CN103275656A - Reactive pressure-sensitive adhesive having performance of structural adhesive after being cured, and preparation method thereof - Google Patents
Reactive pressure-sensitive adhesive having performance of structural adhesive after being cured, and preparation method thereof Download PDFInfo
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- CN103275656A CN103275656A CN2013102058591A CN201310205859A CN103275656A CN 103275656 A CN103275656 A CN 103275656A CN 2013102058591 A CN2013102058591 A CN 2013102058591A CN 201310205859 A CN201310205859 A CN 201310205859A CN 103275656 A CN103275656 A CN 103275656A
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Abstract
The invention relates to a reactive pressure-sensitive adhesive having the performance of a structural adhesive after being cured, and a preparation method thereof. The pressure-sensitive adhesive is prepared from the following materials in parts by weight: a) 100 parts of soluble acrylate copolymer; b) 80 to 120 parts of epoxy resin; and c) 8 to 12 parts of epoxy resin latency curing agent, wherein the soluble acrylate copolymer is formed by polymerizing the following raw materials in a free radical polymerization reaction manner: 50% to 65% of alkyl ester with the acrylic carbon atom number from 1 to 8, 5% to 15% of styrene, 10% to 15% of alkyl ester with the methylacrylic acid carbon atom number from 1 to 8 and 35% to 5% of alkyl acrylate. At the normal temperature, under the action of the plasticization of the epoxy resin to the acrylate polymer, the pressure sensitivity of the acrylate polymer is generated, so that the pressure-sensitive adhesive can be used as an ordinary pressure-sensitive adhesive. After the pressure-sensitive adhesive is heated, the curing agent reacts with the epoxy resin; and the cured epoxy resin is toughened by the acrylic ester, so that the pressure-sensitive adhesive has the adhesion strength of the structural adhesive.
Description
Technical field
The invention belongs to the high polymer material technology research field, but be particularly related to the pressure-sensitive adhesive agent preparation method that a kind of later stage is solidified into high strength structural adhesion, can directly coat by sticking material with this pressure sensitive adhesive and directly to use, also can be made into pressure-sensitive adhesive tape or double sticky tape and use.Purposes such as the response type pressure sensitive adhesive of the present invention's preparation can use as common Pressuresensitive Tape before solidifying, and can do interim location, and is fixing after being heating and curing, can produce the performances such as bonding strength of structure glue level.
Background technology
Pressure-sensitive adhesive agent (Pressure Sensitive Adhesive is called for short PSA) is a kind of special visco-elasticity macromolecular material that self has, and applies less pressure, can rely within a short period of time Van der Waals force to reach suitable bonding strength.Pressure sensitive adhesive has fabulous construction technology, neither need to solidify anchor clamps, also do not need complicated technologies such as heating and illumination, directly act on the adherend surface by moistened surface, suitability is strong, speed is fast, widely at label, automotive trim, adhesive tape, medicine and other fields has obtained using widely.
The pressure sensitive adhesive structure is chemical gel or the physics frozen glue system of lower crosslink density, general plasticized dose and tackifier plasticising.The molecular chain structure of this lower crosslink density has caused the modulus of pressure sensitive adhesive and intensity very low, creep-resistant property is relatively poor, the long-time use, the glue-line easy glide, weathering resistance and solvent resistance are all relatively poor, can't need interim location to need the application of the permanent adhesive occasion of structure glue level again at some, and these special bonding occasions (can't use working fastenings such as anchor clamps), can not directly use structure glue, therefore the response type pressure sensitive adhesive that has the bonding level of structure glue after just need a kind ofly solidifying is applicable to the high strength bonding occasion that needs simple technique for sticking.
Chinese patent CN 1226915A and US Patent No. 6211261, patent name is the manufacturing of heat curing-type pressure-sensitive adhesive and sheet adhesive class thereof, this application case discloses in the acrylic monomer that constitutes optical polymerism composition, adding intramolecularly has the monomer of carboxyl etc., after its photopolymerization, with Resins, epoxy reaction, acrylic polymers and cross linking of epoxy resin combination, obtain under the normal temperature impermanent bondingly, can make its curing at short notice through above-mentioned reaction.This method principle of solidification is only to rely on the side position carboxyl of polyacrylic ester skeleton polymer and Resins, epoxy cross-linking reaction together, acrylate does not wherein contain curing agent for epoxy resin, Resins, epoxy itself is as the linking agent of base resin (acrylate) molecule of pressure sensitive adhesive, therefore the problem that has level of response and crosslinking degree, solidify later bonding strength and also do not reach the bonding strength of structure glue far away, and also need to carry out ultraviolet light polymerization after the coating, preparation technology is comparatively complicated.
Te Kaiping 2-272076 communique, the photopolymer compositions that adds the Resins, epoxy formation in acrylate monomer is done the thermoset pressure-sensitive adhesive agent of raw material, in addition, Te Kaiping 7-2978 communique has also been announced the agent of a kind of heat curing-type pressure-sensitive adhesive, it is done raw material with the photopolymerisable composition of a kind of energy and makes, and said composition is to make after being added into (methyl) alkyl acrylate by a kind of pure and mild (methyl) acrylic acid ester that contains epoxy group(ing) and Resins, epoxy.Relevant with this motion is also contain the latent curing agent of Resins, epoxy in the above-mentioned composition, but in the storage process before photopolymerization or after the photopolymerization, the easy and Resins, epoxy reaction of latent curing agent to be solidified pressure sensitive adhesive gradually and lost pressure-sensitive.The stability in storage existing problems.
Nearly all similar patent all is to introduce Resins, epoxy or epoxy compounds in the photopolymer of acrylate both at home and abroad at present, and solidifies the bonding level that the back bonding strength does not all reach structure glue far away, and storage characteristics also has problems.
Thereby, prepare and can do common pressure sensitive adhesive use under a kind of normal temperature, have good storage characteristics, can reach the response type pressure sensitive adhesive of the bonding level of structure glue after being heating and curing, have boundless prospect in expansion pressure sensitive adhesive use range with in using.
Summary of the invention
The inventor in order to achieve the above object, the result who concentrates on studies is, acrylic ester polymer being carried out the solubility parameters design, makes synthetic acrylate have resolvability; In the solution of the acrylate copolymer that forms, add the latent curing agent of Resins, epoxy and Resins, epoxy.
Can be used as the response type pressure sensitive adhesive that structure glue is used after the curing provided by the invention, it is characterized in that comprising and contain following a)-c) composition:
A) 100 parts of (weight) solubility acrylate copolymers, it is the alkyl ester 50-65%(weight with vinylformic acid carbonatoms 1-8), vinylbenzene 5-15%(weight), alkyl ester 10-15% and the alkyl acrylic 35-5%(weight of methacrylic acid carbonatoms 1-8) be raw material, form by radical polymerization.Its structure is:
R wherein
1,R
2, R
3A kind of in methyl, ethyl, propyl group, the butyl.Two kinds or more kinds of, R
1, R
2, R
3Identical or different;
B) 80 parts of-120 parts of (weight) Resins, epoxy
C) 8 parts-12 parts (weight) Resins, epoxy latent curing agents
Further, wherein, the alkyl ester of vinylformic acid carbonatoms 1-8 be from methyl acrylate, ethyl propenoate, butyl acrylate, acrylic acid-2-ethyl ethyl ester, choose at least a.
Further, wherein, the alkyl ester of methacrylic acid carbonatoms 1-8 be from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, choose at least a.
Further, wherein, alkyl acrylic be from methacrylic acid, 2-hydroxyethyl methacrylic acid, choose at least a.
Further, wherein, Resins, epoxy be from bisphenol F epoxy resin, bisphenol A epoxide resin, allyl group Resins, epoxy, choose at least a.
Further, wherein, it is at least a that the latent curing agent of Resins, epoxy refers to choose in one group of the Dyhard RU 100, imidazoles, ketoimine.
Have the preparation method of the response type pressure-sensitive adhesive agent of structure glue performance after the described curing, it is characterized in that, comprise the steps:
(1) takes by weighing alkyl ester, the vinylbenzene of vinylformic acid carbonatoms 1-8, alkyl ester, the alkyl acrylic of methacrylic acid carbonatoms 1-8 in proportion, obtain polymkeric substance by radical polymerization;
(2) get resulting polymers, becoming mass percent with dissolution with solvents is the polymers soln of 15-50%, and wherein solvent comprises one or several among ethanol, acetone, ethyl acetate, THF, the DMF;
(3) add Resins, epoxy in proportion;
(4) add the latent curing agent of Resins, epoxy in proportion.
After the solution coat, solvent evaporates forms the acrylate copolymer of Resins, epoxy plasticising, make it have pressure-sensitive, can be used as common pressure sensitive adhesive under the normal temperature uses, form pressure-sensitive adhesive, wherein as Resins, epoxy and its latent curing agent generation curing reaction of plasticising, form high cross-linking system, reach the bonding level of structure, the latent curing agent of Resins, epoxy has guaranteed that also pressure sensitive adhesive has good preservation stability at normal temperatures simultaneously.
Description of drawings
Fig. 1 is Fourier's infrared spectra spectrogram of the synthetic acrylate copolymer of embodiment 1;
Fig. 2 is the proton nmr spectra of the synthetic acrylate copolymer of embodiment 1.
Embodiment
The example of enumerating below preferably draws in order to further specify the present invention, is not limited to these embodiment (among the embodiment, all consumptions of mentioning, % or proportion are weight ratio except indicating) in actual applications.
60 parts of butyl acrylates, 12 parts of vinylbenzene, 19 parts of 9 parts of methacrylic acids and methyl methacrylates carry out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 50 parts of ethanol, and add the latent curing agent Dyhard RU 100 of 40 parts of bisphenol A epoxide resin E51 and 4 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
68 parts of butyl acrylates, 8 parts of vinylbenzene, 12 parts of 12 parts of methacrylic acids and methyl methacrylates carry out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 60 parts of acetone, and add the latent curing agent glyoxal ethyline of 46 parts of bisphenol A epoxide resin E51 and 2.6 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
71 parts of butyl acrylates, 7 parts of vinylbenzene, 17 parts of 5 parts of methacrylic acids and methyl methacrylates carry out polyreaction, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 70 parts of toluene, and add the latent curing agent 2-ethyl imidazol(e) of 54 parts of bisphenol A epoxide resin E51 and 3 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
55 parts of butyl acrylates, 14 parts of vinylbenzene, 18 parts of 13 parts of methacrylic acids and methyl methacrylates carry out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 80 parts of acetone, and add the latent curing agent Dyhard RU 100 of 52 parts of bisphenol F epoxy resins and 5.7 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
60 parts of ethyl propenoates, 15 parts of vinylbenzene, 13 parts of 12 parts of methacrylic acids and butyl methacrylate are carried out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 90 parts of toluene, and add the latent curing agent Dyhard RU 100 of 56 parts of allyl group Resins, epoxy and 4 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
52 parts of ethyl propenoates, 8 parts of vinylbenzene, 26 parts of 14 parts of methacrylic acids and butyl methacrylate are carried out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 100 parts of ethanol, and add the latent curing agent 2-phenylimidazole of 42 parts of allyl group Resins, epoxy and 2 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
65 parts of butyl acrylates, 14 parts of vinylbenzene, 12 parts of 9 parts of methacrylic acids and butyl methacrylate are carried out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 110 parts of tetrahydrofuran (THF)s, and add the latent curing agent ketoimine of 55 parts of bisphenol A epoxide resin E51 and 5.5 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
50 parts of butyl acrylates, 5 parts of vinylbenzene, 35 parts of 10 parts of methacrylic acids and methyl methacrylates carry out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 120 parts of ethanol, and add the latent curing agent Dyhard RU 100 of 60 parts of allyl group Resins, epoxy and 6 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
58 parts of butyl acrylates, 11 parts of vinylbenzene, 18 parts of 13 parts of methacrylic acids and butyl methacrylate are carried out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 130 parts of ethanol, and add the latent curing agent glyoxal ethyline of 43 parts of bisphenol F epoxy resins and 2 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
57 parts of methyl acrylates, 13 parts of vinylbenzene, 15 parts of 15 parts of methacrylic acids and butyl methacrylate are carried out Raolical polymerizable, discharging.Namely get composition a.
Get 50 parts of composition a and be dissolved in 140 parts of ethanol, and add the latent curing agent Dyhard RU 100 of 54 parts of bisphenol F epoxy resins and 6 parts of Resins, epoxy.
Be stirred to dissolving fully.
This solvent-borne type pressure sensitive adhesive is coated on respectively not through on the base material of the polyethylene terephthalate manufacturing of 25 μ m of the cleaning of inertization and scribble on the base material that the polyethylene terephthalate of 25 μ m of separant makes, place 2h under the normal temperature then, all cover the base material of the polyethylene terephthalate manufacturing of the 25 μ m that scribble separant.Thereafter severing becomes width 25mm, makes single face sealing tape and the double-faced adhesive tape of heat curing-type pressure-sensitive adhesive agent bondline thickness 30 μ m.
To 180 ° of peeling forces of above preparation single face sealing tape (measuring according to GB/T2792) with hold viscous force (measuring according to GB/T4851-1998), the double-faced adhesive tape back that is heating and curing is measured the mechanical strength of shearing resistance (measuring according to GB/T7124-2008) sign it is as shown in the table:
| Embodiment | 180 ° of peeling force N/25mm | Hold viscous force/h | Shearing force/ |
| 1 | 18.8 | ＞120h | 23.5 |
| 2 | 19.2 | ＞120h | 25.0 |
| 3 | 17.8 | ＞120h | 26.7 |
| 4 | 19.1 | ＞120h | 27.0 |
| 5 | 17.6 | ＞120h | 26.8 |
| 6 | 18.1 | ＞120h | 28.4 |
| 7 | 18.3 | ＞120h | 28.6 |
| 8 | 19.4 | ＞120h | 25.1 |
| 9 | 18.6 | ＞120h | 27.3 |
| 10 | 18.4 | ＞120h | 29.2 |
Claims (7)
1. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing is characterized in that comprising the polymkeric substance that contains according to the composition of following a)-c) composition of parts by weight:
A) 100 parts of solubility acrylate copolymers, it is that alkyl ester 10-15% and alkyl acrylic 35-5% with the alkyl ester 50-65% of vinylformic acid carbonatoms 1-8, vinylbenzene 5-15%, methacrylic acid carbonatoms 1-8 is raw material, forms by radical polymerization.Its structure is:
R wherein
1,R
2, R
3For in methyl, ethyl, propyl group, the butyl a kind of, two kinds or more kinds of, R
1, R
2, R
3Identical or different;
B) 80 parts of-120 parts of Resins, epoxy;
C) 8 parts of-12 parts of Resins, epoxy latent curing agents.
2. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing according to claim 1, wherein, the alkyl ester of vinylformic acid carbonatoms 1-8 be from methyl acrylate, ethyl propenoate, butyl acrylate, acrylic acid-2-ethyl ethyl ester, choose at least a.
3. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing according to claim 1, wherein, the alkyl ester of methacrylic acid carbonatoms 1-8 be from methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, choose at least a.
4. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing according to claim 1, wherein, alkyl acrylic be from methacrylic acid, 2-hydroxyethyl methacrylic acid, choose at least a.
5. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing according to claim 1, wherein, Resins, epoxy be from bisphenol F epoxy resin, bisphenol A epoxide resin, allyl group Resins, epoxy, choose at least a.
6. the response type pressure-sensitive adhesive agent that has the structure glue performance after the curing according to claim 1, wherein, it is at least a that the latent curing agent of Resins, epoxy refers to choose in one group of the Dyhard RU 100, imidazoles, ketoimine.
7. have the preparation method of the response type pressure-sensitive adhesive agent of structure glue performance after the curing according to claim 1, it is characterized in that, comprise the steps:
(1) takes by weighing alkyl ester, the vinylbenzene of vinylformic acid carbonatoms 1-8, alkyl ester, the alkyl acrylic of methacrylic acid carbonatoms 1-8 in proportion, obtain polymkeric substance by radical polymerization;
(2) get resulting polymers, becoming mass percent with dissolution with solvents is the polymers soln of 15-50%, and wherein solvent comprises one or several among ethanol, acetone, ethyl acetate, THF, the DMF;
(3) add Resins, epoxy in proportion;
(4) add the latent curing agent of Resins, epoxy in proportion.
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| CN106512070A (en) * | 2016-09-28 | 2017-03-22 | 四川三和医用材料有限公司 | Medical antiallergic pressure-sensitive adhesive |
| CN110527454A (en) * | 2019-08-20 | 2019-12-03 | 常州都铂高分子有限公司 | A kind of novel high temperature resistant peelable type pressure sensitive adhesive tape |
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| CN112708383A (en) * | 2021-01-21 | 2021-04-27 | 常州时创能源股份有限公司 | Stick splicing adhesive and preparation method thereof, stick splicing adhesive film and preparation method and application thereof |
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| US11049421B2 (en) | 2015-02-05 | 2021-06-29 | Avery Dennison Corporation | Label assemblies for adverse environments |
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| US11685841B2 (en) | 2012-10-09 | 2023-06-27 | Avery Dennison Corporation | Adhesives and related methods |
| US11292942B2 (en) | 2012-10-09 | 2022-04-05 | Avery Dennison Corporation | Adhesives and related methods |
| CN104870589A (en) * | 2013-10-10 | 2015-08-26 | 艾利丹尼森公司 | Adhesives and related methods |
| CN104870589B (en) * | 2013-10-10 | 2018-10-26 | 艾利丹尼森公司 | Adhesive and correlation technique |
| CN109439206A (en) * | 2013-10-10 | 2019-03-08 | 艾利丹尼森公司 | Adhesive and correlation technique |
| CN103980847B (en) * | 2014-05-21 | 2015-11-25 | 天津大学 | Self cure Polyacrylic Ester and Epoxy Resin sizing agent and Preparation method and use |
| CN103980847A (en) * | 2014-05-21 | 2014-08-13 | 天津大学 | Self-curing polyacrylate-epoxy resin adhesive as well as preparation method and application of self-curing polyacrylate-epoxy resin adhesive |
| US11049421B2 (en) | 2015-02-05 | 2021-06-29 | Avery Dennison Corporation | Label assemblies for adverse environments |
| CN106512070A (en) * | 2016-09-28 | 2017-03-22 | 四川三和医用材料有限公司 | Medical antiallergic pressure-sensitive adhesive |
| CN111793194A (en) * | 2019-04-09 | 2020-10-20 | 北京化工大学 | Medium-low temperature latent curing epoxy resin system and preparation method thereof |
| CN111793194B (en) * | 2019-04-09 | 2022-09-20 | 北京化工大学 | Medium-low temperature latent curing epoxy resin system and preparation method thereof |
| CN110527454A (en) * | 2019-08-20 | 2019-12-03 | 常州都铂高分子有限公司 | A kind of novel high temperature resistant peelable type pressure sensitive adhesive tape |
| CN112708383A (en) * | 2021-01-21 | 2021-04-27 | 常州时创能源股份有限公司 | Stick splicing adhesive and preparation method thereof, stick splicing adhesive film and preparation method and application thereof |
| CN113881353A (en) * | 2021-11-09 | 2022-01-04 | 北京天山新材料技术有限公司 | Acrylate structural adhesive composition and acrylate structural adhesive |
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