CN115745844A - Photoinitiator, adhesive using photoinitiator and preparation methods of photoinitiator and adhesive - Google Patents
Photoinitiator, adhesive using photoinitiator and preparation methods of photoinitiator and adhesive Download PDFInfo
- Publication number
- CN115745844A CN115745844A CN202211525224.5A CN202211525224A CN115745844A CN 115745844 A CN115745844 A CN 115745844A CN 202211525224 A CN202211525224 A CN 202211525224A CN 115745844 A CN115745844 A CN 115745844A
- Authority
- CN
- China
- Prior art keywords
- photoinitiator
- adhesive
- parts
- acrylate
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- 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 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 32
- 239000012943 hotmelt Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000003761 preservation solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 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 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 7
- 238000010382 chemical cross-linking Methods 0.000 abstract description 6
- 238000009736 wetting Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012965 benzophenone Substances 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000002390 adhesive tape Substances 0.000 description 13
- 239000003292 glue Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- -1 aryl ketones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a photoinitiator and a preparation method thereof, wherein the photoinitiator is prepared by adopting an acrylic acid monofunctional monomer with a soft polyethylene glycol long molecular chain segment, a benzophenone photoinitiating group is grafted through the reaction with isocyanate, in the chemical crosslinking process after UV irradiation, the long and soft molecular chain ensures that the photoinitiating group can be bonded with an anchor point at a far end, the gap of crosslinking molecules is larger, the rigidity is reduced, the degree of freedom of a branched chain is higher, and the wetting and adhesion performance of a coating is better; the invention also provides an adhesive prepared by applying the photoinitiator and a preparation method thereof, wherein the adhesive comprises the following components in parts by weight: 70-90 parts of soft monomer; 1-20 parts of hard monomer; 1-5 parts of functional monomer; 1-2 parts of a photoinitiator; 0.2-1 part of free radical polymerization initiator, the adhesive can obviously reduce the obvious reduction of the freedom degree of molecular chain segments caused by the improvement of cohesive force, and improve the upper limit of the comprehensive performance which can be realized by a balance point.
Description
Technical Field
The invention relates to the technical field of photo-initiation technology and adhesive, in particular to a photo-initiator, an adhesive using the photo-initiator and preparation methods of the photo-initiator and the adhesive.
Background
Ultraviolet (hereinafter, referred to as UV) curable acrylate hot melt pressure sensitive adhesives have been rapidly developed and commercially used in recent years as a new type of pressure sensitive adhesive. It is 100% solid component without solvent or water, and when it is used, it is heated, melted and coated on the substrate to be bonded, and through UV irradiation, the cross-linking and solidification can be implemented, so that the pressure-sensitive adhesive products with various performances can be obtained. Compared with a rubber system hot melt pressure sensitive adhesive, the hot melt pressure sensitive adhesive has no defect of narrow use temperature range, and has excellent high temperature resistance and solvent resistance due to a chemical crosslinking structure. Compared with a solvent type pressure-sensitive adhesive or an emulsion type pressure-sensitive adhesive, the UV curing acrylate hot-melt pressure-sensitive adhesive does not need drying solvent or water in the coating process, not only is energy-saving and low-carbon, but also does not pollute the environment.
The core of the UV curable acrylate hot melt pressure sensitive adhesive is a polymerizable photoinitiator. Chinese patent CN107531612A discloses a series of polymerizable photoinitiators preparation methods, characterized in that aryl ketones are connected to various linker sequences allowing photoinitiated polymerization through ether bonds, having excellent hot melt viscosity stability; chinese patent CN105585982A discloses a UV-cured cross-linked acrylate hot-melt pressure-sensitive adhesive prepared by using a polymerizable photoinitiator, which adopts a bulk polymerization process and has better adhesive force. Chinese patent CN111087494A discloses a preparation method of a polymerizable photoinitiator, the molecular structure of which contains thioxanthone and amine as an auxiliary initiator, so that the photoinitiator has high initiation efficiency and is not easy to migrate; however, current UV-cured pressure sensitive adhesives suffer from the disadvantage that chemical crosslinking by UV irradiation increases the cohesion of the adhesive layer while also significantly reducing wetting and adhesion, ultimately achieving the adhesion function required for application through a balance of wetting and cohesion. At present, the range of the UV hot melt pressure sensitive adhesive at the equilibrium point is narrow, and the exertion upper limit of the initial adhesion is obviously limited.
In view of the above, the present inventors have specifically designed a photoinitiator, an adhesive using the photoinitiator, and methods for preparing the photoinitiator and the adhesive.
Disclosure of Invention
In order to solve the above problems, the present invention proposes the following technical solutions:
in a first aspect: the present application provides a photoinitiator, the chemical structure of which is shown as the following formula:
wherein R is selected from any one of hydrogen and methyl; n is the number of repeating units, n ≧ 4.
In a second aspect, the present application provides a method for preparing a photoinitiator, which adopts the following technical scheme: a preparation method of a photoinitiator is used for preparing the photoinitiator and comprises the following specific preparation steps:
the method comprises the following steps: adding 1mol of isophorone diisocyanate, 10g of dibutyltin dilaurate serving as a catalyst and 200g of ethyl acetate into a light-tight four-mouth bottle provided with a stirrer, a reflux condenser tube and a thermometer, heating to 70 ℃ under the protection of nitrogen to obtain a mixed solution, slowly dropwise adding 1mol of 4-hydroxybenzophenone into the mixed solution within half an hour, and reacting at 65 ℃ until the-NCO value is 7.2% to obtain a reaction solution;
step two: and (2) adding 1mol of polyethylene glycol (mono-methyl) acrylate and 0.01g of polymerization inhibitor p-hydroxyanisole into the reaction liquid in the step one, reacting until no-NCO characteristic peak is detected by infrared monitoring, and distilling under reduced pressure to remove ethyl acetate to obtain the polymerizable photoinitiator.
According to the technical scheme, the acrylic acid monofunctional monomer with the soft polyethylene glycol long molecular chain segment is adopted, and the benzophenone photoinitiating group is grafted through the reaction with isocyanate. In the chemical crosslinking process after UV irradiation, long and soft molecular chains enable a photoinitiating group to be bonded with anchor points at far ends, the crosslinking molecular gap is larger, the rigidity is reduced, the freedom degree of a branched chain is higher, and the wetting and adhesion performance of the coating is better.
In a third aspect, the invention also provides an adhesive applying the photoinitiator, which comprises the following components in parts by weight:
70-90 parts of soft monomer;
1-20 parts of hard monomer;
1-5 parts of functional monomer;
1-2 parts of polymerizable photoinitiator;
0.2-1 part of free radical polymerization initiator.
Preferably, the soft monomer is selected from any one of n-butyl acrylate, ethyl acrylate and isooctyl acrylate.
Preferably, the hard monomer is selected from any one of methyl acrylate, methyl methacrylate and vinyl acetate.
Preferably, the functional monomer is selected from one of acrylic acid and hydroxyethyl acrylate.
Preferably, the thermal initiator is selected from one of benzoyl peroxide and azobisisobutyronitrile.
The UV-cured acrylate hot-melt pressure-sensitive adhesive provided by the invention has a wider balance point range of wetting and cohesion, and can realize higher initial adhesion performance.
In a fourth aspect, the present invention further provides a preparation method of an adhesive, for preparing the hot melt pressure sensitive adhesive, specifically comprising the following steps: the method comprises the following steps: mixing and stirring 70-90 parts of soft monomer, 1-20 parts of hard monomer, 1-5 parts of functional monomer, 1-2 parts of polymerizable photoinitiator and 0.2-1 part of free radical polymerization initiator, and obtaining a dissolved solution after the photoinitiator and the free radical polymerization initiator are completely dissolved; and step two, adding 30-100 parts of ethyl acetate solvent as a primer into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a dropping funnel, introducing nitrogen to remove oxygen, heating to 80-90 ℃, adding 10% of the total amount of the dissolved solution in the step one into the flask, stirring at medium speed, keeping the temperature of 80-90 ℃ for 20-40 minutes, dropwise adding the rest 90% of the dissolved solution in the step one within 3-4 hours, preserving heat for 1-2 hours to obtain a heat preservation solution, and removing the ethyl acetate solvent from the heat preservation solution through reduced pressure distillation to obtain 100% solid acrylate hot-melt pressure-sensitive adhesive which is the adhesive.
The invention has the beneficial effects that: the UV curing acrylate hot-melt pressure-sensitive adhesive adopts a polymerizable photoinitiator with a soft polyethylene glycol long molecular chain segment, and the gap and the rigidity of a chemical crosslinking structure generated after UV irradiation are adjusted, so that the molecular branch degree of freedom is slowly reduced while the chemical crosslinking degree is increased, more wetting properties are reserved, the range of the UV irradiation adhesive layer reaching the balance advantage is remarkably increased, higher initial adhesion performance can be realized, the influence on vertical nonuniformity of UV irradiation is reduced, and the coating thickness can be applied at higher thickness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Wherein:
FIG. 1 is a schematic diagram of the chemical structure of the photoinitiator according to the invention;
FIG. 2 is a schematic diagram of the mechanism of synthesis of the photoinitiator of the invention;
FIG. 3 is a graph of the adhesion, cohesion of adhesives using photoinitiators not of the present invention as a function of the amount of UV light;
FIG. 4 is a graph of the adhesion and cohesion of adhesives using the polymerizable photoinitiator of the present invention as the amount of UV light is increased.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
In this embodiment 1, a method for preparing a photoinitiator with a chemical structure as shown in fig. 1 is provided, and the method comprises the following steps:
the method comprises the following steps: adding 1mol of isophorone diisocyanate (IPDI), 10g of catalyst dibutyltin dilaurate and 200g of ethyl acetate into a light-proof four-mouth bottle provided with a stirrer, a reflux condenser tube and a thermometer, heating to 70 ℃ under the protection of nitrogen to obtain a mixed solution, slowly dropwise adding 1mol of 4-hydroxybenzophenone into the mixed solution within half an hour, and reacting at 65 ℃ until the-NCO value is 7.2%;
step two: and (3) adding 1mol of polyethylene glycol monomethacrylate HEMA-5 and 0.01g of polymerization inhibitor p-hydroxyanisole, reacting until a-NCO characteristic peak can not be obtained through infrared monitoring, and removing ethyl acetate through reduced pressure distillation to obtain the polymerizable photoinitiator, wherein the number of ethylene glycol repeating units in the second step is 5.
Example 2
An adhesive prepared by the following components and steps: 55 parts by weight of n-butyl acrylate, 30 parts by weight of isooctyl acrylate, 10 parts by weight of methyl methacrylate, 5 parts by weight of acrylic acid, 0.3 part by weight of the photoinitiator obtained in example 1 and 0.5 part by weight of a radical polymerization initiator are mixed and stirred, and a mixed solution is obtained after the photoinitiator and the radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent as a primer into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a dropping funnel, introducing nitrogen to remove oxygen, heating to 85 ℃, adding 10% of the total amount of the mixed solution into the flask, stirring at a medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest of the mixed solution within 3 hours, preserving the temperature for 2 hours after dropwise adding, removing the ethyl acetate solvent from the obtained heat preservation solution through reduced pressure distillation, wherein 100% of solid acrylate hot-melt pressure-sensitive adhesive is the adhesive.
Coating 50g of the hot melt pressure sensitive adhesive on a PET polyester film subjected to corona treatment by melting and heating at 130 ℃ to prepare an adhesive tape, wherein the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 The adhesive tape is tested by adopting a medium-pressure mercury lamp with power of 2000W to irradiate for a plurality of times, just no glue is left on the pasted substrate when the adhesive tape is peeled, and the failure mode is that the adhesive interface has no glue.
Example 3
An adhesive, which is different from example 2 in that: adjusting the components, wherein the adjusted components are as follows: 60 parts of n-butyl acrylate, 20 parts of isooctyl acrylate, 17 parts of methyl methacrylate, 3 parts of acrylic acid, 0.3 part of the photoinitiator obtained in example 1 and 0.7 part of the radical polymerization initiator are mixed and stirred, and a mixed solution is obtained after the photoinitiator and the radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent serving as a primer into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a dropping funnel, introducing nitrogen to remove oxygen, heating to 85 ℃, adding 10% of the total amount of the mixed solution into the flask, stirring at a medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest of the mixed solution within 3 hours, preserving heat for 2 hours after dropwise adding, removing the ethyl acetate solvent from the obtained heat preservation solution through reduced pressure distillation, and obtaining 100% solid acrylate hot-melt pressure-sensitive adhesive which is the adhesive.
Coating 50g of the hot melt pressure sensitive adhesive on a PET polyester film subjected to corona treatment by melting and heating at 130 ℃ to prepare an adhesive tape, wherein the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 The adhesive tape is tested by adopting a medium-pressure mercury lamp with power of 2000W to irradiate for a plurality of times, just no glue is left on the pasted substrate when the adhesive tape is peeled, and the failure mode is that the adhesive interface has no glue.
Example 4
An adhesive, which is different from example 2 in that: adjusting the components, wherein the adjusted components are as follows: 40 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 25 parts of ethyl acrylate, 5 parts of acrylic acid, 0.3 part of the photoinitiator obtained in example 1 and 0.3 part of a radical polymerization initiator are mixed and stirred, and a mixed solution is obtained after the photoinitiator and the radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent as a primer into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a dropping funnel, introducing nitrogen to remove oxygen, heating to 85 ℃, adding 10% of the total amount of the mixed solution into the flask, stirring at a medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest of the mixed solution within 3 hours, preserving the temperature for 2 hours after dropwise adding, removing the ethyl acetate solvent from the obtained heat preservation solution through reduced pressure distillation, wherein 100% of solid acrylate hot-melt pressure-sensitive adhesive is the adhesive.
Coating 50g of the hot melt pressure sensitive adhesive on a PET polyester film subjected to corona treatment by melting and heating at 130 ℃ to prepare an adhesive tape, wherein the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 The adhesive tape is tested by adopting a medium-pressure mercury lamp with power of 2000W to irradiate for a plurality of times, just no glue is left on the pasted substrate when the adhesive tape is peeled, and the failure mode is that the adhesive interface has no glue.
Comparative example
50g of commercially available UV-curable acrylate hot-melt pressure-sensitive adhesive is coated on a PET polyester film subjected to corona treatment to prepare an adhesive tape by melting and heating at 130 ℃, the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 The adhesive tape is irradiated for a plurality of times by a medium-pressure mercury lamp with the power of 2000W, the adhesive tape which is just not left on the adhered base material when the adhesive tape is peeled and has a failure mode that no adhesive exists on an adhesion interface is selected for testing.
The loop-type initial adhesive performance of the PET pressure-sensitive adhesive tape is tested according to GB/T31125-2014; the peeling strength of the PET pressure sensitive adhesive tape is tested according to GB/T2792-2014; the high temperature tack performance of PET pressure sensitive tapes was tested according to GB/T4851-2014, and the results are shown in Table 1 below:
TABLE 1
The adhesive has a downward curve of surface adhesion property and an upward curve of cohesive strength as the amount of UV light irradiation increases, and has practical properties in that the initial adhesion, the peeling force and the shearing force are all good, and the performance of a short plate cannot be obtained, so that the point is theoretically the most balanced and is also the best performance.
Referring to fig. 3 and 4, the height of the cross-over point is the balance point of the performance values of adhesion and cohesion, as shown in fig. 3, the change curve of the adhesion and cohesion of the adhesive without the photoinitiator of the present invention increases with the amount of UV light, wherein the peel force 13, the initial adhesion 10 and the 70-degree holding time of the cross-over point are balanced for 200 hours; referring to fig. 4, the adhesion and cohesion of the adhesive using the photoinitiator of the present invention are shown as a curve with increasing UV light exposure, and the higher the balance of the cross-over points, the release 18, initial 15, and 70 degree hold times of 400 hours can be achieved. While the use of the photoinitiators of the invention shifts the crossover point significantly upward compared to other conventional photoinitiators, in practice the performance obtained is significantly higher regardless of whether the customer sets the uv parameter at the equilibrium point or the left and right range of adjustments.
In conclusion, the prepared adhesive, namely the UV-cured acrylate hot-melt pressure-sensitive adhesive, obtains annular initial adhesion, peeling strength and high-temperature permanent adhesion performance by irradiation of a medium-pressure mercury lamp. Compared with the commercial UV pressure-sensitive adhesive in the comparative example, the test results of examples 2,3 and 4 show that the pressure-sensitive adhesive has more excellent loop-type initial adhesion and peeling strength while having a considerable degree of high-temperature adhesive-holding performance, which shows that the pressure-sensitive adhesive prepared by the invention can remarkably reduce the remarkable reduction of the degree of freedom of molecular chain segments caused by the increase of cohesive force and improve the upper limit of comprehensive performance which can be realized by a balance point.
The applicant states that the preparation method and application of the polymerizable photoinitiator and the UV-curable acrylate hot-melt pressure-sensitive adhesive thereof are illustrated by the above examples, but the invention is not limited by the above examples, i.e. the invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (9)
1. A photoinitiator, wherein the photoinitiator has a chemical structure represented by the following formula:
wherein R is selected from any one of hydrogen and methyl; n is the number of repeating units, and n ≧ 4.
2. A method for preparing a photoinitiator according to claim 1, comprising the steps of:
the method comprises the following steps: adding 1mol of isophorone diisocyanate, 10g of dibutyltin dilaurate serving as a catalyst and 200g of ethyl acetate into a light-tight four-mouth bottle provided with a stirrer, a reflux condenser tube and a thermometer, heating to 70 ℃ under the protection of nitrogen to obtain a mixed solution, slowly dropwise adding 1mol of 4-hydroxybenzophenone into the mixed solution within half an hour, and reacting at 65 ℃ until the-NCO value is 7.2% to obtain a reaction solution;
step two: and (2) adding 1mol of polyethylene glycol (mono-methyl) acrylate and 0.01g of polymerization inhibitor p-hydroxyanisole into the reaction liquid in the step one, reacting until no-NCO characteristic peak is detected by infrared monitoring, and removing ethyl acetate by reduced pressure distillation to obtain the polymerizable photoinitiator.
3. The method of claim 2, wherein the polyethylene glycol (mono-meth) acrylate is polyethylene glycol acrylate or polyethylene glycol monomethacrylate; the number of repeating units of ethylene glycol is ≧ 4.
4. An adhesive using a photoinitiator, wherein the photoinitiator according to claim 1 is used, and comprises the following components in parts by weight:
70-90 parts of soft monomer;
1-20 parts of hard monomer;
1-5 parts of functional monomer;
1-2 parts of polymerizable photoinitiator;
0.2-1 part of free radical polymerization initiator.
5. An adhesive using a photoinitiator according to claim 4, wherein the soft monomer is selected from any one of n-butyl acrylate, ethyl acrylate and isooctyl acrylate.
6. The adhesive of claim 4, wherein the hard monomer is selected from the group consisting of methyl acrylate, methyl methacrylate, and vinyl acetate.
7. The adhesive using a photoinitiator according to claim 4, wherein the functional monomer is selected from one of acrylic acid and hydroxyethyl acrylate.
8. The adhesive of claim 4, wherein the radical polymerization initiator is selected from the group consisting of benzoyl peroxide and azobisisobutyronitrile.
9. A method for preparing an adhesive, which is used for preparing the hot-melt pressure-sensitive adhesive according to any one of claims 4 to 8, and comprises the following steps:
the method comprises the following steps: mixing and stirring 70-90 parts of soft monomer, 1-20 parts of hard monomer, 1-5 parts of functional monomer, 1-2 parts of polymerizable photoinitiator and 0.2-1 part of free radical polymerization initiator, and obtaining a dissolved solution after the photoinitiator and the free radical polymerization initiator are completely dissolved;
step two: adding 30-100 parts of ethyl acetate solvent as a primer into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a dropping funnel, introducing nitrogen to remove oxygen, heating to 80-90 ℃, adding 10% of the total amount of the solution in the step I into the flask, stirring at medium speed, keeping the temperature of 80-90 ℃ for 20-40 minutes, then dropwise adding the remaining 90% of the solution in the step I within 3-4 hours, preserving heat for 1-2 hours after dropwise adding to obtain a heat preservation solution, and removing the ethyl acetate solvent from the heat preservation solution through reduced pressure distillation to obtain 100% solid acrylate hot-melt pressure-sensitive adhesive which is the adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211525224.5A CN115745844B (en) | 2022-11-30 | 2022-11-30 | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211525224.5A CN115745844B (en) | 2022-11-30 | 2022-11-30 | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115745844A true CN115745844A (en) | 2023-03-07 |
| CN115745844B CN115745844B (en) | 2024-04-16 |
Family
ID=85341675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211525224.5A Active CN115745844B (en) | 2022-11-30 | 2022-11-30 | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745844B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056892A (en) * | 2008-06-05 | 2011-05-11 | 爱克发印艺公司 | Multifunctional type II photoinitiators and curable compositions |
| CN103275249A (en) * | 2013-05-24 | 2013-09-04 | 郑州大学 | Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof |
| CN104694057A (en) * | 2015-02-15 | 2015-06-10 | 滁州云林数码影像耗材有限公司 | Breaking-resistant acrylate pressure-sensitive adhesive for walls and preparation method thereof |
| KR20150134154A (en) * | 2014-05-21 | 2015-12-01 | 주식회사 대현에스티 | Manufacturing method of heat-peelable adhesive sheet or adhesive tape using uv curing system |
| CN105585982A (en) * | 2016-03-14 | 2016-05-18 | 昆山久庆塑胶有限公司 | Acrylic-ester hot-melt pressure-sensitive adhesive and preparing method thereof |
| CN107531612A (en) * | 2015-03-20 | 2018-01-02 | 汉高知识产权控股有限责任公司 | Polymeric photoinitiators or polymerizable light trigger in the contact adhesive curable for UV |
| CN107629151A (en) * | 2017-10-27 | 2018-01-26 | 天津久日新材料股份有限公司 | A kind of type light trigger of polymerizable free radical II and preparation method thereof |
| CN108504312A (en) * | 2018-03-14 | 2018-09-07 | 哈尔滨工业大学无锡新材料研究院 | Low-shrinkage UV curing acrylics ester pressure-sensitive, preparation method and low-shrinkage UV curing acrylic ester pressure-sensitive adhesive tapes |
| US20210130520A1 (en) * | 2017-01-05 | 2021-05-06 | Igm Resins Italia S.R.L | Composition useful as a pressure sensitive adhesive, its use and adhesive articles comprising it |
| CN114276279A (en) * | 2021-12-29 | 2022-04-05 | 广州鹿山光电材料有限公司 | Hydrogen abstraction type photoinitiator, preparation method and application thereof |
-
2022
- 2022-11-30 CN CN202211525224.5A patent/CN115745844B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102056892A (en) * | 2008-06-05 | 2011-05-11 | 爱克发印艺公司 | Multifunctional type II photoinitiators and curable compositions |
| CN103275249A (en) * | 2013-05-24 | 2013-09-04 | 郑州大学 | Free radical photoinitiator containing single vinyl ether group or single propenyl ether group, and preparation method thereof |
| KR20150134154A (en) * | 2014-05-21 | 2015-12-01 | 주식회사 대현에스티 | Manufacturing method of heat-peelable adhesive sheet or adhesive tape using uv curing system |
| CN104694057A (en) * | 2015-02-15 | 2015-06-10 | 滁州云林数码影像耗材有限公司 | Breaking-resistant acrylate pressure-sensitive adhesive for walls and preparation method thereof |
| CN107531612A (en) * | 2015-03-20 | 2018-01-02 | 汉高知识产权控股有限责任公司 | Polymeric photoinitiators or polymerizable light trigger in the contact adhesive curable for UV |
| CN105585982A (en) * | 2016-03-14 | 2016-05-18 | 昆山久庆塑胶有限公司 | Acrylic-ester hot-melt pressure-sensitive adhesive and preparing method thereof |
| US20210130520A1 (en) * | 2017-01-05 | 2021-05-06 | Igm Resins Italia S.R.L | Composition useful as a pressure sensitive adhesive, its use and adhesive articles comprising it |
| CN107629151A (en) * | 2017-10-27 | 2018-01-26 | 天津久日新材料股份有限公司 | A kind of type light trigger of polymerizable free radical II and preparation method thereof |
| CN108504312A (en) * | 2018-03-14 | 2018-09-07 | 哈尔滨工业大学无锡新材料研究院 | Low-shrinkage UV curing acrylics ester pressure-sensitive, preparation method and low-shrinkage UV curing acrylic ester pressure-sensitive adhesive tapes |
| CN114276279A (en) * | 2021-12-29 | 2022-04-05 | 广州鹿山光电材料有限公司 | Hydrogen abstraction type photoinitiator, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 魏忠诚编著: "《光纤材料制备技术》", vol. 1, 北京邮电大学出版社, pages: 263 - 264 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115745844B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1796421B (en) | Photoinitiators and UV-crosslinkable acrylic polymers for pressure sensitive adhesives | |
| JP2020117735A (en) | Adhesive composition | |
| EP0772655B1 (en) | Acrylic syrup curable to a crosslinked viscoelastomeric material | |
| CN102449094B (en) | ultraviolet radiation curable pressure sensitive acrylic adhesive | |
| US10711166B2 (en) | UV curable adhesives based on acrylic polymers | |
| US20050209360A1 (en) | Radiation-curable, solvent-free and printable precursor of an adhesive | |
| WO2002038694A1 (en) | Pressure sensitive adhesives possessing high load bearing capability | |
| JP2001240717A (en) | Polymer blend | |
| CN105246922A (en) | Ultraviolet curable pressure sensitive adhesives | |
| JP5639438B2 (en) | Temperature sensitive adhesive | |
| CN113004837B (en) | UV (ultraviolet) curing pressure-sensitive adhesive | |
| US20210292537A1 (en) | Curable composition, pressure-sensitive adhesive, adhesive tape, and adhesive product | |
| JPH0218485A (en) | Ultraviolet polymerized acrylic pressure- sensitive adhesive | |
| JP2686324B2 (en) | Pressure sensitive adhesive composition | |
| JPH0543857A (en) | Radiation-curable self-adhesive and self-adhesive tape prepared therefrom | |
| KR20060130397A (en) | Uv-curable pressure sensitive adhesives containg silicone acrylate and the article bonded by radiation curing with the composition | |
| CN115745844B (en) | Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive | |
| JP3797628B2 (en) | Pressure sensitive adhesive and adhesive sheet thereof | |
| JP4362564B2 (en) | UV curable adhesive composition | |
| CN114891447B (en) | Acrylate/polyisobutylene rubber hybrid pressure-sensitive adhesive composition | |
| JP2003183596A (en) | Method of manufacturing adhesive tape and adhesive tape | |
| JP3510722B2 (en) | Method for manufacturing viscoelastic sheet | |
| JPH11140411A (en) | Ultraviolet-curable tack agent composition | |
| JPH0940928A (en) | Ultraviolet-curable self-adhesive composition | |
| KR100351705B1 (en) | Photosensitive adhesive compositions for dicing tape |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |