CN104292641A - High-transparency filler and preparation method and application thereof - Google Patents
High-transparency filler and preparation method and application thereof Download PDFInfo
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- CN104292641A CN104292641A CN201410564554.4A CN201410564554A CN104292641A CN 104292641 A CN104292641 A CN 104292641A CN 201410564554 A CN201410564554 A CN 201410564554A CN 104292641 A CN104292641 A CN 104292641A
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- Prior art keywords
- transparent
- high transparency
- stopping composition
- transparency
- sodium sulfate
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- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000945 filler Substances 0.000 title description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229920002472 Starch Polymers 0.000 claims abstract description 12
- 239000008107 starch Substances 0.000 claims abstract description 12
- 235000019698 starch Nutrition 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 11
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 27
- 239000012756 surface treatment agent Substances 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920000945 Amylopectin Polymers 0.000 claims description 3
- 229920000856 Amylose Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 229920006280 packaging film Polymers 0.000 abstract description 4
- 239000012785 packaging film Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 16
- 238000012856 packing Methods 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/12—Amylose; Amylopectin; Degradation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/12—Amylose; Amylopectin; Degradation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high-transparency filling material, which comprises the following raw materials in parts by weight: 100 parts of transparent polyolefin resin, 60-600 parts of sodium sulfate, 0-200 parts of starch and 1-50 parts of surface treating agent. The high-transparency filling material is suitable for transparent or semitransparent packaging films or transparent high-filling master batches of packaging bags, and solves the problems that the currently used filling material is poor in transparency and has a large influence on the transparency of the packaging films.
Description
Technical field
The present invention relates to transparent filler technical field.More specifically, a kind of high transparency stopping composition and its preparation method and application is related to.
Background technology
At present, a lot of household electrical appliance have a large packing film or packing bag to cover whole electric equipment products before dispatching from the factory, and user will throw away these packing films or packing bag after this electrical equipment of purchase.These packing films or packing bag are all generally with transparent pure material blowing, and be disposable, the electrical equipment of producer in order to enable user clearly see the inside clearly, the inorganic powder that cannot add the impact such as talcum powder and the calcium carbonate transparency reduces costs, and causes the very large wasting of resources and environmental pollution.
Transparent filling material is compared with common packing material, and maximum feature is added in PP, PE, little on the impact of its transparency, can be applied in the product scope such as packaging film and packing bag widely.As used in PE film, suitable addition affects the transparency of film hardly, has good surface gloss and balanced mechanical property simultaneously.These are all that the inorganic fill masterbatch such as now common calcium carbonate and talcum powder is incomparable.
Therefore, high transparency stopping composition needing to provide a kind of cost low and its preparation method and application.
Summary of the invention
One object of the present invention is to provide a kind of high transparency stopping composition, this high transparency stopping composition is applicable to the transparent high filling master batch of transparent or semitransparent packaging film or packing bag, solve the packing material transparency used at present poor, the problem large on the impact of the packing film transparency.
Another object of the present invention is the preparation method providing a kind of high transparency stopping composition, and the method preparation technology is simple, is easy to industrialization.
For achieving the above object, the present invention adopts following technical proposals:
A kind of high transparency stopping composition, comprises the raw material of following weight fraction: transparent polyolefin resin 100 parts, sodium sulfate 60-600 part, starch 0-200 part and surface treatment agent 1-50 part.
Preferably, described transparent polyolefin resin is the mixture of one or more in transparent or semitransparent polypropylene or polyvinyl resin.
Preferably, described sodium sulfate is the sodium sulfate powder between 500 orders to 2000 orders.
Preferably, described starch is selected from one or both the mixture in amylose starch or amylopectin.
Preferably, described surface treatment agent is selected from the mixture of one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent or stearic acid.
A kind of preparation method of high transparency stopping composition, the surface treatment agent of 100 parts of transparent polyolefin resins, 60-600 sodium sulfate part, 0-200 part starch and 1-50 part is added in homogenizer simultaneously, high-speed stirring 30 minutes, then uses twin screw extruder extruding pelletization, obtains high transparency stopping composition.
The present invention is prepared into high filling master batch by extruding-out process.
The present invention also provides the application of above-mentioned high transparency stopping composition in transparent or semitransparent film.The addition of described high transparency stopping composition is the 15-50% of transparent or semitransparent film raw material.
Beneficial effect of the present invention is as follows:
(1) transparency is good, and addition 20% transmittance still reaches more than 80%;
(2) little to mechanical property loss, the mechanical property requirements of packing film and packing bag can be reached completely;
(3) add 40% and can reduce product cost 20% or more.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
The surface treatment agent of the PE (7042) of 100 weight parts, the sodium sulfate of 500 weight parts, the starch of 100 weight parts and 10 weight parts is added in homogenizer simultaneously, high-speed stirring 30 minutes, then use twin screw extruder extruding pelletization, obtain the transparent master batch of high filling.
Add in LDPE7042 by the obtained transparent master batch of this high filling by weight 20%, bar of drawing a design carries out Performance Detection, and detected result is as shown in the table.
Embodiment 2
The surface treatment agent of the PE (7042) of 100 weight parts, the sodium sulfate of 600 weight parts, the starch of 5 weight parts and 15 weight parts is added in homogenizer simultaneously, high-speed stirring 20 minutes, then use twin screw extruder extruding pelletization, obtain the transparent master batch of high filling.
Add in LDPE7042 by the obtained transparent master batch of this high filling by weight 40%, bar of drawing a design carries out Performance Detection, and detected result is as shown in the table.
| LDPE7042 | 100％ | 60％ |
| The transparent master batch of high filling | 0 | 40％ |
| Performance index | ? | ? |
| Density (g/cm 3)(GB1033) | <1 | 1.11 |
| Melting index (g/10min) (GB3682) | 1.5 | 0.6 |
| Tensile strength (MPa) (GB/T1040)/modulus | 9.4/31.4 | 8.5/39.5 |
| Flexural strength (MPa) (GB/T9341) | 6.68 | 8.29 |
| Modulus in flexure (MPa) (GB/T9341) | 166 | 238 |
| Izod notched impact strength KJ/m 2(GB1843) | 38 | 35.8 |
| Transmittance (%) (GB/T 2410) | 92 | 78 |
Embodiment 3
500 order sodium sulfate of the transparent PP of 100 weight parts, 60 weight parts, the amylose starch of 200 weight parts and the silane coupling agent of 50 weight parts are added in homogenizer simultaneously, high-speed stirring 50 minutes, then use twin screw extruder extruding pelletization, obtain the transparent master batch of high filling.
Fill transparent master batch and add in film raw material as filler by weight 15% using high for obtained this, acquired results and embodiment 1 close.
Embodiment 4
The translucent PP of 100 weight parts, 60 weight part 2000 object sodium sulfate, the amylopectin of 200 weight parts and the titanate coupling agent of 50 weight parts are added in homogenizer simultaneously, high-speed stirring 60 minutes, then use twin screw extruder extruding pelletization, obtain the transparent master batch of high filling.
Fill transparent master batch and add in film raw material as filler by weight 50% using high for obtained this, acquired results and embodiment 2 close.
Embodiment 5
With embodiment 1, its difference is only: described surface treatment agent is respectively aluminate coupling agent or stearic acid.
Comparative example 1
| LDPE7042 | 100％ | 80％ | 80％ |
| The transparent master batch of high filling | 0 | 20％ | ? |
| 85% talcum powder master batch | ? | ? | 20％ |
| Performance index | ? | ? | ? |
| Density (g/cm 3)(GB1033) | <1 | 1.02 | 1.05 |
| Melting index (g/10min) (GB3682) | 1.5 | 0.9 | 1.1 |
| Tensile strength (MPa) (GB/T1040)/modulus | 9.4/31.4 | 8.9/32.1 | 8.2/32.5 |
| Flexural strength (MPa) (GB/T9341) | 6.68 | 7.32 | 7.22 |
| Modulus in flexure (MPa) (GB/T9341) | 166 | 175 | 185 |
| Izod notched impact strength KJ/m 2(GB1843) | 38 | 32.3 | 26.3 |
| Transmittance (%) (GB/T 2410) | 92 | 85 | 65 |
Found by contrast, the height prepared by the present invention is filled after transparent master batch adds LDPE material to, impact property and light transmission be all better than identical weight talcum powder master batch add LDPE material to after performance.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (8)
1. a high transparency stopping composition, is characterized in that, comprises the raw material of following weight fraction: transparent polyolefin resin 100 parts, sodium sulfate 60-600 part, starch 0-200 part and surface treatment agent 1-50 part.
2. high transparency stopping composition according to claim 1, is characterized in that: described transparent polyolefin resin is the mixture of one or more in transparent or semitransparent polypropylene or polyvinyl resin.
3. high transparency stopping composition according to claim 1, is characterized in that: described sodium sulfate is the sodium sulfate powder between 500 orders to 2000 orders.
4. high transparency stopping composition according to claim 1, is characterized in that: described starch is selected from one or both the mixture in amylose starch or amylopectin.
5. high transparency stopping composition according to claim 1, is characterized in that: described surface treatment agent is selected from the mixture of one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent or stearic acid.
6. the preparation method of the high transparency stopping composition as described in any one of claim 1-5, is characterized in that, comprises following preparation process:
Added in homogenizer by the surface treatment agent of 100 parts of transparent polyolefin resins, 60-600 sodium sulfate part, 0-200 part starch and 1-50 part, high-speed stirring 10-60 minute, then uses twin screw extruder extruding pelletization, obtains high transparency stopping composition simultaneously.
7. the application of high transparency stopping composition in transparent or semitransparent film as described in any one of claim 1-5.
8. the application of high transparency stopping composition according to claim 7 in transparent or semitransparent film, is characterized in that, the addition of described high transparency stopping composition is the 15-50% of transparent or semitransparent film raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410564554.4A CN104292641A (en) | 2014-10-21 | 2014-10-21 | High-transparency filler and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410564554.4A CN104292641A (en) | 2014-10-21 | 2014-10-21 | High-transparency filler and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN104292641A true CN104292641A (en) | 2015-01-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410564554.4A Pending CN104292641A (en) | 2014-10-21 | 2014-10-21 | High-transparency filler and preparation method and application thereof |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504506A (en) * | 2015-12-30 | 2016-04-20 | 安徽集虹材料科技有限公司 | Filling master batch for transparent polypropylene and preparation method thereof |
| CN108102189A (en) * | 2017-12-15 | 2018-06-01 | 广东昱升个人护理用品股份有限公司 | A kind of polyolefin micropore ventilated membrane of the high grade of transparency and its preparation method and application |
| CN109306573A (en) * | 2018-12-05 | 2019-02-05 | 河北三超塑料制品有限公司 | Fresh peanut private bag and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293967A (en) * | 2008-06-12 | 2008-10-29 | 王梓刚 | Method for preparing anhydrous sodium sulfate plastic modified master batch |
| CN102329446A (en) * | 2011-07-23 | 2012-01-25 | 佛山市衡龙科技有限公司 | Transparent starch-based degradable agricultural mulching film composite material |
| CN102329445A (en) * | 2011-07-28 | 2012-01-25 | 吴仁康 | High performance inorganic filling masterbatch for polyethylene plastic films |
-
2014
- 2014-10-21 CN CN201410564554.4A patent/CN104292641A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293967A (en) * | 2008-06-12 | 2008-10-29 | 王梓刚 | Method for preparing anhydrous sodium sulfate plastic modified master batch |
| CN102329446A (en) * | 2011-07-23 | 2012-01-25 | 佛山市衡龙科技有限公司 | Transparent starch-based degradable agricultural mulching film composite material |
| CN102329445A (en) * | 2011-07-28 | 2012-01-25 | 吴仁康 | High performance inorganic filling masterbatch for polyethylene plastic films |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504506A (en) * | 2015-12-30 | 2016-04-20 | 安徽集虹材料科技有限公司 | Filling master batch for transparent polypropylene and preparation method thereof |
| CN108102189A (en) * | 2017-12-15 | 2018-06-01 | 广东昱升个人护理用品股份有限公司 | A kind of polyolefin micropore ventilated membrane of the high grade of transparency and its preparation method and application |
| CN108102189B (en) * | 2017-12-15 | 2021-03-26 | 广东昱升个人护理用品股份有限公司 | High-transparency polyolefin microporous breathable film and preparation method and application thereof |
| CN109306573A (en) * | 2018-12-05 | 2019-02-05 | 河北三超塑料制品有限公司 | Fresh peanut private bag and preparation method thereof |
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