Pipe blank of plastic hose for cosmetic bottle, preparation method and plastic hose
阅读说明：本技术 一种化妆品瓶用塑料软管的管坯、制备方法以及塑料软管 (Pipe blank of plastic hose for cosmetic bottle, preparation method and plastic hose ) 是由 杨悦 付克友 王海龙 程文孝 于 2021-07-24 设计创作，主要内容包括：本申请涉及化妆品包装的技术领域,具体公开了一种化妆品瓶用塑料软管的管坯、制备方法以及塑料软管。一种化妆品瓶用塑料软管的管坯,包括如下重量份的组分：聚乙烯40～60份、乙烯辛烯共聚物20～40份、聚二甲基硅氧烷PEG-8聚丙烯酸酯20～40份、增塑剂5～10份和抗氧化剂3～5份；乙烯辛烯共聚物与聚二甲基硅氧烷PEG-8聚丙烯酸酯的加入提高了塑料软管的柔韧性。一种化妆品瓶用塑料软管的管坯的制备方法为：(1)烘料；(2)搅拌；(3)挤塑。一种化妆品瓶用塑料软管,包括注头和管坯,所述注头包括如下的组分：20～30重量份的PE 8008、5～15重量份的PE 2045和1～10重量份的PE 218,所述管身由管坯冷却制得；利用PE 8008、PE 2045和PE 218制得的注头,进一步提高了制得塑料软管的柔韧性。(The application relates to the technical field of cosmetic packaging, and particularly discloses a pipe blank of a plastic hose for a cosmetic bottle, a preparation method and the plastic hose. A tube blank of a plastic hose for a cosmetic bottle comprises the following components in parts by weight: 40-60 parts of polyethylene, 20-40 parts of ethylene octene copolymer, 20-40 parts of polydimethylsiloxane PEG-8 polyacrylate, 5-10 parts of plasticizer and 3-5 parts of antioxidant; the flexibility of the plastic hose is improved by adding the ethylene octene copolymer and the polydimethylsiloxane PEG-8 polyacrylate. A preparation method of a tube blank of a plastic hose for a cosmetic bottle comprises the following steps: (1) drying the materials; (2) stirring; (3) and (3) extrusion molding. The plastic hose for the cosmetic bottle comprises an injection head and a tube blank, wherein the injection head comprises the following components: 20-30 parts by weight of PE 8008, 5-15 parts by weight of PE 2045 and 1-10 parts by weight of PE 218, wherein the pipe body is prepared by cooling a pipe blank; the flexibility of the plastic hose is further improved by the injection heads made of PE 8008, PE 2045 and PE 218.)
1. The pipe blank of the plastic hose for the cosmetic bottle is characterized by comprising the following components in parts by weight: 40-60 parts of polyethylene, 20-40 parts of ethylene octene copolymer, 20-40 parts of polydimethylsiloxane PEG-8 polyacrylate, 5-10 parts of plasticizer and 3-5 parts of antioxidant.
2. A tube blank of a plastic hose for cosmetic bottle according to claim 1, wherein: the plasticizer comprises a mixture of one or more of epoxy butyl oleate, dioctyl phthalate and glyceryl triacetate and nano calcium carbonate.
3. A tube blank of a plastic hose for cosmetic bottle according to claim 2, wherein: the plasticizer comprises a mixture of dioctyl phthalate and nano calcium carbonate in a weight ratio of 1: 1.
4. A tube blank of a plastic hose for cosmetic bottle according to claim 1, wherein: the antioxidant comprises one or more of hydroquinone, dioctadecyl thiodipropionate and diethyl phosphite.
5. A tube blank of a plastic hose for cosmetic bottle according to claim 4, wherein: the antioxidant comprises a mixture of hydroquinone and dioctadecyl thiodipropionate in a weight ratio of 1: 1.
6. A method for preparing a tube blank of a plastic hose for cosmetic bottles as claimed in any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) drying materials: placing polyethylene in a dryer to dry the surface moisture;
(2) stirring: stirring the dried polyethylene, ethylene octene copolymer, polydimethylsiloxane PEG-8 polyacrylate, plasticizer and antioxidant to obtain a mixed raw material;
(3) extrusion molding: and extruding the mixed raw materials at the temperature of 120-130 ℃ to obtain the tube blank.
7. The method for preparing the tube blank of the plastic hose for the cosmetic bottle according to claim 6, wherein the method comprises the following steps: the step (3) is as follows: and (3) mixing the mixed raw materials with EVOH resin with half of the weight of polyethylene, and performing multi-coextrusion tube drawing process to obtain the tube blank.
8. The method for preparing the tube blank of the plastic hose for the cosmetic bottle according to claim 6, wherein the method comprises the following steps: the step (3) is as follows: and (3) mixing the raw materials with EVOH resin and COC resin which are half of polyethylene in parts by weight, and performing multi-coextrusion tube drawing to obtain a tube blank.
9. A plastic hose for cosmetic bottle, which is characterized in that: a tube blank comprising a nozzle and a tube blank according to any one of claims 1 to 8, the nozzle comprising the following components: 20-30 parts of PE 8008, 5-15 parts of PE 2045 and 1-10 parts of PE 218, wherein the pipe body is prepared by cooling a pipe blank.
Technical Field
The application relates to the technical field of cosmetic packaging, in particular to a pipe blank of a plastic hose for a cosmetic bottle, a preparation method and the plastic hose.
Background
At present, the cosmetic packaging usually adopts polyethylene, polypropylene, polyethylene terephthalate and polyvinyl chloride materials, and when the cosmetic packaging bottle needs soft materials, the polyethylene is used more. Polyethylene is classified into high density polyethylene, low density polyethylene and linear low density polyethylene according to the molecular chain structure, and low density polyethylene is most commonly used.
The plastic hose for the cosmetic packaging bottle made of the low density polyethylene facilitates the processing and molding of the plastic hose, but when the cosmetic packaging bottle is used at a low temperature, the cosmetic packaging bottle made of the low density polyethylene is not flexible enough to squeeze the cosmetic from the bottle.
Disclosure of Invention
In order to improve the flexibility of the plastic hose for cosmetic packaging bottles, the application provides a pipe blank of the plastic hose for cosmetic bottles, a preparation method and the plastic hose.
In a first aspect, the application provides a tube blank of a plastic hose for a cosmetic bottle, which adopts the following technical scheme:
a tube blank of a plastic hose for a cosmetic bottle comprises the following components in parts by weight: 40-60 parts of polyethylene, 20-40 parts of ethylene octene copolymer, 20-40 parts of polydimethylsiloxane PEG-8 polyacrylate, 5-10 parts of plasticizer and 3-5 parts of antioxidant.
By adopting the technical scheme, the octene in the ethylene octene copolymer can destroy part of polyethylene crystals, and the octene and the polyethylene chain segments damaged by the crystallization form flexible chain segments together, so that the flexibility of the plastic hose is improved; but the viscosity in the melting system is larger, and the acrylate group in the polydimethylsiloxane PEG-8 polyacrylate improves the motion capability of the ethylene-octene copolymer molecules in the system, so that the ethylene-octene copolymer is fully dispersed in the system and fully reacts with polyethylene.
Preferably, the plasticizer comprises a mixture of one or more of epoxy butyl oleate, dioctyl phthalate and glyceryl triacetate and nano calcium carbonate.
By adopting the technical scheme, under the interaction of epoxy butyl oleate, dioctyl phthalate, glyceryl triacetate and nano calcium carbonate, the secondary valence bonds among polyethylene molecules can be weakened, and the crystallinity of the polyethylene molecule chains is reduced, so that the flexibility of the plastic hose is improved.
Preferably, the plasticizer comprises a mixture of dioctyl phthalate and nano calcium carbonate in a weight ratio of 1: 1.
By adopting the technical scheme, the dioctyl phthalate molecules can weaken the acting force among polyethylene molecular chains, and the improvement of the flexibility of the plastic hose is facilitated, but the dioctyl phthalate is easy to migrate in the polyethylene material, and the nano calcium carbonate reduces the mobility of the dioctyl phthalate in the polyethylene material, so that the dioctyl phthalate and the polyethylene are fully reacted.
Preferably, the antioxidant comprises one or more of hydroquinone, dioctadecyl thiodipropionate and diethyl phosphite.
By adopting the technical scheme, the carbon atoms at the end group of the polyethylene are easy to generate free radicals under the action of oxygen and light, the generated free radicals are combined with each other to generate macromolecular peroxide, and the hydrogen in the hydroquinone, the diethyl phosphite ester and the dioctadecyl thiodipropionate and the peroxide generate hydroperoxide, so that the oxidation rate of the plastic hose is reduced, and the oxidation resistance of the plastic hose is improved.
Preferably, the antioxidant comprises a mixture of hydroquinone and dioctadecyl thiodipropionate in a weight ratio of 1: 1.
By adopting the technical scheme, hydroquinone provides hydrogen protons, and the hydrogen protons are combined with free radicals in polyethylene to obtain hydroperoxide, the hydroperoxide is unstable and can be decomposed continuously, and sulfur atoms in the dioctadecyl thiodipropionate decompose the hydroperoxide into alcohol, so that the free radical reaction is terminated, and the oxidation resistance of the plastic hose is further improved.
In a second aspect, the application provides a method for preparing a tube blank of a plastic hose for a cosmetic bottle, which adopts the following technical scheme:
a preparation method of a tube blank of a plastic hose for a cosmetic bottle comprises the following steps:
(1) drying materials: placing polyethylene in a dryer to dry the surface moisture;
(2) stirring: stirring the dried polyethylene, ethylene octene copolymer, polydimethylsiloxane PEG-8 polyacrylate, plasticizer and antioxidant to obtain a mixed raw material;
(3) extrusion molding: and extruding the mixed raw materials at the temperature of 120-130 ℃ to obtain the tube blank.
By adopting the technical scheme, the material is dried to remove the moisture on the surface of the polyethylene, so that the occurrence of material splash and air marks on the manufactured plastic hose is avoided; then stirring and extruding to prepare the plastic hose with high flexibility; when the temperature is too low, the polyethylene cannot be fully plasticized, and when the temperature is too high, the polyethylene is degraded, so that the manufactured plastic hose turns yellow or black spots appear.
Preferably, the step (3) is: and (3) mixing the mixed raw materials with EVOH resin with half of the weight of polyethylene, and performing multi-coextrusion tube drawing process to obtain the tube blank.
By adopting the technical scheme, the multi-coextrusion tube drawing process is utilized, and the EVOH resin is added, so that the EVOH has extremely high oxygen barrier property, and the oxidation resistance of the plastic hose is further improved.
Preferably, the step (3) is: and (3) mixing the raw materials with EVOH resin and COC resin which are half of polyethylene in parts by weight, and performing multi-coextrusion tube drawing to obtain a tube blank.
By adopting the technical scheme, the EVOH has poor water resistance and is easy to absorb moisture, so that the oxygen resistance effect of the EVOH is reduced, the COC has high water resistance and oxygen resistance, the defect of the EVOH in water resistance is overcome, and the oxidation resistance of the plastic hose can be further improved.
In a third aspect, the application provides a plastic hose for cosmetic bottles, which comprises an injection head and a tube blank, wherein the injection head comprises the following components: 20-30 parts of PE 8008, 5-15 parts of PE 2045 and 1-10 parts of PE 218, wherein the pipe body is prepared by cooling a pipe blank.
By adopting the technical scheme, the flexibility of the plastic hose is further improved by using the injection heads made of PE 8008, PE 2045 and PE 218.
In summary, the present application has the following beneficial effects:
1. in the application, ethylene octene copolymer and polydimethylsiloxane PEG-8 are added into polyethylene
The flexibility of the plastic hose is improved by the polyacrylate.
2. The dioctyl phthalate and the nano calcium carbonate are used in a matched mode, and the flexibility of the plastic hose is further improved.
3. According to the method, the water on the surface of the polyethylene is dried, and then the plastic hose with high flexibility is prepared through stirring and extrusion molding.
4. The injection heads made of PE 8008, PE 2045 and PE 218 improve the flexibility of the plastic hose.
Detailed Description
The present application will be described in further detail with reference to examples.
All the starting materials in the examples are commercially available. Wherein the polyethylene adopts LD150, and is purchased from Ming Yuan plastics Co., Ltd; ethylene octene copolymer CAS no: 26221-73-8; dimethicone PEG-8 polyacrylate CAS No.: 217958-64-0; dioctyl phthalate CAS No.: 117-81-7; nano calcium carbonate CAS No.: 471-34-1; hydroquinone CAS number: 123-31-9; dioctadecyl thiodipropionate CAS number: 693-36-7; the EVOH resin has the model number of SP451B, and is purchased from Jinshixiang plastic raw materials Co., Ltd, Dongguan city; COC resin model EP-7000, available from Haoyang New Material science and technology (Dongguan) Co., Ltd; PE 8008 is available from Beijing Wan plasticator products, Inc.; PE 2045 was obtained from Huilong Plastic materials, Inc., of Dongguan; PE 218 was obtained from the department of Chang Ping Dimin plastics raw materials, Dong guan.
Examples
Examples 1 to 7
As shown in Table 1, examples 1 to 7 are different in the ratio of raw materials.
Example 1
A plastic hose for cosmetic bottles is formed by the following steps:
(1) placing 40kg of polyethylene in a dryer, and drying for 2h at the temperature of 75 ℃;
(2) stirring: stirring 40kg of dried polyethylene, 20kg of ethylene octene copolymer, 20kg of polydimethylsiloxane PEG-8 polyacrylate, 2.5kg of dioctyl phthalate, 2.5kg of nano calcium carbonate, 1.5kg of hydroquinone and 1.5kg of dioctadecyl thiodipropionate by using a stirrer to obtain a mixed raw material;
(3) extrusion molding: feeding the mixed raw materials into an extruder, wherein the melting temperature in the extruder is 125 ℃, and collecting melt resin in the extruder to a die head to obtain a pipe blank;
(4) shaping: cooling the tube blank to obtain a tube body; adding 25kg of PE 8008, 8kg of PE 2045 and 5kg of PE 218 into the injection head machine, and injecting the head into the pipe body; and finally, sealing the tail of the tube body through a tail sealing machine to obtain the plastic hose for the cosmetic bottle.
TABLE 1
Polyethylene
（kg）
Ethylene octene co-olefin
Polymer (kg)
Polydimethylsiloxane PEG-8
Polyacrylate (kg)
Phthalic acid
Dioctyl ester (kg)
Nano carbonic acid
Calcium (kg)
Para benzene bis
Phenol (kg)
Didecyl thiodipropionate
Eight esters (kg)
Example 1
40
20
20
2.5
2.5
1.5
1.5
Example 2
40
20
30
2.5
2.5
1.5
1.5
Example 3
40
20
40
2.5
2.5
1.5
1.5
Example 4
40
30
30
2.5
2.5
1.5
1.5
Example 5
40
40
30
2.5
2.5
1.5
1.5
Example 6
50
30
30
2.5
2.5
1.5
1.5
Example 7
60
30
30
2.5
2.5
1.5
1.5
Example 8
50
30
30
4
4
1.5
1.5
Example 9
50
30
30
5
5
1.5
1.5
Example 10
50
30
30
8
0
1.5
1.5
Example 11
50
30
30
4
4
2
2
Example 12
50
30
30
4
4
2.5
2.5
Example 13
50
30
30
4
4
4
0
Examples 8 to 10
Examples 8 to 10 differ from example 6 in the plasticizer ratio.
Examples 11 to 13
Examples 11 to 13 are different from example 8 in the compounding ratio of the antioxidant.
Example 14
A plastic hose for cosmetic bottles is formed by the following steps:
(1) 50kg of polyethylene is placed in a dryer and dried for 2 hours at the temperature of 75 ℃;
(2) stirring: stirring 50kg of dried polyethylene, 30kg of ethylene-octene copolymer, 30kg of polydimethylsiloxane PEG-8 polyacrylate, 4kg of dioctyl phthalate, 4kg of nano calcium carbonate, 2kg of hydroquinone and 2kg of dioctadecyl thiodipropionate by a stirrer to obtain a mixed raw material;
(3) extrusion molding: feeding the mixed raw materials into a first extruder, feeding 25kg of EVOH resin into a second extruder, wherein the melting temperature in the two extruders is 125 ℃ and 175 ℃ in sequence, and collecting the melt resin in the two extruders to a double-layer composite die head to obtain a tube blank;
(4) shaping: cooling the tube blank to obtain a tube body; adding 25kg of PE 8008, 8kg of PE 2045 and 5kg of PE 218 into the injection head machine, and injecting the head into the pipe body; and finally, sealing the tail of the tube body through a tail sealing machine to obtain the plastic hose for the cosmetic bottle.
Example 15
A plastic hose for cosmetic bottles is formed by the following steps:
(1) 50kg of polyethylene is placed in a dryer and dried for 2 hours at the temperature of 75 ℃;
(2) stirring: stirring 50kg of dried polyethylene, 30kg of ethylene-octene copolymer, 30kg of polydimethylsiloxane PEG-8 polyacrylate, 4kg of dioctyl phthalate, 4kg of nano calcium carbonate, 2kg of hydroquinone and 2kg of dioctadecyl thiodipropionate by a stirrer to obtain a mixed raw material;
(3) extrusion molding: feeding the mixed raw materials into a first extruder, feeding 25kg of EVOH resin into a second extruder, feeding 25kg of COC resin into a third extruder, wherein the melting temperatures in the three extruders are 125 ℃, 175 ℃ and 180 ℃ in sequence, and the melt resins in the three extruders are converged into a three-layer composite die head to obtain a tube blank;
(4) shaping: cooling the tube blank to obtain a tube body; adding 25kg of PE 8008, 8kg of PE 2045 and 5kg of PE 218 into the injection head machine, and injecting the head into the pipe body; and finally, sealing the tail of the tube body through a tail sealing machine to obtain the plastic hose for the cosmetic bottle.
Example 16
Example 16 differs from example 1 in that: (3) extrusion molding: and (3) feeding the mixed raw materials into an extruder, wherein the melting temperature in the extruder is 120 ℃, and the melt resin in the extruder is converged into a die head to obtain a pipe blank.
Example 17
Example 17 differs from example 1 in that: (3) extrusion molding: and (3) feeding the mixed raw materials into an extruder, wherein the melting temperature in the extruder is 130 ℃, and the melt resin in the extruder is converged into a die head to obtain a pipe blank.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that the starting material was composed of the following components: 80kg of polyethylene, 2.5kg of dioctyl phthalate, 2.5kg of nano calcium carbonate, 2.5kg of hydroquinone and 2.5kg of dioctadecyl thiodipropionate.
Comparative example 2
Comparative example 2 differs from example 1 in that the starting material was composed of the following components: 40kg of polyethylene, 40kg of ethylene-octene copolymer, 2.5kg of dioctyl phthalate, 2.5kg of nano calcium carbonate, 2.5kg of hydroquinone and 2.5kg of dioctadecyl thiodipropionate.
Comparative example 3
Comparative example 3 differs from example 1 in that the starting material was composed of the following components: 40kg of polyethylene, 40kg of polydimethylsiloxane PEG-8 polyacrylate, 2.5kg of dioctyl phthalate, 2.5kg of nano calcium carbonate, 2.5kg of hydroquinone and 2.5kg of dioctadecyl thiodipropionate.
Comparative example 4
Comparative example 4 differs from example 1 in that: (4) shaping: cooling the tube blank to obtain a tube body; adding 38kg of PE 8008 into the injection head machine, and injecting the head to the pipe body; and finally, sealing the tail of the tube body through a tail sealing machine to obtain the plastic hose for the cosmetic bottle.
Performance test
And (3) flexibility detection: the hardness of the plastic hose is measured by a type A durometer, the smaller the hardness of the plastic hose is, the higher the flexibility is, and the standard GB/2411-80 Shore hardness test method for plastics is applicable.
Table 2 hardness test results
Sample (I)
Hardness (HD)
Example 1
56
Example 2
55
Example 3
57
Example 4
53
Example 5
54
Example 6
50
Example 7
52
Example 8
46
Example 9
44
Example 10
48
Example 16
44
Example 17
40
Comparative example 1
64
Comparative example 2
63
Comparative example 3
61
Comparative example 4
59
By combining the embodiment 1 and the comparative examples 1 to 3, the hardness of the embodiment 1 is less than that of the comparative examples 1 to 3, so that the flexibility of the plastic hose in the embodiment 1 is better than that of the comparative examples 1 to 3, and it can be seen that the acrylate group in the polydimethylsiloxane PEG-8 polyacrylate improves the motion capability of the ethylene octene copolymer molecule in the system, so that the ethylene octene copolymer is fully dispersed in the system, octene in the ethylene octene copolymer destroys part of polyethylene crystals, octene and polyethylene chain segments destroyed by the ethylene octene and the crystals form a flexible chain segment together, thereby improving the flexibility of the plastic hose.
Combining example 1 and comparative example 4, the hardness in example 1 was less than that in comparative example 4, and thus the flexibility of the plastic hose in example 1 was superior to that in comparative example 4, it can be seen that the injection heads made of PE 8008, PE 2045, and PE 218 further improved the flexibility of the plastic hose made.
With reference to examples 1 to 7, the hardness in example 6 is the lowest, and thus the flexibility of the plastic hose in example 6 is the best, and it can be seen that the mixture ratio of the three raw materials, namely polyethylene, the ethylene octene copolymer and the polydimethylsiloxane PEG-8 polyacrylate, is the best in example 6.
By combining the embodiment 6 and the embodiments 8 to 9, the hardness of the embodiments 8 to 9 is less than that of the embodiment 6, so that the flexibility of the plastic hose in the embodiments 8 to 9 is better than that of the embodiment 6, and it can be seen that the using amount of the plasticizer is added into the raw materials, the secondary bond among polyethylene molecules is weakened by the plasticizer, the crystallinity of the polyethylene molecule chains is reduced, and the flexibility of the plastic hose is improved.
By combining the example 8 and the example 10, the hardness of the example 8 is less than that of the example 10, so that the flexibility of the plastic hose of the example 8 is better than that of the example 10, and it can be seen that the nano calcium carbonate reduces the mobility of the dioctyl phthalate in the polyethylene material, so that the dioctyl phthalate fully reacts with the polyethylene, and the flexibility of the plastic hose is improved.
Combining example 16 and example 17, the hardness in example 17 was less than that in example 16, so that the flexibility of the plastic hose in example 17 was better than that in example 16, and it was found that increasing the melting temperature resulted in sufficient plasticization of the polyethylene, which increased the flexibility of the plastic hose.
And (3) oxidation resistance detection: the plastic hoses in the examples and comparative examples were exposed and tested in a light lamp at 765W/square meter light intensity, and the time to aging and yellowing of the plastic hoses was recorded.
TABLE 3 aging yellowing time
Sample (I)
Aging yellowing time (h)
Example 8
56
Example 11
66
Example 12
70
Example 13
46
Example 14
76
Example 15
82
By combining the embodiment 8 and the embodiments 11 to 12, the aging and yellowing time of the embodiments 11 to 12 is longer than that of the embodiment 8, so that the oxidation resistance of the plastic hoses in the embodiments 11 to 12 is better than that of the embodiment 8, and it can be seen that the use amount of the antioxidant is increased in the raw materials, and the oxidation resistance of the plastic hoses can be improved.
Combining example 11 with example 13, the aging yellowing time of example 11 is longer than that of example 13, so that the oxidation resistance of the plastic hose of example 11 is better than that of example 13, it can be seen that hydroquinone provides hydrogen protons, which combines with the free radicals in polyethylene to obtain hydroperoxide, which is unstable and continues to decompose, and the sulfur atom in the dioctadecyl thiodipropionate decomposes the hydroperoxide into alcohol, so that the free radical reaction is terminated, and the oxidation resistance of the plastic hose is further improved.
Combining example 11 and example 14, the aging yellowing time of example 14 is longer than that of example 11, so that the oxidation resistance of the plastic hose of example 14 is better than that of example 11, and it can be seen that, by adding the EVOH resin, EVOH has extremely high oxygen barrier property, and the oxidation resistance of the plastic hose is further improved.
By combining the embodiment 14 and the embodiment 15, the aging and yellowing time of the embodiment 15 is longer than that of the embodiment 14, so that the oxidation resistance of the plastic hose in the embodiment 15 is better than that of the embodiment 14, it can be seen that the water blocking performance of EVOH is poor, moisture is easy to absorb, and the oxygen blocking effect of EVOH is reduced, COC has higher water and oxygen blocking performance, the deficiency of the water blocking performance of EVOH is made up, and the oxidation resistance of the plastic hose is further improved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
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