CN107254148A

CN107254148A - A kind of high heat-resisting medicinal polyester bottles and its manufacture method

Info

Publication number: CN107254148A
Application number: CN201710476875.2A
Authority: CN
Inventors: 陈洋; 胡红群; 郑文学; 边玉祥; 张亚红
Original assignee: Guizhou Chiba Medicine Packaging Co Ltd By Shares
Current assignee: Guizhou Chiba Medicine Packaging Co Ltd By Shares
Priority date: 2017-06-21
Filing date: 2017-06-21
Publication date: 2017-10-17

Abstract

The present invention relates to medicinal polyester bottles technical field, especially a kind of high heat-resisting medicinal polyester bottles and its manufacture method, PET, PENT and PEN resin make use of to carry out blending and modifying, form the high polymer blend alloy that heat resistance is preferable, processing characteristics is excellent, and introduce inorganic nucleator and ionomer nucleator (Surlyn resins), therefore the heat resisting temperature of product is greatly improved in pole, significantly reduces cost of material；It is controlled with reference to crystallization temperature, crystallization time so that thoroughly avoid the defect that the container neck in blow-molding process easily produces stretcher strain；With reference in blow moulding process due to adding pressurize shaping process, after-contraction phenomenon can not only be eliminated, the stability of container dimensional is ensured, and also improve the heat resistance of container, so that container heat resisting temperature is lifted to more than 97 DEG C by 60 DEG C or so of traditional pure PET resin container, it is fully able to meet the requirement of hot-filling Process and pasteurization process.

Description

A kind of high heat-resisting medicinal polyester bottles and its manufacture method

Technical field

The present invention relates to medicinal polyester bottles technical field, especially a kind of high heat-resisting medicinal polyester bottles and its manufacture method.

Background technology

It is well known that not only light weight, strong shock resistance, physical and mechanical property are good for PET resin container, but also have Excellent chemical resistance, sanitation performance and fragrance protectiveness energy, its outward appearance has very high transparency and surface light in glassy Pool；It is to substitute a kind of ideal plastic products of glass container.However, due to pure PET resin container heat resistance compared with Difference, product that can only be filling 60 DEG C or so, it is therefore necessary to can carry out product cooling to≤60 DEG C filling, seriously hinder life The raising of efficiency is produced, using above receiving certain limitation.

At present, the heat stable resin container of in the market mainly has PEN resins monolayered vessel, PEN resins and PET resin blend composition Monolayered vessel.Although the heat resistance and gas barrier property of PEN resin monolayered vessels are all very good, cost of material is the 3 of PET resin ~4 times, it is difficult to be used as the packing container popularization and application of usual articles.And PEN resins only work as naphthalene content with PET resin blend composition When reaching 40%, its glass transition temperature can reach 93.6 DEG C, and price is still higher, and market still can not receive；In addition, Made using traditional handicraft, using PEN resins and PET resin blend composition in product process, container neck holds in blow-molding process Stretcher strain is also easy to produce, therefore the bottle type container that can be made further is limited；As number of patent application is The manufacture method of 200910102793.7 highly heat resistant wide-mouth polyester container, the moisture content of material is reduced to≤0.005% by it, And by PET resin and PENT-8 mixed with resin, and the viscosity number for limiting two kinds of materials prepares shaping as 0.78~0.85dl/g Base, crystallization processing, blow molding, pressurize, thermal finalization, cooling, die sinking is formed；It causes the container prepared, at filling 80 DEG C Hot water when, its cubical contraction is less than 0.015%, and the filling cubical contraction of 85 DEG C of hot water is less than 0.052%, 95 DEG C filling cubical contraction of hot water is less than 0.15%, and OTR oxygen transmission rate is 9.5cm³/(m²DMPa) below, titanium dioxide Carbon transmitance is 26cm³/(m²DMPa) below, moisture-vapor transmission is 4.2cm³/(m²DMPa) below；But, should The cost of material of method selection still height more of the present invention, and still not high for heat resistance, in consideration of it, this researcher passes through The raw material and preparation method of heat-resisting medicinal polyester bottles are studied, it is proposed that low raw-material cost, and heat resistance More excellent medicinal polyester bottle product.

The content of the invention

In order to solve above-mentioned technical problem present in prior art, an object of the present invention is to provide high heat-resisting medicinal Polyester bottles manufacture method, the polyester container of preparation can be heat-resisting, and its temperature has reached more than 97 DEG C, in the case where 95 DEG C of hot water are filling Volume-diminished rate is up to 0.131%, and the polyester container disclosure satisfy that hot filling and pasteurization process requirement, and Cost is relatively low compared with the prior art.Specifically include following steps：

(1) PET resin, PENT resins, PEN resins, inorganic nucleator, Surlyn resins are chosen as raw material, by raw material Dry；

(2) again by dried material in parts by weight be 60~80 parts of PET resin, 15~30 parts of PENT resins, PEN resins 0~10 part, 0.1~1.0 part of inorganic nucleator particulate, the blending of 0.1~1.0 part of Surlyn resins, in feeding extrusion shaping machine, squeeze Go out, granulated using pelleter；

(3) granule materials are dried, feeding injecting machine material tube is molded into bottle base；

(4) bottle base is placed in crystallization case, in the case where temperature is 170-200 DEG C to bottle base neck crystallization 120s, is cooled to room Temperature, shape 48h；

(5) bottle base after crystalline forming is passed through into gradient preheating device, preheats 40s, be re-fed into mould, with 110-140 DEG C Lower constant pressure blow molding, pressurize 15s is cooled to after 40 DEG C, the demoulding, is produced.

By in such scheme, introducing PENT resins, increase PET and PEN resins compatibility form stable mixture The heat resistance and crystallinity of system, further lifting product；Inorganic nucleator particulate is introduced, reduces crystal grain, crystallization rate Accelerate, the regularity of increase crystallinity and crystal formation lifts the glass transition temperature of PET bottle base, so as to lift the heat resistance of PET bottle； By dry materials, blended chip, base, solidification crystallization and five steps of blow molding are molded into, pelletizing again prepares PP Pipe Compound Blowing technology is completed, dispersive property more preferably melt is obtained, injection bottle base shaped crystalline is evenly；In solidification crystallization process, Select flexible chain most short temperature range and by the bottle base neck crystallization time by original prolonged process to 120s, make crystallinity Theoretical maximum is promoted to, heat resistance is further lifted；Increase pressurize shaping process in blow-moulding process, after can eliminating Shrinkage phenomenon, the stability for ensuring container dimensional, further improve the heat resistance of the PET medicinal bottles.

It is preferred that, in the raw material of the high heat-resisting PET medicinal bottle, the intrinsic viscosity of PET resin is 0.78~0.85dl/g, PENT The intrinsic viscosity of resin is 0.60~0.70dl/g, and the intrinsic viscosity of PEN resins is 0.50~0.60dl/g.

It is preferred that, in the raw material of the high heat-resisting PET medicinal bottle, inorganic nucleator particulate is that granularity is more than 400 mesh neatly One or more combinations in stone, talcum powder, TiO2, SiO2, CaCO3；Surlyn resins be the trade mark be Surlyn 8920 or One kind or the combination of both in Surlyn 8940.

It is preferred that, in the manufacture method of the high heat-resisting PET medicinal bottle, the embodiment of dry materials is：By above-mentioned original Material composition is inserted in high-speed stirring mixer, vacuumizes and 120 DEG C of constant temperature is sufficiently mixed 24h, rotating speed control is 250~500r/ min。

Preferably, 475r/min is selected in rotating speed control.

It is preferred that, in the manufacture method of the high heat-resisting PET medicinal bottle, the embodiment of blended chip is：Will be above-mentioned dry In material composition feeding extrusion shaping machine after dry, melting extrusion, warp in the case where extruder temperature is 270~300 DEG C and certain rotating speed Pelleter granulation is sent into after water cooling；Screw speed need to be adjusted in the range of 60~120r/min, and ensures material in barrel and spiral shell Total time in bar is more than 5min.

Preferably, extruder temperature selects 285 DEG C, screw speed selects 80r/min.

In the manufacture method of the high heat-resisting PET medicinal bottle, the embodiment for being molded into base is：It is dry according to above-mentioned material Dry mode carries out primary drying again, and feeding injecting machine material tube is molded into bottle base, and it is 280~290 to control melt temperature during injection DEG C, screw speed is 72r/min, and injection time, dwell time and cool time control in 7.2s, 5.5s and 7s respectively, mould Temperature water cooling constant temperature is at 35 DEG C.

Preferably, melt temperature selects 285 DEG C.

In the manufacture method of the high heat-resisting PET medicinal bottle, the embodiment of solidification crystallization is：Bottle base is placed in crystallization In case, to bottle base neck crystallization 120s under the conditions of 170~200 DEG C, room temperature sizing 48h is then cooled to.

Preferably, crystallization temperature selects 188 DEG C.

In the manufacture method of the high heat-resisting PET medicinal bottle, the embodiment of blow molding is：By the bottle base after crystallization (i.e. arrival end is 90 DEG C to gradient preheating 40s, and the port of export is 140 DEG C, and intermediate region temperature is 90 under the conditions of being placed in 90~140 DEG C The lifting of~140 DEG C of uniform amplitudes), be re-fed into mould and be blow molded under the conditions of 110~140 DEG C, blowing pressure for 18~ 40 DEG C of demouldings are cooled to after 20bar, pressurize 15s, high heat-resisting medicinal polyester bottle product is ultimately formed.

Preferably, blow temperatures select 132 DEG C, blowing pressure selects 20bar.

In the above-mentioned technical solutions, the chemical name of PET resin is polyethylene terephthalate, the change of PEN resins Scientific name is referred to as PEN, and PENT resins are the copolymers of PET resin and PEN resins.

By in preparation method, to the processing of bottle base neck crystallization, eliminate neck in blowing step and easily occur stretcher strain Defect；With reference to raw mixture formula, crystallization temperature is crystallized at 170~200 DEG C, the shortening of high degree finishes The brilliant time, improve the performance of polyester bottles, with reference to parison from heater box out when temperature close to draft temperature, close to PET glass transition temperature, it is ensured that orientation effect is more excellent, heat resistance is higher, the cubical contraction high degree after being heated Reduction, and combine the processing such as cooling velocity, pressurize, thermal finalization so that the cleanliness factor of product has reached 45~55%, improves Transparency and glossiness, improve heat resistance, reduce heat shrinkability；Especially before system not yet decomposes orientation Product is quenched to glass transition temperature, orientation texture " is freezed ", high polymer can be made to keep higher degree of orientation.

It make use of PET, PENT and PEN resin to carry out blending and modifying, form the height that heat resistance is preferable, processing characteristics is excellent Polymers blend alloy, and inorganic nucleator and ionomer nucleator (Surlyn resins) are introduced, therefore pole is greatly improved The heat resisting temperature of product, significantly reduces cost of material；It is controlled with reference to crystallization temperature, crystallization time so that thoroughly Avoid the defect that the container neck in blow-molding process easily produces stretcher strain；With reference in blow moulding process due to increase Pressurize shaping process, can not only eliminate after-contraction phenomenon, ensure the stability of container dimensional, and also improve container Heat resistance so that container heat resisting temperature, to more than 97 DEG C, is fully able to by 60 DEG C or so liftings of traditional pure PET resin container Meet the requirement of hot-filling Process and pasteurization process.

The basic performance of the polyester bottles is embodied in as shown in table 2 below：

Table 2：

Embodiment

Limited with reference to specific embodiment technical scheme is further, but claimed Scope is not only limited to made description.

Embodiment 1

1) the PENT resins that 75 kilograms of PET resin for being 0.82dl/g by intrinsic viscosity, intrinsic viscosity are 0.57dl/g 17.5 kilograms, 7.5 kilograms of PEN resins, 0.5 kilogram of the hydrotalcite and Surlyn of 1000 mesh granularities that intrinsic viscosity is 0.61dl/g 8940 0.5 kilogram of resins are placed in high-speed stirring mixer, vacuumize and 120 DEG C of constant temperature is sufficiently mixed 24h, rotating speed control is 475r/min；

2) above-mentioned dried material composition is sent into extrusion shaping machine, is 285 DEG C and certain rotating speed in extruder temperature Lower melting extrusion, water cooled rear feeding pelleter granulation；Screw speed need to be adjusted in the range of 80r/min, and ensures that material exists Total time in barrel and screw rod is more than 5min.

3) primary drying, feeding injecting machine material tube note are carried out again to the raw material after pelletizing in the way of above-mentioned dry materials Bottle base is moulded into, melt temperature is 285 DEG C when controlling to be molded, and screw speed is 72r/min, projects time, dwell time and cooling Time controls in 7.2s, 5.5s and 7s respectively, and mold temperature water cooling constant temperature is at 35 DEG C.

4) in the manufacture method of the high heat-resisting PET medicinal bottle, solidification crystallization is：Bottle base is placed in crystallization case, at 188 DEG C Under the conditions of to bottle base neck crystallization 120s, be then cooled to room temperature sizing 48h.

5) in the manufacture method of the high heat-resisting PET medicinal bottle, blow molding is：Bottle base after crystallization is placed in 90~140 (i.e. arrival end is 90 DEG C to gradient preheating 40s, and the port of export is 140 DEG C, and intermediate region temperature is 90~140 DEG C uniform under the conditions of DEG C Amplitude is lifted), it is re-fed into mould and is blow molded under the conditions of 132 DEG C, blowing pressure is to be cooled to 40 DEG C after 20bar, pressurize 15s The demoulding, ultimately forms high heat-resisting medicinal polyester bottle product.

The performance of the polyester bottles of preparation is as shown in table 3 below：

Table 3

Embodiment 2

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN trees that 15 kilograms of PENT resins that g 80 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g Beyond 0.5 kilogram of 5 kilograms of fat, 0.5 kilogram of the hydrotalcite of 1000 mesh granularities and 8940 resins of Surlyn are mixed, remaining step It is rapid same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 4 below：

Table 4

Embodiment 3

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN that 17.5 kilograms of PENT resins that g 75 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The SiO of 7.5 kilograms of resin, 1000 mesh granularities₂Beyond 0.5 kilogram mixes with 0.5 kilogram of 8920 resins of Surlyn, remaining Step is same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 5 below：

Table 5

Embodiment 4

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN trees that 15 kilograms of PENT resins that g 80 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The SiO of 5 kilograms of fat, 1000 mesh granularities₂Beyond 0.5 kilogram mixes with 0.5 kilogram of 8940 resins of Surlyn, remaining step It is same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 6 below：

Table 6

Embodiment 5

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN that 17.5 kilograms of PENT resins that g 75 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The CaCO of 7.5 kilograms of resin, 1000 mesh granularities₃Beyond 0.5 kilogram mixes with 0.5 kilogram of 8920 resins of Surlyn, its Remaining step is same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 7 below：

Table 7

Embodiment 6

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN trees that 15 kilograms of PENT resins that g 80 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The CaCO of 5 kilograms of fat, 1000 mesh granularities₃Beyond 0.5 kilogram mixes with 0.5 kilogram of 8940 resins of Surlyn, remaining step It is rapid same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 8 below：

Table 8

Embodiment 7

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN trees that 30 kilograms of PENT resins that g 65 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The CaCO of 5 kilograms of fat, 1000 mesh granularities₃Beyond 0.5 kilogram mixes with 0.5 kilogram of 8920 resins of Surlyn, remaining step It is rapid same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 9 below：

Table 9

Embodiment 8

On the basis of embodiment 1, other equal be the same as Examples 1, except step 1) in my material by intrinsic viscosity be 0.82dl/ The PEN trees that 30 kilograms of PENT resins that g 65 kilograms of PET resin, intrinsic viscosity are 0.57dl/g, intrinsic viscosity are 0.61dl/g The CaCO of 5 kilograms of fat, 1000 mesh granularities₃Beyond 0.5 kilogram mixes with 0.5 kilogram of 8940 resins of Surlyn, remaining step It is rapid same as Example 1.

The performance of the polyester bottles of preparation is as shown in table 10 below：

Table 10

In the invention, with the increase of PENT, PEN consumption, the reduction of volume of a container shrinkage factor, gas barrier property Improve, little is influenceed on volume when 95 DEG C of hot water are filling, metaboly is not resulted in more, satisfaction is even better than《Hot filling PET Standard》QB/T2665-2004 requirement.

Be necessary herein explanation be：The content that is covered of the present invention, including involved formula, five systems of the product Standby step, the temperature of each step, pressure, time control etc., and those skilled in the art carry out routine on this basis Any change, replacement, improvement, consumption increase and decrease etc. belong to protection scope of the present invention.

Claims

1. a kind of high heat-resisting medicinal polyester bottles manufacture method, it is characterised in that comprise the following steps：

(1) PET resin, PENT resins, PEN resins, inorganic nucleator, Surlyn resins are chosen as raw material, by raw material drying；

(2) again by dried material in parts by weight for 60~80 parts of PET resin, 15~30 parts of PENT resins, PEN resins 0~ 10 parts, 0.1~1.0 part of inorganic nucleator particulate, the blending of 0.1~1.0 part of Surlyn resins, in feeding extrusion shaping machine, extrusion, Granulated using pelleter；

(4) bottle base is placed in crystallization case, in the case where temperature is 170-200 DEG C to bottle base neck crystallization 120s, is cooled to room temperature, it is fixed Type 48h；

(5) bottle base after crystalline forming is passed through into gradient preheating device, preheats 40s, be re-fed into mould, with perseverance at 110-140 DEG C Blow molding is pressed, pressurize 15s is cooled to after 40 DEG C, be stripped, produce.

2. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that the spy of described PET resin Property glutinous number be 0.78~0.85dl/g；The intrinsic viscosity of described PENT resins is 0.60~0.70dl/g；Described PEN resins Intrinsic viscosity be 0.50~0.60dl/g.

3. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that described inorganic nucleator, Its granularity mesh number is >=400 mesh.

4. the high heat-resisting medicinal polyester bottles manufacture method as described in claim 1 or 3, it is characterised in that described inorganic nucleation Agent is talcum powder, TiO₂、SiO₂、CaCO₃In one or more combinations.

5. heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1 high, it is characterised in that described Surlyn resins are Surlyn 8920, one kind in Surlyn 8940 or the combination of both.

6. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that described raw material drying, is Material composition being placed in high-speed stirring mixer, vacuumized, and 120 DEG C of constant temperature is sufficiently stirred for 24h, speed of agitator is 250~ 500r/min。

7. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that described step (2), will be dry It is 270~300 DEG C and screw speed in 60~120r/min in extruder temperature in material composition feeding extrusion shaping machine after dry Lower melting extrusion, realizes total time >=5min of the material in extrusion shaping machine barrel and screw rod.

8. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that described step (3), will make The granule materials of grain, are placed in high-speed stirring mixer, vacuumize, and 120 DEG C of constant temperature is sufficiently stirred for 24h, and speed of agitator is 250 Under~500r/min after drying process, feeding injecting machine material tube is molded into bottle base, and it is 280~290 to control melt temperature during injection DEG C, during screw speed is 72r/min, injection moulding process, the injection time is 7.2s, and the dwell time is 5.5s, and cool time is 7s, mould Tool temperature uses water-cooled process so that constant temperature is at 35 DEG C.

9. high heat-resisting medicinal polyester bottles manufacture method as claimed in claim 1, it is characterised in that described step (5), gradient Preheater, its arrival end temperature is 90 DEG C, and discharge-end temperature is 140 DEG C, and during arrival end to the port of export, its temperature is In 90~140 DEG C of uniform lifts.

10. high heat-resisting medicinal polyester prepared by the high heat-resisting medicinal polyester bottles manufacture method as described in claim any one of 1-9 Bottle, its performance is as shown in table 1 below：

Table 1：