CN107674001B - Multifunctional free radical polymerization active tackifying resin and synthetic method thereof - Google Patents
Multifunctional free radical polymerization active tackifying resin and synthetic method thereof Download PDFInfo
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- CN107674001B CN107674001B CN201710849758.6A CN201710849758A CN107674001B CN 107674001 B CN107674001 B CN 107674001B CN 201710849758 A CN201710849758 A CN 201710849758A CN 107674001 B CN107674001 B CN 107674001B
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- tackifying resin
- free radical
- acrylate
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- radical polymerization
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
Abstract
The invention relates to a multifunctional free radical polymerization active tackifying resin, which is characterized in that the tackifying resin can be copolymerized on an adhesive molecular chain in a free radical polymerization mode, the tackifying resin is isocyanate acrylate modified rosin epoxy acrylate, the synthesis method comprises the steps of sequentially adding rosin epoxy acrylate, isocyanate acrylate, a polymerization inhibitor, an antioxidant and a catalyst into a three-neck flask with a thermometer, stirring at normal temperature until the polymerization inhibitor and the antioxidant are completely dissolved, heating to 70-75 ℃ for reaction for 2-3h, testing the content of NCO groups by using an infrared spectrometer, and stopping heating reaction until NCO group peaks completely disappear to obtain the isocyanate acrylate modified rosin epoxy acrylate. The tackifying resin prepared by the invention can greatly improve the high temperature migration resistance while tackifying, simultaneously improve the strength of a colloid body and the shear strength of a sample piece, and has more balanced and reliable bonding performance.
Description
Technical Field
The invention relates to a preparation method of multifunctional free radical polymerization active tackifying resin, in particular to a preparation method of ultraviolet light initiated free radical polymerization active tackifying resin, belonging to the technical field of light-cured materials.
Background
The photocuring pressure-sensitive adhesive has wide attention and research due to the advantages of high curing speed, low energy consumption, no use of inert solvents, environmental friendliness and the like, and has great market application potential. However, the photo-curing pressure-sensitive adhesive has its own limitations, and in general, a large amount of non-reactive inert tackifying resin is often added to the photo-curing pressure-sensitive adhesive in order to obtain high pressure sensitivity, which can cause the strength of the cured adhesive body to be greatly reduced and affect the shearing performance; on the other hand, under the high-temperature use condition, the low-molecular-weight tackifying resin can migrate between the adhesive layer and the adhered base material, and no covalent bond is formed between the tackifying resin molecules and the adhesive layer molecules, so that the adhesive strength of the adhesive layer to the base material is sharply reduced, and the adhesive failure is further caused. The multifunctional free radical polymerization active tackifying resin can well solve the problems.
Disclosure of Invention
In order to overcome the defects that non-reactive inert tackifying resin in the prior art has poor high temperature migration resistance and reduces the strength of a colloid body and the shear strength, the invention provides multifunctional free radical polymerization active tackifying resin, and aims to achieve the purposes of improving the pressure sensitivity of a pressure-sensitive adhesive, improving the strength of the adhesive layer body and further improving the shear strength while having good high temperature migration resistance.
The technical scheme for solving the problems is as follows: a multifunctional free radical polymerization active tackifying resin, wherein the tackifying resin is isocyanate group acrylate modified rosin epoxy acrylate, isocyanate group acrylate molecules are grafted on the rosin epoxy acrylate molecules, and the molecular structural formula of the multifunctional free radical polymerization active tackifying resin is represented by the following formula (I) or (II):
（II）
wherein: r1Represents CH2CH2Or CH2CH2OCH2CH2；R2Represents H or CH3。
Further, the isocyanate acrylate refers to one or a mixture of more of BEI, MOI, AOI or MOI-EG of Showa Denko K.K., and has a molecular structural formula as follows:
further, the rosin epoxy acrylate is BEAMSET101 resin of Mitsubishi chemical industries, Japan, and has a molecular structural formula as follows:
adding rosin epoxy acrylate and isocyanate acrylate into a three-neck flask with a thermometer according to the molar ratio of 1:1, sequentially adding a polymerization inhibitor accounting for 0.05-0.1% of the total mass, a stabilizer accounting for 0.02-0.07% of the total mass and a catalyst accounting for 0.01-0.05% of the total mass into the three-neck flask, stirring at normal temperature until the polymerization inhibitor and the stabilizer are completely dissolved, heating to 70-75 ℃ for reaction for 2-3 hours, testing the content of NCO groups by using an infrared spectrometer, and stopping heating reaction until the peak of the NCO groups disappears completely to obtain the isocyanate acrylate modified rosin epoxy acrylate; taking BEI as an example, the chemical reaction formula is as follows:
the polymerization inhibitor is p-hydroxyanisole MEHQ, the stabilizer is 2, 6-di-tert-butyl-4-methylphenol BHT, and the catalyst is dibutyltin dilaurate DBTL.
The invention has the beneficial effects that: according to the multifunctional free radical polymerization active tackifying resin prepared by the invention, the tackifying resin is grafted and copolymerized on an adhesive molecular chain through ultraviolet light initiated free radical polymerization reaction to form a covalent bond, so that the high temperature migration resistance is greatly improved while tackifying is achieved, and meanwhile, the crosslinking density of colloid is improved due to the increase of the number of reactive active functional groups, so that the bulk strength of the colloid and the shear strength of a sample are improved, and the defects that the conventional non-reactive inert tackifying resin is poor in high temperature migration resistance and the bulk strength of the colloid and the shear strength of the sample are reduced are overcome.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Examples and comparative examples synthesis of pressure sensitive adhesive prepolymer PSAs:
sequentially adding 60 parts of isooctyl acrylate 2-EHA, 15 parts of butyl acrylate BA, 20 parts of isobornyl acrylate IBOA, 5 parts of acrylic acid AA and 0.1 part of azobisisobutyronitrile AIBN into a three-neck flask with a thermometer, and heating to 70-80 ℃ for reacting for 2 hours to obtain the pressure-sensitive adhesive prepolymer PSA.
The first embodiment is as follows:
428.57g of BEAMSET101 rosin epoxy acrylate, 239.23g of isocyanate acrylate BEI, 0.5g of p-hydroxyanisole MEHQ as a polymerization inhibitor, 0.3g of 2, 6-di-tert-butyl-4-methylphenol BHT as a stabilizer and 0.2g of dibutyltin dilaurate DBTL as a catalyst are sequentially added into a three-neck flask with a thermometer, stirred until the polymerization inhibitor is completely dissolved, heated to 70-75 ℃ for reaction for 2-3h, and stopped when an-NCO group peak disappears by monitoring with an infrared spectrometer to obtain isocyanate acrylate modified rosin epoxy acrylate BEI-PUA; stirring and uniformly mixing the prepolymer PSA, BEI-PUA and the free radical polymerization photoinitiator.
Example two:
428.57g of BEAMSET101 rosin epoxy acrylate, 155.15g of isocyanate acrylate MOI, 0.5g of polymerization inhibitor p-hydroxyanisole MEHQ, 0.3g of stabilizer 2, 6-di-tert-butyl-4-methylphenol BHT and 0.2g of catalyst dibutyltin dilaurate DBTL are sequentially added into a three-neck flask with a thermometer, stirred until the polymerization inhibitor is completely dissolved, heated to 70-75 ℃ for reaction for 2-3h, and the reaction is stopped when an-NCO group peak disappears by monitoring with an infrared spectrometer to obtain isocyanate acrylate modified rosin epoxy acrylate MOI-PUA; and uniformly stirring and mixing the prepolymer PSA, the MOI-PUA and the free radical polymerization photoinitiator.
Comparative example one:
stirring and uniformly mixing the prepolymer PSA, BEAMSET101 and the free radical polymerization photoinitiator.
Comparative example two:
stirring and uniformly mixing the prepolymer PSA, the dehydroabietic acid and the free radical polymerization photoinitiator.
The molecular formula of dehydroabietic acid is as follows:
Table one: composition of raw materials of examples and comparative examples
The pressure sensitivity of the test item is tested by a slope rolling ball method; the migration resistance of the tackifying resin is expressed by the high-temperature load holding time and the high-temperature aging shear strength; and (4) the strength of the body.
The adhesive prepared in the examples and the comparative examples is coated on a PET non-release film by a sample preparation method, the thickness of the adhesive film is 50 mu m, and the adhesive film is irradiated by a UVLED surface light source with the wavelength of 365nm to 2000mJ/cm2And (5) standby.
The test condition 1 is that the inclination angle of the pressure-sensitive inclined plane rolling ball method is 30 degrees, and the maximum number of steel balls is recorded;
2. adhering the adhesive film to a stainless steel plate for a sticking time, placing the adhesive film in a 70 ℃ oven, carrying a load of 1kg, and recording the time for debonding the adhesive film and the steel plate;
3. the adhesive film is attached to a stainless steel plate with shear strength, and the stainless steel plate is placed in a 70 ℃ oven for different times; testing the shear strength;
4. bulk strength GB/T528-1998.
Table two: test results of examples and comparative examples
The test results can be analyzed, and the prepared multifunctional free radical polymerization active tackifying resin has small difference in pressure sensitivity to adhesives and comparative examples, but the high-temperature holding time, the shear strength and the bulk strength are greatly improved. The multifunctional free radical polymerization active tackifying resin prepared by the invention can greatly improve the high temperature migration resistance while tackifying, simultaneously improve the strength of a colloid body and the shear strength of a sample piece, and has more balanced and reliable bonding performance.
The above description is only exemplary of the present invention and should not be taken as limiting the scope of the invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (4)
1. A multifunctional free-radically polymerizable reactive tackifying resin characterized by a molecular structural formula represented by structural formula (I) or (II):
wherein: r1Represents CH2CH2Or CH2CH2OCH2CH2；R2Represents H or CH3；
The multifunctional free radical polymerization active tackifying resin is characterized in that the synthesis method comprises the following steps: adding rosin epoxy acrylate and isocyanate acrylate into a three-neck flask with a thermometer according to the mol ratio of 1:1, then adding a polymerization inhibitor accounting for 0.05-0.1% of the total mass, a stabilizer accounting for 0.02-0.07% of the total mass and a catalyst accounting for 0.01-0.05% of the total mass into the three-neck flask in sequence, stirring at normal temperature until the polymerization inhibitor and the stabilizer are completely dissolved, heating to 70-75 ℃ for reaction for 2-3h, testing the content of NCO groups by using an infrared spectrometer, and stopping heating reaction until NCO group peaks completely disappear to obtain the isocyanate acrylate modified rosin epoxy acrylate.
2. The multifunctional free radical polymerizable reactive tackifying resin of claim 1 wherein said isocyanate acrylate is one or a mixture of BEI, MOI, AOI or MOI-EG and has the following molecular structure:
AOI
3. the multifunctional free radical polymerizable reactive tackifying resin of claim 1 wherein said rosin epoxy acrylate is BEAMSET101 resin having the following molecular structure:
4. the multifunctional free radical polymerizable reactive tackifying resin of claim 1 wherein said polymerization inhibitor is p-hydroxyanisole, stabilizer is 2, 6-di-tert-butyl-4-methylphenol, and catalyst is dibutyltin dilaurate.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08218039A (en) * | 1995-02-17 | 1996-08-27 | New Oji Paper Co Ltd | Biodegradable tacky adhesive sheet |
| JPH08333550A (en) * | 1995-06-08 | 1996-12-17 | New Oji Paper Co Ltd | Tacky sheet |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate |
| CN102408357A (en) * | 2011-07-22 | 2012-04-11 | 北京化工大学 | High-adhesion polyurethane acrylate and synthesis method thereof |
| CN106543404A (en) * | 2015-09-18 | 2017-03-29 | 深圳德邦界面材料有限公司 | A kind of high index of refraction color inhibition resin and its synthetic method |
| CN106543037A (en) * | 2015-09-18 | 2017-03-29 | 深圳德邦界面材料有限公司 | A kind of optical resin and its synthetic method |
-
2017
- 2017-09-20 CN CN201710849758.6A patent/CN107674001B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08218039A (en) * | 1995-02-17 | 1996-08-27 | New Oji Paper Co Ltd | Biodegradable tacky adhesive sheet |
| JPH08333550A (en) * | 1995-06-08 | 1996-12-17 | New Oji Paper Co Ltd | Tacky sheet |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate |
| CN102408357A (en) * | 2011-07-22 | 2012-04-11 | 北京化工大学 | High-adhesion polyurethane acrylate and synthesis method thereof |
| CN106543404A (en) * | 2015-09-18 | 2017-03-29 | 深圳德邦界面材料有限公司 | A kind of high index of refraction color inhibition resin and its synthetic method |
| CN106543037A (en) * | 2015-09-18 | 2017-03-29 | 深圳德邦界面材料有限公司 | A kind of optical resin and its synthetic method |
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