CN107428957B - Medical molded article, extrusion molding method for medical molded article, and extrusion molding device for medical molded article - Google Patents
Medical molded article, extrusion molding method for medical molded article, and extrusion molding device for medical molded article Download PDFInfo
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- CN107428957B CN107428957B CN201680018228.0A CN201680018228A CN107428957B CN 107428957 B CN107428957 B CN 107428957B CN 201680018228 A CN201680018228 A CN 201680018228A CN 107428957 B CN107428957 B CN 107428957B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Abstract
The present application provides a technique capable of manufacturing medical molded articles with low colorability at low cost. A medical molded article obtained by extrusion molding of a composition comprising a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and a zinc soap and a calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass, and the whiteness (W.I.) of the medical molded article is 25 or more and the yellowness (Y.I.) is 3.5 or less, relative to 100 parts by mass of the polyvinyl chloride resin. When extrusion molding is performed on the medical molded article, the composition 11 formed in a solid state is fed to the screw 21 of the extruder 20 in which the depth d of the groove 22 is the same, in a feed amount adjusted so that the shearing heat is not generated in the composition in the extruder. Then, heat from the heaters 41, 42, and 43 is applied to the solid composition supplied to the screw to melt the composition, and the composition in a molten state extruded from the extruder is molded into the shape of the medical molded article 12 through the die 50.
Description
Technical Field
The present application relates to a molded article for medical use, a method for extrusion molding a molded article for medical use, and an extrusion molding apparatus for a molded article for medical use.
Background
As a medical material, a soft polyvinyl chloride resin has been widely used. Since medical supplies are used by returning blood in contact with the medical supplies to a living body, inserting the blood into a living body tissue, or in the vicinity of a patient with physical deterioration, safety is very important, and for this reason, medical supplies are generally used in a sterilized form, and as a sterilization method, radiation sterilization, ethylene oxide sterilization, or autoclaving is generally used. Among them, there is no concern about the residual of ethylene oxide gas as in ethylene oxide sterilization and the exposure of medical instruments to high temperatures as in autoclaving, and therefore, it is adopted as an excellent sterilization method which is sanitary and has little damage to medical materials.
On the other hand, in medical articles produced from the soft polyvinyl chloride resin composition, the soft polyvinyl chloride resin or its compounding agent is deteriorated or deteriorated by radiation or heat, and thus, there is a problem that coloration is promoted.
In view of the above problems, patent document 1 reports a molded article which is not liable to be discolored even when subjected to electron beam sterilization. The above patent document 1 is characterized by molding a polyvinyl chloride resin composition containing a 3-mercaptopropionate of a polyol having 3 or more members in a specific amount.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-057099
Disclosure of Invention
Problems to be solved by the application
The molded article described in patent document 1 is certainly a molded article which is excellent in discoloration resistance against electron beam sterilization and is not liable to be discolored after electron beam sterilization.
On the other hand, a medical molded article made of a polyvinyl chloride resin is a general-purpose article, and is expected to be manufactured at a lower cost than other high-performance medical articles. Therefore, in view of cost reduction, it is desirable to reduce the kinds and amounts of the compounding agents (additives) as much as possible.
Accordingly, the present application has been made in view of the above-described circumstances, and an object thereof is to provide a technique capable of inexpensively producing a medical molded article with reduced coloration (discoloration).
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a technique capable of producing a medical molded article of a polyvinyl chloride resin having a low coloring degree (high whiteness and low yellowness) even if the amount of a metal soap as a heat stabilizer is reduced, and have completed the present application.
That is, the above objects are achieved by a molded article for medical use which is obtained by extrusion molding of a composition comprising a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and a zinc soap and a calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass, and the whiteness (w.i.) of the molded article for medical use is 25 or more and the yellowness (y.i.) is 3.5 or less, relative to 100 parts by mass of the polyvinyl chloride resin.
The extrusion molding method for the medical molded article to achieve the above object is an extrusion molding method for extruding the above composition to form a medical molded article having a whiteness (w.i.) of 25 or more and a yellowness (y.i.) of 3.5 or less. First, the composition formed in a solid state is fed to a screw of an extruder having a groove depth of the same depth in a feed amount adjusted so as not to generate shear heat of the composition in the extruder. Heat from a heater is applied to the solid composition supplied to the screw to melt the composition. Then, the composition in a molten state extruded from the extruder is molded into the shape of a medical molded article through a die.
The extrusion molding apparatus for a medical molded article which achieves the above object is an extrusion molding apparatus for extruding the above composition to form a medical molded article having a whiteness (w.i.) of 25 or more and a yellowness (y.i.) of 3.5 or less. The extrusion molding device comprises: an extruder in which screws having grooves formed to the same depth are rotatably disposed in a barrel; a feeder that supplies the composition formed in a solid state to the screw and freely adjusts a supply amount of the composition; a heater that applies heat that melts the solid composition supplied to the screw; and a die for molding the composition in a molten state extruded from the extruder into a shape of a molded article for medical use. Further, the feeder adjusts the amount of the composition supplied to an amount that does not cause the composition to generate shear heat in the extruder.
Effects of the application
The medical molded article of the present application has a low coloring degree (high whiteness and low yellowness) even when a small amount of metal soap is used. Therefore, the medical molded article of the present application can be manufactured at low cost.
According to the extrusion molding technique of the medical molded article of the present application, the solid composition is supplied in a supply amount adjusted so that the composition does not generate shear heat in the extruder, using a screw having a groove formed to have the same depth. Therefore, the composition can be suppressed from being retained in the extruder, and further, the composition can be suppressed from being excessively sheared and heated in the extruder. Since 2 main factors causing burn marks of the molded article can be suppressed, a molded article for medical use having a low coloring degree (high whiteness and low yellowness) can be produced at low cost even when a small amount of metal soap is used.
Drawings
Fig. 1 is a schematic configuration diagram of an extrusion molding apparatus for medical molded articles according to an embodiment of the present application.
Fig. 2 is a cross-sectional view showing a main part of an extrusion molding apparatus for medical molded articles shown in fig. 1.
Detailed Description
The present application provides a medical molded article obtained by extrusion molding of a composition comprising a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and zinc soap and calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass, and the whiteness (w.i.) of the medical molded article is 25 or more and the yellowness (y.i.) is 3.5 or less, relative to 100 parts by mass of the polyvinyl chloride resin.
The medical molded article satisfying the above constitution has a low coloring degree (high whiteness and low yellowness) even when a small amount of metal soap is used. Therefore, the medical molded article of the present application can be produced at low cost.
In general, molded articles made of medical polyvinyl chloride resin are used for various applications such as infusion bags, blood transfusion bags, and connecting pipes. In this case, in order to easily observe the state (e.g., flow of liquid, color) of the molded article content (e.g., blood, nutrient, etc.), the molded article is preferably an article having a low yellow color and a high white color. Therefore, as described in patent document 1, attempts have been made to suppress discoloration and coloring by using various additives. On the other hand, such a general-purpose medical molded article is required to be inexpensive because it is used in a large amount for various purposes. Therefore, from the viewpoint of cost reduction, the compounding agent (additive) is preferably small in kind and amount. That is, there is a relationship between coloring, suppression/prevention of discoloration, and cost reduction of the medical molded article, and the relationship is a constraint (track-off).
In contrast, the medical molded article of the present application is produced by using specific means described in detail below, and thus, even if a small amount of stabilizer (zinc soap and calcium soap) is used, a medical molded article having high whiteness and low yellowness can be produced.
The components of the polyvinyl chloride resin composition according to the present application will be described in detail below. In the present specification, "X to Y" in the expression ranges include X and Y, and the meaning "X is not less than Y. Unless otherwise specified, the measurement of the operation, physical properties, and the like is performed under the conditions of room temperature (20 to 25 ℃) and 40 to 50% relative humidity.
(molded medical article)
The medical molded article of the present application is produced by extrusion molding the above-described specific composition (polyvinyl chloride resin composition). The medical molded article of the present application has a whiteness (w.i.) of 25 or more and a yellowness (y.i.) of 3.5 or less. In this way, since the molded product having high whiteness and low coloring (yellowness) exhibits high visual confirmation, even if a liquid (for example, blood, nutrient, or the like) flows in the molded product (for example, a tube), the state (for example, flow of the liquid, color) thereof can be visually confirmed well.
In view of the effect of further improving the visual confirmation, the whiteness of the molded article for medical use is preferably 26 or more, more preferably 27 or more, particularly preferably 28 or more. The higher the whiteness of the molded article for medical use, the more preferable, and therefore the upper limit is not particularly set, but a degree of 50 or less is sufficient. Similarly, the yellowness of the molded article for medical use is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less, from the viewpoint of further improving visual confirmation effects. The lower the yellowness of the molded article for medical use, the more preferable, and therefore the lower limit is not particularly set to 0 or more.
In the present specification, whiteness and yellowness of a molded article for medical use are values measured by the following methods.
(method for measuring whiteness and yellowness of molded article for medical use)
The tube (sample tube) having an inner diameter of 3.0mm and an outer diameter of 4.4mm was obtained by extrusion molding. For this sample tube (n=8), whiteness (w.i.) and yellowness (y.i.) were measured according to the method based on ASTM E313-73 under the following conditions, and the average value thereof was used.
[ chemical formula 1]
(measurement conditions)
Using the instrument: COLOR READER CR-14 (whiteness Meter) (Konica Minolta Co., ltd.)
Optical conditions: diffusion light receiving mode (removing specular reflection component) of 8 degree direction illumination
Measurement mode: whiteness (W.I.) and yellowness (Y.I.) based on ASTM E313-73
Diameter measurement:
measurement was performed by placing a sample tube on a reference white paper (whiteness: 86.0, yellowness: -7.7) (n=8 each)
(polyvinyl chloride resin)
The polyvinyl chloride resin is not particularly limited, and generally, a polyvinyl chloride resin used for medical use is similarly used. Therefore, a synthetic product or a commercially available product can be used as the polyvinyl chloride resin. Polyvinyl chloride resins having a polymerization degree of about 1000 to 2000 are preferably used. Examples of commercial products include polyvinyl chloride resins S-400, S1006, S1007, S1008, S1001N, S1003, S1003N, S, KS-1700, KS-2500, KS-3000 (manufactured by Kaneca Corporation, above), and the like. The method for synthesizing the polyvinyl chloride resin is not particularly limited, and examples thereof include a suspension polymerization method and the like. The polyvinyl chloride resin may be used alone or in combination of 2 or more.
(ester plasticizer)
The polyvinyl chloride resin composition according to the present application contains an ester plasticizer in an amount of 30 to 160 parts by mass, preferably 40 to 100 parts by mass, based on 100 parts by mass of the polyvinyl chloride resin. Here, if the blending amount of the ester plasticizer exceeds 160 parts by mass, it is not easy to uniformly mix the ester plasticizer, and thus, there are cases where it is difficult to manufacture a compound of the polyvinyl chloride resin composition. In contrast, if the amount of the ester plasticizer is less than 30 parts by mass, the compatibility with the polyvinyl chloride resin is lowered, and the desired flexibility is not obtained, which is not preferable.
Examples of the ester plasticizer include, but are not particularly limited to, trimellitates such as tri-2-ethylhexyl trimellitate (TOTM); citrate esters such as tributyl acetylcitrate, trihexyl acetylcitrate, and trihexyl n-butyryl citrate; phthalates such as bis (2-ethylhexyl) phthalate (DEHP) (dioctyl phthalate (DOP)), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP); adipates such as dioctyl adipate and diisononyl adipate; phosphate esters such as tricresyl phosphate. Among them, trimellitates and phthalates are preferable from the viewpoints of flexibility (particularly low-temperature flexibility), heat stability and safety, and TOTM and DEHP are more preferable.
The ester plasticizer used in the present application may be a synthetic product or a commercially available product. Examples of commercial products include J-PLUS Co., ltd. Further, as a synthetic method, for example, a method of mixing trimellitic anhydride with alcohol and esterifying the mixture is mentioned.
The above ester plasticizers may be used alone or in combination of 2 or more.
(epoxy plasticizer)
The epoxy plasticizer is blended in an amount of 5 to 25 parts by mass, preferably 7 to 15 parts by mass, relative to 100 parts by mass of the polyvinyl chloride resin. The epoxy plasticizer functions as a plasticizer and a processing aid. In addition, the epoxy plasticizer also functions as a heat stabilization aid for zinc soaps and calcium soaps (stabilizers). Here, if the blending amount of the epoxy plasticizer is too large, there is a concern that deterioration of cytotoxicity and bleeding of the epoxy plasticizer during molding may occur. On the other hand, if the amount of the epoxy plasticizer blended is too small, the desired flexibility, discoloration resistance, heat resistance may be lowered, and coloring may be caused.
Examples of the epoxy plasticizer include epoxy compounds such as epoxidized soybean oil and epoxidized linseed oil.
The epoxy plasticizer used in the present application may be a synthetic product or a commercially available product. As an example of the commercial product, for example, O-130P, O-180A manufactured by ADEKA of Kyowa Co., ltd. Further, as a synthetic method, for example, a method of directly epoxidizing an olefin is given.
The above epoxy plasticizers may be used alone or in combination of 2 or more.
(Zinc soap and calcium soap)
The polyvinyl chloride resin composition of the present application contains zinc soap and calcium soap as stabilizers in an amount of 0.01 to 0.1 parts by mass, preferably 0.03 to 0.08 parts by mass (based on the total amount of zinc soap and calcium soap) based on 100 parts by mass of the polyvinyl chloride resin. Here, if the blending amount is too large, the transparency of the polyvinyl chloride resin composition is lowered. In addition, there is a tendency that coloration of the polyvinyl chloride resin after sterilization increases. On the other hand, if the amount is too small, heat resistance and discoloration resistance may be lowered, or coloring may be caused.
The zinc soap is not particularly limited, and zinc soaps containing a lauryl group, a palmityl group, a stearyl group, or an oleyl group such as zinc laurate, zinc palmitate, zinc stearate, and zinc oleate are preferably used. Zinc soaps having the above alkyl groups are suitable for medical use from the viewpoint of safety.
The zinc soap used in the present application may be a synthetic product or a commercially available product. Examples of the commercial products include zinc stearate manufactured by Sakai Chemical Industry co. Further, as a synthetic method for synthesizing the zinc soap, for example, a method of subjecting an aqueous alkali metal salt solution of a fatty acid to a metathesis reaction with an inorganic metal salt is exemplified.
The calcium soap is not particularly limited, and calcium soaps containing a lauryl group, a palmityl group, a stearyl group, or an oleyl group such as calcium laurate, calcium palmitate, calcium stearate, and calcium oleate are preferably used in the same manner as the zinc soap. Calcium soaps having the above alkyl groups are particularly suitable for medical use from the point of view of safety.
The calcium soap used in the present application may be a synthetic product or a commercially available product. Examples of the commercial products include calcium stearate manufactured by Sakai Chemical Industry co. Further, as a synthetic method for synthesizing the calcium soap, for example, a method of subjecting an aqueous alkali metal salt solution of a fatty acid to a metathesis reaction with an inorganic metal salt is exemplified.
The zinc soap and the calcium soap may be used alone or in combination of 2 or more kinds.
The polyvinyl chloride resin composition according to the present application contains zinc soap and calcium soap. Here, the mixing ratio of the zinc soap and the calcium soap is not particularly limited, and it is preferable that the mixing ratio of the zinc soap and the calcium soap (mass ratio of zinc soap: calcium soap) is preferably 1:1 to 3, more preferably 1:1 to 2. When the mixing ratio is as described above, coloration can be intentionally reduced, and a medical molded article having higher whiteness and lower yellowness can be produced at a lower cost.
The zinc soap and the calcium soap may be blended into the polyvinyl chloride resin composition separately or may be blended into a mixture prepared by blending the zinc soap and the calcium soap in a predetermined ratio. In the latter case, the mixture may be commercially available. Examples of commercial products include stabilizers ADEKA STAB series SC-12, 593, 37, SC-308E (manufactured by ADEKA, inc., above), and the like.
(other Components)
The polyvinyl chloride resin composition forming the molded article of the application may further contain other optional components as long as the object of the application is achieved and the original properties are not particularly impaired. Examples of the optional components include metal oxides, heat resistance improvers, lubricants, pigments, surfactants, and processing aids.
Among them, the metal oxide is not particularly limited, and examples thereof include magnesium oxide, calcium oxide, zinc oxide, and the like.
The heat resistance improver is not particularly limited, and examples thereof include pentaerythritol and hydrotalcite.
The lubricant is not particularly limited, and examples thereof include silicone oil and the like.
The pigment is not particularly limited, and examples thereof include metal complex salt pigments and the like.
The surfactant is not particularly limited, and examples thereof include monoglyceride stearate (stearic acid monoglyceride).
The processing aid is not particularly limited, and examples thereof include an acrylic polymer processing aid and the like.
The blending amount of the blending agent is not particularly limited as long as the safety, heat resistance, and coloring resistance of the polyvinyl chloride resin composition are not impaired. The total amount of the compounding agents is preferably 0.1 to 0.5 parts by mass per 100 parts by mass of the polyvinyl chloride resin composition according to the present application.
The polyvinyl chloride resin composition according to the present application is not particularly limited, and can be produced by extrusion molding the polyvinyl chloride resin composition.
(extrusion molding method of molded medical article and apparatus therefor)
Next, an extrusion molding method capable of producing a medical molded article having high whiteness and low yellowness even with a small amount of stabilizer, and an extrusion molding apparatus 10 specifically implementing the extrusion molding method will be described.
The embodiments are described below with reference to the drawings. For convenience of explanation, the dimensional ratio of the drawings may be exaggerated to be different from the actual ratio.
Fig. 1 is a schematic configuration diagram showing an extrusion molding apparatus 10 for a medical molded article according to an embodiment of the present application, and fig. 2 is a cross-sectional view showing a main part of the extrusion molding apparatus 10 for a medical molded article shown in fig. 1.
Referring to fig. 1 and 2, in summary, the extrusion molding apparatus 10 of the present embodiment performs extrusion molding of the above-described composition 11 to form, for example, a tube as a medical molded article 12 having a whiteness (w.i.) of 25 or more and a yellowness (y.i.) of 3.5 or less. The extrusion molding apparatus 10 includes: an extruder 20 in which a screw 21 having a groove 22 and having a depth d equal to the depth is rotatably disposed in a cylinder 23; a feeder 30 that supplies the composition 11 formed in a solid state to the screw 21 and freely adjusts the supply amount 11 of the composition; heaters 41, 42, 43 for applying heat for melting the solid composition 11 supplied to the screw 21; and a die 50 for molding the composition 11 in a molten state extruded from the extruder 20 into the shape of the molded article 12 for medical use. The feeder 30 adjusts the amount of the composition 11 to be supplied so that the composition 11 does not generate shear heat in the extruder 20. In the extrusion molding apparatus 10 for medical molded articles, the composition 11 formed in a solid state is fed to the screw 21 of the extruder 20 having the same depth d of the groove 22 in a feeding amount adjusted so that the composition 11 does not generate shear heat in the extruder 20. Then, heat from the heaters 41, 42, and 43 is applied to the solid composition supplied to the screw 21 to melt the composition, and the composition 11 in a molten state extruded from the extruder 20 is molded into the shape of the medical molded article 12 through the die 50. The following is a detailed description.
As described above, the composition 11 contains a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and zinc soap and calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, and the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass, with respect to 100 parts by mass of the polyvinyl chloride resin. The composition 11 is formed into solid pellets. The pellets 11 (composition) were heated and dried in a not-shown dehumidification dryer. The pellets 11 are maintained at the water content specified by the resin manufacturer under the drying conditions recommended by the resin manufacturer. The pellets 11 are provided with, for exampleIs a spherical shape of (a). The shape of the pellet 11 is not limited to a spherical shape, and may be a short rod shape, for example.
The extruder 20 has: a cartridge 23 (also referred to as a cylinder); a screw 21 rotatably held in the barrel 23; and a gear train 24 and a motor 25 for rotationally driving the screw 21. The opening in the cylinder 23 is an inlet for injecting molding material. The screw 21 has a charging region C1, a conveying region C2, and a metering region C3 formed in this order from the base end side to the tip end side. The feeding region C1 of the screw 21 and the portion of the base end of the screw 21 adjacent to the inlet of the cylinder 23 constitute a feeding portion 26. When a twin-screw extruder is used, although plasticization and kneading are easy, excessive shear heat generation is applied to the composition 11, resulting in burn marks. Therefore, the extruder 20 is preferably a single-shaft extruder.
The screw 21 has a main body 21a and a screw portion 21b protruding from the outer peripheral surface of the main body 21 a. The screw portion 21b extends in a spiral shape on the outer peripheral surface of the main body portion 21 a. The main body portion 21a has a straight pipe shape with a constant outer diameter. The outer diameter of the threaded portion 21b is a constant size. Thus, the depth d of the groove 22 is formed to be the same depth for the screw 21. The gap size between the charging region C1 of the screw 21 and the inner peripheral surface of the cylinder 23, the gap size between the conveying region C2 and the inner peripheral surface of the cylinder 23, and the gap size between the metering region C3 and the inner peripheral surface of the cylinder 23 are all the same size.
The feeder 30 has: a preliminary hopper 31 for supplying the pellets 11 through a loader (not shown); a main hopper 32 connected to the inlet of the barrel 23 of the extruder 20; and a conveying section 33 for conveying the pellets 11 from the preliminary hopper 31 to the main hopper 32. The conveying section 33 includes: a barrel 35 rotatably holding the feed screw 34; and a motor 36 for rotationally driving the feed screw 34. The feed screw 34 is rotationally driven by the motor 36, so that the pellets 11 dropped and fed from the preliminary hopper 31 are conveyed and fed to the main hopper 32. For the feeder 30, the amount of the composition 11 to be supplied can be adjusted by adjusting the rotational speed of the feed screw 34.
The conveyor 33 may be configured to convey the pellets 11 by a roll, belt, vibration, air, piston, or other method, in addition to the screw type illustrated. The conveying section 33 may be a capacitive quantitative feeder, or a weight quantitative feeder. The main hopper 32 may be provided with a depressurizing means and an inert gas introducing means as appropriate.
Heaters 41, 42, 43 for applying heat for melting the pellets 11 are provided around the barrel 23. The heaters 41, 42, 43 are provided corresponding to the charging region C1, the conveying region C2, and the metering region C3 of the screw 21, respectively. The heaters 41, 42, 43 may be, for example, ribbon heaters as electric heaters for easy temperature control. A heater of a type that circulates a heating medium may also be used. In order to detect the wall temperature of the cylinder 23, the tip ends of the temperature sensors 61, 62, 63 such as thermocouples are buried in the wall of the cylinder 23. The temperature sensors 61, 62, 63 may be attached so that their tip ends are in close contact with the surface of the cylinder 23. By controlling the energization of the band heaters 41, 42, 43, the wall surface temperature of the cylinder 23 can be maintained at a set temperature. The temperature to be set varies depending on the degree of polymerization of the material contained in the composition 11, the type of plasticizer, and the amount of plasticizer added, and is, for example, 160 to 170 ℃.
Die 50 forms a passageway for the passage of composition 11 in the molten state extruded from extruder 20. The opening shape of the tip portion of the die 50 has a shape conforming to the shape of the molded medical article 12. The base end portion of the die head 50 is connected to the front end portion of the extruder 20.
The base end portion and the tip end portion of the die 50 are also provided with die heaters 44 and 45 for applying heat to the composition 11 in a molten state extruded from the extruder 20. As the heaters 41, 42, and 43 provided in the barrel 23, ribbon heaters may be used as the heaters 44 and 45 for the die head. In order to detect the wall temperature of the die 50, tip ends of temperature sensors 64 and 65 such as thermocouples are embedded in the wall of the die 50. The temperature sensors 64 and 65 may be attached so that their tip ends are in close contact with the surface of the die 50. By controlling the switching of the belt heaters 44 and 45, the wall temperature of the die 50 can be maintained at a predetermined temperature. The set temperature is, for example, 160 to 170 ℃.
The extrusion molding apparatus 10 further includes a controller 70 for controlling operations of the extruder 20 and the feeder 30. The operation of the feeder 30 is controlled by the controller 70, and the amount of the composition 11 to be supplied in a solid state can be adjusted so that the composition 11 does not generate shear heat in the extruder 20. The operation of the extruder 20 is controlled by the controller 70, and the rotation number of the screw 21 is adjusted.
In the present embodiment, the screws 21 having the same depth are formed using the depth d of the groove 22. Further, the feeder 30 can supply the composition 11 formed in a solid state in a supply amount adjusted so that the shearing heat generation of the composition 11 is not generated in the extruder 20 by adjusting the rotation speed of the feed screw 34. Therefore, retention of the composition 11 in the extruder 20 can be suppressed, and excessive shear heat generation of the composition 11 in the extruder 20 can be suppressed. Therefore, 2 main causes of burn marks in the molded article can be suppressed.
Here, "an amount of shear heat generation that does not occur in the composition 11 in the extruder 20" means: the amount of the composition 11 to be fed is determined based on the relation with the depth d of the groove 22 of the screw 21, whereby "the amount of the composition 11 that can be retained in the extruder 20 and that can be suppressed from being excessively sheared and heated in the extruder 20" can be suppressed. Therefore, even if the amount of shear heat generation slightly occurs in the composition 11, it is understood that the above-described "amount of shear heat generation slightly occurs in the composition 11" is included in "amount of shear heat generation not to cause the composition 11 to occur in the extruder 20" as long as excessive shear heat generation to cause burn marks is not generated.
From the viewpoint of suppressing excessive shear heat generation of the composition 11 in the extruder 20, it is preferable to control the amount of the composition 11 to be supplied by the feeder 30 so that the temperature of the composition 11 in the extruder 20 becomes "set temperature+5 ℃ or lower", more preferably "set temperature+2 ℃ or lower". This can reliably suppress excessive shear heat generation that causes burn marks in the molded article. The temperature of the composition 11 in the extruder 20 can be easily checked by the temperature sensors 61, 62, 63.
Next, the operation will be described.
First, the composition 11 is formed into a solid pellet 11, and the composition 11 contains a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and zinc soap and calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, and the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass, with respect to 100 parts by mass of the polyvinyl chloride resin.
By switching the heaters 41, 42, 43 and the die heaters 44, 45, the wall temperature of the cylinder 23 and the wall temperature of the die 50 are raised to the set temperatures.
The feeder 30 feeds the pellets 11 to the screw 21 of the extruder 20 having the same depth d of the groove 22. At this time, the feeder 30 can supply the pellets 11 in a supply amount adjusted so as not to generate shear heat of the composition 11 in the extruder 20 by adjusting the rotation speed of the feed screw 34.
The heat from the heaters 41, 42, 43 is applied to the pellets 11 supplied to the screw 21 to melt them. When the molten composition 11 passes through the groove 22 of the screw 21 and reaches the tip of the screw 21, the advancing force becomes weak because the guidance by the groove 22 is lost. Since the progress of the composition 11 in the molten state is suppressed, the pressure of the composition 11 in the molten state in the metering zone C3 slightly increases. However, this increase in pressure does not cause shear heating of composition 11.
Then, the composition 11 in a molten state extruded from the extruder 20 is molded into the shape of the medical molded article 12 through the die 50. In extrusion molding, the wall temperature of the cylinder 23 and the wall temperature of the die 50 can be maintained at the set temperatures by controlling the energization of the heaters 41, 42, 43 and the die heaters 44, 45.
As described above, according to the extrusion molding technique of the medical molded article of the present embodiment, the screw 21 having the same depth d of the groove 22 is used, and the composition 11 formed in the solid state is further fed in a feeding amount adjusted so as not to generate shear heat in the extruder 20. Therefore, retention of the composition 11 in the extruder 20 can be suppressed, and excessive shear heat generation of the composition 11 in the extruder 20 can be suppressed. Since 2 main causes of burn marks in the molded article can be suppressed, the medical molded article 12 having a low coloring degree (high whiteness and low yellowness) can be produced at low cost even when a small amount of metal soap is used.
The temperature of the composition 11 in the extruder 20 was set to "set temperature+5℃. By configuring as described above, excessive shear heat generation that causes burn marks in the molded article can be reliably suppressed, and the medical molded article 12 having a low coloring degree (high whiteness and low yellowness) can be manufactured at low cost even when a small amount of metal soap is used.
The extrusion molding apparatus 10 for molding a tube as the medical molded article 12 is described, but the present application is not limited to the above. The extrusion molding apparatus 10 can be suitably modified for molding into medical molded articles for various purposes such as bags for transfusion and blood transfusion, and tubes connected to these bags.
Examples
The effects of the present application will be described with reference to the following examples and comparative examples. However, the technical scope of the present application is not limited to the following examples. In the following examples, unless otherwise specified, the operation was performed at room temperature (25 ℃). Unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.
Example 1
A polyvinyl chloride resin composition was prepared by mixing 100kg of a polyvinyl chloride resin (manufactured by Kaneca Corporation, KS-1700, average polymerization degree: 1700), 52kg of bis (2-ethylhexyl) phthalate (DEHP) as an ester plasticizer, 8kg of epoxidized soybean oil (manufactured by ADEKA, O-130P) as an epoxy plasticizer, 0.07kg of a Ca-Zn-based stabilizer (manufactured by ADEKA, kyowa, trade name: ADEKA STAB 37, calcium stearate content: about 7.57 mass% and zinc stearate content: about 10.1 mass%), and 0.15kg of silicone oil (believed chemical trade name: KF-50). The polyvinyl chloride resin composition contained calcium stearate and zinc stearate in amounts of 0.0053kg and 0.0077 kg, respectively.
Next, the polyvinyl chloride resin composition was formed into pellets, and the pellets were extrusion molded to obtain a molded article for medical use having an inner diameter by using the extrusion molding apparatus for the molded article for medical useThe outer diameter is-> Is provided. The pellets used haveThe amount of the feed was set to 4 kg/hr. The inner diameter of the barrel of the extruder is +.>The rotational speed of the screw was set at 50rpm. In the extrusion molding apparatus, pellets are fed to the screw of the extruder having a groove depth of the same depth in a feed amount adjusted so that the composition does not generate shear heat in the extruder. Then, heat from a heater is applied to the pellets supplied to the screw to melt them, and the composition in a molten state extruded from the extruder is molded into a tube shape through a die. The heater 41 was set to 160℃and the heaters 42 to 45 were set to 170 ℃.
Whiteness and yellowness were measured for the resulting tubes, and the results were 25.8 and 2.5, respectively. From the above results, it was found that the tube of the present example exhibited high whiteness and low yellowness even in the case where the amount of the stabilizer (zinc soap and calcium soap) was small.
Example 2
In example 1, a tube was produced in the same manner as in example 1 except that the amount of Ca-Zn based stabilizer (product name: ADEKA STAB 37, manufactured by Kyowa Co., ltd.) was changed to 0.21 kg.
Whiteness and yellowness were measured for the resulting tubes, and the results were 28.4 and 1.1, respectively. From the above results, it was found that the tube of the present example exhibited high whiteness and low yellowness even in the case where the amount of the stabilizer (zinc soap and calcium soap) was small.
Example 3
In example 1, a tube was produced in the same manner as in example 1 except that the amount of Ca-Zn based stabilizer (product name: ADEKA STAB 37, manufactured by Kyowa Co., ltd.) was changed to 0.35 kg.
Whiteness and yellowness were measured for the resulting tubes, and the results were 28.0 and 1.2, respectively. From the above results, it was found that the tube of the present example exhibited high whiteness and low yellowness even in the case where the amount of the stabilizer (zinc soap and calcium soap) was small.
Example 4
In example 1, a tube was produced in the same manner as in example 1 except that the amount of Ca-Zn based stabilizer (product name: ADEKA STAB 37, manufactured by Kyowa Co., ltd.) was changed to 0.70 kg.
Whiteness and yellowness were measured for the obtained tube, and the results were 27.6 and 0.8, respectively. From the above results, it was found that the tube of the present example exhibited high whiteness and low yellowness even in the case where the amount of the stabilizer (zinc soap and calcium soap) was small.
The present application is based on japanese patent application No. 2015-064449 filed on 3 months 26 of 2015, the disclosure of which is incorporated herein by reference in its entirety.
Description of the reference numerals
10. Extrusion molding device for medical molded article
11. Granules (composition)
12. Pipe (medical molded product)
20. Extrusion machine
21. Screw rod
22. Groove(s)
23. Charging barrel
30. Feeding machine
34. Feeding screw
41. 42, 43 heater
44. Heater for 45 die head
50. Die head
61. 62, 63 temperature sensor
64. 65 temperature sensor
70. Controller for controlling a power supply
C1 Charging area
C2 Delivery area
C3 Metering zone
Depth of D groove
Claims (8)
1. A medical molded article obtained by extrusion molding of a composition,
the composition comprises a polyvinyl chloride resin, an ester plasticizer, an epoxy plasticizer, and zinc soap and calcium soap, wherein the content of the ester plasticizer is 30 to 160 parts by mass, the content of the epoxy plasticizer is 5 to 25 parts by mass, the total content of the zinc soap and the calcium soap is 0.01 to 0.1 part by mass relative to 100 parts by mass of the polyvinyl chloride resin,
the whiteness (W.I.) of the molded article for medical use is 25 or more, and the yellowness (Y.I.) is 3.5 or less,
the medical molded article is obtained by the extrusion molding method,
supplying the composition formed in a solid state to a screw of an extruder having a groove depth formed to be the same depth in a supply amount adjusted so as not to generate shearing heat of the composition in the extruder,
heat from a heater is applied to the solid-state composition supplied to the screw to melt it,
the composition in a molten state extruded from the extruder is molded into the shape of a molded article for medical use through a die.
2. The molded article for medical use according to claim 1, wherein the temperature of the composition in the extruder is "set temperature +5℃.
3. The extrusion molding method of a medical molded article according to claim 1, wherein the medical molded article is a bag for transfusion, a bag for blood transfusion, or a tube.
4. An extrusion molding apparatus for a medical molded article, which is obtained by extrusion molding a composition according to claim 1 to form a medical molded article having a whiteness (w.i.) of 25 or more and a yellowness (y.i.) of 3.5 or less, comprising:
an extruder in which screws having grooves formed to the same depth are rotatably disposed in a barrel;
a feeder that supplies the composition formed in a solid state to the screw and freely adjusts a supply amount of the composition;
a heater that applies heat that melts the solid composition supplied to the screw;
a die for molding the composition in a molten state extruded from the extruder into a shape of a molded article for medical use,
the feeder adjusts the amount of the composition supplied to an amount that does not cause the composition to generate shear heat in the extruder.
5. The extrusion molding apparatus for a molded medical article according to claim 4, wherein the temperature of the composition in the extruder is "set temperature +5℃.
6. The extrusion molding apparatus for a molded medical article according to claim 4 or 5, further comprising a heater for a die that applies heat to the composition in a molten state extruded from the extruder.
7. The extrusion molding apparatus for a medical molded article according to claim 4 or 5, wherein the medical molded article is a bag for infusion, a bag for blood transfusion, or a tube.
8. The extrusion molding apparatus for a medical molded article according to claim 6, wherein the medical molded article is a bag for transfusion, a bag for blood transfusion, or a tube.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015064449 | 2015-03-26 | ||
| JP2015-064449 | 2015-03-26 | ||
| PCT/JP2016/056880 WO2016152466A1 (en) | 2015-03-26 | 2016-03-04 | Molded article for medical use, extrusion molding method for molded article for medical use, and extrusion molding device for molded article for medical use |
Publications (2)
| Publication Number | Publication Date |
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| CN107428957A CN107428957A (en) | 2017-12-01 |
| CN107428957B true CN107428957B (en) | 2023-09-22 |
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| CN201680018228.0A Active CN107428957B (en) | 2015-03-26 | 2016-03-04 | Medical molded article, extrusion molding method for medical molded article, and extrusion molding device for medical molded article |
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| Country | Link |
|---|---|
| JP (1) | JP6788575B2 (en) |
| CN (1) | CN107428957B (en) |
| WO (1) | WO2016152466A1 (en) |
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| CN112759858B (en) * | 2020-12-24 | 2022-12-06 | 金发科技股份有限公司 | Injection molding grade modified PVC material and preparation method and application thereof |
| TWI762383B (en) * | 2021-07-14 | 2022-04-21 | 臺灣塑膠工業股份有限公司 | Anti-biofouling material, human body tissue-contacting medical tube containing the same and manufacturing method of the same |
| CN113881161B (en) * | 2021-10-20 | 2022-09-23 | 台湾塑胶工业股份有限公司 | Anti-sticking material, medical catheter contacting human tissue containing same and manufacturing method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016152466A1 (en) | 2018-01-18 |
| WO2016152466A1 (en) | 2016-09-29 |
| JP6788575B2 (en) | 2020-11-25 |
| CN107428957A (en) | 2017-12-01 |
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