JP3671127B2 - Multilayer tube and manufacturing method thereof - Google Patents

Description

【００４３】
表１によれば、内面のみに非粘着層を設けた実施例１のチューブでは、外面のタック性以外はいずれも良好な結果が得られた。また、内面および外面の両方に非粘着層を設けた実施例２のチューブでは、全ての項目について良好な結果が得られた。なお、引っ張り強度および伸びについても、母材単独のチューブとほぼ同等の性能を示した。他方、非粘着層を設けない比較例１のチューブでは、内面および外面のいずれもタック性があり、好ましくない。また全体を三元共重合体で構成した比較例２および比較例３のチューブでは、屈曲性および伸びが良好でないことが分かる。また比較例２、３については、硬いため、タック性の測定ができなかった。
【図面の簡単な説明】
【図１】 本発明の一実施例による２層チューブの断面図である。
【図２】 図１の２層チューブを成形するための押出金型の断面図である。
【図３】 本発明の他の実施例による３層チューブの断面図である。
【図４】 図３の３層チューブを成形するための押出金型の断面図である。
【符号の説明】
１ 母材
２ 内面層
３ チューブ
４ 外面層
５ チューブ
１１、２１ 母材入口
１２、２２ 母材流路
１３ 内表面層材料入口
１４、２４ 内表面層材料流路
１５、２６ 合流部
１６、２７ 金型出口
２３ 表面層材料入口
２５ 外表面層材料流路[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a multilayer tube, and more particularly to a multilayer tube having a fluororubber-based thermoplastic elastomer as a base material and having improved surface or inner surface tack. In addition, the present invention provides an internal liquid by utilizing the elastic deformation of the tube, such as a tube for transporting chemicals used in the pharmaceutical industry and the medical industry, a tube pump called a squeezing pump, and a tube fram pump. The present invention relates to a multi-layer tube suitable for a pump having a function of feeding out and a manufacturing method thereof.
[0002]
[Prior art]
Fluororubber and resin have excellent characteristics that are not found in other rubbers and resins in heat resistance, oil resistance, chemical resistance, etc., and are molded into packings, gaskets, tubes, etc., especially in the automotive industry and OA equipment. Widely used in the semiconductor industry, chemical industry, physics and chemistry fields. In particular, fluororubber is used under conditions where it comes into contact with harsh organic solvents, acids, alkalis and other inorganic chemicals, and where flexibility is required in a thermal environment, and the demand for it is increasing in recent years. .
[0003]
However, the processing of fluororubber requires a complicated vulcanization process, and contains vulcanizing agents, stabilizers, fillers, etc., which may cause elution of these.
[0004]
On the other hand, a fluororesin does not have such a defect and a tube that is nearly transparent can be obtained. However, the use place is limited because it has poor flexibility and is not flexible.
[0005]
In recent years, thermoplastic elastomers have been studied as elastic bodies that do not require a vulcanizing agent, and have been put to practical use in various fields. This fluoroelastomer is also developed and actually used in the fluoro rubber system. According to the technology disclosed in Japanese Examined Patent Publication No. 2-36365, the fluororubber-based thermoplastic elastomer has a vinylidene fluoride-tetrafluoroethylene copolymer or an ethylene-tetrafluoroethylene copolymer as its crystal phase. Used as the rubber phase is vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer. The crystalline phase and the rubber phase have a so-called block copolymerized structure, and below the melting point of the crystalline phase, the crystalline phase becomes a physical cross-linking point and expresses the strength of the molded body.
[0006]
Since the crystal melts above the melting point of the crystal phase and the whole is in a fluid state, it can be easily subjected to thermoforming processes such as extrusion molding, injection molding, and compression molding, and molded products of various shapes can be obtained. The tube can be easily processed. Such a fluororubber-based thermoplastic elastomer is, for example, provided on the market by Daikin Industries, Ltd. under the trade name Daiel Thermoplastic.
[0007]
In general, thermoplastic elastomers can be obtained with sufficient strength only by thermoforming, but fluororubber-based thermoplastic elastomers can be chemically crosslinked by irradiating ionized radiation to the molded product. This further improves the physical properties.
[0008]
Unlike general fluororubbers, fluorinated thermoplastic elastomers do not contain additives such as carbon powder, acid acceptor, vulcanizing agent, etc., and are excellent in transparency. It has the characteristic that it does not contaminate or the container.
[0009]
[Problems to be solved by the invention]
There is a pump that transports the liquid in the tube by crushing the tube mounted along the wall body with a plurality of rollers concentrically attached to a rotating body that is driven to rotate by a motor. These pumps are generally referred to as tube pumps and caulking pumps. In addition, the tube is accommodated in a sealed container, and the pressure in the container is alternately increased and decreased to contract and expand (return), and the one-way valve provided on the inlet side and the outlet side of the tube respectively. A tube fram type pump that pumps the liquid in the tube is also known. Since the tube used for such a pump is required to have flexibility, mechanical strength and chemical resistance, the tube is usually produced from a soft synthetic resin such as soft vinyl chloride or silicon. Recently, however, various chemicals and solvents have been used, and chemical resistance has not been sufficient.
[0010]
As described above, fluoroelastomer-based thermoplastic elastomers are extremely excellent in mechanical strength and chemical resistance, and are excellent in transparency. Therefore, they are suitable for chemical transport tubes. Used as a pump tube. And in order to ensure the required softness | flexibility, a flexible fluororubber-type thermoplastic elastomer is especially preferable. However, the surface of the elastomer molded body in this range (inner and outer surfaces in the case of a tube) has tackiness (propensity to stick to each other and adhere to other objects), which may cause various usage problems. is there. For example, when it is used in a tube pump, if it is left in a compressed state with a roller, the inner surfaces are often stuck together and cannot be restored, and they are often closed. In addition, the tackiness of the surface of the tube also has problems such as being easily soiled and sticking to other objects and being difficult to operate.
[0011]
Conventionally, research for improving such tackiness has been conducted, and disclosed in, for example, Japanese Patent Publication Nos. 6-53822 and 6-53823. According to this disclosed technique, in a bag made of a material that is difficult to transmit oxygen, such as nylon, in an atmosphere where the partial pressure of oxygen or ozone is more than 11.4 mmHg and 76 mmHg or less, a flexible fluororubber system By putting a preform of a thermoplastic elastomer and irradiating with ionizing radiation, the surface stickiness after molding is reduced. However, although some effects were recognized, the tackiness of either the surface or the inner surface has not reached a practical level.
[0012]
Further, a two-layer or three-layer tube made of a fluororesin material or a fluororubber material is already well known. In JP-A-9-131833, at least one thermoplastic elastomer layer of a polyester-based thermoplastic elastomer and a polyolefin-based thermoplastic elastomer is bonded to a fluoropolymer layer by interposing an adhesive layer in an intermediate layer. Discloses a three-layer tube. However, the fluorine-containing polymer layer is an ethylene / tetrafluoroethylene copolymer, and the resulting three-layer tube is not sufficiently recovered after compression when used in a tube pump, and is deformed or crushed and damaged. It is not suitable for tube pumps. An object of the present invention is to provide an easy-to-use multilayer tube that does not impair the advantages of conventional fluororubber thermoplastic elastomer tubes, such as recoverability after compression, and that has reduced tackiness. It is.
[0013]
[Means for Solving the Problems]
The first aspect (Claim 1) of the multilayer tube of the present invention has a structure in which the hardness measured based on JIS K 7215 is HDA 40 or more and HDA 70 or less, and the crystal phase and the rubber phase are copolymerized in a block manner. A tube base material made of a flexible fluororubber-based thermoplastic elastomer (A) having a weight ratio of crystal phase to rubber phase of 5 to 60:40 to 95, and an inner surface of the tube base material and / or A non-adhesive layer (tack prevention layer or protective layer) made of a fluororesin (B) having a hardness measured according to JIS K 7215 of HDA 70 or more and HDD 80 or less, laminated on the outer surface, is molded by extrusion molding , The non-adhesive layer is provided on the outer surface of the base material . Moreover, you may provide a non-adhesion layer in the inner surface and outer surface of a base material.
[0014]
The above hardness is a value measured in accordance with a JIS K 7215 (1986) plastic durometer hardness test method. The durometer can be measured by attaching it to a durometer holding base using A hardness (HDA) and D hardness (HDD) manufactured by Kobunshi Keiki Co., Ltd. For example, the sample is obtained by stacking four press sheets having a thickness of 2 mm.
[0015]
The fluororubber thermoplastic elastomer (A) constituting the base material has a crystalline phase of vinylidene fluoride / tetrafluoroethylene, ethylene / tetrafluoroethylene / hexafluoropropylene, 3,3,3-trifluoropropylene- 1 , a polymer chain segment having a molecular weight of 3000 to 400,000 selected from 2-trifluoromethyl-3,3,3-trifluoropropylene-1 or perfluoroalkyl vinyl ether, and the rubber phase is vinylidene fluoride / hexafluoropropylene / Tetrafluoroethylene and perfluoroalkyl vinyl ether / tetrafluoroethylene / vinylidene fluoride polymer chain segment with a molecular weight of 30000-1200000, crystalline phase and rubber The weight ratio of 5 to 60: 40 to 95. Examples of such a fluororubber thermoplastic elastomer (A) include Daiel Thermoplastics T-530 and T-630 manufactured by Daikin Industries, Ltd.
[0016]
Examples of the fluororesin (B) constituting the non-adhesive layer include tetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene- There are ethylene copolymers, and these materials include fluoropolymer thermoplastic elastomers such as Daiel Thermoplastic T-530 manufactured by Daikin Industries, Ltd. and terpolymers such as THV200G manufactured by Sumitomo 3M Co., Ltd. The hardness can be adjusted by adding fluororubber.
[0018]
The molar ratio of each component of the three-component copolymer (B) is tetrafluoroethylene about 30 to 80 mol%, in particular 40 to 70 mol% of vinylidene fluoride is from 40 to 70 mol%, in particular 40 to 60 mol% Hexafluoropropylene is preferably 10 to 50 mol%, particularly preferably 15 to 30 mol%. Specifically, THV500G, THV400G, THV300G, THV200G, etc. manufactured by Sumitomo 3M Co., Ltd. can be used for the ternary copolymer (B).
[0022]
[Operation and effect of the invention]
In the multilayer tube according to the first aspect of the present invention (Claim 1), the material of the base tube is a flexible fluororubber thermoplastic elastomer (A having a hardness of HDA 40 or more and HDA 70 or less measured according to JIS K 7215). ), The recovery force after elastic deformation is high, and the mechanical strength is also high. In addition, since a fluororubber thermoplastic elastomer is used, it has high heat resistance, oil resistance, and chemical resistance. When the hardness is less than HDA 40, the mechanical strength is inferior. Moreover, when it exceeds HDA70, a softness | flexibility and shape recovery property are inferior. In addition, the non-adhesive layer uses a fluororesin (B) having a hardness of HDA 70 or higher and HDD 80 or lower measured according to JIS K 7215, so that it has high heat resistance, oil resistance, and chemical resistance at the same time as imparting non-adhesiveness. Therefore, the flexibility of the base material is not impaired. In addition, since the tackiness of the laminated surfaces is lost, the use becomes easy. When the hardness of the non-adhesive layer is less than HDA 70, adhesiveness occurs, and when it exceeds HDD 80, flexibility is lost.
[0023]
Furthermore, since the chemical composition of both is close, it can be welded easily and does not peel off at the welded surface. Therefore, a tube with a non-adhesive layer laminated on the inner or outer surface is combined with the action of a non-adhesive layer that does not have tackiness and the action of a base material that has flexibility and shape recovery, so that flexibility, chemical resistance, and elastic recovery are achieved. It becomes a multilayer tube having excellent properties such as strength.
[0024]
The fluororesin (B) is, no tackiness with many resin component, the case of using tetrafluoroethylene, vinylidene fluoride, terpolymers material consisting of hexafluoropropylene (B), provided the layer On the side, tackiness is lost and it becomes easier to handle. When the hardness of the non-adhesive layer is less than HDA70, there is adhesiveness, and when it exceeds HDD80, flexibility is lost. This also significantly improves the tackiness while maintaining the favorable properties of the tube such as flexibility. Furthermore, since the base tube and the material of the non-adhesive layer are close in chemical composition, they can be easily welded and do not peel off at the interface.
When the non-adhesive layer is provided on the inner surface of the tube base material (Claim 3), it can be easily restored even if it is deformed so as to be crushed. Further, when the non-adhesive layer is provided on the outer surface (Claim 4), since the tackiness of the outer surface is lost, the tubes do not stick to each other, and it is difficult to stick to other things, so that it is easy to handle. When both surfaces are provided (Claim 5), the tube has both advantages.
[0025]
When used for a pump, the thickness of the multilayer tube may be about the same as that of a conventional pump tube, for example, about 0.1 to 4.0 mm, more preferably about 0.3 to 3.0 mm. If it is thinner than 0.1 mm, the strength is lowered and the restorability is lowered. On the other hand, if it is thicker than 4.0 mm, the flexibility becomes low and it is not suitable for a pump, and the required drive energy becomes high. The thickness of the base material is preferably about 50 to 99.5% of the thickness of the tube, and specifically about 0.1 to 4.0 mm. If it is thinner than 0.1 mm, the strength is lowered and the restorability is lowered. Conversely, if it exceeds 4.0 mm, the flexibility becomes low. The thickness of the non-adhesive layer is preferably reduced, and usually 0.005 mm or more, particularly 0.01 mm or more is used. When it is less than 0.005 mm, molding is difficult and the lamination strength to the base material is inferior. The upper limit of the thickness is about 0.3 mm, especially about 0.2 mm. If it is thicker than that, the flexibility is inferior and it is not suitable for pumps.
[0026]
In the production method of the present invention (Claim 8), since each material is introduced into a common mold and extrusion molding is performed , the adhesive strength between the two is high, and the production can be efficiently performed. Moreover, since the ionizing radiation is irradiated after the extrusion molding, the mechanical properties are improved. The dose suitable for radiation crosslinking is preferably in the range of 10 to 500 kGy. If it is 10 kGy or less, the effect of radiation crosslinking is small, and if it is 500 kGy or more, the material may be deteriorated.
[0028]
The molding temperature in the above production method is preferably above the melting point of the fluororubber thermoplastic elastomer (A), the melting point of the fluororesin (B) or the terpolymer (B), and below the temperature at which no thermal decomposition occurs. . Specifically, 200-290 degreeC is desirable.
[0030]
【Example】
The present invention will be described below with reference to the embodiments shown in the drawings.
[Example 1]
[Formation of two-layer tube]
Daikin Industries, Ltd. Daiel Thermoplastic T-530 (hardness HDA67) was used as the fluorine-based thermoplastic elastomer (A). Moreover, Sumitomo 3M Co., Ltd. THV500G (hardness HDA92-93) was used as a ternary copolymer (B). As an extrusion molding machine, a cylinder diameter: 40 mm and L / D: 16 are used for the elastomer (A) as a base material, and a cylinder diameter: 30 mm and L / D: 12 are used for the terpolymer (B). It was used. FIG. 1 shows a cross section of a two-layer tube 3 using Daiel Thermoplastic T-530 as a base material 1 and THV500G as an inner surface layer 2 according to an embodiment of the present invention. The thicknesses of the inner surface layer 2 and the base material 1 are 0.1 mm and 0.9 mm, respectively.
[0031]
FIG. 2 shows a cross section of an extrusion mold for forming the two-layer tube 3 of FIG. A 40 mm extruder (not shown) is connected to the base material inlet 11 of the mold, and a heated and melted Daiel Thermoplastic T-530 is injected from the base material inlet 11 and passes through the base material flow path 12. Further, a 30 mm extruder is connected to the inner surface layer material inlet 13 of the mold, and the heated and melted THV 500G is injected from the inner surface layer material inlet 13 and passes through the inner surface layer material flow path 14. In the junction 15, Daiel Thermoplastic T-530 and THV500G are welded, and from the mold outlet 16, the two-layer tube 3 having the base material A as Daiel Thermoplastic T-530 and the inner layer B as THV500G is extruded. .
[0032]
The extruded tube 3 is taken up by a take-up machine while being cooled by water cooling and air cooling, and has an inner diameter of 2.0 mm and an outer diameter of 4 mm. A molded product of 0 mm tube was obtained.
[0033]
[Radiation cross-linking of tubes]
The extruded tube was bundled and placed in a normal polyethylene bag, and the inlet was sealed with a heat welding machine. This was irradiated with 50 kGy of ionizing radiation using Co60 as a radiation source to obtain a tube of Example 1. The irradiation atmosphere is in the air.
[0034]
[Evaluation of the physical properties]
The flexibility and tackiness of the obtained tube of Example 1 were measured. The results are shown in Table 1. The tackiness was observed by crushing the tube with a fingertip, bringing the inner surfaces of the tube into close contact with each other, and then recovering the tube away from the finger. Moreover, about the adhesiveness of an outer surface, two tubes were piled up and compressed with the fingertip, and the adhesiveness between tubes was observed. In Table 1, the case where the restoration was made is indicated by “◯”, and the case where it was difficult to restore or the case where the outer surface had adhesiveness was indicated by “X”. The bending state was observed by operating the tube pump. Those that performed well are indicated by “◯”, and those that were destroyed are indicated by “X”.
[0035]
[Example 2]
[Three-layer tube forming]
Daikin Industries, Ltd. Daiel Thermoplastic T-530 was used as the fluorine-based thermoplastic elastomer (A). Moreover, Sumitomo 3M Co., Ltd. THV500G was used as a ternary copolymer (B). For the extrusion molding machine, the base material (A) uses a cylinder diameter: 40 mm, L / D: 16, and the ternary copolymer (B) uses a cylinder diameter: 30 mm, L / D: 12. used.
[0036]
FIG. 3 shows a cross section of a three-layer tube 5 using Daiel Thermoplastic T-530 as the base material 1 and THV500G as the inner surface layer 2 and the outer surface layer 4 according to an embodiment of the present invention. . The thicknesses of the inner surface layer 2, the base material 1, and the outer surface layer 4 are 0.1 mm, 0.8 mm, and 0.1 mm, respectively.
[0037]
FIG. 4 shows a cross section of an extrusion die for forming the tube 5 of FIG. A 40 mm extruder is connected to the base metal inlet 21 of the mold, and the heated and melted Daiel Thermoplastic T-530 is injected from the base material inlet 21 and passes through the base material flow path 22. Further, the 30 mm extruder is connected to the surface layer material inlet 23 of the mold, and the heated and melted THV 500G is injected from the surface layer material inlet 23, and the inner surface layer material flow path 24 and the outer surface layer material flow path 25 are injected. Divided into flows. In the junction portion 26, Daiel Thermoplastic T-530 and THV500G are welded. From the mold outlet 27, the base material 1 is Daiel Thermoplastic T-530, the inner surface layer 2, and the outer surface layer 4 are THV500G three-layer tubes. 5 is extruded.
[0038]
The extruded tube 5 is drawn by a take-up machine at a constant speed while being cooled by water cooling or air cooling, and the inner diameter is 0.1 mm for the inner layer, 0.8 mm for the base material layer, and 0.1 mm for the outer layer: A molded article of 2.0 mm, outer diameter: 4.0 mm tube was obtained. In the same manner as in Example 1, after crosslinking by irradiating 50 kGy radiation using Co60 as a radiation source, Example 2 was obtained by decolorization by heat treatment.
[0039]
[Comparative Example 1]
In Example 1, the tube of Comparative Example 1 was molded under exactly the same extrusion conditions, radiation cross-linking conditions, heat decoloring conditions, etc., except that the material used was Daiel Thermoplastic T-530 alone. The results are shown in Table 1.
[0040]
[Comparative Example 2]
In Example 1, except that the material used was THV200G (hardness HDA 88-89) alone, the extrusion conditions, radiation crosslinking conditions, heat decoloring conditions, etc. were exactly the same, and the tube of Comparative Example 2 was molded. . The obtained tube was colorless and transparent, but was poor in flexibility and immediately destroyed when applied to the tube pump. The physical property evaluation results are shown in Table 1.
[0041]
[Comparative Example 3]
In Example 1, except that the material used was THV500G alone, the forming process of the tube of Comparative Example 3 was carried out under exactly the same extrusion conditions, radiation crosslinking conditions, heating decolorization conditions, and the like. The obtained tube was colorless and transparent, but was less flexible than the tube of THV200G of Comparative Example 2, and immediately destroyed when applied to the tube pump. The evaluated physical properties are shown in Table 1.
[0042]
[Table 1]

[0043]
According to Table 1, in the tube of Example 1 in which the non-adhesive layer was provided only on the inner surface, good results were obtained except for the tackiness of the outer surface. Moreover, in the tube of Example 2 which provided the non-adhesion layer in both the inner surface and the outer surface, the favorable result was obtained about all the items. In addition, the tensile strength and elongation showed almost the same performance as that of the base material alone tube. On the other hand, in the tube of Comparative Example 1 in which the non-adhesive layer is not provided, both the inner surface and the outer surface are tacky, which is not preferable. Moreover, it turns out that the flexibility and elongation are not favorable in the tube of the comparative example 2 and the comparative example 3 which comprised the whole with the ternary copolymer. Further, since Comparative Examples 2 and 3 were hard, tackiness could not be measured.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a two-layer tube according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of an extrusion die for forming the two-layer tube of FIG.
FIG. 3 is a cross-sectional view of a three-layer tube according to another embodiment of the present invention.
4 is a cross-sectional view of an extrusion mold for forming the three-layer tube of FIG. 3. FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Base material 2 Inner surface layer 3 Tube 4 Outer surface layer 5 Tube 11, 21 Base material inlet 12, 22 Base material flow path 13 Inner surface layer material inlet 14, 24 Inner surface layer material flow path 15, 26 Merge part 16, 27 Gold Mold outlet 23 Surface layer material inlet 25 Outer surface layer material flow path

Claims (2)

The hardness measured based on JIS K 7215 is HDA 40 or more and HDA 70 or less, and has a structure in which the crystal phase and the rubber phase are block-copolymerized, and the weight ratio of the crystal phase and the rubber phase is 5 to 60: A tube base material made of a flexible fluororubber-based thermoplastic elastomer (A) of 40 to 95;
The tube base material is provided with a non-adhesive layer made of a fluororesin (B) having a hardness measured in accordance with JIS K 7215 of HDA 70 or more and HDD 80 or less, which is laminated on the inner surface and / or outer surface of the tube base material. And
A multilayer tube in which the non-adhesive layer is provided on the outer surface of a base material . The hardness measured based on JIS K 7215 is HDA 40 or more and HDA 70 or less, and has a structure in which the crystal phase and the rubber phase are block-copolymerized, and the weight ratio of the crystal phase and the rubber phase is 5 to 60: A tube base material made of a flexible fluororubber-based thermoplastic elastomer (A) of 40 to 95;
The tube base material is provided with a non-adhesive layer made of a fluororesin (B) having a hardness measured in accordance with JIS K 7215 of HDA 70 or more and HDD 80 or less, which is laminated on the inner surface and / or outer surface of the tube base material. And
The multilayer tube which provided the said non-adhesion layer in the inner surface and outer surface of a base material .

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