CN106753132A - A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive and preparation method thereof - Google Patents
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive and preparation method thereof Download PDFInfo
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- CN106753132A CN106753132A CN201611247956.7A CN201611247956A CN106753132A CN 106753132 A CN106753132 A CN 106753132A CN 201611247956 A CN201611247956 A CN 201611247956A CN 106753132 A CN106753132 A CN 106753132A
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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
- C08G59/56—Amines together with other curing agents
- C08G59/60—Amines together with other curing agents with amides
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/22—Halogen free 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
- 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
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
It is the good epoxy adhesive of a kind of halogen-free flameproof, double-component fire resistant, pliability the invention discloses a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive and preparation method thereof, ambient temperature curable, working life is long, beneficial to production operation and the construction of large-scale workpiece.The adhesive is made up of component A and component B, and component A raw materials are epoxy resin, tough epoxy resin, toughener, modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, thixotropic agent, diluent and defoamer.Component B raw materials are fatty amine, modified amine, polyamide, thixotropic agent, modified inorganic filler and defoamer.The epoxy resin toughened epoxy resin modified with core-shell copolymerized thing for LNBR in component A, modified inorganic filler is the filler treated through coupling agent mechanical blending in component A, B.The present invention also provides the preparation method of the adhesive, and sqtructural adhesive of the invention has the advantages that environmental protection flame retardant, elevated temperature strength high, good toughness, preparation process is simple.
Description
Technical field
The present invention relates to adhesive area, and in particular to a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive and its preparation
Method.
Background technology
Epoxy adhesive as a kind of good adhesives, because epoxy resin is thermosetting resin, possess cementability it is strong,
A series of excellent properties such as the electrical insulating property that cure shrinkage is small, good corrosion resistance, processing performance are good and good, current
Larger proportion is occupied in the application of adhesive, and by the extensive use in domestic and international field.But epoxy resin tackifier is consolidated
There is the defects such as fragility big, poor toughness, weatherability difference after change, in use because mechanical stress or temperature change are easily sent out
Raw cracking phenomena.Simultaneously because structure and curing process limitation, the temperature tolerance of room temperature curing epoxy is not enough, and highest uses temperature
Degree is no more than 250 DEG C, limits the practical application of epoxy adhesive.
And current people are to the resistant to elevated temperatures research of epoxy adhesive, partly resting on solidification process needs heating so that epoxy
Adhesive is restricted in many fields, although part has studied the adhesive of room curing and high temperature resistant, its consideration
Shear strength, still have very big deficiency and defect in terms of the ductile strengths such as peel strength.It is same consider high temperature resistant with
While toughness, because epoxy adhesive is widely used to the fields such as Aero-Space, high ferro train, increasing epoxy glue
Stick application person also gradually steps up to its resistance to fire-retardant requirement, and the requirement of environment friendly non-halogen also predominantly stays in composite at present
Aspect, and with the extensive application of epoxy adhesive, the requirement of Halogen has gradually been proposed in electronic applications, it is believed that the epoch
Development, is also ready to appear for other application field.
Still there is a certain distance in current China with Foreign Advanced Lerel, and the epoxy adhesive of combination property is still very deficient
It is weary, while high intensity is ensured, it is considered to the toughness of adhesive, it is ensured that while toughness, and the solidification work of adhesive is not influenceed
Skill, it is considered to while convenience for construction, the influence to current environment, secure context when being used under the condition of high temperature is also to be worth
Explore.By the retrieval to existing document, it is found that Chinese patent CN14804691A discloses a kind of room curing and high temperature resistant high
The epoxy adhesive of toughness, shear strength can reach 29Mpa, but T- peel strengths are referred to, combination property sign is unknown,
The problems such as fire resistance when also not accounting for using under hot environment simultaneously.Therefore, how to develop a kind of preparation process is simple,
The prices of raw materials are cheap to be easy to get, the epoxy construction adhesive of excellent combination property is urgent problem.
The content of the invention
Based on the problems of prior art, it is an object of the invention to provide a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy
Adhesive and preparation method thereof, is a kind of high intensity, high tenacity, high temperature resistant, environmental protection while considering the realistic problem of environmental protection flame retardant
The room-temperature curing epoxy adhesive of flame retardant type, the temperature tolerance for overcoming existing room-temperature curing epoxy adhesive is poor with pliability
Shortcoming.
The purpose of the present invention is achieved through the following technical solutions:
The embodiment of the present invention provides a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, and the adhesive is by percentage by weight
The component A 70% and component B 30% of ratio is constituted, and the component A therein includes:Bisphenol A type epoxy resin, bisphenol-f type ring
Oxygen tree fat, toughness modified epoxy, toughener, coupling agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxygen
Agent, thixotropic agent, diluent and defoamer;The toughness modified epoxy is the epoxy resin being modified by liquid nitrile rubber,
The resin obtained after being processed with core shell structure polymer toughening;
The component B includes:Polyamide, fatty amine, modified amine, thixotropic agent, coupling agent modified inorganic filler and defoamer.
The embodiment of the present invention also provides a kind of preparation of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of the present invention
Method, comprises the following steps:
(1) feeding, each material composition of component A, B is taken according to formula of the present invention respectively;
(2) pre-treatment of raw material, prepares the toughness modified epoxy of component A respectively, and prepares component A and component
The coupling agent modified inorganic filler that B is used, wherein, the mode for preparing the toughness modified epoxy of component A is;In room temperature
The lower epoxy resin and 50 weight portion core shell structure polymer that 100 weight portion liquid nitrile rubbers are modified, is thoroughly mixed,
Obtain bright blend as toughness modified epoxy;
The mode for preparing the coupling agent modified inorganic filler that component A and component B is used is:At room temperature, by 100 weight
Part ethanol, the mixing of 5 weight portion coupling agents, under magnetic stirring, are slowly added to 50 parts by weight of inorganic fillers, and rotating speed control exists
100rpm, after stirring 0.5h, vacuum filtration, the solid powder that will be finally given is positioned in culture dish, 50 DEG C of bakings in baking oven
The product obtained after dry grinding is coupling agent modified inorganic filler;
(3) component A is prepared:By bisphenol A type epoxy resin, bisphenol f type epoxy resin, toughness obtained in above-mentioned steps (2)
The defoamer of modified epoxy, toughener, diluent and component A is added in reactor, and at 50~70 DEG C, planetary rotating speed is
30~45Hz, incorporation time 30min, add the coupling agent modified inorganic filler of component A, phosphonium flame retardant, nitrogenous flame ratardant,
The thixotropic agent mixing of antioxidant, component A, planet stirring rotating speed is 20~30Hz, and dispersion impeller rotating speed is 800~900rpm, 30min
Afterwards, vacuum -0.1Mpa, deaeration 30min are opened, then binder is to obtain component A;
(4) component B is prepared:Aliphatic cyclic amine, polyamide, modified amine, the coupling agent modified inorganic of component B obtained above are filled out
The defoamer of material and component B is added in the second reactor, and at 30 DEG C, planet stirring rotating speed is 20~30rpm, incorporation time
30min, in adding thixotropic agent to second reactor of component B, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 800~
900rpm, vacuum -0.1Mpa, deaeration 30min are opened after mixing 30min, and then binder is to obtain component B;
By weight percentage, component A 70% obtained above and component B 30% is used cooperatively and obtains halogen-free flameproof
High temperature resistant tough epoxy adhesive.
As seen from the above technical solution provided by the invention, high temperature tough epoxy provided in an embodiment of the present invention is gluing
Agent has the advantages that compared with existing similar adhesive:
(1) specific toughness modified epoxy, the resin is used to use LNBR-core shell structure in component A
The modification mode of collaboration is blended, it is epoxy resin toughened, solve the big defect of fragility after epoxy resin cure.
(2) component A reduces the consumption of phosphonium flame retardant by using phosphor nitrogen combustion inhibitor cooperative flame retardant adhesive system,
While reduces cost, the effect of environmental protection flame retardant has been reached.
(3) component B is mixed by the ratio using mixed type curing system-polyamide, aliphatic cyclic amine, modified amine, is broken off relations
In the case of heatproof, the harsher shortcoming of curing process is operated and facilitated universal epoxy adhesive in curing process, and room temperature is solid
Change can be completely secured adhesive temperature tolerance and mechanical property does not have any decline.
(4) the epoxy structural rubber bonding agent shear strength is high, T-shaped peel strength is high, to high energy such as metal material, polymer
Surface all has cementability.And it is nonpoisonous and tasteless without any volatile solvent.Adhesive preparation method of the invention is simple, raw material
Simple easy, preparation condition is not harsh.
Specific embodiment
With reference to particular content of the invention, the technical scheme in the embodiment of the present invention is clearly and completely retouched
State, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made,
Belong to protection scope of the present invention.
The embodiment of the present invention provides a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, be a kind of halogen-free flameproof, double groups
The good epoxy adhesive of part high temperature resistant, pliability, ambient temperature curable, working life is long, beneficial to production operation and large-scale workpiece
Construction, the adhesive is made up of component A 70% by weight percentage and component B 30%, and the component A therein includes:
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, toughness modified epoxy, toughener, coupling agent modified inorganic filler, contain
Phosphorus fire retardant, nitrogenous flame ratardant, antioxidant, thixotropic agent, diluent and defoamer;The toughness modified epoxy is by liquid
Acrylonitrile butadiene rubber modified epoxy resin, the resin obtained after being processed with core shell structure polymer toughening, this resin has played two
The synergy of person;
The component B includes:Polyamide, fatty amine, modified amine, thixotropic agent, coupling agent modified inorganic filler and defoamer.
Each composition is relative to the weight ratio of bisphenol A type epoxy resin in the component A of above-mentioned adhesive:Bisphenol F type epoxy
Resin 0.01~0.25, toughness modified epoxy 0.1~0.4, toughener 0.05~0.2, coupling agent modified inorganic filler
0.05~0.1, phosphonium flame retardant 0.05~0.5, nitrogenous flame ratardant 0.05~0.3, antioxidant 0.001~0.05, thixotropic agent
0.05~0.07, diluent 0.02~0.05, defoamer 0.01~0.022;Weight of the other compositions relative to polyamide in component B
Measuring ratio is:Fatty amine 0.5~1, modified amine 0.3~0.5, thixotropic agent 0.05~0.07, coupling agent modified inorganic filler 0.01~
0.015, defoamer 0.01~0.02.
In each composition of the component A of above-mentioned adhesive, the bisphenol A type epoxy resin is selected from:E51、E44、E54、
One or more in each epoxy resin of Der331, EPON828;
The bisphenol f type epoxy resin is selected from:In F51, F44, F48 one or more;
The toughener is with island structure toughener;This toughener is in-situ flexible, and effect substantially, tie by the island
Structure toughener is selected from:One or more in F100, VL4, VL1, VE2, CYH-277.
The phosphonium flame retardant is selected from:One or more in SPB-100, OP930, SP-703H
The nitrogenous flame ratardant is selected from:One kind or many in Melapur MC50, MelapurMC25, MelapurMC15
Kind;
The antioxidant is using Bayer Vulkanox BHT etc.;
The diluent is one or more aliphatic or aliphatic epoxy radicals reactive diluent, is sweet allyl glycidyl
Oily ether, butyl glycidyl ether, 2- hexyl glycidyl ethers, aliphatic cyclohexanediol and the one kind in glycidol ether or
It is several
The toughness modified epoxy is obtained by the following manner:100 weight portion liquid nitrile rubbers are changed at room temperature
The epoxy resin and 50 weight portion core shell structure polymer of property, are thoroughly mixed, and obtain bright blend as toughness
Modified epoxy.
The epoxy resin that liquid nitrile rubber used by above-mentioned toughness modified epoxy is modified is obtained by following manner:
100 parts by weight of bisphenol A types epoxy resin, 20 weight portion liquid butyronitrile resins are mixed at 20~40 DEG C, is heated to 160~170
DEG C, 0.5h is reacted, vacuum defoamation, nitrogen emptying after being cooled to 150 DEG C then adds 5~10 weight portion polyfunctional epoxy resins,
After insulation 0.5h, vacuum defoamation is cooled to more than 100 DEG C nitrogen emptying and obtains the modified asphalt mixtures modified by epoxy resin of liquid nitrile rubber
Fat;
The shell of the core shell structure polymer is polystyrene, and core is rubber elastomer.
In the modified epoxy resin of above-mentioned liquid nitrile rubber, polyfunctional epoxy resin used is selected from:AG70、
One or more in AG80, AFG90, TDE85.
Bisphenol A epoxide resin used is preferably E51 or Der331, multi-functional epoxy in above-mentioned toughness modified epoxy
Resin is preferably TDE85;The speed of heating is preferably 2~5 DEG C/min, is preferably cooled to 60~70 DEG C.
The toughness modified epoxy that the present invention is used can make epoxy resin by the island structure of nitrile (HTBN) resin
Grafting end carboxyl, and produce good chemical reaction with amine curing agent.Then premixed with core shell structure copolymer, connect
Branch reaction, it is dispersible more fully to reach more preferable toughened and reinforced effect when internal stress and external impacts are absorbed, while
Its temperature tolerance is not interfered with.
In above-mentioned adhesive, coupling agent modified inorganic filler used is obtained by following manner in component A and component B:
At room temperature, 100 parts by weight of ethanol, 5 weight portion coupling agents are mixed, under magnetic stirring, is slowly added to 50 parts by weight of inorganic and fills out
Material, after 100rpm, stirring 0.5h, vacuum filtration, the solid powder that will be finally given is positioned in culture dish for rotating speed control,
The product obtained after 50 DEG C of drying grindings in baking oven is coupling agent modified inorganic filler.
In above-mentioned coupling agent modified inorganic filler, inorganic filler used is selected from:Calcium titanate, silica flour, titanium dioxide, pottery
Soil, barite, talcum powder, glass microballoon, aluminum oxide, silicon boride, the grain diameter of the inorganic filler is 5~20 μm.
In above-mentioned adhesive, thixotropic agent used uses aerosil in component A and in component B;
In above-mentioned adhesive, defoamer used uses dimethyl silicone polymer, tributyl phosphate in component A and component B
Or fatty acid metal soaps defoamer;
In each compositions of component B of above-mentioned adhesive, the polyamide is selected from:Polyamide 6 50, polyamide 6 51, polyamide
300th, one or more in Versamid125, Versamid140;
The active hydrogen content of the aliphatic cyclic amine is 90~120, and amine value is 230~280mgKOH/g;
The active hydrogen content towering 120~150 of the modified amine, amine value is 250~300mgKOH/g.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, including
Following steps:
(1) feeding, each material composition of component A, B is taken according to above-mentioned formula respectively;
(2) pre-treatment of raw material, prepares the toughness modified epoxy of component A respectively, and prepares component A and component
The coupling agent modified inorganic filler that B is used, wherein, the mode for preparing the toughness modified epoxy of component A is;In room temperature
The lower epoxy resin and 50 weight portion core shell structure polymer that 100 weight portion liquid nitrile rubbers are modified, is thoroughly mixed,
Obtain bright blend as toughness modified epoxy;
The mode for preparing the coupling agent modified inorganic filler that component A and component B is used is:At room temperature, by 100 weight
Part ethanol, the mixing of 5 weight portion coupling agents, under magnetic stirring, are slowly added to 50 parts by weight of inorganic fillers, and rotating speed control exists
100rpm, after stirring 0.5h, vacuum filtration, the solid powder that will be finally given is positioned in culture dish, 50 DEG C of bakings in baking oven
The product obtained after dry grinding is coupling agent modified inorganic filler;
(3) component A is prepared:By bisphenol A type epoxy resin, bisphenol f type epoxy resin, toughness obtained in above-mentioned steps (2)
The defoamer of modified epoxy, toughener, diluent and component A is added in reactor, and at 50~70 DEG C, planetary rotating speed is
30~45Hz, incorporation time 30min, add the coupling agent modified inorganic filler of component A, phosphonium flame retardant, nitrogenous flame ratardant,
The thixotropic agent mixing of antioxidant, component A, planet stirring rotating speed is 20~30Hz, and dispersion impeller rotating speed is 800~900rpm, 30min
Afterwards, vacuum -0.1Mpa, deaeration 30min are opened, then binder is to obtain component A;
(4) component B is prepared:Aliphatic cyclic amine, polyamide, modified amine, the coupling agent modified inorganic of component B obtained above are filled out
The defoamer of material and component B is added in the second reactor, and at 30 DEG C, planet stirring rotating speed is 20~30HZ, incorporation time
30min, adds in the coupling agent modified inorganic filler of component B, the thixotropic agent of component B to the second reactor, and mixing, stirring turns
Speed is constant, and dispersion impeller rotating speed is 800~900rpm, opens vacuum -0.1Mpa, deaeration 30min after mixing 30min, then binder
Obtain component B;
By weight percentage, component A 70% obtained above and component B 30% is used cooperatively and obtains halogen-free flameproof
High temperature resistant tough epoxy adhesive.
The above-mentioned component A for preparing and component B is mixed, its hardness is tested in cold curing at 25 DEG C after 3 days be 70
~80D, shear strength 30~35Mpa, T-shaped 15~20N/mm of peel strength, flame retardant rating V-0 and test its shore at 150 DEG C
Temperature is 55-60D, and shear strength is still 25~30Mpa, T-shaped 12~15N/mm of peel strength, flame retardant rating V-0.Show this hair
Bright epoxy structural rubber bonding agent shear strength is high, T-shaped peel strength is high, all has to high energy surfaces such as metal material, polymer
There is cementability.
Invention adhesive is described in further detail below in conjunction with specific embodiment.
Embodiment 1
The present embodiment is a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, and according to percentage by weight, its raw material includes:
The component B 30% of component A 70%, the component A includes according to the raw material of percentage by weight:It is bisphenol A type epoxy resin 50%, double
Phenol F types epoxy resin 5%, toughness modified epoxy 15%, toughener 7%, coupling agent modified inorganic filler 5%, phosphorous resistance
Combustion agent 5%, nitrogenous flame ratardant 5%, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component according to
The raw material of percentage by weight includes polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic
Filler 0.5% and defoamer 0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By bisphenol A type epoxy resin, bisphenol f type epoxy resin, tough epoxy resin, toughener, dilute
Release in the defoamer addition reactor of agent and component A, at 70 DEG C, planetary rotating speed is added in 35Hz, incorporation time 30min
The coupling agent modified inorganic filler of the component A, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent mixing of component A,
Planet stirring rotating speed is 850rpm in 20Hz, dispersion impeller rotating speed, and the time is 30min, is then turned on vacuum -0.1Mpa, deaeration
30min, then binder obtain component A;
(3) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planet stirring rotating speed 20HZ, incorporation time 30min adds the thixotropic agent of component B to reacting
In kettle, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa, takes off
30min is steeped, then binder obtains component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
Embodiment 2
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of the present embodiment, includes according to the raw material of percentage by weight:Group
Part component B 30% of A 70%, the component A includes bisphenol A type epoxy resin 54%, Bisphenol F according to the raw material of percentage by weight
Type epoxy resin 1%, toughness modified epoxy 17%, toughener 5%, coupling agent modified inorganic filler 5%, phosphonium flame retardant
5%th, nitrogenous flame ratardant 5%, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component is according to weight
The raw material of percentage includes polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic filler
0.5% and defoamer 0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By the froth breaking of described epoxy resin, tough epoxy resin, toughener, diluent and component A
Agent is added in reactor, and at 70 DEG C, planet stirring rotating speed adds the idol of the component A in 35Hz, incorporation time 30min
Connection agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent mixing of component A, planet stirring rotating speed
It is 20Hz, dispersion impeller rotating speed is 850rpm, and the time is 30min, is then turned on vacuum -0.1Mpa, deaeration 30min, then binder
Obtain component A,
(3) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planet stirring rotating speed is 20HZ, incorporation time 30min adds the thixotropic agent of component B to anti-
Answer in kettle, mixing, speed of agitator is constant, dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa, take off
30min is steeped, then binder obtains component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
Embodiment 3
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of the present embodiment, includes according to the raw material of percentage by weight:Group
Part component B 30% of A 70%, the component A includes bisphenol A type epoxy resin 46%, Bisphenol F according to the raw material of percentage by weight
Type epoxy resin 11%, toughness modified epoxy 15%, toughener 5%, coupling agent modified inorganic filler 5%, phosphor-containing flame-proof
Agent 5%, nitrogenous flame ratardant 5%, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component is according to weight
Measuring the raw material of percentage includes polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic fills out
Material 0.5% and defoamer 0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By the froth breaking of described epoxy resin, tough epoxy resin, toughener, diluent and component A
Agent is added in reactor, and at 70 DEG C, planetary rotating speed adds the coupling agent of the component A in 35Hz, incorporation time 30min
Modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent of component A mix, and planet stirring rotating speed is
20Hz, dispersion impeller rotating speed is 850rpm, and the time is 30min, is then turned on vacuum -0.1Mpa, deaeration 30min, and then binder is obtained
To component A,
(3) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planet stirring rotating speed 20HZ, incorporation time 30min adds the thixotropic agent of component B to reacting
In kettle, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa, deaeration
30min, then binder obtain component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
Comparative example 1
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of this comparative example, includes according to the raw material of percentage by weight:Group
Part A70% components B30%, the component A includes bisphenol A type epoxy resin 54%, bisphenol-f type according to the raw material of percentage by weight
Epoxy resin 5%, toughness modified epoxy 11%, toughener 7%, coupling agent modified inorganic filler 5%, phosphonium flame retardant
5%th, nitrogenous flame ratardant 5%, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component is according to weight
The raw material of percentage includes polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic filler
0.5% and defoamer 0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By the froth breaking of described epoxy resin, tough epoxy resin, toughener, diluent and component A
Agent is added in reactor, and at 70 DEG C, planetary rotating speed is 35Hz, incorporation time 30min, adds the coupling agent of the component A
Modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent mixing of component A, planetary rotating speed divide in 20Hz
Dissipate 850rpm, the time is 30min, is then turned on vacuum -0.1Mpa, deaeration 30min, then binder obtain component A,
(3) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planetary rotating speed is 20HZ, incorporation time 30min adds the thixotropic agent of component B to reactor
In, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa, deaeration
30min, then binder obtain component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
Comparative example 2
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of this comparative example, includes according to the raw material of percentage by weight:Group
Part A70% components B30%, the component A includes bisphenol A type epoxy resin 54%, bisphenol-f type according to the raw material of percentage by weight
Epoxy resin 1%, toughness modified epoxy 17%, toughener 5%, coupling agent modified inorganic filler 5%, phosphonium flame retardant
10%th, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component according to percentage by weight raw material bag
Include polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic filler 0.5% and defoamer
0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By the froth breaking of described epoxy resin, tough epoxy resin, toughener, diluent and component A
Agent is added in reactor, and at 70 DEG C, planet stirring rotating speed is 35Hz, incorporation time 30min, adds the idol of the component A
Connection agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent mixing of component A, planet stirring rotating speed
In 20Hz, dispersion impeller rotating speed is 850rpm, and the time is 30min, is then turned on vacuum -0.1Mpa, deaeration 30min, then binder
Obtain component A,
(3) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planet stirring rotating speed is 20HZ, incorporation time 30min adds the thixotropic agent of component B to anti-
Answer in kettle, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa,
Deaeration 30min, then binder obtain component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
Comparative example 3
A kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive of this comparative example, includes according to the raw material of percentage by weight:Group
Part A70% components B30%, the component A includes bisphenol A type epoxy resin 53%, bisphenol-f type according to the raw material of percentage by weight
Epoxy resin 4%, toughness modified epoxy 15%, toughener 5%, coupling agent modified inorganic filler 5%, phosphonium flame retardant
5%th, nitrogenous flame ratardant 5%, antioxidant 2%, thixotropic agent 3%, diluent 2% and defoamer 1%;The B component is according to weight
The raw material of percentage includes polyamide 50%, fatty amine 26%, modified amine 20%, thixotropic agent 3%, coupling agent modified inorganic filler
0.5% and defoamer 0.5%.
The preparation method of the halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, comprises the following steps that:
(1) feeding, each raw material is weighed according to percentage by weight.
(2) prepared by component A:By the froth breaking of described epoxy resin, tough epoxy resin, toughener, diluent and component A
Agent is added in reactor, and at 70 DEG C, planet stirring rotating speed adds the idol of the component A in 35Hz, incorporation time 30min
Connection agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, the thixotropic agent mixing of component A, planet stirring rotating speed
It is 20Hz, dispersion impeller rotating speed is 850rpm, and the time is 30min, is then turned on vacuum -0.1Mpa, deaeration 30min, then binder
Obtain component A,
(1) prepared by component B:The defoamer of aliphatic cyclic amine, polyamide, modified amine, the inorganic filler of component B, component B is added
To in reactor, at 30 DEG C, planet stirring rotating speed 20HZ, incorporation time 30min adds the thixotropic agent of component B to reacting
In kettle, mixing, speed of agitator is constant, and dispersion impeller rotating speed is 900rpm, time 30min, is then turned on vacuum -0.1Mpa, deaeration
30min, then binder obtain component B.
Component A and component the B mixing that will be prepared, cold curing test its hardness, shearing by force at 25 DEG C after 3 days
Degree, T-shaped peel strength, flame retardant rating.Its shear strength, T-shaped peel strength are tested at 150 DEG C.
The test performance result of embodiment of the present invention 1-3 and comparative example 1-3 is as shown in table 1:
Table 1:The performance test results of embodiment of the present invention 1-3 and comparative example 1-3
In sum, invention adhesive is can be seen that by comparative example 1-3 and comparative example 1-3 to change by toughness
Property epoxy resin addition, there is increasing to be lifted in terms of toughness, and pass through the addition of heat resistance bisphenol f type epoxy resin, also greatly
Temperature tolerance is improved greatly, while halogen-free flame-retardant system has reached environmental protection flame retardant effect, high price phosphonium flame retardant is also reduced
Addition.
By the present invention in that with ordinary epoxy resin and toughness modified epoxy, heat-resistance epoxy resin, phosphorous-nitrogenous
The mixing cured system cooperation of synergistic fire retardant, polyamide realizes adhesive and reaches outstanding toughness, and epoxy resin is inexpensive and holds
Easily obtain, and shear strength and peel strength higher can be kept at high temperature, flame retardant effect has also reached perfect condition,
Cost is reduced, environmental protection flame retardant is realized.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive, it is characterised in that the adhesive is by group by weight percentage
A 70% and component B 30% is divided to constitute, wherein, the component A includes:Bisphenol A type epoxy resin, bisphenol f type epoxy resin,
Toughness modified epoxy, toughener, coupling agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, antioxidant, thixotroping
Agent, diluent and defoamer;The toughness modified epoxy is the epoxy resin being modified by liquid nitrile rubber, uses nucleocapsid knot
The resin obtained after the treatment of structure polymer toughening;
The component B includes:Polyamide, fatty amine, modified amine, thixotropic agent, coupling agent modified inorganic filler and defoamer.
2. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 1, it is characterised in that each in the component A
Composition is relative to the weight ratio of bisphenol A type epoxy resin:Bisphenol f type epoxy resin 0.01~0.15, toughness modified epoxy tree
Fat 0.1~0.4, toughener 0.1~0.2, coupling agent modified inorganic filler 0.05~0.1, phosphonium flame retardant 0.05~0.5 contains
Nitrogen combustion inhibitor 0.05~0.3, antioxidant 0.001~0.05, thixotropic agent 0.05~0.07, diluent 0.02~0.05, defoamer
0.01~0.02;Other compositions are relative to the weight ratio of polyamide in component B:Fatty amine 0.5~1, modified amine 0.3~0.5,
Thixotropic agent 0.05~0.07, coupling agent modified inorganic filler 0.01~0.015, defoamer 0.01~0.02.
3. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 1 or 2, it is characterised in that:The component A's
In each composition, the bisphenol A type epoxy resin is selected from:One kind in each epoxy resin of E51, E44, E54, Der331, EPON828
Or it is several;
The bisphenol f type epoxy resin is selected from:In F51, F44, F48 one or more;
The toughener is with island structure toughener;
The phosphonium flame retardant is selected from:One or more in SPB-100, OP930, SP-703H
The nitrogenous flame ratardant is selected from:One or more in Melapur MC50, MelapurMC25, MelapurMC15;
The antioxidant uses Bayer Vulkanox BHT;
The diluent is one or more aliphatic or aliphatic epoxy radicals reactive diluent, is allyl glycidol
Ether, butyl glycidyl ether, 2- hexyl glycidyl ethers, aliphatic cyclohexanediol and one kind in glycidol ether or several
Kind
The toughness modified epoxy is obtained by the following manner:100 weight portion liquid nitrile rubbers are modified at room temperature
Epoxy resin and 50 weight portion core shell structure polymer, are thoroughly mixed, and obtain bright blend as toughness and are modified
Epoxy resin.
4. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 3, it is characterised in that the liquid butyronitrile rubber
The modified epoxy resin of glue is obtained by following manner:By 100 parts by weight of bisphenol A types epoxy resin, 20 weight at 20~40 DEG C
The mixing of part liquid butyronitrile resin, is heated to 160~170 DEG C, reacts 0.5h, vacuum defoamation, nitrogen emptying after being cooled to 150 DEG C,
5~10 weight portion polyfunctional epoxy resins are then added, after insulation 0.5h, vacuum defoamation is cooled to more than 100 DEG C nitrogen and puts
Sky obtains the modified epoxy resin of liquid nitrile rubber;
The shell of the core shell structure polymer is polystyrene, and core is rubber elastomer.
5. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 3, it is characterised in that the polyfunctional group ring
Oxygen tree fat is selected from:One or more in AG70, AG80, AFG90, TDE85.
6. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 3, it is characterised in that the island structure increases
Tough dose is selected from:One or more in F100, VL4, VL1, VE2, CYH-277.
7. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 1 or 2, it is characterised in that the component A and
Coupling agent modified inorganic filler in component B is obtained by following manner:At room temperature, by 100 parts by weight of ethanol, 5 weight portion idols
Connection agent mixing, under magnetic stirring, is slowly added to 50 parts by weight of inorganic fillers, and rotating speed is controlled in 100rpm, after stirring 0.5h, very
Empty suction filtration, the solid powder that will be finally given is positioned in culture dish, and the product obtained after 50 DEG C of drying grindings in baking oven is i.e.
It is coupling agent modified inorganic filler;
In the component A aerosil is used with the thixotropic agent in component B;
Defoamer in the component A and component B is disappeared using dimethyl silicone polymer, tributyl phosphate or fatty acid metal soaps
Infusion.
8. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 7, it is characterised in that the inorganic filler choosing
From:Calcium titanate, silica flour, titanium dioxide, potter's clay, barite, talcum powder, glass microballoon, aluminum oxide, silicon boride, the inorganic filler
Grain diameter be 5~20 μm.
9. halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as claimed in claim 1, it is characterised in that the component B it is each into
In point, the polyamide is selected from:In polyamide 6 50, polyamide 6 51, kymene 00, Versamid125, Versamid140
One or more;
The active hydrogen content of the aliphatic cyclic amine is 90~120, and amine value is 230~280mgKOH/g;
The active hydrogen content towering 120~150 of the modified amine, amine value is 250~300mgKOH/g.
10. the preparation method of a kind of halogen-free flame-resistant high-temperature-resistant tough epoxy adhesive as described in any one of claim 1 to 9,
It is characterised in that it includes following steps:
(1) feeding, each material composition of component A, B is taken according to the formula described in any one of claim 1 to 9 respectively;
(2) pre-treatment of raw material, prepares the toughness modified epoxy of component A respectively, and to prepare component A equal with component B
The coupling agent modified inorganic filler for using, wherein, the mode for preparing the toughness modified epoxy of component A is;At room temperature
The epoxy resin and 50 weight portion core shell structure polymer that 100 weight portion liquid nitrile rubbers are modified, are thoroughly mixed, and obtain
The toughness modified epoxy is to bright blend;
The mode for preparing the coupling agent modified inorganic filler that component A and component B is used is:At room temperature, by 100 weight portion second
Alcohol, the mixing of 5 weight portion coupling agents, under magnetic stirring, are slowly added to 50 parts by weight of inorganic fillers, and rotating speed is controlled in 100rpm,
After stirring 0.5h, vacuum filtration, the solid powder that will be finally given is positioned in culture dish, after 50 DEG C of drying grindings in baking oven
The product for obtaining is coupling agent modified inorganic filler;
(3) component A is prepared:Bisphenol A type epoxy resin, bisphenol f type epoxy resin, toughness obtained in above-mentioned steps (2) are modified
The defoamer of epoxy resin, toughener, diluent and component A is added in reactor, and at 50~70 DEG C, planetary rotating speed is 30~
45Hz, incorporation time 30min, add coupling agent modified inorganic filler, phosphonium flame retardant, nitrogenous flame ratardant, the antioxygen of component A
Agent, the thixotropic agent mixing of component A, planet stirring rotating speed is 20~30Hz, and dispersion impeller rotating speed is 800~900rpm, after 30min,
Vacuum -0.1Mpa, deaeration 30min are opened, then binder is to obtain component A;
(4) component B is prepared:By aliphatic cyclic amine, polyamide, modified amine, the coupling agent modified inorganic filler of component B obtained above and
The defoamer of component is added in the second reactor, and at 30 DEG C, planet stirring rotating speed is 20~30HZ, incorporation time 30min,
Add in thixotropic agent to second reactor of component B, mixing, speed of agitator is constant, dispersion impeller rotating speed is 800~900rpm,
Vacuum -0.1Mpa, deaeration 30min are opened after mixing 30min, then binder is to obtain component B;
By weight percentage, component A 70% obtained above and component B 30% is used cooperatively and obtains the resistance to height of halogen-free flameproof
Warm tough epoxy adhesive.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101818037A (en) * | 2009-02-27 | 2010-09-01 | 汉高(中国)投资有限公司 | Room-temperature curing epoxy structural adhesive composition and preparation method thereof |
CN102127384A (en) * | 2010-12-27 | 2011-07-20 | 广东风华高新科技股份有限公司 | Impact and light decay-resistant die attach insulation paste and preparation method thereof |
CN104403618A (en) * | 2014-12-18 | 2015-03-11 | 北京天山新材料技术有限公司 | High-strength, halogen-free and self-extinguishing type room temperature cured epoxy casting body and preparation method thereof |
CN104804691A (en) * | 2015-05-04 | 2015-07-29 | 上海都为电子有限公司 | Room temperature curing high-temperature-resistant high-tenacity epoxy adhesive and preparation method thereof |
CN105062396A (en) * | 2015-08-21 | 2015-11-18 | 卡本复合材料(天津)有限公司 | Double-component high-strength building epoxy structural adhesive and preparing method thereof |
-
2016
- 2016-12-29 CN CN201611247956.7A patent/CN106753132A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101818037A (en) * | 2009-02-27 | 2010-09-01 | 汉高(中国)投资有限公司 | Room-temperature curing epoxy structural adhesive composition and preparation method thereof |
CN102127384A (en) * | 2010-12-27 | 2011-07-20 | 广东风华高新科技股份有限公司 | Impact and light decay-resistant die attach insulation paste and preparation method thereof |
CN104403618A (en) * | 2014-12-18 | 2015-03-11 | 北京天山新材料技术有限公司 | High-strength, halogen-free and self-extinguishing type room temperature cured epoxy casting body and preparation method thereof |
CN104804691A (en) * | 2015-05-04 | 2015-07-29 | 上海都为电子有限公司 | Room temperature curing high-temperature-resistant high-tenacity epoxy adhesive and preparation method thereof |
CN105062396A (en) * | 2015-08-21 | 2015-11-18 | 卡本复合材料(天津)有限公司 | Double-component high-strength building epoxy structural adhesive and preparing method thereof |
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