more above the nitrogen permeability coefficient, is within the above range, from the viewpoint of having a practically sufficient nitrogen barrier ^{properties, 1. 0 X 10- 9 (cm} 3 'cm) / there may be a further ^{^{1. 0 X 10- 8 (cm 3}} - cm) / may be ^{(cm 2 - - sec MP a} ) above. In the present specification, the above “nitrogen permeability coefficient” means a value obtained by the following method of obtaining a gas permeability coefficient. That is, a measurement gas is introduced into one of two sealed spaces partitioned by using a measurement sample such as the resin molded body (5) as a boundary film, and is pressurized to a pressure exceeding atmospheric pressure. A differential pressure is established by keeping air at atmospheric pressure, and the amount of gas that has permeated to the atmospheric pressure side is measured and converted to the amount permeated per 1 cm thickness of the measurement sample. In this specification, using a pressurized gas permeation analyzer (trade name: Ga spe rm-100, manufactured by JASCO Corporation), the amount of gas measured using nitrogen as the measurement gas and a differential pressure of 0.2 MPa use.

The PTFE homopolymer and / or modified PTFE for the resin molded article (5) is as described above for the resin molded article (1).

The resin molded product according to the seventh aspect of the present invention comprises a PTFE homopolymer and / or a modified PTFE, has a specific gravity of 2.1 or more, and has an arithmetic average roughness (Ra) of 0.03 μπι or less. It is characterized by having. In the present specification, the “seventh resin molded article of the present invention” is referred to as a resin molded article (6).

When the specific gravity is within the above range, the resin molded article (6) is generally non-porous and has a high degree of crystallinity, so that good barrier properties can be obtained.

As the above specific gravity, a preferred lower limit is 2.14, and a more preferred lower limit is 2. One is five. If the specific gravity is within the above range, it may be less than 2.3, or may be 2.25 or less, from the viewpoint of having practically sufficient high crystallinity and barrier properties. The specific gravity of PTFE is considered to be proportional to the crystallinity when the molecular weight is constant and the obtained molded body has no voids.When the crystallinity is 100%, the specific gravity obtained from the unit cell is 2.3. It is assumed that

In the present specification, the above “specific gravity” means a value obtained using an automatic hydrometer (trade name: automatic hydrometer D-1, manufactured by Toyo Seiki Seisaku-sho, Ltd.).

The resin molded body (6) has an arithmetic average roughness [R a] within the above range, and thus has excellent surface smoothness. Such surface smoothness cannot be obtained by surface treatment such as cutting after molding. The surface smoothness of the resin molded product (6) is particularly excellent when stretched in the method for producing a resin molded product described below. In this case, the stretching makes the unevenness on the surface of the resin molded product (6) averaged. It is thought to be due to

A preferable upper limit of the arithmetic average roughness is 0.0. If the arithmetic average roughness is within the above range, it may be 0.0001 m or more, and even 0.001 / zm or more, from the viewpoint of having practically sufficient surface smoothness. Good. A more preferred upper limit is 0.015 μπι. In the present specification, the “arithmetic mean roughness” is obtained by measuring using a surface roughness measuring instrument (trade name: Surface roughness measuring instrument SV-624, manufactured by Mitutoyo Corporation) in accordance with JISB0601. Mean value.

The PTFE homopolymer and / or the modified PTFE are the same as those described above for the resin molded article (1), and the specific gravity is proportional to the crystallinity as described above. As described above, these PTFEs undergo crystallization during the polymerization process, and generally have a high molecular weight, so that a polymer having a high specific gravity can be obtained by polymerization.In the conventional molding method, the crystals are once melted by firing. Since a high degree of crystallinity cannot be obtained when newly crystallizing during cooling, the specific gravity is reduced. Since the resin molded article (6) has a high degree of crystallinity by the method for producing a resin molded article described later, it can have a high specific gravity within the above range.

The resin molded article of the present invention is preferably in the form of a film. Film-like The resin molded article may have any shape as long as it is a thin film. As the thickness of the film-shaped resin molded body, a preferable upper limit is 5 mm, a more preferable upper limit is 3 mm, a more preferable upper limit is 1 mm, a preferable lower limit is 0.001 mm, and a more preferable lower limit. Is 0.01 mm. The film-shaped resin molded product may be a tube-shaped product described below, which is cut out and spread into a sheet shape. When the resin molded article of the present invention is in the form of a film, it is preferable that the resin molded article be shaped by stretching in the method for producing a resin molded article described below.

The resin molded product of the present invention is preferably in the form of a tube, and the outer peripheral length of the cross-sectional shape of the molded product is preferably 15 Omm or more. The resin molded article of the present invention can easily obtain a high degree of crystallinity and transparency within the above-mentioned range even with such a large-diameter tube. The outer peripheral length may be practically 15 m or less, preferably 1 Om or less, in order to avoid inconveniences such as temperature unevenness when using an existing molding apparatus within the above range. And more preferably 5 m or less. The resin molded article of the present invention having such a shape and size is preferably obtained by shaping by stretching in a method for producing a resin molded article described later.

The above-mentioned tubular shape is also called a tubular shape, and is hollow. In the present specification, the “cylindrical shape” refers to a shape having a longitudinal axis, and a cross section perpendicular to the longitudinal axis direction being substantially the same figure at any point of the longitudinal axis. means. The longitudinal axis is an axis passing through the center of the cylinder. In the present specification, the above-mentioned cross section in the resin molded article of the present invention is referred to as “molded product cross-sectional shape”. Note that these “cylindrical shape”, “longitudinal axis”, “cross-sectional shape of molded product”, and “outer peripheral length of cross-sectional shape of molded product” are concepts similar to those in the first present invention.

The cross-sectional shape of the above-mentioned molded product is generally preferably a circle because the versatility of the molded article (II) described later and the extension described later, particularly the stretching by the blow method, can be easily performed uniformly. When the cross-sectional shape of the molded product is circular, the resin molded product of the present invention is a cylinder.

The outer peripheral length of the cross-sectional shape of the molded product is preferably 150 mm or more as described above, and the resin molded product of the present invention having a relatively large size is manufactured as described below. Forming by stretching in the method, especially by the blow method Thus, it is preferable to stretch the film in a state where an amorphous portion and a trace amount of unmelted crystal portion are mixed in the resin as described later.

The resin molded product (1), the resin molded product (2), the resin molded product (3), the resin molded product (4), the resin molded product (5) and the resin molded product (6) of the present invention are described above. It is made of resin. The method for producing these resin molded articles is that the molded article (II) made of this resin is shaped by stretching at a temperature equal to or higher than the crystal melting start temperature of the resin, and then cooled and solidified. It is a method consisting of As the method, for example, when the resin is PTFE, the same method as the method used for the above-mentioned molded article (I) can be used.

In the present specification, the “molded object (11)” means a molded object on which the shaping is performed. The method for obtaining the molded object (II) is not particularly limited, and for example, a conventionally known method can be used. When the molded object (II) is made of PTFE, the same method as that for obtaining the molded object (I) described above can be used, and the one obtained by paste extrusion molding is preferable. It may be fired or unfired.

The shape of the molded article (II) is not particularly limited, but when the shaping is performed by a blow method described later, a tubular hollow material is preferred from the viewpoint of good stretching efficiency. The tube shape is the same as the tube shape described above for the resin molded article of the present invention. The shape of the cross section is preferably circular because of its versatility.

As a method of the shaping, a method of stretching the molded object (II) is preferable because a molded article having both high crystallinity and high transparency is easily obtained.

The cooling and solidification can be performed by cooling to a temperature lower than the crystal melting start temperature.

The shaping is performed at a temperature equal to or higher than the crystal melting start temperature of the resin. When the temperature is within this range, it is possible to prevent porosity and obtain a resin molded body having a high degree of crystallinity. For example, when a molded body (II) composed of a resin in which a crystal part and an amorphous part are mixed is stretched, it is considered that the molded body becomes porous when the crystal part is stretched. If there is, the crystal part melts and changes into an amorphous part, so the existence ratio of the crystal part is reduced. It is possible to increase the abundance ratio of the amorphous part. Before the crystal part starts to be stretched, it is preferentially stretched in the amorphous part having a low modulus of elasticity, and the whole body (II) is formed without making it porous. It is considered that the amount of deformation caused by the stretching can be increased. Also, the higher the temperature, the greater the amount of deformation due to stretching of the amorphous part due to softening.

If the shaping is performed at a temperature lower than the crystal melting onset temperature of the resin, the abundance of crystal parts cannot be reduced, and before the deformation of the molded body (II) due to stretching as a whole increases. The elongation of the crystal part starts, causing porosity. For example, when the temperature is lower than the crystal melting start temperature of PTFE, since the crystal part has a high elastic modulus and is hard, it is difficult to change the arrangement of the particles by stretching, so that the distance between the particles increases, and the distance increases. As a result, the entangled portion between the particles is drawn out into a fibrous form, and the whole becomes a porous body having fine pores. This porous body increases the irregular reflection of light between the air layer and the resin, which is increased by the porosity, so that the porous body becomes cloudy and has low transparency, and the fine pores are formed, so that the barrier property is deteriorated. Such a porous body is conventionally known as a porous PTFE membrane.

The shaping may be performed in a completely melted state in which the crystals in the molded body (II) are completely melted, but may be locally formed due to uneven thickness and strength of the molded body (II). In the case where the elongation is caused by stretching, it is preferable that the unmelted crystal part is left in a small amount. By leaving the unmelted crystal part, the force for stretching is transmitted to the whole molded object (II), so that local stretching can be prevented.

Therefore, the above-described local elongation is likely to occur when, for example, a blow method described later is used, but an unmelted crystal part exists in the molded body (II) as the upper limit of the stretching temperature at which the stretching is performed. By selecting the temperature, local stretching can be prevented and a uniform molded article can be obtained. ·

The crystal melting onset temperature can be easily determined by measuring the molded body (II) using a differential scanning calorimeter (DSC). The crystal melting onset temperature differs depending on whether the DSC measurement is performed while increasing or decreasing the temperature of the molded body (II). The crystal melting onset temperature is such that when the temperature of the molded body (II) is increased, the curve obtained by endotherm begins to fall away from the baseline. This is the temperature at which the crystal begins to require heat of fusion to begin melting. When the temperature of the molded body (II) is lowered, the curve obtained by heat radiation falls and reaches the base line, where the temperature matches. That is, it is the temperature at which the heat release by crystallization ends. The crystal melting onset temperature differs depending on the type of resin.

Whether or not there is an unmelted crystal part in the green body (II) can be easily determined by the same method as the method for obtaining the crystal melting ratio by DSC used for the green body (I). it can.

As the stretching method, either uniaxial stretching or biaxial stretching is possible.However, in uniaxial stretching, the size decreases in a direction perpendicular to the stretching direction. Preferably, uniaxial stretching is performed in which a constraint is applied so as not to shrink in a direction perpendicular to the direction. Such uniaxial stretching is conveniently referred to as "semini-axial stretching". As the stretching method, biaxial stretching is also preferably used.

The stretching method in the stretching is not particularly limited, and examples thereof include a mechanical method using a roll stretching machine, a tenter and the like, and a professional method using compressed air and the like. The stretching method may be a mechanical method or a blow method. However, since the stretching temperature is high, when a tenter is used, the machine is seized and the molded body (II) is cut off from the chuck portion due to softening. In some cases, stretching unevenness may occur because the entire body is not gripped. In the case of a roll type using a roll stretching machine or the like, only a uniaxially stretched product can be obtained. Therefore, a blow method that does not cause these inconveniences is preferable.

The resin molded article of the present invention obtained by the method for producing a resin molded article has excellent crystallinity, transparency, and barrier properties as described above. Although the mechanism by which the resin molded article of the present invention exhibits such advantageous effects is not clear, it is considered as follows. That is, when, for example, stretching is performed in the method for producing a resin molded article, the molded article (II) has a certain thickness by laminating a plurality of resin particles before stretching. However, this thickness decreases in the stretching direction. Stretching is started in the amorphous part having a low elastic modulus prior to the crystal part having a high modulus, and the individual particles stacked in the amorphous part are slid in the stretching direction sequentially as the part is stretched to be flat. While filling the poid, it is oriented and densely packed. In this slide, each of the individual particles is larger than the particle size before stretching. 5316

35

For example, the particles move not at the size of the secondary particles having a particle diameter of about 500 / xm but at the size of the primary particles having a particle diameter of about 230 nm. Furthermore, the molecular chains are extracted from the primary particles (fibrillation), so that movement at the molecular chain level is also performed, so that the particles become denser. In this densified state, the distance between the molecular chains is close and a crystalline state is formed. Since the resin is cooled and solidified while maintaining this crystalline state, the resin molded article of the present invention is considered to have a high degree of crystallinity. In particular, in the case of PTFE, the melt viscosity is high, and the stress relaxation time is extremely long. Therefore, during cooling and solidification, the crystal state is well preserved, and the crystallinity can be extremely increased.

In the state densified by the stretching, a band-shaped band structure having a width is formed in the stretching direction and in a direction parallel to the stretching direction, and the band structure forms a layer. Since this layer has directionality, transmitted light is hardly scattered, and the resin molded article of the present invention can have high transparency despite its high crystallinity. The layer having the above band structure can be confirmed by observing a cross section of the obtained resin molded product by a TEM (transmission electron microscope) photograph of a replica.

Since the resin molded article of the present invention has a highly crystallized multilayer structure as described above, band structures in which molecular chains are densely oriented are stacked in layers to exhibit high barrier properties.

The resin molded article of the present invention can also obtain surface smoothness that cannot be obtained by surface processing such as cutting after molding by the above stretching.

Therefore, the resin molded article of the present invention can be used, for example, as a material for blocking water vapor, gas, and / or chemicals from those that are not desired to be in contact with them. Such materials may be used, for example, to cover water vapor, gases and / or drugs, to prevent them from seeping out, and to avoid contact with water vapor, gases, and / or drugs. It may be used to cover objects and prevent contact with water vapor, gas and / or chemicals even in an environment where they may be present. The resin molded article of the present invention is also excellent in transparency and surface smoothness, so that it can be used for applications utilizing these properties, for example, applications requiring visibility, washability, and the like. The resin molded article of the present invention can further add a function based on the inherent properties of the resin, depending on the type of resin used. Properties such as TFE's inherent chemical resistance, non-adhesion, release properties, electrical insulation, high-frequency characteristics, and low friction coefficient can be added. Thus, the use of the resin molded article of the present invention can be expanded in many fields.

Examples of the application of the resin molded article of the present invention include those utilizing the barrier properties, such as containers for pharmaceuticals, foods, and other packaging materials; lining applications for containers and pipes; and low-permeability tubes and hoses. In addition to these materials, the protective film of an electroluminescent element or a solar cell; a bag for a drug; a container for collecting, storing, and transporting a gas, a chemical solution, and the like, as well as those that utilize transparency as well as a barrier property. A belt for a fixing unit or a photosensitive unit in an image forming unit of an electrophotographic apparatus may be used as a device utilizing the surface smoothness. The resin molded article of the present invention can be obtained in a large size as described above, and is suitable for a belt of an image forming section and the like.

An eighth aspect of the present invention is directed to a packaging material for blocking moisture in the air, comprising the above-mentioned resin molded article, which is used for covering an object to be wrapped.

Since the above-mentioned packaging material for blocking moisture in the atmosphere is made of the above-mentioned resin molded product, it has excellent barrier properties and effectively blocks moisture in the atmosphere such as water vapor, and has transparency. The package can be visually recognized, is not easily damaged, and can be shielded from various gases and / or chemicals.

In the present specification, the above-mentioned "packaged object" means an object covered with the packaging material for blocking moisture in the air of the present invention. The package is not particularly limited, and for example, a drug, a food, an electroluminescent device, a solar cell, and the like are suitable, and a drug and an electroluminescent device are preferable.

As the packaging material for blocking moisture in the air, a material in which the resin molded body is made of the above-described fluorine-containing resin is preferable from the viewpoint of excellent barrier property against the moisture in the atmosphere. In this case, since the fluorine-containing resin of the packaging material for blocking moisture in the air of the present invention has chemical resistance to a wide variety of chemicals, the material to be packaged is made of various chemicals, reactive gas such as acidic gas, or the like. They are also suitably used, and their applications can be expanded. As the above-mentioned fluorine-containing resin, PTFE is preferable.

The shape of the packaging material for blocking moisture in the atmosphere is not particularly limited. However, a material that can completely cover the packaged object is preferable in order to enhance the barrier property against the moisture in the atmosphere. For example, it may be in the form of a film or a tube as described above.

The packaging material for blocking moisture in the atmosphere may be used so as to have a gap between the packaging material and the packaging material, or may be used in close contact with the packaging product. When the packaging material for blocking moisture in the air is used in close contact with the package, the packaging material is coated with an adhesive or the like, and the packaging material for blocking the moisture in the atmosphere is bonded to the package. The packaging material for blocking moisture in the air may be directly adhered to the packaged object without using such an adhesive or the like.

A ninth aspect of the present invention is directed to a medicine blocking packaging material comprising the above resin molded body.

The above-mentioned medicine blocking packaging material is suitably used for blocking various medicines and those which are not desired to come into contact with the medicines. For example, they cover various medicines and prevent the medicines from seeping out. It may be used to prevent or prevent undesired contact with various drugs, and to prevent contact with various drugs even in an environment where various drugs can exist outside. You may. The packaging material for blocking medicines may be used in combination with other materials such as glass having a barrier property against medicines, and may be used, for example, as a lid of a glass container, a partition film inside a glass container, or the like.

Since the above-mentioned medicine blocking packaging material is made of the above-mentioned resin molded article, it has excellent barrier properties, so that it effectively blocks various kinds of medicines, and also has excellent transparency. It is also possible to see what is covered, hard to break, and to block water vapor and / or various gases. The packaging material for blocking medicines can also be used for acids such as hydrochloric acid.

As the above-mentioned packaging material for blocking medicine, it is preferable that the above-mentioned resin molded body is made of the above-mentioned fluororesin from the viewpoint of excellent barrier properties against medicine. In this case, since the fluorine-containing resin has chemical resistance to a wide variety of chemicals, the use of the above-mentioned chemical-blocking packaging material can be expanded as a blocking material for various types of chemicals. As the above-mentioned fluorine-containing resin, PTFE is preferable from the viewpoint of excellent barrier properties and chemical resistance. According to a tenth aspect of the present invention, there is provided a gas shielding packaging material comprising the above resin molded body.

In the above gas shielding packaging material, contact between various gases and this gas is undesirable. Like the above-mentioned medicine-blocking packaging material of the present invention, for example, as a material covering various gases, a material covering undesired contact with various gases, etc. It may be used, or may be used in combination with other materials such as glass and metal having a barrier property against gas. The gas shielding packaging material is preferably used for nitrogen and oxygen from the viewpoint of excellent barrier properties.

Since the gas blocking packaging material is made of the resin molded body and has excellent barrier properties, it effectively blocks various gases, and is separated from the various gases and this gas by the gas blocking packaging material. Even if there is a difference in pressure, such as air pressure, with the one that has been provided, it has excellent blocking properties. Since the gas-blocking packaging material of the present invention is further excellent in transparency, it is possible to see what is covered with the above-mentioned gas-blocking packaging material, it is difficult to break, and furthermore, it is difficult to break down with water vapor and / or various chemicals. Is also possible. As the gas shielding packaging material, the one in which the resin molded body is made of the above-described fluorine-containing resin is preferable from the viewpoint of excellent gas barrier properties. In this case, the gas blocking packaging material of the present invention is not limited to an inert gas such as nitrogen because the fluorine-containing resin has chemical resistance to a wide variety of chemicals. The application can be expanded to a barrier material for. As the above-mentioned fluororesin, PTFE is preferred from the viewpoint of excellent barrier properties and chemical resistance.

A package according to a thirteenth aspect of the present invention is an article to be packaged, and a package comprising the resin molded article, wherein the resin molded article covers the article to be packaged, and It is characterized by suppressing contact with atmospheric moisture, chemicals and Z or gas.

In the present specification, the phrase “suppresses contact with atmospheric moisture, a drug, and a gas or a gas” means having the above-described barrier properties. The package may be any as long as it suppresses any of contact between the package and the atmospheric moisture, contact between the package and the drug, or contact between the package and the gas. The packaged article may suppress the contact between the packaged article and the atmospheric water and the drug, the atmospheric moisture and the gas, or the gas and the drug, and the packaged article and the atmospheric moisture, the drug and the gas may be suppressed. The contact may be suppressed. The medicine or gas whose contact is suppressed in the package of the present invention is one or more kinds of medicines, or one or more kinds of gases. May be.

The resin molded article in the package is not particularly limited as long as the resin molded article of the present invention is as described above, but is preferably made of a fluorine-containing resin, and more preferably made of PTFE from the viewpoint of excellent barrier properties. preferable.

The package is not particularly limited, but when contact with atmospheric moisture, chemicals, and Z or gas is undesirable, the barrier properties of the package of the present invention can be effectively utilized. Examples of such a package include those similar to those described above for the package in the atmospheric moisture blocking packaging material of the eighth aspect of the present invention, and a drug and an electroluminescent element are preferable. .

In the case where the package body suppresses contact between the packaged object and at least the moisture in the atmosphere, the package includes, for example, the packaged article and the packaging material for blocking atmospheric moisture of the present invention described above. Preferably, the water vapor transmission coefficient at 25 ° C. and a relative humidity of 90% is 0.02 (g (mm) / (m ² -day) or less. The above water vapor transmission coefficient is the same as that described above for the resin molded article (3). In the case where the package body suppresses at least contact between the packaged object and a drug, the packaged body may be composed of, for example, the packaged object and the above-described drug blocking packaging material of the present invention. The permeation coefficient of 35% by weight hydrochloric acid at 25 ° C. is preferably 1.8 × ^{10 11} (g ¹ cm) / (cm ² · second) or less. The permeation coefficient of the hydrochloric acid is the same as that described above for the resin molded product (4).

In the case where the package body suppresses contact between the package object and at least the gas, for example, the package body may include the package object and the above-described gas blocking packaging material of the present invention. It is preferable that the permeability coefficient of nitrogen at 0.2 MPa at 25 ° C. is 6.8 × 10 ¹⁸ (cm ³ · cm) no (cm ² -sec secMPa) or less. The nitrogen transmission coefficient is the same as that described above for the resin molded body (5).

The eleventh belt material of the present invention is made of the above resin molded body, and is characterized in that it is used for a photosensitive portion for forming an image in an electrophotographic apparatus.

In the present specification, the “electrophotographic device” is used for image formation. Means equipment. The electrophotographic device is not particularly limited, and examples thereof include a printer, a facsimile, a copier, and a photographic printing device.

The image formation is to form an image by fixing toner, ink and the like to a transfer material such as paper. The electrophotographic device has a photosensitive unit and a fixing unit for forming the image.

The photosensitive unit is a device for placing charged toner particles and ink on a transfer material on a photoconductor drum by light irradiation. In addition to the photoconductor drum, various rolls such as a developing roll and a transfer roller are provided. including. It is desirable that these drums and rolls have surface smoothness and non-adhesiveness.

Another belt material of the twelfth aspect of the present invention comprises the above-mentioned resin molded article, and is used for a fixing section for forming an image in an electrophotographic apparatus. .

The electrophotographic device and the image formation are the same as described above. The fixing unit is a device for fixing the toner, ink, and the like placed on the transfer material by the above-described photosensitive unit to the transfer material. Usually, the fixing unit includes a fixing roll and a pressure roll that sandwich the transfer material. In other words, a belt may be used instead of a roll. It is desirable that these rolls and belts have surface smoothness and non-adhesiveness.

Since the belt material used for the photosensitive portion or the fixing portion of the present invention is made of the resin molded body, the belt material is excellent in surface smoothness and non-adhesiveness, and can be obtained as a large size. It can be suitably used for the photosensitive section and the fixing section, particularly for the surface layer section of the drums, rolls and belts. The belt material of the present invention is preferably made of PTFE, since it is further excellent in non-adhesiveness and heat resistance. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Example 1

Polytetrafluoroethylene fine powder (F302, manufactured by Daikin Industries, Perfluoroalkyl and butyl ether-modified PTFE, Crystal melting onset temperature after firing about 270 ° C, 100% crystal melting temperature after firing about 335 ° C) 100 parts by weight of Isopar E (manufactured by Exxon Chemical Co., Ltd.) A mixture of 22 parts by weight and aged at 25 ° C for 24 hours are pressed into a cylinder and ram extruder (cylinder inner diameter 9 Omm, mandrel outer diameter 20 mm, die inner diameter 21.6 mm, core pin) (With an outer diameter of 16.6 mm and a die temperature of 60 ° C).

The extrudate was continuously dried and fired in a tunnel furnace (final temperature: 390 ° C) to obtain a PTFE cylindrical article having an outer diameter of 2 'Omm and a wall thickness of 2.5mm. This cylindrical article was cut into an appropriate length, and one end was heated to about 350 ° C and spread into a flared shape to obtain a tubular shaped body.

Next, the method for producing a molded article of the present invention was carried out using a mold shown in a schematic sectional view in FIG. First, the flared portion of the molded body was arranged in the mold by fixing it to the mold head 11 of FIG. 1 with screws using an air joint 15. In this state, the mold head 11 was combined with one of the combination molds of the mold body 12 having a diameter of 6 Omm and the mold bottom 13, and a copper pipe was connected to the air joint 15.

A flange for fixing to the electric furnace was fixed to the mold head 11 by screwing, fixed to a shelf attached to the door of the electric furnace, and the door was closed. One end of the copper tube was exposed outside through a hole in the door. A thermocouple was inserted into the tubular body of the mold through a copper tube, and the temperature of the tubular body was monitored.

In this state, the electric furnace was heated until the temperature of the compact reached 300 ° C. After heating to 300 ° C., the door of the electric furnace was opened, and the other of the mating dies at the mold bottom 13 was quickly fixed with mounting screws while tension was applied to the molded object. A groove is engraved in the mold bottom portion 13, and one end of the molded object is closed by sandwiching the end of the molded object in the groove, whereby an airtight state inside the molded object is secured. Tension is applied to the molded object, and the occurrence of loosening is prevented. In this state, the door was closed and the object was heated again until the temperature of the object reached 330 ° C.

After reaching 330 ° C, the thermocouple was pulled out and the copper tube connected to the air compressor was attached to the copper tube leading to the air joint 15. In this state, open the valve and press the molded body with compressed air of 0.4 MPa to apply a differential pressure to blow stretch. Forming was performed, and PTF E was shaped into the shape of the mold. The door was opened with the pressurized state, and the mold was water-cooled. After cooling, the pressure was released, the mold was opened, and the molded product was taken out to obtain a PTFE bottle-shaped molded product. Example 2

A PTFE bottle under the same conditions as in Example 1 except that a cylindrical molded product with an outer diameter of 12 mm and a wall thickness of 1.5 mm was obtained using a die with an inner diameter of 13.3 mm and a core pin with an outer diameter of 10.3 mm A shaped article was obtained. Example 3

A PTF E bottle-shaped molded product was obtained under the same conditions as in Example 1 except that the temperature of the molded body was changed to 330 ° C. and the blow stretching was performed by heating to 310 ° C. Example 4

Except using PTFE fine powder (F104, manufactured by Daikin Industries, TFE (tetrafluoroethylene) homopolymer, crystal melting onset temperature after firing about 275 ° C, 100% crystal melting temperature after firing about 333 ° C) In the same manner as in Example 1, a PTF E bottle-shaped molded product was obtained. Comparative Example 1

A PTF E pottle-shaped molded product was obtained under the same conditions as in Example 2, except that the temperature of the molded body was heated to 310 ° C. and blow stretching was performed. The body of the bottle-shaped product was whitened. Comparative Example 2

A PTFE bottle-shaped molded product was obtained under the same conditions as in Example 2 except that the temperature of the molded body was 350 ° C and blow stretching was performed. Although molding was possible, the bottom of the bottle-shaped molded product had a fold and was partially stretched, resulting in a large uneven thickness. Embodiment 5.

Figure 3 shows a cross-section of a cylindrical article as an object with an outer diameter of 20 mm and a wall thickness of 0.6 mm obtained using a die with an inner diameter of 21.6 mm and a core pin with an outer diameter of 20.4 mm. After fixing to the mold shown schematically in the figure and heating to 300 ° C, the end of the cylindrical article is tightened by a hand vise using the movable angle 35 attached to the mold bottom 34. A PTFE cylindrical molded product was obtained under the same conditions as in Example 1 except that the portion was fixed. Comparative Example 3

Blow stretch molding was performed under the same conditions as in Example 5 except that the temperature of the molded body was heated to 310 ° C. to perform blow stretch molding. The molded object burst and no molded product was obtained. Comparative Example 4

Blow stretch molding was performed under the same conditions as in Example 5 except that the temperature of the molded body was heated to 350 ° C. to perform blow stretch molding. The molded body burst and no molded product was obtained. Example 6

Example 1 was the same as Example 1 except that the mold used was a mold whose cross-sectional view is schematically shown in FIG. 4 and the object to be molded was the one having an outer diameter of 20 mm and a wall thickness of 0.6 mm described in Example 5. A PTFE molded body was obtained under the same conditions. Comparative Example 5

The professional stretch molding was performed under the same conditions as in Example 6, except that the temperature of the molded body was heated to 350 ° C. to perform blow stretch molding. Molding was possible, but the molded product had folds at the top and bottom, and was partially stretched, resulting in increased thickness deviation. Example 7

As the mold, a mold whose cross section is schematically shown in FIG. 2 is used. A sleeve-shaped fusion member with an outer diameter of 58 mm and a wall thickness of 9 mm, obtained by compression molding of PTFE molding powder (Mil 2, manufactured by Daikin Industries, Ltd.) and subsequent sintering, is attached to the inner fusion sleeve installation part 24. Was placed.

Inside this mold, a die having an inner diameter of 33.4 mm and a core having an outer diameter of 27.4 mm were used as a molded body having an outer diameter of 30 mm and a wall thickness of 3 mm obtained under the same conditions as in Example 1. This was stretched under the same conditions as in Example 1 except that the cylindrical molded product was placed to obtain a pottle-shaped molded product. A screw was formed by cutting the fused member part of the obtained molded product, and a polyethylene lid matching the screw was fitted and tightened.However, the fused member did not peel off, and to the extent that there was no practical problem. Had been fused.

Table 1 shows the conditions and results of the above-mentioned examples and comparative examples, together with the degree of wall thickness deviation of the cylindrical portion of the obtained molded product, measured based on the above equation (1). The specific gravity of the reference body which received the same thermal history except that it was not stretched (d J was 2.14 in any case).

t

Pro-crystal melt-stretching Molded article Molded article Uneven thickness Depth before peak Thickness after stretching ¾ Stretching 贩 Decomposition ratio 舰 Ratio! : (%) (Mm) imm)

ΓΟ (%) (if) (mm) d _b

Min Max Max

Upper Middle Lower Upper Middle

Example 1 330 99 3 60 2.17 9.2 2.45 2.52 0.fi5 0.64 0.62 0.68 0.68 0.67 Good Actual translation 2 330 99 5 60 2.19 26.7 1.44 1.51 0.13 0.16 0.13 0.17 0.17 0.17 Good

¾¾ΓExample Q 310 20 60 2.17 12.4 2.45 2.62 0.62 0.63 0.61 0.68 0.G8 0.67 Good Example 4 330 99 3 60 2.17 13.9 2.38 2.65 0.69 0.68 0.67 0.79 0.78 0.77 Good Example 5 830 99 5 100 2.19 22.2 0.60 0.66 0.08 0.08 0.09 0.10 0.09 0.10 good 雞 example 6 330 99 6 120 2.20 40 0.04 0.04 0.05 0.06 0.06 0.06 good comparative example 1 310 20 5 60 1.71 29.S 1.44 1.51 0.12 0.13 0.11 0.16 0.15 0.14 body comparative example 2 350 100 5 60 2.18 140.4 1.44 1.51 0.11 0.09 0.07 0.14 0.18 0.40 Large uneven thickness Example 3 310 20 5 0.60 0.66 Rupture (transformed whitening) Gland example 4 350 100 0.60 0.66 Fiber (transformed part minimum thickness) Comparative shelf 5 3fi0 100 6 120 2.18 188.2 0.01 0.02 0.01 0.13 0.10 0.33 Large uneven thickness

As is clear from Table 1, in the method for producing a molded article of the present invention, the specific gravity (d _b ) force of the molded article is not less than the specific gravity (d _c ) of the reference body which has received the same heat history except that it is not stretched. Specifically, it is at least 2.1, and a good molded product can be obtained. In addition, the molded article based on the present invention also shows improved results with respect to the wall thickness unevenness of the cylindrical portion of the molded article. According to the present invention, a cylindrical molded article having an improved wall thickness unevenness is manufactured. You can see that it can be done. Production Example 1

PTFE fine powder (trade name: F302, manufactured by Daikin Industries, Ltd., emulsion polymerization type perfluoro (alkyl vinyl ether) modified PTFE, molecular weight: 60000 00, crystal melting start temperature after firing: about 270 ° C, 100% crystal after firing (Melting temperature: about 335 ° C) 22 parts by weight of Isopar E (trade name, manufactured by Exxon Chemical Co., Ltd.) as a molding aid is mixed with 100 parts by weight, and aged at 25 ° C for 24 hours to form a cylinder. It was compacted and extruded into a cylindrical shape using a ram extruder. The ram extruder had a cylinder inner diameter of 90 mm, a mandrenole outer diameter of 20 mni, a die inner diameter of 21.6 mm, a core pin outer diameter of 20.4 mm, and a die temperature of 60.

The extrudate was continuously dried and fired using a tunnel furnace having a final temperature of 420 ° C. to obtain a cylindrical molded body 1 having an outer diameter of 20 mm and a wall thickness of 0.6 mm. Production Example 2

A cylindrical molded body 2 having an outer diameter of 20 mm and a wall thickness of 2.5 mm was obtained under the same conditions as in Production Example 1, except that the outer diameter of the core pin of the ram extruder was changed to 16.6 mm. Production Example 3

PTFE fine powder (trade name: F 201, manufactured by Daikin Industries, Ltd., emulsion polymerization system, trifluoroethylene-modified PT FE, molecular weight: 600000, crystal melting start temperature after firing: about 280 ° C, 1 after firing) A cylindrical molded object 3 was obtained under the same conditions as in Production Example 1 except that the melting temperature was 00% (about 335 ° C.). Production Example 4

PTFE fine powder (trade name: F104, manufactured by Daikin Industries, Ltd., emulsion polymerization type tetrafluoroethylene homopolymer, molecular weight: 600,000, crystal melting start temperature after firing: about 27) A cylindrical molded object 4 was obtained under the same conditions as in Production Example 1 except that 5 ° C. and a 100% crystal melting temperature after firing: about 33 ° C.) were used. Example 8

The molded body 1 obtained in Production Example 1 was urged to a length of 350 mm on the longitudinal axis, and the end was heated to about 350 ° C and spread in a flared shape. Inside the mold 71 (diameter 80 mm, length 200 mm) shown in a schematic cross-sectional view, the flared part was screwed into the mold head 72 using the air joint 75. It was arranged by fixing with. Next, a copper tube (not shown) was connected to the air joint 75, and the mold 71 was set in an electric furnace (not shown). A thermocouple (not shown) is inserted into the molded object 1 in the mold 71 through the copper tube, and the electric furnace is heated while monitoring the temperature of the molded object 1. Heated to 300 ° C. After heating to 300 ° C., the end of the molded body 1 was fixed by tightening with a hand vise (not shown) using a movable angle 74 attached to the mold bottom 73.

Thereafter, the object 1 was heated again until the temperature of the object 1 reached 330 ° C. After the temperature reached 330 ° C, the thermocouple was pulled out, and a copper tube (not shown) connected to an air compressor (not shown) was attached to the copper tube connected to the air joint 75. In this state, the valve (not shown) is opened and the molded object 1 is pressurized with compressed air of 0.4 MPa to apply a differential pressure to perform a semi-axial stretching process by a blow method to form a mold. Shaped. Thereafter, the mold 71 was water-cooled while maintaining the pressurized state. After cooling, the pressure was released and the molded product was taken out to obtain a PTF E stretched molded product.

The thickness of the obtained stretched PTFE molded article was measured, and the specific gravity, crystallinity, haze value, water vapor permeability coefficient, gas permeability coefficient for nitrogen, and ₃₅ wt. The arithmetic mean roughness was determined as the chemical liquid permeability coefficient of and the surface roughness. Table 2 shows the results. Example 9

A PTF E stretched molded article was obtained under the same conditions as in Example 8, except that the molded article 3 obtained in Production Example 3 was used instead of the molded article 1. Example 10

A PTF E stretched molded article was obtained under the same conditions as in Example 8, except that the molded article 4 obtained in Production Example 4 was used instead of the molded article 1. Example 1 1

The mold shown in Fig. 8 (diameter 10 Omm, length 30 Omm) 81 was used as the mold, and P was applied under the same conditions as in Example 8 except that the non-molded body was pressed to 450 mm on the longitudinal axis. A TFE stretch molded article was obtained. Example 1 2

A PTF E stretched molded article was obtained under the same conditions as in Example 11 except that the molded article 2 obtained in Production Example 2 was used instead of the molded article 1. Example 13

3 While being heated to 30 ° C, it is stretched to 4 times the length in the longitudinal axis, and is tightened with a hand vise (not shown) using a movable angle 84 attached to the mold bottom 83. A PTFE stretched molded article was obtained under the same conditions as in Example 11 except that biaxial stretch molding was performed by fixing the end of No. 1. Comparative Example 6

Using a PTF E molding powder (trade name: M-15, manufactured by Daikin Industries, Tetrafluoroethylene homopolymer, suspension polymerization, molecular weight: 8000000), using a mold with an inner diameter of 106 mm φ A PTFE preform was obtained by compression molding (final pressure 20 MPa, holding time 10 minutes). After leaving this PTFE preform for 24 hours or more, put it in an electric furnace and raise the temperature from normal temperature to 365 ° C at 50 ° C, 365 ° C , And cooled to room temperature at 50 ° C / hour to obtain a PTFE molded body. This PTFE molded body was skived to obtain a PTFE sheet-like molded product. Comparative Example 7

PTFE was prepared in the same manner as in Comparative Example 6 except that PTF E molding powder (trade name: M-112, manufactured by Daikin Industries, Ltd., suspension polymerization system, perfluoro (alkyl vinyl ether) modified PTFE, molecular weight 1 X 10 ⁷ ) was used. A sheet-shaped molded product was obtained. Comparative Example 8.

Cool from 365 ° C to 325 ° C at 5 ° C, from 325 ° C to 310 ° C at 1 ° C, from 310 ° C to 250 ° C, from 250 ° C to room temperature. A PTFE sheet-like molded product was obtained in the same manner as in Comparative Example 6, except that the test was performed at 50 ° C / hour. Comparative Example 9

A PTFE sheet-shaped molded product was obtained in the same manner as in Comparative Example 8 except that PTFE molding powder (trade name: M-112, manufactured by Daikin Industries, Ltd.) was used. Comparative Example 10

The physical properties of the molded body 1 obtained in Production Example 1 were determined in the same manner as in Example 8. Comparative Example 1 1

The physical properties of the molded body 3 obtained in Production Example 3 were determined in the same manner as in Example 8. Comparative Example 12

The physical properties of the molded body 4 obtained in Production Example 4 were determined in the same manner as in Example 8.

02 From Table 2, it can be seen that in Examples 8 to 13 in which the molded article was stretched to obtain a PTFE stretched molded article, the specific gravity was 2.1 or more, the crystallinity was 78% or more, and the haze value was 3 or less 0%, the water vapor permeability coefficient is the 0. 02 (g · mm) Z (m 2 · day) or less under a nitrogen permeability coefficient ^{6. 8 X 1 0- 8 (cm} 3 ■ cm) / (cm ² · sec • MP a) or less, the hydrochloric acid permeability coefficient is less than 1.8 × 10 nig.cn/m ² · second), and the arithmetic average roughness is less than 0.03. On the other hand, in Comparative Examples 6 to 12, which are not PTF E stretched molded products, at least one of these physical properties is not within the above range, and particularly, the crystallinity, the water vapor transmission coefficient, the nitrogen transmission coefficient, the hydrochloric acid transmission coefficient, and the arithmetic operation The average roughness was found to be significantly inferior.

X-ray diffraction

The X-ray diffractometer (trade name: RAD-RA, manufactured by Rigaku Denki Co., Ltd.) was used for the molded article 1 obtained in Production Example 1 and the stretched PTFE molded article obtained in Example 11 respectively. An X-ray diffraction chart was obtained. The former is shown in FIG. 9 and the latter is shown in FIG. From Figs. 9 and 10, it was found that the peak at 20 = 16 ° originating from the amorphous part in the molded article 1 disappeared in the expanded PTFE article. The above-mentioned crystallinity was calculated from the obtained X-ray diffraction chart.

Taking a TEM replica photo

For each of the cross sections of the molded article 1 obtained in Production Example 1 and the stretched PTFE molded article obtained in Example 11, a small amount of methyl acetate was dropped on the photographed cross section of the sample, and acetyl A cellulose film was placed. Since acetyl cellulose was dissolved in methyl acetate, the cross section of the sample was transferred to the acetyl cellulose film. After drying, the acetyl cellulose film on which the cross section of the sample was transferred was peeled off from the sample, and the transfer surface was vacuum-deposited with a platinum-palladium alloy (Pt: Pd = 80: 20).

From these samples, the acetyl cellulose film was melted using methyl peroxide to obtain a platinum-palladium alloy film to which the cross section of the sample was transferred. This film was photographed using a transmission electron microscope (TEM, trade name: H-710 OFA, manufactured by Hitachi, Ltd.). The obtained TEM replica photograph was obtained for the molded article 1 obtained in Production Example 1 as shown in FIG. 1, obtained in Example 11 The stretched PTFE molded body is shown in FIG. From FIGS. 11 and 12, it was found that the molded article 1 did not have a band structure, but the stretched PTFE molded article had a band structure. Industrial applicability

Since the molded article of the present invention has the above-described configuration, it can be uniformly maintained while maintaining properties such as PTFE's inherent chemical resistance, non-adhesion, release properties, electrical insulation, high-frequency characteristics, and low friction coefficient. Stretched hollow molded products and large molded products can be obtained. Further, the molded article of the present invention is useful in the fields of chemistry, automobiles, machines, drugs, pharmaceuticals, foods, semiconductors, electricity, and the like. For example, they are useful as pumps, piping, fittings, valve members, wafer and device storage, and moving container members used in supply lines for manufacturing equipment, chemicals, and gases used in semiconductor manufacturing processes. It is also useful for low-permeability materials such as gas, liquid, and moisture, films, sheets, tubes, bags, and molded products having irregular cross-sections that require transparency. Molded products with irregular cross-sectional shapes can be used for containers, linings, etc. Tubular molded products can be used for pipes, hoses, coating films for pipes, hoses, etc., protective films for linings, etc., for chemicals and gases. Large tube-shaped products can be used as endless belts. The tubular molded product is subjected to fusion processing and made into a bag shape, which can be used for collecting, storing, and transporting medicine bags, gases, and chemical solutions. Sheets cut from molded products can be used as mold release, packaging, covers, electrical insulation, protective films from chemicals, gases, etc., diaphragms for pumps and valves, etc.

Since the resin molded article of the present invention has the above-described configuration, it has high crystallinity and high transparency, and also has excellent barrier properties and surface smoothness.

Claims

The scope of the claims

1. A molded article made of polytetrafluoroethylene resin is heated by heating the molded article made of polytetrafluoroethylene resin, stretching the heated molded article, and then cooling the molded article made of polytetrafluoroethylene resin. In the manufacturing method of the molded article to be manufactured,

Stretching of the molded body is performed at a temperature equal to or higher than the crystal melting temperature of the polytetrafluoroethylene resin constituting the molded body. In the presence of the crystal part, using a differential pressure,

The stretched molded body is cooled to a temperature lower than the crystal melting start temperature of the polytetrafluoroethylene resin constituting the molded body while maintaining the differential pressure. Formula:

d _b ≥d _c

(Wherein, d _b is the heating, a stretching and polytetramethylene full O b ethylene resin molded article density produced by cooling, (1., but for the stretching same conditions under (Specific gravity of reference body made of polytetrafluoroethylene resin obtained by heating and cooling the molded body in step)

A method for producing a molded article of polytetrafluoroethylene resin, wherein the method is carried out so as to satisfy the following. 2. When the crystal melting ratio of the polytetrafluoroethylene resin constituting the molded body is

2. The production method according to claim 1, which is at least 25% and less than 100%.

3. The production method according to claim 1, wherein the crystal melting ratio of the polytetrafluoroethylene resin constituting the molded body is at least 30% and less than 100% at the time of elongation.

4. The method according to any one of claims 1, 2 and 3, wherein the stretching ratio is greater than 1 and not more than 3 times.

5. Claims 1, 2 or 3 wherein the stretching ratio is greater than 1 and less than or equal to 5 The method according to any one of the above.

6. The method according to any one of claims 1, 2 or 3, wherein the stretching ratio is more than 1 and not more than 10 times, and the crystal melting ratio is 50% or more and less than 100%.

7. The method according to any one of claims 1, 2, 3, 4, 5, and 6, wherein the polytetrafluoroethylene is a modified polytetrafluoroethylene.

8. The method according to any one of claims 1, 2, 3, 4, 5, 6, and 7, wherein the polytetrafluoroethylene is obtained by emulsion polymerization.

9. The molded article made of polytetrafluoroethylene resin is obtained by paste extrusion molding, any one of claims 1, 2, 3, 4, 5, 6, 7, and 8 The described method.

10. The method according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, and 9, wherein another member is fused using a differential pressure at the time of stretching.

1 1. A molded article made of polytetrafluoroethylene resin obtained by the method according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.

1 2. density d _b is 2.1 or more at which claims moldings ranging first one of claims.

1 3. The molding is cylindrical with a longitudinal axis, and at least one of the sections of the molding perpendicular to the direction of the molding, corresponding to the direction of the longitudinal axis of the molding, is of irregular shape 13. The molded article according to claim 11, which is in a shape.

14. The method according to claim 13, wherein at least one of the cross sections of the molded article perpendicular to the direction of the molded article corresponding to the direction of the longitudinal axis of the molded object is a circular cross section. Molding.

15. The molded object is a cylindrical shape having a longitudinal axis, and the cross-sectional shape of the molded product corresponding to the longitudinal axis of the molded product and perpendicular to the direction of the molded product is all circular. 13. The molded article according to claim 11, wherein said molded articles have the same or different diameters.

16. The molded article according to claim 15, wherein the molded article has a cross-sectional circumference of 15 O ram or more.

1 7. The molded product has the formula:

Deflection degree (%) = (2 (maximum thickness-minimum thickness) Z (maximum thickness + minimum thickness)) X 1 0 0

The molded article according to claim 15 or 16, wherein the thickness deviation expressed by: is 120% or less for a portion having the same cross-sectional shape and the same diameter.

18. A resin molded product having a melting point peak of 250 ° C or more, a crystallinity of 78% or more, and a haze value of 30% or less.

19. The resin molded article according to claim 18, which is made of a fluorine-containing resin.

20. The resin molded article according to claim 19, wherein the fluorine-containing resin comprises a tetrafluoroethylene-based polymer.

21. The fluorine-containing resin is made of a polymer containing a modifier,

The resin molded product according to claim 19 or 20, wherein the haze value is 20% or less.

22. The method according to claim 20, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene homopolymer and / or a modified polytetrafluoroethylene. Resin molding.

23. A resin molded article made of a fluorine-containing resin, wherein the fluorine-containing resin is made of a tetrafluoroethylene-based polymer, and has a crystallinity of 78% or more and a haze value of 30% or less. A resin molded product characterized by the following.

24. A resin molded article comprising tetrafluoroethylene homopolymer and / or modified polytetrafluoroethylene,

A resin molded product having a water vapor transmission coefficient at a relative humidity difference of 90% at 25 ° C of not more than 0.02 (g · mm) / (m ² · day).

25. A resin molded article comprising tetrafluoroethylene homopolymer and / or modified polytetrafluoroethylene,

Permeability coefficient of 35 wt% hydrochloric acid is not more than ^{1. 8 X 10- 11 (g.} Cm) / (cm 2 · sec) at 25 ° C

A resin molded article characterized by the above-mentioned.

26. A resin molded article comprising tetrafluoroethylene homopolymer and Z or modified polytetrafluoroethylene,

25 permeability coefficient of nitrogen ° 〇 in Okeru 0. 2 MP a is ^{^{6. 8 X 10- 8 (cm 3}} cm.) / Is ^{(cm 2 - - sec MP a} ) below

A resin molded article characterized by the above-mentioned.

27. A resin molded article comprising tetrafluoroethylene homopolymer and Z or modified polytetrafluoroethylene,

The specific gravity is 2.1 or more,

Arithmetic mean roughness is less than 0.03; m

A resin molded article characterized by the above-mentioned.

28. The resin molded product according to claim 18, 19, 20, 21, 22, 22, 23, 24, 25, 26, or 27, which is in the form of a film.

29. The range of claims 18 to 19, 20, 20, 21, 22, 23, 24, 25, 26, 27, in the form of a tube, in which the outer peripheral length of the cross-sectional shape of the molded product is 15 Omm or more

Item 29. The resin molded article according to Item 28.

30Consists of the resin molded product described in claims 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29, and is used to cover an object to be packaged Is the thing

A packaging material for intercepting atmospheric moisture.

3 1. The packaging material for blocking moisture in the air according to claim 30, wherein the packaged object is an electroluminescent element.

32. The packaging material for blocking moisture in the air according to claim 30, wherein the packaged product is a drug.

33. It is made of the resin molded product according to claims 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29.

A packaging material for blocking medicine, characterized in that:

34. It is made of the resin molded product according to claims 18, 19, 20, 21, 22, 23, 24, 25, 26 27, 28, or 29.

A gas shielding packaging material characterized by the above-mentioned.

35. A belt material comprising the resin molded product according to claim 18, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29, A belt material used for a photosensitive portion for image formation in electrophotographic equipment.

36. Claims 18, 19, 20, 21, 22, 23, 24, 25, 26,

30. A belt material comprising the resin molded article according to 27, 28 or 29, wherein the belt material is used for a fixing section for forming an image in an electrophotographic apparatus.

37Packaged material and a package consisting of the resin molded product described in paragraphs 18, 19, 20, 21, 22, 22, 23, 24, 25, 26, 27, 2.8 or 29 of the claims At

The resin molded body covers the packaged object,

A package which suppresses contact between the object to be packaged and atmospheric moisture, chemicals and / or gas.

38. The package according to claim 37, wherein the object to be packaged is an elect-emission luminescence element.

39. The package according to claim 37, wherein the packaged substance is a medicine.

40. The package according to claim 37 or 38, wherein the resin molded article suppresses contact between an object to be packaged and atmospheric moisture.