CN105777949A - Polyvinyl alcohol coating film-forming solution for coating composite films, method for preparing polyvinyl alcohol coating film-forming solution and application thereof - Google Patents
Polyvinyl alcohol coating film-forming solution for coating composite films, method for preparing polyvinyl alcohol coating film-forming solution and application thereof Download PDFInfo
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- CN105777949A CN105777949A CN201610289989.1A CN201610289989A CN105777949A CN 105777949 A CN105777949 A CN 105777949A CN 201610289989 A CN201610289989 A CN 201610289989A CN 105777949 A CN105777949 A CN 105777949A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Polymers & Plastics (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to polyvinyl alcohol coating film-forming solution for coating composite films, a method for preparing the polyvinyl alcohol coating film-forming solution and application thereof. The method includes completely dissolving polyvinyl alcohol in water, oxidizing partial hydroxyl in the polyvinyl alcohol by means of oxidation reaction and generating chemically active aldehyde groups from the partial oxidized hydroxyl; carrying out similarly hydroxymethyl reaction on obtained solution and amide substances under alkaline conditions to generate similarly hydroxymethyl derivatives. The polyvinyl alcohol coating film-forming solution, the method and the application have the advantages that condensation reaction is carried out on the similarly hydroxymethyl derivatives to form partially self-crosslinking formed films in coating film-forming procedures at the temperatures of 80-100 DEG C; the composite films are excellent in oxygen barrier property after the modified polyvinyl alcohol (PVA) is coated and the films are formed, and the composite films are particularly excellent in barrier property under the condition of high humidity as compared with polyvinyl alcohol (PVA) films which are not modified.
Description
Technical field
The present invention relates to a kind of polyvinyl alcohol (PVA) coating film forming solution, particularly relate to a kind of coating laminated film
Polyvinyl alcohol (PVA) be applied as coating solution and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is kind of a material with high obstructing performance, and the most under the low humidity, its barrier property is almost
Can match in excellence or beauty with metallic aluminium, compared with other barrier materials (such as EVOH, PVDC etc.) being usually used in production laminated film at present,
Polyvinyl alcohol (PVA) can reach 8 10 times of these barrier materials to the barrier property of oxygen；And polyvinyl alcohol (PVA) has simultaneously
Excellent film property, so being a kind of material prepared and have high obstructing performance laminated film.But owing to polyvinyl alcohol is to finish
Complete water soluble macromolecular material, its chemical attribute has extremely strong polarity and hydrophilic, also makes it prepare high obstructing performance
Laminated film and use application time much limited.So how prepare the polyethylene with certain resistance to water and moisture resistance
Alcohol laminated film is also one of current technology difficult problem.The technology of the present invention is aiming at this technical barrier and develops: pass through
Modification to polyvinyl alcohol so that it is carry out part self-crosslinking in film forming procedure and resistance to water its film forming after and anti-is greatly improved
Wet performance.
The mesh of the present invention is a kind of have high barrier in order to develop and have inexpensive packaging laminated film to provide
A kind of technical solution.Owing to polyvinyl alcohol (PVA) is considered as on the carbon atom being alternately separated by band in chemical constitution
There is the polyhydric alcohol of hydroxyl, so, its chemical method mostly also is typical polyol reaction, such as etherificate, esterification, acetalation etc.: this
Invention is exactly based on the chemical method that these are basic, and polyvinyl alcohol (PVA) carries out chemical modification, introduces and chemically cross-links
Group so that it is in film forming engineering, carry out self-crosslinking and improve its resistance to water and anti humility performance.Its concrete technical method divides three
Step is carried out: 1, under certain condition, by oxidation reaction, makes the part of hydroxyl in polyvinyl alcohol be aoxidized, and part is by oxygen
Hydroxyl after change generates active aldehyde radical；2, in the basic conditions (PH=8.0-10.0) and amide substance carry out class hydroxyl
Methylation reaction, generates a number of class hydroxymethyl derivative；3, in being applied as membrane process, these class hydroxymethyl derivatives
Carry out condensation reaction under certain condition and form self-crosslinking film forming.Its principles of chemistry:
1, under strong oxidizer effect, polyvinyl alcohol molecule is carried out oxidation reaction and generates active aldehyde radical:
2, under neutral or basic conditions, on polyvinyl alcohol, the aldehyde radical of oxidized generation and amide substance carry out class hydroxyl first
Base reaction generation class hydroxymethyl derivative:
3, the class hydroxymethyl derivative generated on the polyvinyl alcohol ,-H contained in its molecule and-OH base have suitable
Chemism, under certain condition, can carry out condensation reaction dehydrated crosslinking, can form O-(ether after its dehydration condensation
Key) ,-CH2The cross-bonds such as-(methine key) and form insoluble polyvinyl alcohol film.Thus it is effectively improved the resistance to of polyvinyl alcohol film
Aqueous and moisture resistance.
Polyvinyl alcohol film after class hydroxymethyl derivative condensation reaction crosslinking film forming, its resistance to water and anti humility performance are big
Width improves, thus ensure that the use application performance of laminated film.This laminated film has high obstructing performance, excellent machinery
Physical property, can print, can seal.Laminated film can be widely applied to the packaging of the fresh food such as water fruits and vegetables, egg fowl；
Can also apply to the direct packaging of other food；Also can apply to cosmetics, the packaging of medicine isoreactivity article and storage.
Summary of the invention
The present invention is that a kind of polyvinyl alcohol (PVA) coating laminated film is applied as coating solution and preparation method thereof, this
Invention is achieved through the following technical solutions, and concrete technical scheme is as follows.
A kind of polyvinyl alcohol (PVA) coating laminated film is applied as the preparation method of coating solution, and its coating film forming is molten
Liquid is to be prepared from after polyvinyl alcohol is carried out chemical modification.Its chemical modification method is implemented in three steps: 1, one
Under fixed condition, by oxidation reaction, make the part of hydroxyl in polyvinyl alcohol be aoxidized, oxidized after hydroxyl generate having
Learn the aldehyde radical of activity；2, under neutral or basic conditions to carry out class methylolation anti-for (PH=8.0-10.0) and amide substance
Should, generate a number of class hydroxymethyl derivative；3, in being applied as membrane process, at 80-100 DEG C, these class methylols spread out
Biology carries out condensation reaction and forming part self-crosslinking film forming.
Further, described polyvinyl alcohol is the polyvinyl alcohol of complete alcoholysis or partial alcoholysis.
Further, in above-mentioned chemical modification method, the 1st step is first polyvinyl alcohol to be carried out chemical oxidation reaction to carry out
Modified；Polyvinyl alcohol described in the technology of the present invention is the polyvinyl alcohol of complete alcoholysis or partial alcoholysis, is described in further detail
It is polyvinyl alcohol-0599, polyvinyl alcohol-1399, polyvinyl alcohol-1599, polyvinyl alcohol-1799, polyvinyl alcohol-2099, poly-second
Enol-2299；The one therein such as polyvinyl alcohol-0588, polyvinyl alcohol-1788, polyvinyl alcohol-2088, polyvinyl alcohol-2488
Or more than one.Its chemical oxidation reaction is carried out in aqueous.
Further, step 1. in: be the proportioning of 8-15% by polyvinyl alcohol weight percentage ratio, polyvinyl alcohol added water
In, fully dissolve at 90-95 DEG C, the polyvinyl alcohol water solution after dissolving, enter in 60-80 DEG C and stirring lower interpolation strong oxidizer
Row chemical oxidation is modified.
Further, described strong oxidizer is hydrogen peroxide, and its addition is the 3 10% of polyvinyl alcohol weight；Chemical oxidation
The modified-reaction time is 60 120 minutes；In course of reaction, the addition manner of hydrogen peroxide is dropping mode, and time for adding is 30
60 minutes；After hydrogen peroxide drips, under selected reaction temperature, it is incubated 30 60 minutes, obtains the polyethylene of part aldehyde radical
Alcohol-water solution.
Further, after obtaining the polyvinyl alcohol water solution after part aldehyde radical, regulate with the organic alkaloids of water solublity
Solution pH value is to 8.0 10.0；Class hydroxymethylation is carried out with the material containing amide-type at 60-80 DEG C；Its chemical reaction
Time is 60 90 minutes.
Further, the organic alkaloids of described water solublity is the organic base apoplexy due to endogenous wind such as diethylamine, triethylamine, triethanolamine
A kind of.
Further, in described class methylol chemical reaction, the material containing amide-type is phosphoamide, at class methylolation
Usage amount in reaction is calculated as 1 5% with pure polyvinyl alcohol weight.
The polyvinylalcohol coats film forming solution of the coating laminated film prepared by described preparation method, in its preparation method
The parts by weight proportioning of each material:
Described polyvinyl alcohol is also configured to aqueous solution with water, and preparation parts by weight are:
Polyvinyl alcohol 8-15
Water 85-92.
Further, in the present invention, a kind of polyvinyl alcohol (PVA) coating laminated film is applied as coating solution, is suitable for
Directly coating processing method carries out compound and obtains laminated film.
Above-mentioned coating processing method carries out laminated film that is compound and that obtain, and its coating thickness is to be calculated as after coating liquid film forming
3-5μm；Coating processing temperature is 80-100 DEG C.
Above-mentioned coating processing method carries out laminated film that is compound and that obtain and has the barrier property of excellence, particularly at height
With through modified polyvinyl alcohol (PVA) thin film contrast under humidity, there is more excellent barrier property:
Through the modified coated film of the technology of the present invention with not through the polyvinyl alcohol film of any modification in different humidity
Under OTR oxygen transmission rate to such as table 1.
Table 1
Note: 1. sample one is the thin film of present invention polyvinylalcohol coats liquid film forming after modified；
2. sample two is not through the polyvinyl alcohol film of any modification.
Test film thickness: 3.5 μm.
Compared with prior art, the invention have the advantages that and technique effect:
What the present invention prepared be applied as, and coating solution is applicable to be coated compound with other plastic film substrates and prepare multiple
Close thin film；Owing to polyvinyl alcohol (PVA) is kind of a water soluble polymer, after coating film forming, its resistance to water moisture resistance is very poor, not only
Seriously limit it and use range of application, and make the performance of laminated film decline to a great extent.Particularly with the presence of moisture content or
Under high humidity environment, compound being easy between laminated film is gone to pot by moisture content or moisture attacks, can lead the when of serious
Separation occur between cause laminated film automatically and departs from, making laminated film lose the combination property after being combined completely.And the present invention
The solution that technology is just specific to this technical barrier and proposes, by polyvinyl alcohol (PVA) coating film forming liquid
Modified so that it is after coating film forming, water-fast anti humility performance to be greatly improved, thus improve the composite quality of laminated film, it is ensured that its tool
There is stable application performance.
Detailed description of the invention
Make the most specifically to describe in detail to the present invention below in conjunction with specific embodiment, but the enforcement of the present invention and guarantor
The scope of protecting is not limited to this.
Embodiment 1
The each combination matching of modified polyvinylalcohol:
After above-mentioned each component is measured in proportion, first soluble in water for polyvinyl alcohol 2099, and be heated to 90-95 DEG C abundant molten
Solving, its polyvinyl alcohol 2099 is 8:92 (weight ratio) with the ratio of water.Polyvinyl alcohol water solution after fully dissolving, is protecting
Holding under solution temperature 60 DEG C and stirring, start to drip hydrogen peroxide, time for adding is 60 minutes；It is warming up to 80 after dripping hydrogen peroxide
DEG C continue reaction 30 minutes.Then regulating solution PH with triethylamine is 10.0, adds above-mentioned meter at keeping solution temperature 80 DEG C
The phosphoamide of amount, carries out hydroxymethylation 60 minutes at 80 DEG C；It is cooled to room temperature and is one of the present invention coating THIN COMPOSITE
The polyvinyl alcohol (PVA) of film is applied as coating solution, and with the laminated film after this coating liquid film forming, the transmitance of oxygen is by it
4.3cm3/m2/ 24h (relative humidity: 60%；Coating liquid coat film thickness 3 μm)；And the most do not carry out any modification
Polyvinyl alcohol film (3 μm) be 42.5cm to the transmitance of oxygen3/m2/24h。
Embodiment 2
The each combination matching of modified polyvinylalcohol:
After above-mentioned each component is measured in proportion, first soluble in water to polyvinyl alcohol 1799 and polyvinyl alcohol 0599, and heat
To 90-95 DEG C of abundant dissolving, its polyvinyl alcohol is 15:85 (weight ratio) with the ratio of water.Polyethylene after fully dissolving
Alcohol-water solution, under keeping solution temperature 70 DEG C and stirring, starts to drip hydrogen peroxide, and time for adding is 45 minutes；Drip double
It is warming up to 75 DEG C after oxygen water and continues reaction 45 minutes.Then regulating solution PH with diethylamine is 9.0, is keeping solution temperature 75 DEG C
The phosphoamide of the lower above-mentioned metering of addition, carries out hydroxymethylation 80 minutes at 75 DEG C；It is cooled to room temperature subsequently and is this
Bright a kind of polyvinyl alcohol (PVA) coating laminated film is applied as coating solution, with the laminated film after this coating liquid film forming its
Transmitance to oxygen is 2.8cm3/m2/ 24h (relative humidity: 70%；Coating liquid coat film thickness 3.5 μm)；And in this condition
Under not carry out the polyvinyl alcohol film (3.5 μm) of any modification be 51.3cm to the transmitance of oxygen3/m2/24h。
Embodiment 3
The each combination matching of modified polyvinylalcohol:
After above-mentioned each component is measured in proportion, first soluble in water to polyvinyl alcohol 2488 and polyvinyl alcohol 0588, and heat
To 90-95 DEG C of abundant dissolving, its polyvinyl alcohol is 12:88 (weight ratio) with the ratio of water.Polyethylene after fully dissolving
Alcohol-water solution, under keeping solution temperature 80 DEG C and stirring, starts to drip hydrogen peroxide, and time for adding is 60 minutes；Drip double
It is cooled to 75 DEG C after oxygen water and continues reaction 60 minutes.Then regulating solution PH with triethanolamine is 8.0, is keeping solution temperature 75
Add the phosphoamide of above-mentioned metering at DEG C, at 75 DEG C, carry out hydroxymethylation 90 minutes；It is cooled to room temperature subsequently and is this
Invent a kind of polyvinyl alcohol (PVA) coating laminated film and be applied as coating solution, with the laminated film after this coating liquid film forming
It is 8.8cm to the transmitance of oxygen3/m2/ 24h (relative humidity: 80%；Coating liquid coat film thickness 5.0 μm)；And at this
The polyvinyl alcohol film (5.0 μm) not carrying out any modification under part is 131.5cm to the transmitance of oxygen3/m2/24h。
Embodiment 4
The each combination matching of modified polyvinylalcohol:
After above-mentioned each component is measured in proportion, first soluble in water to polyvinyl alcohol 1799 and polyvinyl alcohol 1399, and heat
To 90-95 DEG C of abundant dissolving, its polyvinyl alcohol is 15:85 (weight ratio) with the ratio of water.Polyethylene after fully dissolving
Alcohol-water solution, under keeping solution temperature 80 DEG C and stirring, starts to drip hydrogen peroxide, and time for adding is 50 minutes；Drip double
It is cooled to 70 DEG C after oxygen water and continues reaction 60 minutes.Then regulating solution PH with triethanolamine is 8.5, is keeping solution temperature 70
Add the phosphoamide of above-mentioned metering at DEG C, at 70 DEG C, carry out hydroxymethylation 80 minutes；It is cooled to room temperature subsequently and is this
Invent a kind of polyvinyl alcohol (PVA) coating laminated film and be applied as coating solution, with the laminated film after this coating liquid film forming
It is 23.3cm to the transmitance of oxygen3/m2/ 24h (relative humidity: 95%；Coating liquid coat film thickness 4.0 μm)；And at this
The polyvinyl alcohol film (4.0 μm) not carrying out any modification under part is 321.7cm to the transmitance of oxygen3/m2/24h。
Embodiment 5
The each combination matching of modified polyvinylalcohol:
After above-mentioned each component is measured in proportion, first soluble in water for polyvinyl alcohol 1788, and be heated to 90-95 DEG C abundant molten
Solving, its polyvinyl alcohol 1788 is 15:85 (weight ratio) with the ratio of water.Polyvinyl alcohol water solution after fully dissolving,
Keeping, under solution temperature 80 DEG C and stirring, starting to drip hydrogen peroxide, time for adding is 40 minutes；Temperature is kept after dripping hydrogen peroxide
Spend 80 DEG C and continue reaction 45 minutes.Then regulating solution PH with triethanolamine is 9.0, adds at keeping solution temperature 80 DEG C
State the phosphoamide of metering, at 80 DEG C, carry out hydroxymethylation 60 minutes；It is cooled to room temperature and is one of the present invention coating again
The polyvinyl alcohol (PVA) closing thin film is applied as coating solution, and with the laminated film after this coating liquid film forming, oxygen is passed through by it
Rate is 5.9cm3/m2/ 24h (relative humidity: 60%；Coating liquid coat film thickness 3 μm)；And the most do not carry out any
Modified polyvinyl alcohol film (3 μm) is 54.6cm to the transmitance of oxygen3/m2/24h。
Above example is merely to illustrate technical scheme, is not intended to limit.Although with reference to preferred embodiment
Being described in detail the present invention, it will be understood by those skilled in the art that still can be to the concrete reality of the present invention
The mode of executing is modified or portion of techniques feature is carried out equivalent, without deviating from the spirit of technical solution of the present invention, its
All should contain among the technical scheme scope of present invention request.
Claims (10)
1. the preparation method coating laminated film polyvinylalcohol coats film forming solution, it is characterised in that it coats film forming
Solution is to be prepared from after polyvinyl alcohol is carried out chemical modification；Specifically include following steps: the most under certain condition, will
Polyvinyl alcohol is completely dissolved in water, by oxidation reaction, makes the part of hydroxyl in polyvinyl alcohol be aoxidized, partially oxidized
After hydroxyl generate there is chemically active aldehyde radical；The most in the basic conditions step 1. gained solution is carried out with amide substance
Class hydroxymethylation, generates class hydroxymethyl derivative.
Preparation method the most according to claim 1, it is characterised in that: described polyvinyl alcohol is complete alcoholysis or part alcohol
The polyvinyl alcohol solved.
Preparation method the most according to claim 1, it is characterised in that: described polyvinyl alcohol is polyvinyl alcohol-0599, gathers
Vinyl alcohol-1399, polyvinyl alcohol-1599, polyvinyl alcohol-1799, polyvinyl alcohol-2099, polyvinyl alcohol-2299；Polyvinyl alcohol-
0588, polyvinyl alcohol-1788, polyvinyl alcohol-2088, polyvinyl alcohol-2488 etc. therein one or more.
Preparation method the most according to claim 1, it is characterised in that step 1. in: be 8 by polyvinyl alcohol weight percentage ratio
The proportioning of-15%, is added to the water polyvinyl alcohol, fully dissolves, the polyvinyl alcohol water solution after dissolving at 90-95 DEG C, in
60-80 DEG C of add strong oxidizers lower with stirring carry out chemical oxidation modification.
Preparation method the most according to claim 4, it is characterised in that described strong oxidizer is hydrogen peroxide, its addition is poly-
The 3 10% of vinyl alcohol weight；The chemical oxidation modified-reaction time is 60 120 minutes；In course of reaction, adding of hydrogen peroxide
Add mode is dropping mode, and time for adding is 30 60 minutes；After hydrogen peroxide drips, it is incubated under selected reaction temperature
30 60 minutes, obtain the polyvinyl alcohol water solution of part aldehyde radical.
Preparation method the most according to claim 5, it is characterised in that obtain the polyvinyl alcohol water solution after part aldehyde radical
After, with water solublity organic alkaloids regulation solution pH value to 8.0 10.0；With the thing containing amide-type at 60-80 DEG C
Matter carries out class hydroxymethylation；Its chemical time is 60 90 minutes.
Preparation method the most according to claim 6, the organic alkaloids of described water solublity is diethylamine, triethylamine, three second
The one of the organic base apoplexy due to endogenous wind such as hydramine.
Preparation method the most according to claim 6, it is characterised in that in described class methylol chemical reaction, containing amide-type
Material be phosphoamide, the usage amount in class hydroxymethylation is calculated as 1 5% with pure polyvinyl alcohol weight.
9. the polyvinylalcohol coats film forming of the coating laminated film prepared by preparation method described in any one of claim 1-8 is molten
Liquid, the parts by weight proportioning of each material in its preparation method:
Polyvinyl alcohol 100
Hydrogen peroxide 3-10
Phosphoamide 15
The organic bases of water solublity is appropriate；
Described polyvinyl alcohol is also configured to aqueous solution with water, and preparation parts by weight are:
Polyvinyl alcohol 8-15
Water 85-92.
10. the application of a kind of polyvinylalcohol coats film forming solution coating laminated film described in claim 9, its feature exists
In with directly coating processing method, make polyvinylalcohol coats film forming solution can carry out condensation reaction and forming part self-crosslinking film；
Its coating thickness is to be calculated as 3-5 m after coating liquid film forming；Coating processing temperature is 80-100 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610289989.1A CN105777949B (en) | 2016-04-30 | 2016-04-30 | One kind coating laminated film polyvinylalcohol coats film forming solution and preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610289989.1A CN105777949B (en) | 2016-04-30 | 2016-04-30 | One kind coating laminated film polyvinylalcohol coats film forming solution and preparation method and application |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991002024A1 (en) * | 1989-08-07 | 1991-02-21 | Butterfly S.R.L. | Polymer compositions for the production of articles of biodegradable plastics material and method for their preparation |
| CN102675786A (en) * | 2012-05-07 | 2012-09-19 | 华南理工大学 | Preparation method for raw material used for bag film with two different water-soluble speeds on different parts |
| CN102898668A (en) * | 2012-10-13 | 2013-01-30 | 华南理工大学 | Water soluble preservative film for fruits and vegetables and preparation method of preservative film |
| JP2015212068A (en) * | 2014-04-18 | 2015-11-26 | 尾池工業株式会社 | Gas barrier film having hot water resistance, and medical infusion packaging material and food packaging material each using the film |
-
2016
- 2016-04-30 CN CN201610289989.1A patent/CN105777949B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991002024A1 (en) * | 1989-08-07 | 1991-02-21 | Butterfly S.R.L. | Polymer compositions for the production of articles of biodegradable plastics material and method for their preparation |
| CN102675786A (en) * | 2012-05-07 | 2012-09-19 | 华南理工大学 | Preparation method for raw material used for bag film with two different water-soluble speeds on different parts |
| CN102898668A (en) * | 2012-10-13 | 2013-01-30 | 华南理工大学 | Water soluble preservative film for fruits and vegetables and preparation method of preservative film |
| JP2015212068A (en) * | 2014-04-18 | 2015-11-26 | 尾池工業株式会社 | Gas barrier film having hot water resistance, and medical infusion packaging material and food packaging material each using the film |
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| CN105777949B (en) | 2018-04-13 |
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Effective date of registration: 20190517 Address after: 518116 New Village of Longgang Tongle Chiwu Villagers Group, Longgang District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Sailong Glass Fiber Co. Ltd. Address before: 510640 No. 381 Wushan Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: South China University of Technology |
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