CN1687264A - Method for fabricating obstruction coating film of modified polyvinyl alcohol and coating film produced thereby - Google Patents
Method for fabricating obstruction coating film of modified polyvinyl alcohol and coating film produced thereby Download PDFInfo
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- CN1687264A CN1687264A CN 200510066498 CN200510066498A CN1687264A CN 1687264 A CN1687264 A CN 1687264A CN 200510066498 CN200510066498 CN 200510066498 CN 200510066498 A CN200510066498 A CN 200510066498A CN 1687264 A CN1687264 A CN 1687264A
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Abstract
The present invention provides a modified polyvinyl alcohol high-barrier coating film and its preparation method. Said method uses PVOH as raw material, and adopts the following steps: after the raw material is catalyzed, making modification, then adding adjuvant to make them into coating material, applying said coating material on the base film so as to form high-barrier coating film. After the PVOH molecular chain is partially catalyzed and condensed, the hydrogen bond action force in the molecular can be reduced, so that its water-proof property can be greatly raised.
Description
Technical field
The present invention relates to a kind of environment protection soft packing coated film, is a kind of high barrier packaging film and manufacture method thereof, is applied to the packing of products such as high-end food, medicine, cigarette.
Background technology
The leading product of high-barrier flexible packing material are polyvinylidene dichloride (PVDC is hereinafter to be referred as PVDC) class composite membranes at present, are applied to the packing of products such as high-end food, medicine, cigarette.The PVDC molecular symmetry is good, forms crystallization easily, contains a large amount of polarity chlorine atoms in the molecule again, and intermolecular magnetism is strengthened greatly, arranges closely intrinsic good barrier.But also, following shortcoming is arranged also because the PVDC molecule contains a large amount of chlorine atoms:
(1) PVDC is difficult for natural decomposition, degraded, can produce obnoxious flavour when being used as the waste product burning, and its waste can pollute environment.
(2) the PVDC series products can decomposite a small amount of hydrogen chloride gas in wrapping process, and packaging machine is got rusty.
(3) in the PVDC coating process, can producers' health be worked the mischief.
Because environmental protection pressure serious day by day, PVDC becomes the problem that people pay close attention to once more, press for a kind ofly can not pollute environment, non-harmful high-barrier flexible packing material.Therefore, development of new high barrier environment-friendly package material is trend of the times to replace PVDC, and this problem becomes the focus of China's packaging industry.Polyvinyl alcohol (Poly vinylealcohol, i.e. PVOH is hereinafter to be referred as PVOH) is the ideal material that replaces PVDC.Compare with PVDC, the PVOH series products can not produce obnoxious flavour when burning, also can not produce producers' health in the coating process to threaten, and under dry state, the barrier properties for gases of PVOH series products far is superior to the PVDC series products.
PVOH series products under the dry state has excellent oxygen resistance, but because intramolecularly contains the hydroxyl of a large amount of strongly hydrophilics, hygrometric state forms hydrogen bond with water down easily, and associates with water with the form of hydrogen bond, the variation of the PVOH product performance generation matter after associating with water.Relative humidity was at 50% o'clock, and the PVOH series products has just lost its original gas barrier property, does not have use value basically.This makes present PVOH can't directly be used as the coating material of high-barrier flexible packaging film again, at present, the external method of once reporting about casting film manufactured PVOH composite membrane, but this method investment is too high, the maintenance of equipment expense is also high, corresponding manufacturing cost is big, is not suitable for medium-sized and small enterprises, does not also meet China's national situation.Therefore the PVOH class high-barrier soft packaging coated film that does not also also have at present actual application value occurs.
Summary of the invention
The problems referred to above at present high-barrier flexible packing material and technology existence thereof, the present invention is based on modified polyvinyl alcohol (PVOH) molecular structure, under the condition that keeps the high obstructing performance that its molecular structure had, reduce the reactive force of hydrogen bond as far as possible, seeking breakthrough mouth aspect water tolerance, make PVOH product after the modification under high hygrometric state, still have a high-barrier, thereby provide a kind of less investment, practical modified polyvinyl alcohol to intercept the manufacture method of coated film.
Another object of the present invention then is to provide a kind of modified polyvinyl alcohol to intercept coated film, and the existing very high barrier property of this coated film can not produce environmental pollution again simultaneously, is that a kind of environment-friendly high is every flexible packing material.
The present invention adds auxiliary agent again and makes coating by to carrying out modification after the PVOH catalysis, is coated onto to be formed on the coated film that dry state and hygrometric state all have high-barrier on the base material, has solved it effectively and lose the difficult problem of barrier property under hygrometric state.The preparation method that this modified polyvinyl alcohol intercepts coated film is:
(1) polyvinyl alcohol and condensing agent are carried out condensation reaction under the condensation catalyst effect and carry out modification, the polymerization degree of polyvinyl alcohol is 1700-1900, saponification degree is more than 88%, add defoamer, viscosity-depression agent and anti again and make polyvinyl alcohol modification coating, raw materials used and the weight content of coating be polyvinyl alcohol 7-11%, distilled water 85-90%, condensation catalyst 0.04-0.1%, condensing agent O.7-2%, defoamer 0.5-0.8%, viscosity-depression agent 1-1.5%, anti 0.15-0.2%, described condensing agent is that general formula is R (NH
2)
2Compound, wherein R represents alkylidene group or carbonyl.
(2) polyvinyl alcohol modification coating is coated with at the base material film single or double, and then dries, make coated thin film.
Described condensation catalyst can be 1,4-morpholine or triethylamine.
Described defoamer can be the mixture of ethylene glycol and polysiloxane or tributyl phosphate, triethyl phosphate.
Described viscosity-depression agent can be Sodium hexametaphosphate 99.
Described anti can be 2,6 di tert butyl 4 methyl phenol or Diacetylmonoxime.
The preferable surface covered of described coating process be 100-200 rice/minute, base material film thickness is 8-300 μ m, thickness of coating layer is 0.4-0.7 μ m.
Described drying course can adopt far infrared drying, the preferred temperature of oven dry is 100-130 ℃, the time is 20-50 second.
For improving the smooth property and the adhesion inhibiting properties of coated film, preferable mode is that polyvinyl alcohol modification coating added 2-3% (in coating weight) vinegar surface slip agent and 0.7-1% (in coating weight) silicon-dioxide anti before painting process, and under 2800-3200 rev/min rotating speed high degree of agitation 30 minutes.
The present invention also provides a kind of modified polyvinyl alcohol to intercept coated film, comprise base material film and be coated in the dope layer of base material film single or double, it is characterized in that: described dope layer is by polyvinyl alcohol and condensing agent condensation and modification, the polymerization degree of polyvinyl alcohol is 1700-1900, saponification degree is more than 88%, and adding defoamer, viscosity-depression agent and anti are made polyvinyl alcohol modification coating, raw materials used weight percentage is polyvinyl alcohol 7-11%, distilled water 85-90%, condensation catalyst 0.04-0.1%, condensing agent 0.7-2%, defoamer 0.5-0.8%, viscosity-depression agent 1-1.5%, anti 0.15-0.2%, described condensing agent are that general formula is R (NH
2)
2Compound, wherein R represents alkylidene group or carbonyl.
Also contain vinegar slipping agent and silicon-dioxide anti in the described dope layer, its content is respectively vinegar surface slip agent 2-3%, silicon-dioxide anti 0.7-1% in coating weight.
Modified polyvinyl alcohol of the present invention intercepts coated film and manufacture method thereof, carries out modification, adjacent hydroxyl of the intramolecular part of PVOH and condensing agent R (NH by PVOH catalysis and condensing agent are carried out condensation reaction
2)
2Dehydration reaction takes place, and forms a kind of irregular PVOH modified compound.Behind the PVOH molecular chain process part catalyzing and condensing, reduced intramolecular hydrogen bond action power, improve its water resistance greatly, efficiently solve it and under hygrometric state, lose the difficult problem of barrier property, make coating by in the PVOH of modification, adding auxiliary agent again, be coated onto the coated film that base material film forms high-barrier.Therefore this coated film has following advantage:
1, adopt PVOH as dope layer, so have the crystallization of height, have best oxygen barrier property, its resistance oxygen and water vapor barrier under dry state and hygrometric state condition all is higher than the PCDC coated film;
2, resistance flavor fragrance protectiveness is strong, can effectively protect the taste of content;
3, extraordinary transparency and gratifying high gloss performance;
4, film surface has extremely strong surperficial absorption characteristic, comprises the printing of water-based inks so the PVOH series products is applicable to all printing ink;
5, the material property price of excellence ratio and extremely low glue spread, manufacturing cost reduces greatly.
6, has very strong heat sealability, product applied widely.
7, the coated film of composite membrane for adopting coating process to produce made the method for PVOH composite membrane with curtain coating system embrane method, has to invest for a short time, and the maintenance of equipment expense is low, and production cost is low, is applicable to the characteristics of medium-sized and small enterprises.
Embodiment
Below in conjunction with specific embodiment modified polyvinyl alcohol obstruct coated film of the present invention and manufacture method thereof are described further, to help understanding content of the present invention.
Embodiment one:
Take by weighing 48 kilograms of PVOH raw materials, throw to the 1000L reactor, reactor heats with the mode of electric heating, have thermometer, leaf formula stirring rod and return line respectively, slowly inject 618.2L distilled water, normal temperature stirred 1 hour down fast, stirring velocity was transferred to 150 rev/mins then, begin to heat up, temperature is controlled at 93 ℃-95 ℃, is incubated two hours, takes out sample, drip two potassiumiodide liquid, no blue particle is dissolving fully.Naturally put cold, treat that temperature drops to 50 ℃, drip the 410ml triethylamine, stir 5.1 kilograms of quadrols of adding after 20 minutes, keep 50 ℃, stirring velocity transfers to 250 rev/mins, reacting took a sample after two hours does thin-layer chromatography, the qualified back of sample system is put and is chilled to 45 ℃, adds 5.0 kilograms of tributyl phosphates, 7.1 kilograms of Sodium hexametaphosphate 99s and 1.41 kilograms of Diacetylmonoximes respectively, promptly gets modified paint.28 μ PE base material films are carried out corona treatment, put into coating machine then.Modification PVOH coating is added 3% (in coating weight) vinegar surface slip agent and 1.1% (in coating weight) silicon-dioxide anti, stirred 30 minutes, take off coating, inject in the coating machine.The coating condition is strict controlled in: surface covered is 120 meters/minute; Drying temperature is 105 ℃; Be 30 seconds time of drying.In addition, dry with the mode of far-infrared heating.Glue spread is 0.4 μ, solidifies under 40 ℃ of conditions promptly to get product of the present invention in 2 days.Recording the oxygen transit dose when relative humidity 50% is 1.5cm
3/ cm
224h0.1Mpa steam penetrating capacity is 4.5cm
3/ cm
224h0.1Mpa.
Embodiment two:
Take by weighing 60 kilograms of PVOH raw materials, throw to the 1000L reactor, reactor heats with the mode of electric heating, have thermometer, leaf formula stirring rod and return line respectively, slowly inject 606.7L distilled water, normal temperature stirred 1 hour down fast, stirring velocity was transferred to 150 rev/mins then, begin to heat up, temperature is controlled at 93 ℃-95 ℃, is incubated two hours, takes out sample, drip two potassiumiodide liquid, no blue particle is dissolving fully.Naturally put cold, treat that temperature drops to 60 ℃, Dropwise 5 00ml triethylamine stirs 10.1 kilograms of quadrols of adding after 20 minutes, keeps 60 ℃, stirring velocity transfers to 250 rev/mins, reacting after two hours sampling and doing thin-layer chromatography, the qualified back of sample system is put and is chilled to 35 ℃, adds 4.01 kilograms of tributyl phosphates, 8.1 kilograms of Sodium hexametaphosphate 99s and 1.13 kilogram 2 respectively, 6-di-tert-butyl-4-methy phenol, high degree of agitation promptly get modified paint after 30 minutes.22 μ Biaxially oriented polypropylene film (BOPP) base material films are carried out corona treatment, put into coating machine then.Modification PVOH coating is added 2% (in coating weight) vinegar surface slip agent and 0.9% (in coating weight) silicon-dioxide anti, and high degree of agitation is 30 minutes under 3000 rev/mins rotating speed, takes off coating, injects in the coating machine.The coating condition is strict controlled in: surface covered is 150 meters/minute; Drying temperature is 105 ℃; Be 20 seconds time of drying.In addition, dry with the mode of far-infrared heating.Glue spread is 0.4 μ, solidifies under 42 ℃ of conditions promptly to get product of the present invention in 2 days.Recording the oxygen transit dose when relative humidity 50% is 0.7cm
3/ cm
224h0.1Mpa steam penetrating capacity is 3.8cm
3/ cm
224h0.1Mpa.
Embodiment three:
Take by weighing 70 kilograms of PVOH raw materials, throw to the 1000L reactor, reactor heats with the mode of electric heating, have thermometer, leaf formula stirring rod and return line respectively, slowly inject 596L distilled water, normal temperature stirred 1 hour down fast, stirring velocity was transferred to 150 rev/mins then, begin to heat up, temperature is controlled at 93 ℃-95 ℃, is incubated two hours, takes out sample, drip two potassiumiodide liquid, no blue particle is dissolving fully.Naturally put cold, treat that temperature drops to 60 ℃, 1 of Dropwise 5 80ml, 4-morpholine, stir and add 13.5 kg urea after 20 minutes, keep 60 ℃, stirring velocity transfers to 250 rev/mins, and reacting took a sample after two hours does thin-layer chromatography, the qualified back of sample system is put and is chilled to 35 ℃, add 4.22 kilograms of triethyl phosphates, 10.1 kilograms of Sodium hexametaphosphate 99s and 1.32 kilograms of 2,6 di tert butyl 4 methyl phenols respectively, high degree of agitation promptly gets modified paint after 30 minutes.25 μ Biaxially oriented polypropylene film (BOPP) (BOPP) base material films are carried out corona treatment, put into coating machine then.Modification PVOH coating is added 1.9% (in coating weight) vinegar surface slip agent and 1% (in coating weight) silicon-dioxide anti, and high degree of agitation is 30 minutes under 3000 rev/mins rotating speed, takes off coating, injects in the coating machine.The coating condition is strict controlled in: surface covered is 150 meters/minute; Drying temperature is 115 ℃; Be 20 seconds time of drying.In addition, dry with the mode of far-infrared heating.Glue spread is 0.4 μ, solidifies under 44 ℃ of conditions promptly to get product of the present invention in 2 days.Recording the oxygen transit dose when relative humidity 50% is 1.5cm
3/ cm
224h0.1Mpa steam penetrating capacity is 4.8cm
3/ cm
224h0.1Mpa.
Claims (10)
1, a kind of modified polyvinyl alcohol intercepts the preparation method of coated film, it is characterized in that this method comprises following process:
(1) polyvinyl alcohol and condensing agent are carried out condensation reaction under the condensation catalyst effect and carry out modification, the polymerization degree of polyvinyl alcohol is 1700-1900, saponification degree is more than 88%, and adding defoamer, viscosity-depression agent and anti are made polyvinyl alcohol modification coating, raw materials used and the weight content of coating is polyvinyl alcohol 7-11%, distilled water 85-90%, condensation catalyst 0.04-0.1%, condensing agent 0.7-2%, defoamer 0.5-0.8%, viscosity-depression agent 1-1.5%, anti 0.15-0.2%, and described condensing agent is that general formula is R (NH
2)
2Compound, wherein R represents alkylidene group or carbonyl.
(2) polyvinyl alcohol modification coating is coated with at the base material film single or double, and then dries, make coated thin film.
2, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, and it is characterized in that: described condensation catalyst is 1,4-morpholine or triethylamine.
3, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, it is characterized in that: described defoamer is the mixture of ethylene glycol and polysiloxane or tributyl phosphate, triethyl phosphate.
4, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, and it is characterized in that: described viscosity-depression agent is a Sodium hexametaphosphate 99.
5, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, and it is characterized in that: described anti is 2,6 di tert butyl 4 methyl phenol or Diacetylmonoxime.
6, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, it is characterized in that: the surface covered of described coating process be 100-200 rice/minute, base material film thickness is 8-300 μ m, thickness of coating layer is 0.4-0.7 μ m.
7, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, and it is characterized in that: the employing far infrared drying of described drying course, the temperature of oven dry are 100-130 ℃, and the time is 20-50 second.
8, modified polyvinyl alcohol as claimed in claim 1 intercepts the preparation method of coated film, it is characterized in that: added in the vinegar surface slip agent of coating weight 2-3% and the silicon-dioxide anti of 0.7-1% before coating at polyvinyl alcohol modification coating, and under 2800-3200 rev/min rotating speed, stir.
9, a kind of modified polyvinyl alcohol intercepts coated film, comprise base material film and be coated in the dope layer of base material film single or double, it is characterized in that: described dope layer is by polyvinyl alcohol and condensing agent condensation and modification, the polymerization degree of polyvinyl alcohol is 1700-1900, saponification degree is more than 88%, and adding defoamer, viscosity-depression agent and anti are made polyvinyl alcohol modification coating, raw materials used weight percentage is polyvinyl alcohol 7-11%, distilled water 85-90%, condensation catalyst 0.04-0.1%, condensing agent 0.7-2%, defoamer 0.5-0.8%, viscosity-depression agent 1-1.5%, anti 0.15-0.2%, described condensing agent are that general formula is R (NH
2)
2Compound, wherein R represents alkylidene group or carbonyl.
10, modified polyvinyl alcohol as claimed in claim 9 intercepts coated film, it is characterized in that: also contain vinegar slipping agent and silicon-dioxide anti in the described dope layer, its content is respectively vinegar surface slip agent 2-3%, silicon-dioxide anti 0.7-1% in coating weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510066498 CN1687264A (en) | 2005-04-26 | 2005-04-26 | Method for fabricating obstruction coating film of modified polyvinyl alcohol and coating film produced thereby |
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|---|---|---|---|
| CN 200510066498 CN1687264A (en) | 2005-04-26 | 2005-04-26 | Method for fabricating obstruction coating film of modified polyvinyl alcohol and coating film produced thereby |
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| CN102248729A (en) * | 2011-05-04 | 2011-11-23 | 海南赛诺实业有限公司 | Heat-sealing polyvinylidene chloride coating film and manufacture method thereof |
| CN102277049A (en) * | 2011-08-06 | 2011-12-14 | 海南必凯水性涂料有限公司 | Self-adhesive modified polyvinylalcohol coating and preparation method thereof |
| WO2011157085A1 (en) * | 2010-06-16 | 2011-12-22 | 海南赛诺实业有限公司 | Modified polyvinyl alcohol coated film used for printing and preparation method thereof |
| CN102382526A (en) * | 2010-08-27 | 2012-03-21 | 山东泉林包装有限公司 | High-resistance polymer coating fluid |
| CN103042811A (en) * | 2012-12-26 | 2013-04-17 | 海南赛诺实业有限公司 | Post-curing method for polyvinyl alcohol coating film |
| CN103382677A (en) * | 2013-07-25 | 2013-11-06 | 海南必凯水性涂料有限公司 | High-barrier polyving akohol coating for coating lined paper and preparation method thereof |
| CN104118156A (en) * | 2013-11-28 | 2014-10-29 | 海南必凯水性涂料有限公司 | High-barrier environmental-friendly coating lined paper and manufacturing method thereof |
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2005
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9200173B2 (en) | 2010-06-16 | 2015-12-01 | Hainan Shiner Industrial Co., Ltd. | Modified polyvinyl alcohol coated film used for printing and preparation method thereof |
| WO2011157085A1 (en) * | 2010-06-16 | 2011-12-22 | 海南赛诺实业有限公司 | Modified polyvinyl alcohol coated film used for printing and preparation method thereof |
| CN102382526B (en) * | 2010-08-27 | 2013-07-10 | 纷美(北京)贸易有限公司 | High-resistance polymer coating fluid |
| CN102382526A (en) * | 2010-08-27 | 2012-03-21 | 山东泉林包装有限公司 | High-resistance polymer coating fluid |
| CN102382527A (en) * | 2010-08-27 | 2012-03-21 | 山东泉林包装有限公司 | Preparation method of high-resistance polymer coating fluid |
| CN102382527B (en) * | 2010-08-27 | 2013-12-04 | 纷美(北京)贸易有限公司 | Preparation method of high-resistance polymer coating fluid |
| CN102248729B (en) * | 2011-05-04 | 2013-08-21 | 海南赛诺实业有限公司 | Manufacture method of heat-sealing polyvinylidene chloride coating film |
| CN102248729A (en) * | 2011-05-04 | 2011-11-23 | 海南赛诺实业有限公司 | Heat-sealing polyvinylidene chloride coating film and manufacture method thereof |
| CN102277049B (en) * | 2011-08-06 | 2013-07-10 | 海南必凯水性涂料有限公司 | Self-adhesive modified polyvinylalcohol coating and preparation method thereof |
| CN102277049A (en) * | 2011-08-06 | 2011-12-14 | 海南必凯水性涂料有限公司 | Self-adhesive modified polyvinylalcohol coating and preparation method thereof |
| CN103042811A (en) * | 2012-12-26 | 2013-04-17 | 海南赛诺实业有限公司 | Post-curing method for polyvinyl alcohol coating film |
| CN103042811B (en) * | 2012-12-26 | 2015-10-28 | 海南赛诺实业有限公司 | A kind of post cure procedures of polyvinyl alcohol coated film |
| CN103382677A (en) * | 2013-07-25 | 2013-11-06 | 海南必凯水性涂料有限公司 | High-barrier polyving akohol coating for coating lined paper and preparation method thereof |
| CN103382677B (en) * | 2013-07-25 | 2015-11-04 | 海南必凯水性涂料有限公司 | A kind of high-barrier polyvinyl alcohol coating for internal lining paper coating and preparation method thereof |
| CN104118156A (en) * | 2013-11-28 | 2014-10-29 | 海南必凯水性涂料有限公司 | High-barrier environmental-friendly coating lined paper and manufacturing method thereof |
| CN104118156B (en) * | 2013-11-28 | 2016-08-24 | 海南必凯水性涂料有限公司 | A kind of high-barrier environmental protection coating internal lining paper and manufacture method thereof |
| CN113717588A (en) * | 2021-09-02 | 2021-11-30 | 海南必凯水性新材料有限公司 | PVA emulsion for stone paper, preparation method and application thereof |
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