CN116285274A - Double-layer packaging hose for paste cosmetics and preparation method thereof - Google Patents

Double-layer packaging hose for paste cosmetics and preparation method thereof Download PDF

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Publication number
CN116285274A
CN116285274A CN202310421999.6A CN202310421999A CN116285274A CN 116285274 A CN116285274 A CN 116285274A CN 202310421999 A CN202310421999 A CN 202310421999A CN 116285274 A CN116285274 A CN 116285274A
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double
packaging
package
layer
paste cosmetics
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CN116285274B (en
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黄泽松
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Guangzhou Amy Plastic Tube Co ltd
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Guangzhou Amy Plastic Tube Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02Body construction
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)

Abstract

The invention discloses a double-layer packaging hose for paste cosmetics, and belongs to the technical field of degradable high polymer materials. Comprises an outer layer package and an inner layer package; the outer packaging comprises: PLA, poly (trimethylene carbonate), cinnamon essential oil, D-lactic acid, epoxidized soybean oil, triphenyl phosphate ADR-4300; the inner package comprises: PBAT, PHBV, papyrus fiber, calcium carbonate, polyhexamethylene guanidine hydrochloride, organoclay, PBO, ADR-4300. The double-layer material prepared by the invention is biodegradable and environment-friendly; meanwhile, the antibacterial agent has good mechanical property, antibacterial property and chemical stability.

Description

Double-layer packaging hose for paste cosmetics and preparation method thereof
Technical Field
The invention belongs to the technical field of degradable high polymer materials, and particularly relates to a double-layer packaging hose for paste cosmetics.
Background
The plastic is a petroleum product with extremely wide application range, and has the advantages of strong corrosion resistance, durability, water resistance, light weight, low cost, easy plasticity and the like; is widely applied to various fields. In the cosmetic field, the plastic package is used for more than 95% except for a small part of the glass container.
Cosmetic packaging materials are divided into a packaging hose, a hard packaging box and a packaging film. The packaging hose is a material directly used for containing cosmetics, plays roles of blocking and guaranteeing quality, and directly influences the storage and quality of the cosmetics
At present, the cosmetic packaging material generally adopts PVC (polyethylene) as a main body; however, polyethylene has poor barrier properties; the biological degradation is impossible, the secondary use (abuse) is possibly caused, and certain potential safety hazards exist; incineration is generally adopted, so that on one hand, resources are wasted, and on the other hand, the environment is seriously polluted; is unfavorable for the green development of cosmetic packaging materials.
Polylactic acid (PLA) is the only transparent biodegradable material, and has good hot processing performance and biocompatibility; the PLA has wide application prospect, but has poor toughness due to high strength, so that the development of the PLA is limited to a certain extent; thus, there is a need to provide a degradable plastic package for the particular needs of cosmetic packages.
Disclosure of Invention
The invention provides a double-layer packaging hose for paste cosmetics, which is modified by various parts to meet the requirements of paste cosmetics.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging;
the outer packaging comprises the following components in parts by mass:
Figure BDA0004187201570000011
Figure BDA0004187201570000021
the inner layer package comprises the following components in parts by mass:
Figure BDA0004187201570000022
the inner layer package comprises at least 60% of the total mass.
In particular, the particle size of the calcium carbonate is in the range of 20-100nm.
In particular, the PLA is a l-polylactic acid.
In particular, the organoclay is kaolin or/and montmorillonite.
The invention also provides a preparation method of the double-layer packaging hose for the paste cosmetics, which specifically comprises the following steps:
the preparation method of the outer package comprises the following steps: uniformly mixing the raw materials according to the proportion, and then melting, plasticizing and granulating in a double-screw extruder;
the preparation method of the inner layer package comprises the following steps: the raw materials are uniformly mixed according to the proportion, and then melted, plasticized and granulated in a double-screw extruder.
And (5) blowing the outer package and the inner package into films by adopting a coextrusion machine.
In the invention, the following components are added:
PLA (polylactic acid) refers to polylactic acid;
PLLA (Poly-L-lactic acid) refers to Poly-L-lactic acid;
PBAT (Poly (butylene glycol-co-terephthalate)) refers to a butylene adipate and butylene terephthalate copolymer;
PHBV (Polyhydroxybutyrate-co-valerate) refers to Polyhydroxybutyrate valerate copolyester;
PBO (Poly-p-phenylene benzobisoxazole) refers to Poly-p-phenylene benzobisoxazole fibers;
ADR-4300 refers to the Pasteur (BASF) chain extender ADR-4300.
The outer packaging of the invention mainly needs to have high elasticity, high transparency and high barrier property, and mainly serves to protect the inner packaging from abrasion and external pollution.
Therefore, the outer package of the invention takes highly transparent PLLA as a main body, and simultaneously adopts the poly (trimethylene carbonate) and the cinnamon essential oil as mechanical improvement and antibacterial components, so that the tensile strength and the elongation at break of the outer package can be greatly improved; meanwhile, since cosmetics are generally placed in a relatively humid space such as a bathroom, good antibacterial properties are required.
The D-lactic acid can reduce the ventilation quantity of PLLA and increase the barrier property of PLLA; triphenyl phosphate is used as a heat stabilizer; ADR-4300 is a good chain extender and is a good processing aid; meanwhile, the material also has a certain improvement effect on mechanical properties.
The inner package of the present invention is used as a direct contact content while it is necessary to print commodity information on the outer surface of the inner package, so that the main requirements of the inner package are antibacterial, barrier, printability and chemical stability.
Therefore, the inner package adopts PBAT and PHBV as main degradable materials, and simultaneously adds the paper sedge fiber to increase writability (printing) and antibacterial property, and simultaneously has good toughening and blocking effects. The three blends are used as main materials, and in order to enhance the antibacterial performance, calcium carbonate, polyhexamethylene guanidine hydrochloride and organoclay are added for compound antibacterial.
The Paper sedge fiber of the invention is Paper sedge Paper fiber (Paper) which is native to Egypt, the ignition point of the Paper sedge fiber is lower and is slightly higher than the melting temperature (Tm) of PHBV; however, the invention discovers that under the condition of uniform mixing, the paper sedge fiber still cannot burn under the premise of being higher than the ignition temperature, because the oxygen in the extruder is insufficient, and meanwhile, the air is difficult to contact under the blending mode, and in addition, the components such as calcium carbonate, organoclay and the like have better flame retardant performance under the condition, and the combustion of the components is prevented under the action of various reasons.
Meanwhile, the calcium carbonate is used as a filler, so that the mechanical property can be improved; the polyhexamethylene guanidine hydrochloride and the organoclay can also effectively reduce the air permeability and enhance the barrier property; PBO belongs to a coupling agent in the present invention for improving dispersibility between components.
The double-layer material prepared by the invention is biodegradable and environment-friendly; meanwhile, the antibacterial agent has good mechanical property, antibacterial property and chemical stability.
Detailed Description
For a better understanding of the present invention, reference will now be made to the following description of specific examples, which are included in the terminology used to describe specific embodiments of the invention and are not intended to limit the scope of the invention.
The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1
A double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging;
the outer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000041
the inner layer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000042
the mass ratio of the outer package to the inner package is 4:6;
the preparation method of the outer package comprises the following steps: uniformly mixing the raw materials according to the proportion, and then melting, plasticizing and granulating in a double-screw extruder; the temperature of the extruder from the feeding area to the five sections of the head area is 180 ℃, 190 ℃, 205 ℃, 210 ℃ and 215 ℃ in sequence; the temperature difference in the zone is not more than +/-2 ℃.
The preparation method of the inner layer package comprises the following steps: the raw materials are uniformly mixed according to the proportion, and then melted, plasticized and granulated in a double-screw extruder. The temperature of the extruder from the feeding area to the head area is 175 ℃, 185 ℃, 190 ℃, 200 ℃ and 205 ℃ in sequence; the temperature difference in the zone is not more than +/-2 ℃.
Blowing the outer layer package and the inner layer package into films by adopting a coextrusion machine; the temperature of blow molding from the feeding area to the machine head is 190 ℃, 200 ℃, 210 ℃ and the traction rate is 2.0m/min in sequence; the temperature difference in the zone is not more than +/-2 ℃.
Example 2
A double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging;
the outer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000051
the inner layer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000052
the mass ratio of the outer package to the inner package is 4:6;
the outer wrap, inner wrap and blown film process were the same as in example 1.
Example 3
A double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging; the outer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000061
the inner layer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000062
the mass ratio of the outer package to the inner package is 4:6;
the outer wrap, inner wrap and blown film process were the same as in example 1.
Example 4
A double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging; the outer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000063
Figure BDA0004187201570000071
the inner layer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000072
the mass ratio of the outer package to the inner package is 4:6;
the outer wrap, inner wrap and blown film process were the same as in example 1.
Example 5
A double-layer packaging hose for paste cosmetics comprises an outer layer packaging and an inner layer packaging; the outer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000073
the inner layer package is prepared from the following raw materials in parts by weight:
Figure BDA0004187201570000074
Figure BDA0004187201570000081
the mass ratio of the outer package to the inner package is 4:6;
the outer wrap, inner wrap and blown film process were the same as in example 1.
Performance tests were performed on the previous embodiments, wherein:
tensile strength: according to standard GB/T1040.3-2006.
Elongation at break: according to standard GB/T1040.3-2006.
Relative biodegradation rate: according to standard GB/T19277.1-2011 (180 days).
Water vapor transmission amount: according to standard GB/T2653-2010.
Oxygen transmission rate: according to standard GB/T1038.1-2022.
Antibacterial properties: testing according to ASTM E2149-2010, the test flora being escherichia coli and staphylococcus aureus;
the test results are shown in table 1 below.
TABLE 1 Performance test results
Example 1 Example 2 Example 3 Example 4 Example 5
Tensile Strength(Mpa) 31.5 32.1 32.7 31.9 32.4
Elongation at break (%) 332 308 298 322 286
Relative biodegradation rate (%, 180 days) 82.4 84.6 83.1 82.1 83.4
Water vapor transmission rate (g/(m) 2 ·day) 0.091 0.092 0.091 0.091 0.090
Oxygen transmission (g/(m) 2 ·day) 0.019 0.020 0.019 0.019 0.018
Antibacterial ratio (%, large)Enterobacteria 86.2 85.1 86.4 85.9 84.8
Bacteriostasis rate (%, staphylococcus aureus) 83.1 82.5 82.7 81.2 80.7
As can be seen from table 1, the present invention has higher tensile strength, which represents that this has good strength and toughness; meanwhile, the biodegradation rate, the elongation at break and the antibacterial rate all belong to good levels in 180 days, and the comprehensive performance of the composite material is proved to be good; meanwhile, the invention has very low water vapor transmission rate and oxygen transmission rate, and has excellent sealing effect.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the principles and spirit of the invention, but such changes and modifications fall within the scope of the invention.

Claims (6)

1. The double-layer packaging hose for the paste cosmetics is characterized by comprising an outer layer packaging and an inner layer packaging;
the outer packaging comprises the following components in parts by mass:
Figure FDA0004187201560000011
the inner layer package comprises the following components in parts by mass:
Figure FDA0004187201560000012
the inner layer package comprises at least 60% of the total mass.
2. The dual packaging tube for paste cosmetics according to claim 1, wherein said calcium carbonate has a particle size ranging from 20 to 100nm.
3. The dual packaging tube for paste cosmetics according to claim 1, wherein said PLA is a l-polylactic acid.
4. The double-layer packaging tube for paste cosmetics according to claim 1, wherein said organoclay is kaolin or/and montmorillonite.
5. A method for producing the double-layer packaging tube for a paste cosmetic according to any one of claims 1 to 4, characterized in that the outer packaging and the inner packaging are blown into a film by using a coextrusion machine.
6. The method for manufacturing a double-layered packaging tube for paste cosmetics according to claim 5, wherein the method for manufacturing the outer packaging is as follows: uniformly mixing the raw materials according to the proportion, and then melting, plasticizing and granulating in a double-screw extruder;
the preparation method of the inner layer package comprises the following steps: the raw materials are uniformly mixed according to the proportion, and then melted, plasticized and granulated in a double-screw extruder.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993656A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Biodegradable barrier thin film, as well as preparation method and application thereof
CN104212136A (en) * 2014-07-24 2014-12-17 昆明理工大学 Polylactic acid anti-bacterial-activity packaging material and preparation method thereof
CN110341271A (en) * 2019-07-12 2019-10-18 青岛周氏塑料包装有限公司 A kind of high strength Fully-biodegradable composite membrane and its production technology and application
CN110387112A (en) * 2019-07-23 2019-10-29 湖南工业大学 A kind of degradable food packaging membrane material and preparation process
CN115093721A (en) * 2022-06-07 2022-09-23 甡物科技(深圳)有限公司 Tea fiber/PHBV/PBAT ternary composite material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993656A (en) * 2012-11-23 2013-03-27 金发科技股份有限公司 Biodegradable barrier thin film, as well as preparation method and application thereof
CN104212136A (en) * 2014-07-24 2014-12-17 昆明理工大学 Polylactic acid anti-bacterial-activity packaging material and preparation method thereof
CN110341271A (en) * 2019-07-12 2019-10-18 青岛周氏塑料包装有限公司 A kind of high strength Fully-biodegradable composite membrane and its production technology and application
CN110387112A (en) * 2019-07-23 2019-10-29 湖南工业大学 A kind of degradable food packaging membrane material and preparation process
CN115093721A (en) * 2022-06-07 2022-09-23 甡物科技(深圳)有限公司 Tea fiber/PHBV/PBAT ternary composite material and preparation method and application thereof

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