CN108102556A - A kind of double cured adhesives of two-component - Google Patents
A kind of double cured adhesives of two-component Download PDFInfo
- Publication number
- CN108102556A CN108102556A CN201711386322.4A CN201711386322A CN108102556A CN 108102556 A CN108102556 A CN 108102556A CN 201711386322 A CN201711386322 A CN 201711386322A CN 108102556 A CN108102556 A CN 108102556A
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- China
- Prior art keywords
- component
- cured adhesives
- double cured
- arbitrary
- mixing
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Classifications
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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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of double cured adhesives of two-component, and it includes free redical polymerization ingredient, redox type free radical aggretion type catalyst system, epoxide and polythiol hardeners.The adhesive can optionally toughener, auxiliary agent and filler, the adhesive includes A, B component, the component A includes, (a) at least one free radical polymerization monomer, (b) at least one tertiary amine-type reducing agent and (c) polythiol hardener；The B component includes, the oxidant that (d) epoxide, (e) can at ambient temperature be reacted with reducing agent.The present invention is mainly characterized by not on the basis of excessively change acrylic acid adhesive formula, introduces epoxy curing systems.The problem of improving surfaces of tacky when acrylic acid adhesive cures, improves adhesive strength, temperature tolerance and the weatherability of acrylic acid adhesive.
Description
Technical field
The invention belongs to adhesive areas, and in particular to a kind of double cured adhesives of two-component, which can be in environment
At a temperature of be carried out at the same time radically curing and epoxy addition and cure, by acrylic tackifier and epoxy adhesive fusion one
It rises.
Background technology
Presently commercially available two-component acrylate structural adhesive is mostly oxidation-reduction type curing system, at room temperature can be quick
Cure, form cross-linked structure, be suitble to binding metal, engineering plastics and other base materials.Acrylate adhesive has high shear
The advantages that intensity, peel strength, impact strength and chemical resistance, cohesible base material range is wide, required surface treatment
It is few.
But it is more and more extensive with the application of adhesive, client is to the performance of adhesive it is also proposed that higher and higher will
It asks.The adhesive of single composition is difficult to meet various demands, therefore by different types of monomer or resin-bonded together, is formed
The superior adhesive system of performance is the hot spot studied at present.Epoxy adhesive has better compared with acrylic acid adhesive
The advantages such as temperature tolerance, higher bulk strength, but epoxy adhesive is relative complex with construction and curing mode, it is tough after curing
The shortcomings of property is inadequate.The present invention provides a kind of double cured adhesives of two-component, effectively solve acrylic acid and epoxy simultaneously
The problem of crosslinking curing.
It is well known that bi-component acrylic adhesive has surfaces of tacky when curing, producing cause is usual
It is caused by surface oxygen inhibition.It is that the hydrogen such as addition mercaptan supply one of in a manner of surfaces of tacky is mitigated or eliminated to inhibit oxygen inhibition
Body, and mercaptan is used at the same time as the room temperature curing agent of epoxy.When mercaptan is as epoxy room temperature curing agent, tertiary amine need to be added
Class basic catalyst, reducing agent when tertiary amine cures at the same time as acrylic acid adhesive.Therefore, without excessively changing double groups
Epoxy curing systems can be introduced wherein on the basis of part acrylic acid adhesive formula.
The content of the invention
To solve the problems, such as that different curing system is co-curing to promote properties of product, the present invention provides a kind of two-components
Double cured adhesives, have can rapid curing acrylic system and epoxy systems at ambient temperature, have that adhesive strength is high,
The advantages that temperature tolerance and good weatherability.
The invention discloses a kind of double cured adhesives of two-component, and it includes free redical polymerization ingredient, redox
Type radical polymerization mould assembly catalyst system, epoxide and polythiol hardener.The adhesive can optionally toughener, auxiliary agent and
Filler, the adhesive include A, B component, and the component A includes, and (a) at least one free radical polymerization monomer, (b) are at least
A kind of tertiary amine-type reducing agent and (c) polythiol hardener；The B component includes, and (d) epoxide, (e) can be with reducing agents in ring
The oxidant reacted at a temperature of border.
Above-mentioned free radical polymerization monomer is olefinic type monomers, such as (methyl) esters of acrylic acid or phenylethylene.
Above-mentioned free radical polymerization monomer includes methacrylic acid, methyl methacrylate, methacrylic acid tetrahydrochysene furan
One kind or the arbitrary two or more mixing muttered in ester.
Above-mentioned tertiary amine-type reducing agent includes N, accelerine, N, N- dihydroxyethyl p-toluidines, 2,4,6-three
(dimethylamino methyl) phenol, one kind in triethylenediamine or arbitrary two or more mixing.
Above-mentioned polythiol hardener be selected from aliphatic mercaptan, aromatic mercaptans, the mercaptan containing heterocycle, have at least two mercaptos
One kind or arbitrary two or more mixing in the mercaptan compound of base.
Above-mentioned epoxide include bisphenol A epoxide resin, bisphenol F epoxy resin, aliphatic epoxy, have epoxy official
One kind or arbitrary two or more mixing in the epoxide that can be rolled into a ball.
Above-mentioned oxidant includes organic peroxide.
Above-mentioned component A also includes toughener, auxiliary agent and filler.
Above-mentioned toughener includes ABS, SBS, nitrile rubber, one kind in polyester or arbitrary two or more mixing.
Above-mentioned auxiliary agent includes paraffin, aerosil, zinc dimethacrylate, one kind in silane coupling agent or appoints
It anticipates two or more mixing.
Above-mentioned filler include talcum powder, calcium carbonate, wollastonite, aluminium oxide, one kind in barium sulfate or it is arbitrary two kinds with
On mixing.
Above-mentioned B component also includes auxiliary agent and filler.
Above-mentioned auxiliary agent includes plasticizer, is specially benzoates.
Above-mentioned filler include talcum powder, calcium carbonate, wollastonite, aluminium oxide, one kind in barium sulfate or it is arbitrary two kinds with
On mixing.
The present invention is mainly characterized by not on the basis of excessively change acrylic acid adhesive formula, introduces curable epoxide body
System.The problem of improving surfaces of tacky when acrylic acid adhesive cures, improves adhesive strength, the temperature tolerance of acrylic acid adhesive
And weatherability.
The present invention combines epoxy resin and acrylic acid adhesive, and the mercaptan in acrylate glue formula resists
Oxygen resist and Tertiary amine reducing agents can be used for the curing of epoxy resin, and at ambient temperature, acrylic acid and epoxy are co-curing, improve
The intensity and heat-resisting quantity of adhesive, and improve the weatherability of product.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment：
A kind of double cured adhesives of two-component
The double cured adhesives of the two-component are made of following parts by weight of component：
The adhesive includes A, B component, and the component A is by 30 parts of (methyl) acrylic ester monomers, 3 parts of (methyl) propylene
Acid, 30 parts of toughener, 2 parts of reducing agents, 3 parts of mercaptan, 5 parts of auxiliary agents, 16 parts of filler compositions；B component is by 50 parts of epoxy resin 8
Part oxidant, 47 parts of fillers, 10 parts of auxiliary agents compositions.
By above-mentioned adhesive with volume ratio A:B=4:1 ratio mixing, coats 3mm thickening bondlines, observation is not on aluminium-foil paper
With hardening time surface viscosity.Shearing test piece is produced, tests tensile shear strength.
To further demonstrate that the invention advantage, the performance difference of following control group, comparative example and control group is set
Control group 1：Component A is by 30 parts of (methyl) acrylic ester monomers, 3 parts of (methyl) acrylic acid, 30 parts of toughener, and 2
Part reducing agent, 3 parts of mercaptan, 5 parts of auxiliary agents, 16 parts of fillers compositions；B component is by 8 parts of oxidants, 47 parts of fillers, 10 parts of auxiliary agent compositions.
Control group 2：Component A is by 30 parts of (methyl) acrylic ester monomers, 3 parts of (methyl) acrylic acid, 30 parts of toughener, and 2
Part reducing agent, 5 parts of auxiliary agents, 16 parts of fillers compositions；B component is by 50 parts of epoxy resin, and 8 parts of oxidants, 47 parts of fillers, 10 parts are helped
Agent forms.
Performance test data is as shown in table 1：
Table 1
It is good to can be seen that the double cured adhesive surface drying effects of two-component of the present invention by 1 data of table, temperature tolerance with it is resistance to old
The property changed has obtained larger promotion, solves the problems, such as that existing acrylic acid adhesive temperature tolerance and weatherability are insufficient.Also illustrate simultaneously
In the invention, acrylic acid has a good synergistic effect in formula with epoxy resin.
Claims (16)
1. a kind of double cured adhesives of two-component, it is characterised in that the adhesive includes A, B component, and the component A includes,
(a) at least one free radical polymerization monomer, (b) at least one tertiary amine-type reducing agent and (c) polythiol hardener；The B component
Comprising the oxidant that (d) epoxide, (e) can at ambient temperature be reacted with reducing agent.
2. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The free radical polymerization monomer is
Olefinic type monomers.
3. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The olefinic type monomers are (methyl) third
Olefin(e) acid esters or phenylethylene.
4. the double cured adhesives of two-component as claimed in claim 3, it is characterised in that：Described (methyl) the esters of acrylic acid bag
Include one kind in methacrylic acid, methyl methacrylate, tetrahydrofurfuryl methacrylate or arbitrary two or more mixing.
5. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The tertiary amine-type reducing agent includes N,
Accelerine, N, in N- dihydroxyethyl p-toluidines, 2,4,6-three (dimethylamino methyl) phenol, triethylenediamine
One kind or arbitrary two or more mixing.
6. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The polythiol hardener is selected from fat
One kind or two kinds arbitrary in race's mercaptan, aromatic mercaptans, the mercaptan containing heterocycle, the mercaptan compound at least two sulfydryls
Above mixing.
7. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The epoxide includes bis-phenol
One kind or arbitrary two in A epoxy resin, bisphenol F epoxy resin, aliphatic epoxy, the epoxide with epoxy-functional
Kind or more mixing.
8. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The oxidant includes organic peroxy
Compound.
9. the double cured adhesives of two-component as described in claim 1, it is characterised in that：The component A also includes toughener, helps
Agent and filler.
10. the double cured adhesives of two-component as claimed in claim 9, it is characterised in that：The toughener include ABS,
One kind or arbitrary two or more mixing in SBS, nitrile rubber, polyester.
11. the double cured adhesives of two-component as claimed in claim 9, it is characterised in that：The auxiliary agent includes paraffin, gas phase
One kind or arbitrary two or more mixing in silica, zinc dimethacrylate, silane coupling agent.
12. the double cured adhesives of two-component as claimed in claim 9, it is characterised in that：The filler, including talcum
One kind or arbitrary two or more mixing in powder, calcium carbonate, wollastonite, aluminium oxide, barium sulfate.
13. the double cured adhesives of two-component as claimed in claim 9, it is characterised in that：B component also includes auxiliary agent and filler.
14. the double cured adhesives of two-component as claimed in claim 13, it is characterised in that：The auxiliary agent includes plasticizer.
15. the double cured adhesives of two-component as claimed in claim 14, it is characterised in that：The plasticizer is benzoic ether
Class.
16. the double cured adhesives of two-component as claimed in claim 13, it is characterised in that：The filler include talcum powder,
One kind or arbitrary two or more mixing in calcium carbonate, wollastonite, aluminium oxide, barium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711386322.4A CN108102556A (en) | 2017-12-20 | 2017-12-20 | A kind of double cured adhesives of two-component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711386322.4A CN108102556A (en) | 2017-12-20 | 2017-12-20 | A kind of double cured adhesives of two-component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108102556A true CN108102556A (en) | 2018-06-01 |
Family
ID=62210640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711386322.4A Pending CN108102556A (en) | 2017-12-20 | 2017-12-20 | A kind of double cured adhesives of two-component |
Country Status (1)
| Country | Link |
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| CN (1) | CN108102556A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110682638A (en) * | 2018-07-04 | 2020-01-14 | 康利源科技（天津）股份有限公司 | Formula of DMD (DMD) insulating paper |
| CN111334198A (en) * | 2020-03-27 | 2020-06-26 | 顺德职业技术学院 | UV double-component double-curing structural adhesive |
| CN111394013A (en) * | 2020-03-14 | 2020-07-10 | 拓迪化学(上海)有限公司 | Bi-component structural adhesive capable of being subjected to nondestructive testing, preparation method and application thereof, and electronic product |
| WO2020192185A1 (en) * | 2019-03-25 | 2020-10-01 | 3M Innovative Properties Company | Curable compositions, articles therefrom, and methods of making and using same |
| JP2021531389A (en) * | 2018-07-25 | 2021-11-18 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Fast Curing Epoxy Acrylic Liquid Sim |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110682638A (en) * | 2018-07-04 | 2020-01-14 | 康利源科技（天津）股份有限公司 | Formula of DMD (DMD) insulating paper |
| JP2021531389A (en) * | 2018-07-25 | 2021-11-18 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Fast Curing Epoxy Acrylic Liquid Sim |
| JP7259006B2 (en) | 2018-07-25 | 2023-04-17 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Fast curing epoxy acrylic liquid shim |
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| CN111394013A (en) * | 2020-03-14 | 2020-07-10 | 拓迪化学(上海)有限公司 | Bi-component structural adhesive capable of being subjected to nondestructive testing, preparation method and application thereof, and electronic product |
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| CN111334198A (en) * | 2020-03-27 | 2020-06-26 | 顺德职业技术学院 | UV double-component double-curing structural adhesive |
| CN111334198B (en) * | 2020-03-27 | 2021-10-15 | 顺德职业技术学院 | UV double-component double-curing structural adhesive |
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Application publication date: 20180601 |