CN1670106A - Modified epoxy resin adhesive and its preparation process - Google Patents
Modified epoxy resin adhesive and its preparation process Download PDFInfo
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- CN1670106A CN1670106A CN 200510024307 CN200510024307A CN1670106A CN 1670106 A CN1670106 A CN 1670106A CN 200510024307 CN200510024307 CN 200510024307 CN 200510024307 A CN200510024307 A CN 200510024307A CN 1670106 A CN1670106 A CN 1670106A
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Abstract
The invention discloses a thermosetting multi-component modified epoxy binder for using in the middle between IC cores and insulating underlay base boards and its preparation process, which belongs to the electronic device packaging technical field. The said binding agent is made of combined modified epoxide resin, latent curing agent, filler and addition auxiliary agent in a correct proportion, wherein the combined modified epoxide resin is made of bisphenol ethylene oxide resin as the main resin, alicyclic rings and naphthalene epoxide resin as the modified resin, the said latent curing agent is aromatic terminal group amine or alicyclic ring terminal group amine, the said filler is inorganic powder prepared by tensioactive treatment, the said addition auxiliary agent contains toning agent, accelerating agent, flame retardant and phenols curing agent. The said binding agent in the invention has many advantages such as high glass transition temperature, high adhesive property, high heat resistance, middle-and-low graded curing temperature and short curing time.
Description
Technical field
The invention belongs to electron device package material technology field, specifically relate to many components of thermoset modified epoxy resin adhesive between a kind of IC of being used for chip and the insulating substrate substrate and preparation method thereof.
Technical background
Organosilicon superpolymer and Resins, epoxy all are the electron device package materials of often selecting for use in the electronic industry.Organosilicon material, has low temperature flexibility (Tg=120 ℃), low surface energy, high temperature resistant, weather, corrosion-resistant, hydrophobic nature good, the dielectric strength advantages of higher, but also has the poor and wear resistance of mechanical mechanics property, anti-solvent, relatively poor, the more high shortcoming of cost of cohesive force.Resins, epoxy then has good mechanical property, chemical solvent resistance energy, antioxygen gas perviousness, water-repellancy, adhesiveproperties and better reaches easy machine-shaping, advantage such as with low cost.But form the 3 D stereo reticulated structure because the back takes place to solidify for Resins, epoxy and solidifying agent, lack relatively sliding between the macromolecular chain, and C-C key and C-O key are much smaller with respect to the bond energy of Si-O key, have higher surface energy, and have the polar hydroxyl on the macromolecular chain, thereby make it easily produce bigger internal stress, easy embrittlement behind the curing molding, the crazing degree is big, and high temperature is degraded chain rupture easily down, is subject to water absorption and the reduction flexural strength.Use modifying epoxy resin by organosilicon, promptly blend, copolymerization or the graft reaction by between the two reaches and can reduce the Resins, epoxy internal stress to form intramolecularly again toughness reinforcing, reaching reduction internal stress minimizing crazing reduces fragility, improve resistance to elevated temperatures, also improve organosilyl waterproof, grease proofing, antioxidant property simultaneously.The present epoxy resin encapsulation adhesive that uses, the set time long (＞18 hours), the solidification value height (＞150 ℃) that need can not satisfy the requirement that on the production line short, middle low temperature of encapsulation material solidifies time is encapsulated.And contain bromo element in the main encapsulation binding agent colloid composition, environment is polluted.Therefore, research and development can be under middle cold condition, and quick-setting environmental type caking agent has important Practical significance.
Summary of the invention
The object of the present invention is to provide modified epoxy resin adhesive of a kind of used for sealing electronic device and preparation method thereof.
The modified epoxy resin adhesive that the present invention proposes is a kind of liquid adhesive, and it is made up of following component: (A) complex modified epoxy, (B) latent curing agent, (C) filler, (D) add auxiliary agent.Wherein:
Component A: complex modified epoxy adds modified resin by matrix resin and forms.
This resin body is the bis-phenol structure, and epoxy group(ing) is at the two ends of molecule, and structure is designated as F shown in molecular formula (1)
1:
(1) in the formula when n=0 or 1, main body is a bispheno type epoxy ethane colophony, R
1And R
2Be C
1-C
3Alkoxyl group or hydroxyl, also can be replaced by nitrogen, phosphorus or methyl, ethyl.
In bisphenol type, add the Resins, epoxy of fats, alicyclic ring class or naphthalene type, the bisphenol type resin is made up modification, to reduce the viscosity of resin, strengthen its flowability, improve cementability.The resin that adds is preferably as follows some structure formations:
(a) naphthalene is a Resins, epoxy, and its structure is designated as F shown in molecular formula (2)
2:
R in the formula
3, R
4Be C
1-C
4The straight or branched alkyl, be preferably R
3, R
4Be methylene radical simultaneously.
(b) naphthalene is a Resins, epoxy, and structure is designated as F shown in molecular formula (3)
3: n=1～3 wherein:
(c) both-end base poly epoxy resin, structure is designated as F respectively shown in molecular formula (4), (5)
4, F
5:
N=0 in the formula, 1,2 is preferably n=1.
(d) two (3, the 4-epoxycyclohexyl) acetoacetic ester, structure is designated as F shown in molecular formula (6)
6:
Among the component A, the resin of adding can be selected F for use
2, F
3, F
4, F
5, F
6In the 2-3 kind, add-on is matrix resin F
130-40wt%, the add-on of 2-3 kind modified resin can be impartial.
B component: latent curing agent
Latent curing agent is fragrant end group amine or alicyclic ring type end group amine.Should synthesize by the raw material and the long-chain halohydrocarbon shown in molecular formula (9) of structure shown in molecular formula (7) or (8) by latentization solidifying agent:
R wherein
5, r
6Be C
1-C
10The straight or branched alkyl, be preferably C
1-C
5(7) material of formula is designated as G
1, the material of (8) formula is designated as G
2
Another active reaction thing is the long-chain halohydrocarbon, and structural formula is:
X-CH
2-R
7????????????????????????????(9)
Wherein, X is chlorine, bromine, iodine or hydroxyl, is preferably chlorine, bromine.R
7Be C
1-C
20Long-chain saturated alkane structure is preferably C
5-C
15The material of note (9) formula is G
3
The preparation method of latent curing agent: with reactant G
1Or G
2And another reactant G
3Add in the glass reactor, the two kinds of reactant quality in front and back are than being 1.1-3.9: 1, be preferably 1.5-2.5: and 1, temperature of reaction is 80-200 ℃, is preferably 90-120 ℃.After rising to temperature of reaction, adding weight concentration is the basic solution of 5%-30%, is preferably NaOH, KOH and Na
2CO
3, K
2CO
3Weight concentration is the alkaline aqueous solution of 10%-20%.Add-on is the 3-6% of the weight of reaction system, and the reaction times is 2-8 hour, wherein is preferably 3-6 hour.Reaction is used organic solvent extraction after finishing, and back rotary distillation removes and desolvates.The organic solvent that uses is liquid alkane commonly used in the organic chemistry, ketone, and alcohols etc. do not add strict restriction at this, can dissolve the organism that generates and get final product, and are preferably normal hexane, hexanaphthene.Obtaining product is colourless or yellowish transparent liquid product.
Component C: filler
The filler that uses among the present invention is inorganic powder, as molten silicon micro mist, silicon-dioxide, aluminum oxide, titanium oxide and aluminium nitride, titanium nitride, silicon carbide etc., is preferably molten silicon micro mist, silicon-dioxide.Filler adds the 0.1-5% that weight range is a system weight, is preferably 1.5-4%, and median size is answered＜20 μ m, is preferably＜10 μ m.
Generally can carry out surface-active-treatment earlier to inorganic powder, to increase the caking ability between epoxy resin surface and the powder particle, surface in contact is long-pending between the increase particle.Handling the employed tensio-active agent of inorganic powder among the present invention is organo-siloxane, specifically can adopt polydimethylsiloxane, the polysiloxane that contains vinyl that contains Si-H, the siloxanes that contains end oxygen base etc., and general structure can be expressed as follows:
R in the formula
8, R
9, R
10Be the polar group of facile hydrolysiss such as methyl, ethyl or aldehyde methyl, Y is amino, epoxy group(ing) or methacrylic acid isoreactivity group, can combine with the organic group in the resin, increases the adhesive power between the molecule.Filler is immersed in the above-mentioned silane, and high-speed stirring is heated to more than 100 ℃ after mixing, and removes excessive silane, and grind material cooling back, stand-by.
The surface-active-treatment method of filler:
In surfactant soln, be preferably the organic solution that adds inorganic powder in the organo-siloxane, organic solvent commonly used is small molecule alcohol, small molecules ethers or ketone, is preferably methyl alcohol or acetone.The system vigorous stirring, speed is 4000-6000rpm, makes it fully disperse, and is warming up to the solvent refluxing temperature then, reduce stir speed (S.S.), reaction times 1-5 hour, continuing to heat up steamed organic solvent, and controlled temperature is within 60～100 ℃, be preferably 80-95 ℃, this temperature range internal reaction 14-30 hour, treat that surface treatment is finished after, excessive tensio-active agent is removed in underpressure distillation; System is cooled to room temperature, separates, drying, then with distilled water or deionized water filter wash repeatedly, and adopts dehydrated alcohol to carry out processed, grinds to form fine powder after the vacuum-drying, promptly gets surface-active filler.
D, interpolation auxiliary agent
Add auxiliary agent and mainly contain toning agent (as white carbon black, carbon black), catalyzer (as phenmethyl imidazoles, imidazoles), fire retardant (as phosphorous, nitrogenous Resins, epoxy and aromatics Resins, epoxy) and phenols curing agent etc.The scope of adding the addition of auxiliary agent is 0.01～0.5wt%.
Binder formula of the present invention is formed content and is seen the following form 1:
Table 1 binder formula
Component per-cent (wt, %)
Complex modified epoxy 70-90
Latent curing agent 5～30
Filler 0.1～5
Add auxiliary agent 0.01～0.5
The each component total amount satisfies 100%.
The adhesive preparation method:
With F
1For basic ester, be equipped with F
2, F
3, F
4, F
5, F
62～3 kinds of resins wherein, its mass mixing ratio is for example gone up shown in the table 1.Subsequently respectively with it at 20-50 ℃ of following preheating 10-50min, preheating 15-20min when being preferably 30-35 ℃ adds diluting solvent, thinner is the lower small molecules organic solvent of boiling point, comprise alcohols, ketone, ethers and ester class, be preferably pimelinketone, normal hexane, dimethylbenzene.Induction stirring mixes it, vacuum (700mmHg) deaeration 15-25min, static 25-35min; Add filler microparticle (0.1～5%) then through surface-active-treatment, the intensification reflux, temperature is controlled to be 60～90 ℃, and the reaction times is 12～30 hours, adds dive property amine type solidifying agent (0.5～10%), filler (0.1-5%) and auxiliary agent (0.01-0.5) simultaneously successively.Add auxiliary agent toning agent (0～0.4), catalyzer (phenmethyl imidazoles or imidazoles) (0.1～0.5%), fire retardant (phosphorous, nitrogenous Resins, epoxy, ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.) (0～0.05%), phenols curing agent etc. are arranged; After the reaction, removal of solvent under reduced pressure promptly obtains the light yellow transparent colloid of heavy-gravity.The binding agent lucifuge sealing of making is preserved.Because of the fused silicon powder after surface-active-treatment, on the surface grafted alkyl lipophilic group can with the alkyl in the epoxy resin class mixture in the component, alkoxyl groups etc. have good consistency, impel the fused silicon powder to be uniformly dispersed; Simultaneously, also also hydroxyl generation dehydration reaction on the macromolecular chain in the blending epoxy of grafted epoxide group or unsaturation hydroxyl disappears the hydroxyl on the macromolecular chain on the fused silicon powder surface, has improved the colloidal water repelling property when reducing internal stress.The main performance index of this binding agent sees Table 2.
Table 2 binding agent the key technical indexes
| Mode of appearance | Faint yellow transparent colloid |
| Density (g/cm 3) (25 ℃ of viscosity, cp.s) solidification value (℃) (100 ℃ of heat-resisting poach of (h) elasticity set time, 24 hours) second-order transition temperature (Tg, ℃) | 1.05～1.15 150～300 40～60 4～16 fine crackles 120～135 that do not occur |
The binding agent advantage that the present invention proposes is as follows: have transparent, smooth, soft, warping strength characteristics, preparation process condition is simple, solidification value lower (middle temperature), lack set time (＜16h).Under room temperature state, can't play katalysis in the catalyzer that adds, thus under the air-tight state during 25 ℃ of room temperatures the colloid shelf lives also longer.And good to colloid to the encapsulation adhesion, various coating, paint also there are not the lacquer of stinging phenomenon, can on various base materials, use, base material can be a metal, can be various soft materials also, as PVC, PET, dacron chip base, ordinary rigid paper etc.
Embodiment
Further specify the present invention below in conjunction with embodiment, but embodiment does not limit protection scope of the present invention.
The preparation of I latent curing agent
Embodiment 1
Reactant 4-(4-ammonia benzyl) aniline molecular structural formula is as follows:
Reaction process:
Reactant ammonia benzylaniline 29.7g (0.15mol) and 1-chlorodecane 17.6g (0.1mol) are added in the glass reactor, add 15% NaOH basic solution 80ml, stir speed (S.S.) 1500rpm.Temperature of reaction is 90 ℃, rise to temperature of reaction after, the reaction 3h.After reaction finished, with the hexanaphthene extraction is arranged, rotary distillation removed and desolvates, and obtaining product is colourless or yellowish transparent liquid.Viscosity 320mp, condition of cure: heat up and solidify no effect under the low temperature more than 60 ℃.
Embodiment 2
The structural formula of reactant 4-(2-amino-ethyl)-1-methyl cyclohexylamine is as follows:
Reaction process:
Reactant 4-(2-amino-ethyl)-1-methyl cyclohexylamine 46.9g (0.3mol) and 12.1g (0.1mol) are joined in the glass reactor, add 15% Na
2CO
3100ml, stir fast.Temperature of reaction is 120 ℃, reaction 6h.After reaction finishes, use n-hexane extraction, after three times, rotary distillation removes and desolvates, must faint yellow transparent viscous liquid.Viscosity is 280mp.Low temperature does not have effect, is warming up to 45 ℃ and plays solidification.
The surface-active-treatment of II filler
The surface treatment of embodiment 3 silicon powders
In 50ml organo-siloxane solution, add the methanol solution (maximum diameter of silicon powder should less than 10 μ m) of 4.5% molten silicon micro mist, vigorous stirring 5000rpm, impel silicon powder fully to disperse in system, then be warming up to backflow, middling speed stirs, reaction times 1h, continuing to heat up steams methyl alcohol.Controlled temperature within 80～100 ℃, at this temperature range internal reaction 20h, treat that surface treatment is finished after, excessive siloxanes is removed in underpressure distillation.System is cooled to room temperature.Separate, after the drying,, and adopt dehydrated alcohol to carry out processed, grind to form fine powder after the vacuum-drying and obtain the surface treated molten silicon micropowder filler of 2.6g with distilled water or deionized water filter wash repeatedly.
The surface treatment of embodiment 4 SiO 2 powders
In organo-siloxane solution, add 5% SiO
2Ethanolic soln (maximum diameter should less than 8 μ m), stir 6000rpm fast, fully heat up after the dispersing and mixing, reduce stir speed (S.S.), reaction times 1.5h, continuing to heat up steams ethanol.Controlled temperature is at 90 ℃, reaction 18h, treat that surface treatment is finished after, excessive siloxanes is removed in underpressure distillation.System is cooled to room temperature.Separate, after the drying, with distilled water or deionized water filter wash repeatedly, and adopt dehydrated alcohol to carry out processed, it is standby to grind to form fine powder after the vacuum-drying.
The III binder making
Embodiment 5
Base ester F
1For bisphenol A type epoxy resin structured as follows:
F
2Structure be:
Two (3, the 4-epoxycyclohexyl) acetoacetic ester F
6Structure as follows:
Above-mentioned three kinds of resins all can directly be bought from the domestic market.
Join gluing method: get 9.0g bisphenol A type epoxy resin and each 1.5g of F2, F6 at 3: 1 by the quality proportioning, be dissolved in the dimethylbenzene of 15ml 30 ℃ of following preheatings 30 minutes, induction stirring mixes it, vacuum defoamation 20min and static 20min.The mixed ester class is joined in the there-necked flask of 100ml, fully mix, add simultaneously as solidifying agent 1.5g that example 1 is made, get in the experiment 3 through surface-treated molten silicon micro mist 0.5g, and fire retardant 0.03g, carbon black 0.01g is warming up to 80 ℃ in vain, along with the increase of temperature adds catalyzer phenmethyl imidazoles 0.01g gradually, 80 ℃ of controlled temperature, reaction is 24 hours under this temperature, and reaction finishes, remove excessive solvent, obtain light yellow transparent colloid after the cooling.
When the colloid condition of cure is 60 ℃ 8 hours, 80 ℃ of colloids solidified 3 hours.
Table 3 product colloidal condensate technical indicator
Appearance transparent elastomerics, little Huang
Bubble does not have obvious bubble
Transmittance＞90%
35 °～45 ° of intensity (Shao Shi)
Volume specific resistance＞1010
Density (g/cm
3) 1.05
Embodiment 6
Base fat F
1Structure be expressed as follows: (Mitsui Chemicals provides)
F
3Resin structure is expressed as follows: (Dongdu changes into)
F
4Resin structure is expressed as follows:
F
5Resin structure is expressed as follows:
F
4, F
5Shown in the resin domestic market on sale.
Get F by the quality proportioning
1Base fat 60g, F
3, F
4And F
5Respectively get 10g, be dissolved in the hexanaphthene of 150ml at 50 ℃ of following preheating 30min, induction stirring mixes it, vacuum defoamation 20min and static 20min.The mixed ester class is joined in the there-necked flask of 250ml, fully mix, add simultaneously as example 2 made solidifying agent 4g, get in the experiment 4 through surface-treated silicon dioxide powder 3.5g, and fire retardant 0.1g, carbon black 0.3g is warming up to 80 ℃ in vain, along with the increase of temperature adds catalyzer imidazoles 0.2g gradually, 70 ℃ of controlled temperature react 24h under this temperature, reaction finishes, remove excessive solvent, obtain light yellow transparent colloid after the cooling.
When the colloid condition of cure is 45 ℃ 5 hours, 60 ℃ of colloids solidified 3 hours.
Be applicable to printed board packaging plastic usefulness, base material can be soft base material, also can be metal base.
Storage requirement:
Packaging plastic should be loaded in the vinyon bucket of sealing, and it is shady and cool, dry that storage at should keep, and storing optimal temperature is 25 ℃, preserves to be more than 1 year proper storage period.
Embodiment 7
Base ester F
1For bisphenol A type epoxy resin structured as follows:
F
3Structure be:
F
5Resin structure is expressed as follows:
Above-mentioned three kinds of resins all can directly be bought from the domestic market.
Join gluing method: get 60g bisphenol A type epoxy resin and F3, each 10g of F5, be dissolved in the normal hexane of 20ml 25 ℃ of following preheatings 40 minutes, induction stirring mixes it, static 20min behind the vacuum defoamation 20min.The mixed ester class is joined in the there-necked flask of 100ml, fully mix, add simultaneously as solidifying agent 16.4g that example 2 is made, get in the example 4 through surface-treated SiO 2 powder 3g together with fire retardant 0.2g, carbon black 0.3g is warming up to 65 ℃ in vain, along with the increase of temperature adds catalyzer phenmethyl imidazoles 0.1g gradually, 65 ℃ of controlled temperature react 30h under this temperature, reaction finishes, remove excessive solvent, obtain light yellow transparent colloid after the cooling.
4.0h when the colloid condition of cure is 60 ℃, 80 ℃ of colloids solidify 1.5h.The colloidal condensate index is as shown in the table:
Table 4 product colloidal condensate technical indicator
Appearance transparent elastomerics, little Huang
Bubble does not have obvious bubble
Transmittance＞90%
45 °～50 ° of intensity (Shao Shi)
Volume specific resistance＞1010
Density (g/cm
3) 1.04
Embodiment 8
Base fat F
1Structure be expressed as follows: (Mitsui Chemicals provides)
F
2Structure be:
F
4Resin structure is expressed as follows:
Two (3, the 4-epoxycyclohexyl) acetoacetic ester F
6Structure as follows:
F
2, F
4, F
6Shown in the structural resin domestic market on sale.
Get F by the quality proportioning
1Base fat 70g, F
3, F
4And F
5Respectively get 5g, be dissolved in the dimethylbenzene of 250ml at 50 ℃ of following preheating 30min, induction stirring mixes it, static 30min behind the vacuum defoamation 20min.The mixed ester class is joined in the there-necked flask of 500ml, fully mix, add simultaneously as example 1 made solidifying agent 10g, get in the experiment 4 through surface-treated silicon dioxide powder 4.5g, and fire retardant 0.1g, carbon black 0.2g is warming up to 90 ℃ in vain, along with the increase of temperature adds catalyzer imidazoles 0.2g gradually, 90 ℃ of controlled temperature react 24h under this temperature, reaction finishes, remove excessive solvent, obtain the transparent colloid of oyster white after the cooling.
When the colloid condition of cure is 45 ℃ 8 hours, be 2 hours 70 ℃ of colloid set times.
Be applicable to printed board packaging plastic usefulness, base material can be soft base material, also can be metal, ceramic base material.
Storage requirement:
Packaging plastic should be loaded in the vinyon bucket of sealing, and it is shady and cool, dry that storage at should keep, and storing optimal temperature is 25 ℃, preserves to be more than 1 year proper storage period.
Claims (8)
1, a kind of modified epoxy resin adhesive is characterized in that being made up of following component: the A component: complex modified epoxy, B component: latent curing agent, C component: filler, D component: add auxiliary agent; The weight percent content of each component is:
Complex modified epoxy 70-90%
Latent curing agent 5-30%
Filler 0.1-5%
Add auxiliary agent 0.01-0.5%
Total amount satisfies 100%; Wherein:
The A component: complex modified epoxy, add modified resin by matrix resin and form, described matrix resin is the bis-phenol structural resin, is designated as F
1, structure shown in molecular formula (1),
In the formula, R
1And R
2Be C
1-C
3Alkoxyl group or hydroxyl, or substitute by nitrogen, phosphorus or methyl, ethyl,
The modified resin that adds is the Resins, epoxy of fats, alicyclic ring class or naphthalene type.
2, binding agent according to claim 1 is characterized in that the modified resin that adds is following F
2, F
3, F
4, F
5, F
6In the 2-3 kind, add-on is the 30-40wt% of matrix resin weight;
(a) naphthalene is a Resins, epoxy, and its structure is designated as F shown in molecular formula (2)
2:
R in the formula
3, R
4Be C
1-C
4The straight or branched alkyl;
(b) naphthalene is a Resins, epoxy, and structure is designated as F shown in molecular formula (3)
3: n=1～3 wherein:
(c) both-end base poly epoxy resin, structure is designated as F respectively shown in molecular formula (4), (5)
4, F
5:
N=0 in the formula, 1,2;
(d) two (3, the 4-epoxycyclohexyl) acetoacetic ester, structure is designated as F shown in molecular formula (6)
6:
3, binding agent according to claim 1 and 2, it is characterized in that described latent curing agent is fragrant end group amine or alicyclic ring type end group amine, this latentization solidifying agent is synthetic by raw material and the long-chain halohydrocarbon as molecular formula (9) shown in of structure shown in molecular formula (7) or (8):
R wherein
5, R
6Be C
1-C
10The straight or branched alkyl, the raw material of (7) formula is designated as G
1, the material of (8) formula is designated as G
2The structural formula of long-chain halohydrocarbon is:
X-CH
2-R
7??????????????????(9)
Wherein, X is chlorine, bromine, iodine or hydroxyl, R
7Be C
1-C
20Long-chain saturated alkane structure, the material of note (9) formula is G
3
4, binding agent according to claim 1 and 2 is characterized in that described filler is an inorganic powder: molten silicon micro mist, silicon-dioxide, aluminum oxide, titanium oxide and aluminium nitride, titanium nitride, silicon carbide, median size＜20 μ m.
5, binding agent according to claim 1 and 2 is characterized in that described interpolation auxiliary agent has toning agent, catalyzer, fire retardant and phenols curing agent.
6, a kind of preparation method as binding agent as described in one of claim 2-5 is characterized in that concrete steps are as follows: with F
1For basic ester, be equipped with F
2, F
3, F
4, F
5, F
62～3 kinds of resins wherein, respectively with it at 20-50 ℃ of following preheating 10-50min, add diluting solvent, induction stirring mixes it, vacuum defoamation 15-25min, static 25-35min; Add the filler microparticle through surface-active-treatment then, intensification reflux, temperature are controlled to be 60～90 ℃, and the reaction times is 12～30 hours, add dive property amine type solidifying agent, filler and auxiliary agent, phenols curing agent simultaneously successively; After the reaction, removal of solvent under reduced pressure promptly obtains the light yellow transparent colloid of heavy-gravity.
7, preparation method according to claim 6 is characterized in that the preparation process of described latent curing agent is as follows: with reactant G
1Or G
2And another reactant G
3Add in the glass reactor, the two kinds of reactant quality in front and back are than being 1.1-3.9:1, temperature of reaction is 80-200 ℃, after rising to temperature of reaction, adding weight concentration is the basic solution of 5%-30%, and add-on is the 3-6% of the weight of reaction system, reaction times is 2-8 hour, reaction is used organic solvent extraction after finishing, and back rotary distillation removes and desolvates.
8, preparation method according to claim 6, it is characterized in that the active treatment process of described filling surface is as follows: selecting organo-siloxane for use is tensio-active agent, select small molecule alcohol for use, small molecules ethers or organic solvent of ketone, system stirs, speed is 4000-6000rpm, make it fully disperse, be warming up to the solvent refluxing temperature then, reduce stir speed (S.S.), reaction times 1-5 hour, continuing to heat up steamed organic solvent, controlled temperature is within 60～100 ℃, this temperature range internal reaction 14-30 hour, treat that surface treatment is finished after, excessive tensio-active agent is removed in underpressure distillation; System is cooled to room temperature, separates, drying, then with distilled water or deionized water filter wash repeatedly, and adopts dehydrated alcohol to carry out processed, grinds to form fine powder after the vacuum-drying, promptly gets surface-active filler.
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