CN100357374C - Water insoluble modified polyvinyl alcohol coating liquid and its producing process - Google Patents
Water insoluble modified polyvinyl alcohol coating liquid and its producing process Download PDFInfo
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- CN100357374C CN100357374C CNB2005100658426A CN200510065842A CN100357374C CN 100357374 C CN100357374 C CN 100357374C CN B2005100658426 A CNB2005100658426 A CN B2005100658426A CN 200510065842 A CN200510065842 A CN 200510065842A CN 100357374 C CN100357374 C CN 100357374C
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- water
- modified pva
- polyvinyl alcohol
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- pva paint
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000007788 liquid Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 title description 5
- 230000008569 process Effects 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003973 paint Substances 0.000 claims description 56
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000007822 coupling agent Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- -1 inorganics Substances 0.000 claims description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 230000003750 conditioning effect Effects 0.000 claims description 19
- 239000004927 clay Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000004902 Softening Agent Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 6
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 230000004888 barrier function Effects 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000003205 fragrance Substances 0.000 abstract description 2
- 238000002310 reflectometry Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 21
- 210000002469 basement membrane Anatomy 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 13
- 230000000149 penetrating effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种不溶于水的改性聚乙烯醇涂布液及其制作工艺。本发明的产品是由聚乙烯醇、调节剂、无机物、交连剂、催化剂和水组成的。本发明制作工艺是：将聚乙烯醇、调节剂、无机物和水充分混合后，升温、搅拌，待温度达到90-95℃时保温，使聚乙烯醇充分溶解后，待温度降至常温后，再加入交连剂，充分搅拌即得本发明产品的A组分；待开始使用前，再加入本发明产品的B组分：催化剂，充分搅拌。本发明的产品不溶于水，具有很好的可加工性，成膜后的耐水性，对紫外光和红外光的反射性，耐磨性，阻透性，和与基膜的粘接性。其氧气透过量降低了10倍以上，水蒸气透过量降低了5倍以上。能满足对一切需要阻隔性包装的产品的需要，且大大延长了被包装产品的保质期，并具有出色的保香性。The invention discloses a water-insoluble modified polyvinyl alcohol coating liquid and a preparation process thereof. The product of the invention is composed of polyvinyl alcohol, regulator, inorganic matter, cross-linking agent, catalyst and water. The production process of the present invention is: after fully mixing polyvinyl alcohol, regulator, inorganic matter and water, heating up and stirring, and keeping warm when the temperature reaches 90-95°C, after the polyvinyl alcohol is fully dissolved, after the temperature drops to normal temperature , and then add cross-linking agent, fully stirred to obtain the A component of the product of the present invention; before starting to use, then add the B component of the product of the present invention: catalyst, and fully stirred. The product of the invention is insoluble in water, has good processability, water resistance after film formation, reflectivity to ultraviolet light and infrared light, wear resistance, barrier property, and adhesion to base film. The oxygen transmission rate is reduced by more than 10 times, and the water vapor transmission rate is reduced by more than 5 times. It can meet the needs of all products that require barrier packaging, and greatly prolongs the shelf life of the packaged products, and has excellent fragrance retention.
Description
One, affiliated technical field
The invention belongs to a kind of modified PVA paint and manufacture craft thereof.
Two, background technology
In separated packaging material, PVAC polyvinylalcohol is that a kind of polyhydroxylated polymer, its molecular formula are CH
2-CHOHn, water-absorbent is strong, can be water-soluble, because the effect of its intermolecular hydrogen bonding, the compactness height, barrier property is good, but its fusing point height and decomposition temperature is low, because these constructional features of PVA make it be difficult to thermoplasticity processing.Commercially available PVA film adopts solution casting method production mostly at present, but the shortcoming that casting method is produced is: the production cycle is long, production efficiency is low, thickness, quality instability, the cost height, the water-absorbent of film is strong, can be water-soluble, thus limited applying of PVA film, but in the prior art, adopt melamine class to do properties-correcting agent, though solved water-fast problem after the PVA coating film forming, because in the modifying process of PVA, softening agent, additions such as properties-correcting agent are excessive, make its purity drop, Air permenbility increases, and gas barrier properties is subjected to temperature, humidity effect is very big, and this coating fluid quality guaranteed period is short, must in 3-7 hour, use up, otherwise, the jelly shape will be become, can't use, so it is prepared coating fluid only voluntarily and uses voluntarily, can't satisfy the requirement of using as merchandise sales; And must adopt expensive special-purpose coating machine to produce, yield poorly, the energy consumption height, its manufacturing cost height has restricted it and has used widely, is polypropylene PP at basement membrane, and thickness is 25 μ m, and polyethylene coating thickness is 10 μ m, and its oxygen transit dose is 3cm
3/ m
224h0.1Mpa steam penetrating capacity is 4g/m
224h.Adopt aluminium foil to make barrier layer, because it is opaque, so, can't be applied to the occasion that needs transparent container, moreover its price is also higher, can't satisfy the requirement of society to high-barrier class packing.
Three, summary of the invention
Purpose of the present invention solves the above-mentioned problems in the prior art exactly, a kind of water-fast modified PVA paint and manufacture craft thereof are provided, after this coating fluid was applied to the basement membrane film forming, its water-resistant coating can be good, and the transit dose of oxygen and water vapour is very low.
For finishing a kind of purpose of the present invention, its technical solution is: a kind of water-fast modified PVA paint, it is made up of polyvinyl alcohol, conditioning agent, inorganics, coupling agent, catalyzer and water.
Each components contents of above-mentioned described water-fast modified PVA paint, each component concentration all by weight percentage, polyvinyl alcohol is 1%-20%, conditioning agent is 1%-40%, inorganics is 0.01%-5%, coupling agent is 0.5%-10%, and catalyzer is 0.1%-5%, and water is 20%-97.39%.
The preferable range of above-mentioned described water-fast each components contents of modified PVA paint is: polyvinyl alcohol is that 8%-12.2%, conditioning agent are that 15%-20%, inorganics are that 0.5%-1%, coupling agent are that 4%-7%, catalyzer are that 2%-3%, water are 56.8%-70.47%.
Conditioning agent in the above-mentioned described water-fast modified PVA paint component is a methyl alcohol; Ethanol; Methyl alcohol and alcoholic acid mixture.
Inorganics in the above-mentioned described water-fast modified PVA paint component is a nano silicon oxide; Clay; Nano-titanium oxide; The mixture of clay and nano-titanium oxide; The mixture of clay and nano silicon oxide; The mixture of nano silicon oxide and nano-titanium oxide; The mixture of clay, nano silicon oxide and nano-titanium oxide.
Coupling agent in the above-mentioned described water-fast modified PVA paint component is terpolycyantoamino-formaldehyde resin, urea-formaldehyde resin.
Catalyzer in the above-mentioned described water-fast modified PVA paint component is hydrochloric acid, phosphoric acid.
Also can contain coupling agent in the above-mentioned described water-fast modified PVA paint component, account for the 0.01%-0.3% of whole total amount, its optimum ratio scope is 0.03%-0.2%, and it is aminosilane, titanate, vinyl silanes.
Also can contain softening agent in the above-mentioned described water-fast modified PVA paint component, account for the 0.05%-20% of whole total amount, its optimum ratio scope is 5%-15%, and it is in glycerol, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol, Sorbitol Powder, thanomin, tetramethylolmethane, polyglycerol, glycol ether, propylene glycol, oxirane compound, propylene oxide compound, glyceryl ether, the Racemic glycidol one or more.
Also can contain anti UV agent in the above-mentioned described water-fast modified PVA paint component, account for the 0.01%-1% of whole total amount, its optimum ratio scope is 0.2%-0.6%, and it is 783, BP-4.
The present invention also can add oxidation inhibitor, defoamer, tinting material, spices, tensio-active agent and nano inorganic powder etc. according to actual needs therein.
For finishing another object of the present invention, technical solution of the present invention is: the manufacture craft of above-mentioned described water-fast modified PVA paint is: behind polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, add coupling agent again, fully stir promptly get product of the present invention the A component; Before waiting to bring into use, add the B component of product of the present invention again: catalyzer, fully stir, promptly get the modified PVA paint that the present invention has good water resistance.
In the above-mentioned described water-fast modified polyvinyl alcohol manufacture craft: the proportioning of polyvinyl alcohol is 1%-20%, and preferable range is: 8%-12.2%; The proportioning of conditioning agent is 1%-40%, and preferable range is: 15%-20%; The proportioning of inorganics is 0.01%-5%, and preferable range is: 0.5%-1%; Catalyst proportion is 0.1%-5%, and preferable range is: 2%-3%; The coupling agent proportioning is 0.5%-10%, and preferable range is: 4%-7%; The water proportioning is 20%-97.39%, and preferable range is: 56.8%-70.47%.
In the above-mentioned described modified PVA paint manufacture craft, with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, can add proportioning simultaneously is 0.01%-0.3%, and preferable range is: the coupling agent of 0.03%-0.2%.
In the above-mentioned described modified PVA paint manufacture craft, when adding coupling agent, can add proportioning simultaneously is 0.01%-1%, and preferable range is: the anti UV agent of 0.2%-0.6%.
In the above-mentioned described modified PVA paint manufacture craft, when adding coupling agent, can add proportioning simultaneously is 0.05%-20%, and preferable range is the softening agent of 5%-15%.
In the above-mentioned described modified PVA paint manufacture craft, when adding coupling agent, can add proportioning simultaneously is 0.01%-1%, and preferable range is: the anti UV agent of 0.2%-0.6%, with proportioning be 0.05%-20%, preferable range is the softening agent of 5%-15%.
In the above-mentioned described modified PVA paint manufacture craft, with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, can add proportioning simultaneously is 0.01%-0.3%, and preferable range is: the coupling agent of 0.03%-0.2%; When adding coupling agent, can add proportioning simultaneously is 0.05%-20%, and preferable range is the softening agent of 5%-15%.
In the above-mentioned described modified PVA paint manufacture craft, with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, can add proportioning simultaneously is 0.01%-0.3%, and preferable range is: the coupling agent of 0.03%-0.2%; When adding coupling agent, can add proportioning simultaneously is 0.01%-1%, and preferable range is: the anti UV agent of 0.2%-0.6%.
In the above-mentioned described modified PVA paint manufacture craft, with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, can add proportioning simultaneously is 0.01%-0.3%, and preferable range is: the coupling agent of 0.03%-0.2%; When adding coupling agent, can add proportioning simultaneously is 0.01%-1%, and preferable range is: the anti UV agent of 0.2%-0.6% and proportioning are 0.05%-20%, and preferable range is the softening agent of 5%-15%.
Because the present invention has adopted such scheme, the unusual physicochemical characteristics such as coordination deficiency that make full use of the high surfactivity of inorganics nanoparticle, surface-area are big, surface energy is high, the surface is serious, the high and specific molecular structure characteristics of compactness in conjunction with the polyvinyl alcohol molecule can effectively prevent gas-permeable.And utilize the inorganics nanoparticle easily and the oxygen in the macromolecular material play bonding action, improve intermolecular bonding force, simultaneously be easy to be distributed in the space of macromolecular chain again, thereby increase substantially the intensity of material, toughness, ductility, compactness, elasticity, wear resistance, water tolerance, optical characteristics, mechanism such as thermostability, by inorganics is carried out surface treatment, mechanical dispersion etc., make in the space of its macromolecular chain that fully is distributed to polyvinyl alcohol, thereby effectively raise the workability of polyvinyl alcohol water solution, gas barrier after the film forming, water tolerance, reflectivity to UV-light and infrared light, wear resistance, the cementability of polyethylene coating and basement membrane.Compare with prior art, product of the present invention is applied to has good water tolerance after the film forming on the basement membrane, by in cold water, soaking more than 5 days, coating is still kept intact, dissolution phenomena does not appear, and have fabulous luminance brightness and smoothness, and the oxygen transit dose has reduced more than 10 times, and steam penetrating capacity has reduced more than 5 times.As being when being coated with this product thickness on the 18 μ m polypropylene BOPP films and being 2.5 μ m at thickness, its oxygen transit dose is 0.61cm
3/ m
224h0.1Mpa steam penetrating capacity is 0.86g/m
224h, its barrier be very near the level of aluminium foil and glass, and have very good transparency.Be the product of the present invention that coating only has 0.75 μ m on the polyester PET thin film of 12 μ m at thickness, its oxygen transit dose is 1.5cm
3/ m
224h0.1Mpa, be 23 ℃ in temperature, the oxygen transit dose when relative humidity is rh90% is 0.9cm
3/ (m
2Day).At thickness is on the kraft paper of 100 μ m during coating 1 μ m product of the present invention, and its oxygen transit dose is 1.2cm
3/ m
224h0.1Mpa.At thickness is on the polythene PE film of 95 μ m, and when being coated with the product of the present invention of 0.65 μ m, its oxygen transit dose is 3.55cm
3/ m
224h0.1Mpa.At thickness is the product of the present invention that applies 5 μ m thickness on the 65 μ m polythene PE basement membranes, and its oxygen transit dose is 0.31cm
3/ m
224h0.1Mpa steam penetrating capacity is 0.78g/m
224h.Its barrier is better than other multipolymer of the prior art far away, and manufacturing cost has very good cost/performance ratio than adopting EVOH to reduce nearly 10 times.The preservation period of coating fluid has also extended to 90 days, be very beneficial for the marketization of this product, just can satisfy the requirement of all kinds of needs barrier packagings simultaneously with compound the need double-layer structures (coating/basement membrane) of basement membrane, save a procedure, reduced the total thickness and the manufacturing cost of film, and nonpoisonous and tasteless.The penetration and promotion of this product is used, will promote the development of whole packing business, pack with this and can make present preservation period 30 days, adopt the fresh milk of UHT sterilization, extend to more than 120 days, and have outstanding fragrance protectiveness, beautiful with aluminium foil packing glass bottle packaging ratio fully, and price only for aluminium foil class packing 1/7th, great using value is arranged.Can adopt coating machine, dry compound machine, curtain coating compounding machine that coating fluid is coated on polythene PE film, polypropylene PP film, polymeric amide PA film, polyester PET thin film, sheet material and the paper, be used to pack varieties of food items, cigarette, clothes, sealing up for safekeeping of leatherware, industrial art, manuscript archive, industrial chemicals and intermediate, medicine, precision instrument, opticinstrument, eyeglass etc. are the article of deterioration by oxidation easily.
Four, embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1: present embodiment is by 8% polyvinyl alcohol, 15% methyl alcohol and alcoholic acid mixture, and 1% clay, 10% terpolycyantoamino-formaldehyde resin, 0.1% hydrochloric acid, 1% BP-4,0.05% oxirane compound and 64.85% water are formed.Behind polyvinyl alcohol, methyl alcohol and alcoholic acid mixture, clay and the water thorough mixing with said ratio, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, add terpolycyantoamino-formaldehyde resin, BP-4 and the oxirane compound of said ratio, fully stir; Before waiting to bring into use, add hydrochloric acid again, fully stir, promptly get the modified PVA paint that the present invention has good water resistance.Be the product of the present embodiment that coating 4 μ m are thick on the polypropylene PP basement membrane of 25 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 0.31cm
3/ m
224h0.1Mpa steam penetrating capacity is 0.78g/m
224h, coating is water insoluble.
Embodiment 2: present embodiment is by 7% polyvinyl alcohol, 30% ethanol, 5% nano silicon oxide, 0.5% terpolycyantoamino-formaldehyde resin, 5% phosphoric acid, 5% the oxirane compound and the mixture of glycol ether, 0.3% titanate and 47.2% water are formed.Behind polyvinyl alcohol, ethanol, nano silicon oxide, titanate and the water thorough mixing with said ratio, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, the mixture that adds terpolycyantoamino-formaldehyde resin, oxirane compound and the glycol ether of said ratio fully stirs; Before waiting to bring into use, add phosphoric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 2 μ m are thick on the polymeric amide PA basement membrane of 20 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 2.4cm
3/ m
224h0.1Mpa steam penetrating capacity is 1.2g/m
224h, coating is water insoluble.
Embodiment 3: present embodiment is made up of the mixture of 1% polyvinyl alcohol, 20% methyl alcohol, 0.01% clay and nano-titanium oxide, 2.9% terpolycyantoamino-formaldehyde resin, 3% phosphoric acid, 0.6% BP-4,0.01% aminosilane and 72.48% water.Behind mixture, aminosilane and the water thorough mixing with polyvinyl alcohol, methyl alcohol, clay and the nano-titanium oxide of said ratio, heat up, stir, insulation when treating that temperature reaches 90-95 ℃, polyvinyl alcohol is fully dissolved after, treat that temperature is reduced to normal temperature after, the terpolycyantoamino-formaldehyde resin and the BP-4 that add said ratio, fully stir, before waiting to bring into use, add phosphoric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 5 μ m are thick on the polythene PE basement membrane of 65 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 0.31cm
3/ m
224h0.1Mpa steam penetrating capacity is 0.78g/m
224h, coating is water insoluble.
Embodiment 4: present embodiment is made up of the mixture of 18% polyvinyl alcohol, 1% methyl alcohol, 3.02% nano-titanium oxide and nano silicon oxide, 5% urea-formaldehyde resin, 2.5% hydrochloric acid, 0.01% BP-4 and 70.47% water.Behind the mixture and water thorough mixing with polyvinyl alcohol, methyl alcohol, nano-titanium oxide and the nano silicon oxide of said ratio, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, the urea-formaldehyde resin and the BP-4 that add said ratio fully stir; Before waiting to bring into use, add hydrochloric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 1 μ m is thick on the paper of 110 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 1.9cm
3/ m
224h0.1Mpa coating is water insoluble.
Embodiment 5: present embodiment is by 20% polyvinyl alcohol, 35% ethanol, and 0.03% nano-titanium oxide, 3.97% urea-formaldehyde resin, 1% hydrochloric acid, the mixture of 20% glycerol, polyoxyethylene glycol and glycol ether and 20% water are formed.Behind polyvinyl alcohol, ethanol, nano-titanium oxide and the water thorough mixing with said ratio, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, the urea-formaldehyde resin that adds said ratio, the mixture of glycerol, polyoxyethylene glycol and glycol ether fully stirs; Before waiting to bring into use, add hydrochloric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.At thickness is on the polymeric amide PA basement membrane of 20 μ m, is coated with the product of the thick present embodiment of 4 μ m, and behind the drying and forming-film, its oxygen transit dose is 0.79cm
3/ m
224h0.1Mpa steam penetrating capacity is 1.1g/m
224h, coating is water insoluble.
Embodiment 6: present embodiment is by 11% polyvinyl alcohol, 5% methyl alcohol, alcoholic acid mixture, the mixture of 1.5% clay, nano-titanium oxide and nano silicon oxide, 7% terpolycyantoamino-formaldehyde resin, 3.3% phosphoric acid, 0.2% vinyl silanes, the mixture of 15% Diethylene Glycol, Sorbitol Powder and glyceryl ether, 0.2% 783 and 56.9% water is formed.With the polyvinyl alcohol of said ratio, methyl alcohol, alcoholic acid mixture, the mixture of clay, nano-titanium oxide and nano silicon oxide, vinyl silanes, after the water mixing, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, add the terpolycyantoamino-formaldehyde resin of said ratio, the mixture of Diethylene Glycol, Sorbitol Powder and glyceryl ether, with 783, fully stir; Before waiting to bring into use, add phosphoric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 2 μ m are thick on the polypropylene PP basement membrane of 18 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 3.55cm
3/ m
224h0.1Mpa steam penetrating capacity is 1.8g/m
224h, coating is water insoluble.
Embodiment 7: present embodiment is by 12.2% polyvinyl alcohol, 40% methyl alcohol, alcoholic acid mixture, 0.5% the clay and the mixture of nano silicon oxide, 4% terpolycyantoamino-formaldehyde resin, 2% phosphoric acid, 0.03% vinyl silanes and 41% water are formed.Polyvinyl alcohol with said ratio, methyl alcohol, alcoholic acid mixture, the mixture of clay and nano silicon oxide is after vinyl silanes and water mix, heat up, stir, insulation when treating that temperature reaches 90-95 ℃, polyvinyl alcohol is fully dissolved after, treat that temperature is reduced to normal temperature after, the terpolycyantoamino-formaldehyde resin that adds said ratio fully stirs; Before waiting to bring into use, add phosphoric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 2 μ m are thick on the polypropylene PP basement membrane of 18 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 2.5cm
3/ m
224h0.1Mpa steam penetrating capacity is 1.6g/m
224h, coating is water insoluble.
Embodiment 8: present embodiment is by 1% polyvinyl alcohol, 1% methyl alcohol, and 0.01% clay, 0.5% terpolycyantoamino-formaldehyde resin, 0.1% hydrochloric acid and 97.39% water are formed.With the polyvinyl alcohol of said ratio, methyl alcohol after clay and water mix, heats up, stirs, insulation when treating that temperature reaches 90-95 ℃, polyvinyl alcohol is fully dissolved after, treat that temperature is reduced to normal temperature after, add the terpolycyantoamino-formaldehyde resin of said ratio, fully stir; Before waiting to bring into use, add hydrochloric acid again, fully stir, promptly get the water-fast modified PVA paint of the present invention.Be the product of the present embodiment that coating 3 μ m are thick on the polypropylene PP basement membrane of 18 μ m at thickness, behind the drying and forming-film, its oxygen transit dose is 3.0cm
3/ m
224h0.1Mpa steam penetrating capacity is 1.9g/m
224h, coating is water insoluble.
Claims (19)
1. water-fast modified PVA paint, it contains:
Polyvinyl alcohol;
Be selected from the conditioning agent of methyl alcohol, ethanol or methyl alcohol and alcoholic acid mixture;
Be selected from the coupling agent of terpolycyantoamino-formaldehyde resin or urea-formaldehyde resin;
Water;
Be selected from the inorganics of the mixture of the mixture of mixture, nano silicon oxide and nano-titanium oxide of mixture, clay and nano-titanium oxide of nano silicon oxide, clay, nano-titanium oxide, clay and nano silicon oxide or clay and nano silicon oxide and nano-titanium oxide; With
Be selected from the catalyzer of hydrochloric acid or phosphoric acid.
2. water-fast modified PVA paint according to claim 1, it is characterized in that: described each components contents, each component concentration all by weight percentage, polyvinyl alcohol is 1%-20%, conditioning agent is 1%-40%, and inorganics is 0.01%-5%, and coupling agent is 0.5%-10%, catalyzer is 0.1%-5%, and water is 20%-97.39%.
3. water-fast modified PVA paint according to claim 1 is characterized in that: the described components contents that is equipped with is: polyvinyl alcohol is that 8%-12.2%, conditioning agent are that 15%-20%, inorganics are that 0.5%-1%, coupling agent are that 4%-7%, catalyzer are that 2%-3%, water are 56.8%-70.47%.
4. according to each described water-fast modified PVA paint of claim 1-3, it is characterized in that described coating fluid is divided into the A component before use: polyvinyl alcohol, conditioning agent, inorganics, water and coupling agent; And B component: catalyzer.
5. according to each described water-fast modified PVA paint of claim 1-3, it is characterized in that: also contain anti UV agent in the described modified PVA paint component, account for the 0.01%-1% of whole total amount, it is 783 or BP-4.
6. water-fast modified PVA paint according to claim 5, it is characterized in that: also contain softening agent in the described modified PVA paint component, account for the 0.05%-20% of whole total amount, it is in glycerol, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol, Sorbitol Powder, thanomin, tetramethylolmethane, polyglycerol, glycol ether, propylene glycol, oxirane compound, propylene oxide compound, glyceryl ether, the Racemic glycidol one or more, and condition is that each component concentration sum of described coating fluid is 100%.
7. water-fast modified PVA paint according to claim 6, it is characterized in that: also contain coupling agent in the described modified PVA paint component, account for the 0.01%-0.3% of whole total amount, it is aminosilane, titanate or vinyl silanes.
8. water-fast modified PVA paint according to claim 5, it is characterized in that: also contain coupling agent in the described modified PVA paint component, account for the 0.01%-0.3% of whole total amount, it is aminosilane, titanate or vinyl silanes, and the consumption sum of described coating fluid all the components is 100%.
9. according to each described water-fast modified PVA paint of claim 1-3, it is characterized in that: also contain softening agent in the described modified PVA paint component, account for the 0.05%-20% of whole total amount, it is in glycerol, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol, Sorbitol Powder, thanomin, tetramethylolmethane, polyglycerol, glycol ether, propylene glycol, oxirane compound, propylene oxide compound, glyceryl ether, the Racemic glycidol one or more, and the consumption sum of described coating fluid all the components is 100%.
10. water-fast modified PVA paint according to claim 9, it is characterized in that: also contain coupling agent in the described modified PVA paint component, account for the 0.01%-0.3% of whole total amount, it is aminosilane, titanate or vinyl silanes.
11. according to each described water-fast modified PVA paint of claim 1-3, it is characterized in that: also contain coupling agent in the described modified PVA paint component, account for the 0.01%-0.3% of whole total amount, it is aminosilane, titanate or vinyl silanes.
12. the manufacture craft of the described water-fast modified PVA paint of claim 4: it is characterized in that: behind polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing, heat up, stir, treat to be incubated when temperature reaches 90-95 ℃, after polyvinyl alcohol is fully dissolved, after treating that temperature is reduced to normal temperature, add coupling agent again, fully stir and promptly get the A component; Before waiting to bring into use, add the B component again: catalyzer, fully stir.
13. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, add the coupling agent that proportioning is 0.01%-0.3% simultaneously.
14. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: when adding coupling agent, add the anti UV agent that proportioning is 0.01%-1% simultaneously.
15. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: when adding coupling agent, add the softening agent that proportioning is 0.05%-20% simultaneously, the consumption sum of described coating fluid all the components is 100%.
16. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: when adding coupling agent, add the anti UV agent that proportioning is 0.01%-1% simultaneously, with proportioning be the softening agent of 0.05%-20%, the consumption sum of fast coating fluid all the components be 100%.
17. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, add the coupling agent that proportioning is 0.01%-0.3% simultaneously; When adding coupling agent, add the softening agent that proportioning is 0.05%-20% simultaneously, the consumption sum of described coating fluid all the components is 100%.
18. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, add the coupling agent that proportioning is 0.01%-0.3% simultaneously; When adding coupling agent, add the anti UV agent that proportioning is 0.01%-1% simultaneously, the consumption sum of described coating fluid all the components is 100%.
19. the manufacture craft of water-fast modified PVA paint according to claim 12: it is characterized in that: with polyvinyl alcohol, conditioning agent, inorganics and water thorough mixing the time, add the coupling agent that proportioning is 0.01%-0.3% simultaneously; When adding coupling agent, adding anti UV agent and the proportioning that proportioning is 0.01%-1% simultaneously is the softening agent of 0.05%-20%, and the consumption sum of described coating fluid all the components is 100%.
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| CNB2005100658426A CN100357374C (en) | 2004-04-12 | 2005-04-11 | Water insoluble modified polyvinyl alcohol coating liquid and its producing process |
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|---|---|---|---|
| CN200410034458 | 2004-04-12 | ||
| CN200410034458.5 | 2004-04-12 | ||
| CNB2005100658426A CN100357374C (en) | 2004-04-12 | 2005-04-11 | Water insoluble modified polyvinyl alcohol coating liquid and its producing process |
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| CN100357374C true CN100357374C (en) | 2007-12-26 |
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| CN101280141B (en) * | 2007-04-06 | 2010-11-10 | 刘建林 | Non-aqueous high-obstructing coating liquid and coat thereof |
| CN101481565B (en) * | 2008-01-07 | 2012-07-04 | 刘建林 | Aqueous high isolation coating solution and boiling resistant high isolation coating obtained thereby |
| CN104558656A (en) * | 2014-12-04 | 2015-04-29 | 南宁市金装塑料彩印有限公司 | Method for preparing high barrier thin film by using modified polyvinyl alcohol |
| CN115368595A (en) * | 2021-05-18 | 2022-11-22 | 华南理工大学 | Polyvinyl alcohol organic dielectric layer and preparation method and application thereof |
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| CN1303895A (en) * | 1999-12-09 | 2001-07-18 | 共同印刷株式会社 | Composition of gas barrier paint and gas barrier film |
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| CN1017918B (en) * | 1987-05-25 | 1992-08-19 | 埃米特放射技术股份有限公司 | Hollow shaft made of material with low elasticity modulus |
| CN1112878A (en) * | 1994-01-26 | 1995-12-06 | 吴羽化学工业株式会社 | Gas barrier laminated product and method for producing the same |
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| JPH101515A (en) * | 1996-04-16 | 1998-01-06 | Toppan Printing Co Ltd | Polyvinyl alcohol composition, method for producing the same, and packaging material |
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