CN107337900A - A kind of composition epoxy resin and its preparation method and application - Google Patents
A kind of composition epoxy resin and its preparation method and application Download PDFInfo
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- CN107337900A CN107337900A CN201611206445.0A CN201611206445A CN107337900A CN 107337900 A CN107337900 A CN 107337900A CN 201611206445 A CN201611206445 A CN 201611206445A CN 107337900 A CN107337900 A CN 107337900A
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N O=C(C1C2CCCC1)OC2=O Chemical compound O=C(C1C2CCCC1)OC2=O MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to LED support encapsulating material field, disclose a kind of composition epoxy resin and its preparation method and application, characterized in that, the composition epoxy resin includes epoxy resin, curing agent, accelerator, inorganic filler, colouring agent, stress modifying agent and releasing agent；The epoxy resin has the structure as shown in formula (1)；Wherein, n is 1 10, R1For the straight chained alkyl of H or C1 C5 straight or branched alkyl, preferably H or C1 C3, more preferably H or methyl；R2For H orR ' is H or C1 C6 straight or branched alkyl, and preferably R ' is H or C1 C4 straight chained alkyl, and further preferred R ' is methyl or ethyl.The composition epoxy resin has higher continuously shaped property and reflectivity.
Description
Technical field
The present invention relates to LED support encapsulating material field, in particular it relates to a kind of composition epoxy resin and its preparation side
Method and application.
Background technology
In recent years, LED industry undergoes an unusual development rapid, and LED lamp bead is obtained with the features such as its luminous efficiency is high, energy-conserving and environment-protective
The favor of ordinary consumer, and have the trend of substitution traditional lighting industry completely greatly.But constantly carried with the power of LED chip
Rise, its requirement for the auxiliary material such as high temperature resistant of support, packaging plastic etc., resistance to ultraviolet ability and reliability is also constantly lifted.Pass
The exotic material of system such as PPA, PCT etc. are used for a long time at high temperature, it may appear that serious xanthochromia problem.Simultaneously because at present
The organic silicon packaging glue of main flow is low for the surface bonding force of the thermoplastics such as PPA, causes the air-tightness deficiency of lamp bead, seriously
Influence the lamp bead life-span.The resin material that epoxy resin is commonly used as electronic device, is mixed with curing agent, filler and all kinds of modifying agent
Composition after conjunction, have the characteristics that color inhibition, curing rate fast, forming, cost it is low, suitable for large-scale production, be new
The focus on research direction of LED support material.
Domestic disclosed Patents at present, such as the patent (Authorization Notice No. of Hitachi Chemical Co., Ltd.
CN101461070B proposed in) using resin based on fulminuric acid three-glycidyl amine (TGIC), and be solid using acid anhydrides
Composition epoxy resin obtained by agent, mixture of white pigment.But the solidification intensity of this resin combination is low, poor toughness, adds
Epoxy resin small molecule presence, make easily to pollute mould during its shaping without easy mold release, it is poor in turn result in continuously shaped property
(being less than 100 moulds), it is not suitable with current LED support packing forms.
The content of the invention
The purpose of the present invention is to overcome the composition epoxy resin of the prior art applied to LED support encapsulating material to connect
A kind of the defects of continuous insufficient formability, there is provided composition epoxy resin and its preparation method and application.
To achieve these goals, the present invention provides a kind of composition epoxy resin, wherein, the composition epoxy resin
Including epoxy resin, curing agent, accelerator, inorganic filler, colouring agent, stress modifying agent and releasing agent；The epoxy resin tool
There is structure shown as the formula；
Wherein, n 1-10, R1For H or C1-C5 straight or branched alkyl, preferably H or C1-C3 straight chained alkyl, enter
One step is preferably H or methyl；R2For H orR ' be H or C1-C6 straight or branched alkyl, preferably R ' be H or
C1-C4 straight chained alkyl, further preferred R ' are methyl or ethyl.
Present invention also offers a kind of preparation method of composition epoxy resin, wherein, the preparation method includes：(1) make
Standby epoxy resin；(2) by the epoxy resin and curing agent, accelerator, inorganic filler, colouring agent, stress modifying agent and the demoulding
Agent is kneaded；Wherein, epoxy resin is prepared to comprise the following steps：
A. the compound shown in formula (2) is reacted with compound A；
B. step a reaction product and the compound shown in formula (3) are reacted；
Wherein, compound A is water or R4COOH, R3For H or C1-C5 straight or branched alkyl, preferably H or C1-C3's
Straight chained alkyl, more preferably H or methyl；R4For H or C1-C6 straight or branched alkyl, preferably H or C1-C4's is straight
Alkyl group, preferably methyl or ethyl.
Present invention also offers the composition epoxy resin prepared by preparation method of the present invention.
Present invention also offers application of the composition epoxy resin of the present invention as LED support encapsulating material.
Modified epoxy in composition epoxy resin of the present invention is compared with isocyanuric acid three-glycidyl ester (TGIC)
Itself there is larger molecular weight, and there is higher softening point and viscosity, so as to improve the continuous of composition epoxy resin
Mouldability (continuously shaped number is more than 200), and there is high reflectivity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of composition epoxy resin, wherein, the composition epoxy resin includes epoxy resin, consolidated
Agent, accelerator, inorganic filler, colouring agent, stress modifying agent and releasing agent；The epoxy resin has as shown in formula (1)
Structure；
Wherein, n 1-10, R1For H or C1-C5 straight or branched alkyl, preferably H or C1-C3 straight chained alkyl, enter
One step is preferably H or methyl；R2For H orR ' be H or C1-C6 straight or branched alkyl, preferably R ' be H or
C1-C4 straight chained alkyl, further preferred R ' are methyl or ethyl.
In the present invention, the C1-C5Straight or branched alkyl instantiation include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl or neopentyl.
In the present invention, the C1-C6Straight or branched alkyl instantiation include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl or different
Hexyl.
Epoxy resin of the present invention for example can be any one in table 1, but the selection being not limited in table 1.
Table 1
| Structure | n | R1 | R2 |
| Epoxy resin 1 | 10 | Methyl | H |
| Epoxy resin 2 | 8 | Methyl | CH3-CO- |
| Epoxy resin 3 | 9 | H | H |
| Epoxy resin 4 | 7 | Ethyl | H |
| Epoxy resin 5 | 5 | Methyl | C2H5-CO- |
| Epoxy resin 6 | 6 | The tert-butyl group | CH3-CO- |
| Epoxy resin 7 | 3 | Isopentyl | C3H7-CO- |
In the present invention, modified TGIC epoxy resin has larger molecular weight in itself relative to TGIC, so that institute
Stating epoxy resin has higher softening point and viscosity.The softening point of the epoxy resin is 30-120 DEG C, preferably 50-110
DEG C, more preferably 60-100 DEG C；Viscosity at 150 DEG C is 10-5000cp, preferably 120-4500cp, more preferably 1000-
4000cp。
In the present invention, counted by 100 parts by weight of the gross weight of the composition epoxy resin, the content of the epoxy resin
For 5-15 parts by weight (preferably 8-13 parts by weight), the content of the curing agent is 3-12 parts by weight (preferably 7-10 parts by weight), institute
The content for stating accelerator is 0.05-1 parts by weight (preferably 0.1-0.5 parts by weight), and the content of the inorganic filler is 30-80 weight
Part (preferably 40-60 parts by weight), the content of the colouring agent is 10-50 parts by weight (preferably 15-35 parts by weight), and the stress changes
Property agent content be 0.1-2 parts by weight (preferably 0.8-1.5 parts by weight), the content of the releasing agent for 0.1-1 parts by weight (preferably
0.3-0.8 parts by weight).
In the present invention, the curing agent is preferably alicyclic acid anhydrides, such as the curing agent can be THPA, methyl
One or more in THPA, HHPA and methyl hexahydrophthalic anhydride, more preferably HHPA and/or methyl six
Hydrogen phthalic anhydride, most preferably HHPA.It is above-mentioned most preferably in the case of, can further improve the resistance to of composition epoxy resin
Ageing properties.
In the present invention, the accelerator is one kind or more in organic phosphine compound, tertiary amine compound or imidazolium compounds
Kind, more preferably organic phosphine compound and tertiary amine compound；Due to organic phosphine compound than tertiary amine compound with more
Excellent yellowing-resistant ability, therefore, accelerator is preferably organic phosphine compound.
In the present invention, the organic phosphine compound is triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt, tetrabutyl O,
One or more in O- diethyldithioposphoric acid phosphines；The tertiary amine compound is triethanolamine and/or the (diformazans of 2,4,6- tri-
Aminomethyl) phenol；The imidazolium compounds is one kind in methylimidazole, diethyl tetramethyl imidazoles and diphenyl-imidazole
It is or a variety of.
In the present invention, the inorganic filler be SiO 2 powder, aluminum oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and
One or more in aerosil, preferably SiO 2 powder and/or aluminum oxide.Due to being applied to for the present invention
The loading of the inorganic filler of the composition epoxy resin of LED support encapsulating material it is higher to resist epoxy resin cure when produce
Contraction, and because the mobility of SiO 2 powder is preferable, therefore, most preferably in the case of, the inorganic filler is dioxy
SiClx powder.
In the present invention, the colouring agent is favorably improved the reflectivity of the composition epoxy resin, under preferable case, institute
Colouring agent is stated as the one or more in titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide, more preferably titanium dioxide
At least one of titanium, barium sulfate and antimony oxide, more preferably titanium dioxide.
In the present invention, the stress modifying agent helps to reduce cure shrinkage and the caused stress that expands with heat and contract with cold, preferably
In the case of, the stress modifying agent is the one or more in organic silicon modified by polyether oil, rubber and silicones, more preferably poly-
Ether modification organic silicon oil.
In the present invention, the releasing agent helps to make composition epoxy resin smoothly from mould deviate from, under preferable case,
The releasing agent is the one or more in Brazil wax, Tissuemat E, polypropylene wax and esterified wax；In order to reduce releasing agent
Influence to the reflectivity of composition epoxy resin, in the case of further preferred, the releasing agent is Tissuemat E.
Present invention also offers a kind of preparation method of composition epoxy resin, wherein, the preparation method includes：(1) make
Standby epoxy resin；(2) by the epoxy resin and curing agent, accelerator, inorganic filler, colouring agent, stress modifying agent and the demoulding
Agent is kneaded；Wherein, epoxy resin is prepared to comprise the following steps：
A. the compound shown in formula (2) is reacted with compound A；
B. step a reaction product and the compound shown in formula (3) are reacted；
Wherein, compound A is water or R4COOH, R3For H or C1-C5 straight or branched alkyl, preferably H or C1-C3's
Straight chained alkyl, more preferably H or methyl；R4For H or C1-C6 straight or branched alkyl, preferably H or C1-C4's is straight
Alkyl group, preferably methyl or ethyl.
In the present invention, the C1-C5Straight or branched alkyl instantiation include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl or neopentyl.
In the present invention, the C1-C6Straight or branched alkyl instantiation include but is not limited to：Methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl or different
Hexyl.
The selection of compound and compound A shown in Chinese style (2) of the present invention can be for example the combination shown in table 2, but simultaneously
It is not limited to these combinations.
Table 2
| Combination number | Compound shown in formula 2 | Compound A |
| 1 | R3For methyl | Water |
| 2 | R3For methyl | Acetic acid |
| 3 | R3For H | Water |
| 4 | R3For ethyl | Water |
| 5 | R3For methyl | Propionic acid |
| 6 | R3For the tert-butyl group | Acetic acid |
| 7 | R3For isopentyl | Butyric acid |
In the present invention, by TGIC epoxy resin modifications, increasing its molecular weight so that the epoxy resin have compared with
High softening point and viscosity, and then make the composition epoxy resin containing the epoxy resin that there is more preferable continuously shaped property, together
When with higher reflectivity, LED support encapsulating material can be preferably applied to.It should be noted that the chemical combination shown in formula (2)
Thing is anhydride compound, and the anhydride compound can be typically commercially available, if in the anhydride compound being commercially available in itself
Contain free acid (free acid content is less than 1 weight %), then above-mentioned step can be omitted when preparing the modified epoxy
Rapid a.
In the present invention, to the compound shown in the formula (2) in the step a for preparing epoxy resin and compound A use
There is no particular limitation for amount, as long as compound A dosage can be such that the compound shown in formula (2) reacts completely.Preferable case
Under, in the step a for preparing epoxy resin, the ratio of the dosage and compound A dosage of the compound shown in formula (2) is
20-1000：1, preferably 100-500：1.
In the present invention, in the step b for preparing epoxy resin, if the dosage of the compound shown in formula (3) and formula (2) institute
The compound amount shown can then cause to waste raw material compared to excessively, if shown in the dosage of the compound shown in formula (3) and formula (2)
Compound amount compared to very few, then epoxy resin can be made directly to solidify because producing cross-linked structure.In the case of it is therefore preferable that,
In the step b for preparing epoxy resin, the ratio of the dosage and the compound amount shown in formula (2) of the compound shown in formula (3)
It is worth for 8-20：1, preferably 13-17：1.Under the preferable case, the epoxy resin has higher softening point and viscosity.
In the present invention, to the reaction condition in the step a for preparing epoxy resin, there is no particular limitation, can be this
The conventional selection in field, under preferable case, in the step a for preparing epoxy resin, the condition of the reaction includes：Temperature is
10-80 DEG C, preferably 30-60 DEG C；Time is 1-30min, preferably 5-15min.
In the present invention, in the step b for preparing epoxy resin, the condition of the reaction can include：Temperature is 60-
180 DEG C, preferably 100-150 DEG C；Time is 5-60min, preferably 20-40min.Under the reaction conditions, can be by formula (3)
Epoxide group open loop in the shown compound and reaction product obtained with step a is fully reacted, it is higher so as to obtain having
Softening point and viscosity epoxy resin.
A preferred embodiment of the invention, described the step of preparing epoxy resin, can also include：By step a
Reaction product reacted with the compound shown in formula (3) before first will be thawed shown in formula (3), it is described to melt
The temperature of journey is 100-150 DEG C.
In the present invention, counted by 100 parts by weight of the gross weight of the composition epoxy resin, the dosage of the epoxy resin
For 5-15 parts by weight (preferably 8-13 parts by weight), the dosage of the curing agent is 3-12 parts by weight (preferably 7-10 parts by weight), institute
The dosage for stating accelerator is 0.05-1 parts by weight (preferably 0.1-0.5 parts by weight), and the dosage of the inorganic filler is 30-80 weight
Part (preferably 40-60 parts by weight), the dosage of the colouring agent is 10-50 parts by weight (preferably 15-35 parts by weight), and the stress changes
Property agent dosage be 0.1-2 parts by weight (preferably 0.8-1.5 parts by weight), the dosage of the releasing agent for 0.1-1 parts by weight (preferably
0.3-0.8 parts by weight).
In the present invention, the curing agent is preferably alicyclic acid anhydrides, such as the curing agent can be THPA, methyl
One or more in THPA, HHPA and methyl hexahydrophthalic anhydride, more preferably HHPA and/or methyl six
Hydrogen phthalic anhydride, most preferably HHPA.It is above-mentioned most preferably in the case of, can further improve the resistance to of composition epoxy resin
Ageing properties.
In the present invention, the accelerator is one kind or more in organic phosphine compound, tertiary amine compound or imidazolium compounds
Kind, more preferably organic phosphine compound and tertiary amine compound；Due to organic phosphine compound than tertiary amine compound with more
Excellent yellowing-resistant ability, therefore, accelerator is preferably organic phosphine compound.
In the present invention, the organic phosphine compound is triphenylphosphine, methyl tributyl phosphine di(2-ethylhexyl)phosphate formicester salt, tetrabutyl O,
One or more in O- diethyldithioposphoric acid phosphines；The tertiary amine compound is triethanolamine and/or the (diformazans of 2,4,6- tri-
Aminomethyl) one or more in phenol；The imidazolium compounds is methylimidazole, diethyl tetramethyl imidazoles and hexichol
One or more in base imidazoles.
In the present invention, the inorganic filler be SiO 2 powder, aluminum oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and
One or more in aerosil, preferably SiO 2 powder and/or aluminum oxide.Due to being applied to for the present invention
The loading of the inorganic filler of the composition epoxy resin of LED support encapsulating material it is higher to resist epoxy resin cure when produce
Contraction, and because the mobility of SiO 2 powder is preferable, therefore, most preferably in the case of, the inorganic filler is dioxy
SiClx powder.
In the present invention, the colouring agent is favorably improved the reflectivity of the epoxy resin, under preferable case, the coloring
Agent is the one or more in titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide, more preferably titanium dioxide, sulfuric acid
At least one of barium and antimony oxide, more preferably titanium dioxide.
In the present invention, the stress modifying agent helps to reduce cure shrinkage and the caused stress that expands with heat and contract with cold, preferably
In the case of, the stress modifying agent is the one or more in organic silicon modified by polyether oil, rubber and silicones, more preferably
Organic silicon modified by polyether oil.
In the present invention, the releasing agent helps to make composition epoxy resin smoothly from mould deviate from, under preferable case,
The releasing agent is the one or more in Brazil wax, Tissuemat E, polypropylene wax, esterified wax；In order to reduce releasing agent
Influence to the reflectivity of composition epoxy resin, in the case of further preferred, the releasing agent is Tissuemat E.
According to another preferred embodiment of the present invention, the process of the mixing includes：
(1) carried out after mixing inorganic filler and colouring agent scattered for the first time；
(2) accelerator and stress modifying agent are sequentially added in the mixture obtained to first time after scattered, carried out second
It is scattered；
(3) epoxy resin, curing agent and releasing agent are added into second of mixture obtained after scattered, carries out third time
It is scattered；
(4) mixture that third time obtains after scattered is kneaded.
During above-mentioned mixing, the time scattered for the first time can be 4-8 minutes, and second time disperseed can be with
For 4-8 minutes, the third time scattered time can be 8-15 minutes；The mode for adding accelerator and stress modifying agent be preferably with
Spray mode is implemented；Preferably, epoxy resin and curing agent are first ground into particle diameter before epoxy resin and curing agent add
Less than 30 mesh powders.The process that the mixture that third time obtains after scattered is kneaded is specifically as follows：By third time point
In the mixture input storage tank obtained after dissipating, uniformly it is delivered in double screw extruder with feeder, is carried out at 80-90 DEG C
It is kneaded 10-30min；Material after mixing forms flow-like and flowed out from extruder mouth, to rolling mill roller on be calendered flakiness,
It is hardened, then is crushed after cooling, it is final to obtain the graininess composition epoxy resin that maximum particle diameter is 10 mesh.
Present invention also offers the composition epoxy resin prepared by preparation method of the present invention.The epoxy resin group
Compound has higher continuously shaped property, and keeps high reflectivity.
Present invention also offers application of the composition epoxy resin of the present invention as LED support encapsulating material.This
The described composition epoxy resin of invention has higher continuously shaped property, and keeps high reflectivity, is highly suitable for conduct
LED support encapsulating material.
The present invention will be described in detail by way of examples below.In following preparation example, embodiment and comparative example,
The performance measurement of epoxy resin：
1st, softening point：Measured by ring and ball method, specifically according to GB 12007.6-1989 epoxy resin softening point measurement methods
Ring and ball method determines；
2nd, the viscosity at 150 DEG C：Measured by cone-plate viscosimeter, be specially：0.2g samples are taken, using cone-plate viscosimeter
Determine the viscosity at 150 DEG C.
The performance measurement of composition epoxy resin：
1st, measuring reflectance：
(1) composition epoxy resin of preparation is used into mould under 175 DEG C of mold temperature, hardening time 120s process conditions
Press transmission is molded into specific mould, is allowed to curing molding as thin slice thick 1mm；
(2) initial reflectance：By the thin slice after 150 DEG C solidify 4 hours, integrating sphere type spectrophotometer V770 is used
Reflectivity under test wavelength 550nm；
(3) aging back reflection rate：By the thin slice of step (2) again after 130 DEG C of agings 1000 hours, test wavelength again
Reflectivity under 550nm.
2nd, forming ability (continuously shaped number) determines：
(1) composition epoxy resin of preparation is used into mould under 175 DEG C of mold temperature, hardening time 120s process conditions
Press transmission is molded into specific mould, is allowed to curing molding as diameter 5mm, height 5mm cylinder；
(2) off-type force is tested：After above-mentioned composition epoxy resin shaping, mould is taken out immediately, with hand-held thrust meter
The cylinder of shaping is released, maximum thrust now is off-type force；
(3) every 50 mould test off-type force, until off-type force is more than 100N, mould number now is continuously shaped number.
In following preparation example, embodiment and comparative example, TGIC is the commercially available product that the Nissan Chemical company trade mark is TEPIC-S；
Methyl hexahydrophthalic anhydride is the commercially available product that the Puyang Hui Cheng companies trade mark is Me-HHPA；
Curing agent HHPA is the commercially available product that the Puyang Hui Cheng companies trade mark is HHPA；
Accelerator methyl tributyl phosphine dimethyl phosphate salt is the city that Nippon Chemical Ind's trade mark is PX-4MP
Sell product；
Inorganic filler SiO 2 powder is the commercially available product that the trade mark of Jiangsu Lian Rui companies is DQ1200；
Colouring agent titania powder is the commercially available product that the trade mark of Shi Yuan chemical companies is R780；
Stress modifying agent polyether modified silicon oil is the commercially available product that the trade mark of Dow Corning Corporation is SF8421；
The commercially available product that releasing agent Tissuemat E is PE520 for the trade mark of gram Lay benefactor department.
Preparation example 1
(1) by methyl hexahydrophthalic anhydride (compound shown in formula (2), the wherein R of 1 parts by weight3For methyl) and 0.01 weight
The water mixing of part, react 5min at being 30 DEG C in temperature；
(2) by TGIC (compound shown in formula (3)) the input reactors of 13 parts by weight, open and heat and temperature is set
For 150 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reactor,
30min is reacted at being 125 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A1 (has the knot as shown in formula (1)
Structure, R1For methyl, R2For H, n=10).
A1 softening point and viscosity is determined, as a result as shown in table 3.
Preparation example 2
(1) by methyl hexahydrophthalic anhydride (compound shown in formula (2), the wherein R of 1 parts by weight3For methyl) and 0.05 weight
(compound A is R to the acetic acid of part4COOH, wherein R4For methyl) mixing, react 15min at being 60 DEG C in temperature；
(2) by TGIC (compound shown in formula (3)) the input reactors of 17 parts by weight, open and heat and temperature is set
For 120 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reactor,
40min is reacted at being 150 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A2 (has the knot as shown in formula (1)
Structure, R1For methyl, R2For R '-CO-, R ' is methyl, n=8).
A2 softening point and viscosity is determined, as a result as shown in table 3.
Preparation example 3
(1) by HHPA (compound shown in formula (2), the wherein R of 1 parts by weight3For H) mixed with the water of 0.03 parts by weight
Close, react 10min at being 50 DEG C in temperature；
(2) by TGIC (compound shown in formula (3)) the input reactors of 15 parts by weight, open and heat and temperature is set
For 100 DEG C；
(3) after TGIC is completely melt, stirring is opened, the reaction product that step (1) obtains is slowly injected into reactor,
200min is reacted at being 100 DEG C in temperature.Reaction terminates, and stops stirring, and obtaining epoxy resin A3 (has as shown in formula (1)
Structure, R1For H, R2For H, n=9).
A3 softening point and viscosity is determined, as a result as shown in table 3.
Preparation example 4
Method according to preparation example 1 prepares epoxy resin, unlike, step (3) reaction temperature is 50 DEG C.Obtain epoxy
Resin A 4.
A4 softening point and viscosity is determined, as a result as shown in table 3.
Preparation example 5
Method according to preparation example 1 prepares epoxy resin, unlike, step (3) reaction time is 2min.Obtain epoxy
Resin A 5.
A5 softening point and viscosity is determined, as a result as shown in table 3.
Contrast preparation example 1
Method according to preparation example 1 prepares epoxy resin, unlike, methyl is replaced using the acetic anhydride of identical weight part
HHPA, obtain epoxy resin D1.
D1 softening point and viscosity is determined, as a result as shown in table 3.
Table 3
| Project | A1 | A2 | A3 | A4 | A5 | D1 | TGIC |
| Softening point/DEG C | 100 | 110 | 90 | 80 | 70 | 20 | -- |
| Viscosity/cp | 2000 | 1500 | 1700 | 1300 | 1200 | 100 | 5 |
Embodiment 1
(1) 12 parts by weight epoxy resin A1 and 9 parts by weight HHPAs are crushed using pulverizer respectively, obtains grain
Footpath is less than 30 mesh powders；
(2) 52 parts by weight of silica powder and 25 parts by weight of titanium dioxide powder are put into high-speed mixer respectively,
Start high-speed mixer, carry out two kinds of materials scattered for the first time；
(3) when first time dispersion process is carried out to 5min, 0.3 parts by weight methyl tributyl is successively added with spray mode
Phosphine dimethyl phosphate salt, 1.2 parts by weight polyether modified silicon oils, carry out second of scattered 5min；
(4) epoxy resin A1 and HHPA, 0.5 weight account polyethylene wax after input crushes respectively, third time is carried out
Scattered 10min, obtains uniform powder mixture；
(5) in the mixture input storage tank obtained step (4), uniformly it is delivered to feeder in double screw extruder
Mixing 15min is carried out at 80 DEG C, material after mixing forms flow-like and flowed out from extruder mouth, to rolling mill roller on pressed
Prolong flakiness, be hardened after cooling, then crushed, it is final to obtain the composition epoxy resin Z1 that maximum particle diameter is 10 mesh.Survey
Determine Z1 reflectivity and continuously shaped number, as a result as shown in table 4.
Embodiment 2-5
Method according to embodiment 1 prepares composition epoxy resin, unlike, be respectively adopted identical weight part A2,
A3, A4, A5 replace epoxy resin A1.Respectively obtain Z2, Z3, Z4, Z5.Determine Z2, Z3, Z4, Z5 reflectivity and continuously shaped
Number, as a result as described in Table 4.
Embodiment 6
(1) the epoxy resin A1 and HHPA of parts by weight same as Example 1 are crushed using pulverizer respectively,
Obtain particle diameter and be less than 30 mesh powders；
(2) the epoxy resin A1 powder, HHPA powder and the parts by weight same as Example 1 that obtain step (1)
SiO 2 powder, titania powder, methyl tributyl phosphine dimethyl phosphate salt, polyether modified silicon oil and Tissuemat E mix
Close, obtained mixture is put into storage tank, is uniformly delivered in double screw extruder with feeder and is mixed at 80 DEG C
Refine 15min, material after mixing forms flow-like and flowed out from extruder mouth, to rolling mill roller on be calendered flakiness, through cold
But it is hardened, then is crushed afterwards, it is final to obtain the composition epoxy resin Z6 that maximum particle diameter is 10 mesh.Determine Z6 reflectivity and
Continuously shaped number, as a result as shown in table 4.
Embodiment 7
Method according to embodiment 1 prepares composition epoxy resin, unlike, epoxy resin A1 dosage is 15 weight
Part, the dosage of curing agent HHPA is 5 parts by weight.It is final to obtain the composition epoxy resin Z8 that maximum particle diameter is 10 mesh.Survey
Determine Z8 reflectivity and continuously shaped number, as a result as shown in table 4.
Comparative example 1
Method according to embodiment 1 prepares composition epoxy resin, unlike, replaced using the TGIC of identical weight part
Epoxy resin A1.Obtain DZ1.DZ1 reflectivity and continuously shaped number are determined, as a result as described in Table 4.
Comparative example 2
Method according to embodiment 1 prepares composition epoxy resin, unlike, D1 generations of identical weight part are respectively adopted
For epoxy resin A1.Respectively obtain DZ2.DZ2 reflectivity and continuously shaped number are determined, as a result as described in Table 4.
Table 4
Result as shown in Table 3, which can be seen that modified epoxy of the present invention, has high softening point and viscosity；
Result as shown in Table 4, which can be seen that composition epoxy resin of the present invention, has high continuously shaped ability, has simultaneously
High reflectivity.Epoxy containing epoxy resin of the present invention it can be seen from the measurement result of embodiment 1 and comparative example 1
Resin combination reflectivity compared with the composition epoxy resin containing TGIC is suitable, but contains epoxy resin of the present invention
Composition epoxy resin there is higher continuously shaped ability；It can relatively be seen by the measurement result of embodiment 1 and comparative example 2
Go out, the composition epoxy resin containing epoxy resin of the present invention has more preferable continuously shaped ability.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of composition epoxy resin, it is characterised in that the composition epoxy resin includes epoxy resin, curing agent, rush
Enter agent, inorganic filler, colouring agent, stress modifying agent and releasing agent；The epoxy resin has the structure as shown in formula (1)；
Wherein, n 1-10, R1For H or C1-C5 straight or branched alkyl, preferably H or C1-C3 straight chained alkyl, further
Preferably H or methyl；R2For H orR ' is H or C1-C6 straight or branched alkyl, and preferably R ' is H or C1-
C4 straight chained alkyl, further preferred R ' are methyl or ethyl.
2. composition epoxy resin according to claim 1, wherein, the softening point of the epoxy resin is 30-120 DEG C,
Preferably 50-110 DEG C；Viscosity is 10-5000cp, preferably 120-4500cp at 150 DEG C.
3. composition epoxy resin according to claim 1 or 2, wherein, with the gross weight of the composition epoxy resin
For 100 parts by weight meters, the content of the epoxy resin is 5-15 parts by weight, and the content of the curing agent is 3-12 parts by weight, institute
The content for stating accelerator is 0.05-1 parts by weight, and the content of the inorganic filler is 30-80 parts by weight, the content of the colouring agent
For 10-50 parts by weight, the content of the stress modifying agent is 0.1-2 parts by weight, and the content of the releasing agent is 0.1-1 weight
Part.
4. composition epoxy resin according to claim 1 or 2, wherein, the curing agent is alicyclic acid anhydrides, preferably
Ground, the curing agent are the one or more in THPA, methyl tetrahydro phthalic anhydride, HHPA and methyl hexahydrophthalic anhydride, are entered
One step is preferably HHPA and/or methyl hexahydrophthalic anhydride；
And/or the accelerator is the one or more in organic phosphine compound, tertiary amine compound and imidazolium compounds, enters one
Step is preferably organic phosphine compound and tertiary amine compound；It is highly preferred that the organic phosphine compound is triphenylphosphine, the fourth of methyl three
One or more in base phosphine di(2-ethylhexyl)phosphate formicester salt and tetrabutyl O, O- diethyldithioposphoric acid phosphine；The tertiary amine compound is
Triethanolamine and/or 2,4,6- tri- (dimethylamino methyl) phenol；The imidazolium compounds is methylimidazole, diethyl tetramethyl
One or more in base imidazoles and diphenyl-imidazole；
And/or the inorganic filler is SiO 2 powder, aluminum oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and gas phase two
One or more in silica, preferably SiO 2 powder and/or aluminum oxide；
And/or the colouring agent is the one or more in titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide；
And/or the stress modifying agent is the one or more in organic silicon modified by polyether oil, rubber and silicones；
And/or the releasing agent is the one or more in Brazil wax, Tissuemat E, polypropylene wax and esterified wax.
5. a kind of preparation method of composition epoxy resin, it is characterised in that the preparation method includes：(1) epoxy resin is prepared；
(2) epoxy resin and curing agent, accelerator, inorganic filler, colouring agent, stress modifying agent and releasing agent are kneaded；
Wherein, epoxy resin is prepared to comprise the following steps：
A. the compound shown in formula (2) is reacted with compound A；
B. step a reaction product and the compound shown in formula (3) are reacted；
Wherein, compound A is water or R4COOH, R3For H or C1-C5 straight or branched alkyl, preferably H or C1-C3 straight chain
Alkyl, more preferably H or methyl；R4For H or C1-C6 straight or branched alkyl, preferably H or C1-C4 straight chain alkane
Base, preferably methyl or ethyl.
6. preparation method according to claim 5, wherein, in the step a for preparing epoxy resin, shown in formula (2)
The ratio of the dosage of compound and compound A dosage is 20-1000：1, preferably 100-500：1；
Preferably, in the step b for preparing epoxy resin, dosage and the chemical combination shown in formula (2) of the compound shown in formula (3)
The ratio of thing dosage is 8-20：1, preferably 13-17：1.
7. the preparation method according to claim 5 or 6, wherein, in the step a for preparing epoxy resin, the reaction
Condition include：Temperature is 10-80 DEG C, preferably 30-60 DEG C；Time is 1-30min, preferably 5-15min；
Preferably, in the step b for preparing epoxy resin, the condition of the reaction includes：Temperature is 60-180 DEG C, is preferably
100-150℃；Time is 5-60min, preferably 20-40min.
8. the preparation method according to claim 5 or 6, wherein, described the step of preparing epoxy resin, also includes：By step
A reaction product first will be thawed shown in formula (3) before being reacted with the compound shown in formula (3), the thawing
The temperature of process is 100-150 DEG C.
9. the preparation method according to claim 5 or 6, wherein, using the gross weight of the composition epoxy resin as 100 weights
Measure part meter, the dosage of the epoxy resin is 5-15 parts by weight, and the dosage of the curing agent is 3-12 parts by weight, the accelerator
Dosage be 0.05-1 parts by weight, the dosage of the inorganic filler is 30-80 parts by weight, and the dosage of the colouring agent is 10-50
Parts by weight, the dosage of the stress modifying agent is 0.1-2 parts by weight, and the dosage of the releasing agent is 0.1-1 parts by weight.
10. the preparation method according to claim 5 or 6, wherein, the curing agent is alicyclic acid anhydrides, it is preferable that described
Curing agent is the one or more in THPA, methyl tetrahydro phthalic anhydride, HHPA and methyl hexahydrophthalic anhydride, further preferably
For HHPA and/or methyl hexahydrophthalic anhydride；
And/or the accelerator is the one or more in organic phosphine compound, tertiary amine compound and imidazolium compounds, enters one
Step is preferably organic phosphine compound and tertiary amine compound；It is highly preferred that the organic phosphine compound is triphenylphosphine, the fourth of methyl three
One or more in base phosphine di(2-ethylhexyl)phosphate formicester salt and tetrabutyl O, O- diethyldithioposphoric acid phosphine；The tertiary amine compound is
Triethanolamine and/or 2,4,6- tri- (dimethylamino methyl) phenol；The imidazolium compounds is methylimidazole, diethyl tetramethyl
One or more in base imidazoles and diphenyl-imidazole.
And/or the inorganic filler is SiO 2 powder, aluminum oxide, magnesium hydroxide, aluminium hydroxide, calcium carbonate and gas phase two
One or more in silica, preferably SiO 2 powder and/or aluminum oxide；
And/or the colouring agent is the one or more in titanium dioxide, barium sulfate, antimony oxide, zinc sulphide and zinc oxide；
And/or the stress modifying agent is the one or more in organic silicon modified by polyether oil, rubber and silicones；
And/or the releasing agent is the one or more in Brazil wax, Tissuemat E, polypropylene wax and esterified wax.
11. preparation method according to claim 5, wherein, the process of the mixing includes：
(1) carried out after mixing inorganic filler and colouring agent scattered for the first time；
(2) accelerator and stress modifying agent are sequentially added in the mixture obtained to first time after scattered, carries out second and disperse；
(3) epoxy resin, curing agent and releasing agent are added into second of mixture obtained after scattered, carries out third time point
Dissipate；
(4) mixture that third time obtains after scattered is kneaded.
12. the composition epoxy resin prepared as the preparation method described in claim 5-11.
13. composition epoxy resin the answering as LED support encapsulating material in claim 1-4 and 12 described in any one
With.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109082256A (en) * | 2018-08-21 | 2018-12-25 | 盐城东山精密制造有限公司 | A kind of packaging plastic and preparation method thereof |
| CN109096971A (en) * | 2018-07-10 | 2018-12-28 | 西安贝克电子材料科技有限公司 | A kind of high cohesive force composition epoxy resin |
| CN109504328A (en) * | 2018-11-28 | 2019-03-22 | 深圳市明粤科技有限公司 | Micro LED display encapsulating material |
| TWI693257B (en) * | 2018-08-17 | 2020-05-11 | 景美實業股份有限公司 | Epoxy-silicone composite composition |
| CN111633787A (en) * | 2020-05-26 | 2020-09-08 | 长江水利委员会长江科学院 | Make smooth concrete external mold device of concrete surface mirror surface |
| CN111944270A (en) * | 2019-05-16 | 2020-11-17 | 衡所华威电子有限公司 | Epoxy resin composition, process for producing the same and use thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496122A (en) * | 1967-07-14 | 1970-02-17 | Ciba Ltd | Modified triglycidylisocyanurate resins |
| CN103140536A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Epoxy resin composition, prepreg and fiber enforced complex material |
-
2016
- 2016-12-23 CN CN201611206445.0A patent/CN107337900B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496122A (en) * | 1967-07-14 | 1970-02-17 | Ciba Ltd | Modified triglycidylisocyanurate resins |
| CN103140536A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Epoxy resin composition, prepreg and fiber enforced complex material |
Non-Patent Citations (1)
| Title |
|---|
| XING HONG ZHANG ET AL.: ""Novel Nitrogen-Containing Epoxy Resin. I. Synthetic Kinetics"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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| CN109096971A (en) * | 2018-07-10 | 2018-12-28 | 西安贝克电子材料科技有限公司 | A kind of high cohesive force composition epoxy resin |
| TWI693257B (en) * | 2018-08-17 | 2020-05-11 | 景美實業股份有限公司 | Epoxy-silicone composite composition |
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| CN111944270A (en) * | 2019-05-16 | 2020-11-17 | 衡所华威电子有限公司 | Epoxy resin composition, process for producing the same and use thereof |
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| CN111633787B (en) * | 2020-05-26 | 2021-11-26 | 长江水利委员会长江科学院 | Make smooth concrete external mold device of concrete surface mirror surface |
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