CN115745844B - Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive - Google Patents
Photoinitiator, adhesive using same and preparation methods of photoinitiator and adhesive Download PDFInfo
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- CN115745844B CN115745844B CN202211525224.5A CN202211525224A CN115745844B CN 115745844 B CN115745844 B CN 115745844B CN 202211525224 A CN202211525224 A CN 202211525224A CN 115745844 B CN115745844 B CN 115745844B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000034 method 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 33
- 239000012943 hotmelt Substances 0.000 claims description 22
- 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 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 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
- 238000004821 distillation Methods 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 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
- 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 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 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 3
- 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
- 238000012544 monitoring process Methods 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 compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003761 preservation solution Substances 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 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 5
- 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
- 230000006872 improvement Effects 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 239000002390 adhesive tape Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- -1 aryl ketones Chemical class 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 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
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a photoinitiator and a preparation method thereof, wherein the photoinitiator is prepared from an acrylic acid monofunctional monomer with a soft polyethylene glycol long molecular chain segment, a benzophenone photoinitiating group is grafted through reaction with isocyanate, and in the chemical crosslinking process after UV irradiation, the long and soft molecular chain enables the photoinitiating group to be bonded with a far-end anchor point, the crosslinking molecular gap is larger, the rigidity is reduced, the degree of freedom of a branched chain is higher, and the wetting and adhesion properties of a coating are 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 photoinitiator; 0.2 to 1 part of free radical polymerization initiator, the adhesive can obviously reduce the degree of freedom of a molecular chain segment caused by the improvement of cohesion, and the upper limit of the comprehensive performance of the balance point can be improved.
Description
Technical Field
The invention relates to the technical field of photoinitiation technology and adhesives, in particular to a photoinitiator, an adhesive using the photoinitiator and preparation methods of the photoinitiator and the adhesive.
Background
Ultraviolet light (hereinafter referred to as UV) curable acrylic hot melt pressure sensitive adhesives have been rapidly developed and commercially used in recent years as a novel pressure sensitive adhesive. The adhesive is 100% solid component without solvent or water, and is coated on the adhered substrate by heating and melting when in use, and the degree of crosslinking solidification is controllable by UV irradiation, thus obtaining pressure-sensitive adhesive products with various performances. 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 solvent-type pressure-sensitive adhesives or emulsion-type pressure-sensitive adhesives, the UV curing acrylic hot-melt pressure-sensitive adhesive does not need to dry solvents or water in the coating process, so that the energy is saved, the carbon is low, and the environment is not polluted.
The core of the UV curable acrylate hot melt pressure sensitive adhesive is a polymerizable photoinitiator. Chinese patent CN107531612a discloses a series of preparation methods of polymerizable photoinitiators characterized in that aryl ketones are linked to various linker sequences allowing photoinitiated polymerization via ether linkages, having excellent hot melt viscosity stability; chinese patent CN105585982a discloses a UV-curable crosslinked acrylate hot-melt pressure-sensitive adhesive prepared using a polymerizable photoinitiator, which has a good adhesion by a bulk polymerization process. Chinese patent CN111087494a discloses a preparation method of a polymerizable photoinitiator, wherein the molecular structure contains thioxanthone and co-initiator amine, and the initiator has high initiation efficiency and is not easy to migrate; however, the existing UV-cured pressure-sensitive adhesive has the defects that chemical crosslinking generated by UV irradiation improves cohesive force of the adhesive layer, simultaneously obviously reduces wetting and adhesiveness, and finally realizes the adhesive function required by application through the balance of wetting and cohesive force. The range of the balance point of the current UV hot-melt pressure-sensitive adhesive is very narrow, and the upper limit of primary adhesion is obviously limited.
In view of this, the present inventors have specifically devised a photoinitiator, an adhesive using the same, and a method for preparing the same, which resulted from the above.
Disclosure of Invention
In order to solve the problems, the invention provides the following technical scheme:
first aspect: the application provides a photoinitiator, wherein the chemical structure of the photoinitiator 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.gtoreq.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:
step one: adding 1mol of isophorone diisocyanate, 10g of catalyst dibutyl tin dilaurate and 200g of ethyl acetate into a light-resistant four-port 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: adding 1mol of polyethylene glycol (monomethyl) acrylate and 0.01g of polymerization inhibitor para-hydroxyanisole into the reaction liquid in the step one, reacting until the infrared monitoring is finished without-NCO characteristic peak, and distilling under reduced pressure to remove ethyl acetate, thereby obtaining 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 photoinitiating groups to be bonded with more distal anchor points, crosslinking molecular gaps are larger, rigidity is reduced, the degree of freedom of branched chains is higher, and wetting and adhesion properties of the coating are better.
In a third aspect, the present invention also provides an adhesive using 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 to 2 parts of a polymerizable photoinitiator;
0.2 to 1 part of a 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 curing acrylic ester hot-melt pressure-sensitive adhesive provided by the invention has wider range of balance points of wetting and cohesive force, and can realize higher initial adhesion performance.
In a fourth aspect, the present invention also provides a method for preparing an adhesive, which is used for preparing the hot-melt pressure-sensitive adhesive, and specifically comprises the following preparation steps: step one: 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 solution after the photoinitiator and the free radical polymerization initiator are completely dissolved; adding 30-100 parts of ethyl acetate solvent as a base agent into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, introducing nitrogen to remove oxygen, heating to 80-90 ℃, adding 10% of the total amount of the solution in the first step into the flask, stirring at medium speed, keeping the temperature of 80-90 ℃ for 20-40 minutes, then dropwise adding the residual 90% of the solution in the first step within 3-4 hours, and preserving the temperature for 1-2 hours after dropwise adding to obtain a heat preservation solution, and removing the ethyl acetate solvent by reduced pressure distillation to obtain the 100% solid acrylate hot-melt pressure-sensitive adhesive, namely the adhesive.
The invention has the beneficial effects that: the UV curing acrylic ester hot-melt pressure-sensitive adhesive adopts a polymerizable photoinitiator with a soft polyethylene glycol long molecular chain segment, realizes the slow reduction of the degree of freedom of molecular branches while the chemical crosslinking degree is increased by adjusting the gap and rigidity of a chemical crosslinking structure generated after UV irradiation, and retains more wettability, thereby remarkably improving the range when the UV irradiation adhesive layer reaches the balance advantage, not only realizing higher initial adhesion performance, but also reducing the influence on the vertical non-uniformity caused by the UV irradiation and being applied with higher coating 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 do not constitute a limitation on the invention.
Wherein:
FIG. 1 is a schematic representation of the chemical structure of the photoinitiator of the present invention;
FIG. 2 is a schematic representation of the synthesis mechanism of the photoinitiators of the present invention;
FIG. 3 is a plot of adhesion, cohesion as a function of increasing UV light exposure for adhesives using photoinitiators not according to the invention;
fig. 4 is a graph showing the change in adhesion and cohesion with increasing UV light of an adhesive to which the polymerizable photoinitiator of the present invention is applied.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the 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 for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
In this embodiment 1, a preparation method of a photoinitiator is provided, the chemical structure of the photoinitiator is shown in fig. 1, and the preparation method is as follows:
step one: adding 1mol of isophorone diisocyanate IPDI and 10g of catalyst dibutyl tin dilaurate, 200g of ethyl acetate into a light-proof four-port bottle provided with a stirrer, a reflux condenser 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: adding 1mol of polyethylene glycol monomethacrylate HEMA-5 and 0.01g of polymerization inhibitor para-hydroxyanisole, reacting until the infrared monitoring does not show-NCO characteristic peak, and removing ethyl acetate by 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 is prepared by the following components and steps: 55 parts of n-butyl acrylate, 30 parts of isooctyl acrylate, 10 parts of methyl methacrylate, 5 parts of acrylic acid, 0.3 part of the photoinitiator obtained in the example 1 and 0.5 part of the free radical polymerization initiator are mixed and stirred according to parts by weight, and a mixed solution is obtained after the photoinitiator and the free radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent serving as a base agent into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser 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 medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest mixed solution within 3 hours, and preserving the heat for 2 hours after dropwise adding, wherein the ethyl acetate solvent is removed from the obtained heat-preserving solution through reduced pressure distillation, and the 100% solid acrylate hot-melt pressure-sensitive adhesive is the adhesive.
50g of the hot-melt pressure-sensitive adhesive is melted and heated at 130 ℃ and coated on a PET polyester film subjected to corona treatment to prepare an adhesive tape, the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 And (3) irradiating for a plurality of times by using a medium-pressure mercury lamp with power of 2000W, selecting the adhesive tape with the failure mode of adhesive interface without adhesive, and testing the adhesive tape without adhesive on the adhered substrate.
Example 3
An adhesive differs 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 the example 1 and 0.7 part of the free radical polymerization initiator are mixed and stirred, and a mixed solution is obtained after the photoinitiator and the free radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent serving as a base agent into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser 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 medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest mixed solution within 3 hours, and preserving the heat for 2 hours after dropwise adding, wherein the ethyl acetate solvent is removed from the obtained heat-preserving solution through reduced pressure distillation, and the 100% solid acrylate hot-melt pressure-sensitive adhesive is the adhesive.
50g of the hot-melt pressure-sensitive adhesive is melted and heated at 130 ℃ and coated on a PET polyester film subjected to corona treatment to prepare an adhesive tape, the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 And (3) irradiating for a plurality of times by using a medium-pressure mercury lamp with power of 2000W, selecting the adhesive tape with the failure mode of adhesive interface without adhesive, and testing the adhesive tape without adhesive on the adhered substrate.
Example 4
An adhesive differs 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 the example 1 and 0.3 part of the free radical polymerization initiator are mixed and stirred, and a mixed solution is obtained after the photoinitiator and the free radical polymerization initiator are completely dissolved.
Adding 100 parts of ethyl acetate solvent serving as a base agent into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser 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 medium speed, keeping the temperature of 85 ℃ for reaction for 30 minutes, then dropwise adding the rest mixed solution within 3 hours, and preserving the heat for 2 hours after dropwise adding, wherein the ethyl acetate solvent is removed from the obtained heat-preserving solution through reduced pressure distillation, and the 100% solid acrylate hot-melt pressure-sensitive adhesive is the adhesive.
50g of the hot-melt pressure-sensitive adhesive is melted and heated at 130 ℃ and coated on a PET polyester film subjected to corona treatment to prepare an adhesive tape, the thickness of the film is 25 mu m, and the coating adhesive is controlled at 20g/m 2 Using power 200And irradiating the medium-pressure mercury lamp with the pressure of 0W for a plurality of times, selecting the adhesive tape which is just not remained on the adhered substrate when the adhesive tape is peeled, and testing the adhesive tape when the adhesive interface is not adhered in a failure mode.
Comparative example
50g of commercial UV-cured acrylate hot-melt pressure-sensitive adhesive is prepared by melting and heating at 130 ℃ and coating on a PET polyester film subjected to corona treatment 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 And (3) irradiating for a plurality of times by using a medium-pressure mercury lamp with power of 2000W, selecting the adhesive tape with the failure mode of adhesive interface without adhesive, and testing the adhesive tape without adhesive on the adhered substrate.
The loop-type initial tackiness of the PET pressure-sensitive adhesive tape was tested according to GB/T31125-2014; the peel strength of the PET pressure-sensitive adhesive tape was tested according to GB/T2792-2014; the high temperature tack properties of the PET pressure sensitive adhesive tape were tested in accordance with GB/T4851-2014 and the test results are shown in Table 1 below:
TABLE 1
As the UV light irradiation amount increases, the surface adhesion property of the adhesive tends to be a decreasing curve, while the cohesive strength of the adhesive tends to be an increasing curve, and the practical properties of the adhesive are that the initial adhesion, the peeling force and the shearing force are all good, and the performance of the adhesive cannot be too short, so that the point is the most balanced in theory and is also the best performance.
Referring to fig. 3 and 4, the height of the cross point, i.e. the balance point of the property values of the adhesion and the cohesion, is shown in fig. 3, which is a curve of the change of the adhesion and the cohesion of an adhesive using a photoinitiator not according to the present invention with the increase of UV light, wherein the peel force 13, the initial adhesion 10, and the 70 degree hold time of the cross point are balanced for 200 hours; as shown in fig. 4, the adhesive force and cohesive force of the adhesive using the photoinitiator according to the present invention are changed along with the increase of UV light, and the higher performance of balancing the crossing points can achieve the peeling force 18, the initial adhesion force 15 and the holding time of 70 degrees of 400 hours. The photoinitiator according to the invention is significantly shifted up in cross-point compared to other conventional photoinitiators, and in practical applications, the resulting performance is significantly higher regardless of whether the client sets the uv parameters at the equilibrium point or in a range around.
In summary, the prepared adhesive, namely the UV curing acrylic ester hot-melt pressure-sensitive adhesive, obtains annular initial adhesion, peeling strength and high-temperature adhesion performance through 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 adhesive has relatively high-temperature adhesion performance and relatively excellent annular initial adhesion and peeling strength, so that the pressure-sensitive adhesive prepared by the invention can remarkably reduce the degree of freedom of a molecular chain segment caused by the improvement of cohesion, and the upper limit of the comprehensive performance of a balance point can be improved.
The applicant states that the present invention is illustrated by the above examples as well as the preparation method and application of the polymerizable photoinitiator and the UV curable acrylate hot melt pressure sensitive adhesive thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (2)
1. A preparation method of a polymerizable photoinitiator containing polyethylene glycol chain segments is characterized in that the chemical structure of the photoinitiator is shown as the following formula:
wherein R is selected from methyl; n is the number of repeating units, n=5;
the preparation method of the photoinitiator comprises the following steps:
step one: adding 1mol of isophorone diisocyanate, 10g of catalyst dibutyl tin dilaurate and 200g of ethyl acetate into a light-resistant four-port 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: adding 1mol of polyethylene glycol monomethacrylate and 0.01g of polymerization inhibitor para-hydroxyanisole into the reaction liquid in the step one, reacting until the infrared monitoring is finished without detecting the-NCO characteristic peak, and distilling under reduced pressure to remove ethyl acetate, thereby obtaining the polymerizable photoinitiator.
2. A method for preparing a pressure sensitive adhesive using a polymerizable photoinitiator containing a polyethylene glycol segment, which is characterized in that the polymerizable photoinitiator containing the polyethylene glycol segment as described in claim 1 is adopted 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 to 2 parts of a polymerizable photoinitiator;
0.2 to 1 part of a radical polymerization initiator;
the soft monomer is selected from any one of n-butyl acrylate, ethyl acrylate and isooctyl acrylate;
the hard monomer is selected from any one of methyl acrylate, methyl methacrylate and vinyl acetate;
the functional monomer is selected from one of acrylic acid and hydroxyethyl acrylate;
the free radical polymerization initiator is selected from one of benzoyl peroxide and azodiisobutyronitrile;
the specific preparation steps of the pressure sensitive adhesive containing the polyethylene glycol chain segment polymerizable photoinitiator are as follows:
step one: 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 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 base agent into a three-neck flask provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, introducing nitrogen to remove oxygen, heating to 80-90 ℃, adding 10% of the total amount of the solution in the first step into the flask, stirring at medium speed, keeping the temperature of 80-90 ℃ for reacting for 20-40 minutes, then dropwise adding the solution in the first step for the rest 90% within 3-4 hours, and preserving the temperature for 1-2 hours after dropwise adding to obtain a heat preservation solution, and removing the ethyl acetate solvent by reduced pressure distillation to obtain the 100% solid acrylate hot-melt pressure-sensitive adhesive, namely the adhesive.
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Citations (9)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2801675T3 (en) * | 2017-01-05 | 2021-01-12 | Igm Resins Italia Srl | Composition useful as a pressure sensitive adhesive, its use and adhesive articles comprising it |
-
2022
- 2022-11-30 CN CN202211525224.5A patent/CN115745844B/en active Active
Patent Citations (9)
| 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 |
| 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》.北京邮电大学出版社,2016,(第1版),第263-264页. * |
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