CN106945368A - A kind of high-temperature resistant membrane and preparation method thereof - Google Patents
A kind of high-temperature resistant membrane and preparation method thereof Download PDFInfo
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention provides a kind of high-temperature resistant membrane and preparation method thereof, belong to thin film technique field.The high-temperature resistant membrane of the present invention, including outer layer, middle level, the part of internal layer three, the outer layer weight accounts for the 10~30% of film gross weight, the middle layer weight accounts for the 50~70% of film gross weight, the interior layer weight accounts for the 10~30% of film gross weight, wherein, by weight percentage, the preparing raw material of the outer layer and internal layer includes PP M800E；The preparing raw material in the middle level includes 60~80% MDPE 5400 and 20~40% LDPE TN00.The high-temperature resistant membrane of the present invention is simple in construction, there is good impact resistance, tear resistance, and can not produce performance change in high temperature environments, will not discharge harmful material, heat distortion temperature is up to more than 150 DEG C.
Description
Technical field
The invention belongs to thin film technique field, it is related to a kind of high-temperature resistant membrane and preparation method thereof.
Background technology
With the change of people's habits and customs, increasing quick consumer food, these quick consumer foods are occurred in that
Food product packing film can be used in storage and transportation, food product packing film is used for being wrapped in food surface, is mainly used to
The entrance of microbial bacterial and external contaminant is decomposed in isolation, prevents and extend the high polymer material of food spoilage.Packaging for foodstuff
Except meeting commodity packaging, the packaging material such as the mechanical property of needs, printing performance, display performance must have film in itself
Outside performance, there is very high requirement countries in the world to the sanitation performance for foodstuff article packaging material, for example, require material
Color and luster is normal, free from extraneous odour, high temperature resistant, antibacterial etc..At present, packaging need not be removed during many quick consumer food heating, this is just
Resistance to elevated temperatures to thin-film material proposes very high requirement.
CN104669739A discloses a kind of digestion resistant type thin-film material, and it uses seven-layer co-extrusion blow molding process, raw
Output structure is PE/TIE/PP/EVOH/PP/TIE/PE digestion resistant plastic thin-film material.With this kind of thin-film material system
Standby packaging bag, can be effectively protected pack content, and can not occur performance change under thermophilic digestion environment.Will not
Discharge harmful material safe to the human body, but the structure level number of this film is many, it is necessary to the parameter of control is complicated, and high temperature resistant
Performance has much room for improvement.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of high-temperature resistant membrane, simple in construction, resistance to
High-temperature behavior is good.
For up to this goal of the invention, the present invention uses following technical scheme：
A kind of high-temperature resistant membrane, including outer layer, middle level, the part of internal layer three, the outer layer weight account for film gross weight 10~
30%, such as 10%, 12%, 15%, 16%, 17%, 19%, 20%, 22%, 24%, 25%, 28%, 30%；The middle level
Weight accounts for the 50~70% of film gross weight, such as 50%, 51%, 52%, 53%, 54%, 55%, 56%, 58%, 60%, 62%,
65%th, 66%, 68%, 70%, the interior layer weight accounts for the 10~30% of film gross weight, such as 10%, 12%, 15%, 16%,
17%th, 19%, 20%, 22%, 24%, 25%, 28%, 30%；Wherein, by weight percentage,
The outer layer of the present invention and the preparing raw material of internal layer include PP M800E；PP has relative hardness height, proportion
Small, tensile strength is high, the transparency is good, anti-stress cracking and chemical-resistance are good, resistance to heat deflection temperature is high and have fabulous note
Plasticity energy, arbitrarily it can stretch and orient, the advantages of can be with other materials blending and modifying, PP materials are to acid-alkali salt and many solvents
Etc. there is stability, and resistance to elevated temperatures is excellent, can for a long time be used in the range of 100-120 DEG C, can do outer layer, inner layer material direct
Contacted with food, harmful substance will not be produced.The present invention, as the preparing raw material of outer layer and internal layer, makes preparation using PP M800E
High-temperature resistant membrane there is good transparency, stretch-proof, resistance to elevated temperatures.
By weight percentage, the preparing raw material in the middle level includes 60~80% MDPE's 5400 and 20~40%
LDPE TN00, such as MDPE weight ratio be 60%, 62%, 64%, 65%, 66%, 67%, 68%, 69%, 70%,
72%th, 75%, 76%, 78%, 80%；LDPE TN00 weight ratio be 20%, 21%, 22%, 25%, 26%, 27%,
28%th, 29%, 30%, 32%, 33%, 35%, 36%, 37%, 39%, 40%.Low density polyethylene (LDPE) (LDPE) material has
Good ductility, tear resistance and impact resistance and transparency are high, heat sealability is good, and the performance of medium density polyethylene (MDPE) is situated between
HDPE rigidity is maintained between the two, both in high density polyethylene (HDPE) (HDPE) and low density polyethylene (LDPE) (LDPE), there is LDPE again
Flexibility, creep resistant, its advantage is the long-term retentivity with good environmental stress crack resistance and intensity.In the present invention
The middle level of film is using MDPE 5400 and LDPE TN00 as raw material, and the two synergy makes obtained film have good resistance to punching
Hitting property, tear resistance, and performance change can not be produced in high temperature environments, harmful material will not be discharged.
Wherein, by weight percentage, the outer layer weight accounts for the 15~25% of film gross weight, such as 15%, 16%,
17%th, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%；The middle layer weight accounts for the 55~65% of film gross weight,
Such as 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%；It is total that the interior layer weight accounts for film
The 15~25% of weight, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%；This hair
The bright thickness to film is that every layer of film has reformed optimization, and each layer of thickness accounts for the percentage by weight of film gross weight by every layer weight
Embody, and every layer of thickness has affected indirectly the performance of film.Preferably, by weight percentage, the middle level
Preparing raw material includes 65~75% MDPE 5400 and 25~35% LDPE TN00, such as MDPE 5400 weight percent
Than for 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, LDPE TN00 weight hundred
Divide than being 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%.
Preferably, the outer layer weight accounts for the 20% of film gross weight, and the middle layer weight accounts for the 60% of film gross weight, the internal layer
Weight accounts for the 20% of film gross weight.It is highly preferred that described high-temperature resistant membrane, by weight percentage, the preparation in the middle level are former
Material includes 70% MDPE 5400 and 30% LDPE TN00.
Preferably, nano-Ag particles are also included in the preparing raw material of the outer layer and internal layer, the addition of nano-Ag particles makes
Film has good anti-microbial property.It is highly preferred that the weight ratio (1~5) of the nano-Ag particles and the PP M800E：50,
Such as 1:10、1:25、1:50、2:25、3:50.If the weight ratio of nano-Ag particles and PP M800E is less than 1:50 do not have it is good
Good antibacterial effect, if higher than 1:10 can influence the performance of film.
Wherein, preparing for the middle level also includes age resister in material, can increase the service life of film.Preferably,
The weight of the age resister accounts for the 1~2% of the MDPE 5400, such as 1%, 1.2%, 1.5%, 1.6%, 1.7%,
1.8%th, 2%.
Wherein, it is additionally provided with thermal insulation layer between the outer layer and the middle level, it is preferable that by weight percentage, it is described
The preparing raw material of thermal insulation layer includes 50~70% MDPE 5400,0.5~5% nano silicon and 20~50%
LDPE 2420H；Such as MDPE 5400 be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%,
60%th, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%；Nano silicon be 0.5%,
1%th, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%；LDPE 2420H be 20%, 22%, 25%, 28%,
30%th, 32%, 35%, 38%, 40%, 42%, 45%, 46%, 48%, 50%.Nano silicon is extremely important height
One of ultra tiny New Inorganic Materials of science and technology, because of its particle diameter very little, specific surface area is big, and superficial attractive forces are strong, and surface can be big, and chemistry is pure
Spend in terms of height, good dispersive property, thermal resistance, resistance with special performance.Nano silicon in the present invention is used as nanometer
Poromerics, with good heat-proof quality, is added in MDPE5400 and LDPE 2420H and plays good heat-blocking action.Its
In, if the weight ratio shared by nano silicon is higher than 0.5~5%, the stretch-proof of film in itself, tear-resistant performance can be influenceed,
Good heat-blocking action is not had if less than 0.5~5%.
The second object of the present invention is to provide a kind of preparation method of high-temperature resistant membrane as described above, and technique is simple,
The preparation method comprises the following steps：
1) batch mixing, prepares the middle level raw mixture of high-temperature resistant membrane after the preparing raw material in the middle level of formula ratio is mixed；
2) dispensing, by step 1) prepare high-temperature resistant membrane middle level raw mixture and preparing raw material, the internal layer of outer layer
Preparing raw material by proportioning carry out dispensing；
3) blown film, by step 2) membrane material coextrusion blow shaping after dispensing.
Wherein, step 3) in, the coextrusion blow process is, by the preparing raw material of outer layer, middle level raw mixture, internal layer
Preparing raw material by proportioning add three-layer co-extruded inflation film machine it is outer, in, in internal layer hopper, heat and simultaneously gradually heat up, outer layer,
Middle level, the extrusion temperature of internal layer are controlled at 170~185 DEG C, and high-temperature resistant membrane is made in extruded blow molding.
Preferably, the preparation method comprises the following steps：
1) batch mixing, prepares the middle level raw mixture of high-temperature resistant membrane after the preparing raw material in the middle level of formula ratio is mixed,
The thermal insulation layer raw mixture of high-temperature resistant membrane is prepared after the preparing raw material of the thermal insulation layer of formula ratio is mixed；
2) dispensing, by step 1) prepare the middle level raw mixture of high-temperature resistant membrane, thermal insulation layer raw mixture with it is outer
The preparing raw material of layer, the preparing raw material of internal layer carry out dispensing by proportioning；
3) blown film, by step 2) membrane material coextrusion blow shaping after dispensing.
Preferably, the heat-insulated layer weight accounts for the 10~30% of film gross weight, such as 10%, 11%, 12%, 13%, 15%,
16%th, 18%, 20%, 24%, 25%, 26%, 28%, 30%.
Compared with prior art, beneficial effects of the present invention are：The high-temperature resistant membrane of the present invention, outer layer and inner layer material choosing
Use PP M800E, tensile strength is high, transparent good, anti-stress cracking and chemical-resistance are good, heat-resisting to deflect temperature high；Adopt in middle level
With MDPE 5400 and LDPE TN00 as raw material, the two synergy makes obtained film have good impact resistance, anti-tear
Fragility, transverse tensile strength in more than 58Mpa, longitudinal tensile strength in more than 65Mpa, transverse breakage elongation up to 657% with
On, longitudinal elongation at break rate can not produce performance change in high temperature environments up to more than 553%, and will not discharge has to human body
Harmful material, heat distortion temperature is up to more than 150 DEG C.
Embodiment
Technical scheme is further illustrated below by embodiment.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this area
Obtain.
Embodiment 1
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 10% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 30% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E；
The preparing raw material in middle level is made up of 80% MDPE 5400 and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is as follows：
1) batch mixing, prepares the middle level raw mixture of high-temperature resistant membrane after the preparing raw material in the middle level of formula ratio is mixed；
2) dispensing, by step 1) prepare high-temperature resistant membrane middle level raw mixture and preparing raw material, the internal layer of outer layer
Preparing raw material by proportioning carry out dispensing；
3) blown film, by step 2) membrane material coextrusion blow shaping after dispensing.Wherein, step 3) in, the coextrusion blow
Process is, the preparing raw material of the preparing raw material of outer layer, middle level raw mixture, internal layer is thin by the three-layer co-extruded blowing of proportioning addition
Film machine it is outer, in, in internal layer hopper, heat and gradually heat up, outer layer, middle level, the extrusion temperature control of internal layer are 170~185
DEG C, high-temperature resistant membrane is made in extruded blow molding.
Embodiment 2
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 30% of film gross weight,
Middle layer weight accounts for the 50% of film gross weight, and interior layer weight accounts for the 20% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E；
The preparing raw material in middle level is made up of 60% MDPE 5400 and 40% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 3
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 30% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 10% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E；
The preparing raw material in middle level is made up of 70% MDPE 5400 and 30% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 4
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 20% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 20% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E；
The preparing raw material in middle level is made up of 65% MDPE 5400 and 35% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 5
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 10% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 30% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：50；
The preparing raw material in middle level is made up of 80% MDPE 5400 and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 6
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 10% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 30% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：25；
The preparing raw material in middle level is made up of 80% MDPE 5400 and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 7
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 10% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 30% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：10；
The preparing raw material in middle level is made up of 80% MDPE 5400 and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 8
The high-temperature resistant membrane of the present embodiment, including outer layer, middle level, the part of internal layer three, outer layer weight account for the 10% of film gross weight,
Middle layer weight accounts for the 60% of film gross weight, and interior layer weight accounts for the 30% of film gross weight, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：10；
The preparing raw material in middle level is made up of 78% MDPE 5400,2% antiager and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 1, will not be repeated here.
Embodiment 9
The high-temperature resistant membrane of the present embodiment, including outer layer, thermal insulation layer, middle level, the part of internal layer three, outer layer weight account for film gross weight
10%, heat-insulated layer weight accounts for the 10% of film gross weight, and middle layer weight accounts for the 50% of film gross weight, and interior layer weight accounts for film gross weight
30%, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：10；
By 50% MDPE 5400,3% nano silicon and 47% LDPE 2420H in the preparing raw material of thermal insulation layer
Composition.
The preparing raw material in middle level is made up of 78% MDPE 5400,2% antiager and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is substantially the same manner as Example 1, and difference is outer layer with
Thermal insulation layer is additionally provided between layer, be will not be repeated here.
Embodiment 10
The high-temperature resistant membrane of the present embodiment, including outer layer, thermal insulation layer, middle level, the part of internal layer three, outer layer weight account for film gross weight
10%, heat-insulated layer weight accounts for the 10% of film gross weight, and middle layer weight accounts for the 50% of film gross weight, and interior layer weight accounts for film gross weight
30%, wherein, by weight percentage,
The preparing raw material of outer layer and internal layer is PP M800E, nano-Ag particles, the weight of nano-Ag particles and PP M800E
Amount compares 1：10；
By 70% MDPE 5400,5% nano silicon and 25% LDPE 2420H in the preparing raw material of thermal insulation layer
Composition.
The preparing raw material in middle level is made up of 78% MDPE 5400,2% antiager and 20% LDPE TN00.
The preparation method of the high-temperature resistant membrane of the present embodiment is same as Example 9, will not be repeated here.
The performance of the embodiment 1-10 high-temperature resistant membranes prepared is tested, test result is as shown in table 1.
Table 1
The high-temperature resistant membrane of the present invention is simple in construction, has good impact resistance, tear resistance, transverse tensile strength exists
More than 58Mpa, longitudinal tensile strength is in more than 65Mpa, and transverse breakage elongation is up to more than 657%, and longitudinal elongation at break rate reaches
More than 553%, and performance change can not be produced in high temperature environments, harmful material, heat distortion temperature will not be discharged
Up to more than 150 DEG C.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of high-temperature resistant membrane, including outer layer, middle level, the part of internal layer three, it is characterised in that the outer layer weight accounts for film gross weight
10~30%, the middle layer weight accounts for the 50~70% of film gross weight, and the interior layer weight accounts for the 10~30% of film gross weight, its
In, by weight percentage,
The preparing raw material of the outer layer and internal layer includes PP M800E；
The preparing raw material in the middle level includes 60~80% MDPE 5400 and 20~40% LDPE TN00.
2. high-temperature resistant membrane according to claim 1, it is characterised in that the outer layer weight account for film gross weight 15~
25%, the middle layer weight accounts for the 55~65% of film gross weight, and the interior layer weight accounts for the 15~25% of film gross weight, wherein, by weight
Percentages are measured, the preparing raw material in the middle level includes 65~75% MDPE5400 and 25~35% LDPE TN00.
3. high-temperature resistant membrane according to claim 1 or 2, it is characterised in that the outer layer weight accounts for the 20% of film gross weight,
The middle layer weight accounts for the 60% of film gross weight, and the interior layer weight accounts for the 20% of film gross weight.
4. the high-temperature resistant membrane according to one of claim 1-3, it is characterised in that by weight percentage, the middle level
Preparing raw material include 70% MDPE 5400 and 30% LDPE TN00.
5. the high-temperature resistant membrane according to one of claim 1-4, it is characterised in that the preparing raw material of the outer layer and internal layer
In also include nano-Ag particles.
6. high-temperature resistant membrane according to claim 5, it is characterised in that the nano-Ag particles are with the PP M800E's
Weight ratio (1~5)：50.
7. the high-temperature resistant membrane according to one of claim 1-6, it is characterised in that preparing in material for the middle level is also wrapped
Include age resister；
Preferably, the weight of the age resister accounts for the 1~2% of the MDPE 5400.
8. the high-temperature resistant membrane according to one of claim 1-7, it is characterised in that between the outer layer and the middle level also
It is provided with thermal insulation layer；
Preferably, by weight percentage, the preparing raw material of the thermal insulation layer include 50~70% MDPE5400,0.5~
5% nano silicon and 20~50% LDPE 2420H.
9. the preparation method of the high-temperature resistant membrane according to one of claim 1-7, it is characterised in that the preparation method bag
Include following steps：
1) batch mixing, prepares the middle level raw mixture of high-temperature resistant membrane after the preparing raw material in the middle level of formula ratio is mixed；
2) dispensing, by step 1) prepare high-temperature resistant membrane middle level raw mixture and preparing raw material, the system of internal layer of outer layer
Standby raw material carries out dispensing by proportioning；
3) blown film, by step 2) membrane material coextrusion blow shaping after dispensing.
10. the preparation method of high-temperature resistant membrane according to claim 9, it is characterised in that the preparation method is included such as
Lower step：
1) batch mixing, prepares the middle level raw mixture of high-temperature resistant membrane, will match somebody with somebody after the preparing raw material in the middle level of formula ratio is mixed
The thermal insulation layer raw mixture of high-temperature resistant membrane is prepared after the preparing raw material mixing of the thermal insulation layer of side's amount；
2) dispensing, by step 1) the middle level raw mixture of high-temperature resistant membrane, thermal insulation layer raw mixture and the outer layer that prepare
Preparing raw material, the preparing raw material of internal layer carry out dispensing by proportioning；
3) blown film, by step 2) membrane material coextrusion blow shaping after dispensing；
Preferably, the heat-insulated layer weight accounts for the 10~30% of film gross weight；
Preferably, step 3) in, the coextrusion blow process is, by the preparing raw material of outer layer, thermal insulation layer raw mixture, middle level
Raw mixture, internal layer preparing raw material by proportioning add inflation film machine hopper in, heat simultaneously gradually heat up, outer layer, every
Thermosphere, middle level, the extrusion temperature of internal layer are controlled at 170~185 DEG C, and high-temperature resistant membrane is made in extruded blow molding.
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