CN102260477B - Pressure-sensitive adhesive for biaxially-oriented polypropylene (BOPP) protective film and preparation method thereof - Google Patents
Pressure-sensitive adhesive for biaxially-oriented polypropylene (BOPP) protective film and preparation method thereof Download PDFInfo
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- CN102260477B CN102260477B CN201010587737XA CN201010587737A CN102260477B CN 102260477 B CN102260477 B CN 102260477B CN 201010587737X A CN201010587737X A CN 201010587737XA CN 201010587737 A CN201010587737 A CN 201010587737A CN 102260477 B CN102260477 B CN 102260477B
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- bopp
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 100
- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims abstract description 80
- 230000001681 protective effect Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims abstract description 78
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000000178 monomer Substances 0.000 claims description 61
- 239000012528 membrane Substances 0.000 claims description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 50
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 34
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 31
- 229920001519 homopolymer Polymers 0.000 claims description 28
- 238000009413 insulation Methods 0.000 claims description 28
- 230000007704 transition Effects 0.000 claims description 28
- -1 0.01-15 weight part Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 14
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 12
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004902 Softening Agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- SKFMNMKQJBQBNA-UHFFFAOYSA-N 2-methylprop-2-enoic acid tetradecane Chemical compound C(C(=C)C)(=O)O.CCCCCCCCCCCCCC SKFMNMKQJBQBNA-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- WQUYGVLLSSYSRD-UHFFFAOYSA-N C(C=C)(=O)OCC(C)O.CC=CC(=O)O Chemical compound C(C=C)(=O)OCC(C)O.CC=CC(=O)O WQUYGVLLSSYSRD-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- DOBPEHKISOHXTE-UHFFFAOYSA-N heptyl but-2-enoate Chemical compound CCCCCCCOC(=O)C=CC DOBPEHKISOHXTE-UHFFFAOYSA-N 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 2
- PWYYERNADDIMJR-UHFFFAOYSA-N pentyl but-2-enoate Chemical compound CCCCCOC(=O)C=CC PWYYERNADDIMJR-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a pressure-sensitive adhesive for a biaxially-oriented polypropylene (BOPP) protective film and a preparation method thereof. The pressure-sensitive adhesive comprises the following raw materials in parts by weight: 100 parts of acrylate copolymer A and/or acrylate copolymer B, 0.01-15 parts of crosslinking agent, 0.001-5 parts of silane coupling agent, 0.001-5 parts of plasticizer and 20-45 parts of solvent. The pressure-sensitive adhesive for the BOPP protective film has a strong adaptability to a BOPP base film, has the characteristics of high bonding property, high temperature resistance and the like and can be widely applied to BOPP protective films. The invention also provides a preparation method of the pressure-sensitive adhesive for the BOPP protective film.
Description
Technical field
The present invention relates to a kind of pressure sensitive adhesive and preparation method thereof, relate in particular to a kind of BOPP of being used for protective membrane pressure sensitive adhesive and preparation method thereof.The invention still further relates to BOPP protective membrane that utilizes the pressure sensitive adhesive preparation and preparation method thereof.
Background technology
The BOPP protective membrane is a kind of non-toxic and non-pollution ep-type material, and characteristics such as have that transparency height, glossiness are good, product good planeness, brilliant point are little, high temperature resistant, wear-resisting are used for the surface protection of five metals, plastic cement, electronic product more.The BOPP protective membrane is mainly formed through processes such as coating, drying, slakings by BOPP film and pressure sensitive adhesive (pressure sensitive adhesive), and wherein, the quality of pressure sensitive adhesive plays a decisive role to the quality of BOPP protective membrane.Because the surface energy of BOPP film is little, adopt the general pressure sensitive adhesive of being sold on the market, be difficult to moistening its surface.In order to improve its sticking power, in the method that adopts at present, the one, the BOPP film is carried out corona treatment, improve its surface tension, but there are shortcomings such as poor stability, amount of investment are big in this method; The 2nd, the BOPP film is carried out primary coat handle, improve its surface tension, but this method exists shortcomings such as technology is loaded down with trivial details, cost height.
In order to overcome above-mentioned shortcoming, research and develop a kind of cheap, technology is simple, performance is good BOPP protective membrane and the production and the Application Areas of surface protection film had very realistic meanings with pressure sensitive adhesive.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of pressure sensitive adhesive of the BOPP of being used for protective membrane, this pressure sensitive adhesive is a kind of high temperature resistant, pressure sensitive adhesive that binding property is high.
The present invention also aims to provide the preparation method of above-mentioned pressure sensitive adhesive.
For achieving the above object, the invention provides a kind of pressure sensitive adhesive of the BOPP of being used for protective membrane, it has following raw material and forms:
Yodo Sol GH 28 A and/or Yodo Sol GH 28 B, 100 weight parts, linking agent, 0.01-15 weight part, silane coupling agent, 0.001-5 weight part, softening agent, 0.001-5 weight part, solvent, 20-45 weight part.
In above-mentioned pressure sensitive adhesive, preferably, the amount of Yodo Sol GH 28 A is the 30-100 weight part, and the amount of Yodo Sol GH 28 B is the 0-70 weight part; More preferably, the amount of Yodo Sol GH 28 A is more than or equal to 30 weight parts, less than 100 weight parts, and the amount of Yodo Sol GH 28 B is greater than 0 weight part, smaller or equal to 70 weight parts.
In above-mentioned pressure sensitive adhesive provided by the invention; The molecular weight of said Yodo Sol GH 28 A is 250-300 ten thousand; It can be to be prepared for (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.01-10 weight part and the organic solvent copolymerization of 70-100 weight part for-90 ℃ to-50 ℃ of the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 60-90 weight part by the second-order transition temperature of 1-20 weight part; And; After preparing, get the raw material of this Yodo Sol GH 28 of 30-100 weight part A as pressure sensitive adhesive;
The molecular weight of said Yodo Sol GH 28 B is 30-70 ten thousand; It can be to be prepared for (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.01-10 weight part and the organic solvent copolymerization of 70-100 weight part for-90 ℃ to-50 ℃ of the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 60-90 weight part by the second-order transition temperature of 5-25 weight part; And; After preparing, get the raw material of this Yodo Sol GH 28 of 0-70 weight part B as pressure sensitive adhesive.
Wherein, the functional group that has in the Acrylic Acid Monomer of functional group is preferably the functional group that can be crosslinked, and can be hydroxyl, carboxyl, carboxamido-group and/or acid anhydrides etc.
In the present invention, (methyl) acrylate monomer is meant methacrylate monomers and acrylate monomer, and this is common literary style, and the compound title of other similar literary styles also all has the above-mentioned similar meaning, enumerates no longer one by one here.
In pressure sensitive adhesive provided by the invention; Preferably, said Yodo Sol GH 28 A prepares (methyl) acrylate monomer of homopolymer for the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 60-80 weight part for-90 ℃ to-50 ℃ be used to and the Acrylic Acid Monomer copolymerization with functional group of 5-15 weight part prepares by the second-order transition temperature of 5-15 weight part;
Said Yodo Sol GH 28 B prepares (methyl) acrylate monomer of homopolymer for the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 70-80 weight part for-90 ℃ to-50 ℃ be used to and the Acrylic Acid Monomer copolymerization with functional group of 5-25 weight part prepares by the second-order transition temperature of 10-20 weight part.
In pressure sensitive adhesive provided by the invention, preferably, the solvent that is adopted comprises one or more in ETHYLE ACETATE, toluene, YLENE and the butanone etc.; The organic solvent that is adopted during the preparation Yodo Sol GH 28 comprises one or more in ETHYLE ACETATE, butanone, methyl alcohol and the toluene etc.
In Yodo Sol GH 28, (methyl) acrylate monomer that the second-order transition temperature that is adopted prepares homopolymer for-45 ℃ to 10 ℃ be used to can strengthen force of cohesion, but with performances such as the adhesion durability of keeping pressure sensitive adhesive and cuttings; It preferably includes in (methyl) NSC 20949, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid 3-methyl butyl ester, n octyl methacrylate and the methylacrylic acid n-tetradecane base ester etc. one or more.
In Yodo Sol GH 28, (methyl) acrylate monomer that the second-order transition temperature that is adopted prepares homopolymer for-90 ℃ to-50 ℃ be used to can increase the polymkeric substance chain flexibility, thereby gives prepared pressure sensitive adhesive with voltage-dependent characteristic; It preferably includes in (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, methylacrylic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid 2-ethyl butyl ester, (methyl) NSC 11786, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems and the methylacrylic acid dodecyl ester etc. one or more.
In Yodo Sol GH 28, acrylate monomer can improve the force of cohesion of polymkeric substance, thereby improve the performance of pressure sensitive adhesive through with the linking agent reaction cohesive force being provided.The Acrylic Acid Monomer that the present invention adopted can be independent a kind of Acrylic Acid Monomer; It also can be the mixture of multiple Acrylic Acid Monomer; Preferably; The Acrylic Acid Monomer with functional group that the present invention adopted comprises that the 0.3-5 weight part has the Acrylic Acid Monomer of hydroxyl, 0.2-4 has the Acrylic Acid Monomer of epoxy group(ing) and the Acrylic Acid Monomer that 0.5-1 has carboxyl; More preferably; Above-mentioned Acrylic Acid Monomer with hydroxyl can comprise one or more in (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate and (methyl) vinylformic acid 2-hydroxyl glycol ester etc., and above-mentioned Acrylic Acid Monomer with epoxy group(ing) can be (methyl) acrylic acid epoxy propyl ester, and above-mentioned Acrylic Acid Monomer with carboxyl can comprise one or more in (methyl) vinylformic acid, toxilic acid and the maleic anhydride etc.Through adopting the combination of multiple Acrylic Acid Monomer, can improve the flexibility of BOPP film greatly, and can reduce production cost of products.
In pressure sensitive adhesive provided by the invention, linking agent can with functional group reactions among Yodo Sol GH 28 A and the B to increase the force of cohesion of pressure sensitive adhesive; The linking agent that is adopted preferably includes isocyanic ester, epoxy compounds, nitrogen third is stung with metallo-chelate etc. in one or more, wherein, be good with isocyanic ester.Particularly, above-mentioned isocyanic ester can comprise one or more in toluene-2,4-diisocyanate, xylene diisocyanate, two isocyanic acid phenylbenzene methyl esters, two isocyanic acids, six methylene esters, isomery vulcabond and the two isocyanic acid tetramethyl xylene esters etc.; Above-mentioned epoxy compounds can comprise one or more in ethylene glycol diglycidylether, triglycidyl ether and the trihydroxymethylpropanyltri diglycidyl ether etc.; Above-mentioned nitrogen third is stung and can be comprised N, and N '-Toluene-2,4-diisocyanate .4-two (1-nitrogen third is stung carbonyl), N, N '-ditan-4,4 '-two (1-nitrogen third is stung carbonyl), triethylene trimeric cyanamide and oxidation three-1-a word used for translation third sting one or more in basic phosphine etc.; Above-mentioned metallo-chelate can comprise one or more in polyvalent metals such as aluminium, iron, tin, titanium, antimony, magnesium or vanadium and the coordinate compounds such as methyl ethyl diketone or ethylacetoacetone(EAA,HEAA).
In pressure sensitive adhesive provided by the invention, the initiator that is adopted is preferably BPO and/or Diisopropyl azodicarboxylate etc.
In pressure sensitive adhesive provided by the invention, silane coupling agent can improve the adhesion stability and the resistance toheat of pressure sensitive adhesive.The silane coupling agent that the present invention adopted preferably includes one or more in vinyltrimethoxy silane, vinyltriethoxysilane, γ-glycidyl ether propyl trimethoxy silicane and the γ-methacryloxypropyl trimethoxy silane etc.
In pressure sensitive adhesive provided by the invention, softening agent can improve acrylic acid flowability, improves the bounding force of pressure sensitive adhesive and BOPP base material.The softening agent that the present invention adopted preferably includes one or more in dioctyl sebacate, dioctyl terephthalate, tributyl citrate, tributyl acetylcitrate and the tributyl phosphate etc.
The present invention also provides the preparation method of the pressure sensitive adhesive of the above-mentioned BOPP of being used for protective membrane, and it may further comprise the steps:
Step 1: preparation Yodo Sol GH 28 A
The second-order transition temperature of 1-10 weight part is put into reaction kettle for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, the second-order transition temperature of 10-30 weight part for-90 ℃ to-50 ℃ (methyl) acrylate monomer that is used to prepare homopolymer, the initiator of 0.01-0.5 weight part and the organic solvent of 20-40 weight part, be heated to 60-80 ℃ and insulation reaction 10-60 minute;
Remaining second-order transition temperature is prepared mixed being incorporated in of (methyl) acrylate monomer of homopolymer, the Acrylic Acid Monomer with functional group, initiator and organic solvent and is added drop-wise to reaction kettle in 1-3 hour for-90 ℃ to-50 ℃ be used to for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, second-order transition temperature; Be heated to 60-70 ℃ and insulation reaction 2-5 hour then, obtain Yodo Sol GH 28 A;
Step 2: preparation Yodo Sol GH 28 B
The second-order transition temperature of 5-25 weight part is put into reaction kettle for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, the second-order transition temperature of 60-90 weight part for-90 ℃ to-50 ℃ (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.005-0.5 weight part and the organic solvent of 40-60 weight part, be heated to 60-80 ℃ and insulation reaction 10-60 minute;
With remaining initiator and solvent and in 0.5-1 hour, be added drop-wise in the reaction kettle, be heated to 60-70 ℃ and insulation reaction 2-5 hour then, obtain Yodo Sol GH 28 B;
Step 3: mix and stir
30-100 parts by weight of acrylic ester copolymer A and 0-70 parts by weight of acrylic ester copolymer B are mixed; Obtain the mixture of 100 parts by weight of acrylic ester copolymer A and Yodo Sol GH 28 B; Again the softening agent of the silane coupling agent of 0.001-5 weight part and 0.001-5 weight part being put into reaction kettle mixes; When stirring, add the solvent and the 0.01-15 parts by weight of cross-linking agent of 20-40 weight part, obtain the pressure sensitive adhesive of the said BOPP of being used for protective membrane.
The present invention also provides a kind of BOPP protective membrane, and it is made up of BOPP film and the pressure-sensitive adhesive layer that is coated on the said BOPP film, and wherein, said pressure-sensitive adhesive layer is to be processed by the pressure sensitive adhesive of the BOPP of being used for protective membrane provided by the invention.
The present invention also provides the preparation method of above-mentioned BOPP protective membrane, and it may further comprise the steps:
Adopt 50-70 purpose coating roll, the pressure sensitive adhesive of the BOPP of being used for protective membrane provided by the invention is applied to the surface of BOPP film, be heated to 80-100 ℃ of dry 0.5-1 minute with the mode of scraper coating;
After dry the completion,, form pressure-sensitive adhesive layer, obtain the BOPP protective membrane 50 ℃ of slakings 24 hours.
The preparation method of above-mentioned BOPP protective membrane provided by the invention only is the preferred embodiment among the various preparing methods of this protective membrane; Those skilled in the art can expect carrying out according to other ordinary methods of this area the preparation of BOPP protective membrane, perhaps according to routine operation, parameter the preparation method of BOPP protective membrane are adjusted.
The pressure sensitive adhesive that is used for the BOPP protective membrane provided by the invention is strong to the flexibility of BOPP basement membrane, has high characteristics such as bonding, high temperature resistant, can widespread use in the BOPP protective membrane.
Embodiment
To understand in order technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification at present practical range of the present invention.
Embodiment 1
Present embodiment provides pressure sensitive adhesive of a kind of BOPP of being used for protective membrane and preparation method thereof, and wherein, the raw material of pressure sensitive adhesive is formed as shown in table 1.
Table 1
| Feed composition | Weight (kg) |
| Yodo Sol GH 28 A | 10 |
| Yodo Sol GH 28 B | 20 |
| ETHYLE ACETATE | 7 |
| Vinyltriethoxysilane | 0.005 |
| Tributyl acetylcitrate | 0.005 |
| Toluene-2,4-diisocyanate | 0.7 |
The preparation method of the pressure sensitive adhesive that present embodiment provides is following:
Step 1, preparation Yodo Sol GH 28 A
1): 3 kilograms of 2-EHAs, 4 kilograms of Bing Xisuandingzhis, 2 kilograms of TEB 3Ks, 7 kilograms of ETHYLE ACETATE and 0.03 kilogram of BPO are joined in the reaction kettle, be heated to 70 ℃ of insulation reaction 30 minutes;
2): 6 kilograms of 2-EHAs, 8 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 1.2 kilograms of vinylformic acid 2-hydroxyl ethyl esters, 0.6 kilogram of toxilic acid, 2 kilograms of acrylic acid epoxy propyl ester, 14 kilograms of ETHYLE ACETATE and 0.05 kilogram of BPO are mixed; Mode to drip was added drop-wise in the aforesaid reaction vessel in 2 hours; After being added dropwise to complete; Be heated to 65 ℃, and when stirring insulation reaction 3 hours, obtain Yodo Sol GH 28 A.
Step 2, preparation Yodo Sol GH 28 B
1): with 10 kilograms of 2-EHAs, 4 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 3 kilograms of methylacrylic acid 2-hydroxyl ethyl esters, 0.5 kilogram of vinylformic acid, 1 kilogram of acrylic acid epoxy propyl ester, 10 kilograms of ETHYLE ACETATE and 0.03 kilogram of Diisopropyl azodicarboxylate; Join in the reaction kettle, be heated to 68 ℃ of insulation reaction 30 minutes;
2): 2 kilograms of ETHYLE ACETATE and 0.05 kilogram of Diisopropyl azodicarboxylate are mixed; Mode to drip was added drop-wise in 1 hour in the aforesaid reaction vessel, after being added dropwise to complete, was heated to 67 ℃; And when stirring insulation reaction 3 hours, obtain Yodo Sol GH 28 B.
Step 3, mix
10 kilograms of Yodo Sol GH 28 A, 20 kilograms of Yodo Sol GH 28 B, 0.005 kilogram of vinyltriethoxysilane, 0.005 kilogram of tributyl acetylcitrate and 7 kilograms of ETHYLE ACETATE are joined in the reaction kettle; Mix; Add 0.7 kilogram of toluene-2,4-diisocyanate again; Stir, obtain the pressure sensitive adhesive of present embodiment.
The preparation method of BOPP protective membrane:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned pressure sensitive adhesive, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Embodiment 2
Present embodiment provides pressure sensitive adhesive of a kind of BOPP of being used for protective membrane and preparation method thereof, and wherein, the raw material of pressure sensitive adhesive is formed as shown in table 2.
Table 2
| Feed composition | Weight (kg) |
| Yodo Sol GH 28 A | 10 |
| Yodo Sol GH 28 B | 24 |
| ETHYLE ACETATE | 10 |
| Vinyltriethoxysilane | 0.006 |
| Tributyl acetylcitrate | 0.007 |
| Toluene-2,4-diisocyanate | 0.5 |
The preparation method of the pressure sensitive adhesive that present embodiment provides is following:
Step 1, preparation Yodo Sol GH 28 A:
1): 4 kilograms of 2-EHAs, 3 kilograms of Bing Xisuandingzhis, 2 kilograms of TEB 3Ks, 7 kilograms of ETHYLE ACETATE and 0.03 kilogram of BPO are joined in the reaction kettle, be heated to 72 ℃ of insulation reaction 20 minutes;
2): 8 kilograms of 2-EHAs, 6 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 3 kilograms of methylacrylic acid 2-hydroxyl ethyl esters, 1 kilogram of vinylformic acid, 1 kilogram of acrylic acid epoxy propyl ester, 14 kilograms of ETHYLE ACETATE and 0.05 kilogram of BPO are mixed; Mode to drip was added drop-wise in the reaction kettle in 2 hours; After being added dropwise to complete; Be heated to 67 ℃, and when stirring insulation reaction 3 hours, obtain Yodo Sol GH 28 A.
Step 2, preparation Yodo Sol GH 28 B
1): with 7 kilograms of 2-EHAs, 8 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 1.2 kilograms of vinylformic acid 2-hydroxyl ethyl esters, 0.6 kilogram of toxilic acid, 2 kilograms of acrylic acid epoxy propyl ester, 10 kilograms of ETHYLE ACETATE and 0.04 kilogram of Diisopropyl azodicarboxylate; Join in the reaction kettle, be heated to 68 ℃ of insulation reaction 30 minutes;
2): 4 kilograms of ETHYLE ACETATE and 0.06 kilogram of Diisopropyl azodicarboxylate are mixed; Mode to drip was added drop-wise in the aforesaid reaction vessel in 30 minutes, after being added dropwise to complete, was heated to 64 ℃; And when stirring insulation reaction 4 hours, obtain Yodo Sol GH 28 B.
Step 3, mix
10 kilograms of Yodo Sol GH 28 A, 24 kilograms of Yodo Sol GH 28 B, 0.006 kilogram of vinyltriethoxysilane, 0.007 kilogram of tributyl acetylcitrate and 10 kilograms of ETHYLE ACETATE are joined in the reaction kettle; Mix; Add 0.5 kilogram of toluene-2,4-diisocyanate again; Stir, obtain the pressure sensitive adhesive of present embodiment.
The preparation method of BOPP protective membrane:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned pressure sensitive adhesive, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Embodiment 3
Present embodiment provides a kind of pressure sensitive adhesive and preparation method of the BOPP of being used for protective membrane, and wherein, the raw material of pressure sensitive adhesive is formed as shown in table 3.
Table 3
| Feed composition | Weight (kg) |
| Yodo Sol GH 28 A | 10 |
| Yodo Sol GH 28 B | 20 |
| ETHYLE ACETATE | 10 |
| Vinyltriethoxysilane | 0.006 |
| Tributyl acetylcitrate | 0.007 |
| Xylene diisocyanate | 0.3 |
The preparation method of the pressure sensitive adhesive that present embodiment provides is following:
Step 1, preparation Yodo Sol GH 28 A:
1): 4 kilograms of 2-EHAs, 3 kilograms of Bing Xisuandingzhis, 2 kilograms of TEB 3Ks, 7 kilograms of ETHYLE ACETATE and 0.03 kilogram of BPO are joined in the reaction kettle, be heated to 72 ℃ of insulation reaction 20 minutes;
2): 8 kilograms of 2-EHAs, 6 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 3 kilograms of vinylformic acid 2-hydroxy methacrylates, 1.5 kilograms of vinylformic acid, 3 kilograms of acrylic acid epoxy propyl ester, 14 kilograms of ETHYLE ACETATE and 0.05 kilogram of BPO are mixed; Mode to drip was added drop-wise in the reaction kettle in 2 hours; After being added dropwise to complete; Be heated to 70 ℃, and when stirring insulation reaction 3 hours, obtain Yodo Sol GH 28 A.
Step 2, preparation Yodo Sol GH 28 B:
1): with 7 kilograms of 2-EHAs, 8 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 1 kilogram of methylacrylic acid-2 hydroxy methacrylate, 0.6 kilogram of vinylformic acid, 3 kilograms of acrylic acid epoxy propyl ester, 10 kilograms of ETHYLE ACETATE and 0.04 kilogram of Diisopropyl azodicarboxylate; Join in the reaction kettle, be heated to 70 ℃ of insulation reaction 30 minutes;
2): 4 kilograms of ETHYLE ACETATE and 0.06 kilogram of Diisopropyl azodicarboxylate are mixed; Mode to drip was added drop-wise in the aforesaid reaction vessel in 35 minutes, after being added dropwise to complete, was heated to 69 ℃; And when stirring insulation reaction 4 hours, obtain Yodo Sol GH 28 B.
Step 3, mix
At last; 10 kilograms of Yodo Sol GH 28 A, 20 kilograms of Yodo Sol GH 28 B, 0.006 kilogram of vinyltriethoxysilane, 0.007 kilogram of tributyl acetylcitrate and 10 kilograms of ETHYLE ACETATE are joined in the reaction kettle; Mix; Add 0.6 kilogram of xylene diisocyanate again, stir, obtain the pressure sensitive adhesive of present embodiment.
The preparation method of BOPP protective membrane:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned pressure sensitive adhesive, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Embodiment 4
Present embodiment provides pressure sensitive adhesive of a kind of BOPP of being used for protective membrane and preparation method thereof, and wherein, the raw material of pressure sensitive adhesive is formed as shown in table 4.
Table 4
| Feed composition | Weight (kg) |
| Yodo Sol GH 28 A | 10 |
| Yodo Sol GH 28 B | 25 |
| ETHYLE ACETATE | 15 |
| Vinyltriethoxysilane | 0.005 |
| Tributyl acetylcitrate | 0.005 |
| Toluene-2,4-diisocyanate | 1 |
The preparation method of the pressure sensitive adhesive that present embodiment provides is following:
Step 1, preparation Yodo Sol GH 28 A
1): 4 kilograms of 2-EHAs, 3 kilograms of Bing Xisuandingzhis, 2 kilograms of TEB 3Ks, 7 kilograms of ETHYLE ACETATE and 0.03 kilogram of BPO are joined in the reaction kettle, be heated to 68 ℃ of insulation reaction 20 minutes;
2): 8 kilograms of 2-EHAs, 6 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 1 kilogram of methylacrylic acid-2 hydroxy methacrylate, 2 kilograms of vinylformic acid, 2 kilograms of acrylic acid epoxy propyl ester, 14 kilograms of ETHYLE ACETATE and 0.05 kilogram of BPO are mixed; Mode to drip was added drop-wise in the reaction kettle in 2 hours; After being added dropwise to complete; Be heated to 65 ℃, and when stirring insulation reaction 3 hours, obtain Yodo Sol GH 28 A.
Step 2, preparation Yodo Sol GH 28 B
1): with 7 kilograms of 2-EHAs, 8 kilograms of Bing Xisuandingzhis, 4 kilograms of TEB 3Ks, 3 kilograms of vinylformic acid 2-hydroxy methacrylates, 0.5 kilogram of vinylformic acid, 3 kilograms of acrylic acid epoxy propyl ester, 10 kilograms of ETHYLE ACETATE and 0.04 kilogram of Diisopropyl azodicarboxylate; Join in the reaction kettle, be heated to 70 ℃ of insulation reaction 30 minutes;
2): 4 kilograms of ETHYLE ACETATE and 0.06 kilogram of Diisopropyl azodicarboxylate are mixed; Mode to drip was added drop-wise in 1 hour in the aforesaid reaction vessel, after being added dropwise to complete, was heated to 67 ℃; And when stirring insulation reaction 4 hours, obtain Yodo Sol GH 28 B.
Step 3, mix
10 kilograms of Yodo Sol GH 28 A, 25 kilograms of Yodo Sol GH 28 B, 0.005 kilogram of vinyltriethoxysilane, 0.005 kilogram of tributyl acetylcitrate and 15 kilograms of ETHYLE ACETATE are joined in the reaction kettle; Mix; Add 1 kilogram of toluene-2,4-diisocyanate again; Stir, obtain the pressure sensitive adhesive of present embodiment.
The preparation method of BOPP protective membrane:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned pressure sensitive adhesive, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Embodiment 5
Present embodiment provides pressure sensitive adhesive of a kind of BOPP of being used for protective membrane and preparation method thereof, and wherein, the raw material of pressure sensitive adhesive is formed as shown in table 5.
Table 5
| Feed composition | Weight (kg) |
| Yodo Sol GH 28 A | 10 |
| Yodo Sol GH 28 B | 20 |
| ETHYLE ACETATE | 10 |
| Vinyltriethoxysilane | 0.005 |
| Tributyl acetylcitrate | 0.005 |
| N, N '-ditan-4,4 '-two (1-nitrogen third is stung carbonyl) | 1 |
The preparation method of the pressure sensitive adhesive that present embodiment provides is following:
Step 1, preparation Yodo Sol GH 28 A
1): 3 kilograms of 2-EHAs, 3 kilograms of Bing Xisuandingzhis, 2 kilograms of TEB 3Ks, 7 kilograms of ETHYLE ACETATE and 0.03 kilogram of BPO are joined in the reaction kettle, be heated to 72 ℃ of insulation reaction 10 minutes;
2): 7 kilograms of 2-EHAs, 8 kilograms of Bing Xisuandingzhis, 6 kilograms of TEB 3Ks, 4 kilograms of 2-hydroxyethyl methacrylates, 1.5 kilograms of vinylformic acid, 2 kilograms of acrylic acid epoxy propyl ester, 21 kilograms of ETHYLE ACETATE and 0.07 kilogram of BPO are mixed; Mode to drip was added drop-wise in the reaction kettle in 3 hours; After being added dropwise to complete; Be heated to 70 ℃, and when stirring insulation reaction 2 hours, obtain Yodo Sol GH 28 A.
Step 2, preparation Yodo Sol GH 28 B
1): with 9 kilograms of 2-EHAs, 6 kilograms of Bing Xisuandingzhis, 7 kilograms of TEB 3Ks, 3 kilograms of 2-hydroxyethyl methacrylates, 0.6 kilogram of vinylformic acid, 2 kilograms of acrylic acid epoxy propyl ester, 10 kilograms of ETHYLE ACETATE and 0.04 kilogram of Diisopropyl azodicarboxylate; Join in the reaction kettle, be heated to 69 ℃ of insulation reaction 30 minutes;
2): 4 kilograms of ETHYLE ACETATE and 0.06 kilogram of Diisopropyl azodicarboxylate are mixed; Mode to drip was added drop-wise in the aforesaid reaction vessel in 40 minutes, after being added dropwise to complete, was heated to 69 ℃; And when stirring insulation reaction 4 hours, obtain Yodo Sol GH 28 B.
Step 3, mix
10 kilograms of Yodo Sol GH 28 A, 20 kilograms of Yodo Sol GH 28 B, 0.005 kilogram of vinyltriethoxysilane, 0.005 kilogram of tributyl acetylcitrate and 10 kilograms of ETHYLE ACETATE are joined in the reaction kettle; Mix; Add 1 kilogram of N again, N '-ditan-4,4 '-two (1-nitrogen third is stung carbonyl); Stir, obtain the pressure sensitive adhesive of present embodiment.
The preparation method of BOPP protective membrane:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned pressure sensitive adhesive, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Comparative Examples 1
This Comparative Examples provides a kind of BOPP protective membrane, and wherein, the 005B type PE protective membrane of producing with commercially available Kailanda Industry Co., Ltd., Shanghai prepares pressure-sensitive adhesive layer with high bonding pressure sensitive adhesive at the BOPP film surface, and its preparation method is following:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned glue, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Comparative Examples 2
This Comparative Examples provides a kind of BOPP protective membrane, and wherein, the 007B type PVC protective membrane of producing with commercially available Kailanda Industry Co., Ltd., Shanghai prepares pressure-sensitive adhesive layer with high bonding pressure sensitive adhesive at the BOPP film surface, and its preparation method is following:
Adopt 70 order coating rolls, be applied to the surface of the thick BOPP film of 50 μ m to above-mentioned glue, be heated to 100 ℃ of dryings 1 minute with the mode of scraper coating; Rolling; Slaking 24 hours in 50 ℃ curing chamber then, forming thickness is the pressure-sensitive adhesive layer of 10 μ m, obtains the BOPP protective membrane.
Performance test:
The performance of the BOPP protective membrane that embodiment 1-5 and Comparative Examples 1-2 is provided according to following method detects, and test result is as shown in table 6:
180 ° of peel strength tests: test according to GB2792-81;
Resistance to elevated temperatures test: it is on 10 the stainless steel plate that protective membrane is attached to surfaceness; Placing temperature then is in 80 ℃ the baking oven aging 12 hours, takes out steel plate, is cooled to room temperature naturally; Test 180 ° of stripping strengths, and observe on the steel plate whether cull or offset printing are arranged.
Table 6 The performance test results
From test result, can find out; The BOPP protective membrane that utilizes pressure sensitive adhesive provided by the invention to process has higher stripping strength and higher resistance to elevated temperatures; This explanation, pressure sensitive adhesive provided by the invention has high adherence, resistance to elevated temperatures, is fit to be used as the BOPP protective membrane and uses pressure sensitive adhesive.Can find out that from the The performance test results of Comparative Examples 1 and 2 the BOPP protective membrane substitutes with high bonding pressure sensitive adhesive with PE and the PVC protective membrane that pressure sensitive adhesive can not adopt on the market to be sold.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; And be not used in qualification protection scope of the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. pressure sensitive adhesive that is used for the BOPP protective membrane, it has following raw material and forms:
Yodo Sol GH 28 A and/or Yodo Sol GH 28 B, 100 weight parts, linking agent, 0.01-15 weight part, silane coupling agent, 0.001-5 weight part, softening agent, 0.001-5 weight part, solvent, 20-45 weight part;
The molecular weight of said Yodo Sol GH 28 A is 250-300 ten thousand; It is to be prepared for (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.01-10 weight part and the organic solvent copolymerization of 70-100 weight part for-90 ℃ to-50 ℃ of the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 60-90 weight part by the second-order transition temperature of 1-20 weight part; And; After preparing, (this Yodo Sol GH 28 of weight part A is as the raw material of pressure sensitive adhesive to get 30-10;
The molecular weight of said Yodo Sol GH 28 B is 30-70 ten thousand; It is to be prepared for (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.01-10 weight part and the organic solvent copolymerization of 70-100 weight part for-90 ℃ to-50 ℃ of the second-order transition temperature of (methyl) acrylate monomer that is used to prepare homopolymer of-45 ℃ to 10 ℃, 60-90 weight part by the second-order transition temperature of 5-25 weight part; And; After preparing, get the raw material of this Yodo Sol GH 28 of 0-70 weight part B as pressure sensitive adhesive.
2. pressure sensitive adhesive as claimed in claim 1, wherein, said solvent comprises one or more in ETHYLE ACETATE, toluene, YLENE and the butanone; Said organic solvent comprises one or more in ETHYLE ACETATE, butanone, methyl alcohol and the toluene.
3. according to claim 1 or claim 2 pressure sensitive adhesive; Wherein, said second-order transition temperature (methyl) acrylate monomer of preparing homopolymer for-45 ℃ to 10 ℃ be used for comprises one or more of (methyl) NSC 20949, (methyl) n-butyl acrylate, (methyl) propyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid 3-methyl butyl ester, n octyl methacrylate and methylacrylic acid n-tetradecane base ester;
(methyl) acrylate monomer that said second-order transition temperature prepares homopolymer for-90 ℃ to-50 ℃ be used for comprises one or more of (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, methylacrylic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid 2-ethyl butyl ester, (methyl) NSC 11786, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems and methylacrylic acid dodecyl ester;
Said Acrylic Acid Monomer compsn with functional group comprises that the 0.3-5 weight part has the Acrylic Acid Monomer of hydroxyl, 0.2-10 has the Acrylic Acid Monomer of epoxy group(ing) and the Acrylic Acid Monomer that 0.5-5 has carboxyl; Wherein, Said Acrylic Acid Monomer with hydroxyl comprises one or more in (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate and (methyl) vinylformic acid 2-hydroxyl glycol ester; Said Acrylic Acid Monomer with epoxy group(ing) is (methyl) acrylic acid epoxy propyl ester, and said Acrylic Acid Monomer with carboxyl comprises one or more in (methyl) vinylformic acid and the toxilic acid.
4. according to claim 1 or claim 2 pressure sensitive adhesive, wherein, said linking agent comprises one or more in isocyanic ester, epoxy compounds, Soluol XC 100 and the metallo-chelate; Said isocyanic ester comprises one or more in toluene-2,4-diisocyanate, xylene diisocyanate, two isocyanic acid phenylbenzene methyl esters, two isocyanic acids, six methylene esters, isomery vulcabond and the two isocyanic acid tetramethyl xylene esters;
Said epoxy compounds comprises one or more in ethylene glycol diglycidylether, triglycidyl ether and the trihydroxymethylpropanyltri diglycidyl ether;
Said Soluol XC 100 comprises N, N '-Toluene-2,4-diisocyanate .4-two (1-Soluol XC 100 carbonyl), N, N '-ditan-4, one or more in 4 '-two (1-Soluol XC 100 carbonyls), triethylene trimeric cyanamide and the oxidation three-1-aziridinyl phosphine;
Said metallo-chelate comprises one or more in aluminium, iron, tin, titanium, antimony, magnesium or vanadium and methyl ethyl diketone or the ethylacetoacetone(EAA,HEAA) coordinate compound.
5. according to claim 1 or claim 2 pressure sensitive adhesive, wherein, said initiator is BPO and/or Diisopropyl azodicarboxylate.
6. according to claim 1 or claim 2 pressure sensitive adhesive; Wherein, said silane coupling agent comprises one or more in vinyltrimethoxy silane, vinyltriethoxysilane, γ-glycidyl ether propyl trimethoxy silicane and the γ-methacryloxypropyl trimethoxy silane.
7. according to claim 1 or claim 2 pressure sensitive adhesive, wherein, said softening agent comprises one or more in dioctyl sebacate, dioctyl terephthalate, tributyl citrate, tributyl acetylcitrate and the tributyl phosphate.
8. each described preparation method who is used for the pressure sensitive adhesive of BOPP protective membrane of claim 1-7, it may further comprise the steps:
Step 1: preparation Yodo Sol GH 28 A
The second-order transition temperature of 1-10 weight part is put into reaction kettle for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, the second-order transition temperature of 10-30 weight part for-90 ℃ to-50 ℃ (methyl) acrylate monomer that is used to prepare homopolymer, the initiator of 0.01-0.5 weight part and the organic solvent of 20-40 weight part, be heated to 60-80 ℃ and insulation reaction 10-60 minute;
Remaining second-order transition temperature is prepared mixed being incorporated in of (methyl) acrylate monomer of homopolymer, the Acrylic Acid Monomer with functional group, initiator and organic solvent and is added drop-wise to reaction kettle in 1-3 hour for-90 ℃ to-50 ℃ be used to for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, second-order transition temperature; Be heated to 60-70 ℃ and insulation reaction 2-5 hour then, obtain Yodo Sol GH 28 A;
Step 2: preparation Yodo Sol GH 28 B
The second-order transition temperature of 5-25 weight part is put into reaction kettle for (methyl) acrylate monomer that is used for preparing homopolymer of-45 ℃ to 10 ℃, the second-order transition temperature of 60-90 weight part for-90 ℃ to-50 ℃ (methyl) acrylate monomer that is used to prepare homopolymer, the Acrylic Acid Monomer with functional group of 1-20 weight part, the initiator of 0.005-0.5 weight part and the organic solvent of 40-60 weight part, be heated to 60-80 ℃ and insulation reaction 10-60 minute;
With remaining initiator and solvent and in 0.5-1 hour, be added drop-wise in the reaction kettle, be heated to 60-70 ℃ and insulation reaction 2-5 hour then, obtain Yodo Sol GH 28 B;
Step 3: mix and stir
30-100 parts by weight of acrylic ester copolymer A and 0-70 parts by weight of acrylic ester copolymer B are mixed; Obtain the mixture of 100 parts by weight of acrylic ester copolymer A and Yodo Sol GH 28 B; Again the softening agent of the silane coupling agent of 0.001-5 weight part and 0.001-5 weight part being put into reaction kettle mixes; When stirring, add the solvent and the 0.01-15 parts by weight of cross-linking agent of 20-40 weight part, obtain the pressure sensitive adhesive of the said BOPP of being used for protective membrane.
9. BOPP protective membrane, it is made up of BOPP film and the pressure-sensitive adhesive layer that is coated on the said BOPP film, and wherein, said pressure-sensitive adhesive layer is to be processed by the pressure sensitive adhesive of each the described BOPP of being used for protective membrane of claim 1-7.
10. the preparation method of the described BOPP protective membrane of claim 9, it may further comprise the steps:
Adopt 50-70 purpose coating roll, the pressure sensitive adhesive of each the described BOPP of being used for protective membrane of claim 1-7 is applied to the surface of BOPP film, be heated to 80-100 ℃ of dry 0.5-1 minute with the mode of scraper coating;
After dry the completion,, form pressure-sensitive adhesive layer, obtain said BOPP protective membrane 50 ℃ of slakings 24 hours.
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