CN100588693C - Low-temperature heat sealed high resistant foodstuff package cotating film latex and preparation method thereof - Google Patents

Low-temperature heat sealed high resistant foodstuff package cotating film latex and preparation method thereof Download PDF

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CN100588693C
CN100588693C CN200810120694A CN200810120694A CN100588693C CN 100588693 C CN100588693 C CN 100588693C CN 200810120694 A CN200810120694 A CN 200810120694A CN 200810120694 A CN200810120694 A CN 200810120694A CN 100588693 C CN100588693 C CN 100588693C
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latex
reactor
total amount
preparation
mixed monomer
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CN101358054A (en
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葛飞雄
方勇
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Hainan BNK Water Based New Materials Co Ltd
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NINGBO NASOER RUBBER LATEX TECHNOLOGY Co Ltd
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Abstract

The invention relates to a low-temperature heat-sealing high-barrier food packaging film coating latex. The composition points of the mixed monomer of the latex is that vinylidene chloride accounts for 80 to 93 percent of the total amount of the mixed monomer; methyl acrylate, methyl ethyl oxalate, methyl methacrylate, butyl ester, acrylonitrile or methacrylonitrile account for 2 to 10 percent ofthe total amount of the mixed monomer; itaconic acid, acrylic acid, methacrylic acid account for 0.5 to 5 percent of the total amount of the mixed monomer; the surfactants added are 0.7 portion of SASand 0.3 portion of sodium dodecyl sulfate; the additive 3 is 0.01 portion of metallic salt. The preparation method includes the following steps: deionized water, surfactant and additive are added ina reactor; the reactor is vacuumized and the gas is replaced by nitrogen gas; the mixed monomer is added. The product of the invention has the advantages of low temperature heat sealing and high barrier performance, and the food using the product has longer shelf life.

Description

High barrier food package coated membrane latexes by thermal sealing at low temperature and preparation method
Technical field
The present invention relates to a kind of high barrier food package coated membrane latexes by thermal sealing at low temperature and preparation method.
Background technology
Latex is used in many products, the coating of the building decoration of using that has, and keep a public place clean in the surface of catering trade food box tool.But up to now, be used under the cold condition heat-sealing, and the food package coated membrane latex with high-barrier does not appear on the market as yet.Because of the heat-sealing temperature with a kind of plastic material will be close with the fusing point of material substantially, not so both fusion difficulty are big, do not reach the effect of heat-sealing.
Summary of the invention
For overcoming above-mentioned deficiency, the object of the invention provides a kind of preparation method of high barrier food package coated membrane latexes by thermal sealing at low temperature, it can be solved under cold condition seal, and have the technical problem of high-barrier characteristic.The objective of the invention is to adopt following technical scheme to realize.
A kind of high barrier food package coated membrane latexes by thermal sealing at low temperature, the main points of the configuration of the mix monomer of this latex are:
(1) vinylidene chloride accounts for 80%~93% of mix monomer total amount;
(2) methyl acrylate, ethyl ester, methyl methacrylate, butyl ester, vinyl cyanide or methacrylonitrile account for 2%~10% of mix monomer total amount;
(3) methylene-succinic acid, vinylformic acid, methacrylic acid account for 0.5%~5% of mix monomer total amount;
(4) adding tensio-active agent is 0.7 part of secondary sodium alkanesulfonate, 0.3 part of sodium lauryl sulphate;
(5) adding auxiliary agent 3 is 0.01 part of metal-salt.
(6) adding auxiliary agent 4 is 0.01 part in ionogen such as zinc sulfate.
A kind of preparation method of high barrier food package coated membrane latexes by thermal sealing at low temperature, this latex production technique is emulsion polymerisation process preparation commonly used, interrupter method, the latex of preparation is used in polypropylene BOPP, polyester PET, polymeric amide OPA goes up coating film forming, be used for the food package coated membrane surface, to airborne water, oxygen possesses high barrier.Described high-barrier is exactly by the made latex of the present invention, be coated on the surface of food package coated membrane, the food in the film will play and guarantee the quality, fresh-keeping effect, because coated film latex is with airborne water, oxygen has carried out the isolation of height blocking type, so be called " high-barrier ".Its key points in design is:
In reactor, add 42 parts of deionized waters, 0.7 part of the secondary sodium alkanesulfonate of tensio-active agent, 0.3 part of sodium lauryl sulphate, 0.001 part of auxiliary agent 1 (Glacial acetic acid), 0.0001 part of auxiliary agent 2 (ferrous ion), auxiliary agent 3 (ionogen, NaCl, KCl) 0.02 part, add in the reactor, vacuumize, use nitrogen replacement, vacuumize, use nitrogen replacement, vacuumize, twice half operations add 50 parts of mix monomers in reactor, cold dispersion half an hour, described cold dispersion is added to raw material in the reactor exactly, start stirring, reacting kettle jacketing adds the tap water cooling, is warming up to 52 ℃ thereafter, add 0.02 part of 0.02 part of initiator tertbutyl peroxide that configures and the initiator B formolation Sodium Thiosulfate that configures continuously, when reaction pressure was reduced to negative pressure, reaction finished, and added auxiliary agent 4,0.01 part, vacuumize and take off suction, earlier temperature is risen to 70 ℃~75 ℃, open vacuum pump, open bottom valve on a small quantity, feed the steam of 0.1~0.2MPa, open vacuum, be evacuated to-the 0.09MPa treatment time is 4~5 hours, be cooled to 38 ℃, filter discharging by 120 orders;
Advantage of the present invention: the temperature of low-temperature heat-sealing is 110 ℃, possesses high obstructing performance, prolongs shelf-lives, the quality guaranteed period of food.
By BOPP, BOPET, BOPA being carried out the test after the PVDC emulsion is coated with preceding and coating
Figure C20081012069400041
Chocolate is packed respectively with heat-sealing type BOPP and PVDC,,, under the 50% relative humidity condition, carried out fuchsin(e)test and sensory evaluation at 25 ℃ to estimate the degree of protection of two kinds of materials to biscuit.Found that the former after four months fragility obviously reduce, lose chocolate taste after six months, rate of moisture absorption reaches 1.88% after four months, and the latter is after seven months, fragility is still fine, does not lower chocolate taste after nine months on mouthfeel, and rate of moisture absorption reached 1.58% in seven months.The packing bag of PVDC through the coating of this latex is described, to airborne water, oxygen has high barrier, makes the fresh-keeping effect of food good.
Description of drawings
Fig. 1 is a technological process block-diagram.
Earlier auxiliary agent, deionized water, surfactant are added in the reactor, add nitrogen, vacuumize, will mix Close monomer and be added in the reactor, cold dispersion half an hour, be warming up to 52 ℃, add simultaneously initiator A, B, When reactor Pressure Drop during to-0.01Mpa, add auxiliary agent 4, the vacuum desorption is cooled to 38 ℃, filters out Become product.
Embodiment
Scheme 1
Preparation: 0.02 part of adding of initiator A tertbutyl peroxide 8kg deionized water is standby;
0.02 part of adding of initiator B formolation time sodium bisulfite 8kg deionized water is standby;
Still material: deionized water 82kg
Auxiliary agent 10.02kg
Auxiliary agent 20.002kg
Auxiliary agent 30.04kg
Emulsifying agent: secondary sodium alkanesulfonate 1.4kg
Dodecyl acid sulphur sodium 0.6kg
Mix monomer vinylidene chloride 92.5kg
Vinyl cyanide 7kg
Methylene-succinic acid 0.5kg
The still material is added in 200 liters of reactors, vacuumized nitrogen, at last the pressure of reactor is reduced to-0.08~-0.095MPa, suck mix monomer, cold dispersion half an hour, when being warming up to 52 ℃, add the initiator A tertbutyl peroxide that configures continuously, initiator B formolation time sodium bisulfite, temperature keeps 52 ℃, and the reaction times is 10-15 hour, when pressure is reduced to 0.01MPa, stop adding initiator, open reactor and add auxiliary agent 4 zinc sulfate, heat up to take off and inhaled 4 hours, be cooled to 38 ℃, filter discharging by 120 order stainless (steel) wires.The acquisition physical index is as follows:
Solid content (%) 50 ± 1
Surface tension (mN/m)≤50
Viscosity (mPa.s)≤10
PH 2-3
Density (g/m m) 1.25~1.29
Scheme 2
Preparation, still material, tensio-active agent, deionized water are identical with scheme 1.
Mix monomer: vinylidene chloride 92.5kg
Ethyl propenoate 6.5kg
Vinylformic acid 1kg
The acquisition physical index is as follows:
Solid content (%) 50 ± 1
Surface tension (mN/m)≤50
Viscosity (mPa.s)≤10
PH 2-3
Density (g/mm) 1.25~1.29
Scheme 3
Preparation, still material, tensio-active agent, deionized water are identical with scheme 1.
Mix monomer: vinylidene chloride 92.5kg
Methyl methacrylate 6.5kg
Methacrylic acid 1kg
Solid content (%) 50 ± 1
Surface tension (mN/m)≤50
Viscosity (mPa.s)≤10
PH 2-3
Density (g/mm) 1.25~1.29
The use introduction of latex: coated film applies latex again behind coating primer (polyamine fat or water-soluble primer), latex is operational version 1,2,3 separately; Or select scheme 1 latex 80kg for use; Scheme 2 latex 20kg mix coating; Or select scheme 1 latex 80kg for use, and scheme 3 latex 20kg mix coating, and the mixing of this latex can be adjusted use according to customer requirement.
The working conditions of latex
Drying tunnel top temperature: 110~125 ℃ glue spread: 2.5~3g/ square metre
Set time: 45 ℃ of 48 hours solid contents in the drying room: 50% ± 1%
One, latex allotment
Before the latex warehouse-in, the user contrasts the quality certificate content, as requested, suitably does a little allotments, and the equipment of contact latex should be corrosion resistant
Two, pH value is regulated
If generally speaking, the latex pH value is 1~3, and is all useful to transparency after cohesive strength, the film forming and uvioresistant lamp, but coating apparatus this acidity of ability not, can add 3% ammonia soln and allocate, and should add under fully stirring.
Three, surface tension adjustment
Reduce surface tension of latex, can add the secondary sodium alkanesulfonate of tensio-active agent below 20%, add under fully stirring, the emulsifying agent consumption should be less than 1% of latex solid content, otherwise will influence coating quality.
Four, glued membrane temperature and heat energy mode
The latex minimum film-forming temperature is generally 16~28 ℃, therefore, hopper, version roller operating temperature should be lower than 15 ℃.About 90 ℃ of base material coating after drying temperature, preferably with the outer thermal source of far infrared rays from the substrate backside radiative oven dry, otherwise cause vaporific film easily.
Five, drying tunnel temperature distributes
Drying tunnel easily adopts gradient increased temperature, at the last shelves of drying tunnel outlet, moment film temperature about 110 ℃, it is fully plastified, the easy like this film that makes reaches desirable degree of crystallinity.
Six, the application of poly-cold roller
Must collect suddenly the film temperature drop is arrived room temperature, unlikely adhesion when helping the film forming rolling like this through poly-cold roller (interior logical cold water) after going out drying tunnel.
Seven, set time
The PVDC coated film must be placed on 45 ℃ of drying rooms 48 hours, made it reach maximum degree of crystallinity, and its barrier property can reach application indexes.
Eight, equipment washing
Coating system should be rinsed well with tap water when shutting down at once, otherwise can influence coating next time by conjunctiva, can use hot-water soak if any conjunctiva, and conjunctiva can remove.

Claims (1)

1, a kind of preparation method of high barrier food package coated membrane latexes by thermal sealing at low temperature, this latex production technique is emulsion polymerisation process preparation commonly used, interrupter method, the latex of preparation is used in polypropylene BOPP, polyester PET, polymeric amide OPA goes up coating film forming, be used for the food package coated membrane surface, to airborne water, oxygen has high barrier, it is characterized in that:
In reactor, add 42 parts of deionized waters, 0.7 part of the secondary sodium alkanesulfonate of tensio-active agent, 0.3 part of sodium lauryl sulphate, 0.001 part in auxiliary agent 1 Glacial acetic acid, 0.0001 part of auxiliary agent 2 ferrous ion, 0.02 part of auxiliary agent 3NaCl or KCl; Vacuumize in reactor, use nitrogen replacement, vacuumize, use nitrogen replacement, vacuumize, twice half operations add 50 parts of mix monomers in reactor, cold dispersion half an hour; Described cold dispersion is added to raw material in the reactor exactly, start stirring, reacting kettle jacketing adds the tap water cooling, thereafter be warming up to 52 ℃, add 0.02 part of 0.02 part of initiator tertbutyl peroxide that configures and the initiator formolation Sodium Thiosulfate that configures continuously, when reaction pressure was reduced to negative pressure, reaction finished, add 0.01 part in auxiliary agent 4 zinc sulfate, vacuumize and take off suction, earlier temperature is risen to 70 ℃~75 ℃, open vacuum pump, open bottom valve on a small quantity, feed the steam of 0.1~0.2MPa, open vacuum, be evacuated to-the 0.09MPa treatment time is 4~5 hours, be cooled to 38 ℃, filter discharging by 120 orders; Described mix monomer is made up of following material:
(1) vinylidene chloride accounts for 80%~93% of mix monomer total amount;
(2) methyl acrylate, ethyl ester, methyl methacrylate, butyl ester, vinyl cyanide or methacrylonitrile account for 2%~10% of mix monomer total amount;
(3) methylene-succinic acid, vinylformic acid, methacrylic acid account for 0.5%~5% of mix monomer total amount.
CN200810120694A 2008-09-04 2008-09-04 Low-temperature heat sealed high resistant foodstuff package cotating film latex and preparation method thereof Expired - Fee Related CN100588693C (en)

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CN102650111B (en) * 2012-05-10 2015-05-20 海南必凯水性涂料有限公司 High-solid coating containing polyvinylidene chloride for paper coating and preparation method of coating
CN103087249B (en) * 2012-12-26 2015-12-23 海南聚能功能薄膜技术开发有限公司 Food packaging latex and its preparation method and application
CN103044602B (en) * 2012-12-26 2015-04-08 海南必凯水性涂料有限公司 Paper coating water-based emulsion and preparation method and applications thereof
CN103059198B (en) * 2012-12-26 2015-07-22 海南必凯水性涂料有限公司 Polyvinylidene chloride copolymer emulsion used for glass fiber dip coating and preparation thereof and application thereof
CN103059197B (en) * 2012-12-26 2015-04-08 海南必凯水性涂料有限公司 Aqueous antiseptic metal undercoat polyvinyl dichloride (PVDC) copolymer emulsion and preparation method thereof and application
CN103059193B (en) * 2012-12-26 2016-01-20 海南聚能功能薄膜技术开发有限公司 Special PVDC latex coating of cigarette film and its preparation method and application
CN103059200B (en) * 2012-12-26 2015-12-23 海南聚能功能薄膜技术开发有限公司 Glassine paper coating PVDC emulsion and its preparation method and application
CN103044604B (en) * 2012-12-26 2015-04-08 海南必凯水性涂料有限公司 Polyvinylidene chloride copolymer emulsion for glass fiber dip-coating liquid, as well as preparation method and use thereof
CN103059194B (en) * 2012-12-26 2015-06-24 海南必凯水性涂料有限公司 Polyvinyl dichloride (PVDC) latex special for slick paper used for food packaging and preparation method thereof and application thereof
CN103319642B (en) * 2013-05-17 2015-09-30 海南必凯水性涂料有限公司 A kind of heat-sealing type PVDC emulsion possessing anti-fog function and preparation method thereof
JP6739202B2 (en) * 2016-03-28 2020-08-12 株式会社クレハ Method for producing vinylidene chloride resin film and method for recycling pile liquid used in the method

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