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CN111154441A - Low-temperature curing single-component epoxy adhesive and preparation method and application thereof - Google Patents

Low-temperature curing single-component epoxy adhesive and preparation method and application thereof Download PDF

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CN111154441A
CN111154441A CN202010006172.5A CN202010006172A CN111154441A CN 111154441 A CN111154441 A CN 111154441A CN 202010006172 A CN202010006172 A CN 202010006172A CN 111154441 A CN111154441 A CN 111154441A
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epoxy
epoxy resin
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fluorine
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CN111154441B (en
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丁远有
李有刚
何彬
余中孝
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Chongqing Zhongke Litai Polymer Materials Co ltd
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Chongqing Zhongke Litai Polymer Materials Co ltd
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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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a low-temperature cured single-component epoxy adhesive and a preparation method and application thereof, belonging to the field of electronic packaging materials. The epoxy glue comprises the following materials in parts by weight: 40-75 parts of epoxy resin, 20-40 parts of fluorine-containing epoxy resin, 5-20 parts of monoepoxy fluorine-containing epoxy monomer, 40-100 parts of latent mercaptan, 0.1-10 parts of accelerator, 0.1-5 parts of coupling agent and 1-10 parts of thixotropic thickener. According to the invention, the fluorine-containing epoxy resin and the single epoxy group fluorine-containing epoxy monomer are adopted, the contents of the epoxy resin, the latent mercaptan curing agent, the accelerator, the coupling agent, the thixotropic thickener and other components are scientifically matched, and the fluorine-containing epoxy resin and the latent mercaptan are combined skillfully, so that the storage stability problem of the low-temperature curing epoxy adhesive is solved, the adhesive obtains excellent water and oxygen resistance, and the reliability in the edge sealing field of the electronic paper display is greatly improved.

Description

Low-temperature curing single-component epoxy adhesive and preparation method and application thereof
Technical Field
The invention belongs to the field of electronic packaging materials, and particularly relates to a low-temperature cured single-component epoxy adhesive and a preparation method and application thereof.
Background
The electronic paper technology is a generic name of a technology, and is generally called as E-paper, and mostly adopts an electrophoretic display (EPD) technology as a display panel, and the display effect of the electronic paper is close to the natural paper effect, so that the reading fatigue is avoided, and therefore, the electronic paper technology is generally called as a display technology which can achieve comfortable reading, ultrathin, light weight, bending and ultra-low power consumption like paper. In the EPD electrophoretic display technology, permeation of oxygen and moisture affects display quality and damages an electronic paper film, and thus a sealing process for an electronic paper protective film is required. The high-hydrophobicity and high-density low-temperature curing epoxy glue is an ideal material for manufacturing the electronic paper seal edge; meanwhile, the electronic paper membrane is not high-temperature resistant, so that the single-component epoxy adhesive with low-temperature curing performance is the first choice.
The existing low-temperature curing epoxy adhesive for edge sealing of electronic paper needs to be stored and transported at-40 ℃, has high transportation cost and short service life, and has defects in oxygen and moisture barrier performance. Therefore, the problems of storage, low-temperature rapid curing and water and oxygen resistance of the adhesive are urgently needed to be solved in the field.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a low temperature cured single-component epoxy adhesive; the second purpose of the invention is to provide a preparation method of the low-temperature curing single-component epoxy adhesive; the invention further aims to provide application of the low-temperature cured single-component epoxy adhesive in the aspect of edge sealing of the electronic paper display.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the low-temperature curing single-component epoxy adhesive comprises the following materials in parts by weight: 40-75 parts of epoxy resin, 20-40 parts of fluorine-containing epoxy resin, 5-20 parts of monoepoxy fluorine-containing epoxy monomer, 40-100 parts of latent mercaptan, 0.1-10 parts of accelerator, 0.1-5 parts of coupling agent and 1-10 parts of thixotropic thickener.
Preferably, the fluorine-containing epoxy resin is one or more of diphenol hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether and bis- (hexafluorohydroxypropyl) benzene diglycidyl ether.
Preferably, the monoepoxy fluorine-containing epoxy monomer is one or more of glycidoxypropyl tetrafluoropropyl ether, glycidoxypropyl hexafluoro butyl ether, glycidoxypropyl octafluoropentyl ether and glycidoxypropyl dodecafluoroheptyl ether.
Preferably, the latent mercaptan is prepared by: sequentially adding an epoxy group-containing compound and a monothiocarboxylic acid compound, adding a quaternary ammonium salt as a catalyst, reacting for 2-6 h at 60-100 ℃, and distilling under reduced pressure to obtain latent mercaptan;
the compound containing the epoxy group is any one or more of trimethylolpropane triglycidyl ether, 1,3, 5-triglycidyl isocyanurate and pentaerythritol tetraglycidyl ether;
the monothiocarboxylic acid compound is thioacetic acid or thiopropionic acid;
the molar ratio of epoxy groups in the epoxy group-containing compound to monothiocarboxylic acid compounds is 1: 1.2-1.5; the mass of the catalyst accounts for 0.5-1.0% of the total mass of the compound containing the epoxy group and the monothiocarboxylic acid compound.
More preferably, the quaternary ammonium salt is tetrabutylammonium bromide.
Preferably, the epoxy resin is one or more of bisphenol a epoxy resin 128, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol a epoxy resin, alicyclic epoxy resin and epoxy modified silicone resin.
Preferably, the accelerator is an imidazole adduct or a tertiary amine adduct.
More preferably, the imidazole adduct is one or more of PN-23, PN-23J and PN-40 of the ajinomoto.
More preferably, the tertiary amine adduct is one or more of MY-24, MY-25 and MY-H of the japanese gourmet powder
Preferably, the coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane (KH-560), gamma-glycidoxypropyltriethoxysilane (KH-561), gamma-glycidoxypropylmethyldimethoxysilane (KH-562), gamma-glycidoxypropylmethyldiethoxysilane (KH-563), or 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane (KH-530).
Preferably, the thixotropic thickener is fumed silica treated by a coupling agent or a long-chain fatty acid.
More preferably, the fumed silica is carbopol TS720 and watt
Figure BDA0002355375140000021
H18, H20, degussa R972 or R974.
2. The preparation method of the low-temperature curing single-component epoxy adhesive comprises the following steps:
(1) adding epoxy resin, fluorine-containing epoxy resin, a monoepoxy fluorine-containing epoxy monomer, a coupling agent and a thixotropic thickening agent into a planetary reaction kettle, and stirring for 1-1.5 hours at 30-60 ℃ to disperse the epoxy resin, the fluorine-containing epoxy resin, the monoepoxy fluorine-containing epoxy monomer and the thixotropic thickening agent;
(2) after the reaction in the step (1) is finished, cooling to below 30 ℃, sequentially adding latent mercaptan and an accelerant, and stirring for 1-1.5 hours at below 30 ℃;
(3) and (3) taking out the mixture after the stirring in the step (2), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
Preferably, the dispersing stirring speed of the reaction kettle is 1000-1500 r/min, the revolution stirring speed is 30-80 r/min, and the vacuum degree is-0.09-0.1 MPa in the stirring process.
3. Application of low-temperature cured single-component epoxy adhesive in edge sealing of electronic paper display
The invention has the beneficial effects that:
1. the invention discloses a low-temperature cured single-component epoxy adhesive, which can improve the hydrophobicity of a polymer system, reduce the surface energy of the polymer and greatly improve the oxygen-blocking and water-blocking performances of the polymer by adopting fluorine-containing epoxy resin and a monoepoxy fluorine-containing epoxy monomer; meanwhile, the contents of epoxy resin, a latent mercaptan curing agent, an accelerator, a coupling agent, a thixotropic thickener and other components are scientifically matched to obtain the single-component epoxy adhesive with low-temperature curing performance;
2. according to the invention, by skillfully combining the fluorine-containing epoxy resin and the latent mercaptan, the problem of storage stability of the low-temperature curing epoxy adhesive is solved, the adhesive has excellent water and oxygen resistance, and the reliability in the field of edge sealing of electronic paper displays is greatly improved;
3. the epoxy adhesive contains the latent mercaptan curing agent, can perform a ring-opening reaction with an epoxy group at a proper temperature to realize a curing effect, does not need to add a stabilizer, does not need low-temperature storage, reduces the storage and transportation cost, and greatly prolongs the service life of the adhesive, and the latent mercaptan curing agent has the advantages that the latent mercaptan curing agent performs an addition reaction with thioacetic acid through the epoxy group of an epoxy compound, takes quaternary ammonium salt as a catalyst, performs a reaction at a temperature of 60-100 ℃, has short reaction time and high conversion rate, protects a mercapto group in the thiocarboxylic acid after the reaction is completed, seals the thiol group, exists in the form of β -hydroxythiocarboxylate, can perform rearrangement reaction with the thiol group to transfer to a hydroxyl oxygen atom at the proper temperature of the catalyst, exposes the thiol group, and performs a ring-opening reaction with the epoxy group to realize the curing effect;
4. the invention also provides a preparation method of the low-temperature curing single-component epoxy adhesive, which has the advantages of simple operation, mild reaction conditions and short reaction time, and can realize industrial mass preparation.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
The low-temperature curing single-component epoxy adhesive is prepared by the following method:
(1) preparation of latent mercaptan: sequentially adding an epoxy-containing compound (1,3, 5-triglycidyl isocyanurate) and thioacetic acid, wherein the molar ratio of epoxy groups in the 1,3, 5-triglycidyl isocyanurate to the thioacetic acid is 1:1.2, adding tetrabutylammonium bromide serving as a catalyst (the mass of the tetrabutylammonium bromide is 0.5 percent of the total mass of the 1,3, 5-triglycidyl isocyanurate and the thioacetic acid), reacting for 2 hours at 95 ℃, and distilling under reduced pressure to obtain latent mercaptan TGICS;
(2) adding 45 parts by weight of bisphenol A epoxy resin 128, 20 parts by weight of bisphenol S epoxy resin, 20 parts by weight of diphenol hexafluoropropane diglycidyl ether, 15 parts by weight of glycidyl propyl octafluoropentyl ether, 1.0 part by weight of coupling agent (KH-560) and 1.0 part by weight of thixotropic thickening agent (Kabot TS720) into a planetary reaction kettle, and stirring for 1.5 hours at 30 ℃ to disperse the bisphenol A epoxy resin, wherein the high-speed dispersion rate in the stirring process is 1400r/min, the revolution stirring rate is 50r/min and the vacuum degree is-0.1 MPa;
(3) after the reaction in the step (2) is finished, cooling to below 30 ℃, sequentially adding 100 parts of latent mercaptan TGICS and 1.0 part of PN-23 accelerator, stirring for 1.0h, setting the high-speed dispersion rate to be 1000r/min, the revolution stirring rate to be 80r/min and the vacuum degree to be-0.09 MPa;
(4) and (4) taking out the mixture after the stirring in the step (3), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
Example 2
The low-temperature curing single-component epoxy adhesive is prepared by the following method:
(1) preparation of latent mercaptan: sequentially adding an epoxy-containing compound (trimethylolpropane triglycidyl ether) and a monothiopropionic acid compound (thiopropionic acid), wherein the molar ratio of epoxy groups in the trimethylolpropane triglycidyl ether to the thiopropionic acid is 1:1.5, adding tetrabutylammonium bromide as a catalyst (the mass of the tetrabutylammonium bromide is 1.0 percent of the total mass of the trimethylolpropane triglycidyl ether and the thiopropionic acid), reacting at 85 ℃ for 6h, and distilling under reduced pressure to obtain latent mercaptan TMPEGS;
(2) 20 parts by weight of UVR6103 epoxy resin, 10 parts by weight of bisphenol F epoxy resin, 25 parts by weight of 4080E hydrogenated bisphenol A epoxy resin, 40 parts by weight of octafluorobiphenyl diglycidyl ether, 5 parts by weight of glycidylpropyldodecafluoroheptyl ether, 2.0 parts by weight of coupling agent (KH-561) and 5.0 parts by weight of thixotropic thickener (Wake's Ke)
Figure BDA0002355375140000041
H18) Adding into a planetary reaction kettle, and stirring at 60 deg.C for 1h to disperse, wherein the high speed dispersion rate in the stirring process is 1300r/min, the revolution stirring rate is 60r/min, and the vacuum degree is-0.09 MPa;
(3) after the reaction in the step (2) is finished, cooling to below 30 ℃, sequentially adding 60 parts of latent mercaptan TMPEGS and 5.0 parts of accelerant PN-40, stirring for 1.5 hours at below 30 ℃, and setting the high-speed dispersion rate to be 1500r/min, the revolution stirring rate to be 30r/min and the vacuum degree to be-0.1 MPa in the stirring process;
(4) and (4) taking out the mixture after the stirring in the step (3), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
Example 3
The low-temperature curing single-component epoxy adhesive is prepared by the following method:
(1) preparation of latent mercaptan: sequentially adding an epoxy group-containing compound (pentaerythritol tetraglycidyl ether) and a monothioic acid compound (thioacetic acid), wherein the molar ratio of epoxy groups in the pentaerythritol tetraglycidyl ether to the thioacetic acid is 1:1.3, adding tetrabutylammonium bromide as a catalyst (the mass of the tetrabutylammonium bromide is 0.8 percent of the total mass of the pentaerythritol tetraglycidyl ether and the thioacetic acid), reacting for 4 hours at 90 ℃, and distilling under reduced pressure to obtain latent mercaptan PETEGS;
(2) adding 25 parts by weight of UVR6103 epoxy resin, 40 parts by weight of 4080E hydrogenated bisphenol A epoxy resin, 25 parts by weight of bis- (hexafluorohydroxypropyl) benzene diglycidyl ether, 10 parts by weight of glycidyl propyl hexafluoro butyl ether, 1.0 part by weight of coupling agent (KH-563) and 3.0 parts by weight of thixotropic thickener (Desgassic R972) into a planetary reaction kettle, and stirring at 40 ℃ for 1.2h to disperse, wherein the high-speed dispersion rate in the stirring process is 1200R/min, the revolution stirring rate is 70R/min and the vacuum degree is-0.095 MPa;
(3) after the reaction in the step (2) is finished, cooling to below 30 ℃, sequentially adding 72 parts of latent mercaptan PETEGS and 5.0 parts of MY-H accelerator, stirring for 1.2 hours at below 30 ℃, and setting the high-speed dispersion rate to be 1200r/min, the revolution stirring rate to be 60r/min and the vacuum degree to be-0.095 MPa in the stirring process;
(4) and (4) taking out the mixture after the stirring in the step (3), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
Example 4
The low-temperature curing single-component epoxy adhesive is prepared by the following method:
(1) preparation of latent mercaptan: sequentially adding an epoxy-containing compound (trimethylolpropane triglycidyl ether) and a monothiopropionic acid compound (thiopropionic acid), wherein the molar ratio of epoxy groups in the trimethylolpropane triglycidyl ether to the thiopropionic acid is 1:1.4, adding tetrabutylammonium bromide as a catalyst (the mass of the tetrabutylammonium bromide is 0.6 percent of the total mass of the trimethylolpropane triglycidyl ether and the thiopropionic acid), reacting for 3 hours at 95 ℃, and distilling under reduced pressure to obtain latent mercaptan TMPEGS;
(2) adding 25 parts by weight of UVR6103 epoxy resin, 35 parts by weight of epoxy modified organic silicon resin, 20 parts by weight of diphenol hexafluoropropane diglycidyl ether, 20 parts by weight of glycidyl propyl tetrafluoropropyl ether, 1.0 part by weight of coupling agent (KH-530) and 5.0 parts by weight of thixotropic thickening agent (R974) into a planetary reaction kettle, and stirring for 1.2 hours at 50 ℃ to disperse the materials, wherein the high-speed dispersion rate in the stirring process is 1400R/min, the revolution stirring rate is 55R/min, and the vacuum degree is-0.09 MPa;
(3) after the reaction in the step (2) is finished, cooling to below 30 ℃, sequentially adding 72 parts of latent mercaptan TMPEGS and 3.0 parts of PN-23J accelerator, stirring for 1.2 hours at below 30 ℃, and setting the high-speed dispersion rate to be 1200r/min, the revolution stirring rate to be 60r/min and the vacuum degree to be-0.095 MPa in the stirring process;
(4) and (4) taking out the mixture after the stirring in the step (3), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
Comparative example 1
According to parts by weight, 25 parts of UVR6103 epoxy resin, 35 parts of epoxy modified organic silicon resin, 20 parts of diphenol hexafluoropropane diglycidyl ether, 20 parts of glycidyl propyl tetrafluoropropyl ether, 72 parts of trimethylolpropane tri (3-mercaptopropionic acid) ester, 3.0 parts of PN-23J accelerator, 0.5 part of barbituric acid, 1.0 part of coupling agent (KH-560) and 5.0 parts of thixotropic thickener (Kabot TS720) are prepared to form the epoxy glue.
Comparative example 2
According to parts by weight, 40 parts of 128 epoxy resin, 30 parts of 4080E hydrogenated bisphenol A epoxy resin, 30 parts of UVR6103 epoxy resin, 60 parts of latent mercaptan TMPEGS, 3.0 parts of PN-23J accelerator, 1.0 part of coupling agent (KH-560) and 0.3 part of epoxy resin
Defoaming agent, 3.0 thixotropic thickener (R-974) to form epoxy glue.
The epoxy adhesives prepared in examples 1 to 4 and comparative examples 1 to 2 were tested for storage stability, water absorption, shear strength and moisture permeability, and the corresponding epoxy adhesive was used for edge sealing of the electronic paper display and then water seepage was observed, and the obtained results are shown in table 1.
TABLE 1 Performance test results for different epoxy glues
Figure BDA0002355375140000061
As can be seen from the performance comparison results in Table 1, the low-temperature cured single-component epoxy adhesive is obtained by adopting the fluorine-containing epoxy resin and the monoepoxy fluorine-containing epoxy monomer to prepare the latent mercaptan, scientifically matching the contents of the components such as the epoxy resin, the latent mercaptan curing agent, the accelerator, the coupling agent, the thixotropic thickener and the like, and can improve the hydrophobicity of the epoxy adhesive, reduce the surface energy of a polymer and greatly improve the oxygen-blocking and water-blocking performances of the epoxy adhesive; meanwhile, the problem of storage stability of the low-temperature cured epoxy adhesive is solved, the adhesive has excellent water resistance and oxygen resistance, and the reliability in the field of edge sealing of electronic paper displays is greatly improved.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (10)

1. The low-temperature curing single-component epoxy adhesive is characterized by comprising the following materials in parts by weight: 40-75 parts of epoxy resin, 20-40 parts of fluorine-containing epoxy resin, 5-20 parts of monoepoxy fluorine-containing epoxy monomer, 40-100 parts of latent mercaptan, 0.1-10 parts of accelerator, 0.1-5 parts of coupling agent and 1-10 parts of thixotropic thickener.
2. The low-temperature curing single-component epoxy adhesive as claimed in claim 1, wherein the fluorine-containing epoxy resin is one or more of diphenol hexafluoropropane diglycidyl ether, octafluorobiphenyl diglycidyl ether and bis- (hexafluorohydroxypropyl) benzene diglycidyl ether.
3. The low-temperature curing single-component epoxy adhesive as claimed in claim 1, wherein the monoepoxy fluorine-containing epoxy monomer is one or more of glycidoxypropyl tetrafluoropropyl ether, glycidoxypropyl hexafluoro butyl ether, glycidoxypropyl octafluoropentyl ether and glycidoxypropyl dodecafluoroheptyl ether.
4. The low-temperature curing one-component epoxy adhesive according to claim 1, wherein the latent mercaptan is prepared by the following method: sequentially adding an epoxy group-containing compound and a monothiocarboxylic acid compound, adding a quaternary ammonium salt as a catalyst, reacting for 2-6 h at 60-100 ℃, and distilling under reduced pressure to obtain latent mercaptan;
the compound containing the epoxy group is any one or more of trimethylolpropane triglycidyl ether, 1,3, 5-triglycidyl isocyanurate and pentaerythritol tetraglycidyl ether;
the monothiocarboxylic acid compound is thioacetic acid or thiopropionic acid;
the molar ratio of epoxy groups in the epoxy group-containing compound to monothiocarboxylic acid compounds is 1: 1.2-1.5; the mass of the catalyst accounts for 0.5-1.0% of the total mass of the compound containing the epoxy group and the monothiocarboxylic acid compound.
5. The low-temperature curing single-component epoxy adhesive according to claim 1, wherein the epoxy resin is one or more of bisphenol A epoxy resin 128, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, alicyclic epoxy resin and epoxy modified silicone resin.
6. The low-temperature curing one-component epoxy adhesive as claimed in claim 1, wherein the accelerator is an imidazole adduct or a tertiary amine adduct; the thixotropic thickener is fumed silica treated by a coupling agent or long-chain fatty acid.
7. The low-temperature curing single-component epoxy adhesive as claimed in claim 1, wherein the coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane.
8. The preparation method of the low-temperature curing one-component epoxy glue as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) adding epoxy resin, fluorine-containing epoxy resin, a monoepoxy fluorine-containing epoxy monomer, a coupling agent and a thixotropic thickening agent into a planetary reaction kettle, and stirring for 1-1.5 hours at 30-60 ℃ to disperse the epoxy resin, the fluorine-containing epoxy resin, the monoepoxy fluorine-containing epoxy monomer and the thixotropic thickening agent;
(2) after the reaction in the step (1) is finished, cooling to below 30 ℃, sequentially adding latent mercaptan and an accelerant, and stirring for 1-1.5 hours at below 30 ℃;
(3) and (3) taking out the mixture after the stirring in the step (2), subpackaging the mixture into a needle cylinder, and performing centrifugal defoaming to obtain the low-temperature cured single-component epoxy adhesive.
9. The preparation method of the low-temperature curing single-component epoxy glue according to claim 8, wherein the stirring speed of the reaction kettle is 1000-1500 r/min, the revolution stirring speed is 30-80 r/min, and the vacuum degree is-0.09-0.1 MPa in the stirring process.
10. The use of the low-temperature curing one-component epoxy adhesive of any one of claims 1 to 7 in edge sealing of electronic paper displays.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112625218A (en) * 2020-12-17 2021-04-09 成都硅宝科技股份有限公司 Epoxy resin for cutting water-resistant silicon rod and preparation method thereof
CN114085638A (en) * 2021-12-22 2022-02-25 南宝树脂（佛山）有限公司 Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof
CN114891470A (en) * 2022-04-12 2022-08-12 重庆邦锐特新材料有限公司 Epoxy sealant and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0319919A2 (en) * 1987-12-08 1989-06-14 Daikin Industries, Limited Adhesive composition
US20020058210A1 (en) * 1998-03-10 2002-05-16 Hiromichi Noguchi Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same
JP2005181986A (en) * 2003-11-28 2005-07-07 Shin Etsu Chem Co Ltd Sealing agent composition for liquid crystal display element
RU2285709C1 (en) * 2005-04-18 2006-10-20 Михаил Юрьевич Квасников Water-resistant epoxy composition
CN102191002A (en) * 2011-04-02 2011-09-21 烟台德邦科技有限公司 High-humidity and high-temperature resisting single component epoxy adhesive and its preparation method
CN105837798A (en) * 2015-01-14 2016-08-10 中国科学院宁波材料技术与工程研究所 Latent polythiol curing agent, and synthetic method and application of latent polythiol curing agent
CN107033330A (en) * 2017-05-24 2017-08-11 浙江工业大学 A kind of resin of thiol group containing resting form, its cured product and synthetic method with epoxy resin
CN107188869A (en) * 2017-06-22 2017-09-22 华中师范大学 The preparation and application of fluorine-containing epoxy resin monomer and performed polymer and its initiator
CN108977145A (en) * 2017-05-31 2018-12-11 烟台信友新材料股份有限公司 A kind of high moisture-proof temperature curing epoxy low glue and preparation method thereof
CN110499130A (en) * 2018-05-17 2019-11-26 深圳市绎立锐光科技开发有限公司 Visible light curing adhesive and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0319919A2 (en) * 1987-12-08 1989-06-14 Daikin Industries, Limited Adhesive composition
US20020058210A1 (en) * 1998-03-10 2002-05-16 Hiromichi Noguchi Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same
JP2005181986A (en) * 2003-11-28 2005-07-07 Shin Etsu Chem Co Ltd Sealing agent composition for liquid crystal display element
RU2285709C1 (en) * 2005-04-18 2006-10-20 Михаил Юрьевич Квасников Water-resistant epoxy composition
CN102191002A (en) * 2011-04-02 2011-09-21 烟台德邦科技有限公司 High-humidity and high-temperature resisting single component epoxy adhesive and its preparation method
CN105837798A (en) * 2015-01-14 2016-08-10 中国科学院宁波材料技术与工程研究所 Latent polythiol curing agent, and synthetic method and application of latent polythiol curing agent
CN107033330A (en) * 2017-05-24 2017-08-11 浙江工业大学 A kind of resin of thiol group containing resting form, its cured product and synthetic method with epoxy resin
CN108977145A (en) * 2017-05-31 2018-12-11 烟台信友新材料股份有限公司 A kind of high moisture-proof temperature curing epoxy low glue and preparation method thereof
CN107188869A (en) * 2017-06-22 2017-09-22 华中师范大学 The preparation and application of fluorine-containing epoxy resin monomer and performed polymer and its initiator
CN110499130A (en) * 2018-05-17 2019-11-26 深圳市绎立锐光科技开发有限公司 Visible light curing adhesive and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
WANG, CZ 等: "Improvement of surface and moisture resistance of epoxy resins with fluorinated glycidyl ether", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
李雪等: "含氟环氧树脂的研究进展", 《中国胶粘剂》 *
王成忠等: "含氟缩水甘油醚的合成及表征", 《化工新型材料》 *
陈卫东等: "高性能环氧树脂胶黏剂研究概况", 《化工科技》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112625218A (en) * 2020-12-17 2021-04-09 成都硅宝科技股份有限公司 Epoxy resin for cutting water-resistant silicon rod and preparation method thereof
CN112625218B (en) * 2020-12-17 2023-02-14 成都硅宝科技股份有限公司 Epoxy resin for cutting water-resistant silicon rod and preparation method thereof
CN114085638A (en) * 2021-12-22 2022-02-25 南宝树脂（佛山）有限公司 Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof
CN114085638B (en) * 2021-12-22 2023-02-21 南宝树脂（佛山）有限公司 Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof
CN114891470A (en) * 2022-04-12 2022-08-12 重庆邦锐特新材料有限公司 Epoxy sealant and preparation method thereof
CN114891470B (en) * 2022-04-12 2023-08-04 重庆邦锐特新材料有限公司 Epoxy sealant and preparation method thereof

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