CN114644882A - Coating liquid composition, coating liquid, coated rubber plug and preparation method thereof - Google Patents
Coating liquid composition, coating liquid, coated rubber plug and preparation method thereof Download PDFInfo
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- CN114644882A CN114644882A CN202011495631.7A CN202011495631A CN114644882A CN 114644882 A CN114644882 A CN 114644882A CN 202011495631 A CN202011495631 A CN 202011495631A CN 114644882 A CN114644882 A CN 114644882A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/02—Polysilicates
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Abstract
The invention relates to the technical field of production of medicinal rubber plugs, and discloses a coating liquid composition, a coating liquid, a film-coated rubber plug and a preparation method thereof, wherein the composition contains an inorganic silicon precursor, ethanol, water, organic silicon and a coupling agent; wherein the preparation method of the silicon film is an ultraviolet curing method; relative to 100 parts by weight of the inorganic silicon precursor, the content of the ethanol is 80-400 parts by weight, the content of the water is 35-150 parts by weight, the content of the organic silicon is 80-250 parts by weight, the content of the coupling agent is 60-220 parts by weight, and the content of the catalyst is 0.01-3 parts by weight. The coated rubber plug provided by the invention has low surface friction coefficient, and has better tolerance with common medicines such as chlorpromazine hydrochloride because the coating on the surface of the coated rubber plug does not fall off.
Description
Technical Field
The invention relates to the technical field of production of medicinal rubber plugs, in particular to a coating liquid composition for a film-coated rubber plug, a coating liquid and a preparation method thereof, and a film-coated rubber plug and a preparation method thereof.
Background
In the prior art, the rubber plug is usually subjected to silicification treatment, but the silicification treatment brings technical defects that after the medicine filling is finished, high-pressure sterilization with a plug is required, and silicone oil residues are released from the rubber plug and dissolved into the medicine; additionally, silicidation can also result in insoluble particles and visible foreign matter being rejected for inspection and rework or scrapping.
Therefore, scientists at home and abroad carry out a great deal of work.
CN105907298A discloses a graft type rubber plug spraying liquid and a method for processing the surface of a rubber plug, wherein the graft type rubber plug spraying liquid comprises the following components in parts by weight: 100 parts of hydroxyl-terminated polydimethylsiloxane, 2-4 parts of hydrogen-containing silicone oil, 3-5 parts of catalyst, 30-50 parts of coupling agent and 10000 parts of organic solvent of 2500-. At present, concentrated sulfuric acid is mostly used as a catalyst in the industrial esterification reaction, but the concentrated sulfuric acid easily causes environmental problems of complex post-treatment, large wastewater discharge amount, serious equipment corrosion and the like. With the continuous enhancement of consciousness and the increasing perfection of environmental protection regulations of fully utilizing resources, simplifying process flow, improving economic benefits and protecting living environment, the use of an environment-friendly catalyst to replace concentrated sulfuric acid has become an exploration direction for synthesizing ester compounds.
CN101301795B discloses a production method of a rubber plug partially coated with a PET film, which is characterized in that the surface fluorination treatment is carried out on a PET film, and then the PET film is applied to the rubber plug partially coated with the PET film.
However, the surface of the rubber plug is fully coated with a film or the neck is coated with a film, so that the adhesion force of the film material is weak, the film is easy to fall off, the elasticity of the film material is poor, the hardness of the coated rubber plug is high, the problems of poor self-sealing performance, poor needling performance and the like are easy to occur, and the price is high.
Therefore, there is a need to optimize and improve the prior art methods for making film coated rubber plugs.
Disclosure of Invention
The invention aims to overcome the problems that the film material has weak adhesion and the film is easy to fall off and the silicone oil residue can be released from a rubber plug in the prior art, and provides a coating liquid composition, a coating liquid, a film-coated rubber plug and a preparation method thereof. The coated rubber plug has better adhesive force and better tolerance with chlorpromazine hydrochloride because the coated film (silicon-containing compound) on the surface of the coated rubber plug does not fall off.
In order to achieve the above object, a first aspect of the present invention provides a coating liquid composition, wherein the coating liquid composition contains two or more of the following components stored in a mixed manner or stored independently of each other:
inorganic silicon precursor, ethanol, water, organic silicon, coupling agent and catalyst;
wherein the catalyst is selected from hydrochloric acid and/or molecular sieves;
relative to 100 parts by weight of the inorganic silicon precursor, the content of the ethanol is 80-400 parts by weight, the content of the water is 35-150 parts by weight, the content of the organic silicon is 80-250 parts by weight, the content of the coupling agent is 60-220 parts by weight, and the content of the catalyst is 0.01-3 parts by weight.
The second aspect of the invention provides a method for preparing the coating liquid for the film-coated rubber plug by using the coating liquid composition for the film-coated rubber plug, which is characterized in that components containing an inorganic silicon precursor, ethanol, water, organic silicon, a coupling agent and a catalyst are subjected to contact reaction.
The third aspect of the invention provides a coating liquid for the film-coated rubber plug prepared by the method.
The invention provides a method for preparing a film-coated rubber plug, wherein the method comprises the following steps:
(1) mixing and contacting the coating liquid for the film-coated rubber plug and a photoinitiator to obtain spraying liquid;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and carrying out photocuring treatment on the sprayed rubber plug.
The fifth aspect of the invention provides a coated rubber plug prepared by the method.
Through the technical scheme, the invention has the following technical advantages:
the preparation process of the film-coated rubber plug provided by the invention is simple, efficient, economic, ecological and energy-saving, does not influence the quality of the rubber plug, does not need repeated treatment, is easy to implement and has obvious effect.
Moreover, the rubber plug obtained by the invention can avoid a silicification process in the rubber plug production process, has good chemical resistance, can isolate the rubber plug from medicines and liquid medicines, avoids mutual diffusion and permeation, reduces particle pollution, protects the stability of the medicines, meets the requirement of the compatibility of the rubber plug and the medicines, and has very reliable biological safety and biological stability.
Further, the results of the examples of the present invention show that compared with the traditional silicone oil siliconized rubber plug, the rubber plug of the present invention has a low surface friction coefficient, and has better tolerance with common drugs such as chlorpromazine hydrochloride because the coating on the surface of the rubber plug does not fall off.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, normal pressure means one atmospheric pressure unless otherwise specified.
The first aspect of the present invention provides a coating liquid composition, wherein the coating liquid composition contains the following components stored in a mixed manner or independently:
inorganic silicon precursor, ethanol, water, organic silicon, coupling agent and catalyst;
wherein the catalyst is selected from hydrochloric acid and/or molecular sieves;
relative to 100 parts by weight of the inorganic silicon precursor, the content of the ethanol is 80-400 parts by weight, the content of the water is 35-150 parts by weight, the content of the organic silicon is 80-250 parts by weight, the content of the coupling agent is 60-220 parts by weight, and the content of the catalyst is 0.01-3 parts by weight.
The inventor of the invention finds out through research that: the preparation method comprises the steps of carrying out contact reaction on components containing an inorganic silicon precursor, ethanol, water, organic silicon, a coupling agent and a catalyst, carrying out hydrolysis reaction on the inorganic silicon precursor, the organic silicon and the coupling agent under the action of the catalyst and under the reaction condition that the water and the ethanol are used as solvents, carrying out dehydration condensation on hydroxyl groups carried in hydrolysis reaction products and also carrying out dealcoholization condensation on alkoxy groups, and finally forming a space network structure which is mutually connected by taking Si-O-Si bonds as a framework, thereby preparing coating liquid for the film-coated rubber plug, solidifying the coating liquid in at least part of the area of the rubber plug to be sprayed to form the film-coated rubber plug, wherein the coating liquid is directly solidified on the surface of the rubber plug, and the coupling agent can enable the coating liquid to react with the components of the rubber plug and be bonded together through chemical bonds, so that a film (silicon-containing compound) on the surface of the film-coated rubber plug does not fall off, has better adhesive force and better tolerance with chlorpromazine hydrochloride.
According to the present invention, it is preferable that the ethanol is contained in an amount of 100-360 parts by weight, the water is contained in an amount of 50-130 parts by weight, the silicone is contained in an amount of 100-240 parts by weight, the coupling agent is contained in an amount of 70-180 parts by weight, and the catalyst is contained in an amount of 0.02-2.5 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
More preferably, the ethanol content is 110-300 parts by weight, the water content is 60-120 parts by weight, the organosilicon content is 110-200 parts by weight, the coupling agent content is 80-160 parts by weight, and the catalyst content is 0.03-2 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
Still more preferably, the content of the ethanol is 150-180 parts by weight, the content of the water is 85-100 parts by weight, the content of the organosilicon is 180-200 parts by weight, the content of the coupling agent is 90-110 parts by weight, and the content of the catalyst is 0.8-1.2 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
According to the invention, the contents of the inorganic silicon precursor, the ethanol, the water, the organic silicon, the coupling agent and the catalyst are limited to be within the range, so that the coating liquid for the film-coated rubber plug can be prepared by adopting the coating liquid composition, and the coating liquid is solidified in at least part of the area of the rubber plug to be sprayed, so that the formed film (silicon-containing compound) on the surface of the film-coated rubber plug can not fall off, and the film-coated rubber plug has better adhesive force and better tolerance with chlorpromazine hydrochloride. In addition, in the invention, the addition amount of water cannot be excessive, on one hand, excessive addition of water tends to form a body-shaped structure, the viscosity is increased, and the stability of the polymer is reduced; on the other hand, adding too much water also tends to cause large volume shrinkage upon curing and drying, to cause cracking, and to increase the drying time. The viscosity of the polymer can be effectively reduced and the stability time of the polymer can be prolonged by increasing the amount of the ethanol, but the ethanol cannot be increased without limit, so that the environmental pollution can be caused; on the other hand, the excessive addition of ethanol can inhibit the hydrolysis reaction, so that the hydrolysis speed is reduced, even the hydrolysis is difficult, the condensation reaction is affected, the polymerization degree is reduced, and the subsequent coating liquid coating and curing film forming are not facilitated.
According to the invention, the inorganic silicon precursor is selected from one or more of methyl orthosilicate, ethyl orthosilicate and sodium silicate, and is preferably ethyl orthosilicate.
According to the invention, the organosilicon is selected from one or more of methyltriethoxysilane, methyltrimethoxysilane, triethoxysilane, diphenyldimethoxysilane and methylphenyldimethoxysilane; preferably, the organosilicon is selected from one or more of methyltriethoxysilane, methyltrimethoxysilane, diphenyldimethoxysilane, and triethoxysilane. In the present invention, when the silicone is selected from two or more silicones, the amount of any two silicones is 1: 1.
according to the invention, the coupling agent is selected from one or more of an aminosilane coupling agent, an epoxy silane coupling agent and an alkyl alkoxy silane coupling agent; preferably, the coupling agent is selected from gamma-methacryloxypropyltrimethoxysilane (KH-570) and/or vinyltrimethoxysilane (A-171).
According to the invention, the molecular sieve is an acidic molecular sieve, preferably the molecular sieve is selected from one or more of H-type mordenite, H-type Y-molecular sieve, H-type beta molecular sieve and H-type ZSM-5 molecular sieve; wherein, the silicon-aluminum molecule (SiO) of the H-type mordenite2/Al2O3) The molar ratio is 8.4-20, preferably 10-18; silicon-aluminum molecules (SiO) of the H-type Y-molecular sieve2/Al2O3) The molar ratio is 3-7, preferably 4-6; wherein, the silicon-aluminum molecule (SiO) of the H-type beta molecular sieve2/Al2O3) The molar ratio is 20-60, preferably 25-40; wherein, the silicon-aluminum molecule (SiO) of the H-type ZSM-5 molecular sieve2/Al2O3) The molar ratio is from 25 to 300, preferably from 38 to 100.
According to the invention, the coating liquid composition further comprises optional auxiliary agents, wherein the auxiliary agents are selected from one or more of a leveling agent, a defoaming agent, an adhesion promoter, a wetting agent, a delustering agent and a polymerization inhibitor, and the content of the auxiliary agents is 0-15 parts by weight, preferably 1-10 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
The invention provides a method for preparing coating liquid for the film-coated rubber plug by adopting the coating liquid composition for the film-coated rubber plug, which is characterized in that components containing an inorganic silicon precursor, ethanol, water, organic silicon, a coupling agent and a catalyst are subjected to contact reaction.
It should be noted that, in the present invention, when the product of the present invention is sold as a commercial product, the components of the inorganic silicon precursor, ethanol, water, silicone, coupling agent and catalyst may be stored separately for convenience of transportation and storage, etc., and may be prepared according to the method of the present invention before being applied to a coating.
The types of the components involved in the second aspect of the present invention are the same as the types of the components in the composition described in the first aspect of the present invention, and in order to avoid repetition, the present invention will not be described herein again, and those skilled in the art will not be understood as limiting the present invention.
According to the invention, the conditions of the contact reaction include: the temperature is 25-100 ℃, and the time is 1-10 h; preferably, the contacting is at a temperature of 35-80 ℃ for 2-8h, more preferably at a temperature of 60-70 ℃ for 6-7 h.
According to the invention, the method further comprises: and carrying out solid-liquid separation on the mixture obtained after the contact reaction to obtain the coating liquid for the film-coated rubber plug.
The step of the solid-liquid separation in the present invention is not particularly limited, and may be a conventional choice in the art as long as the purpose of spatially separating the liquid and the solid in the mixture obtained after the contact reaction can be achieved. The purpose of the solid-liquid separation in the present invention is to separate the catalyst from the mixture obtained after the contact reaction. Preferably, the means of solids separation is centrifugation and/or filtration. The equipment for carrying out said centrifugation and/or filtration can be chosen by the person skilled in the art according to the actual needs.
The third aspect of the invention provides a coating liquid for the film-coated rubber plug prepared by the method.
The invention provides a method for preparing a film-coated rubber plug, wherein the method comprises the following steps:
(1) mixing and contacting the coating liquid for the film-coated rubber plug and a photoinitiator to obtain spraying liquid;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and carrying out photocuring treatment on the sprayed rubber plug.
According to the invention, the method of the invention further comprises: in the step (1), the coating solution for the film-coated rubber plug is mixed with a photoinitiator and an optional auxiliary agent to contact with the coating solution to obtain a spraying solution.
According to the present invention, the areas to be coated by the spraying liquid in the process of preparing the rubber plug are well known to those skilled in the art, and the partial areas include, but are not limited to, the crown surface, the neck surface and the bottom surface of the rubber plug, and the coating can be performed by those skilled in the art according to the actual needs.
According to the present invention, it is well known to those skilled in the art that the preparation process of the rubber plug further includes, but is not limited to, the following steps before the spraying liquid is coated with the rubber plug: mixing rubber, discharging rubber sheets, molding, vulcanizing, cutting, cleaning and drying. Further, if necessary, the method for preparing the film-coated rubber plug provided by the invention can further comprise the following steps: and (3) punching, cleaning, sterilizing and the like the cured rubber plug.
According to a preferred embodiment of the present invention, the conditions of the uv curing include: the power of the medium-pressure mercury lamp is 300-3000W, the irradiation distance is 10-50cm, and the curing time is 10-360s, preferably, the power of the medium-pressure mercury lamp is 1500-2000W, the irradiation distance is 15-30cm, and the curing time is 30-180 s. In the present invention, the uv curing may be performed in an inert atmosphere or an oxygen-containing atmosphere, and in order to reduce the production cost, the uv curing is performed in the air. Under the preferred embodiment, the rubber plug cured by ultraviolet light has lower surface friction coefficient, and has better ultraviolet resistance, chemical resistance and aging resistance.
Preferably, the material of the rubber plug to be sprayed is selected from at least one of isoprene rubber, butyl rubber and halogenated butyl rubber.
According to the invention, in step (1), the conditions of the mixing contact comprise: the temperature is 20-40 deg.C, and the time is 10-60 min; preferably, the temperature is 25-35 deg.C and the time is 20-50 min.
According to the invention, the photoinitiator is selected from one or more of benzophenone ultraviolet light absorber, benzotriazole ultraviolet light absorber, hindered amine light stabilizer and hexamethylphosphoric triamide; preferably, the photoinitiator is a benzophenone ultraviolet light absorber, and the benzophenone ultraviolet light absorber is 2-hydroxy-2-methyl-1-phenyl acetone and/or 1-hydroxy-cyclohexyl-phenyl ketone;
preferably, the photoinitiator is contained in an amount of 5 to 40 parts by weight, preferably 6 to 35 parts by weight, and more preferably 23 to 28 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
According to a particularly preferred embodiment of the present invention, the method for preparing the coating liquid for the film-coated rubber plug by using the coating liquid composition for the film-coated rubber plug comprises:
the composition of the coating composition is: 100g of ethyl orthosilicate, 180g of ethanol, 85-100g of water, 180g of organosilicon (methyltriethoxysilane and diphenyldimethoxysilane), 90-110g of coupling agent (KH-570), 0.8-1.2g of catalyst (H-type mordenite catalyst, H-type Y-molecular sieve, H-type beta-molecular sieve or H-type ZSM-5 molecular sieve) and 23-28g of photoinitiator (2-hydroxy 2-methyl-1-phenyl-1-propyl ketone).
The preparation process of the non-siliconized rubber plug of the embodiment comprises the following specific steps:
(1) the ethyl orthosilicate, the ethanol, the water, the organic silicon, the coupling agent and the catalyst are subjected to contact reaction according to the weight ratio (the contact reaction condition comprises the temperature of 60-70 ℃ and the time of 6-7 hours) to prepare a mixture solution;
(2) centrifuging the mixture solution to obtain a coating solution;
(3) mixing the above mixture solution with 23-28g photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propyl ketone) at 28-32 deg.C for 28-32min to obtain spray solution;
(4) filling the prepared spraying liquid into silicon spraying equipment, and spraying the crown surface of the vulcanized rubber sheet;
(5) carrying out ultraviolet curing treatment on the sprayed rubber plug, wherein the power of a medium-pressure mercury lamp is 1000-1500W, the irradiation distance is 20-22cm, and the curing time is 30-50 s;
(6) and (3) punching, cleaning and sterilizing the treated rubber plug (brominated butyl rubber).
As a result, the coated rubber plug prepared by the particularly preferred embodiment of the invention has better adhesive force and better tolerance with chlorpromazine hydrochloride because the coating (silicon-containing compound) on the surface of the coated rubber plug does not fall off.
The fifth aspect of the invention provides a coated rubber plug prepared by the method.
According to the invention, the film-coated rubber plug comprises a rubber plug to be sprayed and a coating film coated on at least partial region of the rubber plug to be sprayed;
preferably, the thickness of the coating film is 30 to 80nm, preferably 30 to 60nm, more preferably 32 to 50nm, still more preferably 34 to 37 nm.
Preferably, the surface friction coefficient of the coated plug is 0.7-1.2, preferably 0.7-1, more preferably 0.7481-0.7896.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the rubber plug is made of the following materials: the brominated butyl rubber and the chlorinated butyl rubber are purchased from the medical rubber and plastic Limited company of Huafeng medicine in Anhui, and the brands are respectively HFG-08B, HFG-10;
ethyl orthosilicate is available from Bailingwei technologies, Beijing;
ethanol was purchased from Beijing chemical plant;
the water is self-made deionized water;
molecular sieves were purchased from tianjin south chemical catalyst ltd;
organosilicon: methyltriethoxysilane, methyltrimethoxysilane, triethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane are available from Bailingwei technologies, Beijing;
coupling agent: KH-570 and A-171, both available from Bailingwei technologies, Beijing;
photoinitiator (2): 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxy-cyclohexyl-phenyl-methanone were purchased from Beijing carbofuran technologies, Inc.;
auxiliary agent: BYK-UV3530 (German Bike leveling agent 3530) was purchased from Guangzhou Baohua trade, Inc.;
chlorpromazine hydrochloride was purchased from Beijing Bailingwei science and technology Co.
The ultraviolet curing machine is a product which is purchased from Beijing Hongchang electromechanical device Limited and has the brand number of LDST13002-11 AZ.
The silicone oil particles tested in the present invention were tested using a model GWJ-4 instrument from precision instruments of Tianjin university.
The room temperature in the following preparation process means 25. + -. 1 ℃.
Example 1
The material of the coated rubber plug of the embodiment is brominated butyl rubber, and the coated rubber plug comprises a coating solution prepared from a coating solution composition, the coating solution is coated on the surface of the cleaned and dried rubber plug, and the coating solution and the coating are subjected to curing treatment.
Wherein, the composition of the coating composition is as follows: 100g of tetraethoxysilane, 176g of ethanol, 87g of water, 200g of organosilicon (methyl triethoxysilane and diphenyl dimethoxysilane, wherein the weight ratio of the used amount of the methyl triethoxysilane to the used amount of the diphenyl dimethoxysilane is 1: 1), 100g of coupling agent (KH-570), 1g of H-type mordenite catalyst (the molar ratio of silicon to aluminum is 13, and the shape of a cylinder) and 25g of photoinitiator (2-hydroxy 2-methyl-1-phenyl-1-propyl ketone).
The preparation process of the coated rubber plug comprises the following specific steps:
(1) according to the weight ratio, carrying out contact reaction on ethyl orthosilicate, ethanol, water, organic silicon, a coupling agent and a catalyst (the contact reaction condition comprises that the temperature is 70 ℃ and the time is 6 hours) to prepare a mixture solution;
(2) centrifuging the mixture solution to obtain a coating solution;
(3) mixing the above mixture solution with 25g photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone (under the condition of 30 deg.C for 30min) to obtain spray coating solution;
(4) filling the prepared spraying liquid into silicon spraying equipment, and spraying the crown surface of the vulcanized rubber sheet;
(5) carrying out ultraviolet curing treatment on the sprayed rubber plug, wherein the power of a medium-pressure mercury lamp is 1500W, the irradiation distance is 20cm, and the curing time is 30 s;
(6) and performing punching, cleaning and sterilization processes on the treated rubber plug.
Specific process conditions are listed in table 1.
Results the properties of the resulting coated plug are shown in table 2.
Examples 2 to 7
This example illustrates the preparation of a coating solution using the coating solution composition of the present invention and the preparation of a coated rubber plug using the coating solution.
A film-coated composition, a coating liquid and a film-coated rubber plug were prepared in the same manner as in example 1, except that: the components and component contents in the coating composition, the components and component contents in the coating liquid, and the preparation conditions were changed, specifically, as shown in tables 1 and 2.
Comparative example 1
Coating solution compositions, coating solutions and film-coated rubber plugs were prepared in the same manner as in example 1, except that: the H-type mordenite (13 silica to alumina molar ratio, cylindrical) was replaced with dibutyltin dilaurate, as shown in tables 1 and 2.
Comparative example 2
Coating solution compositions, coating solutions and film-coated rubber plugs were prepared in the same manner as in example 1, except that: the content of each component in the coating composition is not within the range defined by the present invention, specifically, as shown in tables 1 and 2.
Comparative example 3
The rubber plug is treated by the traditional silicification method, namely the content of the dimethyl silicone oil is 0.01-0.03mg/cm per square centimeter of specific surface area2Preparing dimethyl silicone oil spraying liquid, and utilizing the dimethyl silicone oil spraying liquid before and after cleaning the rubber plugThe spraying equipment carries out spraying operation to the plug surface for dimethylsilicone oil adsorbs on the plug surface, in order to play lubricated effect.
Results the properties of the resulting coated plug are shown in table 2.
TABLE 1
TABLE 1 (continuation)
TABLE 2
| Thickness of coating film (nm) | Surface friction coefficient of film coated rubber plug | |
| Example 1 | 35 | 0.7481 |
| Example 2 | 59 | 1.1658 |
| Example 3 | 68 | 1.0256 |
| Example 4 | 41 | 0.9121 |
| Example 5 | 43 | 0.8123 |
| Example 6 | 34 | 0.7896 |
| Example 7 | 37 | 0.7548 |
| Comparative example 1 | 65 | 1.3245 |
| Comparative example 2 | 90 | 1.3442 |
| Comparative example 3 | 30 | 1.3246 |
From the above results, it can be seen that the rubber stoppers provided by the present invention have a lower surface friction coefficient than the comparative examples 1 to 3.
Test example 1
And (3) detecting the adhesive force of the coating: the coating adhesion was measured by the cross-hatch method, the evaluation criteria are shown in table 3:
TABLE 3
The test results are shown in Table 4.
Test example 2
The silicone oil particle test is carried out on the rubber plugs prepared in the preparation examples and the comparative examples, and the method comprises the following steps: two groups of three batches of injection liquid rubber plug finished products in the same batch are taken to carry out silicone oil particle test (refer to a light resistance method in a packaging material insoluble particle determination method YBB00272016 issued by the State food and drug administration), the average value is taken, and the test results are listed in Table 4.
Test example 3
The rubber stoppers obtained in the above preparation examples and comparative examples were subjected to a packaging treatment of chlorpromazine hydrochloride placed in an ampoule, inverted, subjected to high temperature tests for 10 days and 30 days under constant temperature and constant humidity conditions (60 ℃, 75% RH), and compared in terms of turbidity (refer to second part appendix ix of pharmacopoeia of the people's republic of china, 2000 edition), and the test results are shown in table 4.
TABLE 4
Note: in the silicone oil microparticles, not less than 10 μm represents the number of insoluble microparticles of not less than 10 μm per 1mL of the infusion solution, and not less than 25 μm represents the number of insoluble microparticles of not less than 25 μm per 1mL of the infusion solution;
a turbidity of < 0.5 indicates a value of turbidity mean below the turbidity standard No. 0.5; a turbidity of 0.5 to 1 means a mean value of turbidity between the values of the standard solutions of turbidity No. 0.5 to turbidity No. 1.
The results in table 2 show that compared with the conventional silicone oil silicone rubber plug of the comparative example 1, the silicone oil on the surface of the rubber plug provided by the present invention does not fall off, so the rubber plug has better adhesion and better resistance to chlorpromazine hydrochloride.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. The coating liquid composition is characterized by comprising the following components which are stored in a mixing way or independently:
inorganic silicon precursor, ethanol, water, organic silicon, coupling agent and catalyst;
wherein the catalyst is selected from hydrochloric acid and/or molecular sieves;
relative to 100 parts by weight of the inorganic silicon precursor, the content of the ethanol is 80-400 parts by weight, the content of the water is 35-150 parts by weight, the content of the organic silicon is 80-250 parts by weight, the content of the coupling agent is 60-220 parts by weight, and the content of the catalyst is 0.01-3 parts by weight.
2. The composition as claimed in claim 1, wherein the content of ethanol is 100-360 parts by weight, the content of water is 50-130 parts by weight, the content of organosilicon is 100-240 parts by weight, the content of coupling agent is 70-180 parts by weight, and the content of catalyst is 0.02-2.5 parts by weight, relative to 100 parts by weight of the inorganic silicon precursor.
3. The composition of claim 1 or 2, wherein the inorganic silicon precursor is selected from one or more of methyl orthosilicate, ethyl orthosilicate, and sodium silicate, preferably ethyl orthosilicate;
preferably, the organosilicon is selected from one or more of methyltriethoxysilane, methyltrimethoxysilane, triethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane.
4. The composition of claim 1 or 2, wherein the coupling agent is selected from one or more of an aminosilane coupling agent, an epoxysilane coupling agent, and an alkylalkoxysilane coupling agent; preferably, the coupling agent is selected from gamma-methacryloxypropyltrimethoxysilane and/or vinyltrimethoxysilane.
5. The composition of claim 1 or 2, wherein the molecular sieve is an acidic molecular sieve;
preferably, the molecular sieve is one or more of H-type mordenite, H-type Y-molecular sieve, H-type beta molecular sieve and H-type ZSM-5 molecular sieve;
preferably, the Si/Al molecular mole ratio of the H-type mordenite is 8.4-20;
preferably, the molar ratio of silicon to aluminum molecules of the H-type Y-molecular sieve is 3-7;
preferably, the molar ratio of silicon to aluminum molecules of the H-type beta molecular sieve is 20-60;
preferably, the H-type ZSM-5 molecular sieve has a silicon-aluminum molecular molar ratio of 25-300.
6. The method for preparing the coating liquid for the coated rubber plug by using the coating liquid composition for the coated rubber plug according to any one of claims 1 to 5 is characterized in that components containing an inorganic silicon precursor, ethanol, water, organosilicon, a coupling agent and a catalyst are contacted for reaction.
7. The method of claim 6, wherein the conditions of the contact reaction comprise: the temperature is 25-100 ℃ and the time is 1-10 h.
8. The method of claim 6 or 7, wherein the method further comprises: and carrying out solid-liquid separation on the mixture obtained after the contact reaction to obtain the coating liquid for the film-coated rubber plug.
9. A coating liquid for a film-coated rubber plug prepared by the method of any one of claims 6 to 8.
10. A method of making a coated rubber plug, the method comprising:
(1) mixing and contacting the coating solution for the film-coated rubber plug of claim 9 with a photoinitiator to obtain a spraying solution;
(2) coating the spraying liquid on at least part of the area of the rubber plug to be sprayed to obtain the sprayed rubber plug;
(3) and carrying out photocuring treatment on the sprayed rubber plug.
11. The method of claim 10, wherein in step (1), the conditions of the mixing contact comprise: the temperature is 20-40 deg.C, and the time is 10-60 min.
12. The method of claim 10 or 11, wherein the photoinitiator is selected from one or more of a benzophenone-based ultraviolet light absorber, a benzotriazole-based ultraviolet light absorber, a hindered amine-based light stabilizer, and hexamethylphosphoric triamide; preferably, the photoinitiator is a benzophenone ultraviolet light absorber, and the benzophenone ultraviolet light absorber is 2-hydroxy-2-methyl-1-phenyl acetone and/or 1-hydroxy-cyclohexyl-phenyl ketone;
preferably, the photoinitiator is contained in an amount of 5 to 40 parts by weight, preferably 6 to 35 parts by weight, with respect to 100 parts by weight of the inorganic silicon precursor.
13. A coated rubber plug prepared by the method of any one of claims 10-12.
14. The coated rubber plug of claim 13, wherein the coated rubber plug comprises a rubber plug to be sprayed and a coating film coated on at least a partial region of the rubber plug to be sprayed;
preferably, the thickness of the coating film is 30 to 80 nm;
preferably, the surface friction coefficient of the film-coated rubber plug is 0.7-1.2.
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| CN102585700A (en) * | 2012-01-16 | 2012-07-18 | 南昌航空大学 | Method for preparing UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating |
| CN105907298A (en) * | 2016-05-25 | 2016-08-31 | 郑州翱翔医药科技股份有限公司 | Grafted rubber plug spraying fluid and treatment method of grafted rubber plug spraying fluid on surface of rubber plug |
| CN107629240A (en) * | 2017-11-08 | 2018-01-26 | 江阴市海华橡塑有限公司 | A kind of preparation technology for exempting from silication plug |
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| CN102585700A (en) * | 2012-01-16 | 2012-07-18 | 南昌航空大学 | Method for preparing UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating |
| CN105907298A (en) * | 2016-05-25 | 2016-08-31 | 郑州翱翔医药科技股份有限公司 | Grafted rubber plug spraying fluid and treatment method of grafted rubber plug spraying fluid on surface of rubber plug |
| CN107629240A (en) * | 2017-11-08 | 2018-01-26 | 江阴市海华橡塑有限公司 | A kind of preparation technology for exempting from silication plug |
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