CN100515381C - Plastic ampoule filled with medicinal liquid and its manufacturing method - Google Patents
Plastic ampoule filled with medicinal liquid and its manufacturing method Download PDFInfo
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- CN100515381C CN100515381C CNB2004800106848A CN200480010684A CN100515381C CN 100515381 C CN100515381 C CN 100515381C CN B2004800106848 A CNB2004800106848 A CN B2004800106848A CN 200480010684 A CN200480010684 A CN 200480010684A CN 100515381 C CN100515381 C CN 100515381C
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Abstract
The invention provides a plastic ampoule filled with liquid medicine and having the functions of blocking gas, water vapor and light and preventing medicine from permeating, absorbing and adsorbing and a preparation method thereof. The plastic ampoule 10 for filling a drug solution of the present invention comprises a container body part 11, a fused part 13 for closing an opening part 12 thereof, and a twist-off grip part 14 attached thereto. The ampoule 10 is formed using a parison having 2 or more layers, at least 1 of which is a functional layer having at least 1 property selected from the group consisting of gas permeation prevention, water vapor permeation prevention, light permeation prevention, drug permeation prevention, and drug absorption, and adsorption prevention. That is, the parison is extruded from a multi-layer blow mold, and the container body portion 11 is formed by being sandwiched by a lower separable die, and after the liquid medicine 15 is filled therein, the opening portion 12 is sandwiched by an upper separable die, and the fused portion 13 and the holding portion 14 are formed, thereby producing the product of the present invention.
Description
Technical field
The present invention relates to a kind of plastic ampoule that is pre-charged with medicinal liquid.In more detail, relate to a kind of gas, light or medicine beyond the water vapour, water vapour (medicament, medicinal liquid, their solvent etc.) of can preventing and immerse or leach to ampoule is outside to ampoule is inner, the medicament that perhaps can prevent from ampoule, to hold, medicinal liquid, solvent etc. to the ampoule inner surface absorb, the plastic ampoule and the manufacture method thereof of the filling medicinal liquid of absorption.
Background technology
At present, the ampoule of receiving medical liquids is to use glass mostly.But glass ampule causes the dissolved problem of alkaline thin slice at the medicinal liquid pH Gao Shihui that holds.And the fragment of the danger of problem that finger is hurt easily when the ampoule of Kaifeng and ampoule breakage, generation when breaking a seal is sneaked into the problems such as danger in the medicinal liquid in addition.And then the danger that contained aluminum is dissolved in the medicinal liquid in glass ampule also appears in the warning of U.S. food pharmaceuticals office (FDA).Therefore, in recent years constantly with there not being the plastic ampoule of above-mentioned danger to replace.
General polyethylene (PE), the polypropylene polyolefin such as (PP) that flexibility is arranged and confirm safety that use of the plastics that form ampoule.PE and PP are to the acid and highly stable material of alkalescent medicine, but very high because of its absorption, permeability to oxygen, air, carbon dioxide etc., are not suitable as the formation material of the ampoule of the medicament that holds easy oxidation, medicinal liquid.Particularly under the situation of the ampoule of low capacity,, can produce the problem that liquor strength enlarges markedly because follow seeing through inner capacities and can reducing of moisture.
Therefore, the moulding material for blow molded products such as film shaped goods such as transfusion bag and infusion bottles is carrying out various researchs and is adopting the polylayer forest (laminated body) of giving the ability (barrier) that prevents in gas and the steam permeable container.
The laminated body of plastics extensively adopts when the manufacturing of thin film and thin plate, but because it is inappropriate using thin film or thin plate in the manufacturing of ampoule, must adopt blow molding in the manufacturing of ampoule.
The ampoule that forms according to blow molding is recorded in No. 2914826 communique of patent and the clear 60-24844 communique of Te Kai.The ampoule (health product container) of the former record is to use the goods of poly-cycloolefin blow molding, and the ampoule of latter's record (container that the inclosure injection medicament is used) is to have the anti-gas-bearing formation that made by the saponification resultant of ethylene-vinyl acetate copolymer (EVA) etc. the goods as the intermediate layer.
But, only put down in writing the theme that only forms ampoule in these documents by blow molding.And the sealing of ampoule is by after injecting medicinal liquid or dropping into medicament in these documents, seals this opening with the heat-sealing that does not produce joint, finishes sealing like this.In this case, have and when forming heat seal lands, follow the ruined worry of heating multiple structure, the incident worry that prevents that effect, effect such as gas permeation from suffering damage when its result has the multiple structure that adopts poly-cycloolefin and EVA.
On the other hand, other manufacture methods as the plastic ampoule of filling medicinal liquid can enumerate so-called blowing, fill, seal method (opens clear 33-8078 communique with reference to the spy, special public clear 36-5985 communique, the homepage of rommelag company " Welcome torommelag (R); " " BFS Process-The bottelpack (R) Process ", " retrieval on March 19th, 2003 ", the Internet＜URL; Http:// www.rommelag.com/ 〉).
Blowing, fill, the method for sealing is to form ampoule itself by the molten plastic parison of living tubular with main die clamp, after then filling medicinal liquid, carry out the formation and the sealing of ampoule head continuously with head mould, because the filling of the shaping of ampoule, medicinal liquid, the sealing of ampoule are carried out continuously, be the method that differs widely not only with only comparing with blow-moulding process, and can realize further that aseptic medicinal liquid injects, having can mass-produced advantage.
But, by blowing, the ampoule of filling, sealing manufactured is well known that the individual layers by polyolefin prepared such as PE and PP.Thereby, existing situation be for by blowing, fill, seal the ampoule of manufactured multiple structure, and 1 floor that forms this laminated construction for gas, water vapour, light and medicine prevent the ability (barrier) that sees through and to the ability that prevents of the absorption absorption of medicine all without any correlational study (with reference to the homepage of special public clear 33-8078 communique, special public clear 36-5985 communique, aforesaid rommelag company, the homepage of mutual company (" packaging facilities-container be shaped aseptic fill system ", " retrieval on March 19th, 2003 ", the Internet＜URL; Http:// www.mutual.co.jp 〉), homepage (" polyethylene bottle ", " retrieval on March 19th, 2003 ", the Internet＜URL of Ri Xin drugmaker; Http:// www.yg-nissin.co.jp/BFS.htm 〉)).
For give to gas, water vapour, light and medicine prevent see through (barrier), to the ability that prevents of drug absorption absorption, for example consider to have and in having the bag of gasproof body permeability, hold the preservation ampoule, or prevent that with having the material that light sees through ability (light barrier) from covering the ampoule surface, or the method for carrying out outer package.But these methods must separately be used the material of bag container and covering surfaces, thereby manufacturing step becomes complicated, have problems such as manufacturing cost rising.
Summary of the invention
The object of the present invention is to provide gas, light or the medicine that can prevent beyond water vapour, the water vapour to leach to the inner immersion of ampoule or to the ampoule outside, the medicament that perhaps holds in ampoule, medicinal liquid, solvent etc. are to the medicinal liquid filled plastics ampoule and the manufacture method thereof of the absorption absorption of ampoule inner surface.
In order to solve above-mentioned problem, the feature of filling medicinal liquid plastic ampoule of the present invention is as follows, it has the container body part of flexibility, the fused portion that seals the opening of this container body part twists off the grip portion that fused portion is used with being connected on this fused portion, the said vesse main part, fused portion and grip portion are with having 2 layers or above integrally formed the making of tubular parison, the said vesse main part is to be shaped with dividing die clamp to live in to state parison, medicinal liquid is filled by portion within it, the closed peristome position makes then, and at least 1 layer of above-mentioned parison prevents gas permeation for having to be selected from, prevent steam permeable, prevent that light from seeing through, prevent that medicine from seeing through and preventing the functional layer of at least one characteristic of the ability that drug absorption is adsorbed.
According to the plastic ampoule of above-mentioned filling medicinal liquid,, can under aseptic condition, realize injection, the sealing of medicinal liquid because in the manufacturing of ampoule, adopt blowing, fill, seal method.In addition, the filling medicinal liquid of the invention described above with plastic ampoule with by behind the filling medicament in the ampoule of the hollow that forms to blow molding, fuse product (with reference to No. 2914826 communique of patent or special record of opening in the clear 60-24844 communique) difference that opening prepares in the mode that does not produce joint, in the fusion of opening, do not have layer and constitute the worry that is damaged.Therefore, filling medicinal liquid plastic ampoule of the present invention can also be given full play to the desired characteristic (barrier properties for gases etc.) in ampoule shaping back.
The desired characteristic of functional layer of the present invention can be enumerated and prevent gas permeation (barrier properties for gases), prevents steam permeable (water vapor barrier), prevent that light from seeing through (light barrier), preventing that medicine from seeing through (medicine barrier) and preventing the ability that drug absorption is adsorbed.These characteristics kind according to the plastic material in the part of using as functional layer in the parison and its compounding agent as described below decides.
In addition, open the spy and to have put down in writing the plastic ampoule that can twist off the filling medicinal liquid that handle part assigns to break a seal in the 2001-70399 communique, so put down in writing this ampoule can be with blowing, fill, seal the theme of manufactured and multiple stratification or give the theme (section [0007], [0012]) of its light-proofness as required.But, to about multiple stratification parison itself, or give the barrier of the whole expectation of ampoule without any concrete record and suggestion in this communique by in parison, mixing the layer that material with above-mentioned functions makes.
The innermost layer of filling medicinal liquid plastic ampoule of the present invention used parison in it is shaped preferably forms by the resin that contains polyolefin or poly-cycloolefin.
By with containing the innermost layer of the resin of polyolefin or poly-cycloolefin as parison, fill medicinal liquid with the innermost layer of plastic ampoule can be to use also that the resin that contains polyolefin or poly-cycloolefin makes layer.Polyolefin and poly-cycloolefin are the materials stable, that safety obtains confirming, thereby at its innermost layer the filling medicinal liquid that polyolefin or poly-cycloolefin make are set and are suitable as container for medical use with plastic ampoule.
Filling medicinal liquid plastic ampoule of the present invention, the parison that uses during it is shaped is to have at least 1 layer to be the layer that at least one medicament that mixed to be selected from coloring agent, UV absorbent and oxygen absorbent makes except innermost layer, and than the layer of this layer inside preferably have prevent medicine see through ability layer.
To make the layer that mixed colorant and/or UV absorbent form except at least 1 layer of parison innermost layer, can give the filling medicinal liquid thus and see through ability (the light barrier is the barrier to light, ultraviolet etc. specifically) to prevent light with plastic ampoule.And, mix the layer that oxygen absorbent forms by making except at least 1 layer of parison innermost layer, can give the filling medicinal liquid thus and use plastic ampoule in case block gas sees through ability (oxygen-barrier property).
Mixed layer that coloring agent, UV absorbent or oxygen absorbent make in the worry that has the contained strippings such as coloring agent in its inside when medicinal liquid etc. directly contacts.But, according to above-mentioned filling medicinal liquid plastic ampoule because the layer that has mixed coloring agent etc. inboard be provided with to have prevent that medicine from seeing through the layer of ability, can prevent to produce coloring agent etc. and be dissolved in such problem in the medicinal liquid that ampoule holds.
As the layer that has mixed above-mentioned coloring agent etc. inboard that be provided with, have and prevent that the layer that medicine sees through ability from can enumerate polyhydric alcohol layer described later, polyester layer and poly-cycloolefin layer.
Filling medicinal liquid plastic ampoule of the present invention, the functional layer of its used parison in being shaped is preferably
(i) contain the goods of aramid layer,
The goods that (ii) contain the polyhydric alcohol layer,
The goods that (iii) contain polyester layer, perhaps
The goods that (iv) contain poly-cycloolefin layer.
When preparing the functional layer of the aramid layer that contains above-mentioned (i), can give the ability that medicinal liquid prevents gas permeation with plastic ampoule and prevents steam permeable of filling.Thereby this ampoule can be suitable for holding for example easily oxidation, the medicinal liquid that can not preserve in the presence of oxygen and because the medicinal liquid of significant change takes place the variation drug effect of moisture etc.
When preparation contains the functional layer of above-mentioned polyhydric alcohol layer (ii), can give the filling medicinal liquid and prevent gas permeation, prevent steam permeable, prevent that medicine from seeing through and preventing the ability of drug absorption absorption with plastic ampoule.Thereby this ampoule can be suitable for holding the medicinal liquid that for example can not preserve and the medicinal liquid of significant change can be taken place by variation drug effect of moisture etc. in the presence of oxygen.
For example, when ampoule has the layer of medicaments such as containing coloring agent, UV absorbent, oxygen absorbent,, can prevent that mentioned reagent is dissolved in the medicinal liquid of filling in the ampoule by the polyhydric alcohol layer is set in this layer inboard.
When preparation contains the functional layer of above-mentioned polyester layer (iii), can give the filling medicinal liquid and prevent gas permeation, prevent steam permeable, prevent that medicine from seeing through and preventing the ability of drug absorption absorption with plastic ampoule.Thereby this ampoule can be suitable for holding the medicinal liquid that for example can not preserve and the medicinal liquid of significant change can be taken place by variation drug effect of moisture etc. in the presence of oxygen.And, by using the innermost layer of polyester layer, can prevent absorption or the absorption of medicine to the ampoule innermost layer as ampoule.
Poly-cycloolefin because have prevents that medicament from absorbing, the ability of absorption, prevent the ability (medicine barrier) that medicine sees through, the ability that prevents steam permeable, and the transparency is good, and the formation material (spy opens flat 5-277154 communique) of attempting using it for container for medical use has been arranged.Thereby preparation is when containing the functional layer of above-mentioned poly-cycloolefin layer (iv), can give filling medicinal liquid and preventing that with plastic ampoule medicine from seeing through (medicine barrier), prevent drug absorption absorption, preventing the ability of steam permeable.
And, for example, when ampoule has the layer of medicaments such as containing coloring agent, UV absorbent, oxygen absorbent,, can prevent that the mentioned reagent stripping is in the medicinal liquid that is filled in the ampoule by poly-cycloolefin layer is set in this layer inboard.
When using poly-cycloolefin layer, can prevent absorption or the absorption of medicine to the ampoule innermost layer as the ampoule innermost layer.And then in this case, preferably using glass transition temperature (Tg) as the poly-cycloolefin that forms innermost layer is 110 ℃ or following product.By using the poly-cycloolefin of glass transition temperature at innermost layer in above-mentioned scope, for blowing, fill, seal joint (joint of main mould and the head mould) part of the finishing die of method, can prevent to fill, the sealing back produces the liquid leakage at content liquid.The glass transition temperature of poly-cycloolefin in above-mentioned scope preferred especially 60～105 ℃, more preferably 60～80 ℃.
In addition, open the example of having put down in writing the ampoule that uses poly-cycloolefin shaping in the flat 5-293159 communique the spy, but in the document for blowing, fill, seal the manufactured ampoule without any record, leak the generation of problem and solution liquid thereof not instruction and hint for above-mentioned liquid.
By the way, the glass transition temperature of poly-cycloolefin surpasses 110 ℃, generally has shortage to the patience of bending stress, more crisp feature itself.Thereby, use has with glass transition temperature at the innermost layer of 110 ℃ or following poly-cycloolefin preparation with contain the polylayer forest of layer that glass transition temperature surpasses 110 ℃ poly-cycloolefin and form and fill the medicinal liquid plastic ampoule, can prevent that filling, sealing back at content liquid from producing the liquid leakage, and pass through the fused portion (thin place) of crooked or distortion ampoule etc., can easily carry out the Kaifeng operation of ampoule.
In addition, compare with the general and poly-cycloolefin of polymer that acyclic alkene makes, the flexibility of its formed body is higher, excellent impact resistance.Thereby, when the lamilated body that forms plastic ampoule not only has the layer that contains cyclic olefin, when also having the polyolefinic layer of the non-annularity of containing, can improve the impact resistance of plastic ampoule integral body.
Filling medicinal liquid plastic ampoule of the present invention also can be with the connector of a plurality of ampoules of broken thin part connection, prepares the management that such connector for example can easily hold a plurality of ampoules of medicinal liquid of the same race.
Filling medicinal liquid plastic ampoule of the present invention is when layer that has the steam permeable of preventing or prevent the drug absorption absorbability in functional layer, can be the ampoule of 0.5～20mL as inner capacities.That is, the aramid layer of above-mentioned for having (i), above-mentioned (ii) the polyhydric alcohol layer, above-mentioned (iii) polyester layer or above-mentioned (iv) poly-cycloolefin layer as the plastic ampoule of functional layer, being suitable for inner capacities is the low capacity ampoule of 0.5～20mL.Inner capacities is that the ampoule of 0.5～20mL is few because of the absolute magnitude that it holds solution, following the volatilization of solvent or medicament to be absorbed during ampoule holds is adsorbed onto on the ampoule, can produce the so-called problem of holding the character significant change of solution, prevent steam permeable, prevent good aramid layer, polyhydric alcohol layer, polyester layer or poly-cycloolefin layers etc. such as drug absorption absorbability by setting, can prevent the generation of this problem.
Filling medicinal liquid of the present invention is characterized in that comprising the following steps: can dividing die clamp firmly to have the tubular parison of 2 or above layer with the partially-formed usefulness of container body following with the manufacture method of plastic ampoule, wherein at least 1 layer is to have to be selected to prevent gas permeation, prevent steam permeable, prevent that light from seeing through, preventing that medicine from seeing through and preventing the functional layer of at least one characteristic of drug absorption, absorption, after the inside of tubular parison forms the cavity and comes the forming containers main part
In this container body part, fill medicinal liquid, then,
Use the opening that can divide die clamp to live this container body part, the fused portion that forms this opening of sealing is used to twist off the grip portion of fused portion with linking to each other with this fused portion.
According to above-mentioned manufacture method, can under aseptic condition, realize to filling medicinal liquid with injecting, seal medicinal liquid in the plastic ampoule.And, after filling medicinal liquid, during the opening of fusion sealing ampoule, can not destroy the layer structure of laminated plastics, form fused portion.
Thereby, above-mentioned manufacture method of the present invention be very suitable for making can prevent gas, water vapour, light and medicament to inner or outside see through or ampoule in medicament, medicinal liquid, solvent etc. absorb or the filling medicinal liquid plastic ampoule of absorption to inner surface.
Filling medicinal liquid of the present invention preferably uses (a) its innermost layer to be formed by the resin that contains polyolefin or poly-cycloolefin with the parison in the manufacture method of plastic ampoule, perhaps (b) except at least 1 layer of its innermost layer layer at least one medicament that mixed to be selected from coloring agent, UV absorbent and oxygen absorbent, and the layer of this layer inboard prevents that for having medicine from seeing through the layer of ability.
Under the situation of above-mentioned (a), can more safely make container for medical use with plastic ampoule by the filling medicinal liquid that said method obtains.
In above-mentioned (a), innermost layer is by under the situation that contains the resin formation that gathers cycloolefin, according to reason same as described above, preferably use glass transition temperature at 110 ℃ or following product as this poly-cycloolefin, more preferably using glass transition temperature is 60～105 ℃ product.
And, under the situation of above-mentioned (a), according to reason same as described above, as parison preferably use have the innermost layer that forms at 110 ℃ or following poly-cycloolefin by glass transition temperature and by glass transition temperature surpass that 110 ℃ poly-cycloolefin forms layer product.
Under the situation of above-mentioned (b), can give the filling medicinal liquid that obtains by said method and see through ability (to the barrier of light, ultraviolet etc.) to prevent light with plastic ampoule.
Brief description of drawings
Fig. 1 is the partial cross section figure of expression filling medicinal liquid of the present invention with an embodiment of plastic ampoule, (a) is front elevation, (b) is right hand view.
Fig. 2 is the partial cross section front elevation of expression filling medicinal liquid of the present invention with other embodiments of plastic ampoule.
The specific embodiment
The filling medicinal liquid that then present invention will be described in detail with reference to the accompanying plastic ampoule and preparation method thereof.
＜filling medicinal liquid plastic ampoule 〉
Fig. 1 and Fig. 2 are the accompanying drawing of expression filling medicinal liquid of the present invention with an embodiment of plastic ampoule.
Filling medicinal liquid shown in Fig. 1 with plastic ampoule 10 have the container body part 11 of flexibility and closed container main part opening 12 fused portion 13, be connected in the grip portion 14 on the fused portion 13.
Filling medicinal liquid shown in Fig. 2 is the same with ampoule 10 shown in Figure 1 with plastic ampoule 18, have the container body part 11 of flexibility and closed container main part opening 12 fused portion 13, be connected in the grip portion 14 on the fused portion 13.For this ampoule 18, between lateral edge portions 17, connect by the coupling part 19 that can twist off.
Filling medicinal liquid can separate from fused portion 13 by crooked or distortion with the grip portion 14 of plastic ampoule.Twist off grip portion 14, it is separated with container body part 11 from fused portion 13, the opening portion 12 of container body part 11 is opened, can obtain, sealing in the amount discharge container main part 11, the medicinal liquids 15 of filling.
In addition, when the polylayer forest that forms ampoule 10,18 has the layer that contains the poly-cycloolefin of glass transition temperature above 110 ℃,, can carry out lock out operation simply from fused portion 13 according to aforementioned reason.
Form filling medicinal liquid, to it is characterized by its at least 1 layer with the plastics 16 of plastic ampoule be to have to be selected to prevent gas permeation, prevent steam permeable, prevent that light from seeing through, preventing that medicine from seeing through and preventing the functional layer of at least one characteristic of drug absorption absorbability.
Fill medicinal liquid with the lateral edge portions 17 of plastic ampoule for by the blowing of this ampoule, when filling, sealing the method shaping, sandwich parison with die head and form.Filling medicinal liquid for example can use the bull coventry type die head coventry that has with corresponding die head of the number of the ampoule that is connected and mould to be shaped with plastic ampoule 18.
＜ampoule moulding material 〉
For filling medicinal liquid plastic ampoule of the present invention, the functional layer that contains in this ampoule has following feature as mentioned above, and it has to be selected from and prevents gas permeation, prevents steam permeable, prevents that light from seeing through, preventing that medicine from seeing through and preventing at least one characteristic of drug absorption absorbability.Corresponding about the kind of this characteristic and the plastic material that in this functional layer, uses, as mentioned above.
As operable polyamide among the present invention without limits, for example nylon-6, nylon-6 can have been enumerated, 6, nylon-6,12, PA-12, xyxylene diamidogen polyamide etc. at this.
As operable polyester among the present invention without limits, still for example polyethylene terephthalate (PET), PEN, polybutylene terephthalate (PBT) etc. can have been enumerated at this.
As operable polyhydric alcohol among the present invention without limits, still for example polyvinyl alcohol (PVOH), ethylene-vinyl alcohol copolymer (EVOH) etc. can have been enumerated at this.
As operable poly-cycloolefin among the present invention without limits, can enumerate the ring opening copolymer thing of the copolymer of copolymer, ethylene and the norborene compounds of ethylene and bicyclopentadiene class, the ring-opening polymerization polymer of cyclopentadiene derivant, a plurality of cyclopentadiene derivants and hydrogenated products thereof etc. at this.
Among the present invention, especially preferably use the hydrogenation products of open loop (being total to) polymer of the hydrogenation products of copolymer of ethylene and norborene compounds or a kind or above cyclopentadiene derivant in the above-mentioned poly-cycloolefin that exemplifies.Should gather cycloolefin by using, and can prepare ampoule intensity and prevent that moisture from seeing through the better layer of ability, and can also give the ability that ampoule prevents gas permeation.
For above-mentioned poly-cycloolefin, can enumerate the polymer that for example has the repetitive of representing with the repetitive and the general formula (1 ') of general formula (1) expression, have polymer with the repetitive of general formula (2) expression.
(in formula (1) and the formula (1 '), R
1, R
1', R
2And R
2' can be identical or different, expression hydrogen, hydrocarbon residue or halogen, ester group, nitro, pyridine radicals isopolarity group.R
1, R
1', R
2And R
2' ring formation also can mutually combine.M and m ' are the integer more than 1 or 1, and n and n ' are the integer more than 0 or 1 or 1.)
(in the formula (2), R
3And R
4Can be identical or different, expression hydrogen, hydrocarbon residue or halogen, ester group, nitro, pyridine radicals isopolarity group.R
3And R
4Ring formation also can mutually combine.X and z are the integer more than 1 or 1, and y is the integer more than 0 or 1 or 1.)
The polymer of repetitive with general formula (1) and (1 ') expression is by a kind of known ring-opening polymerization method polymerization or 2 kinds or the monomer more than it, perhaps the product that makes of the ring-opening polymerization polymer hydrogenation that then will obtain like this with conventional method.Can enumerate the commodity of the commodity " ゼ オ ノ ア (registered trade mark) " by name that Japanese ゼ オ Application company makes, the commodity " ARTON (registered trade mark) " by name that Japan SYnthetic Rubber Co. Ltd makes etc. as the object lesson of this polymer.
Polymer with construction unit of general formula (2) expression is as monomeric a kind or 2 kinds or norborneol alkene monomer and ethylene more than it, and/or with its product with the conventional method hydrogenation preparing by the known method addition copolymerization.Can enumerate the commodity of the commodity " ア ペ Le (registered trade mark) " by name of Mitsui Chemicals company manufacturing, the commodity " ト パ ス (registered trade mark) " by name that テ イ コ Na GmbH company makes etc. as the object lesson of this polymer.
Have in the polymer of repetitive of above-mentioned general formula (1), (1 ') and (2) expression, because any of its hydrogenation products all is saturated polymer, it is except having gas shield and covering property of moisture, from the thermostability and the transparency, further also good from stability.
The melt flow index of the poly-cycloolefin that uses among the present invention (MFR) is from the formability of ampoule and the preferred 4～30g/10 of viewpoints such as mechanical characteristic minute (190 ℃) of molded article.
The molecular weight of the poly-cycloolefin that uses among the present invention is not particularly limited, but number-average molecular weight (Mn) is preferred 10,000～100,000, and more preferably 20,000～50,000.Need to prove that molecular weight for example can be measured by gel permeation chromatography (GPC) analysis of cyclohexane give solvent.
Among the present invention, except above-mentioned example, can also enumerate improved polyalkene for example, Vingon (have the gas permeation of preventing, prevent the ability of steam permeable), polyacrylonitrile (have the gas permeation of preventing, prevent steam permeable, prevent that medicine from seeing through, preventing the ability of drug absorption absorption) etc. as the resin that can in the shaping of functional layer, use.
Can enumerate product (for example improved polyalkene of unsaturated carboxylic acid such as glycerol polymerization maleic acid etc.) of functional group such as addition carboxyl in polyolefin such as non-polar polymer polyethylene or polypropylene etc. as the polyolefin of modification.Concrete example has the cementability polyolefin that Mitsui Chemicals company for example makes [trade name " ア De マ-(R) LB540 ", " ア De マ-(R) NF510 ", " ア De マ-(R) UF300 " etc.]; The high adhesiveness resin [trade name " モ デ ィ ッ Network-AP (R) P512V ", " モ デ ィ ッ Network-AP (R) L103 " etc.] that Mitsubishi Chemical Ind makes etc.These improved polyalkenes can be selected aptly according to the resin kind of adhesion layer.
Have prevent light see through ability (light barrier) the layer formation in, can in plastics, mix following pigment, UV absorbent.As the pigment that in the formation of light barrier material, uses without limits, for example can enumerate inorganic pigment such as titanium oxide, zinc oxide, carbon black, iron oxide red, silicon dioxide and phthalocyanine system, azo system at this, quinoline a word used for translation ketone is organic pigment etc.
On the other hand, as the UV absorbent of using in the formation of light barrier material at this without limits, for example having enumerated, salicylic acid such as phenyl salicytate, salicylic acid p-octyl octylphenyl is a UV absorbent; 2, benzophenone series UV absorbent such as 4-dihydroxy benaophenonel, two (2-methoxyl group-4-hydroxyl-5-benzo base phenyl) methane; 2-ethylhexyl-2-cyano group-3,3-diphenylacrylate ester and ethyl-2-cyano group-3, cyanoacrylates such as 3-diphenylacrylate ester are UV absorbent; 2-(5-methyl-2-hydroxy phenyl) benzotriazole, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-benzotriazole systems such as 5-chlorinated benzotriazole etc.Above-mentioned pigment or UV absorbent are added about preferably with 0.01～5 weight % in the plastics that constitute light barrier layer.
Have prevent gas permeation ability (barrier properties for gases) the layer in, particularly have oxygen-barrier property the layer formation in, can in plastics, mix oxygen absorbents such as ferrum, sodium sulfite, sodium sulfite, pyrogallol, ascorbic acid, tocopherol.Oxygen absorbent adds about preferably with 0.15～5 weight % in the plastics that form the oxygen-barrier property layer.
For filling the plastic ampoule that medicinal liquid is used among the present invention, the general use of the layer polyolefin except this functional layer forms and is fit to.Can enumerate used various polyolefin in the existing medical plastic containers such as polyethylene, polypropylene as this polyolefin.And, can also mix adhesive resins such as unsaturated carboxylic acid-modified polyethylene, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer at interlayer as required.For the plastics that form these other layers, cooperate the shape of layer structure and container etc., character such as density, MFR can suit to select in relative broad range.
Operable polyolefin is not particularly limited among the present invention, can adopt known various polyolefin at present.In addition, in various polyolefin, especially preferably use polyethylene or polypropylene.
In polyethylene (PE), can use so-called high-pressure process (chain) low density polyethylene (LDPE) (HP-LDPE), straight chain shape low density polyethylene (LDPE) (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) various PE such as (HDPE).The density of PE can be at 0.900g/cm
3～0.965g/cm
3The general range of PE plastics in suitable the selection.From considering, preferably in more low-density scope, be specially 0.910～0.930g/cm with the formability of the layer that makes with poly-cycloolefin or the viewpoints such as mechanical characteristic of ampoule
3Scope in select.The melt flow index of PE (MFR) considers to be preferably 0.2～20g/10 minute (190 ℃) from the formability of the layer that makes with poly-cycloolefin and the viewpoints such as mechanical characteristic of ampoule.
PE is not limited to homopolymer, also can be copolymer.This moment is as alpha-olefines such as the preferred 1-butylene of comonomer, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene.The content ratio of comonomer is preferably at 20 moles of % or following, more preferably about 3～20 moles of %.
Kind, the character of polypropylene (PP) also are not particularly limited, and adopt general isotaxy PP or a rule PP (being the crystallinity homopolymer) or are fit to its crystallinity copolymer of making main composition as PP.Comonomer in this crystallinity copolymer is preferably alpha-olefines such as ethylene, 1-butylene.Containing of comonomer is proportional preferably at 30 moles of % or following, more preferably about 2～30 moles of %, more preferably about 3～25 moles of %.The melt flow index of PP (MFR) is from considering to be preferably 0.2～20g/10 minute (190 ℃) with the formability of the layer that makes with poly-cycloolefin and the viewpoints such as mechanical characteristic of ampoule.
In order to give the ability (oxygen-barrier property) that plastic ampoule of the present invention prevents that oxygen from seeing through, can in plastics, mix oxygen absorbents such as ferrum, sodium sulfite, sodium sulfite, pyrogallol, ascorbic acid, tocopherol.Oxygen absorbent preferably adds with the amount about 0.15～5 weight % in the plastics that form the oxygen-barrier property layer.And, form in the plastics of plastic ampoule of the present invention and can suit to mix in right amount stabilizing agents such as butylated hydroxytoluene, eight decyls-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester; Antibacterial such as silver-zeolite, hinokitiol; Plasticizers such as phthalic acid ester etc.Under the situation of the plastics that use to mix these additives, preferably ampoule is made polylayer forest, and the plastic layer that will mix above-mentioned additive is made the layer beyond the internal face.
The layer structure of＜ampoule 〉
The innermost layer of the plastic ampoule of filling medicinal liquid of the present invention preferably uses with polyethylene or polypropylene polyolefin or the poly-cycloolefin as representative.Polyolefin or poly-cycloolefin will have the safety and the stability of pair medicament, medicinal liquid as mentioned above, and then require fused property also good.
Have and prevent that the layer that medicine sees through ability (medicine barrier) is arranged on the innermost layer outside of plastic ampoule, and, can give full play to the action effect of medicine barrier layer, so preferred in the inboard of other functional layer.
＜intermixture etc. 〉
Forming filling medicinal liquid of the present invention also can mix as required with the plastics of plastic ampoule.And, can suit to mix in right amount stabilizing agents such as butylated hydroxytoluene, eight decyls-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester as required; Antibacterial such as silver-zeolite, hinokitiol; Plasticizers such as phthalic acid ester etc.
Preferably be arranged on the outside of medicine barrier layer for mixing layer that such additive makes.
＜manufacture method etc. 〉
Filling medicinal liquid of the present invention can use the blowing, filling, the sealing machine that have multilamellar extruder and multilamellar blowing mould to make with plastic ampoule.
Specifically, at first use the multilamellar blowing mould to be formed with 2 tubular parisons with the upper strata by extrusion molding.At least 1 layer of use has to be selected from and prevents gas permeation (barrier properties for gases), prevents steam permeable (moisture barrier), prevents that light from seeing through (optics barrier), preventing that medicine from seeing through (medicament barrier) and preventing the functional layer of at least one characteristic of the ability of drug absorption absorption in this parison.Then, live this tubular parison, air is pressed into its inside, perhaps attract parison to form the container body part, at the medicinal liquid of partially filled regulation of this container body and ormal weight with the die face hole with the following die clamp that can divide of the partially-formed usefulness of container body.And then, use the peristome that can divide die clamp to live this container body part, by fused portion that forms this opening of sealing and the grip portion that fused portion is used that twists off that is connected on this fused portion, can make filling medicinal liquid plastic ampoule of the present invention.The layer structure of parison can suit to set according to the desired layer of the plastic ampoule of filling medicinal liquid structure.
According to blowing, the ampoule of filling, sealing method creates conditions and is not particularly limited, can be according to common creating conditions.Melt extruding temperature or melt extruding speed of parison can be according to the suitable settings such as shape of used resin and purpose container.
About preferred 300～2000 μ m of gross thickness of the plastic ampoule of filling medicinal liquid.The thickness of functional layer is not particularly limited, and can wait suitable the selection according to the kind and the application target of the function that this layer had, and is preferably usually about 10～300 μ m.
＜medicament, the medicinal liquid that can hold 〉
The medicinal liquid that holds in the plastic ampoule of the present invention is not particularly limited, and can suit according to the functional characteristic that functional layer has to select.
For example, in the plastic ampoule of the present invention, can hold with the goods that have the layer that prevents gas permeation ability (barrier properties for gases) for the solution of easy oxidation medicament.Can enumerate for example vitamins such as vitamin A as easy oxidation medicament; Aminoacid such as cysteine, tryptophan; Reduced glutathion, lipomul, Liposomal formulation etc.
For the solution of light deterioration medicament, in the ampoule of the present invention, can with have prevent light see through ability (light barrier) the layer goods hold.Can enumerate for example vitamins such as vitamin B2, vitamin B12 as light deterioration medicament; Hydrochloric acid bromhexine, saccharated iron oxide agent, atropine sulfate, neostigmine, dimethyl-aminopropionyl-aminoanti-pyrine, haloperidol, ephedrine hydrochloride etc.
For the solution that absorbs the adsorptivity medicament, can hold with the goods that have the layer that prevents the drug absorption absorbability in the ampoule of the present invention.Vitaminss such as vitamin D for example can have been enumerated as absorbing the adsorptivity medicament; Nitroglycerine; Elcatonin (elcatonin) etc.
[embodiment]
Then enumerate the plastic ampoule that embodiment illustrates medicinal liquid filling usefulness of the present invention.
Fill the formation material of the plastic ampoule of usefulness for medicinal liquid, its abbreviation, rerum natura etc. are shown below.
(polyolefin)
PE1: ethylene butene-1 copolymer (density 0.92g/cm
3, melt flow index (MFR) 1.0g/10min (190 ℃), trade name " ウ Le ト ゼ ッ Network ス 2010B ", Mitsui Chemicals company makes)
PE2: every part of goods that mix the organic pigment (trade name " Network ロ モ Off Le イ エ ロ-GR " and " Network ロ モ Off Le イ エ ロ-AGR " are that チ バ ガ イ ギ-company makes) of 0.2 weight % in PE1.(have and prevent that ultraviolet from seeing through the plastics of function (ultraviolet isolating))
PE3: the goods that in PE1, mix the sodium sulfite as oxygen absorbent (mean diameter is about 8 μ m) of 10 weight %.(have and prevent that oxygen from seeing through the plastics of function (oxygen-barrier property))
PP1: isotactic polypropylene (density 0.91g/cm
3, MFR1.6g/10min (230 ℃), Article Number " J704 ", Mitsui Chemicals company makes)
PP2: every part of goods that mix the organic pigment (trade name " Network ロ モ Off Le イ エ ロ-GR " and " Network ロ モ Off Le イ エ ロ-AGR ") of 0.2 weight % in PP1.(have and prevent that ultraviolet from seeing through the plastics of function)
(improved polyalkene)
AD1: maleic acid modified poly ethylene (density 0.92g/cm
3, MFR0.9g/10min (190 ℃), trade name " ア De マ-NB550 ", Mitsui Chemicals company makes)
(polyhydric alcohol)
EVOH1: ethylene-vinyl alcohol copolymer (175 ℃ of fusing points, MFR1.6g/10min (190 ℃), trade name " エ バ-Le EP-H101 ", Network ラ レ company makes)
(poly-cycloolefin)
COP1: norborene is monomeric ring-opening polymerization polymer hydrogenation products (105 ℃ of glass transition temperatures (Tg), trade name " ゼ オ ノ ア 1020R ", Japanese ゼ オ Application company makes for proportion 1.01, MFR20g/min (280 ℃))
COP2: norborene is monomeric ring-opening polymerization polymer hydrogenation products (Tg is 70 ℃ for proportion 1.01, MFR27g/min (280 ℃), trade name " ゼ オ ノ ア 750R ", Japanese ゼ オ Application company makes)
COP3: norborene is monomeric ring-opening polymerization polymer hydrogenation products (Tg is 136 ℃ for proportion 1.01, MFR20g/min (280 ℃), trade name " ゼ オ ノ ア 1420R ", Japanese ゼ オ Application company makes)
COC1: the copolymer of ethylene and tetracyclododecen (Tg is 105 ℃ for proportion 1.03, MFR25g/10min (260 ℃), trade name " ア ペ Le APL6011T ", Mitsui Chemicals company makes)
COC2: the copolymer of ethylene and tetracyclododecen (Tg is 80 ℃ for proportion 1.02, MFR40g/10min (190 ℃), trade name " ア ペ Le APL6509 ", Mitsui Chemicals company makes)
COC3: the copolymer of ethylene and tetracyclododecen (Tg is 70 ℃ for proportion 1.02, MFR40g/10min (190 ℃), trade name " ア ペ Le APL8008 ", Mitsui Chemicals company makes)
(polyamide)
NY1: m-xylene diamine-adipic acid condensation polymer (SANLING gas chemical company makes for 243 ℃ of fusing points, trade name " MX nylon 6001 ")
(polyester)
PET1: polyethylene terephthalate (trade name " Mitsui PET ", Mitsui Chemicals company makes)
The manufacturing of the plastic ampoule of＜filling medicinal liquid 〉
(embodiment 1)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, prepare outer by COP1 (poly-cycloolefin) preparation internal layer, PE1 (polyolefin), and 0.005% nitroglycerine aqueous solution 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 10mL) that 2 layers of structure are arranged.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 100 μ m, outer 700 μ m.
(embodiment 2)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, by COP1 (poly-cycloolefin) and PE1 (polyolefin) with the plastics of the mixed of 50: 50 (weight ratio) prepare internal layer, PP1 (polyolefin) prepares skin, and 0.005% nitroglycerine aqueous solution 20mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 20mL) that 2 layers of structure are arranged.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 100 μ m, outer 700 μ m.
(embodiment 3)
Use has blowing, filling, the sealing machine of 3 layers of blowing mould, prepare outer by PE1 (polyolefin) preparation internal layer, COP1 (poly-cycloolefin) preparation intermediate layer, PE1, and 0.005% nitroglycerine aqueous solution 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 10mL) of the structure that haves three layers.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, intermediate layer 100 μ m, outer 700 μ m.
(embodiment 4)
As the plastics that form the intermediate layer, use COP1 and PE1 (polyolefin) to replace only using COP1 (poly-cycloolefin) with the plastics of the mixed of 50: 50 (weight ratio), the internal volume of ampoule is 5mL, and the amount of the 0.005% nitroglycerine aqueous solution of filling in ampoule is 5mL, carry out 3 identical operations in addition, make filling medicinal liquid plastic ampoule with 3-tier architecture with embodiment.
(embodiment 5)
Use has blowing, filling, the sealing machine of 5 layers of blowing mould, prepare intermediate layer (internal layer side), COP1 by PE1 (polyolefin) preparation internal layer, COP1 (poly-cycloolefin) and PE1 with the plastics of the mixed of 50: 50 (weight ratio) and prepare that intermediate layer (pars intermedia), COP1 and PE1 prepare intermediate layer (outer layer side) with the plastics of the mixed of 50: 50 (weight ratio) and PE1 prepares skin, and 0.005% nitroglycerine aqueous solution 20mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 20mL) of the structure that is of five storeys.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, and intermediate layer (internal layer side, intermediate layer and outer layer side) respectively is 100 μ m, outer 500 μ m.
(embodiment 6)
As the plastics that form intermediate layer (pars intermedia), use COP1 and PE1 (polyolefin) to replace only with COP1 (poly-cycloolefin) with the plastics of the mixed of 80: 20 (weight ratio), the internal volume of ampoule is 10mL, and the amount at inner 0.005% the nitroglycerine aqueous solution of filling of ampoule is 10mL, carry out 5 identical operations in addition, make medicinal liquid filling plastic ampoule with 5 layers of structure with embodiment.
The performance evaluation of＜plastic ampoule 〉
Filling medicinal liquid to embodiment 1～6 was implemented autoclaving 40 minutes down at 106 ℃ respectively with plastic ampoule, preserved for 2 weeks down at 60 ℃ then, was determined at the content of the nitroglycerine of the nitroglycerine aqueous solution of filling in the ampoule.In addition, the medicament that nitroglycerine is absorption, adsorptivity is high.
The measurement result of any one ampoule all is that the remaining quantity of preserving the nitroglycerine after 2 weeks is more than the 95 weight %, and nitroglycerine is to the absorption of ampoule internal face, absorption and soaking into, discharging and also obviously obtained sufficient inhibition to the ampoule outside.That is, the ampoule of embodiment 1～6 is any one prevents drug absorption absorption and prevents that the ability that medicine sees through is all good.This thinks because the ampoule of embodiment 1～6 all has poly-cycloolefin layer.
＜table 1 〉
Above: in the middle of the material: below the mixed proportion of resin (weight ratio): layer thickness
The manufacturing of the plastic ampoule of＜filling medicinal liquid 〉
(embodiment 7)
Use has blowing, filling, the sealing machine of 3 layers of blowing mould, prepare outer by PE1 (polyolefin) preparation internal layer, EVOH1 (polyhydric alcohol) preparation intermediate layer, PE1, and 0.1% tryptophan aqueous solution 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 10mL) of the structure that haves three layers.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, intermediate layer 100 μ m, outer 700 μ m.
(embodiment 8)
Use has blowing, filling, the sealing machine of 5 layers of blowing mould, prepare intermediate layer (outer layer side) and PE1 preparation skin by PE1 (polyolefin) preparation internal layer, AD1 (improved polyalkene) preparation intermediate layer (internal layer side), EVOH1 (polyhydric alcohol) preparation intermediate layer (pars intermedia), AD1, and 0.1% tryptophan aqueous solution 5mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 5mL) of the structure that is of five storeys.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, and intermediate layer (internal layer side and outer layer side) respectively is 10 μ m, and intermediate layer (pars intermedia) is 100 μ m, outer 700 μ m.
(embodiment 9)
Use has blowing, filling, the sealing machine of 4 layers of blowing mould, outer by PE1 (polyolefin) preparation internal layer, PE3 (plastics that oxygen-barrier property is arranged) preparation intermediate layer (internal layer side), EVOH1 (polyhydric alcohol) preparation intermediate layer (outer layer side) and PE1 preparation, and 0.1% tryptophan aqueous solution 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 10mL) that 4 layers of structure are arranged.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, and intermediate layer (internal layer side and outer layer side) respectively is 100 μ m, outer 600 μ m.
The performance evaluation of＜plastic ampoule 〉
Filling medicinal liquid to embodiment 7～9 was implemented autoclaving 40 minutes down at 106 ℃ respectively with plastic ampoule, preserved for 2 weeks down at 60 ℃ then, was determined at the content of the tryptophan of the tryptophan aqueous solution of filling in the ampoule.In addition, tryptophan is the medicament of easy oxidation.
The measurement result of any one ampoule all is that the remaining quantity of tryptophan after preserving for 2 weeks is more than the 95 weight %, shows that the oxidative degradation of tryptophan has obtained sufficient inhibition.That is, showing that the ampoule of embodiment 7～9 is any one prevents gas permeation (barrier properties for gases, special than be oxygen-barrier property) and prevents that the ability that medicine sees through is all good.This thinks because the ampoule of embodiment 7～9 all has the polyhydric alcohol layer.
The manufacturing of the plastic ampoule of＜filling medicinal liquid 〉
(embodiment 10)
Use has blowing, filling, the sealing machine of 3 layers of blowing mould, prepare outer by PE1 (polyolefin) preparation internal layer, COP1 (poly-cycloolefin) preparation intermediate layer, PE2 (ultraviolet isolating plastics), and 0.05% vitamin B2 aqueous solution 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 10mL) of the structure that haves three layers.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, intermediate layer 100 μ m, outer 700 μ m.
The performance evaluation of＜plastic ampoule 〉
Filling medicinal liquid to embodiment 10 was implemented autoclaving 40 minutes with plastic ampoule down at 106 ℃, preserved for 2 weeks down at 60 ℃ then, was determined at the content of the vitamin B2 of the vitamin B2 aqueous solution of filling in the ampoule.In addition, vitamin B2 is the medicament of photodegradation.
Measurement result is that the remaining quantity of vitamin B2 after preserving for 2 weeks is more than the 95 weight %, shows that its photodegradation has obviously obtained sufficient inhibition.That is, the ampoule of embodiment 10 prevents that the ability (optics barrier) that light sees through is good.This thinks to have mixed the layer that coloring agent (organic pigment) makes because the ampoule of embodiment 10 has.
And the vitamin B2 aqueous solution has also obviously obtained abundant inhibition to the dissolving of contained pigment in the skin.This thinks because the layer inboard that mixed colorant (organic pigment) makes has poly-cycloolefin layer.
The manufacturing of the plastic ampoule of＜filling medicinal liquid 〉
(embodiment 11)
Use has blowing, filling, the sealing machine of 5 layers of blowing mould, by PE1 (polyolefin) preparation internal layer, AD1 (improved polyalkene) preparation intermediate layer (internal layer side), NY1 (polyamide; M-xylene diamine-adipic acid condensation polymer) preparation intermediate layer (pars intermedia), AD1 prepare intermediate layer (outer layer side) and PP2 (ultraviolet isolating plastics) preparation skin, and Palmic acid (acid of パ Le チ ミ Application) the vitamin A solubilize liquid 2mL of 400IU/mL fills in portion within it, makes the filling medicinal liquid plastic ampoule (internal volume 2mL) of the structure that is of five storeys.This ampoule 10 has shape shown in Figure 1, and thickness of pipe wall is internal layer 50 μ m, and intermediate layer (internal layer side and outer layer side) respectively is 10 μ m, and intermediate layer (pars intermedia) is 100 μ m, outer 500 μ m.
The performance evaluation of＜plastic ampoule 〉
The filling medicinal liquid of embodiment 11 is implemented autoclaving 40 minutes with plastic ampoule down at 106 ℃, under 60 ℃, 60%RH, preserved for 2 weeks then, be determined at the content of the Palimitate-A of the Palimitate-A solubilize liquid of filling in the ampoule.In addition, Palimitate-A is the medicament of easily oxidizable and photodegradation.
Measurement result is that the remaining quantity of Palimitate-A after preserving for 2 weeks is more than the 95 weight %, shows that its oxidative degradation and photodegradation have obtained sufficient inhibition.That is, the ampoule of embodiment 11 prevents the ability of gas permeation (barrier properties for gases, particularly oxygen barrier performance) and prevents that the ability (light barrier) that light sees through is good.This thinks because the ampoule of embodiment 11 has the layer that aramid layer and mixed colorant (organic pigment) make.
And, show that Palimitate-A solubilize liquid has obtained abundant inhibition to the dissolving of contained pigment in the skin.This thinks because the layer inboard that mixed colorant (organic pigment) makes has aramid layer.
In addition, the layer structure of the plastic ampoule that obtains among the embodiment 7～11 etc. is summarised in the table 2.
＜table 2 〉
Above: in the middle of the material: below the mixed proportion of resin (weight ratio): layer thickness
The manufacturing of the plastic ampoule of＜filling medicinal liquid 〉
(embodiment 12)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, prepare skin by COP2 (poly-cycloolefin) preparation internal layer, PE1 (polyolefin), and normal saline 10mL fills in portion, makes the filling medicinal liquid plastic ampoule that 2 layers of structure are arranged within it.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is internal layer 200 μ m, outer 500 μ m.
(embodiment 13)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, and by COP2 (poly-cycloolefin) preparation internal layer, COP3 (poly-cycloolefin) preparation skin, and normal saline 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule that 2 layers of structure are arranged.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is internal layer 200 μ m, outer 500 μ m.
(embodiment 14)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, prepare skin by COC1 (poly-cycloolefin) preparation internal layer, PE1 (polyolefin), and normal saline 10mL fills in portion, makes the filling medicinal liquid plastic ampoule that 2 layers of structure are arranged within it.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is internal layer 200 μ m, outer 500 μ m.
(embodiment 15)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, and by COC2 (poly-cycloolefin) preparation internal layer, PE1 (poly-cycloolefin) preparation skin, and normal saline 10mL fills in portion within it, makes the filling medicinal liquid plastic ampoule that 2 layers of structure are arranged.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is internal layer 200 μ m, outer 500 μ m.
(embodiment 16)
Use has blowing, filling, the sealing machine of 2 layers of blowing mould, prepare skin by COC3 (poly-cycloolefin) preparation internal layer, PE1 (polyolefin), and normal saline 10mL fills in portion, makes the filling medicinal liquid plastic ampoule that 2 layers of structure are arranged within it.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is internal layer 200 μ m, outer 500 μ m.
(comparative example 1)
Use blowing, filling, sealing machine, by COP3 (poly-cycloolefin, Tg is 136 ℃) preparation, and normal saline 10mL fills in portion within it, makes the plastic ampoule of single layer structure.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is 800 μ m.
(reference example 1)
Use blowing, filling, sealing machine, by COP2 (poly-cycloolefin, Tg is 70 ℃) preparation, and normal saline 10mL fills in portion within it, makes the plastic ampoule 18 of single layer structure.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is 800 μ m.
(reference example 2)
Use blowing, filling, sealing machine, by COC1 (poly-cycloolefin, Tg is 105 ℃) preparation, and normal saline 10mL fills in portion within it, makes the plastic ampoule 18 of single layer structure.This ampoule 18 has 5 disjunctor shapes shown in Figure 2, and thickness of pipe wall is 800 μ m.
The performance evaluation of＜plastic ampoule 〉
Confirming to have aneroid to leak for the plastic ampoule range estimation that obtains in the foregoing description 12～16, comparative example 1 and the reference example 1～2 takes place.To be poly-cycloolefin and glass transition temperature (Tg) all do not detected liquid at 50 ampoules (ampoules of 10 5 disjunctors) of 110 ℃ or following embodiment 12～16 to the plastics that consequently form internal layer leaks.Relative therewith, 8 one-tenth of 50 ampoules of comparative example 1 is that 40 ampoules have all detected the liquid leakage.
In addition, shown in reference example 1 and 2, plastic ampoule also can be the individual layers that is made by a kind of poly-cyclic olefin in actual use.At this moment, the poly-cycloolefin that forms ampoule integral body preferably uses glass transition temperature at 110 ℃ or following poly-cycloolefin.The glass transition temperature of poly-cycloolefin is preferably 60～105 ℃, more preferably 60～80 ℃.
The layer structure of the plastic ampoule that obtains in embodiment 12～16, comparative example 1 and the reference example 1～2 etc. is summarised in the table 3.
＜table 3 〉
Above: below the material (glass transition temperature ℃): layer thickness
As mentioned above, plastic ampoule provided by the invention can be used for aseptic and stably take care of, preserves easy oxidation medicament, photodegradation medicament, absorbs absorption preparation etc., and then applicable to the manufacturing of this plastic ampoule.
Claims (10)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP118901/2003 | 2003-04-23 | ||
| JP2003118901 | 2003-04-23 | ||
| JP364971/2003 | 2003-10-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2518505Y (en) * | 2002-02-05 | 2002-10-30 | 张俊杰 | Eye drops bottle |
-
2004
- 2004-04-19 CN CNB2004800106848A patent/CN100515381C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2518505Y (en) * | 2002-02-05 | 2002-10-30 | 张俊杰 | Eye drops bottle |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104379069A (en) * | 2012-03-28 | 2015-02-25 | 伊西康内外科公司 | Tissue thickness compensator comprising a reservoir |
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| Publication number | Publication date |
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| CN1777406A (en) | 2006-05-24 |
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