CN106590392A - Water-based OP protecting agent for pharmaceutical packaging and preparation method thereof - Google Patents

Water-based OP protecting agent for pharmaceutical packaging and preparation method thereof Download PDF

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Publication number
CN106590392A
CN106590392A CN201611049542.3A CN201611049542A CN106590392A CN 106590392 A CN106590392 A CN 106590392A CN 201611049542 A CN201611049542 A CN 201611049542A CN 106590392 A CN106590392 A CN 106590392A
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CN
China
Prior art keywords
aqueouss
protective agent
medical packaging
water
diisocyanate
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Pending
Application number
CN201611049542.3A
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Chinese (zh)
Inventor
谭雪梅
李有刚
杨芳
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Ke Litai Macromolecular Material Limited-Liability Co In Chongqing
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Ke Litai Macromolecular Material Limited-Liability Co In Chongqing
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Priority to CN201611049542.3A priority Critical patent/CN106590392A/en
Publication of CN106590392A publication Critical patent/CN106590392A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/58Epoxy resins
    • C08G18/585Epoxy resins having sulfur
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents
    • 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

Abstract

The invention belongs to the chemical field and relates to a water-based OP protecting agent for pharmaceutical packaging. The water-based OP protecting agent comprises, by mass, 40% to 49.5% of an anionic polyurethane emulsion, 25% to 30% of an ethanol solution having a volume fraction of 95%, 25% to 30% of deionized water and 0.2% to 2% of an antisticking agent. The water-based OP protecting agent is prepared from environmentally friendly raw materials, does not cause the damage to the personnel and pollution on the environment, can meet the requirements of wetting spreading on the aluminum foil without use of a leveling wetting assistant, has low readily oxidizable substance content amd good normal temperature stability, can be operated simply and can form a film having good adhesive force, smoothness and transparency. The OP protecting agent has good temperature resistance.

Description

Aqueouss OP protective agent for medical packaging and preparation method thereof
Technical field
The invention belongs to chemical field, and in particular to for the aqueouss OP protective agent and preparation method thereof of medical packaging.
Background technology
PTP aluminium foils are the important component parts of blister package, and OP protective layers are the important component parts of PTP aluminium foils, its master It is to make PTP aluminium foil surface lights smooth to act on, and improves the antiacid alkali erosiveness of PTP aluminium foils, extends the shelf-life of medicine, with And protection printing layer, ink is effectively bonded with Al foil substrate, prevent ink from coming off.
Protective agent used by coating PTP protection foil layers is referred to as OP protective agents.OP protective agents currently used in the market are more All it is solvent based product, is coated with after the organic solvent dilutings such as front ethyl acetate and uses.Suffer from the drawback that:Ethyl acetate solvent Highly volatile, is easy to burning and causes production accident in high temperature drying tunnel;Cleaning equipment needs to use organic solvent, organic in recent years Solvent substantial appreciation of prices, increased production cost;A large amount of solvents are volatized into surrounding enviroment in coating process, strong to environment and human body Health forms harm, and especially plant operations workman, can cause damage to the liver of human body and nervous system;It is organic used in production Solvent can not possibly be escaped all from coating in a short time, and with drug packaging, and the organic solvent remained in coating will be by Gradually volatilize, spread, accumulating in bubble-cap, being adsorbed by medicine, so will then cause the potential safety hazard of drug packaging;Temperature tolerance compared with Difference, the heat-sealing in high speed blister package medicine produces high temperature, and OP protective agents are easily carbonized and produce pungent taste and color change, this " greenization " package development trend will not all be met a bit.Also minority aqueous aluminum foil protecting agent uses in test, but generally Have the following disadvantages:Need during coating with the dilution of the hydrophilic organic solvents such as part ethanol, isopropanol;Due to the surface tension of water Greatly, shrinkage cavity phenomenon is usually occurred on base material aluminium foil;Aqueous aluminum foil protecting agent drying temperature is higher than solvent-borne type;Thermostability and Adhesive force is not as good as traditional solvent-borne protective agent etc..
The content of the invention
In view of this, it is an object of the invention to provide a kind of aqueouss OP protective agent for medical packaging.
To realize object above, the technical scheme is that:
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 40%~49.5%, volume fraction is 95% ethanol solution 25%~30%, deionized water 25%~30% and antiplastering aid 0.2%~2%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Polyhydric alcohol 9.6%~14%, Bisphenol-s epoxy resin 1.2%~1.75%, diisocyanate 5%~7.5%, polyalcohols chain extender 0.8%~ 2.25%th, hydrophilic chain extender 0.8%~1.5%, fatty amines chain extender 0.02%~0.125%, catalyst 0.01%~ 0.025% and deionized water 75%~80%.
The bisphenol-s epoxy resin is 185S or 300SS.
Further, the antiplastering aid is wax emulsion.
Further, the polyhydric alcohol is PEPA, polyether polyol, benzoic anhydride polyester polyol, polycaprolactone polyol One or more in alcohol, polycarbonate polyol.
Further, the diisocyanate is toluene di-isocyanate(TDI), 1,6- hexamethylene diisocyanates, isophorone Diisocyanate, methyl diphenylene diisocyanate, XDI, naphthalene -1,5- diisocyanate, tetramethyl One or more in XDI.
Further, the polyalcohols chain extender is ethylene glycol, Propylene Glycol, neopentyl glycol, 1,6- hexanediol, diethyl two Alcohol, dipropylene glycol, 3- methyl isophthalic acids, 5- pentanediols, 1,3 butylene glycol, BDO, diglycol, trihydroxy methyl third One or more in alkane, dihydromethyl propionic acid, dimethylolpropionic acid;
Further, the hydrophilic chain extender is ethylenediamine base ethylsulfonic acid sodium.
Further, the fatty amines chain extender be ethylenediamine, isophorone diamine and 4,4 '-diaminourea -3,3 '-dichloro One or more in diphenyl-methane.
Further, the fatty amines chain extender is by ethylenediamine, isophorone diamine and 4,4 '-diaminourea -3,3 '-dichloro Diphenyl-methane is according to 3:1:1 quality is formed than proportioning.
Further, the catalyst is one or more in dibutyl tin laurate, stannous octoate, isooctyl acid bismuth.
The present invention also aims to the protectant preparation method of aqueouss OP for medical packaging is protected, including such as Lower step:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By polyhydric alcohol and bisphenol-s epoxy resin in 100 DEG C~120 DEG C temperature The lower vacuum dehydration 2h of degree, is cooled to 70 DEG C~80 DEG C, adds 0.5~1h of di-isocyanate reaction, adds polyalcohols chain extension Agent and catalyst, react 3~5h at a temperature of 70 DEG C~80 DEG C, and period adds the acetone equivalent to 1~2.5 times of reactant liquor quality The viscosity of performed polymer is adjusted, then is cooled to 40 DEG C~45 DEG C, add hydrophilic chain extender 10~25min of insulation reaction, add reaction The water emulsification that 3~5 times of liquid quality, adding fatty amines chain extender carries out rear 30~60min of chain extension, and vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Antiplastering aid is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The beneficial effects of the present invention is:
(1) the formula material environmental protection of the application, due to as diluent, do not result in only with ethanol personnel injury and The pollution of environment, while the wetting and spreading on aluminium foil also can be met in the case of without levelling wetting aid.(2) formula In be not added with the conventional amino resins of traditional OP protective coatings, readily oxidizable substance content is low.(3) formula does not require the use of firming agent, For one-component coating, ordinary temperature stability is good, simple to operate.(4) film forming postadhesion power, smooth degree and the transparency are good.(5) in formula Special source materials bisphenol-s epoxy resins used in the aqueous polyurethane emulsion synthesis for using, due to introducing-SO2- pole Property group, have more preferable adhesive property, heat stability, toughness, dimensional stability and preferable chemistry than bisphenol A type epoxy resin Stability, its heat distortion temperature improves 60~70 DEG C than bisphenol A type epoxy resin, makes OP protective agents have preferable temperature tolerance.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is unreceipted in preferred embodiment The experimental technique of actual conditions, generally according to normal condition.Wax emulsion in following examples is purchased from Germany KEIM-ADDITEC Company, model E-389.
Embodiment 1
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 49.5%, volume fraction is 95% ethanol solution 25%, deionized water 25% and wax emulsion 0.5%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:PEPA (molecular weight 2000) 14%, bisphenol-s epoxy resin 185S 1.75%, toluene di-isocyanate(TDI) 5%, ethylene glycol 2.25%, ethylenediamine base Ethylsulfonic acid sodium 1.5%, ethylenediamine 0.125%, dibutyl tin laurate 0.025% and deionized water 75.35%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By PEPA and bisphenol-s epoxy resin 185S at 100 DEG C DEG C At a temperature of vacuum dehydration 2h, be cooled to 70 DEG C, add toluene di-isocyanate(TDI) reaction 0.5h, add ethylene glycol and tin dilaurate Dibutyl tin, reacts 5h at a temperature of 70 DEG C, and period adds and adjusts the viscous of performed polymer equivalent to the acetone of 2.5 times of reactant liquor quality Degree, then it is cooled to 45 DEG C, ethylenediamine base ethylsulfonic acid sodium insulation reaction 25min is added, add the water and milk of 5 times of reactant liquor quality Change, adding ethylenediamine carries out rear chain extension 30min, and vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 2
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 40%, volume fraction is 95% ethanol solution 28%, deionized water 30% and wax emulsion 2%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Polyether polyol (molecular weight 2000) 9.67%, bisphenol-s epoxy resin 300SS 1.2%, 1,6- hexamethylene diisocyanates 7.5%, Propylene Glycol 0.8%th, ethylenediamine base ethylsulfonic acid sodium 0.8%, isophorone diamine 0.02%, stannous octoate 0.01% and deionized water 80%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By polyether polyol and bisphenol-s epoxy resin 300SS at 120 DEG C At a temperature of vacuum dehydration 2h, be cooled to 80 DEG C, add 1,6- hexamethylene diisocyanates reaction 1h, add Propylene Glycol and pungent Sour stannous, react 3h at a temperature of 80 DEG C, and period adds the viscosity that performed polymer is adjusted equivalent to the acetone of 1 times of reactant liquor quality, 40 DEG C are cooled to again, ethylenediamine base ethylsulfonic acid sodium insulation reaction 10min is added, and add the water emulsification of 3 times of reactant liquor quality, then Isophorone diamine is added to carry out rear chain extension 60min, vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 3
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 42.7%, volume fraction is 95% ethanol solution 28.5%, deionized water 28.5% and wax emulsion 0.3%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:PEPA (molecular weight 2000) 10%, benzoic anhydride polyester polyol (molecular weight 1000) 2.5%, bisphenol-s epoxy resin 185S 1.6%, isophorone Diisocyanate 7.5%, trimethylolpropane 0.4%, dihydromethyl propionic acid 1.6%, ethylenediamine base ethylsulfonic acid sodium 1.35%, Isophorone diamine 0.04%, dibutyl tin laurate 0.01% and deionized water 75%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By PEPA, benzoic anhydride polyester polyol and bisphenol S type epoxy Resin 185S vacuum dehydration 2h at a temperature of 120 DEG C, are cooled to 80 DEG C, add isoflurane chalcone diisocyanate reaction 0.5h, then Trimethylolpropane, dihydromethyl propionic acid and dibutyl tin laurate are added, 3.5h is reacted at a temperature of 80 DEG C, period adds The viscosity of performed polymer is adjusted equivalent to 2 times of acetone of reactant liquor quality, then is cooled to 45 DEG C, addition ethylenediamine base ethylsulfonic acid sodium Insulation reaction 10min, adds the water emulsification of 3 times of reactant liquor quality, and adding isophorone diamine carries out rear chain extension 30min, subtracts Pressure distills out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 4
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 43.3%, volume fraction is 95% ethanol solution 28.25%, deionized water 28.25% and wax emulsion 0.2%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:PEPA (molecular weight 2000) 9.3%, polycaprolactone polyol (molecular weight 2000) 2%, bisphenol-s epoxy resin 300SS 1.5%, isophorone Diisocyanate 7.3%, trimethylolpropane 0.3%, 1,4- butanediols 0.9%, dihydromethyl propionic acid 0.5%, tin dilaurate Dibutyl tin 0.01%, ethylenediamine base ethylsulfonic acid sodium 1.17%, isophorone diamine 0.02% and deionized water 77%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By PEPA, polycaprolactone polyol and bisphenol S type epoxy tree Fat 300SS vacuum dehydration 2h at a temperature of 110 DEG C, are cooled to 75 DEG C, add isoflurane chalcone diisocyanate reaction 1h, add Trimethylolpropane, dihydromethyl propionic acid, dimethylolpropionic acid and dibutyl tin laurate, at a temperature of 75 DEG C 4h is reacted, Period adds and adjusts the viscosity of performed polymer equivalent to the acetone of 1.8 times of reactant liquor quality, then is cooled to 40 DEG C, adds ethylenediamine base Ethylsulfonic acid sodium insulation reaction 15min, adds the water emulsification of 3.5 times of reactant liquor quality, adds after isophorone diamine carries out Chain extension 30min, vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 5
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 45%, volume fraction is 95% ethanol solution 27%, deionized water 27% and wax emulsion 1%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Benzoic anhydride polyester polyol (point Son amount 2000) 5.2%, benzoic anhydride polyester polyol (molecular weight 1000) 5.2%, bisphenol-s epoxy resin 300SS 1.6%, 1, 6- hexamethylene diisocyanates 3.2%, isophorone diisocyanate 3.2%, trimethylolpropane 0.4%, 1,4- fourths two Alcohol 0.8%, neopentyl glycol 0.4%, dihydromethyl propionic acid 0.6%, stannous octoate 0.015%, ethylenediamine base ethylsulfonic acid sodium 1.35%th, isophorone diamine 0.035% and water 78%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:Benzoic anhydride polyester polyol and bisphenol-s epoxy resin 300SS are existed Vacuum dehydration 2h at a temperature of 115 DEG C, is cooled to 80 DEG C, adds 1,6- hexamethylene diisocyanates, the Carbimide. of isophorone two Ester reacts 1h, neopentyl glycol, BDO, trimethylolpropane, dihydromethyl propionic acid and stannous octoate is added, at 75 DEG C At a temperature of react 4h, period adds and adjusts the viscosity of performed polymer equivalent to the acetone of 2.2 times of reactant liquor quality, then is cooled to 42 DEG C, ethylenediamine base ethylsulfonic acid sodium insulation reaction 15min is added, the water emulsification of 4 times of reactant liquor quality is added, add different Fo Er Ketone diamidogen carries out rear chain extension 45min, and vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 6
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 49.5%, volume fraction is 95% ethanol solution 25%, deionized water 25% and wax emulsion 0.5%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Polycarbonate polyol (point Son amount 2000) 2.4%, benzoic anhydride polyester polyol (molecular weight 1000) 7.2%, bisphenol-s epoxy resin 185S 1.75%, two Methylenebis phenyl isocyanate 5%, isophorone diisocyanate 2.5%, trimethylolpropane 1.25%, neopentyl glycol 1%, Isooctyl acid bismuth 0.025%, ethylenediamine base ethylsulfonic acid sodium 1.5%, isophorone diamine 0.125% and deionized water 78.875%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By polycarbonate polyol 2.5%, benzoic anhydride polyester polyol and bis-phenol S type epoxy resin 185S vacuum dehydration 2h at a temperature of 120 DEG C, are cooled to 80 DEG C, add methyl diphenylene diisocyanate, different Isophorone diisocyanate reacts 1h, adds trimethylolpropane, neopentyl glycol and isooctyl acid bismuth, reacts at a temperature of 75 DEG C 5h, period adds and adjusts the viscosity of performed polymer equivalent to the acetone of 1.9 times of reactant liquor quality, then is cooled to 42 DEG C, adds second two Amido ethylsulfonic acid sodium insulation reaction 15min, adds the water emulsification of 4 times of reactant liquor quality, and adding isophorone diamine is carried out Chain extension 45min afterwards, vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 7
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 43%, volume fraction is 95% ethanol solution 30%, deionized water 26% and wax emulsion 1%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Benzoic anhydride polyester polyol (point Son amount 1000) 4.8%, polycaprolactone polyol (molecular weight 2000) 3.6%, polycarbonate polyol (molecular weight 2000) 3.2%th, bisphenol-s epoxy resin 300SS 1.2%, XDI 2%, naphthalene -1,5- diisocyanate 2%th, tetramethylxylylene diisocyanate 1%, 1,6-HD 0.15%, diethylene glycol 0.15%, dipropylene glycol 0.1%th, 3- methyl isophthalic acids, 5- pentanediols 0.3%, 1,3 butylene glycol 0.1%, ethylenediamine base ethylsulfonic acid sodium 1.345%, ethylenediamine 0.03%th, isophorone diamine 0.01%, 4,4 '-diaminourea -3,3 '-dichloro diphenyl methane 0.01%, di lauric dibutyl Stannum 0.01%, stannous octoate 0.005%, isooctyl acid bismuth 0.01% and deionized water 79.98%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:Benzoic anhydride polyester polyol, polycaprolactone polyol, Merlon is more The first alcohol and bisphenol-s epoxy resin 300SS vacuum dehydration 2h at a temperature of 105 DEG C, is cooled to 72 DEG C, adds phenylenedimethylidyne two Isocyanates, naphthalene -1,5- diisocyanate, tetramethylxylylene diisocyanate reaction 1h, add 1,6 hexanediol, Diethylene glycol, dipropylene glycol, 3- methyl isophthalic acids, it is 5- pentanediols, 1,3 butylene glycol, dibutyl tin laurate, stannous octoate, different pungent Sour bismuth, reacts 4h at a temperature of 75 DEG C, and period adds the viscosity that performed polymer is adjusted equivalent to the acetone of 1.6 times of reactant liquor quality, 42 DEG C are cooled to again, ethylenediamine base ethylsulfonic acid sodium insulation reaction 10min is added, and add the water emulsification of 5 times of reactant liquor quality, then Add ethylenediamine, isophorone diamine and 4,4 '-diaminourea -3 that rear chain extension 30min is carried out in 3 '-dichloro diphenyl methane, reduce pressure Distill out acetone and obtain Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Embodiment 8
For the aqueouss OP protective agent of medical packaging, it is made up of following mass percent component:Anionic polyurethane breast Liquid 46%, volume fraction is 95% ethanol solution 28.3%, deionized water 25.5% and wax emulsion 0.2%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Polycarbonate polyol (point Son amount 2000) 14%, bisphenol-s epoxy resin 185S 1.75%, naphthalene -1,5- diisocyanate 7.475%, a contracting diethyl two Alcohol 0.3%, dihydromethyl propionic acid 0.2%, dimethylolpropionic acid 0.2%, ethylenediamine base ethylsulfonic acid sodium 1%, 4,4 '-diamino Base -3,3 '-dichloro diphenyl methane 0.05%, stannous octoate 0.025% and deionized water 75%.
The protectant preparation method of aqueouss OP for medical packaging, comprises the steps:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By polycarbonate polyol and bisphenol-s epoxy resin 185S 110 Vacuum dehydration 2h at a temperature of DEG C, is cooled to 75 DEG C, adds naphthalene -1,5- di-isocyanate reaction 0.5h to add a contracting diethyl two Alcohol, dihydromethyl propionic acid, dimethylolpropionic acid and stannous octoate, react 4h at a temperature of 70 DEG C, and period is added equivalent to reaction The acetone that 1 times of liquid quality adjusts the viscosity of performed polymer, then is cooled to 40 DEG C, addition ethylenediamine base ethylsulfonic acid sodium insulation reaction 18min, adds the water emulsification of 3 times of reactant liquor quality, adds 4, and 4 '-diaminourea -3,3 '-dichloro diphenyl methane carries out rear chain extension 30min, vacuum distillation goes out acetone and obtains Polyurethane Emulsion of Negative-ion Type;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and Wax emulsion is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
The aqueouss OP protective agent that the present embodiment is obtained is coated on medical aluminium foil, is dried at 160 DEG C, then takes polyester adhesive Adhesive tape laterally homogeneously pressing specimen surface, is peeled off rapidly with 160 °~180 ° directions, and protective agent surface is without substantially coming off;Will examination The protective agent of sample is overlapped with aluminium foil former material, in being placed in heat-sealing instrument, is sealed (heat seal condition:200 DEG C of temperature, pressure 0.2Mpa, Time 1s), taking-up lets cool, and sample is separated with aluminium foil former material, and observation protective agent surface is without obvious stick-down.
Finally illustrate, above example is only unrestricted to illustrate technical scheme, although with reference to compared with Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention Art scheme is modified or equivalent, and without deviating from the objective and scope of technical solution of the present invention, it all should cover at this In the middle of the right of invention.

Claims (10)

1. the aqueouss OP protective agent of medical packaging is used for, it is characterised in that be made up of following mass percent component:Anionic Polyaminoester emulsion 40%~49.5%, volume fraction is 95% ethanol solution 25%~30%, deionized water 25%~30% With antiplastering aid 0.2%~2%;
The Polyurethane Emulsion of Negative-ion Type is prepared from by following mass percent component:Polyhydric alcohol 9.6%~14%, bis-phenol S types epoxy resin 1.2%~1.75%, diisocyanate 5%~7.5%, polyalcohols chain extender 0.8%~2.25%, parent Water chain extender 0.8%~1.5%, fatty amines chain extender 0.02%~0.125%, catalyst 0.01%~0.025% and go Ionized water 75%~80%.
2. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the antiplastering aid is wax breast Liquid.
3. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the polyhydric alcohol is polyester One or more in polyhydric alcohol, polyether polyol, benzoic anhydride polyester polyol, polycaprolactone polyol, polycarbonate polyol.
4. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the diisocyanate is Toluene di-isocyanate(TDI), 1,6- hexamethylene diisocyanates, isoflurane chalcone diisocyanate, diphenylmethane diisocyanate One kind in ester, XDI, naphthalene -1,5- diisocyanate, tetramethylxylylene diisocyanate Or it is various.
5. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the polyalcohols chain extension Agent be ethylene glycol, Propylene Glycol, neopentyl glycol, 1,6- hexanediol, diethylene glycol, dipropylene glycol, 3- methyl isophthalic acids, 5- pentanediols, 1, 3- butanediols, BDO, diglycol, in trimethylolpropane, dihydromethyl propionic acid, dimethylolpropionic acid Plant or various.
6. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the hydrophilic chain extender is Ethylenediamine base ethylsulfonic acid sodium.
7. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the fatty amines chain extension Agent is ethylenediamine, isophorone diamine and 4,4 '-diaminourea -3,3 ' one or more in-dichloro diphenyl methane.
8. the aqueouss OP protective agent of medical packaging is used for according to claim 7, it is characterised in that the fatty amines chain extension Agent is by ethylenediamine, isophorone diamine and 4,4 '-diaminourea -3,3 '-dichloro diphenyl methane is according to 3:1:1 quality is than proportioning Into.
9. the aqueouss OP protective agent of medical packaging is used for according to claim 1, it is characterised in that the catalyst is February One or more in dilaurylate, stannous octoate, isooctyl acid bismuth.
10. the protectant preparation method of aqueouss OP for medical packaging described in claim 1, it is characterised in that include as Lower step:
A. the preparation of Polyurethane Emulsion of Negative-ion Type:By polyhydric alcohol and bisphenol-s epoxy resin at a temperature of 100 DEG C~120 DEG C Vacuum dehydration 2h, is cooled to 70 DEG C~80 DEG C, adds 0.5~1h of di-isocyanate reaction, add polyalcohols chain extender and Catalyst, reacts 3~5h at a temperature of 70 DEG C~80 DEG C, and period adds and adjusted equivalent to the acetone of 1~2.5 times of reactant liquor quality The viscosity of performed polymer, then it is cooled to 40 DEG C~45 DEG C, hydrophilic chain extender 10~25min of insulation reaction is added, add reactant liquor matter 3~5 times of water emulsification of amount, adding fatty amines chain extender carries out rear 30~60min of chain extension, vacuum distillation go out acetone obtain it is cloudy from Subtype polyaminoester emulsion;
B. the protectant preparation of aqueouss OP:By aqueous polyurethane emulsion obtained in step A and ethanol solution, deionized water and anti-stick Agent is mixed and stirred for uniformly, obtains final product the aqueouss OP protective agent for medical packaging.
CN201611049542.3A 2016-11-25 2016-11-25 Water-based OP protecting agent for pharmaceutical packaging and preparation method thereof Pending CN106590392A (en)

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CN104017532A (en) * 2014-06-27 2014-09-03 重庆中科力泰高分子材料股份有限公司 High-strength solvent-free polyurethane adhesive and preparation method thereof
CN105086915A (en) * 2015-08-31 2015-11-25 重庆中科力泰高分子材料股份有限公司 Aqueous VC binder used for pharmaceutical packaging and preparation method thereof
CN105131243A (en) * 2015-08-31 2015-12-09 重庆中科力泰高分子材料股份有限公司 Epoxy-modified sulfonic waterborne polyurethane emulsion and preparing method and application thereof

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CN103450778A (en) * 2013-08-20 2013-12-18 广东新供销天保再生资源发展有限公司 Waterborne OP protective agent for PTP aluminum foils for foods and drugs and preparation method thereof
CN104017532A (en) * 2014-06-27 2014-09-03 重庆中科力泰高分子材料股份有限公司 High-strength solvent-free polyurethane adhesive and preparation method thereof
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