CN114891470A - Epoxy sealant and preparation method thereof - Google Patents
Epoxy sealant and preparation method thereof Download PDFInfo
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- CN114891470A CN114891470A CN202210381442.XA CN202210381442A CN114891470A CN 114891470 A CN114891470 A CN 114891470A CN 202210381442 A CN202210381442 A CN 202210381442A CN 114891470 A CN114891470 A CN 114891470A
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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
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- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
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- 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
- C08G59/50—Amines
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The epoxy sealant comprises a component A and a component B, wherein the component A comprises the following components in mass percent: 40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-30 parts of filler, 0-3 parts of anti-settling agent, 0-3 parts of coupling agent and 0-3 parts of whitening agent; the component B comprises a curing agent, and the curing agent comprises modified imidazole. The epoxy sealant has the characteristics of low water vapor permeation and oxygen barrier, low viscosity, low-temperature quick curing and the like through modification, and the reworkability is obviously improved.
Description
Technical Field
The invention relates to the field of materials, in particular to an epoxy sealant and a preparation method thereof.
Background
Electronic paper, also called digital paper and digital paper, is an ultra-thin and ultra-light display screen. The display effect of the liquid crystal display is close to that of common paper, so that people can read comfortably, and the liquid crystal display can be converted and refreshed to display new contents like a common liquid crystal display. Electronic ink is applied to the display screen to display information such as text and pictures. Because the use of the electronic paper reduces the felling of wood and is beneficial to realizing green ecology, people pursue the electronic paper.
The electronic paper has the advantages of convenience in reading and carrying, large information storage capacity, resource saving, high transmission speed and the like, and the electronic paper is gradually integrated into the life of people due to the advantages, so that the electronic paper has a wide development prospect.
The existing paper books are thick, the time of people is always scattered, and people can only carry the books with one book when wanting to read the whole book. Compared with a paper book, the volume of the electronic paper is smaller, new reading physical examination is given to the ultrathin pages, and the book contents only need to be downloaded to the electronic paper. On a bus, on a subway and under the condition that you want to read by utilizing scattered time, the user only needs to take the electronic paper out of the bag and click to read to see the wanted content. Although mobile devices such as ordinary mobile phones and pads also have the function of reading electronic books, the electronic paper is not beneficial to protecting eyes, and the electronic paper can protect the eyes. The electronic paper simulates a paper book, adopts a non-backlight system, and obviously enhances the protection effect on eyes compared with a mobile phone, a Pad and the like.
Electronic paper can be considered as a special thin film. People can display information such as characters, pictures and the like by coating electronic ink on the thin film and carrying out background control according to different contents. The display technology of electronic paper is mainly classified into four display technologies, namely, cholesteric liquid crystal display (Ch-LCD), electrophoretic display (EPD), bistable nematic liquid crystal display (BiT NLCD), and electronic powder liquid crystal display (QR-LPD). The four different display technologies have advantages and disadvantages, but their promotion to the development of electronic paper technology is undoubted.
The electronic paper screen is sensitive to water vapor and oxygen, and when water vapor and oxygen enter the device, the adhesion between the cathode and the light-emitting layer can be influenced, so that chemical reaction occurs in the organic film layer. These all lead to a drastic degradation of the optoelectronic properties during the process, resulting in rapid aging and failure of the device. Consequently when the electronic paper screen equipment, the frame need seal with the glue that the one deck can separation steam and separation oxygen infiltration, and electronic screen subassembly is not high temperature resistant, and the frame belongs to the line of a thread seam in the assembly process moreover, therefore glue needs fine mobility. The existing glue can not meet the sealing requirement.
The existing sealant for sealing the electronic paper screen frame is poor in flexibility, poor in repairability and poor in barrier property, and needs to be solved urgently.
Disclosure of Invention
According to a first aspect, in one embodiment, an epoxy sealant is provided, which comprises a component A and a component B, wherein the component A comprises the following components by mass:
40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-30 parts of filler, 0-3 parts of anti-settling agent, 0-3 parts of coupling agent and 0-3 parts of whitening agent;
the component B comprises a curing agent, and the curing agent comprises modified imidazole.
According to a second aspect, in one embodiment, there is provided a method for preparing an epoxy sealant according to the first aspect, comprising:
the preparation step of the component A comprises the steps of mixing epoxy resin, polyfunctional epoxy resin, diluent, filler, anti-settling agent, coupling agent and whitening agent according to the formula amount to prepare the component A;
the preparation step of the component B comprises the steps of mixing all the curing agents according to the formula amount to prepare the component B;
and the mixing step comprises mixing the component A and the component B according to the formula amount to obtain the sealant.
According to the epoxy sealant and the preparation method thereof disclosed by the embodiment, the epoxy sealant disclosed by the invention has the characteristics of low water vapor permeability, oxygen barrier, low viscosity, low-temperature rapid curing and the like through modification, and the repairability is obviously improved.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. Wherein like elements in different embodiments are numbered with like associated elements. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances. In some instances, certain operations related to the present application have not been shown or described in detail in order to avoid obscuring the core of the present application from excessive description, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification are for the purpose of clearly describing one embodiment only and are not meant to be necessarily order unless otherwise indicated where a certain order must be followed.
The numbering of the components as such, e.g., "first", "second", etc., is used herein only to distinguish the objects as described, and does not have any sequential or technical meaning. The terms "connected" and "coupled" when used herein, unless otherwise indicated, include both direct and indirect connections (couplings).
In one embodiment, the invention provides an epoxy sealant applicable to a frame of an electronic paper display screen, which has the characteristics of low water vapor permeation and oxygen barrier, low viscosity, low-temperature rapid curing and the like.
According to the first aspect, in one embodiment, an epoxy sealant is provided, which comprises a component A and a component B, wherein the component A comprises the following components by mass:
40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-30 parts of filler, 0-3 parts of anti-settling agent, 0-3 parts of coupling agent and 0-3 parts of whitening agent;
the component B comprises a curing agent, and the curing agent comprises modified imidazole. Latent curing agents having low viscosity, high purity, and long working time are preferred.
According to the invention, the component A and the component B are mixed to prepare the epoxy sealant finished product, and the component A and the component B do not need to be prepared at present when in use, so that the use convenience of the product is effectively improved, and the performance of the product is more stable.
In one embodiment, component a comprises the following components by mass:
40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-28.5 parts of filler, 0.5-3 parts of anti-settling agent, 0.5-3 parts of coupling agent and 0.5-3 parts of whitening agent.
In one embodiment, component a: and the component B is (100-110): (5-30).
In one embodiment, the component a: and the component B is (100-110): 10.
in one embodiment, component a: and the component B is (100-101): 10.
in one embodiment, the curing agent is a self-made liquid imidazole modified curing agent. Polyol glycidyl ether with low viscosity is used for reacting with imidazole, and H atoms on 1 position of imidazole and epoxy groups are subjected to addition reaction to prepare the low-viscosity, flexible and latent modified imidazole.
In one embodiment, the modified imidazole includes, but is not limited to, at least one of modified imidazoles (r), (g), and (g) shown in the following structures:
the structural formula of the modified imidazole is as follows:
n is an integer of 1 to 3;
the structural formula of the modified imidazole is as follows:
n is an integer of 1 to 3;
the structural formula of the modified imidazole is as follows:
in one embodiment, the synthesis method of the modified imidazoles (i), (ii) and (iii) is as follows:
modified imidazole: 164g of 2-methylimidazole and xylene were put in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 652g of polypropylene glycol diglycidyl ether were added dropwise at 120 ℃ over 2 h. The reaction product was insoluble in xylene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct.
Modified imidazole (II): 220g of 2-ethyl-4-methylimidazole and xylene are placed in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 652g of polypropylene glycol diglycidyl ether were added dropwise at 120 ℃ over 2 h. The reaction product was insoluble in xylene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct.
Modified imidazole (III): 220g of 2-ethyl-4-methylimidazole and xylene are placed in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 202g of butanediol diglycidyl ether are added dropwise at 120 ℃ over a period of 2 h. The reaction product was insoluble in xylene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct.
In one embodiment, the epoxy resin includes, but is not limited to, at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, aromatic polyacrylate type epoxy resin, hydrogenated epoxy resin, resorcinol diglycidyl ether (CAS number: 101-90-6), aliphatic alcohol polyglycidyl ether, and the like. High purity, low viscosity bisphenol F type epoxy resins are preferred.
In one embodiment, the multifunctional epoxy resin includes, but is not limited to, at least one of glycerol glycidyl ether (CAS No.: 25038-04-4), pentaerythritol glycidyl ether (CAS No.: 3126-63-4), triglycidyl-m-aminophenol (CAS No.: 71604-74-5), tetraglycidyl diaminodiphenylmethane, N, N, N ', N' -tetracyclooxypropyl-4, 4 '-diaminodiphenylmethane (CA S No.: 28768-32-3), 2, 2' - [ methine-tris (phenoxymethylene) ] tris (ethylene oxide) (CAS No.: 66072-38-6), ethylene oxide, 2,2- [ [2- (ethylene oxide YL methoxy) -1, 3-phenyl ENE ] bis (methylene) ] bis (CAS No.: 13561-08-5), and the like, among them, low-viscosity and high-purity glycerol glycidyl ether is preferable.
In one embodiment, the diluent includes, but is not limited to, at least one of 4-tert-butylphenyl glycidyl ether (also known as p-tert-butylphenyl glycidyl ether, CAS registry No. 3101-60-8), phenyl glycidyl ether (CAS registry No. 122-60-1), 2-toluene glycidyl ether (also known as o-benzyl glycidyl ether, CAS registry No. 2210-79-9), cyclohexanedimethanol diglycidyl ether, dipropylene glycol monomethyl ether, and the like. Preferably, a high purity diluent is used.
In one embodiment, the filler includes at least one of an organic filler and an inorganic filler.
In one embodiment, the filler has an average particle size of 3 to 15 μm.
In one embodiment, the organic filler includes, but is not limited to, at least one of polyethylene (powder), polypropylene (powder), polyacrylonitrile (also known as PAN, in powder form), polymethylmethacrylate (PMMA powder), ABS high-rubber powder, polybutadiene rubber, and the like.
In one embodiment, the polybutadiene rubber comprises a polybutadiene rubber having a core-shell structure.
In one embodiment, the inorganic filler includes, but is not limited to, at least one of hydrophobic silica powder, talc powder, ball silica, mica powder, montmorillonite, alumina, and the like. The inorganic filler can improve the water vapor barrier property of the cured epoxy system in the system. The spherical silicon is spherical silicon dioxide.
In one embodiment, the inorganic filler is preferably at least one of hydrophobic silica flakes, talc, mica powder, montmorillonite, alumina, and the like.
In one embodiment, the anti-settling agent includes, but is not limited to, fumed silica.
In one embodiment, the coupling agent includes, but is not limited to, at least one of gamma- (2, 3-epoxypropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane.
In one embodiment, the whitening agent includes, but is not limited to, titanium dioxide.
In one embodiment, the sealant is used for sealing the frame of the electronic paper display screen.
According to a second aspect, in one embodiment, there is provided a method for preparing an epoxy sealant according to the first aspect, comprising:
the preparation step of the component A comprises the steps of mixing epoxy resin, polyfunctional epoxy resin, diluent, filler, anti-settling agent, coupling agent and whitening agent according to the formula amount to prepare the component A;
the preparation step of the component B comprises the steps of mixing all the curing agents according to the formula amount to prepare the component B; if the component B only contains one curing agent, the curing agent is weighed according to the formula amount.
And the mixing step comprises mixing the component A and the component B according to the formula amount to obtain the sealant.
The preparation steps of the component A and the component B are not sequential, and any one of the steps can be carried out first, or the two steps can be carried out simultaneously.
In one embodiment, in the mixing step, the temperature of the material is less than or equal to 10 ℃ during mixing.
In one embodiment, in the mixing step, the relative humidity of the air is less than or equal to 30% during mixing.
In one embodiment, in the mixing step, the mixing is performed under vacuum.
The temperature and the humidity both reduce the activity of the system and improve the storage stability of the system, and the vacuum function is to extract air bubbles, small molecules and partial water vapor in the system so as to improve the stability of the system.
In one embodiment, in the mixing step, the prepared sealant is stored at-40 ± 2 ℃. The main functions of low-temperature storage are to reduce the activity of the product in the storage process and improve the storage Life (Shelf Life) of the product.
In one embodiment, in the step of preparing the component A, the component A is prepared and then refrigerated at-5 ℃ for 10-12 h. The refrigeration is used to lower the temperature of the materials during mixing, and also to reduce the activity of the system.
In one embodiment, in the step of preparing the component B, the component B is refrigerated at-5 ℃ for 12 hours after being prepared. The refrigeration is used to lower the temperature of the materials during mixing, and also to reduce the activity of the system.
In one embodiment, the invention provides a single-component epoxy sealant which is applied to frame sealing of an electronic paper display screen, has low water vapor and oxygen barrier property, low viscosity and low-temperature quick curing. According to the invention, a high-compactness network structure is formed by reacting polyfunctional epoxy resin with polyfunctional hydrophobic curing agent to realize water vapor barrier and oxygen barrier; the organic filler is used as a system filler to reduce the modulus of the cured adhesive layer so as to meet the aging performance test of the product; the low-viscosity main body resin, the curing agent and a small amount of diluent are selected to reduce the viscosity of the system so as to meet the process requirement of sealing the electronic paper frame; the high-purity resin, the curing agent, the filler and the diluent are selected, the hydrophobic curing agent which has longer operation time and can realize low-temperature curing is selected, and a special low-temperature production process is adopted to achieve longer operation time and meet the actual sizing requirement.
The preparation process of the present invention is further described in detail below with reference to several examples.
The preparation method of the electronic paper sealant provided in the embodiment 1-3 and the comparative example 1-6 comprises the following steps:
firstly, preparation of component A
1. Weighing epoxy resin, polyfunctional epoxy resin, diluent, coupling agent, whitening agent and anti-settling agent (gas silicon, namely fumed silica) according to the weight percentage of the raw materials in the component A in the table 1 in the total weight of the raw materials, putting the raw materials into a reaction kettle, and stirring and mixing the raw materials;
2. weighing organic fillers, dividing into three equal batches, adding into the reaction kettle in the step 1, wherein the adding time interval of each batch is 15min, stirring and mixing for 30min after the adding is finished, and then vacuumizing for 2h under the condition of-0.98 Mpa.
3. The prepared component A (namely Part A) is put into a refrigerator at the temperature of minus 5 ℃ for refrigeration for 12 hours for later use.
Secondly, preparation of component B
4. The component B (namely Part B) is measured according to the mass dosage in the table 1, is uniformly dispersed and is put into a refrigerator with the temperature of minus 5 ℃ for refrigeration for 12 hours for standby.
The synthesis method of the modified imidazoles comprises the following steps:
modified imidazole: 164g of 2-methylimidazole and xylene were put in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 652g of polypropylene glycol diglycidyl ether were added dropwise at 120 ℃ over 2 h. The reaction product was insoluble in toluene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct. Commercially available xylenes generally refer to a mixture of the three isomers ortho-xylene, meta-xylene, and para-xylene.
Modified imidazole (II): 220g of 2-ethyl-4-methylimidazole and xylene are placed in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 652g of polypropylene glycol diglycidyl ether were added dropwise at 120 ℃ over 2 h. The reaction product was insoluble in toluene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct.
Modified imidazole (III): 220g of 2-ethyl-4-methylimidazole and xylene are placed in a three-necked flask equipped with a stirrer, a dropping funnel and a condenser, and stirred and mixed at 110 to 120 ℃. 202g of butanediol diglycidyl ether are added dropwise at 120 ℃ over a period of 2 h. The reaction product was insoluble in xylene, separated from xylene after the reaction, and the residual xylene was distilled off at 140 ℃ under 1.3kPa to obtain a dark reddish brown liquid adduct.
Thirdly, preparation of finished product
5. Mixing the component A and the component B according to the mass ratio in the table 1, controlling the temperature of the materials to be lower than 10 ℃, controlling the relative humidity of air to be lower than 30%, stirring in vacuum for 30min, then quickly packaging and storing at-40 ℃. In table 1, each numerical value is a part by mass of the corresponding component.
In Table 1, bisphenol F type resin was obtained from DIC in Japan; ExA-830 CRP.
Glycerol glycidyl ether was purchased from mayo, usa under item number EPON 812.
Pentaerythritol glycidyl ether was purchased from Nagase, Japan, cat # Denacol EX-411.
P-tert-butylphenyl glycidyl ether is available from Aididaceae, Japan under the trade name ED-509S.
Polyethylene powder was purchased from Mitsui chemical, Japan, cat # PM-200.
PMMA powder was purchased from Korea Shanghai chemical, cat # PMMA 160.
The platy talc was purchased from IMERYS, cat # MISTRON CB.
Ball silicon is available from Admatechs under the trade designation 50 SQ-E20.
TS-720 was purchased from Calbot, USA.
Z-6040 was purchased from Dow Corning, Japan. Z-6040 is gamma- (2, 3-epoxypropyl) trimethoxy silane.
Titanium dioxide was purchased from Japan Stone, cat # R930.
TABLE 1
PN-H and HX-3722 belong to modified imidazole latent curing agents and do not belong to polyether amine.
In Table 1, the average particle diameter of each filler is 3 to 15 μm.
The sealants prepared in the above examples and comparative examples were subjected to the following performance tests: the final product was tested for viscosity, cure properties, Water Vapor Transmission Rate (WVTR), coefficient of thermal expansion, glass transition temperature, push-pull force and modulus after curing. The results are shown in Table 2.
The performance indexes of the test are as follows:
1. viscosity of the oil
The test was performed using a rotational viscometer at 25 ℃ according to ASTM D2393 test method.
2. Test for curing Properties
Differential Scanning Calorimetry (DSC) was used to obtain a DSC cure curve, in which the temperature rise rate was 100 deg.C/min and the cure time in units of min at a constant temperature of 70 deg.C was recorded.
3. Water Vapor permeability (Water Vapor Transmission Rate, WVTR for short) test
A100 mm × 100mm × 1mm test piece was prepared using a flat plate mold, oven-cured for 60min, 80 ℃, tested using a water vapor transmission tester (Mocon), test conditions: 50 ℃/100% RH in g/m 2 24h, thickness 1 mm.
4. Coefficient of thermal expansion test (CTE)
The coefficient of thermal expansion was measured using thermomechanical analysis (TMA) according to ASTM D696, with a temperature rise rate of 3 ℃/min and the coefficient of thermal expansion in ppm/deg.C.
5. Glass transition temperature (Tg)
Test gels were prepared, cured at 80 ℃ for 120min, and tested by thermomechanical analysis (TMA) for glass transition temperature in units of ℃ during heating from-60 ℃ to 200 ℃ at a rate of 3 ℃/min.
6. Push-pull force test
The material PET (5X 5mm) + glass, push-pull force, was measured according to ASTM D1002 test method, where the curing conditions were 60min in kg at 80 ℃.
7. Modulus test
Using dynamic thermomechanical analysis (DMA), test mode: the tensile mode sample size was 20X 6X 0.5mm (length, width, respectively,Thickness), placing the prepared glue film in an oven, and curing for 120min at 80 ℃, wherein the temperature rise rate of a DMA test is 3 ℃/min, the curve range is-60-200 ℃, and the modulus unit is N/mm 2 。
8. And (3) testing the working life, namely taking the prepared finished product, hermetically packaging the finished product by using a 30mL syringe, standing the packaged finished product at room temperature (25 ℃), and testing the viscosity once every 1 hour. Specifically, the viscosity is tested every 1 hour within 0-12 hours, the viscosity increase rate of 12 hours is less than 50%, namely ok, otherwise, the viscosity is judged to be unqualified, namely no. The growth rate is (measured viscosity-initial viscosity)/initial viscosity × 100%.
9. Reliability test
Coating the sealant on the frame of the electronic paper screen, placing the electronic paper screen frame in an oven, curing for 60min at 80 ℃, standing for more than 12 hours at normal temperature, and then carrying out reliability test. High temperature and high humidity: 80% 1080H at 60 ℃; high temperature and low humidity: 60 ℃, 35% 840H, one cycle.
And (3) reliability judgment: if the screen is not blackened, whited or damaged, the screen is judged to be ok (namely qualified), otherwise, the screen is judged to be no (namely unqualified).
The results of the data obtained from the tests are shown in table 2.
In table 2, α 1 generally indicates the expansion coefficient in a temperature range lower than Tg (glass transition temperature), and α 2 generally indicates the expansion coefficient in a temperature range higher than Tg (glass transition temperature).
TABLE 2
In Table 2, the lower the modulus, the better the reworkability. The modulus is less than or equal to 2200N/mm 2 (25 ℃) is defined as "ok" for rework.
As can be seen from the table 2, the test results of the adaptation periods of the prepared epoxy sealants are all ok when the three modified imidazoles are respectively used in the embodiments 1 to 3, which indicates that the viscosity increase rate is less than 50% in 12 hours, and the epoxy sealant has a longer applicable period; the modulus is low, specifically 1500-1700N/mm 2 This indicates that the reworkability is good.
Component B of comparative example 1 used PN-H (powder) and epoxy sealant having a modulus of 2800N/mm was obtained 2 And poor reworkability, no. And the viscosity increase rate is more than or equal to 50% in 12 hours, the working life is short, the viscosity is too high, and the glass transition temperature is too high. The viscosity of the epoxy sealant is too high, when the epoxy sealant is used by a client, the dispensing speed is slow, the fluidity of the glue is slow, and filling parts are uneven.
Component B of comparative example 2 was HX-3722 (liquid) and the epoxy sealant modulus was up to 3000N/mm 2 And poor reworkability, no. Moreover, the viscosity is too high and the glass transition temperature is too high.
In comparative example 3, no diluent was added to component A, and the viscosity of the epoxy sealant prepared was too high, as high as 2400 cps. And the glass transition temperature is high.
The component B of the comparative example 4 is PN-H (powder), so that the vapor permeability of the prepared epoxy sealing glue is too high; the modulus is up to 2500N/mm 2 And poor reworkability, no. And the curing time is longer and is up to 120 min. And the water vapor transmission rate is as high as 13g/m 2 24h (sample thickness 1mm), poor water barrier. And the glass transition temperature is relatively high.
The comparative example 5 does not use the component B, and the prepared epoxy sealant has the viscosity increase rate of more than or equal to 50 percent in 12 hours and short working life. And the curing time is longer, up to 150 min. And the water vapor transmission rate is as high as 13g/m 2 24h (sample thickness 1mm), poor water barrier. And the glass transition temperature is too high.
The component B in the comparative example 6 is 20 parts by mass of HX-3722 (liquid), and after the prepared epoxy sealant is used for coating the frame of the electronic paper screen, the screen has the phenomena of blackening, whitening, edge loss and the like, the reliability is poor, and the product is judged to be no. And the water vapor transmission rate is as high as 12g/m 2 24h (sample thickness 1mm), poor water barrier. And the glass transition temperature is too high.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. The epoxy sealant is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by mass:
40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-30 parts of filler, 0-3 parts of anti-settling agent, 0-3 parts of coupling agent and 0-3 parts of whitening agent;
the component B comprises a curing agent, and the curing agent comprises modified imidazole.
2. The epoxy sealant of claim 1 wherein component a comprises the following components by mass:
40-52 parts of epoxy resin, 9-24 parts of polyfunctional epoxy resin, 6-10 parts of diluent, 25-28.5 parts of filler, 0.5-3 parts of anti-settling agent, 0.5-3 parts of coupling agent and 0.5-3 parts of whitening agent.
3. The epoxy sealant according to claim 1 or 2, wherein the component a: and the component B is (100-110): (5-30);
preferably, component a: the component B is (100-110): 10;
preferably, component a: and the component B is (100-101): 10.
4. the epoxy sealant according to claim 1 or 2, wherein the modified imidazole includes but is not limited to at least one of modified imidazoles (r), (g) and (g) shown in the following structures:
the structural formula of the modified imidazole is as follows:
n is an integer of 1 to 3;
the structural formula of the modified imidazole is as follows:
n is an integer of 1 to 3;
the structural formula of the modified imidazole is as follows:
5. the epoxy sealant of claim 1 or 2 wherein the epoxy resin comprises at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, aromatic polyacrylate type epoxy resin, hydrogenated epoxy resin, resorcinol diglycidyl ether, aliphatic alcohol polyglycidyl ether;
preferably, the multifunctional epoxy resin comprises at least one of glycerol glycidyl ether, bisphenol a bis (triethylene glycol glycidyl ether) ether, triglycidyl meta-aminophenol, pentaerythritol glycidyl ether, tetraglycidyl diaminodiphenylmethane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, 2,2 ', 2"- [ methine-tris (phenoxymethylene) ] tris (ethylene oxide), ethylene oxide, 2,2- [ [2- (ethylene oxide YL methoxy) -1, 3-phenyl ENE ] bis (methylene) ] bis-.
6. The epoxy sealant according to claim 1 or 2 wherein the diluent comprises at least one of 4-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, 2-toluene glycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol monomethyl ether;
preferably, the filler comprises at least one of an organic filler and an inorganic filler;
preferably, the average particle size of the filler is 3-15 μm;
preferably, the organic filler comprises at least one of polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate, ABS high rubber powder and polybutadiene rubber;
preferably, the polybutadiene rubber comprises a polybutadiene rubber having a core-shell structure;
preferably, the inorganic filler comprises at least one of hydrophobic silica micropowder, talcum powder, ball silica, mica powder, montmorillonite and alumina.
7. The epoxy sealant of claim 1 or 2 wherein said anti-settling agent comprises fumed silica;
preferably, the coupling agent comprises at least one of gamma- (2, 3-epoxypropyl) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane;
preferably, the whitening agent comprises titanium dioxide;
preferably, the sealant is used for sealing the frame of the electronic paper display screen.
8. The method for preparing the epoxy sealant according to any one of claims 1 to 7, comprising:
the preparation step of the component A comprises the steps of mixing epoxy resin, polyfunctional epoxy resin, diluent, filler, anti-settling agent, coupling agent and whitening agent according to the formula amount to prepare the component A;
the preparation step of the component B comprises the steps of mixing all the curing agents according to the formula amount to prepare the component B;
and the mixing step comprises mixing the component A and the component B according to the formula amount to obtain the sealant.
9. The method according to claim 8, wherein in the mixing step, the temperature of the material is 10 ℃ or lower;
in the mixing step, the relative humidity of air is less than or equal to 30 percent during mixing;
in the mixing step, the mixing is performed under vacuum.
10. The method of claim 8, wherein in the mixing step, the sealant is stored at-40 ± 2 ℃;
in the preparation step of the component A, the component A is refrigerated at the temperature of minus 5 ℃ for 10 to 12 hours after being prepared;
in the preparation step of the component B, the component B is refrigerated at the temperature of minus 5 ℃ for 10 to 12 hours after being prepared.
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| US4684736A (en) * | 1985-01-25 | 1987-08-04 | Ciba-Geigy Corporation | Bisimidazolium salts |
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| CN114149566A (en) * | 2021-12-20 | 2022-03-08 | 潼灏(上海)材料科技有限公司 | Imidazoline epoxy curing agent and application thereof |
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