CN105658539A - Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container - Google Patents
Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container Download PDFInfo
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- CN105658539A CN105658539A CN201480050690.XA CN201480050690A CN105658539A CN 105658539 A CN105658539 A CN 105658539A CN 201480050690 A CN201480050690 A CN 201480050690A CN 105658539 A CN105658539 A CN 105658539A
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- Prior art keywords
- container
- aerosol
- copolyesters
- isosorbide
- preform
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
- B65D83/38—Details of the container body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/10—Handles
- B65D23/102—Gripping means formed in the walls, e.g. roughening, cavities, projections
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
- B65D83/16—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant characterised by the actuating means
- B65D83/20—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant characterised by the actuating means operated by manual action, e.g. button-type actuator or actuator caps
- B65D83/205—Actuator caps, or peripheral actuator skirts, attachable to the aerosol container
- B65D83/206—Actuator caps, or peripheral actuator skirts, attachable to the aerosol container comprising a cantilevered actuator element, e.g. a lever pivoting about a living hinge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
- B65D83/44—Valves specially adapted therefor; Regulating devices
- B65D83/48—Lift valves, e.g. operated by push action
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a plastic preform suitable to be stretch blow molded in order to form an aerosol container (20) or to an injection stretch blow molded aerosol container (20), wherein the preform or container are made of a polymeric material that comprises a copolyester including at least 1 mole % of isosorbide as comonomer and having an intrinsic viscosity of at least 0.7 dL/g.
Description
Technical field
The present invention relates to the aerosol container of Novel injection stretch-blow and applicable stretch-blow to form the novel plastic preform of aerosol container. The present invention also relates to the novel aerosol plastic dispenser for distributing aerosol or other similar pressurized product.
Prior art
Aerosol dispenser is known in this area. More specifically, aerosol dispenser comprises aerosol container, and described aerosol container comprises aerosol (or other similar pressurized product), and is equipped with the valve distribution device for distributing aerosol. The aerosol dispenser comprising the aerosol container being made of plastics such as is disclosed in U.S. Patent application US2004/0149781 and PCT application WO2007/140407.
Term used herein " aerosol " comprises aerosol according to literal meaning, and also comprising other can the product that maybe can flow from the liquid that pressurizing vessel distributes of the mode similar with aerosolization product. The product that other liquid such maybe can flow includes but not limited to foam or gel preparation, or sends from pressurizing vessel but need not be the liquid product of powder-form.
The example of typical case's aerosol composition can significantly but not exhaustivelyly for sterilant, wormer, hair jelly, cosmetic spray, air freshener, detergent, agent of shaving comprise foam and gel.
When plastic containers are for the preparation of aerosol container, the high interior pressure of plastic containers inside can cause the mechanical deformation of plastic aerosol container unfavorablely, and even causes aerosol plastic containers to explode. When this problem of mechanical deformation gentle sol plastic container explosion under the impact pressed in high has the aesthetics with concave side walls grip portions and ergonomic shape when container even more crucial, described container as such as in Fig. 1 or 2 of U.S. Patent application US2004/0149781 or such as PCT application WO2007/140407 Fig. 1,5, the container described in 6B, 6C, 7A to 7F, 8A, 8D, 8E, 8G, 8H. And have with straight sidewall or with compared with the container of the cylinder of convex sidewall, described concave side walls grip portions in fact press in high under easier mechanical deformation.
This be why aerosol plastic containers must withstand voltage with bear high in the reason of pressure. More specifically, at present in the European Community, plastic aerosol divider must meet the technical requirements of the standard FEA621 in March, 2007, and described standard FEA621 meets the regulation of the aerosol dispenser instruction 75/324/EEC in May, 1975 and relates to the measurement of the anti-interior pressure property of the empty receptacle not having valve.
PET (polyethylene terephthalate) is extensively for the preparation of two-way stretch container, more specifically prepares the polyester known of injection drawing blow (ISBM) container.ISBM level PET has the limiting viscosity (IV) of 0.7dL/g to 0.8dL/g and the second-order transition temperature (Tg) of about 75 DEG C to 80 DEG C usually.
Usually, polyester, such as PET homopolymer or multipolymer, in the region more than the natural draw ratio (NSR) of polymkeric substance, when can advantageously show the crystallization of strain inducing when a large amount of orientation. It is well known that, for obtaining the ISBM polyester container with good mechanical properties, the two-way stretch of polyester must be enough important in the strain hardening region of polyester, only slight beyond the NSR of polymkeric substance.
The NSR of polymkeric substance can measure with being familiar with in free blowing is tested. The free blowing of thermoplastics, particularly PET and PET copolymer is the technology known of the rule of thumb data of the stretch behavior for obtaining concrete resin formula. The method of free blowing PET preform is described in " blowing handbook (BlowMoldingHandbook) " that edited in 1989 by DonaldV.Rosato, DominickV.Rosato, Munich. Term " free blowing " refers to the blowing preform when not using mould. Relate to, from preform free blowing bottle, the temperature that preform is heated to more than its second-order transition temperature, then make preform expand at mold exterior, so that its free expansion without limitation, until strain hardening starts. Strain hardening can be detected as the stress following flowing level ground in stress-strain curve and rise. To a great extent, strain hardening is relevant to the molecular assembly process in resin. If the blowing pressure of preform and heating given preform is suitably arranged, then its by continuations expand, until all PET be oriented stretch by near natural draw ratio or slightly exceed natural draw ratio place stopping point.
But, standard I SBM level PET, even if in strain hardening region, usually it is not suitable for the withstand voltage ISBM aerosol container that preparation stands high interior pressure, more generally it is not suitable for the withstand voltage ISBM aerosol container preparing the technical requirements by the standard FEA621 realizing in March, 2007.
Structure the following glycol 1,4:3,6-bis-illustrated dewater-D-glucitol (hereinafter referred to as Isosorbide) easily prepared by renewable resources, such as sugar and starch, the native starch particularly extracted from corn, wheat, potato and pea. Such as, Isosorbide can by the hydrogenation of D-Glucose then acid-catalyzed dehydration preparation.
Isosorbide has been used as and has been incorporated into polyester such as the monomer in PET with low-level. Known Isosorbide mixes the limiting viscosity reducing copolyesters in copolyesters as comonomer.
Therefore, comprise the copolyesters of Isosorbide, particularly comprise the polyethylene terephthalate (PEIT) of isosorbide polymer, and it is known in this area by melt polymerization or by the preparation method of solvent polymeric.
Comprise the copolyesters of Isosorbide, particularly comprise the polyethylene terephthalate (PEIT) of isosorbide polymer, up to now in many application, such as, for the preparation of film or container. Especially, the polyethylene terephthalate (PEIT) comprising Isosorbide may be used for preparing the heat standing high temperature and charges (hot-fillable) container.
As following publication is clearly determined, Isosorbide mixes the second-order transition temperature (Tg) (see the change of Fig. 2 Tg with the mol% of Isosorbide) improving copolyesters in copolyesters as comonomer, and the strain hardening feature of polymkeric substance is had impact.
" comprise characteristic and the strain hardening feature (PropertiesandStrainHardeningCharacterofPolyethyleneTerep hthalateContainingIsosorbide) of the polyethylene terephthalate of Isosorbide ", RameshM.Gohil, PolymersEngineeringandScience-2009 544-553 page.
Although comprising the copolyesters of Isosorbide, the polyethylene terephthalate (PEIT) particularly comprising isosorbide polymer may be used in many application up to now, but can not commercially find the ISBM aerosol container prepared by the copolyesters comprising Isosorbide, the ISBM aerosol container particularly prepared by PEIT polymkeric substance.
Therefore to the withstand voltage aerosol container of the ISBM prepared by the copolyesters comprising Isosorbide, the ISBM particularly prepared by PEIT polymkeric substance is withstand voltage, and aerosol container has the needs not being satisfied.
Goal of the invention
Therefore, the main purpose of the present invention is the Novel pressure-resistant aerosol plastic containers proposing to prepare by the copolyesters comprising Isosorbide, the Novel pressure-resistant aerosol plastic containers that particularly (but being not only) is prepared by PEIT polymkeric substance.
Invention general introduction
First object of the present invention is that applicable stretch-blow is to form plastics preforms or the injection drawing blow aerosol container of aerosol container, described preform or aerosol container are made up of the polymer materials comprising copolyesters, and described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least 0.7dL/g.
The ISBM aerosol container of the present invention shows extraordinary mechanical property, particularly can advantageously stand high interior pressure.
Aerosol container is generally the container with small volume, is usually not more than 750ml. Therefore, when preparing aerosol container with the use of ISBM technology, low stretch ratio only can be implemented.
Isosorbide as comonomer mix in copolyesters the strain hardening region on copolyesters start there is strong impact, more specifically make the NSR of copolyesters raise. Unless otherwise prescribed, comprise the copolyesters of Isosorbide, particularly comprise the polyethylene terephthalate (PEIT) of isosorbide polymer, it is necessary to the elongation more much higher than standard P ET homopolymer is to arrive strain hardening region.
Therefore, before making the present invention, it has been generally acknowledged that the copolyesters using and comprising Isosorbide, especially there is the copolyesters of high-caliber Isosorbide, due to the thermal characteristics that will finally improve container by realizing higher Tg, but because the NSR of copolyesters is too high, therefore it is not suitable for preparation and there is the withstand voltage aerosol ISBM container standing the necessary mechanical property of pressure in common height, be not especially suitable for the withstand voltage aerosol ISBM container that preparation has the small volume of low stretch ratio.
The present invention comprises the limiting viscosity of copolyesters of Isosorbide by improving, and such as time by making the solid-state polymerization (SSP) of copolyesters carry out being enough to realize at least IV of 0.7dl/g eliminates this prejudice. The raising of this IV advantageously reduces the NSR of copolyesters, and can obtain the copolyesters combining high-caliber Isosorbide and lower NSR and being applicable to prepare withstand voltage ISBM aerosol container.
More specifically, the preform of the present invention or ISBM aerosol container can have any one following optional feature:
-preform or container are made up of copolyesters substantially, and described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least about 0.7dL/g.
-described copolyesters is the polyethylene terephthalate (PEIT) comprising Isosorbide.
-described copolyesters comprises the Isosorbide as comonomer of at least 3 moles of %, more specifically the Isosorbide as comonomer of at least 5 moles of %.
-described copolyesters comprises the not Isosorbide as comonomer more than 15 moles of %, it is preferable that not more than the Isosorbide as comonomer of 8 moles of %.
The limiting viscosity of-described copolyesters is at least 0.8.dL/g, is more specifically at least 0.9.dL/g.
The limiting viscosity of-described copolyesters is not more than 2.dL/g.
-described injection drawing blow aerosol container has the axial tensile rate (S being not more than 3a), it is preferable that there is the axial tensile rate (S being not more than 2.55a)��
-described injection drawing blow aerosol container has the radial drawing ratio (S being not more than 2.5r), it is preferable that there is the radial drawing ratio (S being not more than 2.4r)��
-described injection drawing blow aerosol container has the total drawing ratio (S) being not more than 9, it is preferable that have the total drawing ratio (S) being not more than 7.
-described injection drawing blow plastic containers have concave side walls grip portions.
-described injection drawing blow plastic containers have the volume being not more than 750ml, it is preferable that have the volume being not more than 500ml.
The present invention also relates to aerosol dispenser, it valve distribution device comprising above-mentioned injection drawing blow aerosol container and being applicable to distribute the aerosol being contained in aerosol container.
Brief Description Of Drawings
The other technologies feature and advantage of the present invention will read the following detailed description made by non exhaustive and non-limiting example and become clearer after reference the following drawings:
-Fig. 1 is that applicable stretch-blow is to form the cross sectional longitudinal view of the preform of withstand voltage aerosol plastic containers.
-Fig. 2 is the cross sectional longitudinal view of the aerosol dispenser comprising ISBM aerosol container, described ISBM aerosol container is obtained by the preform of two-way stretch blowing Fig. 1, and is equipped with the valve distribution device being applicable to distribute the aerosol being contained in aerosol container.
Describe in detail
With reference to Fig. 2, aerosol dispenser 2 comprises the withstand voltage aerosol container 20 being sealed shut by valve distribution device 21 intentionally. Described valve distribution device 21 comprises closuremember (closure) 210, the open top 200 of described closuremember 210 coating gas collosol container 20, and is connected to the neck 201 of aerosol container 20 with sealing. Described closuremember 210 comprises the valve element 211 with axially extended valve rod 212, and described valve rod 212 can be depressed or tilt to discharge the aerosol being contained in container 20. The structure and function of valve distribution device 21 is known in this area, and will be not described in detail. Those skilled in the art can referring additionally to the open text of US2004/0149781.
According to the present invention, described pressure-resistant plastic aerosol container 20 is injection stretch blow moulding container.
Fig. 1 shows applicable stretch-blow to form the plastics preforms 1 of withstand voltage aerosol plastic containers.
This preform 1 is by having axial length L1Tubular body arranged inside roughly make, described tubular body arranged inside in its bottom close and have at its upper end and topple over opening. Terminate in the neck 10 toppling over opening 100 more particularly, it is seen that preform 1 comprises, form the so-called gate portion 12 of closed bottom end, and the main part 11 extended between described gate portion 12 and described neck 10. Neck 10 comprises the outstanding neck support ring 101 with larger diameter.Main part 11 comprises the main cylindrical body portion 110 and upper transition portion 111 with substantially invariable wall thickness WT. The internal surface of major portion 110 can also be cone.
In this specific examples of Fig. 1, gate portion 12 is made up of the male portion with roughly hemispherical shape, and terminates in the outstanding injection point 20 of little central authorities. The size of this injection point 20 is corresponding to the size of the delivery outlet of the hot-runner nozzle for plastic material injects mould. The shape of gate portion 12 not necessarily semisphere, but gate portion 12 can have other shapes arbitrarily, can be such as cone especially.
When this preform 1 in a mold two-way stretch blowing time, neck 10, for the preform remained in blow mold, is not therefore stretched. Main part 11 by two-way stretch (at longitudinal X with on radial Y) to form the container body with higher volume. Gate portion 12 also by two-way stretch usually to form the base of injection stretch blow moulding container.
Within the scope of the invention, it is possible to use " single stage method " or " two-step approach ". In " single stage method ", the stretch-blow step of preform carries out online immediately after the first injecting step (preform injection). In " two-step approach ", the stretch-blow step of preform postpones, and carries out reheating of preform before this stretch-blow step.
The net shape of container and size are by the stretch ratio of the blow mold and enforcement that depend on use. Such as but be not that therefore preform 1 can be stretched blowing to prepare the withstand voltage aerosol container 20 of Fig. 2.
But, the invention is not restricted to the concrete shape of the aerosol container 20 of Fig. 2 or size.
Specifically, the container that the bottom 202 (Fig. 2) of aerosol container 20 is not necessarily described as Fig. 2 is spherical, but can have arbitrary shape. More specifically, the bottom 202 of aerosol container 20 can also be the center dome (being usually also called " champagne " bottom) comprising inside orientation, can be maybe " petal-shaped " bottom of the bottom of the container of Fig. 8 D of picture such as WO2007/140407.
In the concrete aerosol container 20 of Fig. 2, the sidewall of container comprises main middle body 203, and it is spill, and forms a kind of hyperboloid configuration, and described hyperboloid configuration provides the structure meeting very much human engineering being easy to operate by user. In other variants, the sidewall of container 2 can have other shapes arbitrarily, comprises vertical wall section, concave wall part etc.
According to the present invention, the pressure tight injection stretch-blow aerosol container 20 that can stand high interior pressure to obtain, it is copolyesters for the preparation of the polymer materials of preform 1 or container 2, described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least 0.7dL/g, the limiting viscosity more preferably with at least 0.8dL/g, even more preferably has the limiting viscosity of at least 0.9dL/g.
In order to realize the minimum IV of at least 0.7dL/g of described requirement, the time that the limiting viscosity comprising the copolyesters of Isosorbide generally such as is enough to realize the minimum IV of requirement by making the solid-state polymerization (SSP) of copolyesters carry out raises. The NSR that the rising of this IV advantageously can make to comprise the polyester of Isosorbide reduces, and compensates the rising of the NSR mixing copolyesters by Isosorbide and cause at least partly. But, it is desired to IV level can also directly, that is, when there is no SSP aftertreatment, be obtained by the polymerization process carrying out being applicable to.
More preferably, the polyester comprising Isosorbide comprises copolyesters, and described copolyesters comprises the Isosorbide as comonomer of at least 5 moles of %.
More specifically, the polyester comprising Isosorbide comprises copolyesters, and described copolyesters comprises the not Isosorbide as comonomer more than 15 moles of %, even more preferably not more than the Isosorbide as comonomer of 8 moles of %.
The copolyesters comprising Isosorbide can be formed by any method known in the art. But, it may be preferred that polyester is formed by solvent or melt polymerization.
Preferably, described in comprise Isosorbide copolyesters be the polyethylene terephthalate (PEIT) comprising Isosorbide, but other polyester also be applicable to implement the present invention.
Preferably, the copolyesters comprising Isosorbide described in comprises terephthaloyl base section; Optionally, one or more aromatic diacid parts; Ethylene glycol moieties; Isosorbide moieties; Optionally one or more other glycol moieties.
More particularly, it is seen that terephthaloyl base section can derived from terephthalic acid or dimethyl terephthalate (DMT).
More specifically, the copolyesters comprising Isosorbide can also comprise Diethylene Glycol part.
One or more other glycol moieties aforesaid can derived from having 3-12 carbon and have aliphatic alkylene group glycol or the branched chain aliphatic diol of empirical formula HO-CnH2n-OH, and wherein n is the integer of 3-12; Comprise branched diol, such as 2,2-dimethyl-1,3-propylene glycol; The mixture of cis or trans-1,4-cyclohexane dimethanol and cis and trans-isomer(ide); Triethylene glycol; Two [4-(2-hydroxyl-oxethyl) phenyl] propane of 2,2-; Two [4-(2-hydroxyl-oxethyl) phenyl] hexanaphthene of 1,1-; Two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9,9-; 1,4:1,4:3,6-bis-anhydromannitol; 1,4:1,4:3,6-bis-dewaters iditol; Erythritol anhydrous with 1,4-.
Preferably, but optionally, the quantity of the terephthaloyl base section in polymkeric substance is about 25% to about 75 mole of % (mole % of total polymer).
In a preferred embodiment, ethylene glycol monomers unit exists with the amount of about 5 moles of % to about 49.75 moles of %. Polymkeric substance can also comprise Diethylene Glycol part. According to preparation method, the amount of Diethylene Glycol part is such as about 0.0 mole of % to about 25 moles of %.
Experiment
Use three kinds of different polymer compositions, by injection have 35g weight preform 1 and by described preform two-way stretch being blow molded into the ISBM aerosol container that volume is 335ml, preparation has similar shape and size, more specifically has the ISBM individual layer aerosol container of three different batches (comparison A, comparison B, comparison C) of the sidewall hyperboloid configuration of the container being similar to Fig. 2. The wall thickness (WT) of the main cylindrical main part 11 of preform 1 is about 4.5mm (+/-5%).
Blowing step uses the axial tensile rate S of about 2.4mmaCarry out.
This axial tensile rate (Sa) clearly define in the standard fashion by following formula:
Wherein: L is container length of run (Fig. 2), and l is preform neutral fibre length of run (Fig. 1).
Radial drawing ratio (Sr) it is about 2.55mm. This radial drawing ratio (Sr) clearly define in the standard fashion by following formula:
Wherein D is largest container external diameter (see Fig. 2) and d is maximum preform outer diameter D p (Fig. 1) subtracts wall thickness WT (d=Dp-WT).
The total drawing ratio (S) of aerosol container is about 6.This total drawing ratio (S) is clearly defined in the standard fashion by following formula:
S=Sa��Sr
First batch of (comparison A) ISBM aerosol container is by the polyethylene terephthalate [that is, poly-terephthalic acid (ethene-altogether-Isosorbide) ester] (PEIT) comprising Isosorbide. More particularly, it is seen that PEIT comprises the Isosorbide (PEIT of 5.8 moles of %) of 5.8 moles of %. The PEIT of these 5.8 moles of % is obtained by melt polymerization in known manner. The PEIT of these the 5.8 moles of % produced by melt polymerization stands SSP being enough to make the IV comprising the copolyesters of Isosorbide be increased in for some time up to about 0.95dL/g.
The standard level PET resin that 2nd batch of (comparison B) the ISBM aerosol container is about 0.86dL/g by limiting viscosity is made.
The PET resin that 3rd batch of (comparison C) the ISBM aerosol container is about 0.95dL/g by limiting viscosity is made. Described PET resin is the copolymer p ET that ArteniusTechPolymers sells with trade(brand)name " ArteniusHOT ".
For all three crowdes of A, B and C, the limiting viscosity (IV) of resin before the injection, based on ISO1628 standard, is measured according to following method:
-by 10g material dry 3h at 120 DEG C under vacuo.
-10g material is ground to the order footpath of 0.5mm.
-material that 0.50g grinds is weighed in 100ml volumetric flask.
-add solvent with sample dissolution. Solvent is DCA (dichloro acetic acid).
-heat and stir volumetric flask until all substances dissolve.
-solution is stablized at 25 DEG C and is injected solvent until accurate 100ml volume.
-in special capillary viscosimeter, measure solution and according to ISO1628 criterion calculation IV, the solvent of use is taken into account.
Also implement, as solvent, the limiting viscosity (IV) that aforesaid method measures three batches of preforms with the use of meta-cresol. Result display due to during injection process polymer degradation and cause IV to decline. The IV of the preform of first batch (comparison A) is about 0.8dL/g. The IV of the preform of the 2nd batch (comparison B) is about 0.73dL/g. The IV of the preform of the 3rd batch (comparison C) is about 0.78dL/g.
For all three crowdes of A, B and C, the second-order transition temperature (Tg) of resin is measured by dsc (DSC) with knowing, it may also be useful to from the equipment DSC821e of MettlerToledo. The Tg of 5.8 moles of %PEIT (comparison A) is about 89.6 DEG C. The Tg of the PET resin of the 2nd batch (comparison B) is about 79.6 DEG C. The Tg of the PET resin of the 3rd batch (comparison C) is about 79.5 DEG C.
Three crowdes of aerosol containers A, B and C are carried out following machinery and Thermal test.
Hydraulic test
The object of this test evaluates the container dimensional stability after being pressurizeed by aerosol container. Test pressure is pressed high by 50% in needing ratio in the container of 50 DEG C.
Pressure (P) for hydraulic test calculates: use the pressure that equation for ideal gases (Perfectgaslow) is defined at 50 DEG C.
We suppose do not have creep on container, it means that the volume (V) at 20 DEG C and volume ' (V) identical (stricter than reality) at 50 DEG C.
Equation for ideal gases=> P.V=k.T (k=constant)
If V is constant, then: P(20��)/T(20��)=P(50��)/T(50��)
Pressure=absolute pressure
T ��=definitely T �� (�� K)
P(50��)=P(20��).T(50��)/T(20��)=> 8 bar (definitely). 323 �� of K/293 �� of K=8.82 cling to (definitely)=> 7.82 bar (relatively)
Conclusion: 7 bar obtain 7.82 bar (not considering volumetric expansion) at 50 DEG C at 20 DEG C
Therefore for hydraulic test, in the container at 50 DEG C, pressure is 7.82 bar.
Pressure+50%=> 7.82+50%=11.73 bar=at hydraulic pressure=50 DEG C > test pressure=12 bar
Test as follows subsequently:
Get 10 containers at random
�� is measuring vessel when initial: highly, diameter, shoulder-label-floorage, basal spacing, overflow volume.
�� uses SOMEXDelta3000PET bottle pressure tester, and pressurize to container 25 seconds (the calculating pressure+50% of the container at=50 DEG C) under 12 bar.
�� with the same way measured when initial measuring vessel again.
�� visually evaluates container. Allow the distortion of slight symmetry, as long as container is by burst tearing test.
Temperature-resistant material-fall test
The object of this test evaluates when falling concrete floor and container at different temperatures from the height of 1.8m. Guarantee that test container is statistically random in the orientation fallen, but avoid the direct impact to valve or valve closuremember. Aerosol container must be designed to it and not break or seepage.
�� aerosol container needs to test under 3 kinds of different temperature condition:
��-18 DEG C continues at least 24h
�� room temperature 20-22 DEG C continues at least 1h
�� 55 DEG C continues at least 6h (dry air)
�� for often organizing temperature test get 25 aerosol containers at random,
�� uses water to be full of the overflow volume of container 85%. For the container needing test at 18 DEG C, it may also be useful to the mixture of 50/50 water/frostproofer is full of container,
�� uses the curling valve closure container of metal,
�� uses extruding air to container pressurization under the relative pressure of 8.0 bar (this is the calculating pressure at 50 DEG C),
�� processes 25 containers at 3 kinds of different temperature, continues the time determined,
��, after moving out of container from weather room, directly makes container drop on concrete floor from the height random of 1.8m,
�� is falling postevaluation aerosol container: the container of 3 different groups does not allow seepage or breaks.
Burst tearing test
The object of this test evaluates the ability that aerosol container stands specific interior pressure. The pressure of container ruptures needs minimum than test pressure high by 20%. Equipment for this test is the Delta3000PET bottle pressure tester from SOMEX. Minimum explosion calculation of pressure: the test pressure+20%=> 14.4 bar (relatively) of 12 bar (relatively)
�� gets 10 aerosol containers at random,
�� container is full of water, and the original pressure on container is 4 bar, and the hold-time is 13 seconds, hereafter, with the rising build-up pressure of 0.69 bar/second until container ruptures;
The explosion pressure of all containers of �� needs in 14.4 Palestine and Israels.
Temperature-resistant material-warm air
The object of this test points out the temperature causing container deformation. The Temperature Ratio Tg of this test is low 7 DEG C, and full test temperature is 75 DEG C and minimum temperature is 65 DEG C. Allow container deformation but do not produce breaking or seepage of dangerous environment.
�� gets 25 aerosol containers at random;
�� use water fill container until container overflow volume 15% top void volume;
�� uses the curling valve closure container of metal;
�� uses extruding air to be pressurizeed by container under 8.0 bar (relatively);
�� processes 25 containers in weather cabinet under 75 DEG C of dry airs, minimum lasting 5 hours;
��, when warm air has been tested, evaluates the seepage of container and breaks.
Overall loading
The object of this test evaluates aerosol container before being out of shape first to the tolerance of vertical load. Equipment for this test is INSTRON3366 overall loading tester, and load elements is 5000N.Result be container lose 1% applying swage load before the maximum swage load (kgf) that can stand. Test uses the speed of 50mm/min to carry out.
�� gets 10 aerosol containers at random
�� tests each container individually
�� records deformation position and maximum swage load (test terminates: the swage load of 1% speed) at the end of test.
Accelerated stress ftractures
The object of accelerated stress cracking is the stress that simulation container fills at pressure, transports and experience in storage. This test carries out as follows:
-from sample to be tested random extracting container (normal sample size: 10).
-it is used in the CO of requirement2Soda Ash Light 99.2min. under volume fills each container and adds lid.
-NaOH solution by 0.2% pours otch base (cutbase) into.
-complete
-will immerse in the caustic soln of otch base bottom bottle and start accurate hour meter.
-use accurate hour meter to measure the immersion time until explosion or seepage bottom bottle (when bottle do not show after 30 minutes any failed, stop experiment)
The infiltration of the aerosol container of first batch (comparison A) is also measured according to following penetration testing.
Infiltration
The object of this test measures the oxygen permeability of aerosol container. Being MOCONOxtran2/20 for measuring the equipment of transmitance, it uses coulomb type sensor (Coulox) to measure O2 concentration. The testing method used is derived from ASTMD3985 and ASTMF1307. Aerosol container is fixed in metal fixture and fills N2 to be scavenged into outside bottle by air. When bottle outside contacts (20.9%O with ambient air2) time, O2Permeate through bottle wall and and N2Stream is transported to Coulox sensor together.
Test carries out as follows:
�� gets 2 aerosol containers at random
�� uses 2 component glue to be bonded in metal fixture by container.
�� uses N2 to process bottle 50h
�� (is less than 1% with the difference of the concentration before 10h) when O2 concentration stabilize to be completed to measure
�� result provides-22 DEG C of atmospheric pressure environments air with cc/ group/sky
�� calculates ppm/ days or ppm/
Test result
Hydraulic test
The result of hydraulic test is summarised in Table I A, IB and IC.
Table I A: hydraulic test-comparison A
Table I B: hydraulic test-comparison B
Table I C: hydraulic test-comparison C
The result of the aerosol container that A, B, C are tri-batches is similar, all successfully passes hydraulic test.
Temperature-resistant material-fall test
All aerosol containers of first batch (comparison A) all successfully pass through under three kinds of temperature condition and fall test, described temperature condition namely:
��-18 DEG C continues at least 24h
�� room temperature 20-22 DEG C continues at least 1h
�� 55 DEG C continues at least 6h (dry air)
Burst tearing test
All aerosol containers of three batches (comparison A, B and C) all successfully pass burst tearing test (the explosion pressure of all aerosol containers is all in 14.4 Palestine and Israels).
Temperature-resistant material-warm air
All aerosol containers of first batch (comparison A) all successfully pass through test. The aerosol container of first batch (comparison A) does not show any seepage at 75 DEG C after 5h.
On the contrary, the aerosol container of the 2nd crowd (comparison B) and the 3rd crowd (comparison C) is unsuccessful by testing, and at 75 DEG C after 5h seepage.
Overall loading
The result of hydraulic test is summarised in Table II A, IIB and IIC.
Table II A: load testing-comparison A:
Table II B: load testing-comparison B:
Table II C: load testing-comparison C:
Stress cracking
All aerosol containers of A, B, C tri-crowdes all successfully pass stress cracking test.Explosion and crack do not occur after 30 minutes.
Infiltration
The Permeation Results of the aerosol container of first batch (comparison A) is summed up in table iii.
Table III: infiltration-comparison A
| It is full of volume (ml) | 333.82 |
| (cm3/ sky) | 0.026832 |
| Ppm (my god) | 0.11 |
| Ppm/ | 41.94 |
The invention is not restricted to the injection drawing blow aerosol container being made up of copolyesters, described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least about 0.7dL/g. The present invention can also use blend polymer to implement, described blend polymer comprises described copolyesters and another kind of polymkeric substance, particularly another kind of polyester, described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least about 0.7dL/g.
Claims (15)
1. it is applicable to stretch-blow to form plastics preforms (1) or the injection drawing blow aerosol container (20) of aerosol container (20), wherein said preform or aerosol container are made up of the polymer materials comprising copolyesters, and described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of % and has the limiting viscosity of at least 0.7dL/g.
2. preform according to claim 1 or container, it is made up of copolyesters substantially, and described copolyesters comprises the Isosorbide as comonomer of at least 1 mole of %, and has the limiting viscosity of at least about 0.7dL/g.
3. preform described in claim 1 or 2 or container, wherein said copolyesters is the polyethylene terephthalate (PEIT) comprising Isosorbide.
4. preform described in the arbitrary item of claims 1 to 3 or container, wherein said copolyesters comprises the Isosorbide as comonomer of at least 3 moles of %.
5. preform described in the arbitrary item of claims 1 to 3 or container, wherein said copolyesters comprises the Isosorbide as comonomer of at least 5 moles of %.
6. preform described in the arbitrary item of claim 1 to 5 or container, wherein said copolyesters comprises the not Isosorbide as comonomer more than 15 moles of %, it is preferable that not more than the Isosorbide as comonomer of 8 moles of %.
7. preform described in the arbitrary item of claim 1 to 6 or container, the limiting viscosity of wherein said copolyesters is at least 0.8dL/g.
8. preform described in the arbitrary item of claim 1 to 6 or container, the limiting viscosity of wherein said copolyesters is at least 0.9dL/g.
9. preform described in the arbitrary item of claim 1 to 8 or container, the limiting viscosity of wherein said copolyesters is not more than 2.dL/g.
10. injection drawing blow aerosol container described in the arbitrary item of claim 1 to 9, it has the axial tensile rate (S being not more than 3a), it is preferable that there is the axial tensile rate (S being not more than 2.55a)��
Injection drawing blow aerosol container described in the 11. arbitrary items of claim 1 to 10, it has the radial drawing ratio (S being not more than 2.5r), it is preferable that there is the radial drawing ratio (S being not more than 2.4r)��
Injection drawing blow aerosol container described in the 12. arbitrary items of claim 1 to 11, it has the total drawing ratio (S) being not more than 9, it is preferable that have the total drawing ratio (S) being not more than 7.
Injection drawing blow plastic containers described in the 13. arbitrary items of claim 1 to 12, it has concave side walls grip portions (203).
Injection drawing blow plastic containers described in the 14. arbitrary items of claim 1 to 13, it has the volume being not more than 750ml, it is preferable that have the volume being not more than 500ml.
15. 1 kinds of aerosol dispensers (2), it valve distribution device (21) comprising the injection drawing blow aerosol container (20) described in the arbitrary item of claim 1 to 14 and being applicable to distribute the aerosol being contained in aerosol container.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13180376.9 | 2013-08-14 | ||
| EP20130180376 EP2837581A1 (en) | 2013-08-14 | 2013-08-14 | Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container |
| PCT/EP2014/066958 WO2015022254A1 (en) | 2013-08-14 | 2014-08-07 | Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105658539A true CN105658539A (en) | 2016-06-08 |
Family
ID=48985624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480050690.XA Pending CN105658539A (en) | 2013-08-14 | 2014-08-07 | Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20160185510A1 (en) |
| EP (1) | EP2837581A1 (en) |
| JP (1) | JP2016529171A (en) |
| CN (1) | CN105658539A (en) |
| AU (1) | AU2014307974A1 (en) |
| BR (1) | BR112016002884A2 (en) |
| CA (1) | CA2919889A1 (en) |
| MX (1) | MX2016001991A (en) |
| RU (1) | RU2016108984A (en) |
| WO (1) | WO2015022254A1 (en) |
| ZA (1) | ZA201600794B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109496220A (en) * | 2016-08-02 | 2019-03-19 | 罗盖特公司 | For producing semi-crystalline thermoplastic's polyester of biaxial stretch-formed hollow body |
| CN109563256A (en) * | 2016-08-02 | 2019-04-02 | 罗盖特公司 | For producing semi-crystalline thermoplastic's polyester of aerosol container |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3019803B1 (en) * | 2014-04-10 | 2016-12-23 | Fareva | AEROSOL GENERATOR OF PLASTIC MATERIAL |
| EP3395855B1 (en) * | 2015-12-24 | 2021-03-31 | SK Chemicals Co., Ltd. | Polyester resin, method for producing same, and resin molded product formed therefrom |
| US20170341849A1 (en) * | 2016-05-27 | 2017-11-30 | S.C. Johnson & Son, Inc. | Plastic bottle and base cup for a pressurized dispensing system |
| FR3054804B1 (en) * | 2016-08-05 | 2019-07-12 | Roquette Freres | USE OF A THERMOPLASTIC POLYESTER FOR THE MANUFACTURE OF INJECTED PARTS |
| KR102568743B1 (en) | 2017-05-31 | 2023-08-22 | 에스케이케미칼 주식회사 | Polyester resin, preparation method thereof and resin article formed therefrom |
| WO2018236111A2 (en) | 2017-06-22 | 2018-12-27 | 에스케이케미칼주식회사 | Polyester container and manufacturing method therefor |
| KR102684863B1 (en) | 2017-06-26 | 2024-07-15 | 에스케이케미칼 주식회사 | Polyester film and preparation method thereof |
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- 2014-08-07 JP JP2016533893A patent/JP2016529171A/en active Pending
- 2014-08-07 US US14/911,540 patent/US20160185510A1/en not_active Abandoned
- 2014-08-07 CA CA2919889A patent/CA2919889A1/en not_active Abandoned
- 2014-08-07 CN CN201480050690.XA patent/CN105658539A/en active Pending
- 2014-08-07 AU AU2014307974A patent/AU2014307974A1/en not_active Abandoned
- 2014-08-07 WO PCT/EP2014/066958 patent/WO2015022254A1/en active Application Filing
- 2014-08-07 MX MX2016001991A patent/MX2016001991A/en unknown
- 2014-08-07 BR BR112016002884A patent/BR112016002884A2/en not_active IP Right Cessation
-
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- 2016-02-04 ZA ZA2016/00794A patent/ZA201600794B/en unknown
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| CN2129745Y (en) * | 1992-04-10 | 1993-04-14 | 天津印铁制罐公司 | Two room atomizing container |
| WO1999054533A1 (en) * | 1998-04-23 | 1999-10-28 | E.I. Du Pont De Nemours And Company | Polyester container and method for making same |
| CN1659088A (en) * | 2002-06-11 | 2005-08-24 | 依普技术有限公司 | A dispenser |
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| CN109496220A (en) * | 2016-08-02 | 2019-03-19 | 罗盖特公司 | For producing semi-crystalline thermoplastic's polyester of biaxial stretch-formed hollow body |
| CN109563256A (en) * | 2016-08-02 | 2019-04-02 | 罗盖特公司 | For producing semi-crystalline thermoplastic's polyester of aerosol container |
| CN109563256B (en) * | 2016-08-02 | 2021-09-14 | 罗盖特公司 | Semi-crystalline thermoplastic polyester for producing aerosol containers |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA201600794B (en) | 2017-04-26 |
| JP2016529171A (en) | 2016-09-23 |
| BR112016002884A2 (en) | 2017-08-01 |
| US20160185510A1 (en) | 2016-06-30 |
| MX2016001991A (en) | 2016-05-18 |
| EP2837581A1 (en) | 2015-02-18 |
| CA2919889A1 (en) | 2015-02-19 |
| WO2015022254A1 (en) | 2015-02-19 |
| RU2016108984A (en) | 2017-09-19 |
| AU2014307974A1 (en) | 2016-02-18 |
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Application publication date: 20160608 |