CN85109218A - Rubbing method is made polyvinyl alcohol/polyolefin composite membrane - Google Patents
Rubbing method is made polyvinyl alcohol/polyolefin composite membrane Download PDFInfo
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- CN85109218A CN85109218A CN198585109218A CN85109218A CN85109218A CN 85109218 A CN85109218 A CN 85109218A CN 198585109218 A CN198585109218 A CN 198585109218A CN 85109218 A CN85109218 A CN 85109218A CN 85109218 A CN85109218 A CN 85109218A
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- polyvinyl alcohol
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Abstract
It is with polyethylene that rubbing method is made polyvinyl alcohol/polyolefin composite membrane, and polypropylene screen is a basement membrane, acrylate copolymer or ethene and acetate ethylene copolymer is coated on the basement membrane as adhesive, painting polyethylene alcoholic solution composite membrane-forming on adhesive layer again.Polyethylene film can be without the solution combined film forming of the direct pva coating of glue.This composite membrane has the performance of resistance oxygen, nitrogen and carbon dioxide, and it is good packaging material for food.Raw material and equipment are based on our country, and the source is abundant, and is easy and simple to handle, and reduced investment is applicable to the medium-sized and small enterprises popularization.
Description
The invention belongs to the manufacturing of packaging material for food
Polyvinyl alcohol film has the performance that intercepts oxygen, nitrogen and carbon dioxide, with films such as nylon, polyester relatively, its intercept gas superior performance many.But its cost is well below them.Polyvinyl alcohol and polyethylene, compounded film such as polypropylene are that good food is protected fragrant packaging material with oxygen barrier.The special public clear 50-15826 of Japan Patent, reported the manufacture method of laminated thing: make various compounds so that films such as polyvinyl alcohol film and polyethylene, polypropylene and polyvinyl chloride are compound, the adhesive that adopts has the copolymer (EVA) of ethene and vinyl acetate and with this copolymer partly or the product of whole saponification, be mixed with solution with benzene,toluene,xylene, be coated on polyethylene, polypropylene or the polyvinyl chloride film, after treating solvent seasoning, compound with polyvinyl alcohol film again through mold pressing.J55091-644 has also reported heat sealable polyvinyl alcohol film, coats polyester liquid and compound making by biaxial stretch-formed polyvinyl alcohol film.At present, abroad generally all adopt and earlier polyvinyl alcohol is made film, and then compound or on polyvinyl alcohol film, be coated with polyethylene, polypropylene and polyvinyl chloride with moistureproof and coating easily heat-sealing is produced polyvinyl alcohol compound film.As packaging material for food, the weak point of these methods is complex process equipment, the investment cost height.The extruding of domestic polyvinyl alcohol, blowing become the embrane method suitability for industrialized production that all is unrealized with biaxial stretch-formed etc., and casting filming therapy is not suitable for a large amount of productions again.Therefore, China is used for packaging material for food, also depends on import, expends foreign exchange.For the packaging material for food that satisfies various food exports of China and a large amount of needs in domestic market becomes one of problem anxious to be solved.
The objective of the invention is to have according to polyvinyl alcohol the characteristic of good film forming and obstruct gas, in dry environment, the oxygen flow speed of polyvinyl alcohol film is lower than the nylon of same thickness, a thirtieth of polyester film; Be lower than two one thousandths of polyethylene or polypropylene film.If behind coating compound very thin one deck (～10 μ) polyvinyl alcohol on polyethylene or the polypropylene screen, its oxygen transmission rate just can descend significantly, the polyethylene film of 0.1 millimeters thick for example, 24 hours every square metre of oxygen permeating amounts just can drop to below 5 milliliters behind compound 0.01 millimeter polyvinyl alcohol more than 1000 milliliters.Therefore, be coated with compound polyvinyl alcohol/polyolefin film and provide advantage, for packaging material for food has been opened up new road for food oxygen barrier guarantor perfume (or spice).
Task of the present invention provides protects fragrant polymer composite to the food oxygen barrier, solves the storage, transportation, protection for a long time of current food and does not make food spoilage, guarantees the product market that enjoys a good market both at home and abroad.
Rubbing method provided by the invention is made the primary raw material of polyvinyl alcohol/polyolefin composite thin film,
1. the preparation of polyvinyl alcohol film forming raw material
Polyvinyl alcohol (the available trade mark 1799) 10-17
Deionized water 83-90
Cross linking agent (reactant of available formaldehyde and urea, melamine or aldehydes) is with poly-
Vinyl alcohol consumption meter 3-12%
Catalyst (available strong acid weak base salt is as ammonium chloride etc.) is in the polyvinyl alcohol consumption
1-8%
By above-mentioned prescription weighing polyvinyl alcohol, under agitation, be dissolved into clear solution for 80-100 ℃, add cross linking agent and catalyst, continue to stir 30 minutes, can be coated with after mixing.
2. the adhesive of polyvinyl alcohol/polyolefin composite membrane
(1) acrylate copolymer system
Acrylate copolymer 10-15%
Solvent (available industrial alcohol-acetic acid
Ethyl ester 7: 3 or 8: 2) 85-90%
The recipe ingredient of acrylic copolymer (by weight) is:
Methyl acrylate 2-20 part
Butyl acrylate 2-70 part
2-ethyl hexyl acrylate 2-20 part
Acrylic acid 1-10 part
Vinyl acetate 5-40 part
Styrene 1-10 part
Benzoyl peroxide (being gross weight) 0.1-1%
Ethyl acetate (being gross weight) 30-100%
Optimum formula component (by weight) is
Methyl acrylate 12
Butyl acrylate 50
2-ethyl hexyl acrylate 10
Acrylic acid 3
Vinyl acetate 20
Styrene 5
Benzoyl peroxide (being gross weight) 0.3
Ethyl acetate (being gross weight) 100
With above-mentioned optimum formula component respectively weighing add agitator be housed, in the there-necked flask of reflux condenser and thermometer, 60～90 ℃ of following polymerisations 4～8 hours, the back can be coated with the solution that the industrial alcohol-ethyl acetate mixed solvent of 7: 3 or 8: 2 is diluted to 10-15%.
(2) ethylene and vinyl acetate copolymer adhesive
Ethylene and vinyl acetate copolymer (vinyl acetate content 15～40%)
8-15 part
Solvent (8: 2 mixed solvent of available toluene-acetone) 85-92 part
3. thick 50～90 μ of basement membrane (available polyethylene or polypropylene screen)
4. polyethylene or polypropylene screen are undertaken compound by following process conditions after surface oxidation treatment.
A, polyvinyl alcohol/polyolefin composite membrane
Bondline thickness 2-8 μ
Baking temperature 60-120 ℃
0.5-2 minute drying time
Polyvinyl alcohol film bed thickness 5-13 μ
Baking temperature 90-200 ℃
1-3 minute drying time
3.5～8 meters/minute of coating speeds
Optimum process condition is:
Bondline thickness 1-4 μ
Baking temperature 90-100 ℃
0.5-2 minute drying time
Polyvinyl alcohol film bed thickness 5-10 μ
Baking temperature 120-125 ℃
1-3 minute drying time
3.5 meters/minute of coating speeds
B, polyvinyl alcohol polyethylene composite membrane also can directly be coated with compound without glue
Rubbing method provided by the invention is made the production equipment of polyvinyl alcohol/polyolefin composite membrane
Fig. 1, the coating complex machine structural representation
(1) let off roll, (2) (9) (11) (18) are guide roller, and (5) (14) are for transmitting film roll, and (7) (16) are conveyer belt, (8) (17) are chill roll, (3) be adhesive, (4) (13) applicator roll, (6) are the dry drying tunnel of adhesive, (10) idler roller, (12) polyvinyl alcohol film forming material, the dry drying tunnel of (15) polyvinyl alcohol film, (19) composite membrane wind-up roll.
The main feature of coating complex machine structure is to transmit film roll (5) (14) to be drive roll, adopts the big material of coefficient of friction to make, and plays the film feeding effect. In drying tunnel, bear excessive pulling force in the time of also can preventing simultaneously the stretched film coating and cause deformation. Drying tunnel adopts hot blast following current or adverse current heat drying. Basement membrane by let off roll (1) behind guide roller (2) and applicator roll (4), send into drying tunnel (6) drying by drive roll (5), cool off through chill roll (8) again, carry out the coating second time (being the painting polyethylene alcoholic solution) by idler roller (10), the film of pva coating is sent into drying tunnel (15) drying by drive roll (14), becomes the composite membrane product through chill roll (17) rolling after cooling again.
Thick 80 μ of this product basement membrane, coating total thickness 15 μ, oxygen flow when the composite membrane total thickness is 90～100 μ＜1 milliliter/24 hours rice220 ℃, (sometimes can be zero, be lower than the minimum that instrument can be surveyed), composite membrane is not stratified, wrinkle resistant through water long period of soaking (more than three days), dry rear no significant change, folding 100 times is not stratified ,/2.5 centimetres of interlaminar strengths＞300 grams, this product can be used for the various food of not boiling and the oxygen barrier of product is protected perfume (or spice) and insect protected, anti-oxidation packing.
The invention has the advantages that:
1. coating composite polyvinyl alcohol and commonly used bonding compound comparison can save the polyvinyl alcohol film formation process, make film forming and compoundly finish simultaneously. With the polyethylene compound tense except saving the polyvinyl alcohol film formation process, also can save adhesive and painting process thereof.
2. this product oxygen barrier performance is not less than the composite membrane that nylon, polyester and polyethylene hydrocarbon are made, but its cost is at least low by 20%, and therefore, for the packaging for foodstuff of not boiling, this product can replace the latter fully.
3. the products such as packing milk powder, the extract of malt and milk, dried shrimp can be deposited more than 1 year, and the cured goods of the Pickled such as sausage, hot pickled mustard tube, beans are done, fermented bean curd, stir-fry peanut be more than 3～6 months, and the condiment such as Chinese prickly ash are more than 1 year, and the valuable medicinals such as Radix Angelicae Sinensis can be for a long time insect-free.
4. raw material and equipment are based on our country, and the source is abundant, and is easy and simple to handle, less demanding, and reduced investment (a complete set of equipment is less than 100,000 yuan) is applicable to the medium-sized and small enterprises popularization.
5. obvious economic. Every complete equipment annual earnings is not less than 100,000 yuan, is used for packing various food, and solving food processing, storage and sale has good result. Social benefit is more considerable.
Embodiment:
1. the preparation of polyvinyl alcohol film forming liquid
Add polyvinyl alcohol (trade mark 1799) 225 gram in having 3000 milliliters of three-necked bottles of thermometer, agitator and reflux condenser, deionized water 1275 grams stir, heat temperature raising to 98 ℃, keep 1 hour, and polyvinyl alcohol is dissolved into transparent colourless solution.The cross linking agent system can be used: (A) add trimethylol melamine 18 gram ammonium chlorides 3.9 grams, after mixing, be chilled to 40～50 ℃ and can be incubated to 45 ℃ of coatings; (B) add dimethylol urea 18 grams, ammonium chloride 3.9 grams after mixing, are chilled to 40～50 ℃ and can be incubated in 45 ℃ of coatings.Two kinds of cross linking agent systems must be prepared in the time spent, and the poly-vinyl alcohol solution that is made into should once use up, and should not deposit.
2. the preparation of acrylic copolymer adhesive
Having thermometer, add methyl acrylate 120 grams in 3000 milliliters of three-necked bottles of agitator and reflux condenser, butyl acrylate 500 grams, vinyl acetate 200 grams, styrene 50 grams, acrylic acid 30 grams, benzoyl peroxide 2 grams, ethyl acetate 500 grams, stir after 5 minutes, heat temperature raising to 76～78 ℃, polymerisation 5 hours, conversion ratio is 92-94%.The copolymer that makes is added ester gums 5 grams by per 100 gram butt amounts, and being made into concentration with industrial alcohol-ethyl acetate (7: 3) mixed solvent is 14% coating composite glue solution.
3. basement membrane is with polyethylene or polypropylene thickness 50～90 μ
4. coating combination process
Polyethylene or polypropylene screen are after surface oxidation treatment, and according to Fig. 1, coating complex machine structural representation manufacturing condition carries out compound.
Bondline thickness 1～4 μ
95～100 ℃ of baking temperatures
0.5～2 minute drying time
Polyvinyl alcohol thickness 5-10 μ
120～125 ℃ of baking temperatures
1～3 minute drying time
3.5 meters/minute of coating speeds
Thick 80 μ of this product basement membrane, coating total thickness 15 μ, oxygen permeating amount when the composite membrane total thickness is 90～100 μ＜1 milliliter/meter
224 hours 20 ℃.
Claims (3)
1, the raw material of rubbing method manufacturing polyvinyl alcohol/polyolefin composite membrane and technology [1] are made up of polyvinyl alcohol, polyethylene or polypropylene and adhesive and are it is characterized in that the primary raw material and the technology of producing this composite membrane are:
(1) polyvinyl alcohol film forming raw material
Polyvinyl alcohol 10-17 part
Deionized water 83-90 part
Cross linking agent (in the polyvinyl alcohol consumption) 3-12%
Catalyst (in the polyvinyl alcohol consumption) 1-8%
(2) adhesive of polyvinyl alcohol/polyolefin composite membrane
A, acrylic copolymer adhesive
Acrylic copolymer 10-15%
Solvent (ethanol-ethyl acetate) 85-90%
The recipe ingredient (by weight) of acrylic copolymer preparation is:
Methyl acrylate 2-20 part
Butyl acrylate 2-70 part
2-ethyl hexyl acrylate 2-20 part
Acrylic acid 1-10 part
Vinyl acetate 5-40 part
Styrene 1-10 part
Benzoyl peroxide (being gross weight) 0.1-1%
Ethyl acetate (being gross weight) 30-100%
B, ethylene and vinyl acetate copolymer adhesive
Ethylene and vinyl acetate copolymer (vinyl acetate content 15-40%) 8-15 part
Solvent (toluene-acetone) 85-92 part
(3) the thick 50-90 μ of basement membrane (polyethylene or polypropylene)
(4) polyethylene or polypropylene screen are undertaken compound by following process conditions after surface oxidation treatment:
A, polyvinyl alcohol/polyolefin composite membrane
Bondline thickness 2-8 μ
Baking temperature 60-120 ℃
0.5-2 minute drying time
Polyvinyl alcohol film bed thickness 5-13 μ
Baking temperature 90-200 ℃
1-3 minute drying time
Coating speed 3.5-8 rice/minute
B, polyvinyl alcohol polyethylene composite membrane can directly be coated with compound without glue
2, make polyvinyl alcohol/used primary raw material of polyolefin composite membrane according to the described rubbing method of claim 1 and it is characterized in that cross linking agent is the reactant or the aldehydes of formaldehyde and urea (or melamine) in the polyvinyl alcohol film forming raw material, catalyst is strong acid weak base salt such as ammonium chloride etc.
3, it is characterized in that according to the adhesive (A) in the primary raw material of the described rubbing method manufacturing of claim 1 polyvinyl alcohol/polyolefin composite membrane the optimum formula component (by weight) of this adhesive is:
12 parts of methyl acrylates
50 parts of butyl acrylates
10 parts of 2-ethyl hexyl acrylates
3 parts in acrylic acid
20 parts of vinyl acetates
5 parts of styrene
Benzoyl peroxide (being gross weight) 0.3%
Ethyl acetate (being gross weight) 100%
4, the technology according to the described rubbing method manufacturing of claim 1 polyvinyl alcohol/polyolefin composite membrane is characterized in that the optimum process condition of this technology is:
Bondline thickness 1-4 μ
Baking temperature 95-100 ℃
0.5-2 minute drying time
Polyvinyl alcohol film bed thickness 5-10 μ
Baking temperature 120-125 ℃
1-3 minute drying time
3.5 meters/minute of coating speeds
5, the used equipment (1) of rubbing method manufacturing polyvinyl alcohol/polyolefin composite membrane is characterized in that the main feature of coating complex machine is that the transmission film roll is a drive roll, adopts the big material of coefficient of friction to make, and plays the film feeding effect.In drying tunnel, bear excessive pulling force in the time of can also preventing simultaneously the stretched film coating and cause deformation.Drying tunnel adopts hot blast following current or adverse current heat drying.Basement membrane by let off roll behind guide roller and applicator roll, send into the drying tunnel drying by drive roll, cool off through chill roll again, carry out the coating second time (being the painting polyethylene alcoholic solution) by idler roller, the film of pva coating is sent into the drying tunnel drying by drive roll, becomes the composite membrane product through the chill roll rolling after cooling again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585109218A CN85109218A (en) | 1985-12-01 | 1985-12-01 | Rubbing method is made polyvinyl alcohol/polyolefin composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198585109218A CN85109218A (en) | 1985-12-01 | 1985-12-01 | Rubbing method is made polyvinyl alcohol/polyolefin composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85109218A true CN85109218A (en) | 1986-10-08 |
Family
ID=4796274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198585109218A Pending CN85109218A (en) | 1985-12-01 | 1985-12-01 | Rubbing method is made polyvinyl alcohol/polyolefin composite membrane |
Country Status (1)
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|---|---|
| CN (1) | CN85109218A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431676C (en) * | 2006-09-08 | 2008-11-12 | 浙江工商大学 | Processing technology of polyacrylic acid and cellulose acetate composite membrane |
| CN105315927A (en) * | 2015-11-01 | 2016-02-10 | 华南理工大学 | Special adhesive for polyvinyl alcohol/polyolefine composite film and preparation method of special adhesive |
| CN107746467A (en) * | 2017-10-31 | 2018-03-02 | 华南理工大学 | It is a kind of to use the method that repeatedly coating film-forming process prepares polyvinyl alcohol film |
| CN113388140A (en) * | 2021-08-04 | 2021-09-14 | 广西壮族自治区农业科学院 | Special preservative film containing nano pectin coating for pitaya and preparation method of preservative film |
-
1985
- 1985-12-01 CN CN198585109218A patent/CN85109218A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431676C (en) * | 2006-09-08 | 2008-11-12 | 浙江工商大学 | Processing technology of polyacrylic acid and cellulose acetate composite membrane |
| CN105315927A (en) * | 2015-11-01 | 2016-02-10 | 华南理工大学 | Special adhesive for polyvinyl alcohol/polyolefine composite film and preparation method of special adhesive |
| CN107746467A (en) * | 2017-10-31 | 2018-03-02 | 华南理工大学 | It is a kind of to use the method that repeatedly coating film-forming process prepares polyvinyl alcohol film |
| CN113388140A (en) * | 2021-08-04 | 2021-09-14 | 广西壮族自治区农业科学院 | Special preservative film containing nano pectin coating for pitaya and preparation method of preservative film |
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