CN105199079A - High-strength white reflective epoxy resin composition for LED bracket - Google Patents
High-strength white reflective epoxy resin composition for LED bracket Download PDFInfo
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- CN105199079A CN105199079A CN201510724283.9A CN201510724283A CN105199079A CN 105199079 A CN105199079 A CN 105199079A CN 201510724283 A CN201510724283 A CN 201510724283A CN 105199079 A CN105199079 A CN 105199079A
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Abstract
The invention provides high-strength white reflective epoxy resin composition for an LED bracket. The high-strength white reflective epoxy resin composition mainly comprises epoxy resin, an anhydride or acid curing agent, a curing agent promoter, a coloring agent and a flexibilizer, wherein the epoxy resin is selected from siloxane containing silicon main chains and epoxy groups and modified by four epoxy functional groups; the curing agent anhydride is a multifunctional anhydride with the structure shown in the formula (I). The invention further discloses a preparation method of the epoxy resin composition. The white reflective epoxy resin composition has high hot strength, high crosslinking density and intensity, low warpage, high reflectance and excellent aging resistance, the initial reflectance is higher than 90% in a 450-nm position, the reflectance after 1,000 h ageing at 150 DEG C is increased to be higher than 80%, the high-temperature ageing performance is excellent, the composition is suitable for long-term work after packaging of a high-power LED bracket, the continuous molding performance is improved, the number of molds obtained through continuous molding is increased from 100 to 200, and the operability is improved greatly.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, particularly a kind of LED support high strength white reflexed light ring epoxy resin composition.
Background technology
LED, with its environmental protection, the advantage such as energy-conservation, rises in Lighting Industry rapidly.Meanwhile, along with LED lamp bead also by small power to high-power future development, by illumination send out to industrial application, the LED encapsulation material supporting with it also faces new challenges.Traditional high-temperature nylon, the materials such as PCT are high temperature resistant, and the aspects such as the long-time xanthochromia of high temperature can not meet the demands, and epoxy plastic cement is with its good mechanical property, good ageing-resistant and uv-resistance energy, and the application of the price of rather moderate on LED support gets more and more.Material manufacturer both domestic and external goes into overdrive to research and develop especially, wherein headed by Hitachi and Ya chemistry.Meanwhile, each family has also all delivered relevant patent documentation, and more relates to triazine derivative epoxy resin and methyl hexahydrophthalic anhydride or HHPA as solidifying agent, coordinates white pigment to obtain.And use above-mentioned system at present, after being then easy to occur encapsulated moulding, intensity is lower, LED support is relatively soft, be not easy operation, make continuous moulding property bad, at present the highest problem such as can only to reach about 100 moulds, simultaneously along with the increase of LED luminous power, in high temperature ageing performance, it is also proposed higher requirement to composition epoxy resin, the reflectivity of currently available products at 450nm place after 150 degrees Celsius of 1000h are aging is 70% can not to have met the demands.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provide a kind of new LED support high strength white reflexed light ring epoxy resin composition, said composition has good adhesiveproperties and mechanical property, has good intensity, aging resistance and molding performance simultaneously.
Technical problem to be solved by this invention is achieved through the following technical solutions.The present invention is a kind of LED support high strength white reflexed light ring epoxy resin composition, and be characterized in, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for the 2-25% of composition epoxy resin gross weight.
Silicone compounds in composition epoxy resin of the present invention had both had the main chain of organosilicon structures, and ageing-resistant performance is excellent, had epoxide group again, had higher reactive behavior, and adhesiveproperties and good mechanical performance.
Technical problem to be solved by this invention can also be achieved through the following technical solutions.Above-described LED support high strength white reflexed light ring epoxy resin composition, is characterized in, described acid anhydride type curing agent is the polyfunctional group acid anhydrides with structure shown in formula (1) with multiple reactive behavior point.This solidifying agent adds crosslinking activity point, improve speed of response and shaping after intensity, there is good ageing-resistant performance simultaneously.
Formula (1)
The weight of described polyfunctional group anhydride curing agent accounts for the 2-25% of composition epoxy resin gross weight.
In LED support high strength white reflexed light ring epoxy resin composition of the present invention: described solidifying agent promotor has no particular limits, and solidifying agent promotor can make any known solidifying agent promotor for composition epoxy resin, such as tertiary amine, imidazoles and their organic carboxylate, organo-metallic carboxylate salt, metal-organic chelate compound, aromatic sulfonic acid ester, organo phosphorous compounds, phosphorus compound, with other phosphorus solidifying agent promotor and its salt, these solidifying agent promotor can be used alone also can two kinds or multiple combination use.In these solidifying agent promotor, preferably use quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate etc. for transparent material and the good solidifying agent promotor of bonding force, wherein solidifying agent promotor accounts for the 0.01-3% of composition epoxy resin total amount.
In LED support high strength white reflexed light ring epoxy resin composition of the present invention: described tinting material is used for improving the whiteness of material, for titanium dioxide, zinc oxide, calcium carbonate, Calucium Silicate powder, zirconium white, zinc sulphide, magnesium oxide etc., and preferably use titanium dioxide.The type of titanium dioxide is preferably the excellent rutile-type of weather resistance, and the particle diameter of titanium dioxide is preferably 0.03-5um, and more preferably 0.05-2um, increase its specific surface area and promote covering power.Titanium dioxide can carry out surface treatment to improve consistency and the dispersiveness of itself and resin in advance with inorganic or organic substance, and is particularly preferably aluminium, silicon or the surface coated process of organic compound.The content of tinting material at 2-60%, be preferably 3-40%, add-on very little time, tinting strength is poor, the reflectivity of product is lower, and can not meet customer requirement, add-on is too much, cause the molding performance of product to be deteriorated, flowing property is lower, causes lack of fill or the problem such as mucous membrane, dirty mould.
In LED support high strength white reflexed light ring epoxy resin composition of the present invention: described toughner is any known to the silicone oil in composition epoxy resin field, silicone elastomer, core shell rubbers etc., also the polyalcohols reactive toughening agent such as polyoxyethylene glycol, neopentyl glycol, glycerol can be selected to carry out toughness reinforcing to resin system, control the warpage degree of product simultaneously.Here toughner is preferably the reactive toughening agent of polyalcohols.The addition of toughner is the 0.1-10% of composition epoxy resin total amount, more preferably 0.2-5%,
In LED support high strength white reflexed light ring epoxy resin composition of the present invention: can also mineral filler be added as required.Mineral filler can be the conventional variety in composition epoxy resin field.Comprise the silicon-dioxide, aluminum oxide, silicon nitride, aluminium nitride, boron nitride, glass fibre etc. of the silicon-dioxide of melting, crystallization.Median size and the shape of mineral filler have no particular limits, the mineral filler used in addition can make to comprise silane coupling agent or titante coupling agent process, to strengthen the inorganic active filler of bonding strength between mineral filler and resin through coupling agent.The content of mineral filler accounts for the 5-90% of composition epoxy resin total amount, more preferably 20-80%.
In LED support high strength white reflexed light ring epoxy resin composition of the present invention: as required, coupling agent can also be added to strengthen the intensity between resin and mineral filler.γ-glycidoxypropyltrimewasxysilane that these coupling agents can make composition epoxy resin field back warp commonly use, γ-glycidoxypropyl diethoxy silane and β-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, organoalkoxysilane such as N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane and the N-phenyl-gamma-amino propyl trimethoxy silicane of amino-functional; With the organoalkoxysilane such as γ mercaptopropyitrimethoxy silane of Mercaptofunctional.The content of coupling agent accounts for the 0.01-3% of composition epoxy resin total amount, more preferably 0.05-1.5%.
Technical problem to be solved by this invention can also be achieved through the following technical solutions.Above-described high strength white reflexed light ring epoxy resin composition, be characterized in can also adding releasing agent as required, releasing agent is carnauba wax known in composition epoxy resin field, sour wax, ester type waxes, polyethylene wax, metallic stearate or the good silicone oil of removal.The add-on of releasing agent is 0.01-5%, elects 0.03-3% as further.Content very little, does not then have the effect of the demoulding, and content is too much, then can cause the bonding force deficiency of composition epoxy resin and silver-colored framework, and then loses efficacy in reliability testing below.In order to reach better ageing-resistant performance, be preferably ester type waxes and silicone oil, simultaneously in order to realize better demolding performace, can preferably by releasing agent and epoxy resin and solidifying agent under the condition heated, after fusing, mix, pulverize after cooling, and then according to proportioning, add in the process preparing composition epoxy resin.
Technical problem to be solved by this invention can also be achieved through the following technical solutions.Above-described high strength white reflexed light ring epoxy resin composition, be characterized in can also adding oxidation inhibitor as required, it can be hindered phenol antioxygen, phosphoric acid ester oxidation inhibitor or sulphur oxidation inhibitor, the oxidation inhibitor 2 of such as Hinered phenols, 6-ditertbutylparacresol, butylated hydroxyanisol, 2, 6-di-t-butyl-p-ethyl phenol, stearyl-β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 3, 9-two [1, 1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl] 2, 4, 8, 10-tetra-oxa-volution [5, 5] undecane, 1, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, with 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, and most preferably 2, 6-ditertbutylparacresol.The oxidation inhibitor of phosphoric acid ester: triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, three (nonyl phenyl) phosphorous acid ester, trilauryl phosphite, three (octadecane) base phosphorous acid ester, triphenyl phosphite, distearyl acyl group pentaerythritol diphosphites, three (2, 4-di-tert-butyl-phenyl) phosphorous acid ester, diiso decyl pentaerythritol diphosphites, two (2, 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, three stearyl sorbyl alcohol GW-540s, with four (2, 4-di-tert-butyl-phenyl)-4, 4 '-xenyl bisphosphonates, and most preferably triphenyl phosphite.The oxidation inhibitor of sulphur class: dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate and distearyl-3,3 '-thiodipropionate.
Although these oxidation inhibitor can separately or combinationally using with two or more, phosphorus antioxidant separately or to combinationally use with phenol oxidation inhibitor and phosphorus antioxidant be particularly preferred.Oxidation inhibitor preferably with 0.01-10wt%, and is in particular 0.03-5wt% and is blended in composition epoxy resin.The content of oxidation inhibitor is very few may cause insufficient thermotolerance, and this may cause decolouring, and excessive introducing may cause suppressing solidification, and may not realize sufficient ability to cure and intensity.
In high strength white reflexed light ring epoxy resin composition of the present invention: can also add various additive as required, comprising ion capturing agent, fire retardant etc. can be introduced under the prerequisite not affecting advantage of the present invention.
In high strength white reflexed light ring epoxy resin composition of the present invention: described epoxy resin is except the described siloxanes containing four epoxide groups, following epoxy resin can also be contained: triazine derivative epoxy resin, bisphenol epoxy, such as bisphenol A epoxide resin, bisphenol F epoxy resin, 3, 3 ', 5, 5 '-tetramethyl--4, 4 '-xenol epoxy resin, or 4, 4 '-xenol epoxy resin, phenol novolac epoxy resins, cresol novolac epoxy, bisphenol A novolac epoxy resin, naphthalene glycol epoxy resin, three hydroxyphenyl methane type epoxy resins (trisphenylolmethaneepoxyresin), four hydroxy phenyl ethane epoxy resin, with the phenol dicyclopentadiene novolac epoxy resin that its aromatic ring is hydrogenated.
The content of these epoxy resin accounts for less than 60% of the described siloxanes weight containing four epoxide groups.
In high strength white reflexed light ring epoxy resin composition of the present invention: described solidifying agent is except the polyfunctional group acid anhydrides shown in formula (1), the non-aromatic acid anhydrides or not carbon-to-carbon double bond such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyl Tetra Hydro Phthalic Anhydride and hydrogenating methyl carbic anhydride can also be contained, less than 80% of this polyfunctional group anhydride weight shown in acid anhydrides formula (1), preferably accounts for 10-50%.
Technical problem to be solved by this invention can also be achieved through the following technical solutions.The invention also discloses a kind of preparation method of the high strength white reflexed light ring epoxy resin composition as described in above technical scheme, be characterized in, its step is as follows:
(1) preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely; After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 60-100 DEG C, until the resin intermediate generated, at 150 DEG C of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use;
(2) preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
Compared with prior art, composition and method of making the same of the present invention has following technique effect:
1, high strength white Luminous Ring epoxy resin composition of the present invention, by introducing the epoxy resin containing silicon main chain, improve the ageing-resistant performance of resin, use the solidifying agent with multiple reactive behavior point shown in formula (1) simultaneously, add the reactive behavior point of resin, strengthen intensity and ageing-resistant performance further, make the hot hardness of its 90s after molding more than 80,150 DEG C of 1000h aging after, the reflectivity at 450nm place, more than 80%, is applicable to the encapsulation of LED support more.
2, when prepared by the present invention, by first epoxy resin, solidifying agent, releasing agent and oxidation inhibitor etc. being pre-mixed and reacting, oxidation inhibitor and releasing agent is made to reach molecularly dispersed structure in resin system, and then obtain better stripping result and ageing-resistant performance, simultaneously by the reaction in advance of epoxy resin and solidifying agent, micromolecular material is discharged away, decreases the problems such as composition epoxy resin pore in use.By the solidifying agent shown in formula (1), improve resin combination intensity and ageing-resistant performance further, make its continuous moulding property bring up to 200 moulds by 100 original moulds.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art further understands the present invention, and do not form the restriction to its right.
Embodiment 1, a kind of LED support high strength white reflexed light ring epoxy resin composition, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for the 2-25% of composition epoxy resin gross weight.
Embodiment 2, in the LED support high strength white reflexed light ring epoxy resin composition described in embodiment 1: described acid anhydride type curing agent is for having the polyfunctional group acid anhydrides of structure shown in formula (1):
Formula (1)
The weight of described polyfunctional group acid anhydrides accounts for the 2-25% of composition epoxy resin gross weight.
Embodiment 3, in the LED support high strength white reflexed light ring epoxy resin composition described in embodiment 1 or 2: the epoxy equivalent (weight) in epoxy resin is 0.5-2.5 with the ratio of the anhydride equivalent in acid anhydrides.
Embodiment 4, in LED support high strength white reflexed light ring epoxy resin composition in embodiment 1-3 described in any one: solidifying agent promotor is selected from quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate, and solidifying agent promotor accounts for the 0.01-3% of composition epoxy resin total amount.
Embodiment 5, in the LED support high strength white reflexed light ring epoxy resin composition in embodiment 1-3 described in any one: described tinting material is selected from the rutile titanium dioxide that particle diameter is 0.03-5 μm; And tinting material accounts for the 2-60% of composition epoxy resin total amount.
Embodiment 6, in LED support high strength white reflexed light ring epoxy resin composition in embodiment 5 described in any one: the particle diameter of described titanium dioxide is 0.05-2um, and described titanium dioxide carries out surface coated process with aluminium or silicon materials or organic compound in advance; And tinting material accounts for the 3-40% of composition epoxy resin total amount.
Embodiment 7, in the LED support high strength white reflexed light ring epoxy resin composition in embodiment 1-6 described in any one: described toughner is the reactive toughening agent of polyalcohols; The addition of toughner is the 0.1-10% of composition epoxy resin total amount.
Embodiment 8, LED support in embodiment 1-7 described in any one is with in high strength white reflexed light ring epoxy resin composition: this composition epoxy resin is also containing oxidation inhibitor, described oxidation inhibitor is selected from phosphorus antioxidant, or the composition of phosphorus antioxidant and phenol oxidation inhibitor; Described oxidation inhibitor accounts for the 0.01-10% of composition epoxy resin total amount.
Embodiment 9, the LED support of embodiment 1-8 described in any one preparation method of high strength white reflexed light ring epoxy resin composition, its step is as follows:
(1) preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely.After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 60-100 DEG C, until the resin intermediate generated, at 150 DEG C of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use.
(2) preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
Embodiment 10, a kind of LED support high strength white reflexed light ring epoxy resin composition, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for 10% of composition epoxy resin gross weight.
Described acid anhydride type curing agent is for having the polyfunctional group acid anhydrides of structure shown in formula (1), and the weight of described polyfunctional group acid anhydrides accounts for 8% of composition epoxy resin gross weight.
Described solidifying agent promotor is selected from quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate, and solidifying agent promotor accounts for 1% of composition epoxy resin total amount.
The particle diameter of described titanium dioxide is 0.05um, and described titanium dioxide carries out surface coated process with aluminium or silicon materials in advance; And tinting material accounts for 15% of composition epoxy resin total amount.
Described toughner is the reactive toughening agent of polyalcohols; The addition of toughner is 5% of composition epoxy resin total amount.
This composition epoxy resin is also containing oxidation inhibitor, and described oxidation inhibitor is selected from phosphorus antioxidant, or the composition of phosphorus antioxidant and phenol oxidation inhibitor; Described oxidation inhibitor accounts for 5% of composition epoxy resin total amount.
Its preparation method's step is as follows:
(1) preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely.After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 60-70 DEG C, until the resin intermediate generated, at 150 DEG C of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use.
(2) preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
Embodiment 11, a kind of LED support high strength white reflexed light ring epoxy resin composition, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for 25% of composition epoxy resin gross weight.
Described acid anhydride type curing agent is for having the polyfunctional group acid anhydrides of structure shown in formula (1), and the weight of described polyfunctional group acid anhydrides accounts for 25% of composition epoxy resin gross weight.
Described solidifying agent promotor is selected from quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate, and solidifying agent promotor accounts for 3% of composition epoxy resin total amount.
The particle diameter of described titanium dioxide is 2um, and described titanium dioxide carries out surface coated process with aluminium or silicon materials in advance; And tinting material accounts for 40% of composition epoxy resin total amount.
Described toughner is the reactive toughening agent of polyalcohols; The addition of toughner is 2% of composition epoxy resin total amount.
This composition epoxy resin is also containing oxidation inhibitor, and described oxidation inhibitor is selected from phosphorus antioxidant, or the composition of phosphorus antioxidant and phenol oxidation inhibitor; Described oxidation inhibitor accounts for 2% of composition epoxy resin total amount.
Its preparation method's step is as follows:
(1) preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely.After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 70-80 DEG C, until the resin intermediate generated, at 150 degree of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use.
(2) preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
Embodiment 12, a kind of LED support high strength white reflexed light ring epoxy resin composition, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for 20% of composition epoxy resin gross weight.
Described acid anhydride type curing agent is for having the polyfunctional group acid anhydrides of structure shown in formula (1), and the weight of described polyfunctional group acid anhydrides accounts for 15% of composition epoxy resin gross weight.
Described solidifying agent promotor is selected from quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate, and solidifying agent promotor accounts for 1% of composition epoxy resin total amount.
The particle diameter of described titanium dioxide is 1um, and described titanium dioxide carries out surface coated process with aluminium or silicon materials in advance; And tinting material accounts for 30% of composition epoxy resin total amount.
Described toughner is the reactive toughening agent of polyalcohols; The addition of toughner is 6% of composition epoxy resin total amount.
This composition epoxy resin is also containing oxidation inhibitor, and described oxidation inhibitor is selected from phosphorus antioxidant, or the composition of phosphorus antioxidant and phenol oxidation inhibitor; Described oxidation inhibitor accounts for 10% of composition epoxy resin total amount.
Its preparation method's step is as follows:
(1) preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely.After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 80-90 DEG C, until the resin intermediate generated, at 150 DEG C of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use.
(2) preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
Embodiment 13, experiment of the present invention and result thereof:
Epoxy resin:
The siloxanes of four epoxide group modifications, ProductName X-40-2670, is produced and public offering by Shin-EtsuChemicalCo., Ltd.;
Three (2,3-epoxypropyl) isocyanic ester, ProductName TEPIC-S, is produced by NissanChemicalIndustries, Ltd..
Solidifying agent:
The acid anhydrides of structure shown in formula (1);
HHPA, ProductName HHPA, is provided by ripple woods chemical industry (Changzhou) company limited;
Solidifying agent promotor:
Tetra-n-butylphosphoniumO, O-diethylphosphorodithioate, ProductName HISHICOLINPX-4ET, is provided by NIPPONCHEMICALINDUSTRIAL;
Quaternary phosphonium bromide, ProductName U-CAT-5003, is produced by San-AproLimited;
Tinting material:
Titanium dioxide, rutile-type, ProductName KRONOS2310, is produced by KronosInternationalInc.;
Titanium dioxide, rutile-type, ProductName KRONOS2233, is produced by KronosInternationalInc.;
Toughner:
Ethylene glycol, analytical pure.
Mineral filler:
Fused silica, by Jiangsu, Lian Rui novel material company limited provides;
Oxidation inhibitor:
Phosphorous acid ester, hindered phenol composite antioxidant, name of product PUB-370, by Guangzhou will one, Chemical Co., Ltd. provides;
Releasing agent: distillation mono-glycerides, ProductName, D-95, is produced by Zhangjiagang Zhong Ding additive company limited;
The composition epoxy resin getting this experiment obtained carries out correlation detection test:
(1) gel time: by the experimental technique of SJ/T11197-2013, is heated to 175 ± 1 DEG C by electrothermal disk, get 0.3-0.5g sample and be placed on hot plate, sample shakeouts area and is about 5cm
2, melting starts timing, and by needle-like stirring rod, most advanced and sophisticated or grafter stirs, and powder becomes gel state (sample can not wire drawing become terminal) from fluid gradually, reads required time, operates equally, repeat twice, get its mean value.
(2) mobility: by the experimental technique of SJ/T11197-2013, use EMMI-1-66 helicoidal flow metal die, Spiral flow length (cm) under using transfer mould equipment to measure following condition: die head temperature: 175 DEG C, injection pressure: 6.86Mpa(70kgf/cm2), this result, for evaluating mobility, is measured numerical value and is shown that more greatly mobility is better.
(3) hot hardness 90s(HH90s): die temperature 175 DEG C, injection pressure: 6.86Mpa(70kgf/cm2) condition under, being joined by composition epoxy resin in injection moulding barrel, be molded as length 115mm, width 9.6mm, is highly the batten of 5mm.Molding cycle is 90s, and after completing, rapid die sinking, uses Shore durometer, measure the hardness of sample, often organizes sample and at least measures 5 points, average.Its hot hardness is higher, and after molded, the intensity of product is higher.
(4) reflectivity: utilize transfer mould press, die temperature 175 DEG C, forming pressure 5MPa, set time 120s condition under carry out.According to above-mentioned experiment condition, this resin combination to be prepared into diameter be 30mm thickness is the disk of 2mm, and the UV-3600 instrument of Shimadzu carries out reflectance test.
(5) continuous moulding property: on the press of FushiSanjia, use the mould of 3030, the die temperature of 180 degree, carries out mould three times clearly continuously, after moistening mould three times, under the set time of 120s, becomes model measurement continuously.Until die surface occurs dirty, till one of defects such as red ink inefficacy appear in sticking to mould or LED support.
The prescription of several groups of experiments and result are with reference to following table:
Claims (9)
1. a LED support high strength white reflexed light ring epoxy resin composition, it is characterized in that, said composition comprises: epoxy resin, anhydrides or acids solidifying agent, solidifying agent promotor, tinting material and toughner; Described epoxy resin is selected from the siloxanes containing four epoxy functionality, and the weight of described epoxy resin accounts for the 2-25% of composition epoxy resin gross weight.
2. LED support high strength white reflexed light ring epoxy resin composition according to claim 1, is characterized in that: described acid anhydride type curing agent is for having the polyfunctional group acid anhydrides of structure shown in formula (1):
Formula (1)
The weight of described polyfunctional group acid anhydrides accounts for the 2-25% of composition epoxy resin gross weight.
3. LED support high strength white reflexed light ring epoxy resin composition according to claim 1 and 2, it is characterized in that, the epoxy equivalent (weight) in epoxy resin is 0.5-2.5 with the ratio of the anhydride equivalent in acid anhydrides.
4. LED support high strength white reflexed light ring epoxy resin composition according to claim 1 and 2, it is characterized in that, solidifying agent promotor is selected from quaternary ammonium halides salt, halogenation quaternary alkylphosphonium salt, octylate, and solidifying agent promotor accounts for the 0.01-3% of composition epoxy resin total amount.
5. LED support high strength white reflexed light ring epoxy resin composition according to claim 1 and 2, it is characterized in that, described tinting material is selected from the rutile titanium dioxide that particle diameter is 0.03-5 μm; And tinting material accounts for the 2-60% of composition epoxy resin total amount.
6. LED support high strength white reflexed light ring epoxy resin composition according to claim 5, it is characterized in that: the particle diameter of described titanium dioxide is 0.05-2um, and described titanium dioxide carries out surface coated process with aluminium or silicon or organic compound in advance; And tinting material accounts for the 3-40% of composition epoxy resin total amount.
7. LED support high strength white reflexed light ring epoxy resin composition according to claim 1 and 2, is characterized in that: described toughner is the reactive toughening agent of polyalcohols; The addition of toughner is the 0.1-10% of composition epoxy resin total amount.
8. high strength white reflexed light ring epoxy resin composition according to claim 1 and 2, is characterized in that: this composition epoxy resin is also containing oxidation inhibitor, and described oxidation inhibitor is selected from phosphorus antioxidant, or the composition of phosphorus antioxidant and phenol oxidation inhibitor; Described oxidation inhibitor accounts for the 0.01-10% of composition epoxy resin total amount.
9., as the LED support preparation method of high strength white reflexed light ring epoxy resin composition of claim 1-8 as described in any one, it is characterized in that, its step is as follows:
The preparation of epoxy resin intermediate: at room temperature, by epoxy resin, solidifying agent and the starting material such as the releasing agent related to and oxidation inhibitor, joins in reactor or in kneader according to proportioning, heated and stirred, makes it melt completely;
After having melted, add the absorption of stress agent measured, continue stirring reaction, control temperature of reaction and react in the scope of 60-100 DEG C, until the resin intermediate generated, at 150 DEG C of test I CI viscosity numbers at 0.8-2.0P, fast cooling, stopped reaction, after freezing, pulverize, for subsequent use;
The preparation of composition epoxy resin: by resin intermediate and other required starting material, weigh by proportioning, join in homogenizer and carry out high-speed mixing, the compound of gained is extruded through forcing machine, after calendering, cooling, be ground into suitable particle diameter, obtain powdered epoxy composition.
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| CN109957209A (en) * | 2017-12-25 | 2019-07-02 | 北京科化新材料科技有限公司 | Composition epoxy resin, naval stores and preparation method thereof and resin |
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| CN114908627B (en) * | 2022-05-19 | 2023-09-01 | 西南科技大学 | Basic magnesium sulfate cement-based self-luminous brick material and preparation method thereof |
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Address after: 222047 Jiangsu Lianyungang Lianyungang economic and Technological Development Zone Lingang Industrial Zone, east of Gu Wei Road and East Avenue North. Patentee after: JIANGSU HUAHAI CHENGKE NEW MATERIAL CO., LTD. Address before: 222047 Jiangsu Lianyungang Lianyungang economic and Technological Development Zone Lingang Industrial Zone, east of Gu Wei Road and East Avenue North. Patentee before: Jiangsu Huahai Chengke New Materials Co.,Ltd. |
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