CN103013403B - A kind of Nano-emulsion pressure-sensitive adhesive and preparation method thereof - Google Patents
A kind of Nano-emulsion pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN103013403B CN103013403B CN201210581359.3A CN201210581359A CN103013403B CN 103013403 B CN103013403 B CN 103013403B CN 201210581359 A CN201210581359 A CN 201210581359A CN 103013403 B CN103013403 B CN 103013403B
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 39
- 239000007908 nanoemulsion Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 48
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 23
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 12
- 239000004160 Ammonium persulphate Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 241000237502 Ostreidae Species 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 235000020636 oyster Nutrition 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 abstract description 18
- 239000012528 membrane Substances 0.000 abstract description 16
- 239000000178 monomer Substances 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 11
- 239000003995 emulsifying agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 239000000872 buffer Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 11
- -1 Abex2005 Chemical compound 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001139 pH measurement Methods 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 239000007863 gel particle Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 2
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical class C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention discloses a kind of Nano-emulsion pressure-sensitive adhesive and preparation method thereof.This Nano-emulsion pressure-sensitive adhesive comprises following component by weight ratio: soft monomer 70 ~ 90; Hard monomer 7 ~ 20; Cross-linking monomer 3 ~ 10; Emulsifying agent 1.6 ~ 2.3; Initiator 0.3 ~ 0.6; PH value buffer reagent 0.4 ~ 0.6.The preparation technology of this Nano-emulsion pressure-sensitive adhesive comprises the preparation of pre-emulsion, the preparation of initiator solution and nano-emulsion polymerization.This emulsion-type pressure-sensitive can be diluted by vast scale and there will not be the risk of breakdown of emulsion, and the mechanical stability of emulsion and thermostability are fine, to can be implemented under high solids content coating operations equably; The protective membrane obtained by this emulsion has good removable.
Description
Technical field
The present invention relates to a kind of Nano-emulsion pressure-sensitive adhesive and preparation method thereof, this pressure sensitive adhesive is applicable to the manufacture of PE protective membrane.
Background technology
So-called protective membrane; namely be take plastics film as base material; and being coated with the thin-film material with pressure sensitive adhesive that formed with pressure sensitive adhesive, its effect is attached to need the surface of protection to play to cover protective effect to this surface, prevent the pollution being bruised and being subject to dust etc.
Since a very long time, produce protective membrane mainly based on solvent type acrylic (polyacrylic ester) pressure sensitive adhesive, have a large amount of organic gas discharges in process of production.But due to industrialized development, large to the increasing pressure of environment generally, will ask for help more adopt the Technology of more environmental protection when producing various Industrial products.Protective membrane industry is no exception, and under the pressure of the pressure of environmental pollution and legislations of environmental protection, in recent years, people more and more study and promote to use water-borne pressure sensitive adhesive to produce protective membrane product.
But adopt water-borne pressure sensitive adhesive to substitute (Some substitute) solvent pressure-sensitive adhesive, have also discovered the problem that some are new, these problems adopt solvent pressure-sensitive adhesive to produce:
1, water-borne pressure sensitive adhesive protective membrane is easily being produced vaporific remaining by subsides surface;
2, easily normally carrying out and making product appearance become very poor of gel particle impact coating is produced in water-borne pressure sensitive adhesive coating process.
3, the easy moisture absorption of water-borne pressure sensitive adhesive protective membrane and pressure sensitive adhesive force of cohesion is declined, adds the risk of cull.
The present invention is mainly for solving above-mentioned the first two problem.Through overtesting, we find that emulsion particle diameter is less, the thermostability of emulsion and mechanical stability better, particularly particle diameter is when≤50nm, and performance is better.In reality coating, Jiao Penzhong can not produce particulate matter, and carries out to this Nano-emulsion pressure-sensitive adhesive the phenomenon that breakdown of emulsion and gel also can not occur in vast scale dilution.
About the patent of emulsion-type pressure-sensitive and other documents a lot; such as US Patent No. 5183459A US5952398US8063142 US7786236 US4364972; and a kind of environment-friendly novel nano adhesive disclosed in Chinese patent CN101033381A and preparation method and purposes; a kind of building emulsion for confecting inner-outer wall coating disclosed in CN1709932A; the making method etc. of antibacterial, waterproof, anti-aging nanometer pure-acrylic emulsion, but all there is no the report about Nano-emulsion pressure-sensitive adhesive and application in PE electronic protective film thereof.
Summary of the invention
The present invention relates to protective membrane industry, object is to provide a kind of Nano-emulsion pressure-sensitive adhesive and preparation method thereof.The object of the invention is to be achieved through the following technical solutions:
A kind of Nano-emulsion pressure-sensitive adhesive of the present invention, comprises following component by weight ratio:
Soft monomer 70 ~ 90;
Hard monomer 7 ~ 20;
Cross-linking monomer 3 ~ 10;
Emulsifying agent 1.6 ~ 2.3;
Initiator 0.3 ~ 0.6;
PH value buffer reagent 0.4 ~ 0.6;
Soft monomer of the present invention is one or more in ethyl propenoate, butyl acrylate, ethyl acrylate, isopropyl acrylate.Also can select other the monomer with thiazolinyl with the stable chemical nature of similar second-order transition temperature, they mainly provide visco-elasticity to pressure sensitive adhesive.
Hard monomer of the present invention is one or more in methyl methacrylate, methacrylic acid, vinylformic acid.Suitable use can provide suitable cohesive strength for pressure sensitive adhesive, can be useful to the releasable of protective membrane.
Cross-linking monomer of the present invention is glycidyl methacrylate, Hydroxyethyl acrylate, N hydroxymethyl acrylamide, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, one or more in Rocryl 410.Described glycidyl methacrylate, that one can realize internally crosslinked monomer, mainly provide cohesive strength for pressure sensitive adhesive and strengthen its heat-resisting weathering characteristics, also can select N hydroxymethyl acrylamide, but the former being more suitable for the synthesis of this Nano-emulsion pressure-sensitive adhesive relatively.
Emulsifying agent of the present invention is one or more in OP-10, Abex2005, SDBS.Described OP-10 (polyoxyethylene Zhong Xin phenolic ether-10), being alkyl polyoxyethylene class nonionic emulsifying agent, also can be OP-8 (polyoxyethylene nonylphenol ether series (8) ether) or OP-6 (Nonyl pheno (6) ether).Described Abex2005 is a kind of anionic emulsifier, is more suitable for the emulsion preparing small particle size.Described SDBS is Sodium dodecylbenzene sulfonate, is a kind of widely used anionic emulsifier.
Initiator of the present invention is polymerization initiator, is the one in ammonium persulphate, Potassium Persulphate.
PH value buffer reagent of the present invention is sodium bicarbonate.
Present invention also offers a kind of method of Nano-emulsion pressure-sensitive adhesive, comprise the following steps:
1) pre-emulsion preparation: emulsifying agent is added distilled water stirring and make it to dissolve, then add cross-linking monomer, hard monomer and soft monomer at the uniform velocity successively in 10 ~ 20min, and it is for subsequent use to continue stirring 10 ~ 20min;
2) initiator solution preparation: the 83.3%-91.7% dissolving initiator gross weight with distilled water is for subsequent use;
3) nanoemulsions polymerization: dissolve pH value buffer reagent with distilled water in reaction flask, start stirring and dissolving.Adopt heating in water bath, and temperature is arranged on 78 ~ 85 DEG C, by 1/4 ~ 1/3 of pre-emulsion gross weight and step 2) 28.7% ~ 38.5% of initiator solution weight adding respectively in reaction flask of preparing, at the uniform velocity stir, 78 ~ 80 DEG C are warmed up under heating in water bath, when solution crossfades into light blue from oyster white, continue insulation reaction 1.0 ~ 1.5 hours; In reaction flask, at the uniform velocity drip remaining pre-emulsion and initiator solution again, be added dropwise to complete at 2.0 ~ 3.5 hours; Continue insulation reaction 1.0 ~ 2.0 hours, in reaction flask, add remaining initiator and distilled water, bath temperature is warming up to 81 ~ 83 DEG C, continues insulation reaction 2.0 ~ 3.0 hours, is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.Stirring velocity in above step is routine operations to those skilled in the art.
Preferably, described step 1) in emulsifier aqueous solution, add various monomer when carrying out stirring and emulsifying, be by the uniform velocity adding to weak order by force according to monomer polarity.
Preferably, described step 1) in use emulsifying agent adopt nonionic emulsifying agent and anionic emulsifier coupling use.
This emulsion-type pressure-sensitive can be diluted by vast scale and not have gel particle risk, and the mechanical stability of emulsion and thermostability are fine, can be implemented in even spread operation under high solids content; With the protective membrane that this pressure sensitive adhesive is obtained, there is good peelable release and noresidue characteristic.Compared with the protective membrane that the protective membrane that Nano-emulsion pressure-sensitive adhesive of the present invention obtains is obtained with ordinary emulsion type pressure sensitive adhesive: in stability of emulsion, the former is more stable; In coating homogeneity, the former glue face thickness is more even; In removable, the former is also more excellent than the latter.
Embodiment
Embodiment one:
1, pre-emulsion preparation: 50g distilled water is joined and be equipped with in 250ml tri-mouthfuls of reaction flasks of electric stirring, then 0.6g OP-10 and 1.0g Abex2005 is added wherein, and stirring makes it to dissolve; Then under fast stirring in the following order, with total 10 ~ 20min, in reaction flask, at the uniform velocity add 2.0g Hydroxyethyl acrylate, 3.0g methacrylic acid, 4.0g methyl methacrylate, 1.0g glycidyl methacrylate, 34g ethyl propenoate, 41g butyl acrylate, 15g ethyl acrylate, and it is for subsequent use to continue stirring 10 ~ 20min.
2, initiator solution preparation: dissolve 0.35g ammonium persulphate with 45g distilled water for subsequent use.
3, nanoemulsions polymerization: add 50mg distilled water in 500ml tetra-mouthfuls of reaction flasks that reflux exchanger and electric mixer be housed, then add 0.6g sodium bicarbonate wherein, starts stirring and dissolving.Adopt heating in water bath, and temperature is arranged on 78 ~ 85 DEG C, the 14.7g initiator solution prepared in the 42g pre-emulsion prepared in step 1 and step 2 is added in reaction flask respectively, at the uniform velocity stirs, under heating in water bath, be warmed up to 78 ~ 80 DEG C, note the colour-change of observing material.When color becomes light blue from oyster white gradually, writing time, continue insulation reaction 1.0 ~ 1.5 hours; Afterwards, start in reaction flask, drip remaining pre-emulsion and initiator solution simultaneously, control at the uniform velocity to be added dropwise to complete at 2.5 ~ 3.0 hours; Afterwards, continue insulation reaction after 1.0 ~ 1.5 hours, remaining 0.05g ammonium persulphate and 5.0g distilled water solution is added in reaction flask, bath temperature is elevated to 81 ~ 83 DEG C, continue insulation reaction 2.0 ~ 2.5 hours, insulation reaction terminates, and is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.
Properties technical indicator according to following testing method test pressure sensitive adhesive:
Testing method:
Emulsion particle diameter: adopt MS2000 laser diffraction granularity determinator to measure;
Solid content: measure by GB/T11175-2002;
Viscosity: adopt rotary viscosity design determining;
PH value: adopt PH measurement fixed;
Test result: emulsion particle diameter≤150nm, solid content is 39.6%, viscosity 450mPas, pH value 8.2.
Embodiment two:
1, pre-emulsion preparation: 50g distilled water is joined and be equipped with in 250ml tri-mouthfuls of reaction flasks of electric stirring, then two kinds of emulsifying agent 0.6g OP-10 and 1.0g SDBS (active weight content 30%) are added wherein, and stirring makes it to dissolve; Then under fast stirring in the following order, with total 10 ~ 20min, in reaction flask, at the uniform velocity add 4.0g Hydroxyethyl acrylate, 5.0g methacrylic acid, 10g methyl methacrylate, 3.0g glycidyl methacrylate, 26g ethyl propenoate, 40g butyl acrylate, 12g ethyl acrylate, and it is for subsequent use to continue stirring 10 ~ 20min.
2, initiator solution preparation: dissolve 0.25g ammonium persulphate with 45g distilled water for subsequent use.
3, nanoemulsions polymerization: add 50mg distilled water in 500ml tetra-mouthfuls of reaction flasks that reflux exchanger and electric mixer be housed, then add 0.5g sodium bicarbonate wherein, starts stirring and dissolving.Adopt heating in water bath, and temperature is arranged on 78 ~ 85 DEG C, the 13g initiator solution prepared in the 37.5g pre-emulsion prepared in step 1 and step 2 is added in reaction flask respectively, at the uniform velocity stirs, under heating in water bath, be warmed up to 78 ~ 80 DEG C, note the colour-change of observing material.When color becomes light blue from oyster white gradually, writing time, continue insulation reaction 1.0 ~ 1.5 hours; Afterwards, start in reaction flask, drip remaining pre-emulsion and initiator solution simultaneously, control at the uniform velocity to be added dropwise to complete at 2.5 ~ 3.0 hours; Afterwards, continue insulation reaction after 1.5 ~ 2.0 hours, remaining 0.05g ammonium persulphate and 5.0g distilled water solution is added in reaction flask, bath temperature is elevated to 81 ~ 83 DEG C, continue insulation reaction 2.0 ~ 2.5 hours, insulation reaction terminates, and is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.
Properties technical indicator according to following testing method test pressure sensitive adhesive:
Testing method:
Emulsion particle diameter: adopt MS2000 laser diffraction granularity determinator to measure;
Solid content: measure by GB/T11175-2002;
Viscosity: adopt rotary viscosity design determining;
PH value: adopt PH measurement fixed;
Test result: emulsion particle diameter≤250nm, solid content is 39.7%, viscosity 350mPa.s, pH value 8.1.
Embodiment three:
1, pre-emulsion preparation: 50g distilled water is joined and be equipped with in 250ml tri-mouthfuls of reaction flasks of electric stirring, then 0.45g OP-10 and 1.5gAbex2005 is added wherein, and stirring makes it to dissolve; Then under fast stirring in the following order, with total 10 ~ 20min, in reaction flask, at the uniform velocity add 4.0g Hydroxyethyl acrylate, 3.0g methacrylic acid, 6.0g methyl methacrylate, 2.0g glycidyl methacrylate, 30g ethyl propenoate, 30g butyl acrylate, 25g ethyl acrylate, and it is for subsequent use to continue stirring 10 ~ 20min.
2, initiator solution preparation: dissolve 0.55g ammonium persulphate with 45g distilled water for subsequent use.
3, nanoemulsions polymerization: add 50mg distilled water in 500ml tetra-mouthfuls of reaction flasks that reflux exchanger and electric mixer be housed, then add 0.5g sodium bicarbonate wherein, starts stirring and dissolving.Adopt heating in water bath, and temperature be arranged on 78 ~ 85 DEG C.The 17.5g initiator solution prepared in the 50g pre-emulsion prepared in step 1 and step 2 is added in reaction flask respectively, at the uniform velocity stirs, under heating in water bath, be warmed up to 78 ~ 80 DEG C, note the colour-change of observing material.When color becomes light blue from oyster white gradually, writing time, continue insulation reaction 1.0 ~ 1.5 hours; Afterwards, start in reaction flask, drip remaining pre-emulsion and initiator solution simultaneously, control at the uniform velocity to be added dropwise to complete at 2.0 ~ 3.0 hours; Afterwards, continue insulation reaction after 1.5 ~ 2.0 hours, remaining 0.05g ammonium persulphate and 5.0g distilled water solution is added in reaction flask, bath temperature is elevated to 81 ~ 83 DEG C, continue insulation reaction 2.0 ~ 2.5 hours, insulation reaction terminates, and is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.
Properties technical indicator according to following testing method test pressure sensitive adhesive:
Testing method:
Emulsion particle diameter: adopt MS2000 laser diffraction granularity determinator to measure;
Solid content: measure by GB/T11175-2002;
Viscosity: adopt rotary viscosity design determining;
PH value: adopt PH measurement fixed;
Test result: emulsion particle diameter≤110nm, solid content is 39.4%, viscosity 400mPa.s, pH value 8.1.
Embodiment four:
1, pre-emulsion preparation: 50g distilled water is joined and be equipped with in 250ml tri-mouthfuls of reaction flasks of electric stirring, then 0.3g OP-10 and 2.0g Abex2005 is added wherein, and stirring makes it to dissolve; Then under fast stirring in the following order, with total 10 ~ 20min, in reaction flask, at the uniform velocity add 5.0g Hydroxyethyl acrylate, 4.0g methacrylic acid, 16g methyl methacrylate, 5.0g glycidyl methacrylate, 10g ethyl propenoate, 25g butyl acrylate, 35g ethyl acrylate, and it is for subsequent use to continue stirring 10 ~ 20min.
2, initiator solution preparation: dissolve 0.45g ammonium persulphate with 45g distilled water for subsequent use.
3, nanoemulsions polymerization: add 50mg distilled water in 500ml tetra-mouthfuls of reaction flasks that reflux exchanger and electric mixer be housed, then add 0.4g sodium bicarbonate wherein, starts stirring and dissolving.Adopt heating in water bath, and temperature is arranged on 78 ~ 85 DEG C, the 17.5g initiator solution prepared in the 50g pre-emulsion prepared in step 1 and step 2 is added in reaction flask respectively, at the uniform velocity stirs, under heating in water bath, be warmed up to 78 ~ 80 DEG C, note the colour-change of observing material.When color becomes light blue from oyster white gradually, writing time, continue insulation reaction 1.0 ~ 1.5 hours; Afterwards, start in reaction flask, drip remaining pre-emulsion and initiator solution simultaneously, control at the uniform velocity to be added dropwise to complete at 2.0 ~ 3.0 hours; Afterwards, continue insulation reaction after 1.5 ~ 2.0 hours, remaining 0.05g ammonium persulphate and 5.0g distilled water solution is added in reaction flask, bath temperature is elevated to 81 ~ 83 DEG C, continue insulation reaction 2.5 ~ 3.0 hours, insulation reaction terminates, and is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.
Properties technical indicator according to following testing method test pressure sensitive adhesive:
Testing method:
Emulsion particle diameter: adopt MS2000 laser diffraction granularity determinator to measure;
Solid content: measure by GB/T11175-2002;
Viscosity: adopt rotary viscosity design determining;
PH value: adopt PH measurement fixed;
Test result: emulsion particle diameter≤50nm, solid content is 39.8%, viscosity 550mPa.s, pH value 8.0.
From the above test result to embodiment 1 ~ 4 gained nanoemulsions pressure sensitive adhesive: emulsion-type pressure-sensitive of the present invention can be diluted by vast scale and not have gel particle risk, the mechanical stability of emulsion and thermostability are fine, can be implemented in even spread operation under high solids content; With the protective membrane that this pressure sensitive adhesive is obtained, there is good peelable release and noresidue characteristic.Compared with the protective membrane that ordinary emulsion type pressure sensitive adhesive is obtained (experimental data is omited, but those skilled in the art record by normal experiment), the protective membrane that Nano-emulsion pressure-sensitive adhesive provided by the invention obtains is in stability of emulsion, more stable; In coating homogeneity, glue face thickness is more even; In removable, more excellent.
Claims (1)
1. a Nano-emulsion pressure-sensitive adhesive, is characterized in that, is prepared as follows by weight ratio forms by following component:
1), pre-emulsion preparation: 50g distilled water is joined and be equipped with in 250ml tri-mouthfuls of reaction flasks of electric stirring, then 0.3g OP-10 and 2.0g Abex2005 is added wherein, and stirring makes it to dissolve; Then under fast stirring in the following order, with total 10 ~ 20min, in reaction flask, at the uniform velocity add 5.0g Hydroxyethyl acrylate, 4.0g methacrylic acid, 16g methyl methacrylate, 5.0g glycidyl methacrylate, 10g ethyl propenoate, 25g butyl acrylate, 35g ethyl acrylate, and it is for subsequent use to continue stirring 10 ~ 20min;
2), initiator solution preparation: dissolve 0.45g ammonium persulphate with 45g distilled water for subsequent use;
3), nanoemulsions polymerization: add 50mg distilled water in 500ml tetra-mouthfuls of reaction flasks that reflux exchanger and electric mixer be housed, then add 0.4g sodium bicarbonate wherein, start stirring and dissolving; Adopt heating in water bath, and temperature is arranged on 78 ~ 85 DEG C, the 17.5g initiator solution prepared in the 50g pre-emulsion prepared in step 1 and step 2 is added in reaction flask respectively, at the uniform velocity stirs, under heating in water bath, be warmed up to 78 ~ 80 DEG C, note the colour-change of observing material; When color becomes light blue from oyster white gradually, writing time, continue insulation reaction 1.0 ~ 1.5 hours; Afterwards, start in reaction flask, drip remaining pre-emulsion and initiator solution simultaneously, control at the uniform velocity to be added dropwise to complete at 2.0 ~ 3.0 hours; Afterwards, continue insulation reaction after 1.5 ~ 2.0 hours, remaining 0.05g ammonium persulphate and 5.0g distilled water solution is added in reaction flask, bath temperature is elevated to 81 ~ 83 DEG C, continue insulation reaction 2.5 ~ 3.0 hours, insulation reaction terminates, and is cooled to normal temperature, and discharging also filters the emulsion obtaining light blue band fluorescence.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN105950076A (en) * | 2016-04-01 | 2016-09-21 | 合肥第六元素光电科技有限公司 | Flexible thermally-conductive adhesive designed based on multi-dimension multi-scale microstructure |
| CN105950082A (en) * | 2016-04-01 | 2016-09-21 | 合肥第六元素光电科技有限公司 | Colored pressure-sensitive adhesive, manufacturing method thereof, and manufactured pressure-sensitive adhesive tape |
| CN105950077A (en) * | 2016-04-01 | 2016-09-21 | 合肥第六元素光电科技有限公司 | Thermochromic adhesive and preparation method thereof and adhesive tape made from adhesive |
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| CN107353838B (en) * | 2017-06-27 | 2018-09-21 | 阜南县力韦包装材料有限公司 | A kind of heatproof height sticks the processing technology of double faced adhesive tape |
| CN111073557A (en) * | 2019-12-26 | 2020-04-28 | 南通吉美装饰材料有限公司 | Preparation method of adhesive for benzene-free and ketone-free PVC (polyvinyl chloride) film |
| CN114316853A (en) * | 2020-10-21 | 2022-04-12 | 广东邦固薄膜涂料创新研究院有限公司 | Antibacterial acrylic pressure-sensitive adhesive and preparation method thereof |
| CN114015386A (en) * | 2021-11-05 | 2022-02-08 | 深圳日高胶带新材料有限公司 | Emulsion type acrylate pressure-sensitive adhesive capable of being repeatedly torn off and stuck for use |
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