CN106279871A - Composite for PE Packaging Bottle and preparation method thereof - Google Patents
Composite for PE Packaging Bottle and preparation method thereof Download PDFInfo
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- CN106279871A CN106279871A CN201610640365.XA CN201610640365A CN106279871A CN 106279871 A CN106279871 A CN 106279871A CN 201610640365 A CN201610640365 A CN 201610640365A CN 106279871 A CN106279871 A CN 106279871A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention is provided to the composite of PE Packaging Bottle, its weight portion component includes: PE resin 44～55 parts, filler 10～15 parts, antioxidant 0.1～0.6 part, cross-linking agent 0.5～1 part, lubricant 4～5 parts, compatilizer 3～5 parts, plasticizer 5～6 parts, antibacterial 1～2 parts, Firebrake ZB 10 parts, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5～6 parts.Present invention also offers this preparation method for the composite of PE Packaging Bottle.Thermostability and the light fastness aging of the composite of PE Packaging Bottle of the present invention are the strongest.
Description
Technical field
The present invention relates to composite, particularly relate to the composite and preparation method thereof for PE Packaging Bottle.
Background technology
New packing on China's beverage market in recent years gradually more gets up, and is presently used for the plastics kind of beverage packaging bottle
Class mainly has PE, PP, PVC, PET etc..Wherein, PE (Chinese entitled polyethylene) is the synthetic resin that yield is maximum in the world, also
It it is the plastic package material of consumption maximum.Polyethylene product is divided into again low-density, Midst density and high density three kinds, highly the densest
Degree polyethylene (HDPE) is because having higher degree of crystallinity, and its hardness, air-tightness, mechanical strength, chemical resistance are all preferable,
So being used blow molding to make the hollow containers such as bottle in a large number.Utilize the feature that PE heat sealability is good, production various multiple
The Packaging Bottle that condensation material is made, can contain the various beverage such as Fructus Citri Limoniae juice, fruit juice.
Publication No. CN1413885, publication date are 2003.04.30, apply for artificial SINOPEC Shandong petrochemical industry
The Chinese patent application of company discloses " high-separate layer hollow container and preparation technology thereof ", and it is by EVOH, compatilizer (third
Olefin(e) acid grafted polyethylene) it is prepared as intercepting masterbatch, it is prepared from after being dry mixed with polyethylene the most again.In goods, EVOH is with stratiform
Formal distribution is in base polyethylene, and these goods have the barrier of excellence for Hydrocarbon (especially alcohols, ketone)
Can, goods have good mechanical property simultaneously, and this hollow container can be used for the such as field such as fuel tank of vehicle, Packaging Bottle.So
And, the thermostability of this hollow container is not ideal enough, and light fastness aging is poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide the composite for PE Packaging Bottle, its thermostability and light aging resisting
Property is the strongest.
For solving above-mentioned technical problem, the technical scheme is that
For the composite of PE Packaging Bottle, its weight portion component includes: PE resin 44～55 parts, filler 10～15 parts,
Antioxidant 0.1～0.6 part, cross-linking agent 0.5～1 part, lubricant 4～5 parts, compatilizer 3～5 parts, plasticizer 5～6 parts, antibacterial
1～2 part, Firebrake ZB 10 parts, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5～6 parts；Wherein, described cadmium sulfide is hollow micro-
Ball is prepared by following steps:
(1) Pericarpium Musae is put in distilled water, is heated to 95 DEG C of afterflush 10 minutes, after taking-up with 1200 turns of centrifuge/
It is centrifuged 5 minutes under component velocity, is then placed in bruisher pulling an oar 15 minutes under 5500 revs/min of speed, after taking-up, puts into colloid mill
Middle backflow 2 minutes, obtains Fructus Musae latex；
(2) Fructus Musae latex step (1) obtained with the solid-liquid ratio of 1:10 adds in deionized water, moves after stirring 30 minutes
To microwave hydrothermal reaction kettle, microwave power is set to 180W, and pressure is set to 1MPa, is incubated 30 after temperature rises to 180 DEG C
Minute, it is cooled to discharging after room temperature, with deionized water and dehydrated alcohol by each for product eccentric cleaning 3 times, is placed in baking oven 90 DEG C
Lower drying 4 hours, obtains carbon ball；
(3) carbon ball step (2) obtained adds in deionized water, and ultrasonic disperse obtains carbon ball solution after 30 minutes, will
Thioacetamide adds in the ultra-pure water solution of 0.1mol/L, and stirring is added drop-wise in carbon ball solution after being completely dissolved, and regulates ph
Value is that oil bath is heated to 60 DEG C after 9, is added dropwise to stirring reaction 6 hours after the cadmium sulfate solution of 1mol/L, with super after centrifugation
Pure water and deionized water clean each 3 times, are placed in vacuum drying oven and are dried 10 hours at 90 DEG C, obtain cadmium sulfide carbon coated ball powder
End, wherein, carbon ball, deionized water, thioacetamide, ultra-pure water, the weight ratio of cadmium sulfate are 2:1200:10:3:19；
(4) cadmium sulfide carbon coated ball powder step (3) obtained loads in zirconium oxide crucible, is placed in by zirconium oxide crucible
In Muffle furnace, after being warming up to 550 DEG C with the speed of 2 DEG C/minute, it is incubated 3 hours, is incubated 8 hours after continuing intensification 640 DEG C, is cooled to
Take out after room temperature, obtain cadmium sulfide tiny balloon.
Preferably, PE resin of the present invention is HDPE.
Preferably, filler of the present invention is potter's clay.
Preferably, antioxidant of the present invention is anti-oxidant DLTP.
Preferably, cross-linking agent of the present invention is TAC.
Preferably, lubricant of the present invention is butyl stearate.
Preferably, compatilizer of the present invention is EPDM.
Preferably, plasticizer of the present invention is glycerol.
Preferably, antibacterial of the present invention is hydroxyapatite carrying silver antimicrobials.
Another technical problem that the invention solves the problems that is to provide the preparation method of the above-mentioned composite for PE Packaging Bottle.
For solving above-mentioned technical problem, technical scheme is:
Weigh each component by weight, PE resin, cross-linking agent, butylbenzene powdered rubber added high-speed mixer and mixing uniformly,
After being incubated 1 hour at 90 DEG C, other component is added high mixer, obtain compound after mixing 30 minutes at 90 DEG C, compound is added
Entering in double screw extruder and melt extrude, engine speed is 50 revs/min, and feeding machine rotating speed is 5/ point, the extruded stock 90 that will obtain
DEG C it is dried the composite that obtains for PE Packaging Bottle for 3 hours.
Therefore, compared with prior art, the method have the advantages that
1, Pericarpium Musae is the epidermis of Fructus Musae, is usually taken as food garbage and abandons, and the present invention is first after being collected by Pericarpium Musae
With hot water injection be then centrifuged for, pull an oar, Fructus Musae latex is made in colloid mill backflow, then Fructus Musae latex is processed by microwave hydrothermal
Make stability preferable carbon ball, then it is had nucleocapsid structure with thioacetamide, cadmium sulfate by sol-gel process is prepared
Cadmium sulfide carbon coated ball powder, then eliminate carbon ball template to have obtained mean diameter being the sulfuration about 3 μm by calcining
Cadmium tiny balloon, cadmium sulfide has the strongest optical absorption, can effectively absorb what composite was subject to after being blended with PE matrix
Illumination effect, thus it is greatly improved the light aging resisting property of composite, and also the hollow-core construction of cadmium sulfide tiny balloon can have
Effect trap heat transmission, can be greatly improved thermal insulation and the thermostability of composite with PE group after being therefore blended；
2, the raw material Pericarpium Musae that the present invention is used when preparing cadmium sulfide tiny balloon is food garbage, cheap and easy to get, because of
This can effectively reduce preparation cost, has preferable economic worth.
Detailed description of the invention
The present invention is described in detail, in illustrative examples and the explanation of this present invention below in conjunction with specific embodiment
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 55 parts, 10 parts of potter's clay, anti-oxidant DLTP
0.5 part, TAC 0.5 part, butyl stearate 4.2 parts, EPDM 3.5 parts, glycerol 5 parts, hydroxyapatite carries silver 2 parts, Firebrake ZB 10
Part, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5.5 parts.
Its preparation method is:
1) Pericarpium Musae is put in distilled water, be heated to 95 DEG C of afterflush 10 minutes, with 1200 revs/min of centrifuge after taking-up
It is centrifuged 5 minutes under speed, is then placed in bruisher pulling an oar 15 minutes under 5500 revs/min of speed, puts in colloid mill after taking-up
Reflux 2 minutes, obtain Fructus Musae latex；
(2) Fructus Musae latex step (1) obtained with the solid-liquid ratio of 1:10 adds in deionized water, moves after stirring 30 minutes
To microwave hydrothermal reaction kettle, microwave power is set to 180W, and pressure is set to 1MPa, is incubated 30 after temperature rises to 180 DEG C
Minute, it is cooled to discharging after room temperature, with deionized water and dehydrated alcohol by each for product eccentric cleaning 3 times, is placed in baking oven 90 DEG C
Lower drying 4 hours, obtains carbon ball；
(3) carbon ball step (2) obtained adds in deionized water, and ultrasonic disperse obtains carbon ball solution after 30 minutes, will
Thioacetamide adds in the ultra-pure water solution of 0.1mol/L, and stirring is added drop-wise in carbon ball solution after being completely dissolved, and regulates ph
Value is that oil bath is heated to 60 DEG C after 9, is added dropwise to stirring reaction 6 hours after the cadmium sulfate solution of 1mol/L, with super after centrifugation
Pure water and deionized water clean each 3 times, are placed in vacuum drying oven and are dried 10 hours at 90 DEG C, obtain cadmium sulfide carbon coated ball powder
End, wherein, carbon ball, deionized water, thioacetamide, ultra-pure water, the weight ratio of cadmium sulfate are 2:1200:10:3:19；
(4) cadmium sulfide carbon coated ball powder step (3) obtained loads in zirconium oxide crucible, is placed in by zirconium oxide crucible
In Muffle furnace, after being warming up to 550 DEG C with the speed of 2 DEG C/minute, it is incubated 3 hours, is incubated 8 hours after continuing intensification 640 DEG C, is cooled to
Take out after room temperature, obtain cadmium sulfide tiny balloon；
(5) weigh each component by weight, HDPE, TAC, butylbenzene powdered rubber are added high-speed mixer and mixing uniformly, 90
After being incubated 1 hour at DEG C, other component is added high mixer, obtain compound after mixing 30 minutes at 90 DEG C, add mixture into
Melt extruding in double screw extruder, engine speed is 50 revs/min, and feeding machine rotating speed is 5/ point, the extruded stock 90 DEG C that will obtain
It is dried the composite obtained for PE Packaging Bottle for 3 hours.
Embodiment 2
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 45 parts, 12 parts of potter's clay, anti-oxidant DLTP
0.3 part, TAC 0.8 part, butyl stearate 4 parts, EPDM 5 parts, glycerol 5.2 parts, hydroxyapatite carries silver 1.8 parts, Firebrake ZB 10
Part, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5.6 parts.
Its preparation method is same as in Example 1.
Embodiment 3
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 50 parts, 14 parts of potter's clay, anti-oxidant DLTP
0.1 part, TAC 1 part, butyl stearate 4.8 parts, EPDM 4 parts, glycerol 5.4 parts, hydroxyapatite carries silver 1.6 parts, Firebrake ZB 10
Part, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5 parts.
Its preparation method is same as in Example 1.
Embodiment 4
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 48 parts, 11 parts of potter's clay, anti-oxidant DLTP
0.6 part, TAC 0.5 part, butyl stearate 4.5 parts, EPDM 4.5 parts, glycerol 5.6 parts, hydroxyapatite carries silver 1.4 parts, boric acid
10 parts of zinc, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5.2 parts.
Its preparation method is same as in Example 1.
Embodiment 5
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 52 parts, 13 parts of potter's clay, anti-oxidant DLTP
0.4 part, TAC 0.7 part, butyl stearate 5 parts, EPDM 3 parts, glycerol 5.8 parts, hydroxyapatite carries silver 1.2 parts, Firebrake ZB 10
Part, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 6 parts.
Its preparation method is same as in Example 1.
Embodiment 6
For the composite of PE Packaging Bottle, its weight portion component includes: HDPE 44 parts, 15 parts of potter's clay, anti-oxidant DLTP
0.2 part, TAC 0.9 part, butyl stearate 4.9 parts, EPDM 3.3 parts, glycerol 6 parts, hydroxyapatite carries silver 1 part, Firebrake ZB 10
Part, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5.7 parts.
Its preparation method is same as in Example 1.
Embodiment 1-6 and the thermostability of comparative example and light fastness aging are tested respectively:
Comparative example is the Chinese patent application of Publication No. CN1413885,
Thermostability aspect tests each determinand in 0.45MPa pressure, 120 DEG C/h of intensifications with reference to GB/T 1633-2000
Heat distortion temperature under the conditions of speed, 0.34mm relative deformation, heat distortion temperature is the highest shows that thermostability is the strongest；
Resistance to ag(e)ing aspect is with reference to ISO4892-3 1994 standard, and after irradiating 50 hours at He-Ne lamp, at 40 DEG C, test is each
The elongation at break conservation rate of determinand, elongation at break conservation rate is the highest shows that resistance to ag(e)ing is the strongest.
Test result is as shown in the table:
Thus table can be seen that, the heat distortion temperature of embodiment of the present invention 1-6 and elongation at break conservation rate obviously higher than
Comparative example, shows stronger thermostability and light fastness aging.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause
This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art
All equivalences become are modified or change, and must be contained by the claim of the present invention.
Claims (10)
1. for the composite of PE Packaging Bottle, it is characterised in that its weight portion component includes: PE resin 44～55 parts, filler
10～15 parts, antioxidant 0.1～0.6 part, cross-linking agent 0.5～1 part, lubricant 4～5 parts, compatilizer 3～5 parts, plasticizer 5～6
Part, antibacterial 1～2 parts, Firebrake ZB 10 parts, butylbenzene powdered rubber 7 parts, cadmium sulfide tiny balloon 5～6 parts；Wherein, described sulfuration
Cadmium tiny balloon is prepared by following steps:
(1) Pericarpium Musae is put in distilled water, be heated to 95 DEG C of afterflush 10 minutes, by 1200 revs/min of speed of centrifuge after taking-up
Lower centrifugal 5 minutes of degree, is then placed in bruisher pulling an oar 15 minutes under 5500 revs/min of speed, puts in colloid mill and return after taking-up
Flow 2 minutes, obtain Fructus Musae latex；
(2) Fructus Musae latex step (1) obtained with the solid-liquid ratio of 1:10 adds in deionized water, moves to micro-after stirring 30 minutes
In ripple hydrothermal reaction kettle, microwave power is set to 180W, and pressure is set to 1MPa, is incubated 30 minutes after temperature rises to 180 DEG C,
It is cooled to discharging after room temperature, with deionized water and dehydrated alcohol by each for product eccentric cleaning 3 times, is placed in baking oven and dries at 90 DEG C
4 hours, obtain carbon ball；
(3) carbon ball step (2) obtained adds in deionized water, and ultrasonic disperse obtains carbon ball solution after 30 minutes, by sulfur generation
Acetamide adds in the ultra-pure water solution of 0.1mol/L, and stirring is added drop-wise in carbon ball solution after being completely dissolved, and regulation ph value is 9
Rear oil bath is heated to 60 DEG C, is added dropwise to stirring reaction 6 hours after the cadmium sulfate solution of 1mol/L, after centrifugation with ultra-pure water and
Deionized water cleans each 3 times, is placed in vacuum drying oven and is dried 10 hours at 90 DEG C, obtains cadmium sulfide carbon coated ball powder, its
In, carbon ball, deionized water, thioacetamide, ultra-pure water, the weight ratio of cadmium sulfate are 2:1200:10:3:19；
(4) cadmium sulfide carbon coated ball powder step (3) obtained loads in zirconium oxide crucible, and zirconium oxide crucible is placed in Muffle
In stove, after being warming up to 550 DEG C with the speed of 2 DEG C/minute, it is incubated 3 hours, is incubated 8 hours after continuing intensification 640 DEG C, is cooled to room temperature
Rear taking-up, obtains cadmium sulfide tiny balloon.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described PE resin is HDPE.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: institute's filler is potter's clay.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described antioxidant is antioxidant
DLTP。
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described cross-linking agent is TAC.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described lubricant is stearic acid
Butyl ester.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described compatilizer is EPDM.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described plasticizer is glycerol.
Composite for PE Packaging Bottle the most according to claim 1, it is characterised in that: described antibacterial is hydroxyl phosphorus
Lime stone carrying silver antimicrobials.
10. according to the preparation method of the composite for PE Packaging Bottle described in claim 1～9 any one, its feature
It is:
Weigh each component by weight, PE resin, cross-linking agent, butylbenzene powdered rubber are added high-speed mixer and mixing uniformly, 90 DEG C
Other component was added high mixer after 1 hour by lower insulation, obtained compound after mixing 30 minutes at 90 DEG C, added mixture into double
Melt extruding in screw extruder, engine speed is 50 revs/min, and feeding machine rotating speed is 5/ point, is done by the extruded stock 90 DEG C obtained
The dry composite obtained for PE Packaging Bottle for 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610640365.XA CN106279871A (en) | 2016-08-04 | 2016-08-04 | Composite for PE Packaging Bottle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610640365.XA CN106279871A (en) | 2016-08-04 | 2016-08-04 | Composite for PE Packaging Bottle and preparation method thereof |
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| CN106279871A true CN106279871A (en) | 2017-01-04 |
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| CN201610640365.XA Pending CN106279871A (en) | 2016-08-04 | 2016-08-04 | Composite for PE Packaging Bottle and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110839750A (en) * | 2019-11-08 | 2020-02-28 | 内蒙古蒙牛乳业（集团）股份有限公司 | Frozen beverage with chocolate-cheese mixed coating and preparation method thereof |
| WO2022146379A1 (en) * | 2020-12-30 | 2022-07-07 | T.C. Erci̇yes Üni̇versi̇tesi̇ | Antibacterial pet packaging |
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| CN104212037A (en) * | 2014-09-10 | 2014-12-17 | 四川塑金科技有限公司 | Regenerated HDPE (High-Density Polyethylene) particles and preparation method thereof |
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2016
- 2016-08-04 CN CN201610640365.XA patent/CN106279871A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104212037A (en) * | 2014-09-10 | 2014-12-17 | 四川塑金科技有限公司 | Regenerated HDPE (High-Density Polyethylene) particles and preparation method thereof |
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| 徐扬子等: "CdS包覆SiO2核/壳和空腔结构纳米球制备及发光性能", 《湖北大学学报（自然科学版）》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110839750A (en) * | 2019-11-08 | 2020-02-28 | 内蒙古蒙牛乳业（集团）股份有限公司 | Frozen beverage with chocolate-cheese mixed coating and preparation method thereof |
| WO2022146379A1 (en) * | 2020-12-30 | 2022-07-07 | T.C. Erci̇yes Üni̇versi̇tesi̇ | Antibacterial pet packaging |
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Application publication date: 20170104 |