CN115558189A - Colored plastic ampoule bottle and preparation method thereof - Google Patents

Colored plastic ampoule bottle and preparation method thereof Download PDF

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Publication number
CN115558189A
CN115558189A CN202211468365.8A CN202211468365A CN115558189A CN 115558189 A CN115558189 A CN 115558189A CN 202211468365 A CN202211468365 A CN 202211468365A CN 115558189 A CN115558189 A CN 115558189A
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polyethylene
colored plastic
modified
titanium dioxide
master batch
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CN115558189B (en
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唐仕秀
邓鸿辉
江志伟
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Chengdu Puth Pharmaceutical Co ltd
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Chengdu Puth Pharmaceutical Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D22/00Producing hollow articles
    • B29D22/003Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B3/00Packaging plastic material, semiliquids, liquids or mixed solids and liquids, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
    • B65B3/003Filling medical containers such as ampoules, vials, syringes or the like
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B3/00Packaging plastic material, semiliquids, liquids or mixed solids and liquids, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
    • B65B3/003Filling medical containers such as ampoules, vials, syringes or the like
    • B65B3/006Related operations, e.g. scoring ampoules
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3669Treatment with low-molecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3607Titanium dioxide
    • C09C1/3676Treatment with macro-molecular organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36Compounds of titanium
    • C09C1/3692Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10Treatment with macromolecular organic 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
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/10Applications used for bottles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

The invention discloses a colored plastic ampoule bottle and a preparation method thereof, belonging to the technical field of ampoule bottles, wherein the ampoule bottle comprises the following raw materials in percentage by weight: 96-99% of polyethylene base material and 1-4% of modified color master batch; the preparation method of the modified color master batch comprises the following steps: mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting at 95-105 ℃, adding an organic pigment and methyl methacrylate, and stirring and reacting under the ultraviolet irradiation condition of 60-70 ℃ to obtain a modified material; heating polyethylene to 200-250 ℃ under the condition of stirring, then adding the modified material, stirring and uniformly mixing under the condition of ultraviolet irradiation, continuously adding the lubricant and the ultraviolet absorbent, stirring uniformly, extruding and granulating to obtain the polyethylene. This coloured plastics ampoule need not to set up coloured film externally, has reduced the preparation process, has effectively solved the loaded down with trivial details problem of preparation process that current coloured plastics ampoule exists.

Description

Colored plastic ampoule bottle and preparation method thereof
Technical Field
The invention relates to the technical field of ampoule bottles, in particular to a colored plastic ampoule bottle and a preparation method thereof.
Background
Ampoules are containers for holding substances such as drugs, vaccines, serum or cosmetics, and are typically made of hard glass, but the hard glass tends to produce fine fragments which fall into the medicament during use, which may present a potential hazard in subsequent use. Therefore, a plastic ampoule bottle is developed at present, which can solve the problem of using risk of a hard glass ampoule bottle. The existing plastic ampoule bottles are generally produced by adopting a blow-fill-seal (BFS) technology, and the technology generally adopts polyethylene or polypropylene and other substances as raw materials to produce colorless and transparent plastic ampoule bottles, so that the plastic ampoule bottles are suitable for packaging common conventional medicines or cosmetics, but the polyethylene and polypropylene transparent materials are difficult to block light, so that easily-oxidized liquid medicines and skin care products in the plastic bottles are easy to deteriorate. In order to solve the problem, a colored film is usually bonded outside a transparent plastic ampoule bottle, the purpose of shading light is achieved through the colored film, and the problem that medicines or cosmetics in the ampoule bottle deteriorate due to the illumination effect is solved. The mode of directly adding the pigment into the polyethylene or polypropylene raw material in the preparation process can reduce the operation procedure and improve the production efficiency, but the pigment in the prepared ampoule bottle has the problem of dissolution in the subsequent use process, and the quality of the medicament contained in the ampoule bottle is seriously influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the colored plastic ampoule bottle and the preparation method thereof, the colored plastic ampoule bottle does not need to be externally provided with a colored film, the preparation process is reduced, the problem of complicated preparation process of the existing colored plastic ampoule bottle is effectively solved, the pigment in the ampoule bottle is not easy to dissolve out, and the product quality is not influenced.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is as follows:
a colored plastic ampoule bottle comprises the following raw materials in percentage by weight: 96-99% of polyethylene base material and 1-4% of modified color master batch;
the preparation method of the modified color master batch comprises the following steps:
(1) Mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting for 3-5h at the temperature of 95-105 ℃, then adding an organic pigment and methyl methacrylate, and stirring and reacting for 2-5h under the ultraviolet irradiation condition at the temperature of 60-70 ℃ to obtain a modified material;
(2) Heating polyethylene to 200-250 ℃ under the condition of stirring, then adding the modified material, stirring and uniformly mixing under the condition of ultraviolet irradiation, continuously adding the lubricant and the ultraviolet absorbent, stirring uniformly, extruding and granulating to obtain the polyethylene.
In the scheme, in the mixing reaction process of titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, the cycloalkyl imidazoline quaternary ammonium salt can be used for modifying the titanium dioxide to enable the titanium dioxide to be in a hydrophobic state, then the organic pigment and the methyl methacrylate are added, in the ultraviolet irradiation process, the grafting reaction is carried out among the titanium dioxide, the organic pigment and the methyl methacrylate, the methyl methacrylate is wrapped on the surface of the titanium dioxide, the dispersity of the titanium dioxide is improved, and meanwhile, the organic pigment is grafted on the methyl methacrylate, so that the stability of the organic pigment is improved; the methyl methacrylate grafted on the surface of the titanium dioxide also has active functional groups, and when the methyl methacrylate and the polyethylene are continuously grafted in the subsequent reaction process with the polyethylene, the binding property between the materials is enhanced, and the titanium dioxide and the organic pigment are prevented from falling off in the subsequent use process; meanwhile, because the modified titanium dioxide has the hydrophobic characteristic, the contact between the prepared ampoule bottle and the internal product liquid is limited, and the dissolution of the organic pigment and the titanium dioxide in the ampoule bottle can be further reduced.
Further, the feed comprises the following raw materials in percentage by weight: 96% of polyethylene base material and 4% of modified color master batch.
Further, the mass ratio of the polyethylene, the titanium dioxide, the organic pigment, the lubricant and the ultraviolet absorber in the modified color master batch is 40-50.
Further, the mass ratio of polyethylene, titanium dioxide, organic pigment, lubricant and ultraviolet absorber in the modified color master batch is 50.
Further, the lubricant is polyethylene wax.
Further, the ultraviolet absorbent is benzotriazole, phenyl o-hydroxybenzoate or 2-hydroxy-4-n-octoxybenzophenone.
Further, the organic pigment includes 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide or 4- [2- (2, 5-dichlorophenyl) azo ] -N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-hydroxy-2-naphthamide.
Further, in the process of preparing the modified color master batch, the mass ratio of the titanium dioxide to the cycloalkyl imidazoline quaternary ammonium salt in the cycloalkyl imidazoline quaternary ammonium salt water solution is 10-7.
Further, in the process of preparing the modified color master batch, the mass ratio of titanium dioxide to methyl methacrylate is 10.
Further, the method comprises the following steps: uniformly mixing polyethylene and modified color master batch, putting the mixture into an extruder, preheating the mixture at 165-175 ℃, heating the mixture to 170-180 ℃ for extrusion to form a pipe blank with uniform color, putting the pipe blank into a blowing, filling and sealing all-in-one machine to form a container, injecting a medicament into the container through the blowing, filling and sealing all-in-one machine, and sealing the container to form an ampoule bottle for containing the medicament.
The beneficial effects produced by the invention are as follows:
1. according to the invention, the titanium dioxide is modified in the preparation process of the modified color master batch, so that the hydrophobicity of the titanium dioxide is increased, the contact between the medicament in the ampoule bottle and the bottle body is reduced, the dissolution of the titanium dioxide in the ampoule bottle is avoided, and the use safety is improved. Meanwhile, the modified titanium dioxide and the organic pigment are subjected to grafting reaction with methyl methacrylate by ultraviolet irradiation treatment, the titanium dioxide and the organic pigment are limited and fixed by the methyl methacrylate, and then the active sites on the methyl methacrylate are reacted with polyethylene, so that the connection integration of all the raw materials is realized, the organic pigment is prevented from being dissolved out in use, and the use safety of the ampoule bottle is further improved.
2. The ampoule bottle is manufactured by adopting a blowing, filling and sealing integrated machine, the preparation method is simple and convenient to operate, the operation procedures of film covering are reduced, and the production efficiency is improved; simultaneously, pigment and ultraviolet absorbent are directly added into the ampoule bottle, so that ultraviolet rays can be effectively absorbed, shading is realized, and the influence on the quality of the medicament caused by the influence of illumination on the internal medicament is avoided.
Detailed Description
Example 1
A colored plastic ampoule bottle comprises the following raw materials in percentage by weight: 96% of polyethylene base stock and 4% of modified color master batch;
the modified color master batch comprises the following components in parts by weight: 500 g of polyethylene, 100 g of titanium dioxide, 150 g of 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide, 80 g of polyethylene wax and 3 g of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
The modified color master batch is prepared by the following method:
(1) Mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting for 4 hours at the temperature of 100 ℃, adding 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide and methyl methacrylate, and continuously reacting for 4 hours at the temperature of 65 ℃ under the ultraviolet irradiation condition of 40W to obtain a modified material; wherein the mass ratio of the titanium dioxide to the cycloalkyl imidazoline quaternary ammonium salt in the cycloalkyl imidazoline quaternary ammonium salt water solution is 10; the mass ratio of the titanium dioxide to the methyl methacrylate is 10;
(2) Heating polyethylene to 210 ℃ under the condition of stirring, adding the modified material, uniformly stirring under the condition of 40W ultraviolet irradiation, then continuously adding polyethylene wax and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, uniformly stirring, extruding and granulating to obtain the polyethylene modified material.
The preparation method of the colored plastic ampoule bottle comprises the following steps: uniformly mixing polyethylene and modified color master batch, putting the mixture into an extruder, preheating the mixture at 170 ℃, heating the mixture to 180 ℃ for extrusion to form a pipe blank with uniform color, putting the pipe blank into a blowing, filling and sealing all-in-one machine to form a container, injecting a medicament into the container through the blowing, filling and sealing all-in-one machine, and sealing the container to form an ampoule bottle for containing the medicament.
Example 2
A colored plastic ampoule bottle comprises the following raw materials in percentage by weight: 97% of polyethylene base stock and 3% of modified color master batch;
the modified color master batch comprises the following components in parts by weight: 450 g of polyethylene, 70 g of titanium dioxide, 100 g of 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide, 60g of polyethylene wax and 4 g of phenyl o-hydroxybenzoate.
The modified color master batch is prepared by the following method:
(1) Mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting for 3 hours at the temperature of 96 ℃, then adding 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide and methyl methacrylate, and continuously reacting for 5 hours at the temperature of 62 ℃ under the ultraviolet irradiation condition of 40W to obtain a modified material; wherein the mass ratio of the titanium dioxide to the cycloalkyl imidazoline quaternary ammonium salt in the cycloalkyl imidazoline quaternary ammonium salt aqueous solution is 10.7; the mass ratio of titanium dioxide to methyl methacrylate is 10;
(2) Heating polyethylene to 230 ℃ under the condition of stirring, uniformly stirring under the condition of 40W ultraviolet irradiation, continuously adding polyethylene wax and phenyl ortho-hydroxybenzoate, uniformly stirring, extruding and granulating to obtain the polyethylene-based ink.
The preparation method of the colored plastic ampoule bottle comprises the following steps: uniformly mixing polyethylene and modified color master batch, putting the mixture into an extruder, preheating the mixture at 165 ℃, heating the mixture to 170 ℃ for extrusion to form a pipe blank with uniform color, putting the pipe blank into a blowing, filling and sealing all-in-one machine to prepare a container, injecting a medicament into the container through the blowing, filling and sealing all-in-one machine, and sealing the container to prepare an ampoule bottle containing the medicament.
Example 3
A colored plastic ampoule bottle comprises the following raw materials in percentage by weight: 98% of polyethylene base stock and 2% of modified color master batch;
the modified color master batch comprises the following components in parts by weight: 400 g of polyethylene, 60g of titanium dioxide, 70 g of 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide, 60g of polyethylene wax and 5 g of 2-hydroxy-4-N-octoxybenzophenone.
The modified color master batch is prepared by the following method:
(1) Mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting for 5 hours at 105 ℃, then adding 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide and methyl methacrylate, and continuously reacting for 3 hours at 70 ℃ under the ultraviolet irradiation condition of 40W to obtain a modified material; wherein the mass ratio of the titanium dioxide to the cycloalkyl imidazoline quaternary ammonium salt in the cycloalkyl imidazoline quaternary ammonium salt water solution is 10:1; the mass ratio of the titanium dioxide to the methyl methacrylate is 10: 2;
(2) Heating polyethylene to 230 ℃ under the condition of stirring, uniformly stirring under the condition of 40W ultraviolet irradiation, continuously adding polyethylene wax and 2-hydroxy-4-n-octoxy benzophenone, uniformly stirring, extruding and granulating to obtain the polyethylene wax.
The preparation method of the colored plastic ampoule bottle comprises the following steps: uniformly mixing polyethylene and modified color master batch, putting the mixture into an extruder, preheating the mixture at 175 ℃, heating the mixture to 180 ℃ for extrusion to form a pipe blank with uniform color, putting the pipe blank into a blowing, filling and sealing all-in-one machine to form a container, injecting a medicament into the container through the blowing, filling and sealing all-in-one machine, and sealing the container to form an ampoule bottle for containing the medicament.
Comparative example 1
On the basis of the example 1, the preparation method of the modified color master batch is adjusted as follows: heating polyethylene to 230 ℃ under the condition of stirring, adding titanium dioxide and 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide, uniformly mixing, sequentially adding polyethylene wax and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, uniformly stirring, extruding and granulating to obtain the polyethylene-based resin.
Comparative example 2
On the basis of the embodiment 1, the weight percentage of the polyethylene base material is adjusted to be 90%, and the weight percentage of the modified color master batch is adjusted to be 10%.
Comparative example 3
On the basis of the example 1, the ultraviolet irradiation operation in the preparation process of the modified color master batch is cancelled.
Test examples
1. The performance of the ampoules of examples 1-3 and comparative examples 1-3 were tested, and the results are shown in table 1.
Table 1: ampoule bottle performance
Light transmittance (%) Dispersity (number/100) 2 mm)
Example 1 20% 8
Example 2 24% 7
Example 3 25% 7
Comparison ofExample 1 32% 7
Comparative example 2 21% 7
Comparative example 3 22% 7
As can be seen from the data in the table above, the ampoules obtained by the methods of examples 1-3 and comparative examples 1-3 all had better light blocking properties and dispersion.
2. The ampoules filled with the drugs in examples 1 to 3 and comparative examples 1 to 3 were placed in a cool and dry place for 180 days, the drugs in the ampoules were poured out, and the pigment extract in the drugs was measured by the following specific measurement method: cutting the ampoules in the examples and the comparative examples into 2cm x 0.3cm small pieces, cutting 3 small pieces of the ampoules from each group, respectively placing the small pieces of the ampoules into conical flasks with stoppers, respectively adding 4% acetic acid solution (58-60 ℃) and 65% ethanol solution (23-27 ℃) into the small pieces of the ampoules, respectively adding 50ml of n-hexane (23-27 ℃) into the small pieces of the ampoules, soaking for 2 hours, and comparing each group of soaking solution with a blank solution after soaking by using the same batch of 4% acetic acid solution, 65% ethanol solution and the n-hexane as the blank solution, wherein the specific results are shown in table 2; meanwhile, the transmittance of the ampoule bottle was continuously measured, and the specific results are shown in table 2.
Table 2: light transmittance of ampoule bottle and extract of drug
Transmittance (%) Color contrast
Example 1 20% The color of the soaking solution is consistent with that of the blank solution
Example 2 24% The color of the soaking solution is consistent with that of the blank solution
Example 3 25% The color of the soaking solution is consistent with that of the blank solution
Comparative example 1 45% The color of the soaking solution is darker than that of the blank solution
Comparative example 2 21% The color of the soaking solution is darker than that of the blank solution
Comparative example 3 43% The color of the soaking solution is darker than that of the blank solution
The data in the table above show that, after standing for a long time, the light transmittance of the ampoule bottles in examples 1-3 is unchanged, and the color of the soaking solution is consistent with that of the blank solution, which proves that the pigment in the ampoule bottles does not exude; the ampoule bottles in the comparative examples 1-3 have obviously improved light transmittance, and the color of the soaking solution is darker than that of the blank solution, so that the pigments in the ampoule bottles are leached out after the operation method is changed, so that the medicament pollution is caused, and the use risk is increased.
Compared with the example 1, the comparative example 1 cancels the use of the naphthenic imidazoline quaternary ammonium salt aqueous solution and the methyl methacrylate, so that the fixing effect of the organic pigment in the ampoule bottle is poor, the organic pigment and the titanium dioxide are easily dissolved out in the subsequent placing process, the transmittance of the ampoule bottle is increased, and the color of the medicament solution is deepened.
Compared with the example 1, the comparative example 2 has the advantages that the dosage of the modified color master batch is increased, the free organic pigment in the modified color master batch is increased, the transmittance of the ampoule bottle is reduced, but the organic pigment is easy to dissolve out in the subsequent placing process, and the quality of the medicament is influenced.
Compared with the example 1, the comparative example 3 cancels the ultraviolet irradiation operation, because the grafting reaction can be carried out under the ultraviolet irradiation condition in the preparation process of the modified color master batch, and the ultraviolet irradiation condition is cancelled, the grafting reaction can not be carried out, the grafting and fixing effect on the organic pigment can not be realized, and the organic pigment is easy to dissolve out in the subsequent placing process, thereby influencing the quality of the medicament.

Claims (10)

1. The colored plastic ampoule bottle is characterized by comprising the following raw materials in percentage by weight: 96-99% of polyethylene base material and 1-4% of modified color master batch;
the preparation method of the modified color master batch comprises the following steps:
(1) Mixing titanium dioxide and a cycloalkyl imidazoline quaternary ammonium salt aqueous solution, reacting for 3-5h at the temperature of 95-105 ℃, then adding an organic pigment and methyl methacrylate, and stirring and reacting for 2-5h under the ultraviolet irradiation condition at the temperature of 60-70 ℃ to obtain a modified material;
(2) Heating polyethylene to 200-250 ℃ under the condition of stirring, adding the modified material, stirring and uniformly mixing under the condition of ultraviolet irradiation, continuously adding the lubricant and the ultraviolet absorbent, stirring uniformly, extruding and granulating to obtain the polyethylene.
2. The colored plastic ampoule of claim 1, comprising the following raw materials in weight percent: 96% of polyethylene base material and 4% of modified color master batch.
3. The colored plastic ampoule of claim 1, wherein the weight ratio of polyethylene, titanium dioxide, organic pigment, lubricant and ultraviolet absorber in the modified color masterbatch is 40-50.
4. The colored plastic ampoule of claim 1 or 2, wherein the weight ratio of polyethylene, titanium dioxide, organic pigment, lubricant and uv absorber in the modified masterbatch is 50.
5. The colored plastic ampoule of claim 4, wherein the lubricant is polyethylene wax.
6. The colored plastic ampoule of claim 4, wherein the UV absorber is benzotriazole, phenyl ortho-hydroxybenzoate or 2-hydroxy-4-n-octoxybenzophenone.
7. The colored plastic ampoule of claim 4, wherein the organic pigment comprises 4- [ (2, 5-dichlorophenyl) azo ] -N- (2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide or 4- [2- (2, 5-dichlorophenyl) azo ] -N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-hydroxy-2-naphthamide.
8. The colored plastic ampoule of claim 1, wherein the weight ratio of titanium dioxide to the cycloalkylimidazoline quaternary ammonium salt in the cycloalkylimidazoline quaternary ammonium salt aqueous solution during the preparation of the modified color master batch is 10.7-1.
9. The colored plastic ampoule of claim 1, wherein the weight ratio of titanium dioxide to methyl methacrylate is 10.
10. The method for the production of coloured plastic ampoules according to any one of claims 1 to 9, comprising the steps of: uniformly mixing polyethylene and modified color master batch, putting the mixture into an extruder, preheating the mixture at 165-175 ℃, heating the mixture to 170-180 ℃ for extrusion to form a pipe blank with uniform color, putting the pipe blank into a blowing, filling and sealing integrated machine to prepare a container, injecting a medicament into the container through the blowing, filling and sealing integrated machine, and sealing the container to prepare an ampoule bottle containing the medicament.
CN202211468365.8A 2022-11-22 2022-11-22 Colored plastic ampoule bottle and preparation method thereof Active CN115558189B (en)

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