CN104859128B - Has the manufacturing method of the plastic bottle of pearl effect - Google Patents
Has the manufacturing method of the plastic bottle of pearl effect Download PDFInfo
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- CN104859128B CN104859128B CN201410066372.4A CN201410066372A CN104859128B CN 104859128 B CN104859128 B CN 104859128B CN 201410066372 A CN201410066372 A CN 201410066372A CN 104859128 B CN104859128 B CN 104859128B
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Abstract
A kind of manufacturing method of the plastic bottle of tool pearl effect, including preparing raw material stage, and is made container step.In the preparation raw material stage, the polyolefin polymers of 1 10wt% are first ground into average grain diameter in 500 μm of powder below, and the granular polyethylene terephthalate with 99 90wt% mixes.It is made in container step at this, is first uniformly mixed the raw material with ejection forming technique and Jet forming machine is utilized to project a bottle embryo, then the bottle embryo is blow molded by one plastic bottle of elongation moulding with blow molding processing procedure.The polyolefin polymers are selected from：Polyethylene, polypropylene, polymethylpentene, polyolefin elastomer and ethylene and vinyl acetate co-polymer.By adding powdered polyolefin polymers in polyethylene terephthalate, the plastic bottle with pearl effect can not only be made, additionally it is possible to improve plasticity it is bad with current mark flaw the problem of.
Description
Technical field
The present invention relates to a kind of manufacturing methods, are used for making the plastic bottle with pearl effect more particularly to a kind of
Manufacturing method.
Background technology
Polyethylene terephthalate is the good transparent resin of a kind of good toughness, light weight, resistance to acid and alkali, therefore is often made
It is made miscellaneous plastic bottle.In order to so that product made of polyethylene terephthalate is had just like pearl effect it is outer
It seeing, EP0456929A2 discloses a kind of polyethylene terephthalate containing 99.1wt%-99.99wt%, and
The constituent of the polymethylpentene of 0.01wt%-0.9wt%.
According to the experimental result of the table 1 of the patent of invention Instructions Page 3 it is found that the patent of invention was once tasted at that time in application
Examination is using for example：The polyene of polyethylene, polypropylene, ethylene-vinyl acetate copolymer and polymethyl methacrylate etc.
Hydrocarbon polymer has been found that as material, but in experimentation, and the usage amounts of previous polyolefin polymers is close to 10wt%
When, although preferable pearl effect can be generated, the bad missing of processability is will produce, and make product that there is current mark flaw
Appearance, if the usage amount of polyolefin polymers is reduced to 0.5wt%, although can improve, processability is bad to ask
Topic, but the pearl effect of product is bad, if the usage amount of polyolefin polymers is increased to 3%, only ethylene-
The processability of vinyl acetate co-polymer still remains preferable, but the pearl effect of product is unsatisfactory, remaining polyolefins
Polymer can not all take into account pearl effect and processability.Based on above experimental result, the claims 1 of the European patent not only will
The usage amount of polyolefin polymers is limited in 1wt% hereinafter, poly- methylpent can only be selected by also limiting the polyolefin polymers
Alkene.That is, being learnt by the experimental result of the European patent which kind of polyolefin polymers no matter selected, as long as usage amount
Higher than 1wt%, processability and the pearl effect of plastic bottle can not be all taken into account.
Invention content
The purpose of the present invention is to provide one kind capable of having both pearl effect and processability, and expands material and range can be selected
The plastic bottle with pearl effect manufacturing method.
The present invention has the manufacturing method of the plastic bottle of pearl effect, including：
Prepare raw material stage：By the granular poly- terephthaldehyde of the polyolefin polymers of 1-10wt% and 90-99wt%
Sour second diester mixing；And
Container step is made：Aforementioned raw material is mixed into melting with ejection forming technique and is projected into a bottle embryo, then should
One plastic bottle of bottle embryo blow molding；
In the preparation raw material stage, first the polyolefin polymers are ground, make the polyolefin polymers
Average grain diameter is less than the average grain diameter of the polyethylene terephthalate.
Manufacturing method of the present invention, the average grain diameter of the polyolefin polymers is preferably less than or equal to 500m.
Manufacturing method of the present invention, the polyolefin polymers are existed with the polyethylene terephthalate with temperature
Heat source between 250-300 DEG C heats mixed melting.Wherein, the heat source is to be divided at least three sections of Segmented heating.
Manufacturing method of the present invention, when the bottle embryo will be before the stretching blow moulding plastic bottle, the bottle of bottle embryo
Temperature is between 80-130 DEG C.
Manufacturing method of the present invention, the polyolefin polymers are selected from：Polyethylene, polypropylene, polymethylpentene,
Polyolefin elastomer and ethylene and vinyl acetate co-polymer.
The beneficial effects of the present invention are：In the fabrication process, the average grain diameter of the polyolefins is allowed to be less than poly- pair
The average grain diameter of polyethylene terephthalate, can reduce the degree of phase separation, while promote capacity of heat transmission, make the temperature between each position
Difference reduces, and then improves the processability and current mark flaw of the plastic bottle of tool pearl effect.
Description of the drawings
Fig. 1 is a flow diagram of manufacturing method of the present invention, illustrates a bottle embryo of the embodiment 1 of the manufacturing process
Manufacturing process；
Fig. 2 is another flow diagram of the embodiment 1, illustrates that the bottle embryo is blow molded into the process of a plastic bottle；
Fig. 3 is the finished product photo obtained by the embodiment 1；
Fig. 4 is a finished product photo, is illustrated by the flaw finished product obtained by comparative example 1；
Fig. 5 is a finished product photo, is illustrated by the flaw finished product obtained by comparative example 2；
Fig. 6 is a finished product photo, is illustrated by the flaw finished product obtained by comparative example 3；
Fig. 7 is a finished product photo, is illustrated by the flaw finished product obtained by comparative example 4；
Fig. 8 is a finished product photo, is illustrated by the flaw finished product obtained by comparative example 5.
Specific implementation mode
The present invention has the manufacturing method of the plastic bottle of pearl effect, including：
Prepare raw material stage：By the granular poly- terephthaldehyde of the polyolefin polymers of 1-10wt% and 90-99wt%
Sour second diester mixing；And
Container step is made：Aforementioned raw material is mixed into melting with ejection forming technique and is projected into a bottle embryo, then should
One plastic bottle of bottle embryo blow molding；
In the preparation raw material stage, first the polyolefin polymers are ground, make the polyolefin polymers
Average grain diameter is less than the average grain diameter of the polyethylene terephthalate.Used polyethylene terephthalate
(Polyethylene Terephthalate, referred to as PET) is the recyclable recycling of one kind and is widely used in various packets
The polyester material of packaging container.Due to the use of level it is extensive, so often utilize the material be main component, add other and add
Add object, miscellaneous plastic cement finished product is made.
The main chain that polyolefins (polyolefin) polymer refers to polymer is formed by double bond alkenes key point addition polymerization
Polymer.Specifically for example：Polyethylene (Polyethylene, abbreviation PE), gathers polypropylene (Polypropylene, abbreviation PP)
Methylpentene (Polymethyl pentene, abbreviation PMP), polyolefin elastomer (Polyolefin Elastomer, abbreviation
POE), ethylene and vinyl acetate co-polymer (abbreviation EVA) etc., wherein polyethylene also includes example other than typical structure
Such as：Low density polyethylene (LDPE) (Low-density Polyethylene, abbreviation LDPE), high density polyethylene (HDPE) (High-density
Polyethylene, abbreviation HDPE), linear low density polyethylene (Linear Low-density Polyethylene, referred to as
) etc. LLDPE the derivative of different structure.
The present invention substantially includes in the step of container is made：It is molded bottle embryo step and is blow molded into plastic bottle step
Suddenly, in being molded bottle embryo step, the heat source of the mixed melting polyolefin polymers and the polyethylene terephthalate is heated
Temperature be preferred between 250-300 DEG C with controlling, the heating temperature is about poly- to benzene at 250 DEG C in addition to that can melt fusing point
Dioctyl phthalate second diester can also melt the polyolefin polymers that fusing point is less than 200 DEG C.Due to the mistake in mixing and ejection formation
Cheng Zhong, has a heat loss with time going by, therefore can control processing temperature when projecting higher than 250 DEG C, but is less than
300℃.In addition, the heat source is heated in the segmented method for being divided at least three sections.Preferably, considering heat loss and avoiding excessive volume
Outer thermal energy expends, and the heating temperature of the heat source is divided at least three sections and is heated to 275 DEG C.More preferably, the heat source is to divide five sections
Mode heats, and the temperature setting in the heat source each stage is respectively 250 DEG C, 265 DEG C, 275 DEG C, 275 DEG C, 275 DEG C.
Bottle embryo made by the present invention can be the form of test tube shape, and be manufactured with Jet forming machine, when the bottle embryo exists
After ejection formation before the blow molding plastic bottle, can directly it be carried out when the bottle temperature of bottle embryo is cooled to 80-130 DEG C
It is blow molded into the processing procedure of plastic bottle.The bottle embryo can also ejection formation and be cooled to it is spare after room temperature, until to be blow molded into
When plastic bottle step, then the bottle embryo is warming up to 80-130 DEG C, is then placed in molding in a blow mold.Because to right
High molecular material is processed, and processing temperature must be more than the glass transition temperature of high molecular material, otherwise macromolecule material
Material will can not be handled with hard crisp property as glass.For the polyethylene terephthalate of the main component, glass
Glass conversion temperature is about at 80 DEG C.Similarly, also there is the problem of heat loss in blow molding, therefore usually heating temperature can be set
It is so fixed that come high than the glass transition temperature of polyethylene terephthalate, such as 130 DEG C.Preferably, considering heat loss and keeping away
Exempt from excessive additional thermal energy consuming and time and the energy cost of its postcooling, the temperature of the bottle embryo are adjusted to 100 DEG C.
The creator of the present invention has found after experiment, the previous plastic bottle with pearl effect during fabrication, if poly-
When the additive amount of olefin polymer is higher than 1.0wt%, the plasticity of polyethylene terephthalate is bad, and finished product is outer
Sight easy tos produce current mark.And the reason of leading to current mark flaw, may be from asking for the dispersion unevenness caused by Material property differences
Topic.For polyethylene terephthalate, the structure of ontology is to contain benzene ring structure and oxygen containing condensation polymer, from
With primary structure it is in nature so alkene double bond key point addition, and is polymerize with the polyolefins based on carbon atom and hydrogen atom
Object is different, certainly will have the problem on interface between different material.For the viewpoint of thermodynamics (Thermodynamics),
Mixing between different material, often in order to make surface energy (Surface Energy) decline, substance convergence of the same race gathers together, and makes
The contact area that substance plants substance with him minimizes.This behavior be easy to cause the phase separation (phase of material
Separation) so that finished product generates the appearance with current mark flaw.
When the weight percent for the polyolefins added is small, thermodynamically leading factor is entropy
(Entropy), that is to say, that although polyolefins, which is dispersed in polyethylene terephthalate, can cause relatively high table
Face energy, but because have the case where larger entropy compensation, not will produce phase separation still.But the weight of the polyolefins with addition
The increase of percentage is measured, leading factor will be switched to surface energy by entropy, therefore identical raw material is easy self assemble and generates phase point
From.Different phase separation regions, it is naturally different for the refraction and the ability of reflection of light, and then generate the current mark that can be observed
Flaw.Meanwhile the presence of phase separation, it also be reflected in the variation of the capacity of heat transmission of material.Many caused by phase separation is not
Same region exists there are many boundary (boundary), these zone boundaries can be such that the capacity of heat transmission of material declines, and making can
The problem of plasticity bad problem simultaneous current mark flaw, occurs.
Therefore polyolefin polymers are worn into average grain diameter in advance and are less than or equal to by the present invention before raw material mixing
500 μm of powder, preferably, the polyolefin polymers, which are ground to average grain diameter, is less than or equal to 100 μm of powder, then with
Polyethylene terephthalate Hybrid Heating contributes to the polyolefin polymers of addition in main component poly terephthalic acid second
Dispersion between diester, and reduce the degree of microphase-separated.
Although mixing polyolefin polymers grind into powder and with polyethylene terephthalate, phase separation can be reduced
The case where occur, but when the weight percent of the polyethylene added is more than 10wt%, since polyolefin polymers account for
There is sizable ratio, therefore even if polyolefins grind into powder is mixed with polyethylene terephthalate again, can not still have
Effect improves the case where current mark flaw.Therefore, the manufacturing method of the present invention is useful in the weight percent shared by the polyolefins of addition
Than the situation in 10wt% or less.
【Embodiment 1】
Refering to fig. 1, Fig. 2, Fig. 3 and table 1, embodiment 1 using 95wt% polyethylene terephthalate and 5wt%
Polymethylpentene is raw material, wherein the density of polyethylene terephthalate is 1.40g/cm3, PDI (Polydispersity
Index be 1.48, IV values it is) 0.85 ± 0.02.The density of polymethylpentene is 0.84g/cm3, melt index 22, softening
Temperature is 170 DEG C.
Wherein, which is first ground into powder of the average grain diameter at 500 μm, then with the poly terephthalic acid second two
Ester mixes.The raw material is put into a Jet forming machine 1, and is divided into 250 DEG C, 265 DEG C, 275 DEG C, 275 DEG C, 275 DEG C five sections
It is heated to 275, then by one bottle embryo 2 of the raw material injection molding.The bottle embryo 2 is seated in a temperature regulator 3 again later,
The bottle embryo temperature is regulated and controled to 100 DEG C.Finally 2 embryo of bottle embryo is placed in a mold 4, air is poured into and blow molding is
One plastic bottle 5.The bottle embryo temperature of each section is measured during blow molding, wherein be in the mean temperature of bottle embryo epimere
98 DEG C, the mean temperature in bottle embryo stage casing is 97 DEG C, and the mean temperature of bottle embryo hypomere is 103 DEG C, the average temperature of maximum of bottle embryo entirety
Difference is 6 DEG C.
【Embodiment 2】
Refering to table 1, embodiment 2 is similar with the embodiment 1, and different places is that embodiment 2 is using the poly- of 90wt%
The polyethylene of ethylene terephthalate and 10wt% are raw material, wherein the density of the polyethylene is 0.920g/cm3, MI values
It is 0.7, softening temperature is 90 DEG C, and is ground into powder of the average grain diameter at 500 μm.Bottle is measured during blow molding
Embryo temperature of each section, wherein in the mean temperature of bottle embryo epimere be 94 DEG C, the mean temperature in bottle embryo stage casing is 93 DEG C, bottle embryo hypomere
Mean temperature be 101 DEG C, the maximum mean temperature difference of bottle embryo entirety is 8 DEG C.
【Embodiment 3】
Refering to table 1, embodiment 3 is similar with the embodiment 2, and different places is that embodiment 3 uses poly- pair of 99wt%
The polyethylene of polyethylene terephthalate and 1wt% are raw material.Bottle embryo temperature of each section is measured during blow molding,
In, it is 100 DEG C in the mean temperature of bottle embryo epimere, the mean temperature in bottle embryo stage casing is 99 DEG C, and the mean temperature of bottle embryo hypomere is
103 DEG C, the maximum mean temperature difference of bottle embryo entirety is 4 DEG C.
【Embodiment 4】
Refering to table 1, embodiment 4 is similar with the embodiment 1, and different places is that embodiment 4 is using the poly- of 90wt%
The polypropylene of ethylene terephthalate and 10wt% are raw material, wherein the polyacrylic density is 0.899g/cm3, MFR
It is 25-30% that value, which is 18, Haze values, and is ground into powder of the average grain diameter at 500 μm.Bottle is measured during blow molding
Embryo temperature of each section, wherein in the mean temperature of bottle embryo epimere be 100 DEG C, the mean temperature in bottle embryo stage casing is 101, bottle embryo hypomere
Mean temperature be 108, the maximum mean temperature difference of bottle embryo entirety is 8 DEG C.
【Embodiment 5】
Refering to table 1, embodiment 5 is similar with the embodiment 4, and different places are：The present embodiment is using the poly- of 99wt%
The polypropylene of ethylene terephthalate and 1wt% are raw material.Bottle embryo temperature of each section is measured during blow molding,
In, it is 108 in the mean temperature of bottle embryo epimere, the mean temperature in bottle embryo stage casing is 107 DEG C, and the mean temperature of bottle embryo hypomere is
111 DEG C, the maximum mean temperature difference of bottle embryo entirety is 4 DEG C.
【Embodiment 6】
Refering to table 1, embodiment 6 is similar with the embodiment 3, and different places is that the polyethylene is ground to average grain diameter and exists
100 μm of powder.Bottle embryo temperature of each section is measured during blow molding, wherein be in the mean temperature of bottle embryo epimere
101, the mean temperature in bottle embryo stage casing is 101 DEG C, and the mean temperature of bottle embryo hypomere is 104 DEG C, the average temperature of maximum of bottle embryo entirety
Difference is 3 DEG C.
【Embodiment 7】
Refering to table 1, embodiment 7 is similar with the embodiment 5, and different places is that the polypropylene is ground to average grain diameter and exists
100 μm of powder.During blow molding measure bottle embryo temperature of each section, wherein bottle embryo epimere mean temperature be 109
DEG C, the mean temperature in bottle embryo stage casing is 110 DEG C, and the mean temperature of bottle embryo hypomere is 111 DEG C, the maximum mean temperature difference of bottle embryo entirety
It is 2 DEG C.
【Comparative example 1】
Refering to table 1 and Fig. 4, comparative example 1 is similar with the embodiment 1, and different places is that the polymethylpentene is not ground
At powder, average grain diameter 4mm.By the finished product obtained by this comparative example 1, for a flaw with current mark flaw appearance
Product.By the table 1 it can be found that this comparative example 1 is during blow molding, the maximum mean temperature difference of bottle embryo entirety is 10 DEG C.
【Comparative example 2】
Refering to table 1 and Fig. 5, comparative example 2 is similar with the embodiment 2, and different places is that the polyethylene is not pulverized
End, average grain diameter 5mm.By the finished product obtained by this comparative example 2, for the faulty materials with current mark flaw appearance.By
For the table 1 it can be found that this comparative example 2 is during blow molding, the maximum mean temperature difference of bottle embryo entirety is 12 DEG C.
【Comparative example 3】
Refering to table 1 and Fig. 6, comparative example 3 is similar with the embodiment 2, and different places is using the poly- to benzene of 88wt%
The polyethylene of dioctyl phthalate second diester and 12wt% are raw material.By obtained by this comparative example 3 finished product and one have current mark
The faulty materials of flaw appearance.By the table 1 it can be found that this comparative example 3 is during blow molding, the maximum of bottle embryo entirety is flat
Mean temperature difference is 11 DEG C.
【Comparative example 4】
Refering to table 1 and Fig. 7, comparative example 4 is similar with the embodiment 4, and different places is that the polypropylene is not pulverized
End, average grain diameter 4mm.By the finished product and the faulty materials with current mark flaw appearance obtained by this comparative example 4.
By the table 1 it can be found that this comparative example 4 is during blow molding, the maximum mean temperature difference of bottle embryo entirety is 12 DEG C.
【Comparative example 5】
Refering to table 1 and Fig. 8, comparative example 5 is similar with the embodiment 4, and the present embodiment uses the poly terephthalic acid of 88wt%
The polypropylene of second diester and 12wt% are raw material.By obtained by this comparative example 5 finished product and one have current mark flaw outside
The faulty materials of sight.By the table 1 it can be found that this comparative example 5 is during blow molding, the maximum mean temperature difference of bottle embryo entirety
It is 12 DEG C.
Refering to table 1, it is respectively compared the embodiment 1 and the comparative example 1, the embodiment 2 and the comparative example 2 and the implementation
Example 4 and the comparative example 4 are it can be found that the polyolefin polymers that will be added into advance, that is, polymethylpentene, polyethylene,
And polypropylene is ground into powder of the average grain diameter at 500 μm, both contributes to improve heat conduction property so that implementation of the invention
Maximum mean temperature difference of the example in blow-molding process, comes small compared to corresponding comparative example.
In addition, being respectively compared the embodiment 2 and the comparative example 3, the embodiment 4 is with the comparative example 5 it can be found that in polyene
Hydrocarbon polymer, that is, polyethylene and polyacrylic additive amount, in 10wt%, maximum of the bottle embryo in blow-molding process is average
The temperature difference is all at 8 DEG C.But work as polyethylene and polyacrylic additive amount respectively in 12wt%, even if in advance by polyethylene and polypropylene
It is ground into powder of the average grain diameter at 500 μm, maximum mean temperature difference of the bottle embryo in blow-molding process is also all at 11 DEG C or more.
Finally, compare the embodiment 3 and the embodiment 6, and compare the embodiment 5 with the embodiment 7 it can be found that will
Polyethylene and polypropylene are ground into powder of the average grain diameter at 100 μm in advance, and maximum of the bottle embryo in blow-molding process can be made flat
Mean temperature difference more reduces.
In conclusion manufacturing method of the present invention by mixed weight percentage in 90%-99% poly terephthalic acids second two
Ester and weight percent and grind polyolefin polymers before mixing in the raw material of the polyolefin polymers of 1-10%
The powder that average grain diameter is less than 500 μm is worn into, capacity of heat transmission can be made to be unlikely to be deteriorated, and the temperature difference between different endpoints is made to become
It is small, and with plasticity improve current mark simultaneously there is a situation where therefore can reach the purpose of the present invention really.
Claims (6)
1. a kind of manufacturing method of the plastic bottle of tool pearl effect, including：
Prepare raw material stage：By the granular poly terephthalic acid second of the polyolefin polymers of 1-10wt% and 90-99wt%
Diester mixes；And
Container step is made：Aforementioned raw material is mixed into melting with ejection forming technique and is projected at a bottle embryo, then by the bottle embryo
One plastic bottle of blow molding；
It is characterized in that：In the preparation raw material stage, first the polyolefin polymers are ground, the polyolefin is made to birds of the same feather flock together
The average grain diameter for closing object is less than the average grain diameter of the polyethylene terephthalate；
Wherein, the average grain diameter of the polyolefin polymers is 100 μm~500 μm.
2. the manufacturing method of the plastic bottle of tool pearl effect as described in claim 1, it is characterised in that：The polyolefin is birdsed of the same feather flock together
Object is closed to be selected from：Polyethylene, polypropylene, polymethylpentene, polyolefin elastomer and ethylene and vinyl acetate co-polymer.
3. the manufacturing method of the plastic bottle of tool pearl effect as claimed in claim 2, it is characterised in that：The polyolefin is birdsed of the same feather flock together
Conjunction object is polypropylene.
4. the manufacturing method of the plastic bottle of tool pearl effect as claimed any one in claims 1 to 3, it is characterised in that：
The polyolefin polymers and the polyethylene terephthalate are that the heat source heating with temperature between 250-300 DEG C mix and melted
Melt.
5. the manufacturing method of the plastic bottle of tool pearl effect as claimed in claim 4, it is characterised in that：The heat source is to be divided into
At least three sections of Segmented heating.
6. the manufacturing method of the plastic bottle of tool pearl effect as claimed in claim 5, it is characterised in that：When the bottle embryo will
Before the blow molding plastic bottle, the bottle temperature of the bottle embryo is between 80-130 DEG C.
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