CN102876149A - Autohension polyvinylidene chloride emulsion for coating and preparation method thereof - Google Patents
Autohension polyvinylidene chloride emulsion for coating and preparation method thereof Download PDFInfo
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- CN102876149A CN102876149A CN2012103763759A CN201210376375A CN102876149A CN 102876149 A CN102876149 A CN 102876149A CN 2012103763759 A CN2012103763759 A CN 2012103763759A CN 201210376375 A CN201210376375 A CN 201210376375A CN 102876149 A CN102876149 A CN 102876149A
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- 229920001328 Polyvinylidene chloride Polymers 0.000 title claims abstract description 91
- 239000000839 emulsion Substances 0.000 title claims abstract description 91
- 239000005033 polyvinylidene chloride Substances 0.000 title claims abstract description 80
- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000011248 coating agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 8
- 239000012748 slip agent Substances 0.000 claims abstract description 7
- 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 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 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
- 239000002994 raw material Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound 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
- 239000000203 mixture Substances 0.000 claims description 12
- -1 amino silicane Chemical compound 0.000 claims description 11
- 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
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification 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
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 8
- 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 description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000004203 carnauba wax Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 239000002987 primer (paints) Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000003292 glue Substances 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
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 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
- 238000004945 emulsification Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 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
- 239000013615 primer Substances 0.000 description 1
- 230000009467 reduction Effects 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
Abstract
The invention relates to an autohension polyvinylidene chloride (PVDC) emulsion for coating and a preparation method thereof. The autohension polyvinylidene chloride emulsion for coating comprises, by weight, 65% to 80% of modified PVDC copolymerization emulsion, 0.5% to 5% of adhesion promoters, 3% to 5% of slip agents, 3% to 5% of abherents and 13.5% to 20% of softened water, and the modified PVDC copolymerization emulsion comprises, by weight, 45% to 60% of vinylidene chloride, 1% to 3% of acrylic acid, 2% to 5% of butyl acrylate, 0.5% to 5% of ethyl methacrylate, 0.5% to 3% of acrylonitrile, 0.3% to 0.5% of chain initiators, 0.1% to 1% of emulsifying agents, 35.5% to 37% of softened water and 0.1% to 0.5% of defoaming agents. According to the autohension polyvinylidene chloride emulsion for the coating, the emulsion can be directly coated without coating a base gel during the coating process, a prepared coating film has a good antioxygen performance, the process of precoating the base gel is omitted, the cost is saved, and the autohension polyvinylidene chloride emulsion for the coating is safe and environment-friendly.
Description
Technical field
The present invention relates to a kind of coating with autohension polyvinylidene dichloride (hereinafter to be referred as PVDC) emulsion and preparation method thereof, belong to the novel high polymer material field.
Background technology
In the plastic-coated industry, before the coating function coating materials, need to be coated with first one deck primer to strengthen the cohesive force of coating and plastic basis material film.When producing the isolation-type coated film, select the extraordinary PVDC coating of oxygen barrier on the market, also must the PVDC coating firmly be bonded on the plastics film by primer layer.Existing coating mainly divides solvent-borne type primer and aqueous bottom glue two large classes with primer.The solvent-borne type primer is cheap, highly volatile after the coating, and primer layer can be dry rapidly, but production environment is abominable, does not meet the requirement of environmental protection; And environment-friendly type aqueous primer price is partially expensive, because water content is large, primer layer is difficult for dryly after the coating, and continues to be coated with functional coating at the primer layer of complete drying not, and primer layer does not just play the effect that strengthens cohesive force, finally causes the dope layer big area to come off.Consider that there is as above problem in the coating primer, in conjunction with the requirement of most food product pack to barrier property, if can develop a kind of the coating with the PVDC emulsion that does not need primer, not only after coating, has good oxygen resistance, satisfy the requirement of food product pack, can also make coated film technique reduce painting process one, greatly reduce cost, promote the development of plastic-coated industry.
Summary of the invention
All need the precoating primer when being used for coated film for existing PVDC emulsion, and self there is not the problem of sticking power, the object of the present invention is to provide a kind of coating autohension PVDC emulsion, when this kind emulsion is used for coating process, need not to be coated with primer and directly be coated with this coating, the coated film of making has preferably oxygen resistance.Described sticking power, be exactly that PVDC emulsion self and coated substrate have good cohesive force, the PVDC coating that forms after the coating and the cohesive force of base material film reach the requirement (stripping strength behind compound CPP or the PE is more than or equal to 1.5N/15mm) that the primer coating technique is arranged.Innovative point of the present invention is: added an amount of amino silicane coupling agent as adhesion promoter in the emulsion preparation process 1., silane coupling agent is except carrying out crosslinked with PVDC copolymerization molecule, reach outside certain force of cohesion, two kinds of group amino that its exists and silylation, can be simultaneously with PVDC copolymerization molecular chain in the group such as carboxyl and after corona treatment, carry out chemical bonding with the plastic basis material film surface of a large amount of polar groups, strengthen the sticking power between coating and the base material film; 2. when selecting several mix monomers to prepare the PVDC copolymer emulsion, select and proportioning by suitable monomer, especially add an amount of butyl acrylate, can reduce the second-order transition temperature of polyalcohol integral, very large to the sticking power effect that strengthens the 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 that contains 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 to be become by the preparation of raw material that contains 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 coating adhering 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, so that the smooth performance of product is more even better;
Described release agent is the silicon-dioxide antiblocking agent;
Described chain initiator be in Potassium Persulphate or the 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; Applicable base material film thickness is 12-55 μ m.
The present invention also provides the preparation method of a kind of above-mentioned coating with autohension PVDC emulsion, comprises the steps (each content of subordinate all is weight percentage):
1, gets respectively vinylidene chloride 45-60%, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, five kinds of monomers of vinyl cyanide 0.5-3%, chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, defoamer 0.1-0.5% and softening water 35.5-37% are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above monomer, auxiliary agent and softening water join and mix in the reactor, open stirring, stirring velocity is 120-200 rev/min, slowly is warmed to 55-70 ℃, carries out prepolymerization.Then, successively remaining monomer, chain initiator, emulsifying agent, defoamer and softening water were added in 1 hour continuously equably again, continue to stir 1-2 hour, obtain the modification PVDC copolymer emulsion that solid content is 63-64.5% after cooling is left standstill.
2, get the above-mentioned modification PVDC copolymer emulsion that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again the adhesion promoter of 0.5-5%, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20% adds in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, and namely getting solid content is the PVDC emulsion of 41-51.7%, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.
The autohension PVDC emulsion that the present invention makes, BOPP light film, BOPET, BOPA, the PVC base material at 19-50 μ m carries out coated test respectively, and the coating glue spread is 3.0g/m
2, lower machine solidifies by detecting the data obtained (see Table 1 and table 2), shows not come off that (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 5-10cc/m to oxygen transmission rate after the coating of this kind autohension PVDC emulsion
2.24hr, (oxygen transmission rate is 25-35cc/m to more conventional PVDC coated film
2.24hr) significantly reduction is arranged, printing compound rear its combined strength bination with CPP is 1.5-1.8N/15mm (examination criteria: GBT10004-2008).That is to say, this kind emulsion still keeps having preferably sticking power with base material film in the situation that need not primer, has reduced cost, has also improved barrier property simultaneously.
The conventional PVDC of table 1. with 1. contrast as follows without the coating shedding phenomenon of primer PVDC after the coating of several base materials is solidified
Annotate 1.: detect according to standard GB/T7707-2008
The conventional PVDC of table 2. with compound without primer PVDC printing after whenever to close the intensity data contrast as follows
Annotate: composite structure be PVDC coated film // composite gum //CPP30, spread is 2g/m
2Detection method is according to the GBT10004-2008 standard.
Embodiment
Below in conjunction with specific embodiment coating of the present invention is described further with autohension PVDC emulsion and preparation method thereof.
Embodiment one
Get respectively 18 kilograms of vinylidene chlorides, 1.2 kilograms in vinylformic acid, 2 kilograms of butyl acrylates, 2 kilograms of β-dimethyl-aminoethylmethacrylates, 1.2 kilograms of five kinds of monomers of vinyl cyanide, 0.2 kilogram of ammonium persulphate, 0.4 kilogram of OP-10,14.8 kilograms of 0.2 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 120 rev/mins, slowly is warmed to 55 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 1 hour, obtain 40 kilograms of solid contents after cooling is left standstill and be 63% PVDC copolymer emulsion.
Get 29.25 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 2.25 kilograms amino silicane coupling agent, 2.25 kilograms of silicon-dioxide, 2.25 kilograms of palm waxs, 9 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, makes 45 kilograms of solid contents and be 41% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPP light film base material of 19 μ m, and the coating glue spread is 3.0g/m
2, after solidifying, lower machine detects as can be known, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 10cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is 1.5N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment two
Get respectively 38.4 kilograms of vinylidene chlorides, 2.24 kilograms in vinylformic acid, 3.6 kilograms of butyl acrylates, 3.36 kilograms of β-dimethyl-aminoethylmethacrylates, 2.08 kilograms of five kinds of monomers of vinyl cyanide, 0.4 kilogram of Potassium Persulphate, 0.64 kilogram of OP-10,28.96 kilograms of 0.32 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 140 rev/mins, slowly is warmed to 58 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, Potassium Persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 1 hour, obtain 80 kilograms of solid contents after cooling is left standstill and be 63.8% PVDC copolymer emulsion.
Get 59.84 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 3.7 kilograms amino silicane coupling agent, 4.14 kilograms of silicon-dioxide, 4.05 kilograms of palm waxs, 16.28 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets 88 kilograms of solid contents and be 43.5% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPP light film base material of 22 μ m, the coating glue spread is 3.0g/m2, after solidifying, lower machine detects as can be known, coating (the examination criteria: GB/T7707-2008) that do not come off, (23 ℃ of oxygen transmission rates, be that (examination criteria: ASTM D3985), print compound rear its combined strength bination with CPP is 1.5N/15mm (examination criteria: GBT10004-2008) to 9.2cc/m2.24hr 0%RH).Sticking power effect and oxygen resistance are all fine.
Embodiment three
Get respectively 50 kilograms of vinylidene chlorides, 2.5 kilograms in vinylformic acid, 4.2 kilograms of butyl acrylates, 3 kilograms of β-dimethyl-aminoethylmethacrylates, 2 kilograms of five kinds of monomers of vinyl cyanide, each 0.2 kilogram of Potassium Persulphate and ammonium persulphate, 0.6 kilogram of OP-10,37 kilograms of 0.3 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 150 rev/mins, slowly is warmed to 60 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, ammonium persulphate, ammonium persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 1.5 hours, obtain the double centner solid content after cooling is left standstill and be 63% PVDC copolymer emulsion.
Get 70 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 3.1 kilograms amino silicane coupling agent, 4.2 kilograms of silicon-dioxide, 4 kilograms of palm waxs, 18.7 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets the double centner solid content and be 44.2% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPET base material of 12 μ m, and the coating glue spread is 3.0g/m
2, after solidifying, lower machine detects as can be known, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 9.0cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is 1.6N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment four
Get respectively 63.6 kilograms of vinylidene chlorides, 2.4 kilograms in vinylformic acid, 4.2 kilograms of butyl acrylates, 2.88 kilograms of β-dimethyl-aminoethylmethacrylates, 2.16 kilograms of five kinds of monomers of vinyl cyanide, 0.48 kilogram of ammonium persulphate, OP-100.6 kilogram, 0.36 kilogram of ethanol and softening water kilogram are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 150 rev/mins, slowly is warmed to 62 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 1.5 hours, obtain 120 kilograms of solid contents after cooling is left standstill and be 63.9% PVDC copolymer emulsion.
Get 91.25 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 3.63 kilograms amino silicane coupling agent, 4.63 kilograms of silicon-dioxide, 4.63 kilograms of palm waxs, 20.75 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets 125 kilograms of solid contents and be 46.8% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPA base material of 32 μ m, and the coating glue spread is 3.0g/m
2, after solidifying, lower machine detects as can be known, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 8.5cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is 1.6N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment five
Get respectively 82.5 kilograms of vinylidene chlorides, 2.7 kilograms in vinylformic acid, 4.5 kilograms of butyl acrylates, 2.7 kilograms of β-dimethyl-aminoethylmethacrylates, 1.95 five kinds of monomers of vinyl cyanide kilogram, 0.2 kilogram of Potassium Persulphate, 0.4 kilogram of ammonium persulphate, 0.6 kilogram of OP-10,37 kilograms of 0.3 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 160 rev/mins, slowly is warmed to 65 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, Potassium Persulphate, ammonium persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 1.6 hours, and obtained 150 kilograms of solid contents after cooling is left standstill and be 63.9% PVDC copolymer emulsion.
Get 112.48 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 2.37 kilograms amino silicane coupling agent, 5.03 kilograms of silicon-dioxide, 5.18 kilograms of palm waxs, 22.94 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets 148 kilograms of solid contents and be 48.6% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPP light film base material of 32 μ m, and the coating glue spread is 3.0g/m2, detects as can be known after lower machine solidifies, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 7.8cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is 1.7N/15mm (examination criteria: GBT10004-2008).Sticking power and oxygen resistance are all fine.
Embodiment six
Get respectively 104.4 kilograms of vinylidene chlorides, 2.7 kilograms in vinylformic acid, 4.14 kilograms of butyl acrylates, 2.16 kilograms of β-dimethyl-aminoethylmethacrylates, 1.44 kilograms of five kinds of monomers of vinyl cyanide, 0.54 kilogram of Potassium Persulphate, OP-100.36 kilogram, 63.9 kilograms of 0.36 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 180 rev/mins, slowly is warmed to 68 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, Potassium Persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 2 hours, obtain 180 kilograms of solid contents after cooling is left standstill and be 64.5% PVDC copolymer emulsion.
Get 134.16 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 1.72 kilograms amino silicane coupling agent, 5.5 kilograms of silicon-dioxide, 5.68 kilograms of palm waxs, 24.94 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets 172 kilograms of solid contents and be 50.4% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the BOPA base material of 45 μ m, and the coating glue spread is 3.0g/m
2, after solidifying, lower machine detects as can be known, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 6.5cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is 1.8N/15mm (examination criteria: GBT10004-2008).Sticking power effect and oxygen resistance are all fine.
Embodiment seven
Get respectively 120 kilograms of vinylidene chlorides, 2 kilograms in vinylformic acid, 4 kilograms of butyl acrylates, 1 kilogram of β-dimethyl-aminoethylmethacrylate, 1 kilogram of five kinds of monomer of vinyl cyanide, 0.6 kilogram of ammonium persulphate, the OP-100.2 kilogram, 71 kilograms of 0.2 kilogram of ethanol and softening waters are positioned over separately independently in the Raw material pail.At first, successively will be a small amount of (account for each total amount 1/3rd) above raw material and softening water join and mix in the reactor, open stirring, stirring velocity is 200 rev/mins, slowly is warmed to 70 ℃, carries out prepolymerization.Then, successively remaining 5 kinds of monomers, ammonium persulphate, OP-10, ethanol and softening waters were added in 1 hour continuously equably again, continue to stir 2 hours, obtain 200 kilograms of solid contents after cooling is left standstill and be 64.5% PVDC copolymer emulsion.
Get 160 kilograms of the above-mentioned PVDC copolymer emulsions that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins.Get again 1 kilogram amino silicane coupling agent, 6 kilograms of silicon-dioxide, 6 kilograms of palm waxs, 27 kilograms of softening waters add in the PVDC copolymer emulsion.The stirring timing begins, and to set churning time be 1 hour, filters at last discharging, namely gets 200 kilograms of solid contents and be 51.7% PVDC emulsion, i.e. a kind of coating provided by the invention is with autohension PVDC emulsion.This kind emulsion is carried out coated test at the PVC base material of 55 μ m, and the coating glue spread is 3.0g/m
2, after solidifying, lower machine detects as can be known, and coating does not come off, and (examination criteria: GB/T7707-2008), (23 ℃ 0%RH) are 5cc/m to oxygen transmission rate
2.24hr (examination criteria: ASTM D3985), printing compound rear its combined strength bination with CPP is that (examination criteria: GBT10004-2008), sticking power effect and oxygen resistance are all fine for 1.8N/15mm.
Claims (9)
1. a coating is characterized in that with autohension polyvinylidene dichloride (hereinafter to be referred as PVDC) emulsion: described coating with autohension polyvinylidene dichloride emulsion by the preparation of raw material one-tenth that contains 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 to be become by the preparation of raw material that contains 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%.
2. coating as claimed in claim 1 is with autohension polyvinylidene dichloride emulsion, and it is characterized in that: the solid content of described modification PVDC copolymer emulsion is 63.0-64.5%.
3. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described adhesion promoter is amino silicane coupling agent.
4. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described surface slip agent is water miscible palm wax.
5. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described release agent is the silicon-dioxide antiblocking agent.
6. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described chain initiator is a kind of or any mixing in Potassium Persulphate or the ammonium persulphate.
7. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described emulsifying agent is OP-10.
8. as claimed in claim 1 or 2 any one is coated with autohension polyvinylidene dichloride emulsion, and it is characterized in that: described described defoamer is ethanol.
9. coating as claimed in claim 1 is characterized in that the method comprises the steps (each content of subordinate all is weight percentage) with the preparation method of autohension polyvinylidene dichloride emulsion:
(1) gets respectively vinylidene chloride 45-60%, vinylformic acid 1-3%, butyl acrylate 2-5%, β-dimethyl-aminoethylmethacrylate 0.5-5%, five kinds of monomers of vinyl cyanide 0.5-3%, chain initiator 0.3-0.5%, emulsifying agent 0.1-1%, defoamer 0.1-0.5% and softening water 35.5-37%, be positioned over separately independently in the Raw material pail, will account for successively 1/3rd above monomers of each total amount, auxiliary agent and softening water join in the reactor and mix, and open and stir, stirring velocity is 120-200 rev/min, slowly be warmed to 55-70 ℃, carry out prepolymerization, more successively with remaining monomer, chain initiator, emulsifying agent, defoamer and softening water added in 1 hour continuously equably, continue to stir 1-2 hour, obtain the modification PVDC copolymer emulsion that solid content is 63-64.5% after cooling is left standstill;
(2) get the above-mentioned modification PVDC copolymer emulsion that makes, put into a stainless steel vessel, open and stir, stirring velocity is set as 120 rev/mins, get again the adhesion promoter of 0.5-5%, surface slip agent 3-5%, release agent 3-5%, softening water 13.5-20%, add in the PVDC copolymer emulsion, stir timing and begin, and the setting churning time is 1 hour, filter at last discharging, namely make the present invention and be coated with the emulsion with autohension PVDC.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934942A (en) * | 2014-04-21 | 2014-07-23 | 淄博中南塑胶有限公司 | Production technology of PVC/PVDC (polyvinyl chloride/polyvinyl dichloride) composite sheet |
| CN104371439A (en) * | 2014-10-15 | 2015-02-25 | 海南赛诺实业有限公司 | Self-adhesive PVDC emulsion coated alumina-plated film and manufacturing 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 |
| CN108410280A (en) * | 2018-03-02 | 2018-08-17 | 浙江衢州巨塑化工有限公司 | A kind of preparation method of coating PVDC water-based emulsions |
| CN110183902A (en) * | 2019-06-04 | 2019-08-30 | 云浮市金莱昊化工有限公司 | A kind of aqueous intaglio printing ink and its preparation method and application |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101817247A (en) * | 2010-05-11 | 2010-09-01 | 海南赛诺实业有限公司 | Primer-free coating film and manufacturing method thereof |
| CN102127277A (en) * | 2010-01-19 | 2011-07-20 | 苗小胜 | Water soluble polymer mixed emulsion, coating and preparation method thereof |
| CN102650111A (en) * | 2012-05-10 | 2012-08-29 | 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 |
-
2012
- 2012-09-27 CN CN201210376375.9A patent/CN102876149B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102127277A (en) * | 2010-01-19 | 2011-07-20 | 苗小胜 | Water soluble polymer mixed emulsion, coating and preparation method thereof |
| CN101817247A (en) * | 2010-05-11 | 2010-09-01 | 海南赛诺实业有限公司 | Primer-free coating film and manufacturing method thereof |
| CN102650111A (en) * | 2012-05-10 | 2012-08-29 | 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934942A (en) * | 2014-04-21 | 2014-07-23 | 淄博中南塑胶有限公司 | Production technology of PVC/PVDC (polyvinyl chloride/polyvinyl dichloride) composite sheet |
| CN104371439A (en) * | 2014-10-15 | 2015-02-25 | 海南赛诺实业有限公司 | Self-adhesive PVDC emulsion coated alumina-plated film and manufacturing 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 |
| CN108410280A (en) * | 2018-03-02 | 2018-08-17 | 浙江衢州巨塑化工有限公司 | A kind of preparation method of coating PVDC water-based emulsions |
| 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 |
| CN110183902A (en) * | 2019-06-04 | 2019-08-30 | 云浮市金莱昊化工有限公司 | A kind of aqueous intaglio printing ink and its preparation method and application |
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