CN101280140A - Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom - Google Patents
Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom Download PDFInfo
- Publication number
- CN101280140A CN101280140A CNA2007100907837A CN200710090783A CN101280140A CN 101280140 A CN101280140 A CN 101280140A CN A2007100907837 A CNA2007100907837 A CN A2007100907837A CN 200710090783 A CN200710090783 A CN 200710090783A CN 101280140 A CN101280140 A CN 101280140A
- Authority
- CN
- China
- Prior art keywords
- barrier
- coating fluid
- mixture
- barrier coating
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses non-aqueous barrier property coating liquid which contains barrier resin and non-aqueous organic solvent; the barrier coating layer has high abrasion resistance and/or scuffing resistance, and/or high temperature steaming resistance; meanwhile, good gas barrier property is maintained; the invention also relates to a high barrier property hollow container prepared by the non-aqueous barrier property coating liquid.
Description
Technical field
The present invention relates to a kind of high-obstructing coating liquid,, can obtain to have high-wearing feature and scratch resistance and/or high-barrier hollow container that can the withstand high temperatures boiling, for example bottle by this coating fluid in particular to a kind of non-aqueous high-obstructing coating liquid.The invention still further relates to the high-barrier hollow container that obtains by above-mentioned coating fluid.
Background technology
Though plastic containers, for example bottle has been widely used for wrap food and non-food product wrapping material, and plastics are bad to the barrier property of gas (as oxygen and carbon dioxide) or moisture usually.More requiring during wrap food has barrier to gases such as oxygen, carbonic acid gas.Oxygen in the environment causes Food Oxidation, can cause brown stain, becomes sour, spoiled and peculiar smell, generation mould etc., sometimes health is worked the mischief.Another problem not too serious but that have a commercial value is that if the plastic containers of packing soda pop etc. are not high to the barrier of carbonic acid gas, then beverage will become tasteless in storage process.
People have carried out many effort and have attempted to adopt some polymkeric substance to improve the barrier property of packing articles.Wherein typical polymers comprises polyvinylidene dichloride, polyvinyl alcohol and ethylene-vinyl alcohol copolymer.But the processing of these materials has difficulties.Wherein, the plasticization temperature of polyvinylidene dichloride and decomposition temperature are very approaching, processing difficulties and can't reclaiming, and polyvinylidene dichloride produces Dioxins and causes atmospheric pollution when burning disposal simultaneously.The decomposition temperature of polyvinyl alcohol is lower, and 160 ℃ begin etherificate and begin decomposition at 200 ℃, thereby are difficult to plasticizing processing.When adopting casting method to prepare polyethylene coating, it needs special-purpose coating apparatus and the production cycle is long, efficient is low and the quality instability, and owing to the use of relatively large softening agent and other properties-correcting agent, its gas barrier property reduces simultaneously.When adopting watersoluble modified PVA paint, although improved coating performance and can reach general packing instructions, but the suction and the water dissolution character that cause owing to the polyvinyl alcohol poly-hydroxy, it is fine and close crosslinked and not high with the adhesive power of base material that it can't be realized in water-based system, thereby can't possess scratch resistant performance and wear resistance, and can't stand high temperature steaming.Ethylene-vinyl alcohol copolymer (EVOH) is the improvement material of polyvinyl alcohol, but the barrier property of its oxygen and other gas is subjected to humidity effect equally easily, and has the shortcoming identical with polyvinyl alcohol when adopting the water-based coating fluid.
Therefore, this area still needs to provide a kind of high-obstructing coating liquid, can access the high-barrier hollow container that has high-wearing feature and scratch resistance and/or can stand high temperature steaming by it.
Summary of the invention
The inventor finds can overcome according to coating fluid of the present invention the above-mentioned shortcoming of existing coating fluid through secular further investigation.The hollow container that is obtained by coating fluid of the present invention has excellent high gas-obstructing character, low water vapor transmission rate (WVTR), high-wearing feature and scratch resistance and/or can stand high temperature steaming.And hollow container its barrier under high relative humidity that is obtained by coating fluid of the present invention changes very little.
According to an aspect of the present invention, provide a kind of hollow container that has high-wearing feature and scratch resistance and/or can stand high temperature steaming.Described high-barrier hollow container can obtain by the following coating fluid of coating, and it comprises:
Barrier resin; With
Non-aqueous organic solvent.
Unless otherwise prescribed, all numerical value or the expression at expression composition used herein, reaction conditions etc. is considered to can modify with word " approximately " in all cases.
Many numerical ranges are disclosed in this application.Because these scopes are successive, so they have comprised each value between minimum value and maximum value.Except specific embodiment, do not having under the situation about clearly stipulating in addition, specified in this application various numerical ranges are approximations.
The barrier resin that is applicable to high-obstructing coating liquid of the present invention is preferably polyvinyl alcohol type polymkeric substance, include but not limited to polyvinyl alcohol, ethene-polyvinyl alcohol mixture, ethylene-vinyl alcohol copolymer, propylene-polyvinyl alcohol mixture, polymeric amide-polyvinyl alcohol mixture, and they two or more mixture.The term of Shi Yonging " polyvinyl alcohol type polymkeric substance " comprises the multipolymer and the blend of polyvinyl alcohol, itself and other monomer and/or polymkeric substance herein, and the modified product of above-mentioned polymkeric substance.The term " polymer " of Shi Yonging herein " comprise homopolymer, multipolymer, and comprise prepolymer and oligopolymer.
In high barrier coating fluid of the present invention, operable solvent is non-aqueous organic solvent, especially polar organic solvent, includes but not limited to, amides is such as methane amide, methylformamide, dimethyl formamide, hydroxyethyl formamide, ethanamide; The sulfone class is such as tetramethylene sulfone, dimethyl sulfoxide (DMSO); Amine is such as thanomin, diethanolamine, trolamine and amine salt thereof; Unary alcohol is such as methyl alcohol, ethanol, Virahol; Polyalcohols is such as ethylene glycol, glycerol, polyoxyethylene glycol, triglycol; Ethers is such as methyl ether, ether, glycol ether, propylene glycol, glycidyl ether; Alkylene oxides is such as oxyethane, propylene oxide; Aromatic hydrocarbons is such as toluene, dimethylbenzene; Ketone is such as acetone and butanone or the like.Above-mentioned solvent can use separately, also can be used in combination with two or more as required.
In the process of preparation high barrier coating fluid of the present invention,, may there be water inevitably in the system owing to for example high-hydrophilic of polyvinyl alcohol resin.Simultaneously, when adjusting coating fluid system as described below, can use less water to be used to promote the dissolving of barrier resin and the drying of coating.The coating fluid system that comprises this less water belongs to the present invention equally.In this application, term " non-aqueous organic solvent " is intended to distinguish with conventional " aqueous solvent " system, and it not exclusively gets rid of the existence of less water, as long as solvent system is non-aqueous as a complete unit.For example, can contain 10wt% at the most in the system, for example the water of 1-5wt%.Preferably, high barrier coating fluid of the present invention does not have water basically.
According to a specific embodiments of the present invention, non-aqueous barrier coating fluid of the present invention comprises 0.1～25wt%, preferred 8%～12% barrier resin; With 75～99.9%wt%, preferred 88%～92% non-aqueous organic solvent, based on the gross weight meter of coating fluid.
Because hollow container can adopt higher coat-thickness, for example greater than 1 μ m (micron), thereby linking agent in described non-aqueous coating fluid not necessarily.But promote the crosslinked linking agent of polyvinyl alcohol resin from making the more firmly and more angle of tenable environment humidity of coating, preferably containing in the described non-aqueous coating fluid.Suitable crosslinking agent comprises, but be not limited to acrylamide, (methyl) vinylformic acid formicester, (methyl) Ethyl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid, aminoresin, water soluble amino resin, terpolycyantoamino-formaldehyde resin, melamine resin and derivative, urea-formaldehyde resin and derivative thereof, polymine, boric acid, borax etc.Above-mentioned linking agent can use separately, also can be used in combination with two or more.The content of above-mentioned linking agent in described coating fluid can be for 0.05～10%, be preferably 3～5%, based on the gross weight meter of coating fluid.
Non-aqueous coating fluid of the present invention also can contain catalyzer, to promote the reaction of polyvinyl alcohol and linking agent.Be applicable to that catalyzer of the present invention comprises, but be not limited to that mineral acid is such as hydrochloric acid, phosphoric acid; And other have the compound of promoter action, such as ceric ammonium nitrate, dicumyl peroxide, Potassium Persulphate, Ammonium Persulfate 98.5, sodium bisulfite.They can use separately, also can two or more be used in combination.The content of above-mentioned catalyzer in described coating fluid can be for 0.1～5wt%, be preferably 1～3wt%, based on the gross weight meter of coating fluid.
As required, can also contain nano-inorganic substance in the high barrier coating fluid of the present invention, for example, but be not limited to two or more mixture of nano silicon oxide, clay, nano-titanium oxide, nano zine oxide, nano phase ag_2 o, nano aluminium oxide, mica or they.In this application, term " nano-inorganic substance " is meant particle diameter at 1-1000nm, the particles of inorganic material of preferred 1-100nm.Above-mentioned nano-inorganic substance can account for about 0.001～5wt% of coating fluid gross weight, preferred 0.8-1wt%.
In addition, can also contain tensio-active agent in the high barrier coating fluid of the present invention.Be applicable to that tensio-active agent of the present invention comprises nonionogenic tenside, and ionic surface active agent, for example cats product, anion surfactant and zwitterionics.In a specific embodiments of the present invention, use fluorocarbon surfactant and/or hc-surfactant.The consumption of above-mentioned tensio-active agent can account for 0.001～4wt% of coating fluid gross weight, preferred 0.3～0.5wt%.
For improving ageing-resistant performance, can also contain anti UV agent in the high barrier coating fluid of the present invention.Its consumption can be 0.001～2wt% of coating fluid gross weight, preferred 0.2～0.3wt%.Can use anti UV agent well known in the art.As an example, can preferably use TINUVIN
783 and/or 788 (available from Ciba Specialty Chemicals, Inc. Switzerland) is used for high barrier coating fluid of the present invention as anti UV agent.In addition, can also use other anti UV agent known in the art.
According to a non-limiting embodiments of the present invention, non-aqueous barrier coating fluid of the present invention, comprise: 0.1～25wt% barrier resin, 0.001～5wt% nano-inorganic substance, 0.05～10wt% linking agent, 0.001～4wt% tensio-active agent, 0.1～5wt% catalyzer, 0.001～2wt% anti UV agent, 49～99.747wt% non-aqueous solvent, based on the gross weight meter of coating fluid.
In a preferred embodiment, non-aqueous obstruct coating fluid of the present invention, comprise: 8～12wt% barrier resin, 3～5wt% linking agent, 1%～3wt% catalyzer, 0.8～1wt% nano-inorganic substance, 0.3～0.5wt% tensio-active agent, 0.2～0.3wt% ultraviolet ray agent, 78.2～86.7wt% non-aqueous solvent, based on the gross weight meter of coating fluid.
High barrier coating fluid of the present invention also can add materials such as antiseptic-germicide, tinting material, spices as required therein.
According to a specific embodiments of the present invention, can adopt following coating processes to make high-barrier hollow container of the present invention, comprising:
I) provide the mixture of barrier resin and non-aqueous solvent, preferably be heated to 90 ℃～95 ℃, barrier resin fully is dissolved in forms coating fluid in the non-aqueous solvent;
Ii) coating fluid is applied to as required the internal surface and/or the outside surface of hollow container (for example bottle) respectively, makes coating drying (curing).
For the adhesivity of raising with the hollow container base material, can randomly carry out surface treatment to all types of plastic base material, make its surface energy be not less than 38 dyne.The treatment process that is suitable for includes, but not limited to one or more of corona treatment method, flame surface preparation, Surface Treatment with Plasma method, polishing method, chemical cleaning method and method of chemical treatment.
In addition, for the adhesivity of raising, before applying high-obstructing coating liquid, can also on hollow container, be coated with primary coat glue with the hollow container base material.The primary coat glue that is suitable for includes, but are not limited to polyurethanes, acrylic acid or the like, aminoresin class, Synolac class, epoxy resin primary coat glue, and two or more mixture in them.
Can use any conventional coating process to apply high-obstructing coating liquid of the present invention.For example, can use spraying, dip-coating, spin coating, blade coating, flow coat, roller coat, extrude etc.Preferably can adopt spraying, dip-coating.
As required, can on the high-barrier coating, add stopping off.The protective layer coated material comprises; but be not limited to polyurethanes coating, polyester coating, polyethylene kind coating, polypropylene-base coating, polyamide-based coating, acrylic coating, amino-resin coating, Synolac class coating, and they two or more mixture.
Be applicable to that drying mode of the present invention can adopt, for example heated drying and ultraviolet curing.
According to the present invention, can be any conventional plastic basis material with the hollow container base material of high-obstructing coating liquid coating of the present invention.For example, can include, but are not limited to polythene PE, polypropylene PP, polyester PET, polymeric amide PA, and they two or more mixture.The processing mode that can adopt includes, but are not limited to that individual layer is extruded, multi-layer co-extruded or injection moulding.
According to another preferred embodiment of the present invention, can adopt following coating processes to make high-barrier hollow container of the present invention, comprising:
I ') provides the mixture of barrier resin, nano-inorganic substance, non-aqueous solvent, preferably be heated to 90 ℃～95 ℃, make barrier resin fully be dissolved in the solvent, add linking agent, catalyzer, anti UV agent, tensio-active agent subsequently successively, and fully stirring makes it reaction, obtains barrier coating;
Ii ') coating fluid is applied to as required the internal surface and/or the outside surface of hollow container (for example bottle) respectively, makes coating drying (curing).
Be not wishing to be bound by theory, it is believed that high compactness and distinctive molecular structure owing to the polyvinyl alcohol resin molecule, they can stop the infiltration of gas effectively.By crosslinked in non-aqueous organic solvent system of the present invention,, can improve degree of crosslinking and increase it and the adhesive power of base material or undercoat with crosslinked comparing in aqueous solvent system.When using nano-inorganic substance, it is believed that these nano-inorganic substances can play bonding action with the oxygen on the polyvinyl alcohol resin main chain, improve force of cohesion, be easy to simultaneously be distributed in the space of macromolecular chain, thereby greatly improve the performance such as intensity, toughness, compactness, wear resistance, water tolerance, thermostability of gained coating.Operations such as protective layer can directly be printed, apply to cured coating without any processing.
After armor coated, described high-barrier hollow container can anti-high temperature steaming below 121 ℃.Even when the glue spread of high-obstructing coating liquid of the present invention only was 1 micron, its oxygen transit dose still can reach 0.0095ml/pkgday, preferably can reach 2g/m less than 0.01ml/pkgday, steam penetrating capacity
224h.And hollow container of the present invention is after the boiling and under the situation of high relative humidity, and its barrier properties for gases changes especially little.
Industrial applicibility
Hollow container cost by coating fluid manufacturing of the present invention is lower than vial, and well below the cost of silicon-dioxide vacuum evaporation container, metal pop can, multi-layer co-extruded hollow piece, thereby is very beneficial for market and uses.In addition, hollow container of the present invention is nonpoisonous and tasteless, thickness greatly attenuate, economize on resources, reduced cost, environmental protection and help reclaiming, when having made things convenient for the user, possess great using value, can use in a large number and the packing of all kinds of food that need to intercept, drinks, medicine, agricultural chemicals, military supplies articles for use, all kinds of oil product, industrial chemicals intermediate.
Below, further specify the present invention with non-limiting example.But it should be noted that it is limitation of the present invention that these embodiment should not be considered as.
Embodiment
In present specification and appended claims, unless expressly stated otherwise,, all parts and per-cent are all based on weight.
Test
The oxygen transit dose of being put down in writing is in an embodiment all measured according to standard GB/T1037-1988 according to the steam permeable amount that standard GB/T1038-2000 (isopiestic method) measures, put down in writing.
Embodiment 1
In the present embodiment, by with 8% polyvinyl alcohol 1788,92% methyl alcohol and dimethyl sulfoxide (DMSO) mixed solution (ratio of mixture: 30%-70%) put into heatable container and be warming up to 95 ℃ and stir, treat its thoroughly the dissolving back and high-obstructing coating liquid A of the present invention.
(thickness is: 100 μ m) carry out the low-temperature plasma surface treatment, its surface energy is reached more than 40 dyne to the PET bottle.The PET bottle is impregnated among the high-obstructing coating liquid A, makes coating fluid thoroughly soak into its back, surface and take out.Carry out ultra red ray drying, obtain the high-barrier coating of coating 1 micron thickness.Obtain the high-barrier hollow container thus, its oxygen transit dose is: 0.0095ml/pkgday, and wherein the oxygen transit dose of PET bottle itself is: 4ml/pkgday, and have very good scratch resistance and wear resistance.
Embodiment 2
In the present embodiment, (the nanoparticle diameter is: 60 nanometers by the mixture with ethylene-vinyl alcohol copolymer (EVOH) 3803DN (The Nippon Synthetic Chemical Industry Co., Ltd), nano silicon oxide and the nano phase ag_2 o of following proportioning, ratio of mixture: 60%-40%), and the mixed solution of triglycol, ethanol and tetramethylene sulfone (ratio of mixture: 15%-15%-70%) behind the thorough mixing, put into heatable container and be warming up to 95 ℃ and stirring.Treat that it thoroughly adds aminoresin, phosphoric acid, hc-surfactant FT-TYPEN (ICI company, the U.S.), TINUVIN in the dissolving back
783, obtain high-obstructing coating liquid B of the present invention.
(thickness is: 250 μ m) carry out the flame surface treatment, its surface energy is reached more than 38 dyne to the PE bottle.B sprays on the PE bottle with barrier coating, is coated with the high-barrier coating of 1 micron thickness (dried thickness).Carry out heated drying, spraying one deck UV gloss oil on coating adopts UV curing again.Obtain the high-barrier hollow container thus, its oxygen transit dose is: 0.0307ml/pkgday.Bottle is put into 100 ℃ hot water to be boiled a hour coating and not to have destruction, after treating the dry cooling of bottle, its oxygen transit dose is: 0.037ml/pkgday, and wherein the oxygen transit dose of PE bottle itself is: 5ml/pkgday, and have very good scratch resistance and wear resistance.
Embodiment 3
In the present embodiment, (poly molecular weight is: 130,000, the molecular weight of polyvinyl alcohol is: 250,000 by the polyethylene-polyvinyl alcohol mixture with following proportioning, ratio of mixture: 10%-90%), (the nanoparticle diameter is: 60 nanometers for the mixture of nano aluminium oxide and nano-titanium oxide, ratio of mixture: 60%-40%), the mixed solution of trolamine, butanone and dimethyl formamide (ratio of mixture: 60%-10%-30%) behind the thorough mixing, put into heatable container and be warming up to 95 ℃ and stir.Treat that it thoroughly adds the mixture (ratio of mixture: 35%-60%-5%), Potassium Persulphate, fluorocarbon surfactant FS-300 (Shanghai converge general chemistry), TINUVIN of vinylformic acid, methyl methacrylate, acrylamide in the dissolving back
788, obtain high-obstructing coating liquid C of the present invention.
(thickness is to the PP bottle; 200 μ m) carry out the chemical solvents surface treatment, its surface energy is reached more than 38 dyne.Dip-coating one deck urethane primary coat glue on bottle sprays to barrier coating fluid C on the primary coat glue-line then earlier, is coated with the high-barrier coating of 1 micron thickness (dried thickness).Carry out heated drying, spraying one deck polyester gloss oil on coating adopts heated drying again.Obtain the high-barrier hollow container thus, its oxygen transit dose is: 0.02ml/pkgday.Hour coating of hot water boiling that bottle is put into 121 ℃ does not have destruction, after treating the dry cooling of bottle, its oxygen transit dose is: 0.02ml/pkgday, and wherein the oxygen transit dose of PP bottle itself is: 3.8ml/pkgday, and have very good scratch resistance and wear resistance.
Embodiment 4
In the present embodiment, by with polypropylene-polyvinyl alcohol mixture, nano silicon oxide and the nano phase ag_2 o of following proportioning, the mixture of clay (PP: Shanghai Petrochem. General Plant, molecular weight: 2,000 ten thousand; PVA: Beijing Organic Chemical Plant, ratio of mixture: 50%-20%-20%-10%), the mixed solution of propylene glycol, glycidyl ether, toluene (ratio of mixture: 50%-25%-25%) mix, put into heatable container and be warming up to 95 ℃ and stirring., TINUVIN treat it thoroughly after the dissolving, add the mixture (ratio of mixture: 20%-50%-30%), hc-surfactant (trade mark: FT-TYPEN, manufacturer: of polymine, boric acid and borax ICI Americals, Inc)
783, obtain high-obstructing coating liquid D of the present invention.
(thickness is: the hollow container surface treatment of polishing 300 μ m) reaches more than 38 dyne its surface energy to the PE bottle.D sprays on the PE hollow container with the barrier coating fluid, is coated with the high-barrier coating of 1 micron thickness (dried thickness).Carry out heated drying, spraying one deck Nylon paint RP-1901 (Hebei Barrier Packaging Materials Co., Ltd., thickness: dry back 2 microns) on coating adopts heated drying again.Obtain high-barrier hollow container of the present invention thus, its oxygen transit dose is: 0.015ml/pkgday, wherein the oxygen transit dose of PE bottle itself is: 5ml/pkgday.Bottle is put into 100 ℃ hot water boils a hour coating and do not have destruction, treat the dry cooling of bottle after, its oxygen transit dose is: 0.015ml/pkgday, and have very good scratch resistance and wear resistance.
Embodiment 5
In the present embodiment, by polymeric amide-polyvinyl alcohol mixture JP-1904 (Hebei Brill company with following proportioning, molecular weight: 14000, ratio of mixture: 34%-66%), the mixed solution (ratio of mixture: 20%-30%-50%) mix of nano silicon oxide (25 nanometer), hydroxyethyl formamide, ethanolamine salt and water, put into heatable container and be warming up to 95 ℃, and stir., TINUVIN treat that it thoroughly adds the mixture (ratio of mixture: 70%-30%), sodium bisulfite, hc-surfactant (trade mark: FT-TYPEN, manufacturer: of boric acid and borax ICI Americals, Inc) in the dissolving back
783, obtain high-obstructing coating liquid E of the present invention.
(thickness is: 500 μ m) carry out the flame surface treatment, its surface energy is reached more than 38 dyne to the PE bottle.E sprays on the PE bottle with the barrier coating fluid, is coated with the high-barrier coating of 1 micron thickness (dried thickness).Carry out heated drying, again the mixture GY-99 of spraying one deck aminoresin and Synolac (Hebei Brill company, molecular weight: 4,000 ten thousand), adopt heated drying on coating.Obtain the high-barrier hollow container thus, its oxygen transit dose is: 0.025ml/pkgday, wherein the oxygen transit dose of PE bottle itself is: 5ml/pkgday.Bottle is put into 100 ℃ hot water boils a hour coating and do not have destruction, treat the dry cooling of bottle after, its oxygen transit dose is: 0.025ml/pkgday, and have very good scratch resistance and wear resistance.
Though the present invention is described with regard to some embodiment, the present invention is not limited to disclosed specific embodiments or embodiment, but wishes to cover by the purport of the present invention of appended claims definition and the whole improved forms in the scope.
Claims (11)
1. barrier coating fluid, it comprises:
Barrier resin; With
Non-aqueous organic solvent.
2. the barrier coating fluid of claim 1, wherein said barrier resin is a polyvinyl alcohol resin, be preferably selected from polyvinyl alcohol, ethene-polyvinyl alcohol mixture, ethylene-vinyl alcohol copolymer, propylene-polyvinyl alcohol mixture, polymeric amide-polyvinyl alcohol mixture, and they two or more mixture.
3. the barrier coating fluid of claim 1, wherein said non-aqueous solvent is selected from amides, such as methane amide, methylformamide, dimethyl formamide, hydroxyethyl formamide, ethanamide; The sulfone class is such as tetramethylene sulfone, dimethyl sulfoxide (DMSO); Amine is such as thanomin, diethanolamine, trolamine and amine salt thereof; Unary alcohol is such as methyl alcohol, ethanol, Virahol; Polyalcohols is such as ethylene glycol, glycerol, polyoxyethylene glycol, triglycol; Ethers is such as methyl ether, ether, glycol ether, propylene glycol, glycidyl ether; Alkylene oxides is such as oxyethane, propylene oxide; Aromatic hydrocarbons is such as toluene, dimethylbenzene; Ketone, such as acetone and butanone, and they two or more mixture.
4. the barrier coating fluid of claim 1 comprises:
0.1 the barrier resin of～25wt%; With
The solvent of 75～99.9wt%,
Gross weight meter based on coating fluid.
5. the barrier coating fluid of claim 1, also contain linking agent, be preferably selected from acrylamide, (methyl) vinylformic acid formicester, (methyl) Ethyl acrylate, (methyl) glycidyl acrylate, (methyl) vinylformic acid, aminoresin, water soluble amino resin, terpolycyantoamino-formaldehyde resin, melamine resin and derivative, urea-formaldehyde resin and derivative thereof, polymine, boric acid, borax, and they two or more mixture.
6. the barrier coating fluid of claim 5 also contains catalyzer, is preferably selected from mineral acid such as hydrochloric acid, phosphoric acid; Ceric ammonium nitrate, dicumyl peroxide, Potassium Persulphate, Ammonium Persulfate 98.5, sodium bisulfite, and they two or more mixture.
7. the barrier coating fluid of claim 1 also contains nano-inorganic substance, is preferably selected from two or more mixture of nano silicon oxide, clay, nano-titanium oxide, nano zine oxide, nano phase ag_2 o, nano aluminium oxide, mica or they; Tensio-active agent is preferably selected from fluorocarbon surfactant and/or hc-surfactant; And/or anti UV agent, be preferably selected from
783 and/or 788.
8. the barrier coating fluid of claim 7 comprises:
0.1～25wt% barrier resin, 0.001～5wt% nano-inorganic substance, 0.05～10wt% linking agent, 0.001～4wt% tensio-active agent, 0.1～5wt% catalyzer, 0.001～2wt% anti UV agent, 49～99.747wt% non-aqueous solvent are based on the gross weight meter of coating fluid.
9. the high barrier coating that is obtained by each barrier coating fluid of claim 1-8 is preferably the oxygen permeability with 0.0095ml/pkgday, and wherein coat-thickness is: 1～3 μ m, and base material thickness is; 100～500 μ m.
10. barrier hollow container comprises:
A) hollow container base material is preferably selected from polythene PE, polypropylene PP, polyester PET, polymeric amide PA, and they two or more mixture;
B) Ren Xuan primary coat glue is preferably selected from polyurethanes, acrylic acid or the like, aminoresin class, Synolac class, epoxy resin primary coat glue, and two or more mixture in them;
C) the high barrier coating that obtains by each barrier coating fluid of claim 1-8; With
D) Ren Xuan protective layer coating is preferably selected from polyurethanes, polyester, polyethylene kind, polypropylene-base, polyamide-based, acrylic acid or the like, aminoresin, Synolac class, and they two or more mixture.
11. the method for the barrier hollow container of preparation claim 10 comprises:
I) provide the mixture of barrier resin and non-aqueous solvent, preferably be heated to 90 ℃～95 ℃, barrier resin fully is dissolved in forms coating fluid in the non-aqueous solvent;
Ii) randomly the hollow container base material is carried out surface treatment, be preferably selected from corona treatment method, flame surface preparation, Surface Treatment with Plasma method, polishing method, chemical cleaning method and the method for chemical treatment one or more;
Gummed primary coat glue is applied on the internal surface and/or outside surface of hollow container base material at the bottom of iii) randomly will being preferably selected from polyurethanes, acrylic acid or the like, aminoresin class, Synolac class, epoxy resin;
Iv) each barrier coating fluid of claim 1-8 is applied on the internal surface and/or outside surface of hollow container base material;
V) solidify this barrier coating fluid; With
Vi) randomly on the barrier coating, apply the protective layer coating, be preferably selected from polyurethanes, polyester, polyethylene kind, polypropylene-base, polyamide-based, acrylic acid or the like, aminoresin, Synolac class, and they two or more mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100907837A CN101280140B (en) | 2007-04-06 | 2007-04-06 | Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100907837A CN101280140B (en) | 2007-04-06 | 2007-04-06 | Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101280140A true CN101280140A (en) | 2008-10-08 |
| CN101280140B CN101280140B (en) | 2011-09-07 |
Family
ID=40012816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100907837A Expired - Fee Related CN101280140B (en) | 2007-04-06 | 2007-04-06 | Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101280140B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280141B (en) * | 2007-04-06 | 2010-11-10 | 刘建林 | Non-aqueous high-obstructing coating liquid and coat thereof |
| CN104946037A (en) * | 2015-07-16 | 2015-09-30 | 天津科技大学 | Coating liquid for preparing uvioresistant polyester film and preparation method thereof |
| CN110774713A (en) * | 2019-10-31 | 2020-02-11 | 厦门长塑实业有限公司 | Coating type high-barrier bidirectional-stretching polylactic acid film and preparation method thereof |
| CN111452163A (en) * | 2020-03-17 | 2020-07-28 | 广州傲胜人造草股份有限公司 | Coated cork granule and preparation method thereof |
| CN111868134A (en) * | 2018-03-27 | 2020-10-30 | 美利肯公司 | Compositions and methods for reducing aldehyde content in polyurethane foams |
| CN112277417A (en) * | 2020-10-29 | 2021-01-29 | 广东宝佳利绿印股份有限公司 | Three-layer co-extrusion high-transparency high-barrier BOPET film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280141B (en) * | 2007-04-06 | 2010-11-10 | 刘建林 | Non-aqueous high-obstructing coating liquid and coat thereof |
-
2007
- 2007-04-06 CN CN2007100907837A patent/CN101280140B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280141B (en) * | 2007-04-06 | 2010-11-10 | 刘建林 | Non-aqueous high-obstructing coating liquid and coat thereof |
| CN104946037A (en) * | 2015-07-16 | 2015-09-30 | 天津科技大学 | Coating liquid for preparing uvioresistant polyester film and preparation method thereof |
| CN111868134A (en) * | 2018-03-27 | 2020-10-30 | 美利肯公司 | Compositions and methods for reducing aldehyde content in polyurethane foams |
| CN111868134B (en) * | 2018-03-27 | 2022-07-05 | 美利肯公司 | Compositions and methods for reducing aldehyde content in polyurethane foams |
| CN110774713A (en) * | 2019-10-31 | 2020-02-11 | 厦门长塑实业有限公司 | Coating type high-barrier bidirectional-stretching polylactic acid film and preparation method thereof |
| CN111452163A (en) * | 2020-03-17 | 2020-07-28 | 广州傲胜人造草股份有限公司 | Coated cork granule and preparation method thereof |
| CN112277417A (en) * | 2020-10-29 | 2021-01-29 | 广东宝佳利绿印股份有限公司 | Three-layer co-extrusion high-transparency high-barrier BOPET film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101280140B (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101280141B (en) | Non-aqueous high-obstructing coating liquid and coat thereof | |
| CN101280140B (en) | Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom | |
| CN101481565B (en) | Aqueous high isolation coating solution and boiling resistant high isolation coating obtained thereby | |
| JP7116208B2 (en) | Polyvinyl alcohol and ethylene vinyl alcohol copolymer barrier coating | |
| CA2737036C (en) | Improved barrier layer | |
| JPH0476378B2 (en) | ||
| CN1952027A (en) | Water-insoluble modified polyvinyl alcohol coating liquor and its preparation process | |
| JP2005522573A (en) | Coating composition containing epoxide additive and structure coated | |
| CN104497385A (en) | Aminated graphene oxide/high-density polyethylane nano composite membrane and preparation method thereof | |
| CN102140272B (en) | Ink resin composite used for plastic gravure printing and preparation method thereof | |
| Nuruddin et al. | Gas and water vapor barrier performance of cellulose nanocrystal–citric acid-coated polypropylene for flexible packaging | |
| CN105505020A (en) | Environment-friendly ceramic simulating coating and spraying method thereof | |
| CN102718988B (en) | Polybutylece terephthalate (PBT) coated functional powder and preparation method thereof | |
| CN108264678B (en) | Hydrophobic bubble film and preparation method thereof | |
| CN103998516A (en) | Gas barrier resin composition and gas barrier composite film | |
| Horakova et al. | Investigation of Adhesion Between Metal and Plasma‐Modified Polyethylene | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN106700199A (en) | Wear-resistant plastic bag and processing technology therefor | |
| CN107141816B (en) | A kind of high-barrier biodegradation material and preparation method thereof and application | |
| JP2005248026A (en) | Humidity-preventing coating agent and humidity prevention-processed article by coating the same | |
| CN108047474A (en) | A kind of uvioresistant, the packing film of high barrier and preparation method | |
| JP2001234124A (en) | Gas barrier coating material, method for manufacturing gas barrier coating material, gas barrier film, method for manufacturing gas barrier film, laminate film for easy-to-tear packaging material and laminate film for liquid food package material | |
| CN104892990A (en) | Anti-static full degradable film and preparation method thereof | |
| JP5226175B2 (en) | Moisture-proof coating agent, moisture-proof composition, moisture-proof film and method for producing the same | |
| AU2019202338B2 (en) | Surface Protection Articles and Methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110907 Termination date: 20130406 |