JP5122878B2 - Cylinder member for chemical inflow / outflow and chemical container - Google Patents

Description

The present invention includes a drug solution outflow needful tubular member having a gas gas barrier properties, and to a drug solution container with the drug solution outflow needful tubular member.

  Solutions that are prone to alteration due to volatilization of carbon dioxide such as fat emulsions, amino acid-containing liquids, antibiotic-containing liquids, vitamins-containing liquids that are easily oxidized, bicarbonate Ringer's solution, artificial cerebrospinal fluid, and eye perfusate It must be stored in a container in which gas permeation is suppressed. Conventionally, polyolefins such as polyethylene and polypropylene are frequently used for chemical liquid containers and cylindrical members used for inflow and outflow of chemical liquids from chemical liquid containers from the viewpoint of chemical stability and pharmaceutical safety. Has the feature of being easily permeable to gases such as oxygen and carbon dioxide. For example, plastics with low gas permeability, such as ethylene-vinyl alcohol copolymer, polyamide, polyvinyl chloride, and polyvinyl acetate, so-called gas barrier plastics, generally establish stability against chemicals and pharmaceutical safety. It has not been.

Therefore, in recent years, the chemical liquid inflow / outflow cylindrical member and chemical liquid container are made of polyolefin, and are formed on the inner surface layer in direct contact with the chemical liquid, and on the outer surface side of the inner surface layer, and are made of a gas barrier plastic. (Gas barrier layer) is considered to be used.
Patent Document 1 discloses a hollow cylindrical plug attached to an opening portion of a container body, in which an outermost layer and an intermediate layer in the cylindrical portion of the cylindrical plug are formed of a gas barrier material. Is described. Further, in this document, as a method of manufacturing the above-described cylindrical plug body, a cylinder made of a material having a gas barrier property is previously mounted in an injection mold, and this film is attached to the inner periphery or outer periphery. A method is described in which a member is formed and then the tubular separate member is welded to the inner periphery or the outer periphery of the tubular portion of the tubular plug.

Patent Document 2 describes a container pouring member that has a barrier resin intermediate layer and has a folded portion on the barrier resin intermediate layer on at least one end side. In addition, the same document describes a method for producing the container extraction member, in which a folded portion is provided at the end of the barrier resin intermediate layer and then the folded portion is covered with an inner and outer resin layer.
Patent Document 3 describes a container pouring member having at least a pouring part and a seal part. In the same document, the pouring part has a multilayer structure having a barrier resin layer, and the pouring part and It is described that the seal portion is integrated after being separately molded.
JP-A-11-29159 JP 2002-255200 A JP 2003-291990 A

  However, gas barrier plastics are generally materials that have poor compatibility with polyolefins and poor adhesion. Therefore, when the chemical solution inflow / outflow cylindrical member and the chemical solution container are both laminated bodies of the inner surface layer made of polyolefin and the outer surface layer made of gas barrier plastic, the inner side of the chemical solution inflow / inflow cylinder member The adhesive strength between the surface layer and the outer surface layer of the chemical solution container may be insufficient. For example, there may be a problem that the chemical solution inflow / outflow cylindrical member falls out from the opening of the chemical solution container during use.

  Further, it is required to manufacture the chemical solution inflow / outflow cylindrical member and the chemical solution container by a simple method suitable for mass production. However, in the plug body described in Patent Document 1, it is necessary to mount a gas barrier film in an injection mold in advance when the plug body is formed. In the container pouring member described in Patent Document 2, the formation is performed. Sometimes, it is necessary to form a folded portion at the end of the cylindrical barrier resin intermediate layer. In the container pouring member described in Patent Document 3, the pouring portion and the seal portion that are separately formed In both cases, the manufacturing process becomes complicated.

An object of the present invention includes a drug solution outflow needful tube member that can be manufactured by a simple process using the resin composition used for forming the gas barrier layer in the drug solution outflow needful tubular member or drug container, the drug solution And a chemical container including an inflow / outflow cylinder member.

In order to achieve the above object , the first gas barrier resin composition includes a polyamide resin, an ethylene-vinyl alcohol copolymer, and an adhesive polyolefin, and the polyamide resin and the ethylene-vinyl alcohol copolymer. The content of the polyamide-based resin is 10 to 55% by weight and the content of the ethylene-vinyl alcohol copolymer is 35 to 85% by weight, based on the total amount of the polymer and the adhesive polyolefin, and the adhesive polyolefin The content ratio is 5 to 45% by weight.

The second gas barrier resin composition contains a semi-aromatic polyamide and an adhesive polyolefin, and the content ratio of the semi-aromatic polyamide is 55 to 95 with respect to the total amount of the semi-aromatic polyamide and the adhesive polyolefin. The content ratio of the adhesive polyolefin is 5 to 45% by weight.
According to the first and second gas barrier resin compositions, a thermoplastic resin (for example, polyolefin) that has low gas permeability (that is, excellent gas barrier properties) and is allowed to contact with a chemical solution, It is possible to form a resin molded body having good adhesion.

  The cylindrical member for inflow / outflow of the chemical liquid according to the present invention is a cylindrical member for flowing in / out the chemical liquid attached to the container main body of the chemical liquid container whose inner surface is made of a thermoplastic resin that is allowed to contact with the chemical liquid. A thermoplastic resin comprising a joint part joined to the container body and an exposed part exposed from the container body, wherein the joint part and the exposed part are allowed to contact the chemical solution. An inner peripheral surface layer that is in contact with the chemical solution flowing in and out, and at least the exposed portion is further formed of the first or second gas barrier resin composition, and the outer peripheral surface layer is disposed outside the inner peripheral surface layer. It is characterized by having a gas barrier layer covering from the side.

  According to the cylindrical member for inflow / outflow of the chemical liquid, since the joint portion and the exposed portion include the inner peripheral surface layer formed from a material that is pharmaceutically allowed to contact the chemical liquid, In addition, at least the exposed portion is provided with a gas barrier layer formed of the first or second gas barrier resin composition, so that excellent gas barrier properties can be obtained. Can be obtained. In addition, the chemical solution inflow / outflow cylindrical member substantially has a simple layer structure including two layers of an inner peripheral surface layer and a gas barrier layer, and further, the inner peripheral surface layer and the gas barrier layer include: Both are made of thermoplastic resin. For this reason, the said chemical | medical solution inflow / outflow cylinder member can be manufactured by a simple process by injection molding.

  Moreover, both the first and second gas barrier resin compositions of the present invention forming the gas barrier layer have good adhesion to a thermoplastic resin (for example, polyolefin) that is allowed to contact with a chemical solution. It is. For this reason, the said chemical | medical solution inflow / outflow cylinder member has favorable adhesiveness of an inner peripheral surface layer and a gas barrier layer. In addition, the chemical solution inflow / outflow cylindrical member includes a portion where the gas barrier layer is not covered on the outer side of the inner peripheral surface layer, that is, a portion where the inner peripheral surface layer appears on the outer surface of the bonded portion. ing. For this reason, the joining part of this chemical | medical solution inflow / outflow cylinder member has very good joining property with the inner surface of the container body.

The chemical liquid container of the present invention includes a container main body of a chemical liquid container whose inner surface is formed of a thermoplastic resin that is allowed to contact the chemical liquid, and the chemical liquid that is attached to the container main body and allows the chemical liquid to flow in and out. And an inflow / outflow cylinder member.
According to the chemical liquid container, since the chemical liquid inflow / outflow cylindrical member of the present invention is provided, leakage or intrusion of gas from the chemical liquid inflow / outflow cylindrical member can be suppressed. Further, according to the chemical container, the inner surface of the container body is formed of a thermoplastic resin that is allowed to contact with the chemical liquid, and the chemical liquid is in contact with the chemical liquid at the joint portion of the cylindrical member for inflow and outflow. Since the inner peripheral surface layer formed of the permitted thermoplastic resin appears on the outer surface thereof, the adhesiveness with the chemical solution inflow / outflow cylindrical member is good.

According to the gas barrier resin composition, it is possible to obtain an excellent resin molded gas barrier properties. Therefore, for example, in a chemical solution inflow / outflow cylindrical member or chemical solution container, it is used as a material for forming a gas barrier layer that covers an inner peripheral surface layer formed of a thermoplastic resin that is allowed to come into contact with the chemical solution from the outside. Thus, gas barrier properties can be imparted to the chemical solution inflow / outflow cylindrical member and the chemical solution container.

  Further, according to the chemical liquid inflow / outflow cylindrical member of the present invention and the chemical liquid container provided with the chemical liquid inflow / outflow cylindrical member, safety of the chemical liquid inflow / inflow cylindrical member with respect to contact with the chemical liquid, gas barrier properties, and It is possible to produce a chemical container with a simple method, in which delamination in the cylindrical member for chemical inflow / outflow is suppressed, and the adhesiveness with the cylindrical member for chemical inflow / outflow is good. .

The first gas barrier resin composition contains a polyamide-based resin, an ethylene-vinyl alcohol copolymer, and an adhesive polyolefin.
Examples of the polyamide-based resin include aliphatic polyamides and semi-aromatic polyamides.
Examples of the aliphatic polyamide include nylon-6 (PA6; polycaprolactam), nylon-7 (PA7; poly (7-aminoheptanoic acid)), nylon-9 (PA9; poly (9-aminononanoic acid) ), Nylon-10 (PA 10; poly (10-aminodecanoic acid)), nylon-11 (PA 11; poly (11-aminoundecanoic acid)), nylon-12 (PA 12; polylaurolactam), etc. A polycondensate of amino acids,
For example, nylon-2,6 (PA 26; polyethylene adipamide), nylon-4,6 (PA 46; poly (tetramethylene adipamide)), nylon-6,6 (PA 66; poly (hexamethylene azamide) Poamide)), nylon-6,10 (PA 610; poly (hexamethylene sebacamide)), nylon-6,12 (PA 612; poly (hexamethylene dodecandiamide)), nylon-8,6 (PA 86 Poly (octamethylene adipamide)), nylon-8,10 (PA 810; poly (octamethylene sebamide)), nylon-8,12 (PA 812; poly (octamethylene dodecandiamide)), nylon- 10,6 (PA 106; poly (decamethylene adipamide)), nylon-10,8 (PA 108; poly (deca Methyleneoctanediamide)), nylon-10,10 (PA 1010; poly (decamethylenesebacamide)), nylon-12,12 (PA1212; poly (dodecamethylenedodecandiamide)) and other aliphatic diamines and aliphatic Co-condensation polymer with dicarboxylic acid,
For example, nylon-6 / 12 (caprolactam-laurylactam copolymer), nylon-6 / 9 (caprolactam-9-aminononanoic acid copolymer), nylon-6 / 6,6 (caprolactam-hexamethylenediammonium adipate) Copolymer, nylon-12 / 6,6 (laurolactam-hexamethylenediammonium adipate copolymer, nylon-6 / 6,10 (caprolactam-hexamethylenediammonium sebacate copolymer, nylon-2,6 / 6,6 (ethylenediammonium adipate-hexamethylenediammonium adipate copolymer, nylon-6,6 / 6,10 (copolymers such as hexamethylenediammonium adipate-hexamethylenediammonium sebacate copolymer,
Etc. These aliphatic polyamides are used alone or in admixture of two or more.

Examples of the semi-aromatic polyamide include nylon-6T (PA 6T; poly (hexamethylene terephthalamide)), nylon-6I (PA 6I; poly (hexamethylene isophthalamide)), nylon-9T (PA 9T; poly ( Nonamethylene terephthalamide)), nylon-M5T (PAM5T; poly (2-methylpentamethylene) terephthalamide), poly (2,2,4-trimethylhexamethylene terephthalamide), poly (2,4,4-trimethyl) Aliphatic diamines such as hexamethylene terephthalamide), poly (octamethylene terephthalamide), poly (decamethylene terephthalamide), poly (dodecamethylenediamine terephthalamide), poly (bis (4-aminocyclohexyl) methylene terephthalamide) Or fat Polymers from cyclic diamines and aromatic dicarboxylic acids,
For example, nylon-MXD6 (PA MXD6; poly (metaxylylene adipamide)), poly (metaxylylene sebamide), poly (paraxylylene adipamide), poly (paraxylylene sebacamide), etc. A polymer from an aromatic diamine and an aliphatic dicarboxylic acid,
For example, a copolymer such as nylon 6I / 6T (hexamethylene isophthalamide-hexamethylene terephthalamide copolymer),
Etc. These semi-aromatic polyamides are used alone or in admixture of two or more.

In addition, the polyamide-based resin is preferably aliphatic polyamide among the above, and nylon-6 is particularly preferable.
Examples of the ethylene-vinyl alcohol copolymer (EVOH) include a saponified product of an ethylene-vinyl ester copolymer. The ethylene copolymerization ratio of EVOH is preferably 10 to 55 mol%, more preferably 25 to 45 mol%, and particularly preferably 25 to 35 mol%. When the ethylene copolymerization ratio of EVOH is below the above range, for example, the water resistance at the time of steam sterilization may be lowered for a resin molded body obtained from the first gas barrier resin composition. Conversely, if the ethylene copolymerization ratio of EVOH exceeds the above range, the gas permeability (particularly, oxygen permeability) of the resin molded product obtained from the first gas barrier resin composition cannot be sufficiently reduced. There is a fear. The degree of saponification of the vinyl ester component of EVOH is not particularly limited, but is preferably 85% or more, and more preferably 90% or more. If the saponification degree is below the above range, the gas permeability (particularly oxygen permeability) of the resin molded product obtained from the first gas barrier resin composition may not be sufficiently lowered.

  Examples of the vinyl ester component of EVOH include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, and vinyl pivalate. EVOH may contain a vinylsilane compound as a copolymerization component. In this case, the content ratio of the vinylsilane compound is preferably 0.0002 to 0.2 mol% of the entire EVOH. Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, γ-methacryloxypropylmethoxysilane, and particularly preferably vinyltrimethoxysilane, vinyl. A triethoxysilane is mentioned. Furthermore, as other copolymerization components of EVOH, for example, alkylene such as propylene and butylene, for example, unsaturated carboxylic acid such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, or the like Esters include comonomers such as vinyl pyrrolidone such as N-vinyl pyrrolidone. The content ratio of these comonomers can be appropriately set within a range not impairing the object of the present invention.

  EVOH can be blended with a boron compound as long as the object of the present invention is not obstructed. Examples of the boron compound include boric acids, boric acid esters, borates, borohydrides, and the like. Specifically, examples of boric acids include orthoboric acid, metaboric acid, and tetraboric acid. Examples of boric acid esters include triethyl borate and trimethyl borate. Examples thereof include alkali metal salts, alkaline earth metal salts, and borax of the various boric acids described above. Of these, orthoboric acid is particularly preferable. When a boron compound is blended with EVOH, the content of the boron compound is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. By setting the content of the boron compound in the above range, EVOH in which torque fluctuation during heat melting is suppressed can be obtained. Further, when the content of the boron compound is below the above range, the effect of suppressing torque fluctuation is reduced, and when it exceeds the above range, EVOH may gel and cause poor moldability.

  In addition, EVOH should be blended with an alkali metal salt from the viewpoint of improving compatibility with other resins and improving the weldability between the resin molded body obtained from the first gas barrier resin and the other resin molded bodies. Can do. In this case, the content of the alkali metal salt is preferably 5 to 5000 ppm, more preferably 20 to 1000 ppm, and particularly preferably 30 to 500 ppm in terms of alkali metal elements. Examples of the alkali metal include lithium, sodium, potassium, and the like, and examples of the alkali metal salt include the above-mentioned alkali metal aliphatic carboxylates, aromatic carboxylates, phosphates, metal complexes, and the like. Specific examples of the alkali metal salt include sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, and the like. Of these, sodium acetate, potassium acetate, and sodium phosphate are preferable.

  In addition, a phosphorus compound can be blended with EVOH as long as the object of the present invention is not obstructed. In this case, the content ratio of the phosphorus compound is preferably 2 to 200 ppm, more preferably 3 to 150 ppm, and particularly preferably 5 to 100 ppm in terms of phosphorus element. By setting the content ratio of the phosphorus compound within the above range, the thermal stability of EVOH can be improved. Moreover, when the content rate of a phosphorus compound remove | deviates from the said range, the effect which improves thermal stability will become small. Examples of the phosphorus compound include various acids such as phosphoric acid and phosphorous acid, and salts thereof, and the phosphate includes a primary phosphate, a secondary phosphate, and a tertiary phosphoric acid. Any of salt may be sufficient. The phosphate is preferably, for example, an alkali metal salt or an alkaline earth metal salt, more preferably sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, phosphoric acid. Examples include dipotassium hydrogen.

The melt flow rate (MFR) of EVOH is preferably 0.1 to 50 g / 10 minutes, more preferably 0.3 to 40 g / 10 minutes, particularly preferably under the conditions of a temperature of 190 ° C. and a load of 2160 g. Is 0.5-30 g / 10 min. In addition, MFR about EVOH when melting | fusing point is around 190 degreeC or exceeds 190 degreeC measured MFR at several temperature more than melting | fusing point on the conditions of load 2160g, this horizontal axis | shaft Is a value obtained by plotting the reciprocal of absolute temperature and the vertical axis as the logarithm of MFR and extrapolating to 190 ° C. These EVOH resins can be used alone or in combination of two or more types. Specific examples of EVOH are not limited to these, but for example, trade names “Kuraray Co., Ltd.” Eval (registered trademark) ”.

  Examples of the adhesive polyolefin include a modified polyolefin having a functional group introduced into the polyolefin by a graft reaction or the like, or a saponified product thereof. Examples of the functional group include carboxylic acid, carboxylate, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide, carboxylic acid imide, carboxylic acid halide, ethylenically unsaturated monomer (carbonyl group, cyano group, And those having a functional group such as a hydroxyl group and an ether group). These functional groups are used alone or in combination of two or more.

  Examples of the carboxylic acid include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, and tetrahydrophthalate. And ethylenically unsaturated carboxylic acids such as acid, methyltetrahydrophthalic acid, endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (trade name "Nadic acid (trademark)") Preferably, maleic acid is used. Examples of the carboxylic acid anhydride include ethylenically unsaturated carboxylic anhydrides such as maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and tetrahydrophthalic anhydride. Examples of the ethylenically unsaturated monomer include ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, mono- or diethyl maleate, vinyl acetate, vinyl propionate, γ-hydroxypropyl methacrylate, and β-hydroxyacrylic. Ethylenically unsaturated esters such as ethyl acid, glycidyl acrylate, glycidyl methacrylate, β-N-ethylaminoethyl acrylate, for example ethylenically unsaturated amides or imides such as acrylamide, methacrylamide, maleimide, such as acrolein, methacrolein, Examples include ethyne unsaturated aldehydes or ketones such as vinyl methyl ketone and vinyl butyl ketone.

  A known method is used for graft modification of polyolefins. For example, polyolefins are dissolved in an organic solvent, and then, for example, an unsaturated carboxylic acid or a derivative thereof, a radical initiator, and the like are added to the obtained solution, and usually 60 to 350 ° C., preferably 80 to The polyolefin is graft-modified by reacting at 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours. The organic solvent is not particularly limited as long as it can dissolve polyolefins, for example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, etc., for example, an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, etc. , Etc. In addition, as another method of graft modification of polyolefins, a method of reacting polyolefins with, for example, an unsaturated carboxylic acid or a derivative thereof without solvent in an extruder or the like can be mentioned. As reaction conditions in this case, the reaction temperature is equal to or higher than the melting point of ordinary polyolefins, specifically, 100 to 350 ° C., and the reaction time is usually 0.5 to 10 minutes.

  For graft modification of polyolefins, it is preferable to react in the presence of a radical initiator in order to efficiently graft copolymerize a graft monomer such as an unsaturated carboxylic acid or a derivative thereof. Examples of the radical initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3,1,4- Bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5- Di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpivalate, cumylperpivalate , T-butyl perdiethyl acetate, etc. Compound or organic peresters, for example, azobisisobutyronitrile, azo compounds such as dimethyl azoisobutyrate, and the like. Among them, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butyl) Dialkyl peroxides such as peroxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred. The radical initiator is usually used at a ratio of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyolefins before modification.

The graft modification rate in the unsaturated carboxylic acid or derivative thereof is preferably 0.05 to 10% by weight, and more preferably 0.05 to 5% by weight.
Further, the melt flow rate (MFR) of the adhesive polyolefin is preferably 0.1 to 70 g / 10 minutes, more preferably 0.5 to 40 g / 10, under the conditions of a temperature of 190 ° C. and a load of 2160 g. Minute, particularly preferably 0.5 to 20 g / 10 minutes. If the MFR is below the above range, the moldability of the resin molded product obtained from the first gas barrier resin composition may be reduced. On the other hand, if the MFR exceeds the above range, the impact strength of the resin molded product obtained from the first gas barrier resin composition may be reduced.

Examples of the polyolefin in the adhesive polyolefin include high-density, medium-density or low-density polyethylene, ethylene-α / olefin copolymer, polypropylene, polybutene, polyisobutylene, polybutadiene, polyisoprene, and ionomer resin.
Among the above, the adhesive polyolefin is preferably unsaturated carboxylic acid-modified polyethylene or unsaturated carboxylic acid-modified polypropylene, and more preferably maleic acid-modified polyethylene or maleic acid-modified polypropylene.

Specific examples of the unsaturated carboxylic acid-modified polyethylene or the unsaturated carboxylic acid-modified polypropylene include, but are not limited to, for example, trade name “Admer (registered trademark)” manufactured by Mitsui Chemicals.
The polyamide-based resin is a component that greatly contributes to the suppression of rough skin and cracks of the resin molded body formed of the first gas barrier resin composition, and has a relatively high gas barrier property. EVOH is a component having extremely high gas barrier properties, and adhesive polyolefin has excellent weldability, although gas barrier properties are relatively low. For this reason, by mixing these three components, excellent gas barrier properties can be imparted to the resin molded body formed of the gas barrier resin composition. For example, a chemical liquid inflow / outflow cylindrical member or chemical liquid container This is suitable as a material for forming a gas barrier layer.

  The content ratio of each component of the polyamide resin, EVOH, and adhesive polyolefin is 10 to 55% by weight, preferably 10 to 50% by weight of the polyamide resin, based on the total amount of the polyamide resin, EVOH, and adhesive polyolefin. Wt%, particularly preferably 10 to 40 wt%, EVOH is 35 to 85 wt%, preferably 40 to 80 wt%, particularly preferably 50 to 70 wt%, and the adhesive polyolefin is It is 5-45 wt%, preferably 10-40 wt%, preferably 10-30 wt%. In addition, the sum of the content rate of a polyamide-type resin and the content rate of an ethylene-vinyl alcohol copolymer is 60 to 95 weight%.

  When the content ratio of the polyamide-based resin with respect to the total amount of each component is less than the above range, the EVOH content ratio in the first gas barrier resin composition increases, and therefore the resin formed by the first gas barrier resin composition Cracks and rough skin are likely to occur in the molded body. On the contrary, when the content ratio of the polyamide-based resin with respect to the total amount of each component exceeds the above range, the EVOH content ratio in the first gas barrier resin composition decreases, and therefore the first gas barrier resin composition The gas barrier property of the resin molding to be formed is lowered.

  When the content ratio of EVOH with respect to the total amount of each component is less than the above range, the gas barrier property of the resin molded body formed of the first gas barrier resin composition is lowered. On the contrary, when the EVOH content ratio with respect to the total amount of the respective components exceeds the above range, the polyamide resin content ratio in the first gas barrier resin composition becomes relatively small, and the first gas barrier resin composition Problems such as cracks and rough skin occur in a resin molded body formed of an object.

  When the content of the adhesive polyolefin with respect to the total amount of each component is less than the above range, a thermoplastic resin that is allowed to contact the resin molded body formed of the first gas barrier resin composition and the chemical (for example, Adhesiveness with polyolefin etc.) decreases. Conversely, when the content ratio of the adhesive polyolefin with respect to the total amount of each component exceeds the above range, the content ratio of EVOH in the first gas barrier resin composition becomes relatively small, and the first gas barrier resin composition The gas barrier property of the resin molded body formed of a product is lowered.

The first gas barrier resin composition may further contain other components in addition to the polyamide-based resin, EVOH, and adhesive polyolefin as long as the effects of the present invention are not impaired. Examples of other components include an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, and a filler.
Examples of the filler include mica, sericite, talc, glass flake, glass fiber, ballastite, calcium silicate, aluminum silicate, calcium carbonate, and the like. Among these, the first gas barrier resin composition is used. From the viewpoint of further improving the gas barrier properties of the resin molded product, mica, sericite, talc, and glass flakes are preferable.

  In the first gas barrier resin composition, among the fillers, at least one filler selected from the group consisting of mica, sericite, talc, and glass flakes is blended, and the content ratio of these fillers is set to When the content is 30% by weight or less based on the entire gas barrier resin composition, the gas barrier property of the resin molded body made of the first gas barrier resin composition is further increased. In this case, the content of the filler in the first gas barrier resin composition is preferably 30% by weight or less, more preferably 5 to 30% by weight, and a polyamide-based resin, EVOH, The content ratio of the mixture with the adhesive polyolefin is 70% by weight or more, and more preferably 70 to 95% by weight.

  The first gas barrier resin composition is, for example, a polyamide-based resin, EVOH, and an adhesive polyolefin, blended in the above range, and further blended with the above-mentioned other components as necessary, and known melt-kneading. It can be prepared by melting and kneading with an apparatus. Further, the melt-kneaded material may be pelletized and dried, for example. For melt kneading of each component, for example, a single-screw or twin-screw extruder is used. However, the uniformity of mixing of each component is improved, the generation of gel in the resin molded body, and the accompanying blistering. From the viewpoint of suppressing the formation of the above, it is preferable to use an extruder having a high kneading degree as much as possible, seal the hopper with an inert gas (for example, nitrogen gas) and extrude at a low temperature.

The second gas barrier resin composition contains a semi-aromatic polyamide and an adhesive polyolefin.
Examples of the semi-aromatic polyamide include the same semi-aromatic polyamide used in the first gas barrier resin composition. The said semi-aromatic polyamide is used individually or in mixture of 2 or more types. Among the above, the semiaromatic polyamide is preferably a homopolymer from an aromatic diamine and an aliphatic dicarboxylic acid, and particularly preferably nylon MXD6.

  Examples of the adhesive polyolefin include the same adhesive polyolefin as that used in the first gas barrier resin composition. Moreover, the said adhesive polyolefin is used individually or in mixture of 2 or more types. Among the above, the adhesive polyolefin is preferably unsaturated carboxylic acid-modified polyethylene or unsaturated carboxylic acid-modified polypropylene, and particularly preferably maleic acid-modified polyethylene or maleic acid-modified polypropylene. Specific examples of the unsaturated carboxylic acid-modified polyethylene or the unsaturated carboxylic acid-modified polypropylene include, but are not limited to, for example, trade name “Admer (registered trademark)” manufactured by Mitsui Chemicals.

  The semi-aromatic polyamide is a component that greatly contributes to the gas barrier properties of the resin molded body formed of the second gas barrier resin composition, and has the effect of suppressing rough skin and cracks on the resin molded body. It is relatively good. Adhesive polyolefin has excellent weldability, although it has a relatively low gas barrier property. For this reason, by mixing these two components, it is possible to impart excellent gas barrier properties to the resin molded body formed of the gas barrier resin composition, for example, a chemical liquid inflow / outflow cylindrical member or chemical liquid container This is suitable as a material for forming a gas barrier layer.

The content ratio of the semi-aromatic polyamide and the adhesive polyolefin is 65 to 95% by weight, preferably 70 to 90% by weight, based on the total amount of the semi-aromatic polyamide and the adhesive polyolefin. The content of the adhesive polyolefin is 5 to 35% by weight, preferably 10 to 30% by weight.
When the content ratio of the semi-aromatic polyamide is less than the above range, the gas barrier property of the resin molded body formed of the second gas barrier resin composition is lowered, and rough skin and cracks are likely to occur in the resin molded body. Conversely, if the content ratio of the semi-aromatic polyamide exceeds the above range, a thermoplastic resin that is allowed to contact the resin molded body formed of the second gas barrier resin composition and the chemical (for example, Adhesiveness with polyolefin etc.) decreases.

  The second gas barrier resin composition may further contain other components in addition to the semi-aromatic polyamide and the adhesive polyolefin as long as the effects of the present invention are not impaired. Examples of the other components include the same antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers and the like as the other components used in the first gas barrier resin composition. Moreover, as a filler, the thing similar to the other component used for the 1st gas barrier resin composition is mentioned.

  In the second gas barrier resin composition, among the fillers described above, at least one filler selected from the group consisting of mica, sericite, talc, and glass flakes is blended, and the content ratio of these fillers is adjusted to the second content. When the content of the gas barrier resin composition is 30% by weight or less, the gas barrier property of the resin molded body made of the second gas barrier resin composition is further increased. In this case, the content of the filler in the second gas barrier resin composition is preferably 30% by weight or less, more preferably 5 to 30% by weight, and the semi-aromatic polyamide and the adhesive polyolefin The content of the mixture is 70% by weight or more, more preferably 70 to 95% by weight.

  The second gas barrier resin composition is prepared by blending, for example, a semi-aromatic polyamide and an adhesive polyolefin in the above range, and further blending the above other components as necessary. It can be prepared by melting and kneading. Further, the melt-kneaded material may be pelletized and dried, for example. For melt kneading of each component, for example, a single-screw or twin-screw extruder is used. However, the uniformity of mixing of each component is improved, the generation of gel in the resin molded body, and the accompanying blistering. From the viewpoint of suppressing the formation of the above, it is preferable to use an extruder having a high kneading degree as much as possible, seal the hopper with an inert gas (for example, nitrogen gas) and extrude at a low temperature.

According to the first and second gas barrier resin compositions, a thermoplastic resin (for example, polyolefin, etc.) that has low gas permeability, that is, excellent gas barrier properties and is allowed to contact with a chemical solution. It is possible to form a resin molded body having good adhesion.
Therefore, each of the first and second gas barrier resin compositions is formed of a thermoplastic resin that is allowed to come into contact with a chemical solution in, for example, a chemical solution inflow / outflow cylindrical member or a chemical solution container. It is suitable as a gas barrier layer forming material for covering the peripheral surface layer from the outside and imparting gas barrier properties to the inner peripheral surface layer.

  The cylindrical member for inflow / outflow of the chemical liquid according to the present invention is a cylindrical member for allowing the chemical liquid to flow in and out by being attached to the container body of the chemical liquid container whose inner surface is made of a thermoplastic resin that is allowed to contact the chemical liquid. It is. The chemical liquid inflow / outflow cylindrical member is formed of at least a thermoplastic resin that is allowed to contact with the chemical liquid, and has an inner peripheral surface layer that contacts the chemical liquid flowing in / out, and the first or second gas barrier property. A gas barrier layer formed of a resin composition and covering the inner peripheral surface layer from the outside.

Moreover, the said chemical | medical solution inflow / outflow cylinder member is provided with the junction part joined to the container main body of a chemical | medical solution container, and the exposed part exposed from the said container main body.
In the joint, the chemical solution inflow / outflow cylindrical member includes at least an inner peripheral surface layer. Further, the joint portion has a portion where the inner peripheral surface layer is exposed on the outer surface of the chemical solution inflow / outflow cylindrical member. In this joint portion, the outer surface of the chemical liquid inflow / outflow cylindrical member is covered with the container body of the chemical liquid container, whereby the chemical liquid inflow / outflow cylindrical member and the container main body are joined.

On the other hand, in the exposed portion, the chemical solution inflow / outflow cylindrical member includes an inner peripheral surface layer and a gas barrier layer that covers the inner peripheral surface layer from the outside. Further, in the exposed portion, the outer surface of the chemical liquid inflow / outflow cylindrical member is not covered with the container body. Therefore, in this exposed portion, the outer surface of the chemical liquid inflow / outflow cylindrical member is outside the chemical liquid container. Exposed.
Note that the chemical liquid inflow / outflow cylindrical member may include only the inner peripheral surface layer at the joint portion. For example, the gas barrier layer covering the inner peripheral surface layer at the exposed portion may be exposed to the joint portion. Formed so as to extend from the boundary portion to the joint portion side, that is, from the boundary between the joint portion and the exposed portion, to the joint portion side (to the joint side end portion side of the chemical liquid inflow / outflow cylinder member) May be. In this case, the gas barrier property at the boundary portion between the joint portion and the exposed portion can be further improved.

  Further, in this case, the outer periphery of the gas barrier layer extending from the boundary portion between the joint portion and the exposed portion to the joint portion side is formed with a thermoplastic resin that is allowed to contact the chemical container. The surface layer may be coated. Thereby, the adhesiveness between the chemical solution inflow / outflow cylindrical member and the container main body can be further improved. The outer peripheral surface layer is not limited to this, but, for example, is formed to be continuous with the inner peripheral surface layer at the joint side end of the chemical liquid inflow / outflow cylindrical member, and the inner peripheral surface layer and the outer peripheral surface layer are integrated. It is preferable to make it.

Examples of the thermoplastic resin that forms the inner peripheral surface layer and is allowed to contact with the chemical solution include polyolefin, polycyclic olefin, polyvinyl chloride (PVC), polyethylene terephthalate (PET), and ethylene-vinyl acetate copolymer. Examples thereof include a combination (EVA), and a polyolefin is preferable.
Examples of the polyolefin include polyethylene and polypropylene. Examples of the polyethylene include homopolymers such as high pressure method (branched) low density polyethylene, linear low density polyethylene, medium density polyethylene, and high density polyethylene, and polyethylene copolymers. Examples of the comonomer other than ethylene in the polyethylene copolymer include α-olefins such as propylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, and decene-1. . Moreover, in this polyethylene-type copolymer, the content rate of comonomer other than ethylene becomes like this. Preferably it is 20 mol% or less, More preferably, it is 3-20 mol%. Examples of the polypropylene include homopolymers such as isotactic polypropylene and syndiotactic polypropylene, and polypropylene copolymers. Examples of the comonomer other than propylene in the polypropylene copolymer include α-olefins such as ethylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, octene-1, and decene-1. . In this polypropylene copolymer, the content of comonomer other than propylene is preferably 30 mol% or less, more preferably 2 to 30 mol%, and further preferably 3 to 25 mol%. . Polypropylene is suitable as a material for forming the inner peripheral surface layer when, for example, excellent heat resistance is required for the chemical solution inflow / outflow cylindrical member.

  Various additives can be blended in the thermoplastic resin that forms the inner peripheral surface layer and the outer peripheral surface layer and is allowed to come into contact with the chemical solution, if necessary. The mixing ratio of the additive can be appropriately set within a range in which elution from the inner peripheral surface layer into the chemical solution does not occur, for example. Examples of the additive include an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a lubricant, a colorant, and a filler. Moreover, as a filler, the thing similar to what was illustrated as a compounding agent to the 1st or 2nd gas barrier resin composition is mentioned.

  The contact surface between the inner peripheral surface layer and the gas barrier layer of the chemical solution inflow / outflow cylinder member may be formed in an uneven shape that engages with each other. In this case, the adhesion between the inner peripheral surface layer and the gas barrier layer is improved, and peeling between both layers is further suppressed to a higher degree. Furthermore, this makes it possible to suppress the penetration of water vapor or the like into the contact surface accompanying the separation between the inner peripheral surface layer and the gas barrier layer, and the accompanying decrease in gas barrier properties of the gas barrier layer.

Moreover, the outer surface in the junction part of the cylinder member for chemical | medical solution inflow / outflow may be formed in uneven | corrugated shape. In this case, the adhesiveness between the chemical solution inflow / outflow cylindrical member and the container main body can be further improved.
The chemical solution inflow / outflow cylindrical member is provided with an elastic sealing body for sealing the inside of the inner peripheral surface layer. The elastic sealing body only needs to be able to pierce and hold a hollow needle that uses the chemical liquid stored in the container main body to flow out or the chemical liquid into the container main body to flow in. Therefore, the material for forming the elastic sealing body is not particularly limited, but an elastic material having gas barrier properties is preferable from the viewpoint of suppressing gas leakage or intrusion from the chemical solution inflow / outflow cylindrical member.

  Examples of the material for forming the elastic sealing body include isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), isobutylene-isoprene copolymer rubber (butyl rubber; IIR), IIR halide, acrylonitrile. -Butadiene rubber (NBR), silicone rubber, thermoplastic elastomer (for example, various thermoplastic elastomers such as styrene, olefin, urethane and ester). Among these, from the viewpoint of imparting gas barrier properties to the elastic sealing body itself, IR and IIR are preferable, and IR is more preferable.

Further, a peel seal having gas barrier properties may be provided at the exposed end of the chemical solution inflow / outflow cylindrical member. Examples of the material for forming the peel seal include various films having gas barrier properties, and specific examples include films on which inorganic substances such as alumina and silica are deposited.
As described above, the chemical liquid inflow / outflow cylindrical member is formed of the inner peripheral surface layer formed of a thermoplastic resin that is allowed to come into contact with the chemical liquid, and the first or second gas barrier resin composition. A gas barrier layer and, if necessary, the outer peripheral surface layer described above are provided. Since these layers are all made of a thermoplastic resin, each of the above layers can be formed by injection molding. Further, for example, by using a molding method such as insert molding or two-color molding, each of the above-mentioned layers, in particular, the inner peripheral surface layer and the gas barrier layer are joined to each other, and an integrated chemical inflow / outflow cylindrical member is obtained. Can be manufactured easily.

  Since the chemical liquid inflow / outflow cylindrical member includes an inner peripheral surface layer formed of a thermoplastic resin that is allowed to come into contact with the chemical liquid, the stability against the chemical liquid is excellent. In addition, since the gas barrier layer that covers the inner peripheral surface layer from the outside is provided at least in the exposed portion, it has gas barrier properties and is used for inflow and outflow of the chemical solution in the portion exposed to the outside of the drug container. Gas leakage or intrusion from the cylindrical member can be suppressed. In addition, since the inner peripheral surface layer is exposed on the outer surface of the chemical solution inflow / outflow cylindrical member at the joint portion, it is excellent in adhesion and weldability with the chemical solution container. Further, the chemical solution inflow / outflow cylindrical member is suitable for mass production because it can be manufactured by a simple process. Also, the first and second gas barrier resin compositions that form the gas barrier layer and the thermoplastic resin that forms the inner peripheral surface layer and that is allowed to contact the chemical solution are good. Therefore, delamination between the inner peripheral surface layer and the gas barrier layer can be suppressed.

Therefore, the chemical liquid inflow / outflow cylindrical member is attached to the container body of the chemical liquid container, and is suitable as a cylindrical member for allowing the chemical liquid to flow in / out.
The chemical liquid container of the present invention is a container main body formed of a thermoplastic resin whose inner surface is allowed to contact with the chemical liquid, and the chemical liquid inflow / outflow that is attached to the container main body and allows the chemical liquid to flow in / out A cylindrical member.

  The container body is not particularly limited except that the inner surface is formed of a thermoplastic resin that is allowed to contact with the chemical solution, and various container bodies used for the chemical solution container can be mentioned. Specifically, for example, in a state where two resin films formed of a thermoplastic resin whose inner surface is allowed to contact with a chemical solution are overlapped so that the inner surfaces face each other, A bag-like container main body formed by welding the peripheral edge, for example, a bottle-shaped container main body formed of a thermoplastic resin whose inner surface is allowed to contact with a chemical solution.

  The chemical liquid container has the chemical liquid inflow / outflow cylindrical member arranged at the opening end for allowing the chemical liquid to flow in / out of the container main body, and the joint portion of the chemical liquid inflow / outflow cylindrical member is sandwiched between the inner surfaces of the container main body, It manufactures by welding the said junction part and the inner surface of a container main body with various sealing methods, such as heat welding. From the viewpoint of improving the adhesiveness between the chemical solution inflow / outflow cylindrical member and the container body, the pressure inside the container body with the inner surface of the container body sandwiching the joint portion of the chemical liquid inflow / outflow It is preferable to heat while adding.

  According to the chemical container, since the chemical liquid inflow / outflow cylindrical member is provided as the cylindrical member for allowing the chemical liquid to flow in / out, gas leakage and inflow from the chemical liquid inflow / outflow cylindrical member are highly suppressed. be able to. Therefore, the chemical container contains chemicals that need to be stored and stored in an environment in which gas permeation is suppressed, such as chemicals that are easily oxidized and solutions that are likely to be altered due to the volatilization of carbon dioxide gas. It is suitable as a container for carrying out.

Next, an embodiment of a chemical liquid inflow / outflow cylinder member of the present invention and a chemical liquid container including the same will be described in detail with reference to FIGS.
FIG. 1 is a cross-sectional view showing an embodiment of the chemical liquid inflow / outflow cylindrical member of the present invention, and FIG. 2 is a perspective view showing an embodiment of the chemical liquid container of the present invention. 3-6 is explanatory drawing which shows the manufacturing process by insert molding of the cylinder member for chemical | medical solution inflow / outflow shown in FIG. 7 is a schematic configuration diagram showing an injection molding machine for producing the chemical solution inflow / outflow cylindrical member shown in FIG. 1 by two-color molding, and FIGS. 8 to 12 show the chemical solution inflow / outflow shown in FIG. It is explanatory drawing which shows the manufacturing process by 2 color molding of a cylinder member.

Referring to FIGS. 1 and 2, a chemical liquid inflow / outflow cylindrical member 1 is attached to a container body 2 formed of a material whose inner surface is allowed to contact with the chemical liquid, and together with the container body 2. A chemical solution container 3 is formed.
The chemical liquid inflow / outflow cylindrical member 1 is a cylindrical member for flowing the chemical liquid stored in the container main body 2 to the outside of the container main body 2 or for flowing the chemical liquid from the outside to the inside of the container main body 2. The chemical solution inflow / outflow cylindrical member 1 includes a joint portion 4 joined to the container body 2 and an exposed portion 5 exposed from the container body 2. As will be described later, the joint portion 4 and the exposed portion 5 are continuously formed by insert molding or two-color molding, and are joined and integrated with each other. Further, each of the joint portion 4 and the exposed portion 5 includes a substantially cylindrical inner peripheral surface layer 6 that is formed of a thermoplastic resin that is allowed to come into contact with the chemical solution and that contacts the chemical solution that flows in and out. ing.

  The joining portion 4 includes only the inner peripheral surface layer 6 on the joining side end portion 9 side of the chemical solution inflow / outflow cylindrical member 1. On the other hand, the exposed portion 5 further includes a gas barrier layer 7 that is formed of the first or second gas barrier resin composition and covers the inner peripheral surface layer 6 from the outside. The gas barrier layer 7 covers the outer surface of the inner peripheral surface layer 6 at the exposed portion 5 to prevent the inner peripheral surface layer 6 from being exposed to the outside. Further, the gas barrier layer 7 protrudes from the boundary portion between the joint portion 4 and the exposed portion 5 to the exposed side end portion 8 side of the chemical solution inflow / outflow cylindrical member 1 to cover the outer surface of the inner peripheral surface layer 6. ing.

The thickness of the inner peripheral surface layer 6 in a direction orthogonal to the connection direction x between the joint portion 4 and the exposed portion 5 (hereinafter referred to as “radial direction”, indicated by the symbol y) forms the inner peripheral surface layer 6. Since it is appropriately set according to the mechanical strength of the material to be used, the size of the cylindrical member for inflow and outflow of the chemical solution, etc., it is not particularly limited, but is usually preferably 0.1 to 10 mm, more preferably 0.5. ~ 2.5 mm.
The thickness of the gas barrier layer 7 in the radial direction y is appropriately set according to the degree of gas barrier properties required for the gas barrier layer 7, the mechanical strength of the material forming the gas barrier layer 7, the size of the chemical inflow / outflow cylindrical member, and the like. Therefore, although not particularly limited, it is usually preferably 0.1 to 10 mm, and more preferably 0.1 to 2.5 mm.

The contact surface between the inner peripheral surface layer 6 and the gas barrier layer 7 includes an uneven portion 10 that engages with each other. As described above, by providing the contact surface with the uneven portion 10, delamination between the inner peripheral surface layer 6 and the gas barrier layer 7 can be suppressed.
The chemical solution inflow / outflow cylindrical member 1 is provided with an elastic sealing body 11 on the exposed side end portion 8 side, and by this elastic sealing body 11, the exposed side end portion 8 of the chemical liquid inflow / outflow portion 1 and The flow of the chemical solution between the joining side end portions 9 is blocked. When the chemical solution container is used, the flow of the chemical solution can be realized by allowing the elastic sealing body 11 to pierce the hollow needle.

  Further, the chemical solution inflow / outflow cylindrical member 1 is provided with a peel seal 12 at the exposed end 8 thereof. The peel seal 12 can prevent dirt from adhering to the surface of the elastic sealing body 11. Further, by using a resin film having a gas barrier property for the peel seal 12, even if the elastic sealing body does not have a gas barrier property, the gas between the exposed side end portion 8 and the bonding side end portion 9 can be reduced. Can be suppressed.

  Since this chemical solution inflow / outflow cylindrical member 1 includes the inner peripheral surface layer 6, the chemical solution stability is excellent, and at least the exposed portion 5 exposed to the outside of the drug container has the inner peripheral surface layer 6. Since it has the gas barrier layer 7 which covers from the outside, it has gas barrier properties. In addition, since the inner peripheral surface layer 6 is exposed on the outer surface of the chemical solution inflow / outflow cylinder member 1 in the joint portion 4, it is excellent in adhesion and weldability with the container body 2 of the chemical solution container. Further, the chemical solution inflow / outflow cylindrical member 1 can be manufactured by a simple process described later, and the adhesiveness between the inner peripheral surface layer 6 and the gas barrier layer 7 is good. Can be prevented.

As a manufacturing method of the cylindrical member 1 for chemical | medical solution inflow / outflow, the manufacturing method which passes through the insert molding process shown in FIGS. 3-6 is mentioned, for example.
3 and 4, an injection molding machine 13 for molding the inner peripheral surface layer 6 includes a fixed-side mold plate 14 including an inner peripheral surface layer molding cavity plate 15 and a runner 16, and a resin in the cavity. And a movable side template 18 having an inner peripheral surface layer molding core 19 and an ejector pin 20.

  Referring to FIG. 3, in forming inner peripheral surface layer 6, first, movable side mold plate 18 is moved to fixed side mold plate 14, and injection nozzle 17 is connected to runner 16. Next, a thermoplastic resin allowed to come into contact with the chemical solution is formed between the inner peripheral surface layer molding cavity plate 15 and the inner peripheral surface layer molding core 19 from the injection nozzle 17 through the runner 16. The inner peripheral surface layer 6 is formed by injection into the cavity.

Next, referring to FIG. 4, the movable side mold plate 18 is separated from the fixed side mold plate 14, and the inner peripheral surface layer 6 and the sprue runner 21 are projected by the ejector pins 20, and from the inner peripheral surface layer molding core 19. The inner peripheral surface layer 6 is removed.
5 and 6, an injection molding machine 22 for forming a gas barrier layer 7 is used for injecting a resin into the cavity and a stationary mold plate 23 having a gas barrier layer molding cavity plate 24 and a runner 25. Injection nozzle 26, and movable side mold plate 27 including a gas barrier layer molding core 28 and an ejector pin 29.

Referring to FIG. 5, in molding gas barrier layer 7, first, inner peripheral surface layer 6 removed from inner peripheral surface layer molding core 19 is attached to gas barrier layer molding core 28.
Next, referring to FIG. 6, the movable mold plate 27 is moved to the fixed mold plate 23, and the injection nozzle 26 is connected to the runner 25. Next, the first or second gas barrier resin composition is passed through the runner 25 from the injection nozzle 26 into the cavity formed between the gas barrier layer molding cavity plate 24 and the gas barrier layer molding core 28. The gas barrier layer 7 is formed by injection. After the formation of the gas barrier layer 7, the movable side mold plate 27 is separated from the fixed side mold plate 23, and the chemical solution inflow / outflow cylindrical member 1 and the sprue runner 30 are projected by the ejector pins 29. Thereby, the inner peripheral surface layer 6 and the gas barrier layer 7 that covers the inner peripheral surface layer 6 from the outside are joined to each other, and an integrated laminate is obtained.

Thus, after molding the laminate, the elastic sealing body 11 is inserted from the exposed end 8 of the inner peripheral surface layer 6, the exposed end 8 of the gas barrier layer 7 is heated, bent inward, and elastically sealed. By engaging with the body 11, the chemical solution inflow / outflow cylindrical member 1 can be obtained.
Moreover, as another manufacturing method of the cylindrical member 1 for chemical | medical solution inflow / outflow, the manufacturing method which uses the injection molding machine shown in FIG. 7 and passes through the two-color molding process shown in FIGS.

  Referring to FIG. 7, an injection molding machine 31 for molding the chemical inflow / outflow cylindrical member 1 by two-color molding includes a primary cavity plate 33, a secondary cavity plate 34, a primary runner 35, and A stationary side mold plate 32 having a secondary side runner 36, a primary side injection nozzle 37 for injecting resin into the primary side cavity, and a secondary side injection for injecting resin into the secondary side cavity. A movable side template 39 having a nozzle 38, two cores 40, 41 for forming the inner peripheral surface layer 6, an ejector pin 42 for a sprue runner, an ejector pin 43 for an inner peripheral surface layer, and an ejector pin 44 for a gas barrier layer. And.

  Referring to FIG. 8, in this two-color molding step, first, movable side mold plate 39 is moved to fixed side mold plate 32, and primary side injection nozzle 37 is connected to primary side runner 35. Next, a thermoplastic resin allowed to contact with the chemical solution is formed between the primary cavity plate 33 and the first core 40 through the primary runner 35 from the primary injection nozzle 37. The inner peripheral surface layer 6 is formed by injection into the cavity.

Referring to FIG. 9, next, the movable side mold plate 39 is separated from the fixed side mold plate 32, the sprue runner ejector pin 42 is protruded, and the sprue runner 45 is removed. At this time, the inner peripheral surface layer ejector pin 43 is kept stationary and the inner peripheral surface layer 6 is left on the first core 40. In this way, the movable side template 39 is rotated 180 ° by the rotating shaft 46.
Referring to FIG. 10, the movable side template 39 is moved to the fixed side template 32 after exchanging the positions of the first core 40 and the second core 41 by the rotation of the movable template 39. . Thereby, the first core 40 holding the inner peripheral surface layer 6 is arranged in the secondary cavity plate 34.

Referring to FIG. 11, next, the secondary injection nozzle 38 is connected to the secondary runner 36, and the first or second gas barrier resin composition is discharged from the secondary injection nozzle 38 to the secondary side. The gas barrier layer 7 is formed by injecting through the runner 36 into a cavity formed between the secondary cavity plate 34 and the first core 40.
Referring to FIG. 12, next, the movable side mold plate 39 is separated from the fixed side mold plate 32, and the sprue runner ejector pin 42, the inner peripheral surface layer ejector pin 43 and the gas barrier layer ejector pin 44 are projected out. The inflow / outflow cylindrical member 1 is taken out from the first core 40 and the sprue runner 45 is removed.

Thereby, the inner peripheral surface layer 6 and the gas barrier layer 7 that covers the inner peripheral surface layer 6 from the outside are joined to each other, and an integrated chemical liquid inflow / outflow cylindrical member 1 is obtained.
Referring to FIG. 2 again, the container body 2 of the chemical liquid container 3 includes, for example, at least two films formed of a thermoplastic resin whose one side surface is allowed to contact with the chemical liquid. Are formed so as to be on the inner side, and the periphery is welded by heat sealing to form a bag. In the chemical liquid container 3, the chemical liquid inflow / outflow cylindrical member 1 is attached to the container main body 2 by sandwiching the joint portion 4 between the films and heat-sealing at, for example, 110 to 250 ° C. Since the joint portion 4 of the chemical liquid inflow / outflow cylindrical member 1 is formed of a material that is pharmaceutically allowed to contact the chemical liquid, the container body 2 whose inner surface is formed of the same material as described above. Bondability (particularly weldability) is good.

  Further, at the time of heat sealing, preferably, pressure is applied at 0.1 to 1 MPa, preferably 0.15 to 0.35 MPa, with the joint portion 4 of the cylindrical member 1 for flowing in and out of the chemical solution sandwiched between the films. Is done. For example, as shown in FIG. 1, when the gas barrier layer 7 is included on the outer peripheral surface of the joint portion 4, the chemical solution inflow / outflow cylindrical member 1 and the container main body are sealed by heat sealing while applying pressure under the above conditions. Bondability (weldability) with 2 can be improved.

Next, another embodiment of the chemical inflow / outflow cylinder member of the present invention will be described in detail with reference to FIGS.
FIG. 13 is a cross-sectional view showing another embodiment of the chemical liquid inflow / outflow cylindrical member of the present invention, and FIGS. 14-17 illustrate the manufacturing process by insert molding of the chemical liquid inflow / outflow cylindrical member shown in FIG. FIG.

Referring to FIG. 13, a chemical solution inflow / outflow cylindrical member 47 is attached to a container main body 2 formed of a material whose inner surface is allowed to contact with the chemical liquid. Form.
The chemical solution inflow / outflow cylindrical member 47 is a cylindrical member for flowing out the chemical solution stored in the container main body 2 to the outside of the container main body 2 or flowing the chemical liquid from the outside to the inside of the container main body 2. The cylindrical member 47 for inflow / outflow of the chemical solution includes a joint portion 4 joined to the container body 2 and an exposed portion 5 exposed from the container body 2, and the joint portion 4 and the exposed portion 5 will be described later. In this way, they are continuously formed by insert molding, joined together and integrated. Further, each of the joint portion 4 and the exposed portion 5 includes a substantially cylindrical inner peripheral surface layer 48 that is formed of a thermoplastic resin that is allowed to contact the chemical solution and that contacts the chemical solution that flows in and out. ing.

  The joining portion 4 includes only the inner peripheral surface layer 48 on the joining side end portion 9 side of the chemical solution inflow / outflow cylindrical member 1. On the other hand, the exposed portion 5 further includes a gas barrier layer 49 formed of the first or second gas barrier resin composition and covering the inner peripheral surface layer 48 from the outside. The gas barrier layer 49 covers the outer surface of the inner peripheral surface layer 48 at the exposed portion 5 to prevent the inner peripheral surface layer 48 from being exposed to the outside. Further, the gas barrier layer 49 protrudes from the boundary portion between the joint portion 4 and the exposed portion 5 to the exposed side end portion 8 side of the chemical solution inflow / outflow cylinder member 47 to cover the outer surface of the inner peripheral surface layer 48. ing.

  The joint portion 4 further includes an outer peripheral surface layer 50 that is formed from a material that is pharmaceutically allowed to contact the drug solution and that contacts the inner surface of the container body 2. The outer peripheral surface layer 50 and the inner peripheral surface layer 48 are connected so as to be continuous at the joint side end portion 9 of the chemical solution inflow / outflow cylindrical member 47, and the inner peripheral surface layer 48 and the outer peripheral surface layer 50 are connected to each other. A gas barrier layer 49 extending continuously from the joint 4 side is sandwiched therebetween.

The thickness in the radial direction y of the inner peripheral surface layer 48 and the gas barrier layer 49 is the same as that in the case of the chemical solution inflow / outflow cylindrical member 1 shown in FIG. The thickness in the radial direction y of the outer peripheral surface layer 50 is not particularly limited, and is appropriately set within a range in which sufficient strength is maintained.
The contact surface between the inner peripheral surface layer 48 and the gas barrier layer 49 is provided with a protrusion 51 having an uneven shape that engages with each other. In this manner, by providing the protrusion 51 on the contact surface, delamination between the inner peripheral surface layer 48 and the gas barrier layer 49 can be suppressed.

Further, the outer surface of the joint portion 4 and the outer surface of the exposed portion 5 are formed so as to be substantially flat. Thereby, the weldability between the chemical solution inflow / outflow cylindrical member 47 and the container body 2 of the chemical solution container is further improved.
The chemical solution inflow / outflow cylindrical member 47 includes an elastic sealing body 11 on the exposed side end portion 8 side, and the elastic sealing body 11 allows the chemical liquid outflow / inflow cylindrical member 1 to The flow of the chemical solution between the joining side end portions 9 is blocked. When the chemical solution container is used, the flow of the chemical solution can be realized by allowing the elastic sealing body 11 to pierce the hollow needle. Further, the chemical solution inflow / outflow cylindrical member 47 is provided with a peel seal 12 at the exposed end 8 thereof. The peel seal 12 can prevent dirt from adhering to the surface of the elastic sealing body 11. Further, by using a resin film having a gas barrier property for the peel seal 12, even if the elastic sealing body does not have a gas barrier property, the gas between the exposed side end portion 8 and the bonding side end portion 9 can be reduced. Can be suppressed.

  Since this chemical solution inflow / outflow cylindrical member 47 includes the inner peripheral surface layer 48, the chemical solution stability is excellent, and at least the exposed portion 5 exposed to the outside of the drug container has the inner peripheral surface layer 48. Since it has a gas barrier layer 49 that covers from the outside, it has gas barrier properties. Moreover, since the inner peripheral surface layer 48 is exposed on the outer surface of the chemical solution inflow / outflow cylinder member 47 in the joint portion 4, it is excellent in adhesiveness and weldability with the container body 2 of the chemical solution container. Further, the chemical solution inflow / outflow cylindrical member 47 can be manufactured by a simple process to be described later, and the adhesiveness between the inner peripheral surface layer 48 and the gas barrier layer 49 is good. Can be prevented.

As a manufacturing method of the cylindrical member 47 for chemical | medical solution inflow / outflow, the manufacturing method which passes through the insert molding process shown in FIGS.
Referring to FIGS. 14 and 15, an injection molding machine 52 for molding the gas barrier layer 49 includes a stationary mold plate 53 including a gas barrier layer molding cavity plate 54 and a runner 55, and a resin to be injected into the cavity. And a movable side mold plate 57 including a gas barrier layer molding core 58 and an ejector pin 59.

Referring to FIG. 14, in forming gas barrier layer 49, first, movable side mold plate 57 is moved to fixed side mold plate 53, and injection nozzle 56 is connected to runner 55. Next, the gas barrier layer 49 is formed by injecting the first or second gas barrier resin composition from the injection nozzle 56 into the cavity through the runner 55.
Referring to FIG. 15, next, the movable side mold plate 57 is separated from the fixed side mold plate 53, the gas barrier layer 49 and the sprue runner 60 are projected by the ejector pins 59, and the gas barrier layer 49 is removed from the gas barrier layer molding core 58. Remove.

Referring to FIGS. 16 and 17, an injection molding machine 61 for forming an inner peripheral surface layer 48 includes a fixed side mold plate 62 having an inner peripheral surface layer forming cavity plate 63 and a runner 64, and a resin in the cavity. And a movable side mold plate 66 having an inner peripheral surface layer molding core 67 and an ejector pin 68.
Referring to FIG. 16, in molding inner peripheral surface layer 48, first, gas barrier layer 49 removed from gas barrier layer molding core 58 is attached to inner peripheral surface layer molding core 67.

  Referring to FIG. 17, next, the movable side mold plate 66 is moved to the fixed side mold plate 62, and the injection nozzle 65 is connected to the runner 64. Next, the inner peripheral surface layer 48 is formed by injecting a thermoplastic resin allowed to contact with the chemical solution from the injection nozzle 65 into the cavity through the runner 64. After forming the inner peripheral surface layer 48, the movable side mold plate 66 is separated from the fixed side mold plate 62, and the chemical solution inflow / outflow cylindrical member 47 and the sprue runner 69 are projected by the ejector pins 68. Thereby, the inner peripheral surface layer 48 and the gas barrier layer 49 that covers the inner peripheral surface layer 48 from the outside are joined to each other, and an integrated laminate is obtained.

  Thus, after molding the laminate, the elastic sealing body 11 is inserted from the exposed end 8 of the inner peripheral surface layer 48, the exposed end 8 of the gas barrier layer 49 is heated, bent inward, and elastically sealed. By engaging with the body 11, the chemical solution inflow / outflow cylindrical member 47 can be obtained.

Next, although an example and a comparative example are given and the present invention is explained, the present invention is not limited by the following example.
The following components were used as the forming material of the gas barrier resin composition.
Nylon-6: “Amilan (registered trademark) CM1017” manufactured by Toray Industries, Inc., specific gravity 1130 kg / m ³ , melting point 225 ° C.
Nylon-MXD6: “MX Nylon S6001” manufactured by Mitsubishi Gas Chemical Co., Ltd., melting point 240 ° C.
EVOH (44%): “EVAL (registered trademark) E105” manufactured by Kuraray Co., Ltd., ethylene copolymerization ratio 44 mol%, density 1.14 g / cm ³ , melt flow rate 5.5 g / 10 min (190 ° C. 2160g load)
EVOH (32%): “EVAL (registered trademark) F101” manufactured by Kuraray Co., Ltd., ethylene copolymerization ratio 32 mol%, density 1.19 g / cm ³ , melt flow rate 1.6 g / 10 min (190 ° C. 2160g load)
Adhesive polyolefin: “Admer (registered trademark) NF548” manufactured by Mitsui Chemicals, maleic anhydride-modified polyethylene, density 0.912 g / cm ³ , melt flow rate 4.5 g / 10 minutes (190 ° C., 2160 g load) )
Example 1
-Preparation of single-layer test piece Nylon-6, EVOH having an ethylene copolymerization ratio of 44 mol%, adhesive polyolefin, nylon-6 20% by weight, EVOH 50% by weight, and adhesive polyolefin 30 The mixture was blended at a weight percentage and dry blended with a tumbler mixer. Further, the obtained mixture is put into a twin screw extruder (die temperature 230 ° C.) having a screw diameter of 37 mmφ and a screw length (L / D) of 32, and melt-extruded at a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm. As a result, blend pellets of the gas barrier resin composition were obtained.

Next, the blended pellets are dried and then filled into a press mold of a press molding machine, pressed and heated under the conditions of 150 kg / cm ² , 230 ° C., 10 minutes, and a single layer of a 0.3 mm thick press sheet A specimen was obtained.
-Oxygen permeability coefficient of test piece The oxygen permeability coefficient P at 25 ° C and 60% RH of the above-mentioned single-layer test specimen is determined according to JIS K7126-2 _{: 2006} "Plastics-Film and Sheet-Gas Permeability Test Method-Part 2: The measurement was performed according to the method described in the electrolytic sensor method (Appendix A) of the “isobaric method”. In Example 1 and the following Examples and Comparative Examples, when the measured oxygen permeability coefficient P [cm ³ · mm / (m ² · 24 h · atm)] is less than 0.20, the gas barrier property is extremely high. Evaluation A + was given as being good, and evaluation A was given when gas barrier properties were good when the value was 0.20 or more and less than 0.40. The case where the oxygen permeability coefficient P [cm ³ · mm / (m ² · 24 h · atm)] is 0.40 or more and less than 0.85 is evaluated as B, and the gas permeability is 0.85 or more. Was evaluated as C because it was not suitable for practical use.

-Manufacture of chemical | medical solution inflow / outflow cylinder member The chemical | medical solution inflow / outflow cylinder member 1 shown in FIG. 1 was manufactured through the insert molding process shown in FIGS.
That is, first, the movable side mold plate 18 of the inner peripheral surface layer molding injection molding machine 13 is moved to the fixed side mold plate 14, the injection nozzle 17 is connected to the runner 16, and then the inner peripheral surface layer molding is performed from the injection nozzle 17. Polyethylene (density 0.947 g / cm ³ , melt flow rate 22 g / 10 minutes (190 ° C., 2160 g load)) into the cavity between the cavity plate 15 and the inner peripheral surface layer molding core 19, Inc. The inner peripheral surface layer 6 was formed by injecting prime polymer). The temperature during the injection molding of the polyethylene was 190 ° C., and the thickness of the inner peripheral surface layer 6 was 1 mm at the maximum.

  Next, the inner peripheral surface layer 6 was removed from the inner peripheral surface layer molding core 19 and mounted on the gas barrier layer molding core 28 of the gas barrier layer molding injection molding machine 22. Further, after the movable side mold plate 27 is moved to the fixed side mold plate 23 and the injection nozzle 26 is connected to the runner 25, the gap between the gas barrier layer molding cavity plate 24 and the gas barrier layer molding core 28 is connected from the injection nozzle 26. The gas barrier layer 7 was formed by injecting the blend pellet (gas barrier resin composition) into the cavity. The temperature at the time of injection molding of the gas barrier resin composition was 230 ° C., and the thickness of the gas barrier layer 7 was 1 mm at maximum. In this way, the inner peripheral surface layer 6 and the gas barrier layer 7 covering the inner peripheral surface layer 6 from the outside were joined together to obtain an integrated laminate.

Next, after inserting the elastic sealing body 11 from the exposed side end portion 8 of the inner peripheral surface layer 6 of the laminate, the exposed side end portion 8 of the gas barrier layer 7 is heated and bent inward to form the elastic sealing body 11. To obtain a chemical solution inflow / outflow cylindrical member 1.
Furthermore, the chemical solution inflow / outflow cylindrical member 1 thus obtained was placed in an autoclave and steam sterilized at 121 ° C.

-Evaluation of surface condition The state of the surface after the steam sterilization of the said chemical | medical solution inflow / outflow cylinder member 1 was observed visually, and the surface roughening and the crack were evaluated.
The evaluation of rough skin was evaluated as A when no rough skin was observed in the gas barrier layer after steam sterilization in Example 1 and the following examples and comparative examples. Was evaluated as evaluation B, and the case where skin roughness was remarkable and not suitable for practical use was evaluated as C.

The evaluation of the crack was evaluated as A when no crack was observed in the gas barrier layer after steam sterilization in Example 1 and the following examples and comparative examples. Was evaluated as evaluation B, and when cracks were remarkable and not suitable for practical use, evaluation C was assigned.
-Weldability with polyolefin Laminate obtained by manufacturing the above-mentioned cylindrical member for inflow and outflow of chemicals (inner surface layer 6 and gas barrier layer 7 covering this inner surface layer 6 from the outside are bonded to each other) In which the elastic sealing body 11 is inserted and the exposed end of the gas barrier layer 7 is bent) is placed in an autoclave and steam sterilized at 121 ° C. Thereafter, a penetrant (trade name “AGELESS SEAL CHECK”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is injected between the inner peripheral surface layer 6 and the gas barrier layer 7 from the exposed end 8 side of the laminate. , Let it stand. Forty-eight hours after the injection of the penetrating liquid, the case where the penetrating liquid did not exude at all from the joint-side end portion 9 of the laminate was evaluated as A as the weldability was good. Further, the case where the penetrant liquid oozes out to a part is evaluated as B, and the case where the penetrant liquid oozes out over the entire circumference of the joining side end portion 9 is evaluated as C because the weldability is poor and not suitable for practical use. .

Examples 2, 3, 4, 6 and 7, Comparative Examples 1-3
Nylon-6, EVOH (ethylene copolymerization ratio 44%), and Example 1 except that the content ratio (% by weight) of each component with respect to the total amount of adhesive polyolefin was set to the ratio shown in Table 1 below. Similarly, blend pellets of the gas barrier resin composition were produced. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

Example 5
EVOH having an ethylene copolymerization ratio of 32 mol% is used, and the content ratio (% by weight) of each component with respect to the total amount of nylon-6, EVOH, and adhesive polyolefin is a ratio shown in Table 1 below. A blend pellet of the gas barrier resin composition was produced in the same manner as in Example 1 except that the above was set. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

Comparative Example 4
Nylon-6 and adhesive polyolefin were blended in a proportion of 70% by weight of nylon-6 and 30% by weight of adhesive polyolefin, and dry blended with a tumbler mixer. A blend pellet of the gas barrier resin composition was produced in the same manner as in Example 1 except that the mixture thus obtained was used. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

Comparative Example 5
EVOH having an ethylene copolymerization ratio of 44 mol% and adhesive polyolefin were blended in a proportion of 70% by weight of EVOH and 30% by weight of adhesive polyolefin, and dry blended with a tumbler mixer. A blend pellet of the gas barrier resin composition was produced in the same manner as in Example 1 except that the mixture thus obtained was used. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

Comparative Example 6
EVOH having an ethylene copolymerization ratio of 44 mol% and adhesive polyolefin were blended in a proportion of 40% by weight of EVOH and 60% by weight of adhesive polyolefin EVOH, and dry blended with a tumbler mixer. A blend pellet of the gas barrier resin composition was produced in the same manner as in Example 1 except that the mixture thus obtained was used. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

Comparative Example 7
Nylon-6 and EVOH having an ethylene copolymerization ratio of 44 mol% were blended in a proportion of 30% by weight of nylon-6 and 70% by weight of EVOH, and dry blended with a tumbler mixer. A blend pellet of the gas barrier resin composition was produced in the same manner as in Example 1 except that the mixture thus obtained was used. Furthermore, using the obtained blended pellets, a single layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

In Table 1, “PA 6” indicates nylon-6 and “AD” indicates adhesive polyolefin. “44%” and “32%” in the “EVOH” column both indicate the ethylene copolymerization ratio of EVOH.
As is clear from Table 1, in Examples 1 to 7, rough skin and cracks were suppressed, the gas barrier property was high, and the weldability with the polyolefin resin was good. In particular, in Examples 1 and 2, the gas barrier properties were extremely good. On the other hand, in Comparative Examples 1 and 4-6, rough skin and cracks occurred remarkably, and in Comparative Examples 2-4 and 6, gas barrier properties were insufficient. In Comparative Example 7, the weldability was poor.

Example 8
Nylon-MXD6 and adhesive polyolefin were blended in a proportion of 70% by weight of nylon-MXD6 and 30% by weight of adhesive polyolefin, and dry blended with a tumbler mixer. Further, the obtained mixture was put into a twin screw extruder (die temperature 230 ° C.) having a screw diameter of 37 mmφ and a screw length (L / D) of 32, and melt-extruded at a cylinder temperature of 250 ° C. and a screw rotation speed of 100 rpm. A blend pellet of the gas barrier resin composition was obtained.

Next, a single-layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 1 except that the blend pellet was used. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.
Comparative Examples 8 and 9
Nylon-MXD6 and the content ratio (% by weight) of each component with respect to the total amount of adhesive polyolefin were set to the ratios shown in Table 2 below, in the same manner as in Example 8, except for the gas barrier resin composition. Blend pellets were made. Furthermore, using the obtained blended pellets, a single-layer test piece and a chemical solution inflow / outflow cylindrical member were produced in the same manner as in Example 8. Further, for the single-layer test piece, the oxygen permeability coefficient was measured in the same manner as described above, and for the chemical solution inflow / outflow cylindrical member, the surface state after steam sterilization, polyolefin, and The weldability was evaluated.

In Table 2, “PA MXD6” indicates nylon-MXD6, and “AD” indicates adhesive polyolefin.
As apparent from Table 2, in Example 8, rough skin and cracks were suppressed, the gas barrier property was high, and the weldability with the polyolefin resin was good. On the other hand, in Comparative Examples 8 and 9, rough skin and cracks remarkably occurred, and the gas barrier properties were insufficient.

  The present invention is not limited to the above description, and various design changes can be made within the scope of the matters described in the claims.

It is sectional drawing which shows one Embodiment of the cylinder member for chemical | medical solution inflow / outflow of this invention. It is a perspective view which shows one Embodiment of the chemical | medical solution container of this invention. It is explanatory drawing which shows the manufacturing process by insert molding of the cylinder member for chemical | medical solution inflow / outflow shown in FIG. It is explanatory drawing which shows the continuation of FIG. It is explanatory drawing which shows the continuation of FIG. It is explanatory drawing which shows the continuation of FIG. It is a schematic block diagram which shows the injection molding machine for manufacturing the cylinder member for chemical | medical solution inflow / outflow shown in FIG. 1 by 2 color molding. It is explanatory drawing which shows the manufacturing process by 2 color molding of the cylinder member for chemical | medical solution inflow / outflow shown in FIG. It is explanatory drawing which shows the continuation of FIG. FIG. 10 is an explanatory diagram showing a continuation of FIG. 9. It is explanatory drawing which shows the continuation of FIG. It is explanatory drawing which shows the continuation of FIG. It is sectional drawing which shows other embodiment of the cylinder member for chemical | medical solution inflow / outflow of this invention. It is explanatory drawing which shows the manufacturing process by insert molding of the cylinder member for chemical | medical solution inflow / outflow shown in FIG. It is explanatory drawing which shows the continuation of FIG. It is explanatory drawing which shows the continuation of FIG. It is explanatory drawing which shows the continuation of FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1,47: Tube member for chemical | medical solution inflow / outflow, 2: Container body, 3: Chemical solution container, 4: Joining part, 5: Exposed part, 6,48: Inner peripheral surface layer, 7, 49: Gas barrier layer Side end, 9: Join side end

Claims (3)

A cylindrical member for allowing a chemical solution to flow in and out attached to a container body of a chemical solution container whose inner surface is formed of a thermoplastic resin that is allowed to contact the chemical solution,
A joining portion joined to the container body, and an exposed portion exposed from the container body,
The joining portion and the exposed portion are formed of a thermoplastic resin that is allowed to contact the chemical solution, and include an inner peripheral surface layer that contacts the chemical solution flowing in and out,
At least the exposed portion, further, are formed by gas gas barrier resin composition, comprising a gas barrier layer covering the inner surface layer from the outside,
The gas barrier composition includes a polyamide-based resin, an ethylene-vinyl alcohol copolymer, and an adhesive polyolefin made of a modified polyolefin having a functional group introduced into the polyolefin by a graft reaction or a saponified product thereof,
The content ratio of the polyamide resin is 10 to 55% by weight with respect to the total amount of the polyamide resin, the ethylene-vinyl alcohol copolymer, and the adhesive polyolefin, and the content ratio of the ethylene-vinyl alcohol copolymer is A cylindrical member for inflow and outflow of chemicals, characterized in that it is 35 to 85% by weight and the content of adhesive polyolefin is 5 to 45% by weight .   A cylindrical member for allowing a chemical solution to flow in and out attached to a container body of a chemical solution container whose inner surface is formed of a thermoplastic resin that is allowed to contact the chemical solution,
  A joining portion joined to the container body, and an exposed portion exposed from the container body,
  The joining portion and the exposed portion are formed of a thermoplastic resin that is allowed to contact the chemical solution, and include an inner peripheral surface layer that contacts the chemical solution flowing in and out,
  At least the exposed portion further includes a gas barrier layer formed of a gas barrier resin composition and covering the inner peripheral surface layer from the outside,
  The gas barrier composition includes a semi-aromatic polyamide and an adhesive polyolefin made of a modified polyolefin having a functional group introduced into the polyolefin by a graft reaction or a saponified product thereof, and the total amount of the semi-aromatic polyamide and the adhesive polyolefin On the other hand, the chemical liquid inflow / outflow cylindrical member is characterized in that the content of the semi-aromatic polyamide is 65 to 95% by weight and the content of the adhesive polyolefin is 5 to 35% by weight. For the inner surface and the container body of the drug solution container are formed of a thermoplastic resin which is allowed to contact with the chemical solution, thereby and out flow of liquid medicine is attached to the container body, according to claim 1 or 2 A chemical solution container, comprising: a chemical solution inflow / outflow cylindrical member.

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