CN115785830A - Preparation method of substrate-free double-sided adhesive tape and double-sided adhesive tape - Google Patents
Preparation method of substrate-free double-sided adhesive tape and double-sided adhesive tape Download PDFInfo
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- CN115785830A CN115785830A CN202211614865.8A CN202211614865A CN115785830A CN 115785830 A CN115785830 A CN 115785830A CN 202211614865 A CN202211614865 A CN 202211614865A CN 115785830 A CN115785830 A CN 115785830A
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- adhesive layer
- exhaust
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012790 adhesive layer Substances 0.000 claims abstract description 61
- 239000004814 polyurethane Substances 0.000 claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 claims abstract description 49
- 230000001070 adhesive effect Effects 0.000 claims abstract description 42
- 239000000853 adhesive Substances 0.000 claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims abstract description 33
- 239000003292 glue Substances 0.000 claims abstract description 30
- 239000002344 surface layer Substances 0.000 claims abstract description 29
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 239000007888 film coating Substances 0.000 claims abstract description 9
- 238000009501 film coating Methods 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000004970 Chain extender Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 Polyethylene adipate Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a substrate-free double-sided adhesive tape, which comprises the following steps: s1: preparing a release film, coating a first glue solution on the surface of the release film, and curing for the first time to obtain a first glue layer; s2: preparing a second glue layer; s3: the first adhesive layer and the second adhesive layer are compounded; s4: tearing off the release film, spraying exhaust film coating liquid on the surface of the first adhesive layer opposite to the second adhesive layer, and curing for the second time after placing to obtain the substrate-free double-sided adhesive tape with the exhaust surface layer; the main component of the first glue solution is a first acrylic acid modified waterborne polyurethane adhesive; the exhaust membrane coating liquid mainly comprises a second acrylic acid modified waterborne polyurethane adhesive, polyvinylpyrrolidone and ethyl acetate. The exhaust surface layer is prepared on the surface of the first adhesive layer back to the second adhesive layer, so that the mechanical strength of the double-sided adhesive tape is maintained, and the surface layer forms a gap to achieve the effect of attaching and exhausting with an adherend.
Description
Technical Field
The invention relates to the technical field of optical adhesives, in particular to a preparation method of a substrate-free double-sided adhesive tape and the double-sided adhesive tape.
Background
With the development of a display screen of the smart phone from a plane to 3D, functional films such as a corresponding toughened film and an explosion-proof film are required to be bendable, namely, bending resistance is achieved. Usually, the functional membrane needs to be connected with the body by AB glue. The AB glue not only has optical properties such as high light transmittance and small haze, but also has the characteristics of high temperature resistance and delamination resistance. However, when the existing functional film is adhered to the body through the AB glue, bubbles are easily generated, and the problem of difficult air exhaust is solved, so that the attractiveness of the body is influenced on one hand, and the definition of images projected on a screen is influenced on the other hand.
CN109203600A discloses a flexible substrate-free AB adhesive and a manufacturing process thereof, wherein the substrate-free AB adhesive comprises an OCA optical adhesive and a silica gel layer. The problem of layering cull easily appears on silica gel layer and OCA optical cement.
CN114621701A discloses a grid self-disappearing exhaust adhesive tape and a preparation method thereof, wherein the AB adhesive comprises an acrylic layer A, a polyester film layer and an acrylic layer B, and a grid release film is arranged on the surface of the acrylic layer A, which is back to the polyester film layer. The polyester film layer is taken as a base material to achieve bending resistance and high temperature resistance, and the process requirement is high in cost; the air exhaust is realized when the grids on the adhesive layer are applied and attached, the air exhaust time and the air exhaust effect are realized by designing grid arrangement on the grid release film, and the contact area is small and the grids are easy to rub off when the adhesive layer of the net surface is attached; and over time, the lattice will gradually disappear and the function of the exhaust will fail.
Disclosure of Invention
One of the objectives of the present invention is to overcome the drawbacks of the prior art, and to provide a method for preparing a substrate-less double-sided tape, in which an exhaust surface layer is prepared on a surface of a first adhesive layer opposite to a second adhesive layer, so that the mechanical strength of the double-sided tape is maintained, and a gap is formed in the surface layer to achieve the effect of attaching to an adherend for exhausting air.
In order to realize the process effect, the technical scheme of the invention is as follows: a preparation method of a substrate-free double-sided adhesive tape comprises the following steps:
s1: preparing a release film, coating a first glue solution on the surface of the release film, and curing for the first time to obtain a first glue layer;
s2: preparing a second glue layer;
s3: the first adhesive layer and the second adhesive layer are compounded;
s4: tearing off the release film, spraying exhaust film coating liquid on the surface of the first adhesive layer opposite to the second adhesive layer, and curing for the second time after placing to obtain the substrate-free double-sided adhesive tape with the exhaust surface layer;
the main component of the first glue solution is a first acrylic acid modified waterborne polyurethane adhesive;
the exhaust membrane coating liquid mainly comprises a second acrylic acid modified waterborne polyurethane adhesive, polyvinylpyrrolidone and ethyl acetate.
The preferable technical scheme is as follows: the exhaust membrane coating liquid mainly comprises, by mass, 100 parts of a second acrylic acid modified aqueous polyurethane adhesive, 1-5 parts of polyvinylpyrrolidone and 30-50 parts of ethyl acetate, wherein the solid content of the second acrylic acid modified aqueous polyurethane adhesive is 30-40%.
The preferable technical scheme is as follows: the first acrylic acid modified waterborne polyurethane adhesive and the second acrylic acid modified waterborne polyurethane adhesive are prepared from polyester polyol, aliphatic polyisocyanate, alcohol and/or amine micromolecule chain extenders, hydrophilic chain extenders, double-bond end capping agents, salt forming agents, modified acrylate monomers and deionized water.
The preferable technical scheme is as follows: the grafting content of the end-capping agent in the first acrylic acid modified waterborne polyurethane adhesive is 10-20%.
The preferable technical scheme is as follows: the grafting content of the end capping agent in the second acrylic acid modified waterborne polyurethane adhesive is 30-40%.
The preferable technical scheme is as follows: the second adhesive layer is an acrylic acid modified polyurethane adhesive layer.
The preferable technical scheme is as follows: the temperature of the first curing is sequentially set as follows: 85 plus or minus 5 ℃,95 plus or minus 5 ℃,105 plus or minus 5 ℃,120 plus or minus 5 ℃ and 100 plus or minus 5 ℃; the temperature of the second curing is set as follows in sequence: 70 plus or minus 5 ℃,80 plus or minus 5 ℃,90 plus or minus 5 ℃,110 plus or minus 5 ℃ and 100 plus or minus 5 ℃.
The preferable technical scheme is as follows: the spraying pressure in the S4 is 0.06-0.1 Mpa, and the standing time is 1-3 min.
The preferable technical scheme is as follows: the layer thickness ratio of the first adhesive layer to the second adhesive layer is 1: (1-10); the thickness ratio of the first adhesive layer to the exhaust surface layer is 1: (0.01-0.06), and the layer thickness of the first adhesive layer is 10-30 μm. Furthermore, the layer thickness of the first glue layer is 10-20 μm.
The second purpose of the present invention is to overcome the defects in the prior art, and to provide a double-sided tape, which is prepared by the above method for preparing a substrate-free double-sided tape.
The invention has the advantages and beneficial effects that:
according to the preparation method of the substrate-free double-sided tape, the first adhesive layer is prepared from the first acrylic acid modified waterborne polyurethane adhesive, the exhaust surface layer is prepared from the second acrylic acid modified waterborne polyurethane adhesive, and the two layers have excellent compatibility and good adhesiveness;
when the second time of curing is carried out, the activity of the hydrophilic group on the surface of the first adhesive layer is enhanced, and the adsorption action between the polyvinylpyrrolidone in the exhaust membrane coating liquid and the surface of the sticky solid first adhesive layer is greater than that between the polyvinylpyrrolidone in the diluted flowing exhaust membrane coating liquid, so that the exhaust surface layer is separated and cured to form a concave-convex structure; the polyvinylpyrrolidone is compatible with the deionized water in the second acrylic acid modified waterborne polyurethane adhesive and is compounded with ethyl acetate, the volatilization speed of the deionized water is changed in the second curing process, and water molecules are continuously evaporated to form an exhaust hole before the exhaust surface layer is completely cured;
the exhaust surface layer is prepared from the surface of the first adhesive layer, which is opposite to the second adhesive layer, so that the mechanical strength of the double-sided adhesive is maintained, and the surface layer forms a gap to achieve the effect of attaching and exhausting with an adherend;
the first adhesive layer and the second adhesive layer are compounded, so that the viscosity of each adhesive layer can be adjusted, and the use in different scenes is met.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Acrylic acid modified waterborne polyurethane adhesive
The synthesis process of the aliphatic polyisocyanate is easy to control, the obtained waterborne polyurethane has good chemical resistance and yellowing resistance, isophorone diisocyanate (IPDI) contains two-NCO with different activities, the reaction rate for preparing the prepolymer is controllable and stable, and the obtained waterborne polyurethane adhesive has excellent optical stability and chemical resistance.
The polyester polyol is used for preparing the waterborne polyurethane adhesive, so that the emulsion is low in viscosity and good in dispersibility; the heat resistance, mechanical strength and elasticity are all good. Among them, the polyester diol formed by hexanediol and oxalic acid shows higher crystallinity compared with the polyester diol formed by butanediol and oxalic acid and the polyester diol formed by ethylene glycol and adipic acid, and the former has higher adhesive property.
The hydrophilic chain extender usually contains some functional groups such as carboxyl, sulfonic acid groups or secondary amine groups, and is combined with a polyurethane molecular chain to be ionized to realize hydrophilicity. Wherein 2,2-dimethylolpropionic acid is cationic hydrophilic chain extender, that is 2,2-dimethylolpropionic acid can react with cationic salt forming agent to form salt, so as to improve hydrophilicity. N-methyldiethanolamine is an anionic hydrophilic chain extender. The polyethylene glycol oxide is non-ionic, and introduces polyethylene glycol oxide hydrophilic segment with small molecular weight. Since polyvinylpyrrolidone (PVP) contained in the exhaust membrane coating liquid is positively charged, the PVP is more easily adsorbed by negatively charged groups or solid particles; on the other hand, positively charged groups or solid particles are more likely to repel PVP. Further, the hydrophilic chain extender is dimethylolpropionic acid DMPA. DMPA and PVP can form adsorption effect.
Intermolecular chain extender
Alcohols and amines are commonly used. The chain extension reaction by adopting the micromolecule chain extender can improve the molecular weight of the oligomer prepolymer. Usually, alcohol chain extenders are added in the preparation stage of the prepolymer, so that the hardness of the waterborne polyurethane is improved, but the waterborne polyurethane prepared by the alcohol chain extenders generates a cross-linked structure, and the water resistance is effectively improved. The amine chain extender is added in the emulsifying and dispersing stage of the aqueous polyurethane because the amine chain extender has high reaction activity with isocyanate.
Salt forming agent
Can react with a hydrophilic chain extender to improve the hydrophilicity of the aqueous polyurethane and improve the self-emulsifying capacity of the aqueous polyurethane. Wherein, the triethylamine emulsion is milky white and translucent in appearance and good in stability. Preparation method of first acrylic acid modified waterborne polyurethane adhesive
Polyethylene adipate glycol PEA (analytically pure, mn = 2000) and isophorone diisocyanate IPDI (content. Gtoreq.99%) in a molar ratio of 1:1.1, adding 1,4-Butanediol (BDO) chain extender which has the mass ratio to IPDI of 0.16 to 1 to react with a dibutyltin dilaurate catalyst to prepare a prepolymer, and keeping the reaction temperature at 80 +/-1 ℃; then adding a dimethylolpropionic acid DMPA (content is more than or equal to 98%) hydrophilic chain extender solution with the mass ratio of 0.2 to IPDI (isophorone diisocyanate), and continuously keeping the temperature at 80 +/-1 ℃ for reaction for 2.5h; cooling to 42 ℃, introducing a mixture of the components with the residual-NCO molar ratio of 0.16:1 (the mol ratio of the double bond end capping agent to the residual-NCO is 100 percent, namely the grafting content of the end capping agent is represented), adding a salt forming agent Triethylamine (TEA) for neutralization until the pH value is 7-8, and adding deionized water for emulsification under high-speed stirring to prepare aqueous polyurethane emulsion; and finally adding the mixture in a mass ratio of 1:1, adding emulsifier Sodium Dodecyl Sulfate (SDS) and initiator Azobisisobutyronitrile (AIBN) into a reactor protected by inert gas (preferably nitrogen), keeping the reaction temperature at 70 +/-1 ℃, and carrying out free radical polymerization to prepare the acrylic modified waterborne polyurethane emulsion with the solid content of 55%.
Preparation method of second waterborne acrylic acid modified polyurethane adhesive
Poly-epsilon-caprolactone diol PCL (industrial purity, mn = 1200) and isophorone diisocyanate IPDI (content ≥ 99%) in a molar ratio of 1:1.2, dropwise adding a dibutyltin dilaurate catalyst, keeping the reaction temperature at 80 +/-1 ℃, and reacting for 1h; then adding the mixture with the mass ratio of IPDI of 0.3:1, continuously keeping the dimethylolpropionic acid DMPA (the content is more than or equal to 98 percent) in a hydrophilic chain extender solution at the temperature of 80 +/-1 ℃ for reacting for 1 hour; then adding 1,4-Butanediol (BDO) chain extender which has the mass ratio to IPDI of 0.14 to act to prepare a prepolymer; cooling to 42 ℃, introducing a mixture of the components with the residual-NCO molar ratio of 0.32:1, adding a double-bond end-capping reagent of hydroxyethyl methacrylate (HEMA), adding a salt forming reagent of Triethylamine (TEA) for neutralization until the pH value is 7-8, and adding deionized water for emulsification under high-speed stirring to obtain an aqueous polyurethane emulsion; and finally adding the mixture in a mass ratio of 1:1, adding emulsifier Sodium Dodecyl Sulfate (SDS) and initiator Azobisisobutyronitrile (AIBN) into a reactor protected by inert gas (preferably nitrogen), keeping the reaction temperature at 70 +/-1 ℃, and carrying out free radical polymerization to prepare acrylic modified waterborne polyurethane emulsion with the solid content of 35%.
Graft content of endcapping agent
The residual-NCO content of the system was determined by the di-n-butylamine method. The grafting content of the end-capping agent HEMA determines the content of acrylate molecules, so that the viscosity and the physical property of the adhesive layer are influenced, the grafting content of the end-capping agent HEMA is increased microscopically, more acrylate molecules are connected with polyurethane molecular chains, and the compatibility between the acrylate molecules and the polyurethane molecular chains is better; on the contrary, the two layers are separated, and the surface of the glue layer has a concave-convex structure.
The grafting content of the end capping agent in the first acrylic acid modified waterborne polyurethane adhesive is 10-20%, a concave-convex structure after phase separation is formed on the surface of the first adhesive layer, the contact area of an interface between the exhaust surface layer and the first adhesive layer is increased, and the adsorption effect of polyvinylpyrrolidone and the surface of the solid adhesive first adhesive layer is further promoted.
The grafting content of the end capping agent in the second acrylic acid modified waterborne polyurethane adhesive is 30-40%, so that the adhesiveness of the film exhaust surface layer is ensured, and the adhesive force between the film exhaust surface layer and the first adhesive layer is improved.
Method for preparing exhaust surface layer
The exhaust film coating liquid can be uniformly covered on the surface of the first adhesive layer by adopting a spraying method, and the thickness of the exhaust surface layer can be adjusted. Compared with the leveling method, the leveling property of the exhaust film coating liquid is influenced due to the concave-convex structure on the surface of the first adhesive layer, so that the spreading smoothness of the exhaust film coating liquid is poor, and the density and the distribution uniformity of the exhaust holes are negatively influenced.
Preparation method of second adhesive layer
The second glue solution comprises 80 parts of NIC N800, 20 parts of NIC N600, 10 parts of curing agent N101 and 200 parts of ethyl acetate, the second glue solution is coated on a release film for curing, and the continuous temperature is sequentially set as follows: 80 plus or minus 5 ℃,90 plus or minus 5 ℃,100 plus or minus 5 ℃,120 plus or minus 5 ℃ and 100 plus or minus 5 ℃.
The second adhesive layer is an acrylic acid modified polyurethane adhesive layer, so that the high temperature resistance of the double-sided adhesive tape is improved; on the other hand, the adhesive prevents the first adhesive layer from delaminating, improves the viscosity of the first adhesive layer and prevents the first adhesive layer from delaminating from the adherend.
The viscosity of the second glue layer is greater than that of the exhaust surface layer, the exhaust surface layer is connected with the shell, and the second glue layer is connected with the protective film.
Thickness of glue layer
The thickness of the first adhesive layer is 10-30 μm, the thickness of the second adhesive layer is 20-100 μm, and the thickness of the exhaust surface layer is 0.1-0.5 μm.
The main composition of the first dope is as follows in table 1:
| first acrylic acid modified waterborne polyurethane adhesive | |
| Sample 1 | The graft content was 16% |
| Sample 2 | The graft content was 26% |
According to the preparation method of the first waterborne acrylic modified polyurethane adhesive, the molar ratio of the introduced residual-NCO to the residual-NCO is 0.16:1, namely the double bond end capping agent hydroxyethyl methacrylate, namely the grafting content of the end capping agent is 16 percent; similarly, the molar ratio of incorporation to residual-NCO was 0.26:1, namely the grafting content of the end capping agent is 26 percent.
The exhaust membrane coating liquid mainly comprises the following components in parts by weight:
by the preparation method of the second waterborne acrylic modified polyurethane adhesive, the molar ratio of the introduced residual-NCO to the residual-NCO is 0.32:1, namely the double bond end capping agent hydroxyethyl methacrylate, namely the grafting content of the end capping agent is 32 percent; similarly, the molar ratio of introduced to residual-NCO was 0.45:1, namely the grafting content of the end capping agent is 45 percent.
The preparation method of the double-sided adhesive tape without the base material comprises the following steps:
s1: configuring a release film, configuring a first glue solution sample according to the upper table 1, coating a first glue solution on the surface of the release film, curing for the first time to obtain a first glue layer, wherein the temperature of the first curing is sequentially set as follows: 85 ℃,95 ℃,105 ℃,120 ℃,100 ℃;
s2: obtaining a second adhesive layer according to the preparation method of the second adhesive layer;
s3: the first adhesive layer and the second adhesive layer are compounded;
s4: tear and leave the type membrane, dispose the exhaust membrane coating liquid according to table 2 above, at the surface spraying exhaust membrane coating liquid of first glue film dorsad second glue film, the no substrate double-sided tape on area exhaust top layer is got to the secondary solidification after the setting, and the temperature of secondary solidification sets gradually: 70 ℃,80 ℃,90 ℃,110 ℃,110 ℃ and 100 ℃.
The compositions and preparation conditions of the examples and comparative examples are as follows in table 3:
wherein the layer thickness of the second glue layer is 38 μm.
Performance test of double-sided adhesive tape
(1) Air-releasing property: the specification of the double-sided adhesive tape without the base material is 10 x 10cm, and the second adhesive layer is attached to the protective film to form a composite film; under guaranteeing dustless environment, paste the exhaust top layer of complex film on black smooth glass testing board, observe its laminating effect, it will be at the uniform velocity to walk gluey speed, paste until completely with testing board, observe and take notes it and walk gluey time, tear the complex film, repeated pad pasting operation, through record self-bleeding time, test 3 times and ask exhaust time average value, the complex film of good exhaust effect applies can self-bleeding and does not basically leave the bubble on the screen, the effect is the better for short when exhausting.
(2) Haze: standard GB/T2410-2008.
(3) Peeling force: standard GB 2792-2014; indicating the peel force of the release film.
(4) Aging property: standard GBT 17875-1999.
The results of the performance tests of the examples and comparative examples are as follows:
wherein the haze is OK when the haze is below 2 percent and NG when the haze is more than 2 percent. The aging performance test meets the following conditions: the haze is not changed, the glue layer does not fall off, the magnitude of the release force does not float to be more than plus or minus 1g, and the mark is OK; and NG is not satisfied.
The excellent composite film prepared by the double-sided adhesive tape without the base material meets the following requirements: the air release time is less than 10s, and the release force of the air release surface layer is less than 5 g.
Compared with the coating liquid of the embodiment 1, the exhaust film coating liquid of the embodiment 2 has more polyvinylpyrrolidone, which is not beneficial to forming fine and dense exhaust holes on the exhaust surface layer, and further prolongs the exhaust time; the phase separation bulges on the exhaust surface layer are increased, and the haze of the composite film is further influenced.
Compared with the embodiment 1, the embodiment 4 has the advantages that the adhesion rate of the modified acrylate monomer in the first acrylic acid modified waterborne polyurethane adhesive of the first glue solution is increased, the flatness of the first surface layer is improved, and the contact area between the first surface layer and the exhaust surface layer is reduced; the polyurethane phase content is less, and the adsorption effect of polyvinylpyrrolidone and the surface of the first adhesive layer is influenced, so that the structure of the exhaust hole is influenced, and the exhaust effect is reduced.
Compared with the embodiment 1, the thickness of the exhaust surface layer is increased in the embodiment 5, which is not beneficial to the formation of the exhaust hole, and further influences the exhaust effect; the peeling force of the vent skin layer also increases.
Compared with example 1, comparative example 1 has a negative influence on the exhaust effect after the exhaust film is coated on the surface of the first adhesive layer opposite to the second adhesive layer and is not placed for a period of time.
In comparison with example 1, in comparative example 2, no polyvinylpyrrolidone was added to the exhaust film coating liquid, no exhaust hole was formed, and the composite film was applied to the screen to generate bubbles.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the double-sided adhesive tape without the base material is characterized by comprising the following steps:
s1: preparing a release film, coating a first glue solution on the surface of the release film, and curing for the first time to obtain a first glue layer;
s2: preparing a second glue layer;
s3: the first adhesive layer and the second adhesive layer are compounded;
s4: tearing off the release film, spraying exhaust film coating liquid on the surface of the first adhesive layer opposite to the second adhesive layer, and curing for the second time after placing to obtain the substrate-free double-sided adhesive tape with the exhaust surface layer;
the main component of the first glue solution is a first acrylic acid modified waterborne polyurethane adhesive;
the exhaust membrane coating liquid mainly comprises a second acrylic acid modified waterborne polyurethane adhesive, polyvinylpyrrolidone and ethyl acetate.
2. The method for preparing the substrate-free double-sided tape according to claim 1, wherein the exhaust film coating liquid mainly comprises 100 parts by mass of a second acrylic acid modified aqueous polyurethane adhesive, 8978 parts by mass of polyvinylpyrrolidone, 8978 parts by mass of zxft 8978 parts by mass of ethyl acetate, and the solid content of the second acrylic acid modified aqueous polyurethane adhesive is 30 to 40%.
3. The method for preparing the substrate-free double-sided tape according to claim 1 or 2, wherein the first acrylic acid modified aqueous polyurethane adhesive and the second acrylic acid modified aqueous polyurethane adhesive are both prepared from polyester polyol, aliphatic polyisocyanate, alcohol and/or amine small molecular chain extender, hydrophilic chain extender, double bond end capping agent, salt forming agent, modified acrylate monomer and deionized water.
4. The method for preparing a substrate-free double-sided tape according to claim 3, wherein the grafting content of the end-capping agent in the first acrylic acid modified waterborne polyurethane adhesive is 10% to 20%.
5. The method for preparing the substrate-free double-sided tape according to claim 3, wherein the graft content of the blocking agent in the second acrylic acid modified waterborne polyurethane adhesive is 30-40%.
6. The method for preparing a double-sided adhesive tape without a substrate according to claim 1, wherein the second adhesive layer is an acrylic modified polyurethane adhesive layer.
7. The method for preparing a substrate-free double-sided adhesive tape according to claim 1, wherein the temperature of the first curing is set as follows in sequence: 85 plus or minus 5 ℃,95 plus or minus 5 ℃,105 plus or minus 5 ℃,120 plus or minus 5 ℃ and 100 plus or minus 5 ℃; the temperature of the second curing is sequentially set as follows: 70 plus or minus 5 ℃,80 plus or minus 5 ℃,90 plus or minus 5 ℃,110 plus or minus 5 ℃ and 100 plus or minus 5 ℃.
8. The method for preparing the double-sided adhesive tape without the base material according to claim 1, wherein the spraying pressure in S4 is 0.06 to 0.1Mpa, and the standing time is 1 to 3min.
9. The method of preparing a substrate-less double-sided tape according to claim 1, wherein the ratio of the layer thicknesses of the first adhesive layer and the second adhesive layer is 1: (1 to 10); the thickness ratio of the first adhesive layer to the exhaust surface layer is 1: (0.01 to 0.06), wherein the layer thickness of the first adhesive layer is 10 to 30 μm.
10. A double-sided tape prepared by the method of claim 1~9.
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| JP2012077255A (en) * | 2010-10-06 | 2012-04-19 | Mitsui Chemicals Inc | Aqueous polyurethane resin, hydrophilic resin and film |
| CN108977157A (en) * | 2018-08-16 | 2018-12-11 | 北京高盟新材料股份有限公司 | A kind of Aqueous Polyurethane Adhesives and preparation method thereof |
| CN111440583A (en) * | 2019-12-30 | 2020-07-24 | 宁波激智创新材料研究院有限公司 | Polyurethane adhesive, polyurethane coating liquid, television edge sealing adhesive tape and preparation method thereof |
| CN211896779U (en) * | 2019-12-23 | 2020-11-10 | 崴思新材料泰州有限公司 | Self-exhaust double-sided tape |
| CN113907952A (en) * | 2021-08-31 | 2022-01-11 | 长沙海润生物技术有限公司 | Non-stick dressing and preparation method thereof |
| CN114057984A (en) * | 2021-12-20 | 2022-02-18 | 广东鸿昌化工有限公司 | Low-VOCs alcohol-water-soluble PVP modified polyurethane resin and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012077255A (en) * | 2010-10-06 | 2012-04-19 | Mitsui Chemicals Inc | Aqueous polyurethane resin, hydrophilic resin and film |
| CN108977157A (en) * | 2018-08-16 | 2018-12-11 | 北京高盟新材料股份有限公司 | A kind of Aqueous Polyurethane Adhesives and preparation method thereof |
| CN211896779U (en) * | 2019-12-23 | 2020-11-10 | 崴思新材料泰州有限公司 | Self-exhaust double-sided tape |
| CN111440583A (en) * | 2019-12-30 | 2020-07-24 | 宁波激智创新材料研究院有限公司 | Polyurethane adhesive, polyurethane coating liquid, television edge sealing adhesive tape and preparation method thereof |
| CN113907952A (en) * | 2021-08-31 | 2022-01-11 | 长沙海润生物技术有限公司 | Non-stick dressing and preparation method thereof |
| CN114057984A (en) * | 2021-12-20 | 2022-02-18 | 广东鸿昌化工有限公司 | Low-VOCs alcohol-water-soluble PVP modified polyurethane resin and preparation method and application thereof |
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