CN103305170A - Bi-component adhesive composition and preparation method thereof - Google Patents
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- CN103305170A CN103305170A CN2012100707121A CN201210070712A CN103305170A CN 103305170 A CN103305170 A CN 103305170A CN 2012100707121 A CN2012100707121 A CN 2012100707121A CN 201210070712 A CN201210070712 A CN 201210070712A CN 103305170 A CN103305170 A CN 103305170A
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Abstract
The invention provides a bi-component adhesive composition composed of an A component and a B component. The A component contains an epoxy resin mixture, a first toughening agent, filler and a thixotropic agent; the B component contains a second toughening agent, a normal temperature curing agent, a high-temperature curing agent and an accelerant; the epoxy resin mixture contains a first epoxy resin, a second epoxy resin and a third epoxy resin, the first epoxy resin is a bisphenol A epoxy resin or a bisphenol A epoxy resin, the second epoxy resin is a chelate modified epoxy resin, and the third epoxy resin is a naphthalene-nucleus modified epoxy resin; the first toughening agent is a core-shell structure rubber nano particle, the second toughening agent is an end-isocyanate polyurethane and/or end-carboxy nitrile rubber. The invention further provides a preparation method of the bi-component adhesive. The adhesive composition provided by the invention is high in adhesion strength, high in heat resistance, low in water adsorption, high in impact resistance, and capable of satisfying the use requirement of structural adhesive for connecting structural members of an automobile.
Description
Technical field
The invention belongs to automobile and use the epoxy structural rubber field, a kind of pair of component sizing agent of specific design composition and method of making the same.
Background technology
At present, automobile structure connects the main welding process that adopts, but along with automobile to weight reduction, reduce energy consumption, improve day by day increasing of security requirement, welding process can not satisfy technical requirements.For example, in order to alleviate tare, in the member of body of a motor car, can partly use the light-weight metal instead of steel such as aluminium alloy or magnesium alloy, and aluminium alloy, magnesium alloy are difficult to welding.In addition, traditional welding process is difficult to improve the anti-collision of automobile, causes the security of automobile not effectively improve.Therefore, welding process is by splicing or glued joint the gradually replacement of mode institute that combines with welding.And the sizing agent that the most often adopts in the bonding mode is epoxy structural rubber.
Automobile needs in the whole ambient temperature range that automobile uses with the various performances of epoxy structural rubber, and in the life-span of automobile use, good result is arranged all.Though common epoxy structural rubber possesses preferably bonding strength, thermostability and ageing resistance, but owing to there being following defective, cause it can not satisfy automobile structure and connect the requirement of using structure glue: (1) ordinary epoxy resin is not high to the bonding strength of oiliness steel plate, aluminium alloy, magnesium alloy, does not reach service requirements; (2) common toughner can reduce thermotolerance when improving epoxy glue toughness, and anti-dynamic impulsion is lower; (3) common epoxy glue is more than 80 ℃ the time, and its performance can decrease, can not satisfy the applied at elevated temperature requirement; (4) water tolerance of common epoxy glue is relatively poor: steam immerses after hydrothermal aging or salt fog are aging, and bonding plane is destroyed, and bonding strength is reduced greatly.
Summary of the invention
The bonding strength that the invention solves common epoxy structural rubber existence of the prior art is low, thermotolerance is connected with water tolerance, at high temperature can not use and relatively poor causing of shock resistance can not connect the technical problem of using structure glue as automobile structure.
The invention provides a kind of pair of component sizing agent composition, described pair of assembly sizing agent is comprised of A component and B component; Contain epoxy resin composition, the first toughner, filler and thixotropic agent in the described A component, contain the second toughner, ambient cure agent, high-temperature curing agent and promotor in the B component;
Contain first ring epoxy resins, the second Resins, epoxy and the 3rd Resins, epoxy in the described epoxy resin composition, wherein the first ring epoxy resins is bisphenol A epoxide resin or bisphenol F epoxy resin, the second Resins, epoxy is the inner complex modified epoxy, and the 3rd Resins, epoxy is naphthalene nucleus modified Resins, epoxy;
The first toughner is nucleocapsid structure rubber nano particle, and the second toughner is isocyanate terminated based polyurethanes and/or nbr carboxyl terminal.
The present invention also provides the preparation method of described pair of component sizing agent composition, may further comprise the steps:
S1, first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy are mixed with the first toughner, then add filler and thixotropic agent, grind and roll into paste, obtain described A component behind the vacuum outgas bubble;
S2, the second toughner, ambient cure agent, high-temperature curing agent and promotor are mixed, grind and roll into paste, obtain the B of institute component behind the vacuum outgas bubble.
Provided by the invention pair of component sizing agent composition compared with common epoxy structural rubber of the prior art, has the following advantages:
(1) by Resins, epoxy is suitably selected, concrete by adopting the inner complex modified epoxy to improve sizing agent to the cohesive strength of various metallic substance, adopt naphthalene nucleus modified Resins, epoxy to reduce water-intake rate, and improve the thermotolerance of sizing agent, so that sizing agent of the present invention all has higher bonding strength when using under hot conditions.
(2) by toughner is suitably selected, the concrete rubber nano particle of employing nucleocapsid structure that passes through is as the first toughner in the sizing agent of the present invention, so that sizing agent of the present invention all has good toughness and shock resistance in the use temperature at automobile under the prerequisite that does not reduce thermotolerance and rigidity, regulate low temperature flexibility and the adhesive power of sizing agent by adopting the second toughner; Use two kinds of toughner so that sizing agent of the present invention all meets service requirements at-40 ℃-80 ℃ by collocation.
(3) by solidifying agent is selected, the mode that specifically combines by employing ambient cure agent and high-temperature curing agent, crosslinking reaction can occur under the room temperature, so that sizing agent of the present invention has higher initial bonding force, solidify through subsequent thermal, further improve bonding strength and the toughness of sizing agent.
Embodiment
A kind of pair of component sizing agent composition provided by the invention, described pair of assembly sizing agent is comprised of A component and B component; Contain epoxy resin composition, the first toughner, filler and thixotropic agent in the described A component, contain the second toughner, ambient cure agent, high-temperature curing agent and promotor in the B component;
Contain first ring epoxy resins, the second Resins, epoxy and the 3rd Resins, epoxy in the described epoxy resin composition, wherein the first ring epoxy resins is bisphenol A epoxide resin or bisphenol F epoxy resin, the second Resins, epoxy is the inner complex modified epoxy, and the 3rd Resins, epoxy is naphthalene nucleus modified Resins, epoxy;
The first toughner is nucleocapsid structure rubber nano particle, and the second toughner is isocyanate terminated based polyurethanes and/or nbr carboxyl terminal.
Among the present invention, take the epoxy resin composition of 100 weight parts as benchmark, the total content of the first toughner and the second toughner is the 20-35 weight part, the content of filler is the 10-30 weight part, the content of thixotropic agent is the 3-6 weight part, the content of ambient cure agent is the 10-50 weight part, and the content of high-temperature curing agent is the 3-5 weight part, and the content of promotor is the 0.5-1.5 weight part.
Among the present invention, by Resins, epoxy is suitably selected, so that sizing agent of the present invention is to the higher cohesive strength of the equal tool of various metals, thermotolerance and water tolerance are stronger simultaneously.Particularly, contain first ring epoxy resins, the second Resins, epoxy and the 3rd Resins, epoxy in the described epoxy resin composition, wherein the first ring epoxy resins is bisphenol A epoxide resin or bisphenol F epoxy resin, the second Resins, epoxy is the inner complex modified epoxy, and the 3rd Resins, epoxy is naphthalene nucleus modified Resins, epoxy.
Wherein, the first ring epoxy resins is the Resins, epoxy of commonly using in the common epoxy structural rubber of prior art, is selected from bisphenol A epoxide resin or bisphenol F epoxy resin.Take the epoxy resin composition of 100 weight parts as benchmark, wherein the content of first ring epoxy resins is the 20-60 weight part.
Among the present invention, described first ring epoxy resins can adopt liquid-state epoxy resin or solid epoxy resin, and the present invention does not have special stipulation.Under the preferable case, described first ring epoxy resins adopts the mixture of liquid-state epoxy resin and solid epoxy resin.Take the epoxy resin composition of 100 weight parts as benchmark, contain the liquid-state epoxy resin of 10-30 weight part and the solid epoxy resin of 10-30 weight part in the described first ring epoxy resins.
Described liquid-state epoxy resin is liquid bisphenol A epoxide resin or bisphenol F epoxy resin, and its epoxy equivalent (weight) is 150-480g/eq.Among the present invention, described liquid-state epoxy resin can directly adopt and be purchased product, such as DER331.Described solid epoxy resin is solid-state bisphenol A epoxide resin or bisphenol F epoxy resin, and its epoxy equivalent (weight) is 400-800g/eq, and softening temperature is 65-100 ℃.Among the present invention, described solid epoxy resin also can directly adopt and be purchased product, for example NPES-901.
Described the second Resins, epoxy is the inner complex modified epoxy, because it contains the inner complex group, form chelate bond by inner complex group and metal ion, make sizing agent and metallic surface produce strong cohesive action, thereby improve the cohesive strength of sizing agent of the present invention.Take the epoxy resin composition of 100 weight parts as benchmark, the content of the second Resins, epoxy is the 30-70 weight part.
Under the preferable case, among the present invention, the epoxy equivalent (weight) of described the second Resins, epoxy is 165-350g/eq, and the content of inner complex group is 10-20wt%.
Inner complex group in the second Resins, epoxy can be the various groups commonly used that can form with metal ion chelate bond in the prior art.Under the preferable case, the inner complex group in described the second Resins, epoxy is sulfonic acid group or phosphate, but is not limited to this.
Among the present invention, described the second Resins, epoxy can directly adopt and be purchased product, for example can be selected from the EP-49-10N of ADEKA company.
Described the 3rd Resins, epoxy is naphthalene nucleus modified Resins, epoxy, i.e. contain the naphthalene nucleus group in the 3rd Resins, epoxy that the present invention adopts, so that described the 3rd Resins, epoxy has preferably thermotolerance and water tolerance simultaneously under the prerequisite with good solidification performance.Take the epoxy resin composition of 100 weight parts as benchmark, the content of the 3rd Resins, epoxy is the 5-10 weight part.
Under the preferable case, among the present invention, the epoxy equivalent (weight) of described the 3rd Resins, epoxy is 120-250g/eq, and the content of naphthalene nucleus group is 40-60wt%.As one embodiment of the present invention, described the 3rd Resins, epoxy can be the Resins, epoxy shown in formula I or the formula II, but is not limited to this.
Among the present invention, described the 3rd Resins, epoxy can directly adopt and be purchased product, for example can be selected from the HP-4700 of company of Japanese Dainippon Ink Chemicals.
Among the present invention, suitably select by toughner, so that of the present invention pair of component sizing agent all has good toughness and shock resistance in the use temperature at automobile under the prerequisite that does not reduce thermotolerance and rigidity, have simultaneously good low temperature flexibility and adhesive power, so that of the present invention pair of component sizing agent all meets service requirements at-40 ℃-80 ℃.Particularly, the first toughner is nucleocapsid structure rubber nano particle, and the second toughner is isocyanate terminated based polyurethanes and/or nbr carboxyl terminal.Take the epoxy resin composition of 100 weight parts as benchmark, the total content of toughner is the 20-35 weight part.
Wherein, the particle diameter as the nucleocapsid structure rubber nano particle of the first toughner is 50-200nm.Wherein, in the first toughner, shell material is according to methyl methacrylate, and nuclear matter is styrene-butadiene rubber(SBR), polyhutadiene or organo-silicone rubber.The epoxy resin composition of 100 weight parts is benchmark, and the content of the first toughner is the 10-20 weight part.
Urethane is the reaction product of polyisocyanates and polyol, and the present invention adopts isocyanate-terminated urethane.Under the preferable case, in the described isocyanate terminated based polyurethanes, isocyanate terminated equivalent is 1000-2000g/eq.Paracril is the polymerisate of divinyl and vinyl cyanide, adopts the paracril of carboxy blocking among the present invention.Under the preferable case, in the described nbr carboxyl terminal, the acrylonitrile group mass contg is 10-25wt%.
As a kind of preferred implementation of the present invention, described the second toughner is isocyanate terminated based polyurethanes and nbr carboxyl terminal.More preferably in the situation, take the epoxy resin composition of 100 weight parts as benchmark, wherein the content of isocyanate terminated based polyurethanes is the 8-15 weight part, and the content of nbr carboxyl terminal is the 5-10 weight part.
Among the present invention, by solidifying agent is selected, so that under the sizing agent room temperature of the present invention crosslinking reaction can occur, have higher initial bonding force, solidify through subsequent thermal, further improve bonding strength and the toughness of sizing agent.Particularly, described solidifying agent comprises ambient cure agent and high-temperature curing agent.
Described ambient cure agent can cause Resins, epoxy generation crosslinking reaction at normal temperatures.Under the preferable case, described ambient cure agent and can be selected from one or more of polymeric amide, triethylene tetramine, diethylenetriamine, polyethylene polyamine, hexanediamine, diethylaminopropylamine, mphenylenediamine, aliphatic cyclic amine, Amino Terminated polyether(ATPE) amine.Wherein polymeric amide adopts the polymeric amide of harmonic component, its molecular weight 200-600.For example, described ambient cure agent can adopt 200
#, 203
#, 300
#, 500
#, 650
#, 651
#Or 600
#Polymeric amide.The molecular weight of described Amino Terminated polyether(ATPE) amine is 200-2000.Take the epoxy resin composition of 100 weight parts as benchmark, the content of ambient cure agent is the 10-50 weight part.
Described high-temperature curing agent is selected from one or more in methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, dimethyl isodigeranyl guanidine, tetramethyl-isodigeranyl guanidine, hexamethyl isodigeranyl guanidine, this guanamine resin, methoxymethyl-ethoxymethyl benzo guanamine, Dyhard RU 100, SA two hydrazides.Take the epoxy resin composition of 100 weight parts as benchmark, the content of high-temperature curing agent is the 3-5 weight part.
Among the present invention, described thixotropic agent is various thixotropic agent commonly used in the prior art, for example can be selected from aerosil, organobentonite or the hydrogenated castor oil one or more, but be not limited to this.Wherein, aerosil can directly be selected and be purchased product, such as TS720.Take the epoxy resin composition of 100 weight parts as benchmark, the content of thixotropic agent is the 3-6 weight part.
Described filler can be selected from one or more in the silicate, Calucium Silicate powder ore deposit, chlorite of silica powder, aluminum oxide, clay, rhombspar, carbon fiber, glass fibre, polymer fiber, titanium oxide, calcium oxide, calcium carbonate and magnesium carbonate, barite, magnalium calcium.Take the epoxy resin composition of 100 weight parts as benchmark, the content of filler is the 10-30 weight part.
As a kind of preferred implementation of the present invention, described filler adopts the mixture of micron order filler and nano-sized filler.Wherein, the particle diameter of micron order filler is the 2-10 micron, and the particle diameter of nano-sized filler is 50-200nm.More preferably in the situation, take the epoxy resin composition of 100 weight parts as benchmark, the content of micron order filler is the 10-15 weight part, and the content of nano-sized filler is the 2-7 weight part.
Described promotor is the catalyzer that causes Resins, epoxy generation curing cross-linked under 120 ℃ or the higher temperature.Among the present invention, described promotor can be selected from modified imidazole, modification guanylurea or 2,4,6-three (dimethylamino methyl) phenol, 4, one or more in 4 '-methylene-bis (phenyl-Dimethylurea).Take the epoxy resin composition of 100 weight parts as benchmark, the content of promotor is the 0.5-1.5 weight part.
The present invention also provides the preparation method of described pair of component sizing agent composition, may further comprise the steps:
S1, first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy are mixed with the first toughner, then add filler and thixotropic agent, grind and roll into paste, obtain described A component behind the vacuum outgas bubble;
S2, the second toughner, ambient cure agent, high-temperature curing agent and promotor are mixed, grind and roll into paste, obtain the B of institute component behind the vacuum outgas bubble.
Among the present invention, the preparation method of described pair of component sizing agent composition is common method of the prior art, only is that selected raw material is different.
Under the preferable case, the temperature that first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy mix with the first toughner among the S1 is 50-100 ℃.Among the present invention, when preparation A component, the first toughner can directly adopt nucleocapsid structure rubber nano particle to be dispersed in the product that is purchased that forms homogeneous system in the ordinary epoxy resin, for example the trade mark is MX-153, wherein nucleocapsid structure rubber nano particle is dispersed among the DER331, the content of nucleocapsid structure rubber nano particle is 37wt%, and wherein the particle diameter of nucleocapsid structure rubber nano particle is 100nm.
The mixing of the second toughner, ambient cure agent, high-temperature curing agent and promotor carry out at normal temperatures among the S2.
Grinding the method that is pressed into paste among S1, the S2 all adopts three-roll grinder to carry out.Among the S1, the time of vacuum outgas bubble is 15-45 minute.Among the S2, the time of vacuum outgas bubble is 15-45 minute.
Sizing agent composition provided by the invention has high bond strength, high heat resistance, low water absorbable and high impact properties, can be used as automobile structure and connects with structure glue in the whole ambient temperature range of automobile use, be widely used in work-ing life.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.Embodiment is that the raw material that adopts all is commercially available in the Comparative Examples, and the present invention does not have particular determination.
Embodiment 1-3
(1) presses proportioning raw materials shown in the table 1, first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy and the first toughner are mixed under 65 ℃, then adding filler and thixotropic agent is mixed to without the powdery attitude, roll into paste at three-roll grinder, the vacuum outgas bubble obtains the A component of two component sizing agent S1-S3 of embodiment 1-3 after 30 minutes.
(2) press proportioning raw materials shown in the table 1, the second toughner, ambient cure agent, high-temperature curing agent and promotor are at room temperature mixed, extremely without the powdery attitude, then roll into paste at three-roll grinder, the vacuum outgas bubble obtains the B component of two component sizing agent S1-S3 of embodiment 1-3 after 30 minutes.
Table 1
Comparative Examples 1-4
Adopt the step identical with embodiment 1-3 to prepare A component and the B component of two component sizing agent DS1-DS4 of Comparative Examples 1-4, difference is, proportioning raw materials is as shown in table 2.
Table 2
Performance test:
After S1-S3 and the DS1-DS4 even mixing of A component, B component separately, be coated in respectively on two block plates that need bonding, again two block plates are bonded together, placed 2 days under the room temperature, then test respectively.
Method for testing shear strength is: GBT 7124-2008, draw speed: 10mm/s;
T peel strength test method is: GBT 2791-1995, draw speed: 100mm/s;
The impact peel strength testing method is: ISO11343, impact velocity: 2m/s;
High bake: storing temperature is 180 ℃, and storing time is 30min;
Hydrothermal aging: humidity: 95%, temperature 50 C ± 2 ℃, 20 days time;
Salt fog is aging: 35 ℃ ± 2 ℃ of temperature, and in the salt-spray cabinet of 5% salt solution, 20 days time.
Test result is shown in table 3 and table 4.
Table 3
Table 4
Relatively can find out from upper table 3 and the test result of table 4, provided by the invention pair of component sizing agent has high-adhesive-strength, high heat resistance, low water absorbable and high impact properties.
Relatively can find out from the test result of S1-S3 and DS1, when not adopting the second Resins, epoxy (being the inner complex modified epoxy), the bonding strength of sizing agent reduces greatly.
Relatively can find out from the test result of S1-S3 and DS2, when not adopting the 3rd Resins, epoxy (being naphthalene nucleus modified Resins, epoxy), the thermotolerance of sizing agent, wet and heat ageing resistant and salt fog aging resistance reduce greatly.
Relatively can find out from the test result of S1-S3 and DS3, when not adopting the first toughner (being nucleocapsid structure rubber nano particle), the shock resistance of sizing agent is not up to standard.
Relatively can find out from the test result of S1-S3 and DS4, when not adopting the ambient cure agent, the initial bonding force of sizing agent is very low.
Sizing agent composition provided by the invention only has and possesses simultaneously above component, could satisfy the service requirements of vehicle structure glue.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a two component sizing agent composition is characterized in that, described pair of assembly sizing agent is comprised of A component and B component; Contain epoxy resin composition, the first toughner, filler and thixotropic agent in the described A component, contain the second toughner, ambient cure agent, high-temperature curing agent and promotor in the B component;
Contain first ring epoxy resins, the second Resins, epoxy and the 3rd Resins, epoxy in the described epoxy resin composition, wherein the first ring epoxy resins is bisphenol A epoxide resin or bisphenol F epoxy resin, the second Resins, epoxy is the inner complex modified epoxy, and the 3rd Resins, epoxy is naphthalene nucleus modified Resins, epoxy;
The first toughner is nucleocapsid structure rubber nano particle, and the second toughner is isocyanate terminated based polyurethanes and/or nbr carboxyl terminal.
2. according to claim 1 pair of component sizing agent composition, it is characterized in that, take the epoxy resin composition of 100 weight parts as benchmark, the total content of the first toughner and the second toughner is the 20-35 weight part, the content of filler is the 10-30 weight part, and the content of thixotropic agent is the 3-6 weight part, and the content of ambient cure agent is the 10-50 weight part, the content of high-temperature curing agent is the 3-5 weight part, and the content of promotor is the 0.5-1.5 weight part.
3. according to claim 1 and 2 pair of component sizing agent composition is characterized in that, take the epoxy resin composition of 100 weight parts as benchmark, the content of the first toughner is the 10-20 weight part;
The second toughner is isocyanate terminated based polyurethanes and nbr carboxyl terminal; Take the epoxy resin composition of 100 weight parts as benchmark, wherein the content of isocyanate terminated based polyurethanes is the 8-15 weight part, and the content of nbr carboxyl terminal is the 5-10 weight part.
4. according to claim 1 pair of component sizing agent composition, it is characterized in that, the particle diameter of described nucleocapsid structure rubber nano particle is 50-200nm, and wherein shell material is according to methyl methacrylate, and nuclear matter is styrene-butadiene rubber(SBR), polyhutadiene or organo-silicone rubber;
In the described isocyanate terminated based polyurethanes, isocyanate terminated equivalent is 1000-2000g/eq; In the described nbr carboxyl terminal, the acrylonitrile group mass contg is 10-25wt%.
5. according to claim 1 pair of component sizing agent composition, it is characterized in that, take the epoxy resin composition of 100 weight parts as benchmark, wherein the content of first ring epoxy resins is the 20-60 weight part, the content of the second Resins, epoxy is the 30-70 weight part, and the content of the 3rd Resins, epoxy is the 5-10 weight part.
6. two component sizing agent compositions according to claim 1 or 5, it is characterized in that, take the epoxy resin composition of 100 weight parts as benchmark, contain the liquid-state epoxy resin of 10-30 weight part and the solid epoxy resin of 10-30 weight part in the described first ring epoxy resins; The epoxy equivalent (weight) of described liquid-state epoxy resin is 150-480g/eq; The epoxy equivalent (weight) of described solid epoxy resin is 400-80g/eq, and softening temperature is 65-100 ℃.
7. two component sizing agent compositions according to claim 1 or 5 is characterized in that, the epoxy equivalent (weight) of described the second Resins, epoxy is 165-350g/eq, and the content of inner complex group is 10-20wt%.
8. according to claim 7 pair of component sizing agent composition is characterized in that, the inner complex group in described the second Resins, epoxy is sulfonic acid group or phosphate.
9. two component sizing agent compositions according to claim 1 or 5 is characterized in that, the epoxy equivalent (weight) of described the 3rd Resins, epoxy is 120-250g/eq, and the content of naphthalene nucleus group is 40-60wt%.
10. according to claim 9 pair of component sizing agent composition is characterized in that, described the 3rd Resins, epoxy is the Resins, epoxy shown in formula I or the formula II:
11. according to claim 1 pair of component sizing agent composition, it is characterized in that, described ambient cure agent is selected from one or more of polymeric amide, triethylene tetramine, diethylenetriamine, polyethylene polyamine, hexanediamine, diethylaminopropylamine, mphenylenediamine, aliphatic cyclic amine, Amino Terminated polyether(ATPE) amine, the molecular weight 200-600 of polymeric amide wherein, the molecular weight of Amino Terminated polyether(ATPE) amine is 200-2000;
Described high-temperature curing agent is selected from one or more in methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, dimethyl isodigeranyl guanidine, tetramethyl-isodigeranyl guanidine, hexamethyl isodigeranyl guanidine, this guanamine resin, methoxymethyl-ethoxymethyl benzo guanamine, Dyhard RU 100, SA two hydrazides.
12. according to claim 1 pair of component sizing agent composition is characterized in that described thixotropic agent is selected from aerosil, organobentonite or hydrogenated castor oil;
Described filler is selected from one or more in the silicate, Calucium Silicate powder ore deposit, chlorite of silica powder, aluminum oxide, clay, rhombspar, carbon fiber, glass fibre, polymer fiber, titanium oxide, calcium oxide, calcium carbonate and magnesium carbonate, barite, magnalium calcium;
Described promotor is selected from modified imidazole, modification guanylurea or 2,4,6-three (dimethylamino methyl) phenol, 4, one or more in 4 '-methylene-bis (phenyl-Dimethylurea).
13. according to claim 1 or 12 described pairs of component sizing agent compositions, it is characterized in that, comprise in the described filler that particle diameter is that micron order filler and the particle diameter of 2-10 micron is the nano-sized filler of 50-200nm; Take the epoxy resin composition of 100 weight parts as benchmark, the content of micron order filler is the 10-15 weight part, and the content of nano-sized filler is the 2-7 weight part.
14. the preparation method of claimed in claim 1 pair of component sizing agent composition is characterized in that, may further comprise the steps:
S1, first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy are mixed with the first toughner, then add filler and thixotropic agent, grind and roll into paste, obtain described A component behind the vacuum outgas bubble;
S2, the second toughner, ambient cure agent, high-temperature curing agent and promotor are mixed, grind and roll into paste, obtain the B of institute component behind the vacuum outgas bubble.
15. preparation method according to claim 14, it is characterized in that, the temperature that first ring epoxy resins, the second Resins, epoxy, the 3rd Resins, epoxy mix with the first toughner among the S1 is 50-100 ℃, and the mixing of the second toughner, ambient cure agent, high-temperature curing agent and promotor carry out at normal temperatures among the S2.
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