CN111117542B - High-temperature-resistant flexible single-component epoxy sealing adhesive and preparation method thereof - Google Patents
High-temperature-resistant flexible single-component epoxy sealing adhesive and preparation method thereof Download PDFInfo
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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
- C08G59/40—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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- 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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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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- 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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- 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
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Abstract
The invention relates to the field of adhesives, in particular to a high-temperature-resistant flexible single-component epoxy sealing adhesive and a preparation method thereof. The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight: 10-40 parts of epoxy resin; mixing and softening resin 10-30 parts; 5-20 parts of an active diluent; 5-20 parts of mixed curing agent; 0.01-1 part of polymerization inhibitor; 0.1-5 parts of fumed silica; 0.01-1 part of infiltration flow promoter; 5-30 parts of spherical silicon micro powder; wherein the mixed curing agent is a mixture of a modified amine latent heat curing agent and a modified imidazole latent heat curing agent; the mixed flexibility-increasing resin is at least two of F100, F300, Capa3050, H2004, HEF750, HEF751 and EP-4000L, EP-4000S. The adhesive disclosed by the invention can be widely applied to a USB port and a sealing process of a high-temperature-resistant reflow soldering process, has good adhesive property to PA46, stainless steel, PC and the like, and ensures excellent waterproof sealing property and plugging resistance of the USB port of an electronic product.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a high-temperature-resistant flexible single-component epoxy sealing adhesive and a preparation method thereof.
Background
With the increasing attention on environmental protection and the development of high-density and miniaturized electronic components, the requirements on the performance of electronic packaging materials are higher and higher. The rapid development of the mobile internet technology enables China to rapidly enter the internet era, and the requirements of people on various aspects such as clothes, eating and housing can be met through the platform of the internet. The basis for realizing the mobile internet society is ubiquitous electronic equipment. The devices comprise mobile phones, notebook computers, tablet computers, vehicle-mounted systems and the like, and the portable and portable development of the electronic devices has higher and higher requirements on waterproof sealing and the like of electronic fast-moving products. Most of the USB port sealing waterproof agents commonly used in the market at present adopt addition type silica gel or epoxy adhesives with high glass transition temperature (Tg) and low Coefficient of Thermal Expansion (CTE), although the addition type silica gel can meet the process requirement of ultrahigh-temperature reflow soldering, the bonding strength of the silica gel is extremely low, and generally only can reach thrust of about 120N; while the adhesive strength of the epoxy adhesive with high Tg and low CTE can meet the requirement, the yield is not high when the epoxy adhesive is subjected to ultrahigh-temperature reflow soldering.
Disclosure of Invention
Aiming at the technical problems, the invention provides the high-temperature-resistant flexible single-component epoxy sealing adhesive and the preparation method thereof, so that the high-temperature-resistant flexible single-component epoxy sealing adhesive can meet the process requirement of over-high-temperature reflow soldering, has good adhesion to various base materials and good sealing and waterproof performance, and improves the use stability of electronic products.
The invention adopts the following technical scheme:
the high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
10-40 parts of epoxy resin;
mixing and softening resin 10-30 parts;
5-20 parts of an active diluent;
5-20 parts of mixed curing agent;
0.01-1 part of polymerization inhibitor;
0.1-5 parts of fumed silica;
0.01-1 part of infiltration flow promoter;
5-30 parts of spherical silicon micro powder;
wherein the mixed curing agent is a mixture of a modified amine latent heat curing agent and a modified imidazole latent heat curing agent; the mixed flexibility-increasing resin is at least two of F100, F300, Capa3050, H2004, HEF750, HEF751 and EP-4000L, EP-4000S.
Further, the content of the modified amine latent heat curing agent is greater than that of the modified imidazole latent heat curing agent.
Furthermore, the weight ratio of the modified amine latent heat curing agent to the modified imidazole latent heat curing agent is 1 (2-3).
Further, the modified amine latent heat curing agent is at least one of EH-4360S, EH-5001P, EH-5031S, EH-5057PK, EH-4357S, FXR-1020, FXR-1081 and FXR-1030; the modified imidazole latent heat curing agent is at least one of EH-5011S, FXR-1121, PN-23, FXR-1201, PN-40 and PN-H. Preferably, the modified amine latent heat curing agent is EH-4360S, and the modified imidazole latent heat curing agent is Taiwan III and synthetic FXR-1201.
Preferably, the hybrid flexibilizing resin has a polyol structure.
Further, the mixed flexibilizing resin is a mixture of H2004 and HEF 750.
Furthermore, the mixed flexibility-increasing resin is formed by mixing H2004 and HEF750 according to the weight ratio of 1 (2.5-3).
Further, the epoxy resin is at least one of bisphenol A epoxy resin and bisphenol F epoxy resin; specifically, the bisphenol A epoxy resin is at least one of KE-8120, YL-980, 828EL and EXA-850CRP, YLE-1300A, and the bisphenol F epoxy resin is at least one of KF-8110, YEL-8130, EXA-830LVP, EXA-830CRL, YL-983, YLE-1300F;
the active diluent is at least one of tertiary carbonic acid glycidyl ether, n-butyl glycidyl ether, p-tert-butylphenyl glycidyl ether, methacrylic acid glycidyl ether, 1, 4-butanediol diglycidyl ether, benzyl glycidyl ether, polypropylene glycol glycidyl ether and 1, 6-hexanediol diglycidyl ether;
the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone, barbituric acid, benzoic acid, oxalic acid and 2, 6-di-tert-butyl-p-cresol;
the fumed silica is at least one of R202, R805, R106, H15, H20, H18, R812S, R8200 and H2000;
the infiltration flow promoter is at least one of Novec FC4430, Novec 2202, TiVida FL2300, FSN-100, MEGAFACE F-477, MEGAFACE F-560 and MEGAFACE F-561;
the spherical silicon micropowder is a silicon micropowder with a spheroidization rate of 100%, and specifically, is at least one of Q010, Q013, Q020, Q0100 and Q0300.
Preferably, the high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
20-30 parts of epoxy resin;
mixing 20-30 parts of flexibility-increasing resin;
15-20 parts of a reactive diluent;
5-10 parts of a mixed curing agent;
0.1-1 part of polymerization inhibitor;
1-5 parts of fumed silica;
0.3-1 part of infiltration flow promoter;
15-30 parts of spherical silicon micropowder.
More preferably, the high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
20 parts of epoxy resin;
mixing 30 parts of flexibility increasing resin;
20 parts of a reactive diluent;
9.6 parts of mixed curing agent;
0.1 part of polymerization inhibitor;
5 parts of fumed silica;
0.3 part of infiltration flow promoter;
15 parts of spherical silicon micropowder.
Preferably, the high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
20 parts of bisphenol F epoxy resin;
softening resin HEF 75022 parts;
softening resin H20048 parts;
20 parts of tertiary carboxylic acid glycidyl ether serving as a reactive diluent;
FXR-12012.6 parts of a modified imidazole latent heat curing agent;
7 parts of modified amine latent heat curing agent EH-4360S;
0.1 part of polymerization inhibitor 2, 6-di-tert-butyl-p-cresol;
fumed silica R82005 parts;
MEGAFACE F-5600.3 parts of infiltration flow promoter;
and Q01015 parts of spherical silicon micropowder.
The invention also provides a preparation method of the high-temperature-resistant flexible single-component epoxy sealing adhesive, which comprises the following steps:
1) adding epoxy resin, mixed softening resin, fumed silica and spherical silicon micropowder into a stirring reaction kettle, heating, stirring in vacuum, dehydrating and cooling;
2) adding a polymerization inhibitor, a wetting flow promoter and a mixed curing agent into a stirring kettle, and stirring in a vacuum state;
3) adding an active diluent into the stirring kettle, uniformly mixing, and then stirring at a controlled temperature in a vacuum state;
4) and continuously stirring and defoaming in vacuum to obtain the single-component epoxy sealing adhesive.
Further, in the step 1), the heating temperature is 75-85 ℃, the stirring time is 1-4h, and the stirring speed is 20-30 r/min; in the step 2), the stirring time is 30-80min, and the stirring speed is 20-30 r/min; in the step 3), the stirring time is 40-80min, and the stirring speed is 25-35 r/min; in the step 4), the stirring time is 10-40min, and the stirring speed is 3-8 r/min.
The high-temperature-resistant flexible single-component epoxy sealing adhesive and the preparation method thereof have the following beneficial effects:
(1) according to the high-temperature-resistant flexible single-component epoxy sealing adhesive, the epoxy resin and the mixed flexibility-increasing resin are used as additives for improving the elasticity and high temperature resistance of the colloid, so that the adhesive still has good flexibility at a high temperature of 265 ℃; the curing agent is a mixture of a modified amine latent heat curing agent and a modified imidazole latent heat curing agent, and the low-temperature modified imidazole latent heat curing agent is used, so that the adhesive can be quickly gelled at low temperature (less than 80 ℃), the situations of glue overflow and glue leakage caused by the flowing of the adhesive are prevented, and the adhesive can be quickly cured at high temperature (150 ℃/30 min) by using the modified amine latent heat curing agent; according to the high-temperature-resistant flexible single-component epoxy sealing adhesive, through the addition and reasonable proportioning of the raw materials, the obtained epoxy sealing adhesive combines the characteristics of flexibility, high temperature resistance and low viscosity of single-component addition type silica gel and the advantages of high Tg, low CET and high bonding strength of the conventional single-component sealing epoxy adhesive on the market, and can still keep high elasticity and high bonding performance after high-temperature reflow soldering.
(2) According to the high-temperature-resistant flexible single-component epoxy sealing adhesive, the modified amine latent heat curing agent is used as the main curing agent to play a role in bonding, so that the adhesive is rapidly cured at a high temperature, and meanwhile, due to the fact that the amine value of the modified imidazole latent heat curing agent is high, the addition amount of the modified amine latent heat curing agent is obviously reduced compared with that of the modified amine latent heat curing agent cured at a low temperature, and the viscosity of the adhesive is increased slightly under the condition that the same effect is achieved.
(3) According to the high-temperature-resistant flexible single-component epoxy sealing adhesive, the total adding amount of the modified amine latent heat curing agent and the modified imidazole latent heat curing agent is less than the equivalent ratio in the raw material formula, the tertiary amine group can catalyze the hydroxyl group to further react with the epoxy group in the epoxy resin at the high temperature of 265 ℃, the hydroxyl group in the flexibility-increasing resin and the hydroxyl group generated by the reaction of the curing agent compete with the crosslinking reaction of the epoxy group, the activity of the hydroxyl group in the flexibility-increasing resin is higher, the preferential reaction is realized, the crosslinking density on a unit molecular chain cannot be greatly increased, the curing of a colloid is more perfect, the flexibility of the adhesive is maintained, the surface of the adhesive is perfect after high-temperature reflow soldering, and no cracking occurs.
(4) According to the high-temperature-resistant flexible single-component epoxy sealing adhesive, the silicon powder with 100% spheroidization rate is added into the raw materials, so that the thermal expansion property of the cured colloid can be improved under the condition of not obviously increasing the viscosity of the adhesive, the relative difference of the expansion coefficients of the colloid before and after the glass transition temperature (Tg) is small, the expansion coefficient before the Tg is 80-90 (ppm/DEG C), and the expansion coefficient after the Tg is 110-130 (ppm/DEG C).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view of spot gluing and curing of the high temperature resistant flexible single-component epoxy sealing adhesive in a USB connector according to the present invention;
FIG. 2 is a schematic view of a narrow gap glue curing simulation by glue dispensing and curing of the high temperature resistant flexible single-component epoxy sealing adhesive on a plate.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75026 parts;
and (3) flexibility increasing resin: h20044 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: modified imidazole latent heat curing agent PN-232.6 parts;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in the embodiment comprises the following steps:
1) adding epoxy resin, mixed softening resin, fumed silica and spherical silicon micropowder into a stirring reaction kettle, heating at 80 ℃, stirring in vacuum for 2h at a stirring speed of 30r/min, dehydrating and cooling;
2) adding a polymerization inhibitor, a wetting flow promoter and a mixed curing agent into a stirring kettle, and stirring for 60min at a stirring speed of 25 r/min under a vacuum state;
3) adding an active diluent into a stirring kettle, uniformly mixing, and stirring at a controlled temperature in a vacuum state for 50min at a stirring speed of 30 r/min;
4) and continuing vacuum stirring and defoaming, wherein the stirring time is 30min, and the stirring speed is 6r/min, so as to obtain the single-component epoxy sealing adhesive.
Example 2
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: modified imidazole latent heat curing agent PN-232.6 parts;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 3
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: 75018 parts of HEF;
and (3) flexibility increasing resin: h200412 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: modified imidazole latent heat curing agent PN-232.6 parts;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 4
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: capa 30508 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: modified imidazole latent heat curing agent PN-232.6 parts;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 5
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: FXR-12011 parts of a modified imidazole latent heat curing agent;
curing agent: 8.6 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 6
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: FXR-12012.6 parts of a modified imidazole latent heat curing agent;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 7
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: FXR-12014 parts of a modified imidazole latent heat curing agent;
curing agent: 5.6 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Example 8
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: FXR-11212.6 parts of a modified imidazole latent heat curing agent;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in this example was the same as in example 1.
Comparative example 1
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: 75030 parts of HEF;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: modified imidazole latent heat curing agent PN-232.6 parts;
curing agent: 7 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in the comparative example is consistent with that of example 1.
Comparative example 2
The high-temperature-resistant flexible single-component epoxy sealing adhesive is prepared from the following raw materials in parts by weight:
epoxy resin: bisphenol F epoxy resin YLE1300F 20 parts;
and (3) flexibility increasing resin: HEF 75022 parts;
and (3) flexibility increasing resin: h20048 parts;
active diluent: tert-carbonic acid glycidyl ether E10P 20 parts;
curing agent: 9.6 parts of modified amine latent heat curing agent EH-4360S;
polymerization inhibitor: 0.1 part of 2, 6-di-tert-butyl-p-cresol BHT;
fumed silica: r82005 parts;
infiltration flow promoter: MEGAFACE F-5600.3 parts;
spherical silicon micropowder: q01015 parts.
The preparation method of the adhesive in the comparative example is consistent with that of example 1.
The adhesives prepared in examples 1-8 and comparative examples 1-2 were subjected to performance testing, and the testing process steps and parameters were as follows:
testing equipment: an SLX-A Shore hardness testing machine frame, a BT301N small-sized desktop reflow oven, an STH-120 small-sized high-temperature oven, an SMZ-168BP type microscope and a Noxin Asymtex S dispenser.
Testing materials: USB connector, FR-4 board.
The test method comprises the following steps:
using an Asymtex S dispenser to dispense glue on a USB connector twice, adding 9 mg of glue on the USB connector, standing for 10 minutes at room temperature, placing the USB connector in a small-sized high-temperature furnace for curing at 150 ℃ for 20 minutes after the glue solution is completely leveled, taking out a cured sample piece, cooling at room temperature, and observing the curing condition and glue overflow condition of the glue, wherein the conditions are shown in figure 1;
placing the solidified sample piece into a BT301N small desktop reflow furnace, reflowing at 265 ℃, taking out and cooling to room temperature, observing the surface glue condition of the USB connector by an SMZ-168BP type microscope, reflowing for three times, and testing the high-temperature reflow cracking condition of the adhesive (raising the experiment condition by 5 ℃ compared with the common high-temperature reflow soldering temperature to ensure that the product meets the customer requirement);
in order to test the curing condition of the glue in a specific very narrow gap, a simple test method for simulating the curing of the glue in the narrow gap is adopted: dispensing on the FR-4 board, pressing another FR-4 board completely, peeling off the FR-4 board after curing, and observing the curing condition of the glue, as shown in figure 2;
testing the hardness of the cured adhesive by using an X-A Shore hardness testing machine frame;
to simulate the actual use of the plant in summer, a pot life of 35 ℃ was measured.
The results of testing the prepared adhesive according to the above test method are shown in tables 1 and 2.
Table 1 adhesive test results one
Table 2 adhesive test results two
As can be seen from tables 1-2, the high-temperature-resistant flexible one-component epoxy sealing adhesive disclosed by the invention combines the characteristics of flexibility, high temperature resistance and low viscosity of the one-component addition type silica gel and the advantages of high Tg, low CET and high bonding strength of the conventional one-component sealing epoxy adhesive on the market by limiting the raw materials and the ratio of the adhesive, especially limiting the flexibilizing resin and the curing agent, and has good high-temperature-resistant backflow non-cracking performance and curing performance. The test results of the examples 1 to 8 show that the epoxy resin and the mixed flexibility-increasing resin are used as the auxiliary agents for improving the elasticity and the high temperature resistance of the colloid, so that the adhesive still has good flexibility at a high temperature of 265 ℃, and the surface of the adhesive is flat and does not crack after being subjected to once high-temperature reflux; the curing agent is a mixture of a modified amine latent heat curing agent and a modified imidazole latent heat curing agent, the low-temperature modified imidazole latent heat curing agent is used, so that the adhesive can be quickly gelled at low temperature (less than 80 ℃), and the adhesive can be quickly cured at high temperature by using the modified amine latent heat curing agent.
As can be seen from Table 1, the use of at least two of F100, F300, Capa3050, H2004, HEF750, HEF751 and EP-4000L, EP-4000S as hybrid flexibilizing resins in the examples of the present invention is superior in high temperature resistance to the HEF750 alone as flexibilizing resin in comparative example 1. The reason is mainly that the air tightness of the colloid after high-temperature reflux is effectively enhanced by adding the polyalcohol into the mixed flexibility-increasing resin. Specifically, hydroxyl can react with an epoxy group under the catalysis of amine at high temperature to increase the cross-linking density of a unit molecular chain, and the hydroxyl of the polyol has small steric hindrance and high activity compared with the hydroxyl generated in the curing process of the epoxy group, and the hydroxyl of the polyol preferentially reacts with the residual epoxy group in the system at high temperature to effectively relieve the increase of the cross-linking density in the unit molecular chain of the colloid, so that the colloid can still maintain good air tightness after high-temperature reflux. More specifically, as can be seen from the comparison of examples 2 and 4, the flexible hyperbranched polyol H2004 of the polyether type has better high-temperature reflow resistance than the trifunctional polyol Capa3050 of the polyester type. Meanwhile, as can be seen from the performance test results in examples 1-4, the addition amount of the polyol should be maintained in a proper range, and when the weight ratio of H2004 to HEF750 is in the range of 1 (2.5-3), the performance of the obtained adhesive is optimal. At 150 ℃, the polyol hardly participates in glue curing, plays a plasticizing role, obviously increases the hardness after too little polyol colloid flows back, and easily loses the air tightness; too much polyol, low crosslinking density of colloid, poor colloid strength, easy occurrence of stickiness, and surface waviness during high-temperature reflux to cause poor appearance.
As can be seen from tables 1 and 2, the type and the collocation of the curing agent play a very key role in the stability of the glue and the control of glue overflow by the glue. As can be seen from the comparison of comparative example 2 with examples 5-8, the addition of the modified imidazole latent curing agent can effectively control the bleeding. As can be seen from examples 5 to 8, the content ratios of different imidazoline curing agents and amine curing agents correspond to different properties of the obtained adhesive, and when the weight ratio of the modified amine latent heat curing agent to the modified imidazole latent heat curing agent is in the range of 1 (2-3), the obtained adhesive has the best performance. Meanwhile, the three imidazole curing agents used in the embodiment of the invention are all curing agents which can be gelled when the temperature is lower than 80 ℃, so that the viscosity of the glue is increased due to the reaction at low temperature and the fluidity of the glue is lost, and the appearance shape after the glue is dispensed is kept, particularly the ultralow temperature epoxy curing agent FXR-1201, the activation temperature of which is as low as 65 ℃, is more excellent in stability and has better diluent resistance compared with PN-23; compared with FXR-1121, the initiation temperature is lower, and the Tg is lower, so that the hardness of the glue after being cured is not increased as obviously as the FXR-1121 in the same proportion.
The high-temperature-resistant flexible single-component epoxy sealing adhesive disclosed by the invention can be widely applied to sealing processes of USB ports and high-temperature-resistant reflow soldering processes, has good adhesive property to PA46, stainless steel, PC and the like, and ensures excellent waterproof sealing property and plugging resistance of USB ports of electronic products.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (6)
1. The high-temperature-resistant flexible single-component epoxy sealing adhesive is characterized by being prepared from the following raw materials in parts by weight:
10-40 parts of epoxy resin;
mixing and softening resin 10-30 parts;
5-20 parts of an active diluent;
5-20 parts of mixed curing agent;
0.01-1 part of polymerization inhibitor;
0.1-5 parts of fumed silica;
0.01-1 part of infiltration flow promoter;
5-30 parts of spherical silicon micro powder;
wherein the mixed flexibility-increasing resin is formed by mixing H2004 and HEF750 according to the weight ratio of 1 (2.5-3);
the mixed curing agent is a mixture of a modified amine latent heat curing agent and a modified imidazole latent heat curing agent, the gelation temperature of the modified imidazole latent heat curing agent is lower than 80 ℃, and the weight ratio of the modified amine latent heat curing agent to the modified imidazole latent heat curing agent is (2-3): 1.
2. The high-temperature-resistant flexible single-component epoxy sealing adhesive as claimed in claim 1, wherein the modified amine latent heat curing agent is at least one of EH-4360S, EH-5001P, EH-5031S, EH-5057PK, EH-4357S, FXR-1020, FXR-1081 and FXR-1030; the modified imidazole latent heat curing agent is at least one of EH-5011S, FXR-1121, PN-23, FXR-1201, PN-40 and PN-H.
3. The high-temperature-resistant flexible one-component epoxy sealing adhesive according to claim 1, characterized in that:
the epoxy resin is at least one of bisphenol A epoxy resin and bisphenol F epoxy resin;
the active diluent is at least one of tertiary carbonic acid glycidyl ether, n-butyl glycidyl ether, p-tert-butylphenyl glycidyl ether, methacrylic acid glycidyl ether, 1, 4-butanediol diglycidyl ether, benzyl glycidyl ether, polypropylene glycol glycidyl ether and 1, 6-hexanediol diglycidyl ether;
the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tert-butyl hydroquinone, barbituric acid, benzoic acid, oxalic acid and 2, 6-di-tert-butyl-p-cresol;
the fumed silica is at least one of R202, R805, R106, H15, H20, H18, R812S, R8200, and H2000;
the infiltration flow promoter is at least one of Novec FC4430, Novec 2202, TiVida FL2300, FSN-100, MEGAFACE F-477, MEGAFACE F-560 and MEGAFACE F-561;
the spherical silicon micropowder is silicon micropowder with 100% spheroidization rate.
4. The high-temperature-resistant flexible one-component epoxy sealing adhesive according to claim 3, characterized in that:
the bisphenol A epoxy resin is at least one of KE-8120, YL-980, 828EL and EXA-850CRP, YLE-1300A;
the bisphenol F epoxy resin is at least one of KF-8110, YEL-8130, EXA-830LVP, EXA-830CRL, YL-983 and YLE-1300F.
5. A preparation method of the high-temperature-resistant flexible one-component epoxy sealing adhesive as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) adding epoxy resin, mixed softening resin, fumed silica and spherical silicon micropowder into a stirring reaction kettle, heating, stirring in vacuum, dehydrating and cooling;
2) adding a polymerization inhibitor, a wetting flow promoter and a mixed curing agent into a stirring kettle, and stirring in a vacuum state;
3) adding an active diluent into the stirring kettle, uniformly mixing, and then stirring at a controlled temperature in a vacuum state;
4) and continuously stirring and defoaming in vacuum to obtain the single-component epoxy sealing adhesive.
6. The preparation method of the high-temperature-resistant flexible one-component epoxy sealing adhesive according to claim 5, characterized by comprising the following steps:
in the step 1), the heating temperature is 75-85 ℃, the stirring time is 1-4h, and the stirring speed is 20-30 r/min;
in the step 2), the stirring time is 30-80min, and the stirring speed is 20-30 r/min;
in the step 3), the stirring time is 40-80min, and the stirring speed is 25-35 r/min;
in the step 4), the stirring time is 10-40min, and the stirring speed is 3-8 r/min.
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| CN103409095A (en) * | 2013-07-30 | 2013-11-27 | 烟台德邦科技有限公司 | Flexible one-component epoxy adhesive and preparation method thereof |
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| JP3060452B2 (en) * | 1995-10-18 | 2000-07-10 | ソニーケミカル株式会社 | Anisotropic conductive adhesive film |
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