CN102848673B - High-oxygen resistant steaming-resistant polyvinylidene chloride coating film and manufacturing method thereof - Google Patents
High-oxygen resistant steaming-resistant polyvinylidene chloride coating film and manufacturing method thereof Download PDFInfo
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- CN102848673B CN102848673B CN201210294409.XA CN201210294409A CN102848673B CN 102848673 B CN102848673 B CN 102848673B CN 201210294409 A CN201210294409 A CN 201210294409A CN 102848673 B CN102848673 B CN 102848673B
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 229920001328 Polyvinylidene chloride Polymers 0.000 title claims abstract description 53
- 239000005033 polyvinylidene chloride Substances 0.000 title claims abstract description 53
- 238000010025 steaming Methods 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000001301 oxygen Substances 0.000 title abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 23
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008234 soft water Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000010408 film Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 20
- 229920002635 polyurethane Polymers 0.000 claims description 20
- 239000010409 thin film Substances 0.000 claims description 20
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- 239000004203 carnauba wax Substances 0.000 claims description 17
- 235000011194 food seasoning agent Nutrition 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000003851 corona treatment Methods 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000004260 weight control Methods 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
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- 238000010790 dilution Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
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- 229920000131 polyvinylidene Polymers 0.000 description 28
- 238000009835 boiling Methods 0.000 description 22
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
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- 230000001954 sterilising effect Effects 0.000 description 15
- 238000004659 sterilization and disinfection Methods 0.000 description 15
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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Abstract
The invention relates to a high-oxygen resistant steaming-resistant polyvinylidene chloride coating film and a manufacturing method thereof. The high-oxygen resistant steaming-resistant polyvinylidene chloride coating film comprises a base, a coating layer on the surface of the base, and a base glue layer between the coating layer and the base. The coating layer is a coating obtained by coating modified high-oxygen resistant steaming-resistant polyvinylidene chloride latex. The modified high-oxygen resistant steaming-resistant polyvinylidene chloride latex comprises: by weight, 30 to 38% of a high-oxygen resistant steaming-resistant polyvinylidene chloride blended emulsion, 1.5 to 6% of a nano-material filler, 1 to 8% of a slip agent, 0.1 to 5% of an abherent and 5 to 60% of softened water. The high-oxygen resistant steaming-resistant polyvinylidene chloride blended emulsion comprises: by weight, 40 to 94% of a vinylidene chloride monomer, 1.5 to 10% of an acrylate, 1 to 6% of one or more of acrylic acid and acrylonitrile, 0.5 to 2% of an initiator, 0.1 to 0.8% of an emulsifier, 0.5 to 1% of a stabilizer and 0 to 55% of soft water.
Description
Art
The present invention relates to a kind of resistant steaming-resistant polyvinylidene chloride coated thin film and manufacture method thereof, belong to novel high polymer material field.
Background technology
Vial and metal filling in the past very over a long time in become the major way of food storage always, the foods packed in carton containers that American Studies in 1958 goes out is packed and is successfully replaced tinplate can, and start commercialization large-scale production, nineteen sixty-eight plays Japan and starts with high-temperature retort bag packaging curry, rice, meat ball etc., thermophilic digestion sterilization becomes a kind of method of conventional prolongation effective period of food quality, but because thermophilic digestion condition is harsh, in addition high-temperature retort bag technical capability waits perfect, so far, every year all can because of the bag that rises occurred in digestion process, broken bag, peculiar smell, delamination, surface wrinkling, crimping, gas leakage, there is the problems such as pin hole and cause quality dispute.At present, when selecting thermophilic digestion bag material, except overcoming the above problems, safety and environmental protection, low cost, excellent barrier property and shelf life can be extended better become the technical parameter that first manufacturer consider.
Summary of the invention
For above problem, the object of the present invention is to provide a kind of resistant steaming-resistant polyvinylidene chloride coated thin film, this coated thin film with the obtained resistant steaming-resistant polyvinylidene chloride latex of modification of the present invention for organic coating, efficiently solve the shortcoming adopting aluminium foil etc. to do composite bed easily to occur pin hole, can digestion resistant and non-whitening is non-yellowing, and safety and environmental protection, there is excellent oxygen barrier property.After dry type compound, decrease to a great extent vacuumize, high pressure, the bag that rises during pressure oscillation, bale broken, gas leak phenomenon, extend shelf life and reduce cost to a great extent.
Resistant steaming-resistant polyvinylidene chloride coated thin film provided by the invention, comprise the dope layer of base material and substrate surface, primer layer between dope layer and base material, described dope layer is the resistant steaming-resistant polyvinylidene chloride coating formed after primer layer surface is also dried by the resistant steaming-resistant polyvinylidene chloride latex-coating that modification obtains by the present invention, described resistant steaming-resistant polyvinylidene chloride latex is formulated by the raw material containing following weight content: resistant steaming-resistant polyvinylidene chloride blending emulsion 30-88%, nanomaterial-filled dose of 1.5-6%, slipping agent 1-8%, antitack agent 0.1-5%, 5-60% demineralized water, described resistant steaming-resistant polyvinylidene chloride blending emulsion is made up of the raw material containing following weight content: the vinylidene of 40-94%, the esters of acrylic acid of 1.5-10% and the acrylic acid of 1-6% and acrylonitrile mixed liquor or any one in both, the initator of 0.5-2%, the emulsifying agent of 0.1-0.8%, the stabilizing agent of 0.5-1%, 0-55% soft water.
Described resistant steaming-resistant polyvinylidene chloride latex, solid content is preferably 45-55%, within the scope of this can for a long time in keep amorphous state, and when drying, there is good film forming ability.
Described nanomaterial-filled dose is any one in CaCO3, TiO2, mica, imvite, by the core that the inorganic material of particle scale and nanoscale is filling-modified, can interface bond strength be improved, prevent from being separated, improve barrier property and mechanical property further.
Described esters of acrylic acid is preferably methyl methacrylate.
Described initator is preferably sodium peroxydisulfate.
Described emulsifying agent is preferably neopelex.
The preferred J-1 stabilizing agent of described stabilizing agent, its feature is to the good stability of light and heat, and transparency is high, can keep in high temperature process not roll banding, do not block, especially there is good later stage heat endurance.
Described acrylate monomer is: methyl acrylate, acrylonitrile monemer, with a small amount of polar group, can change the different vitrification point of copolymer.
Described stabilizing agent, can improve that in PVC synthesis, generate allyl chloride, tertiary carbon chlorine and double bond etc. be destabilizing factor and make polyvinylidene chloride coated film possess high-fire resistance and long-actingization in thermophilic digestion in its molecular chain structure.
Described base material film is biaxially oriented polyester film, and thickness is 8-120 μm.
Described primer layer is the coating that aqueous polyurethane or solvent borne polyurethane add solvent formation, and polyurethane adhesive shows activity and the polarity of height, and the base material containing active hydrogen and coating can be made to have excellent chemical adhesive power.
Described polyurethane adhesive comprises host, curing agent.
Described slipping agent is palm wax slipping agent, has good dispersive property in coating, and suitable consumption can prevent from being clamminess, mildew-resistant.
Described antitack agent is silica anti-blocking agent.
The coating weight of described dope layer is 0.8-5.0g/m
2.
The coating weight of described primer layer is 0.3-1.5g/m
2.
Correspondingly, the present invention also provides a kind of manufacture method of resistant steaming-resistant polyvinylidene chloride coated thin film, and the method comprises the steps:
1, the soft water of 0-55% is first added in a kettle. successively, the initator sodium peroxydisulfate of 0.5-2%, the J-1 stabilizing agent of 0.5-1% and the vinylidene of 40-94%, then--adding nitrogen--row pressure-vacuumize-Jia nitrogen-row pressure is vacuumized, complete twice half operations, Stress control is-0.08Mpa., mixing speed is 60-180 rev/min, heats up and makes temperature control within the scope of 50-85 DEG C, fully stirs 30-60 minute, vinylidene is dissolved completely, obtains seed emulsion.Drip 1.5-10% methyl methacrylate, 1-6% acrylic acid, the emulsifying agent neopelex of 1-6% acrylonitrile and 0.1-0.8%, rate of addition 5-15 gram/minute.Be warming up to 90 DEG C after dripping to continue to keep 30-90 minute, whole system is fully reacted.Finally, be cooled to normal temperature and pressure, obtained resistant steaming-resistant polyvinylidene chloride blending emulsion.
2, in rustless steel container, add above-mentioned obtained resistant steaming-resistant polyvinylidene chloride blending emulsion, stir 20-40 minute, speed 60-200 rev/min, temperature controls within the scope of 40-50 DEG C.Then add nanomaterial-filled dose of 1.5-6%, and then improve temperature of reaction kettle to 55-60 DEG C, material in reactor is fully mixed.Stir while add the palm wax slipping agent of 1-8%, the silica anti-block of 0.1-5% and the demineralized water of 5-60% successively, after stirring resistant steaming-resistant polyvinylidene chloride latex, operation to be coated uses.
3, by polyurethane adhesive host and curing agent in 5: 1 ratio add successively in another rustless steel container, stir and add solvent dilution, solvent proportion is 4 times of host, can form primer after stirring, and next process to be entered uses.
4, arranging unwinding tension is 2-6bar, carry out sided corona treatment to base film, and primer even spread is dried with coating apparatus by the substrate surface after sided corona treatment, and coating speed is 80-250 m/min, and primary coat coating weight control is at 0.2-1.5g/m
2,bake out temperature is 80-160 DEG C, and drying time is 6 seconds.After cooling, then be coated on primer through coating apparatus by resistant steaming-resistant polyvinylidene chloride emulsion uniform obtained for above-mentioned steps 2, coating weight control is 0.8-4.5g/m
2, then dry the film be coated with, coating speed is 80-250 m/min, and bake out temperature is 80-160 DEG C, drying time 8 seconds.Rolling after resistant steaming-resistant polyvinylidene chloride coated and dried, the winding tension rate of decay is 40-55%.Solidify 2 days under coated film volume is placed on 45 DEG C of conditions, obtained resistant steaming-resistant polyvinylidene chloride coated thin film of the present invention.
Coating speed in above-mentioned steps is preferably 150-250m/min, can ensure coating quality and make production efficiency higher; The preferred hot-air seasoning of drying course or Far-infrared Heating are dried, or adopt far infrared and hot-air seasoning two kinds of modes simultaneously; Coating method preferably reverses roller kiss-type coating method, effectively can solve traditional coating method coating and pollute other roller problem, and a difficult problem for coatings lack of homogeneity.
The resistant steaming-resistant coated film that the present invention obtains, most Gao Kenai is thirty minutes long the thermophilic digestion of 135 DEG C, the transparent coated film presentation exterior quality of interior bag thing uniqueness.Table one is compared tool for resistant steaming-resistant coated film have the following advantages with the existing polyvinylidene chloride of resistance to boiling (hereinafter referred to as PVDC) coated film:
Table one
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Detailed description of the invention
Specific embodiment is described further resistant steaming-resistant polyvinylidene chloride coated thin film of the present invention and manufacture method thereof below.
Embodiment one
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 7.5kg
Host: commercially available host 17.5kg
Curing agent: commercially available curing agent 3.5kg
Solvent: commercially available solvent 70kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 175kg
Demineralized water: 300kg
Slipping agent: commercially available palm wax slipping agent 3kg
Anti-blocking agent: commercially available silica anti-block 2.5kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 175kg adds in rustless steel container, stir while add 3kg palm wax slipping agent, nanomaterial-filled dose of 7.5kg, 2.5kg silica anti-block and 300kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 17.5kg host, 3.5kg curing agent adds in another rustless steel container, stir while add 70kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 0.3g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 4.0g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 200m/min.Primer layer baking temperature is 125 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 120 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 6.5 | 8.0 |
| Water penetration (g/m 2.24hr) | 9.3 | 10.1 |
| Mist degree (%) | 3.5 | 3.6 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment two
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 24kg
Host: commercially available host 20kg
Curing agent: commercially available curing agent 4kg
Solvent: commercially available solvent 80kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 200kg
Demineralized water: 152kg
Slipping agent: commercially available palm wax slipping agent 4kg
Anti-blocking agent: commercially available silica anti-block 20kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 200kg adds in rustless steel container, stir while add 4kg palm wax slipping agent, nanomaterial-filled dose of 24kg, 20kg silica anti-block and 152kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 20kg host, 4kg curing agent adds in another rustless steel container, stir while add 80kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 0.3g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 5.0g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 250m/min.Primer layer baking temperature is 160 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 160 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 5.6 | 7.8 |
| Water penetration (g/m 2.24hr) | 9.1 | 10.1 |
| Mist degree (%) | 3.5 | 3.6 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment three
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 5kg
Host: commercially available host 8.8kg
Curing agent: commercially available curing agent 1.76kg
Solvent: commercially available solvent 35.2kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 88kg
Demineralized water: 5.9kg
Slipping agent: commercially available palm wax slipping agent 1kg
Anti-blocking agent: commercially available silica anti-block 0.1kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 88kg adds in rustless steel container, stir while add 1kg palm wax slipping agent, nanomaterial-filled dose of 5kg, 0.1kg silica anti-block and 5.9kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 8.8kg host, 1.76kg curing agent adds in another rustless steel container, stir while add 35.2kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 0.3g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 2.0g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 150m/min.Primer layer baking temperature is 100 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 100 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 6.0 | 8.2 |
| Water penetration (g/m 2.24hr) | 9.6 | 10.2 |
| Mist degree (%) | 3.7 | 3.8 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment four
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 25kg
Host: commercially available host 15kg
Curing agent: commercially available curing agent 3kg
Solvent: commercially available solvent 60kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 150kg
Demineralized water: 275kg
Slipping agent: commercially available palm wax slipping agent 40kg
Anti-blocking agent: commercially available silica anti-block 10kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 150kg adds in rustless steel container, stir while add 40kg palm wax slipping agent, nanomaterial-filled dose of 25kg, 10kg silica anti-block and 275kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 15kg host, 3kg curing agent adds in another rustless steel container, stir while add 60kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 0.9g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 3.5g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 250m/min.Primer layer baking temperature is 160 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 160 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 5.8 | 8.0 |
| Water penetration (g/m 2.24hr) | 9.4 | 10.0 |
| Mist degree (%) | 3.6 | 3.7 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment five
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 4.5kg
Host: commercially available host 25.5kg
Curing agent: commercially available curing agent 5.1kg
Solvent: commercially available solvent 102kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 255kg
Demineralized water: 1.5kg
Slipping agent: commercially available palm wax slipping agent 24kg
Anti-blocking agent: commercially available silica anti-block 15kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 255kg adds in rustless steel container, stir while add 24kg palm wax slipping agent, nanomaterial-filled dose of 4.5kg, 15kg silica anti-block and 1.5kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 25.5kg host, 5.1kg curing agent adds in another rustless steel container, stir while add 102kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 1.0g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 4.0g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 250m/min.Primer layer baking temperature is 160 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 160 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 5.8 | 7.9 |
| Water penetration (g/m 2.24hr) | 9.3 | 10.1 |
| Mist degree (%) | 3.5 | 3.6 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment six
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 9kg
Host: commercially available host 13.5kg
Curing agent: commercially available curing agent 2.7kg
Solvent: commercially available solvent 54kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 135kg
Demineralized water: 135kg
Slipping agent: commercially available palm wax slipping agent 12kg
Anti-blocking agent: commercially available silica anti-block 9kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 135kg adds in rustless steel container, stir while add 12kg palm wax slipping agent, nanomaterial-filled dose of 9kg, 9kg silica anti-block and 135kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 13.5kg host, 2.7kg curing agent adds in another rustless steel container, stir while add 54kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 1.5g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 3.0g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 250m/min.Primer layer baking temperature is 150 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 150 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 5.9 | 8.3 |
| Water penetration (g/m 2.24hr) | 9.6 | 10.2 |
| Mist degree (%) | 3.6 | 3.8 |
Note: 1) oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Embodiment seven
Base material: biaxial stretching polyester (BOPET), thickness is 12 μm.
Nanomaterial-filled dose of 12kg
Host: commercially available host 10kg
Curing agent: commercially available curing agent 2kg
Solvent: commercially available solvent 40kg
Polyvinylidene emulsions: homemade polyvinylidene emulsions 100kg
Demineralized water: 70kg
Slipping agent: commercially available palm wax slipping agent 16kg
Anti-blocking agent: commercially available silica anti-block 2kg
Taking the above-mentioned obtained polyvinylidene chloride blending emulsion of 100kg adds in rustless steel container, stir while add 16kg palm wax slipping agent, nanomaterial-filled dose of 12kg, 2kg silica anti-block and 70kg demineralized water successively, after stirring the modification polyvinylidene emulsions of resistance to boiling, operation to be coated uses.
Take 10kg host, 2kg curing agent adds in another rustless steel container, stir while add 40kg solvent, it is generating polyurethane primer after stirring, sided corona treatment is carried out using after the Biaxially oriented polypropylene base material of base material unreels, evenly transferred on base film by aqueous polyurethane primer by reverse roll kiss formula coating method, coating weight is 0.5g/m
2, after far infrared and hot-air seasoning, forming primer layer, and then evenly transferring on film primer layer by reversing roller kiss-type coating method by the above-mentioned obtained modification polyvinylidene emulsions of resistance to boiling, coating weight is 0.8g/m
2, after far infrared and hot-air seasoning, form modified polyvinilidene dichloroethylene coating, coating speed is 80m/min.Primer layer baking temperature is 80 DEG C, and drying time is 6 seconds, and modified polyvinilidene dichloroethylene coating baking temperature is 80 DEG C, and drying time is 8 seconds.Rolling after modified polyvinilidene dichloroethylene coated and dried, solidifies 2 days under 45 DEG C of conditions, the obtained polyvinylidene chloride of resistance to boiling coated thin film of the present invention.
The resistant steaming-resistant coated film performance that the present embodiment obtains is as follows
| Resistant steaming-resistant condition | 121 DEG C of sterilizations half an hour | 135 DEG C of sterilizations half an hour |
| Outward appearance | Transparent | Transparent |
| Coating shedding situation | Do not come off | Do not come off |
| Oxygen permeability (cc/m 2.24hr) | 6.2 | 8.5 |
| Water penetration (g/m 2.24hr) | 10.0 | 10.5 |
| Mist degree (%) | 3.8 | 4.0 |
Note: oxygen flow testing conditions is: 23 DEG C, 0%RH; Permeable testing conditions is: 38 DEG C, 90%RH.
Claims (4)
1. a manufacture method for resistant steaming-resistant polyvinylidene chloride coated thin film, is characterized in that the method comprises the steps:
(1) soft water of 0-55% is first added in a kettle. successively, the initator sodium peroxydisulfate of 0.5-2%, the J-1 stabilizing agent of 0.5-1% and the vinylidene of 40-94%, then--adding nitrogen--row pressure-vacuumize-add nitrogen-row pressure is vacuumized, complete twice half operations, Stress control is-0.08Mpa, mixing speed is 60-180 revs/min, intensification makes temperature control within the scope of 50-85 DEG C, abundant stirring 30-60 minute, vinylidene is dissolved completely, obtain seed emulsion, drip 1.5-10% methyl methacrylate, 1-6% acrylic acid, the neopelex of 1-6% acrylonitrile and 0.1-0.8%, rate of addition 5-15 gram/minute, be warming up to 90 DEG C after dripping to continue to keep 30-90 minute, whole system is fully reacted, finally be cooled to normal temperature and pressure, obtained resistant steaming-resistant polyvinylidene chloride blending emulsion,
(2) in rustless steel container, above-mentioned obtained resistant steaming-resistant polyvinylidene chloride blending emulsion is added, stir 20-40 minute, speed 60-200 revs/min, temperature controls within the scope of 40-50 DEG C, then nanomaterial-filled dose of 1.5-6% is added, and then improve temperature of reaction kettle to 55-60 DEG C, material in reactor is fully mixed, stir while add the palm wax slipping agent of 1-8% successively, the silica anti-block of 0.1-5% and the demineralized water of 5-60%, after stirring resistant steaming-resistant polyvinylidene chloride latex, operation to be coated uses,
(3) polyurethane adhesive host and curing agent are added in another rustless steel container in the ratio of 5:1 successively, stir while add solvent dilution, solvent proportion is 4 times of host, can form primer after stirring, and next process to be entered uses;
(4) arranging unwinding tension is 2-6bar, carry out sided corona treatment to base film, and primer even spread is dried with coating apparatus by the substrate surface after sided corona treatment, and coating speed is 80-250 m/min, and primary coat coating weight control is at 0.2-1.5g/m
2,bake out temperature is 80-160 DEG C, and drying time is 6 seconds, and after cooling, then be coated on primer through coating apparatus by resistant steaming-resistant polyvinylidene chloride emulsion uniform obtained for above-mentioned steps 2, coating weight control is 0.8-4.5g/m
2then the film be coated with is dried, coating speed is 80-250 m/min, bake out temperature is 80-160 DEG C, drying time 8 seconds, rolling after resistant steaming-resistant polyvinylidene chloride coated and dried, the winding tension rate of decay is 40-55%, solidify 2 days under coated film volume is placed on 45 DEG C of conditions, obtained resistant steaming-resistant polyvinylidene chloride coated thin film of the present invention.
2. the manufacture method of resistant steaming-resistant polyvinylidene chloride coated thin film as claimed in claim 1, is characterized in that: described drying mode adopts hot-air seasoning.
3. the manufacture method of resistant steaming-resistant polyvinylidene chloride coated thin film as claimed in claim 1, is characterized in that: described drying mode adopts Far-infrared Heating to dry.
4. the manufacture method of resistant steaming-resistant polyvinylidene chloride coated thin film as claimed in claim 1, is characterized in that: described drying mode adopts hot blast to add Far-infrared Heating mode and dries.
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| CN103275260B (en) * | 2013-05-13 | 2015-03-25 | 浙江科冠聚合物有限公司 | Preparation method of acrylic plastic-plastic composite latex |
| CN103626909B (en) * | 2013-12-02 | 2015-09-23 | 苏州福斯特光伏材料有限公司 | Weather-proof barrier coating and its application |
| CN105482572A (en) * | 2014-10-09 | 2016-04-13 | 南通瑞普埃尔生物工程有限公司 | Preparation method of PVDC latex for egg freshness retaining coating |
| CN105820304B (en) * | 2016-05-18 | 2018-11-30 | 常德市金润新材料科技有限公司 | A kind of high barrier paper PVDC lotion and preparation method thereof |
| CN106366322A (en) * | 2016-08-27 | 2017-02-01 | 合肥普庆新材料科技有限公司 | Preparation method of waterborne epoxy cationic emulsion for preparing waterborne epoxy steaming and boiling resistant coating |
| CN106221505A (en) * | 2016-08-27 | 2016-12-14 | 合肥普庆新材料科技有限公司 | A kind of preparation method of the high-performance water-based epoxy coating of resistance to steaming and decocting |
| CN108164729B (en) * | 2017-12-21 | 2019-11-01 | 海南赛诺实业有限公司 | It is a kind of to be suitble to light-weight packed low-temperature heat-sealing coated film and its manufacturing method |
| CN110195516B (en) * | 2019-05-07 | 2021-08-06 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Three-dimensional concrete heat preservation elasticity composite maintenance membrane of moisturizing |
| CN112126286B (en) * | 2020-09-09 | 2021-11-19 | 浙江工业大学 | TiO-Ce @ PVDC composite emulsion based on cerium-titanium-oxygen cluster and preparation and application thereof |
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