CN102876149B - A kind of coating autohension polyvinylidene emulsions and preparation method thereof - Google Patents
A kind of coating autohension polyvinylidene emulsions and preparation method thereof Download PDFInfo
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- CN102876149B CN102876149B CN201210376375.9A CN201210376375A CN102876149B CN 102876149 B CN102876149 B CN 102876149B CN 201210376375 A CN201210376375 A CN 201210376375A CN 102876149 B CN102876149 B CN 102876149B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 83
- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000131 polyvinylidene Polymers 0.000 title claims abstract description 10
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 73
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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 claims abstract description 11
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000013530 defoamer Substances 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012748 slip agent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004160 Ammonium persulphate Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 13
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 13
- -1 amino silicane Chemical compound 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007822 coupling agent Substances 0.000 claims description 10
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical group CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 9
- 239000004203 carnauba wax Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 239000002318 adhesion promoter Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002987 primer (paints) Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 8
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 239000003643 water by type Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000013615 primer Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of coating autohension polyvinylidene emulsions and preparation method thereof, this coating is made up of the raw material containing following weight content: modification PVDC copolymer emulsion 65-80%, adhesion promoter 0.5-5%, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20%; Described modification PVDC copolymer emulsion is become by the preparation of raw material containing following weight content: vinylidene chloride 45-60%, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, vinyl cyanide 0.5-3%, chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, softening water 35.5-37%, defoamer 0.1-0.5%.When this kind of emulsion is used for coating process, be directly coated with this coating without the need to being coated with primer, the coated film made has good oxygen resistance, saves precoating primer operation, cost-saving and safety and environmental protection.
Description
Technical field
The present invention relates to a kind of coating autohension polyvinylidene dichloride (hereinafter referred to as PVDC) emulsion and preparation method thereof, belong to novel high polymer material field.
Background technology
In plastic-coated industry, before coating function coating materials, need first to be coated with one deck primer to strengthen the cohesive force of coating and plastic basis material film.When producing isolation-type coated film, selecting the extraordinary PVDC coating of oxygen barrier on market, also PVDC coating just can must be made firmly to glue on a plastic film by primer layer.Existing coating primer mainly divides solvent-borne type primer and the large class of aqueous bottom glue two.Solvent-borne type primer is cheap, highly volatile after coating, and primer layer can be dry rapidly, but production environment is severe, does not meet the requirement of environmental protection; And environment-friendly type aqueous primer price is partially expensive, because water content is large, after coating, primer layer is not easily dry, and on the primer layer of non-complete drying, continue to be coated with functional coating, and primer layer does not just play the effect strengthening cohesive force, finally causes dope layer big area to come off.Consider that coating primer exists as above problem, in conjunction with the requirement of most food product pack to barrier property, if a kind of PVDC emulsion be coated with not needing primer can be developed, not only there is good oxygen resistance after coating, meet the requirement of food product pack, coated film technique can also be made to reduce by one painting process, greatly reduce costs, promote the development of plastic-coated industry.
Summary of the invention
Precoating primer is all needed when being used for coated film for existing PVDC emulsion, and self do not have hesive problem, the object of the present invention is to provide a kind of coating autohension PVDC emulsion, when this kind of emulsion is used for coating process, directly be coated with this coating without the need to being coated with primer, the coated film made has good oxygen resistance.Described sticking power, be exactly that PVDC emulsion self and coated substrate have good cohesive force, the PVDC coating formed after coating and the cohesive force of base material film reach existing the requirement of primer coating technique (stripping strength after compound CPP or PE is more than or equal to 1.5N/15mm).Innovative point of the present invention is: 1. in emulsion preparation process, add appropriate amino silicane coupling agent as adhesion promoter, silane coupling agent is except being cross-linked with PVDC copolymerization molecule, reach outside certain force of cohesion, two kinds of groups amino that it exists and silylation, simultaneously with the group such as the carboxyl in PVDC copolymerization molecular chain with carry out chemical bonding with the plastic basis material film surface of a large amount of polar group after corona treatment, the sticking power between coating and base material film can be strengthened; 2., when selecting several mix monomer to prepare PVDC copolymer emulsion, being selected and proportioning by suitable monomer, especially adding appropriate butyl acrylate, the second-order transition temperature of polyalcohol integral can be reduced, very large to the sticking power effect strengthening PVDC coating.
The invention provides a kind of coating autohension PVDC emulsion, the solid content of this emulsion is 41.1-51.7%, become by the proportioning raw materials containing following weight content: modification PVDC copolymer emulsion 65-80%, adhesion promoter 0.5-5%, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20%; Described modification PVDC copolymer emulsion (solid content is 63.0-64.5%) is become by the preparation of raw material containing following weight content: vinylidene chloride 45-60%, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, vinyl cyanide 0.5-3%, these five kinds of mix monomers are adding chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, softening water 35.5-37%, defoamer 0.1-0.5%.
Described adhesion promoter is amino silicane coupling agent, is applicable to the attachment of coating on the plastic basis materials such as BOPP, BOPET, PA, PVC;
Described surface slip agent is water miscible palm wax, has good dispersing property in coating, makes the smooth Performance comparision of product all even excellent;
Described release agent is silicon-dioxide anti blocking agent;
Described chain initiator be in Potassium Persulphate or ammonium persulphate any one or mix arbitrarily;
Described emulsifying agent is OP-10;
Described defoamer is ethanol;
This emulsion is applicable to the base material film coatings such as Biaxially oriented polypropylene film (BOPP) (BOPP) film, biaxial stretching polyester (BOPET) film, polyethylene (PA) film and polyvinyl chloride (PVC) film; The base material film thickness be suitable for is 12-55 μm.
The present invention also provides a kind of preparation method of above-mentioned coating autohension PVDC emulsion, comprises the steps (each content of subordinate is all weight percentage):
1, vinylidene chloride 45-60% is got respectively, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, vinyl cyanide 0.5-3% five kinds of monomers, chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, defoamer 0.1-0.5% and softening water 35.5-37%, is positioned in respective independently Raw material pail.First, joined in reactor by a small amount of (accounting for 1/3rd of each total amount) above monomer, auxiliary agent and softening water successively and mix, open and stir, stirring velocity is 120-200 rev/min, is slowly warmed to 55-70 DEG C, carries out prepolymerization.Then, more remaining monomer, chain initiator, emulsifying agent, defoamer and softening water were added equably continuously in 1 hour successively, continue to stir 1-2 hour, cooling obtains the modification PVDC copolymer emulsion that solid content is 63-64.5% after leaving standstill.
2, get above-mentioned obtained modification PVDC copolymer emulsion, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the adhesion promoter of 0.5-5% again, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20%, add in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that solid content is 41-51.7%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.
The autohension PVDC emulsion that the present invention obtains, respectively 19-50 μm BOPP light film, BOPET, BOPA, PVC base carries out coated test, coating applications amount is 3.0g/m
2, through detecting the data obtained (see table 1 and table 2) after lower machine solidification, do not come off (examination criteria: GB/T7707-2008) after showing this kind of autohension PVDC emulsion coating, oxygen transmission rate (23 DEG C, 0%RH) is 5-10cc/m
2.24hr, (oxygen transmission rate is 25-35cc/m to more conventional PVDC coated film
2.24hr) have and significantly reduce, after printing compound with CPP, its combined strength bination is 1.5-1.8N/15mm (examination criteria: GBT10004-2008).That is, this kind of emulsion, when without the need to primer, still keeps there is good sticking power with base material film, reduces cost, also improve barrier property simultaneously.
The conventional PVDC of table 1. with on several base material, be coated with the coating shedding phenomenon after solidifying without primer PVDC and 1. contrast as follows
Note 1.: detect according to standard GB/T7707-2008
The conventional PVDC of table 2. with print the often conjunction intensity data after compound without primer PVDC and contrast as follows
Note: composite structure is PVDC coated film // composite gum //CPP30, and spread is 2g/m
2.Detection method is according to GBT10004-2008 standard.
Embodiment
Below in conjunction with specific embodiment, coating autohension PVDC emulsion of the present invention and preparation method thereof is described further.
Embodiment one
Get vinylidene chloride 18 kilograms respectively, 1.2 kilograms, vinylformic acid, butyl acrylate 2 kilograms, β-dimethyl-aminoethylmethacrylate 2 kilograms, vinyl cyanide 1.2 kilograms of five kinds of monomers, ammonium persulphate 0.2 kilogram, OP-100.4 kilogram, ethanol 0.2 kilogram and softening water 14.8 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 120 revs/min, is slowly warmed to 55 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 1 hour, cooling obtains the PVDC copolymer emulsion that 40 kilograms of solid contents are 63% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 29.25 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 2.25 kilograms again, silicon-dioxide 2.25 kilograms, palm wax 2.25 kilograms, softening water 9 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, and obtained 45 kilograms of solid contents are the PVDC emulsion of 41%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPP light film base material of 19 μm, and coating applications amount is 3.0g/m
2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), and oxygen transmission rate (23 DEG C, 0%RH) is 10cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.5N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment two
Get vinylidene chloride 38.4 kilograms respectively, 2.24 kilograms, vinylformic acid, butyl acrylate 3.6 kilograms, β-dimethyl-aminoethylmethacrylate 3.36 kilograms, vinyl cyanide 2.08 kilograms of five kinds of monomers, Potassium Persulphate 0.4 kilogram, OP-100.64 kilogram, ethanol 0.32 kilogram and softening water 28.96 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 140 revs/min, is slowly warmed to 58 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, Potassium Persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 1 hour, cooling obtains the PVDC copolymer emulsion that 80 kilograms of solid contents are 63.8% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 59.84 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 3.7 kilograms again, silicon-dioxide 4.14 kilograms, palm wax 4.05 kilograms, softening water 16.28 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that 88 kilograms of solid contents are 43.5%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPP light film base material of 22 μm, coating applications amount is 3.0g/m2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), oxygen transmission rate (23 DEG C, 0%RH) be 9.2cc/m2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.5N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment three
Get vinylidene chloride 50 kilograms respectively, 2.5 kilograms, vinylformic acid, butyl acrylate 4.2 kilograms, β-dimethyl-aminoethylmethacrylate 3 kilograms, vinyl cyanide 2 kilograms of five kinds of monomers, Potassium Persulphate and each 0.2 kilogram of ammonium persulphate, OP-100.6 kilogram, ethanol 0.3 kilogram and softening water 37 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 150 revs/min, is slowly warmed to 60 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, ammonium persulphate, ammonium persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 1.5 hours, cooling obtains the PVDC copolymer emulsion that double centner solid content is 63% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 70 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 3.1 kilograms again, silicon-dioxide 4.2 kilograms, palm wax 4 kilograms, softening water 18.7 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that double centner solid content is 44.2%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPET base material of 12 μm, and coating applications amount is 3.0g/m
2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), and oxygen transmission rate (23 DEG C, 0%RH) is 9.0cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.6N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment four
Get vinylidene chloride 63.6 kilograms respectively, 2.4 kilograms, vinylformic acid, butyl acrylate 4.2 kilograms, β-dimethyl-aminoethylmethacrylate 2.88 kilograms, vinyl cyanide 2.16 kilograms of five kinds of monomers, ammonium persulphate 0.48 kilogram, OP-100.6 kilogram, ethanol 0.36 kilogram and softening water kilogram, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 150 revs/min, is slowly warmed to 62 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 1.5 hours, cooling obtains the PVDC copolymer emulsion that 120 kilograms of solid contents are 63.9% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 91.25 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 3.63 kilograms again, silicon-dioxide 4.63 kilograms, palm wax 4.63 kilograms, softening water 20.75 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that 125 kilograms of solid contents are 46.8%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPA base material of 32 μm, and coating applications amount is 3.0g/m
2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), and oxygen transmission rate (23 DEG C, 0%RH) is 8.5cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.6N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment five
Get vinylidene chloride 82.5 kilograms respectively, 2.7 kilograms, vinylformic acid, butyl acrylate 4.5 kilograms, β-dimethyl-aminoethylmethacrylate 2.7 kilograms, vinyl cyanide kilogram 1.95 five kinds of monomers, Potassium Persulphate 0.2 kilogram, ammonium persulphate 0.4 kilogram, OP-100.6 kilogram, ethanol 0.3 kilogram and softening water 37 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 160 revs/min, is slowly warmed to 65 DEG C, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, Potassium Persulphate, ammonium persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour again, continue stirring 1.6 hours, cooling obtains the PVDC copolymer emulsion that 150 kilograms of solid contents are 63.9% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 112.48 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 2.37 kilograms again, silicon-dioxide 5.03 kilograms, palm wax 5.18 kilograms, softening water 22.94 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that 148 kilograms of solid contents are 48.6%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPP light film base material of 32 μm, coating applications amount is 3.0g/m2, and detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), oxygen transmission rate (23 DEG C, 0%RH) is 7.8cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.7N/15mm (examination criteria: GBT10004-2008).Sticking power and oxygen resistance are all fine.
Embodiment six
Get vinylidene chloride 104.4 kilograms respectively, 2.7 kilograms, vinylformic acid, butyl acrylate 4.14 kilograms, β-dimethyl-aminoethylmethacrylate 2.16 kilograms, vinyl cyanide 1.44 kilograms of five kinds of monomers, Potassium Persulphate 0.54 kilogram, OP-100.36 kilogram, ethanol 0.36 kilogram and softening water 63.9 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 180 revs/min, is slowly warmed to 68 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, Potassium Persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 2 hours, cooling obtains the PVDC copolymer emulsion that 180 kilograms of solid contents are 64.5% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 134.16 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 1.72 kilograms again, silicon-dioxide 5.5 kilograms, palm wax 5.68 kilograms, softening water 24.94 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that 172 kilograms of solid contents are 50.4%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test on the BOPA base material of 45 μm, and coating applications amount is 3.0g/m
2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), and oxygen transmission rate (23 DEG C, 0%RH) is 6.5cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.8N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment seven
Get vinylidene chloride 120 kilograms respectively, 2 kilograms, vinylformic acid, butyl acrylate 4 kilograms, β-dimethyl-aminoethylmethacrylate 1 kilogram, vinyl cyanide 1 kilogram of five kinds of monomer, ammonium persulphate 0.6 kilogram, OP-100.2 kilogram, ethanol 0.2 kilogram and softening water 71 kilograms, be positioned in respective independently Raw material pail.First, a small amount of (accounting for 1/3rd of each total amount) above raw material and softening water are joined in reactor successively and mix, open and stir, stirring velocity is 200 revs/min, is slowly warmed to 70 DEG C, carries out prepolymerization.Then, more remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added equably continuously in 1 hour successively, continue stirring 2 hours, cooling obtains the PVDC copolymer emulsion that 200 kilograms of solid contents are 64.5% after leaving standstill.
Get above-mentioned obtained PVDC copolymer emulsion 160 kilograms, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min.Get the amino silicane coupling agent of 1 kilogram again, silicon-dioxide 6 kilograms, palm wax 6 kilograms, softening water 27 kilograms, adds in PVDC copolymer emulsion.Stirring timing starts, and to set churning time be 1 hour, finally filters discharging, obtains the PVDC emulsion that 200 kilograms of solid contents are 51.7%, i.e. a kind of coating autohension PVDC emulsion provided by the invention.This kind of emulsion is carried out coated test in the PVC base of 55 μm, and coating applications amount is 3.0g/m
2, detect known after lower machine solidification, coating does not come off (examination criteria: GB/T7707-2008), and oxygen transmission rate (23 DEG C, 0%RH) is 5cc/m
2.24hr (examination criteria: ASTMD3985), after printing compound with CPP, its combined strength bination is 1.8N/15mm (examination criteria: GBT10004-2008), and sticking power effect and oxygen resistance are all fine.
Claims (7)
1. be coated with the preparation method with autohension polyvinylidene emulsions, it is characterized in that the method comprises the steps, each content of subordinate is all weight percentage:
(1) vinylidene chloride 45-60% is got respectively, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, vinyl cyanide 0.5-3% five kinds of monomers, chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, defoamer 0.1-0.5% and softening water 35.5-37%, be positioned in respective independently Raw material pail, more than/3rd monomers of each total amount will be accounted for successively, auxiliary agent and softening water join in reactor and mix, open and stir, stirring velocity is 120-200 rev/min, slowly be warmed to 55-70 DEG C, carry out prepolymerization, again successively by remaining monomer, chain initiator, emulsifying agent, defoamer and softening water added equably continuously in 1 hour, continue to stir 1-2 hour, cooling obtains the modification PVDC copolymer emulsion that solid content is 63-64.5% after leaving standstill,
(2) get above-mentioned obtained modification PVDC copolymer emulsion, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 revs/min, get the amino silicane coupling agent of 0.5-5% again, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20%, add in PVDC copolymer emulsion, stir timing and start, and to set churning time be 1 hour, finally filter discharging, i.e. obtained coating autohension PVDC emulsion.
2. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: the solid content of described modification PVDC copolymer emulsion is 63.0-64.5%.
3. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: described surface slip agent is water miscible palm wax.
4. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: described release agent is silicon-dioxide anti blocking agent.
5. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: described chain initiator is one in Potassium Persulphate or ammonium persulphate or mixes arbitrarily.
6. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: described emulsifying agent is OP-10.
7. the coating preparation method of autohension polyvinylidene emulsions as claimed in claim 1, is characterized in that: described defoamer is ethanol.
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| CN103934942B (en) * | 2014-04-21 | 2016-03-02 | 淄博中南塑胶有限公司 | The production technology of PVC/PVDC composite sheet |
| CN104371439B (en) * | 2014-10-15 | 2016-08-24 | 海南赛诺实业有限公司 | The plating pellumina of a kind of tack PVDC emulsion coating and manufacture method thereof |
| CN105585726A (en) * | 2015-12-25 | 2016-05-18 | 江苏东材新材料有限责任公司 | High-barrier polyester film and preparation method thereof |
| CN108410280B (en) * | 2018-03-02 | 2020-11-13 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC aqueous emulsion for coating |
| CN110205030A (en) * | 2019-05-29 | 2019-09-06 | 张家港市天源制漆涂装有限公司 | A kind of aqueous bottom surface unification coating and preparation method thereof |
| CN110183902B (en) * | 2019-06-04 | 2022-08-02 | 云浮市金莱昊化工有限公司 | Water-based gravure printing ink and preparation method and application thereof |
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| CN101003706A (en) * | 2007-01-15 | 2007-07-25 | 东阳市野风塑胶有限公司 | Rustproofing primer of aqueous polyvinylidene chloride, and preparation method |
| CN101638159A (en) * | 2009-08-31 | 2010-02-03 | 浙江比例包装股份有限公司 | Liquid packaging composite film and manufacturing method thereof |
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