CN105061993A - Environment-friendly white epoxy molding compound, preparation method therefor and application thereof - Google Patents
Environment-friendly white epoxy molding compound, preparation method therefor and application thereof Download PDFInfo
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- CN105061993A CN105061993A CN201510433967.3A CN201510433967A CN105061993A CN 105061993 A CN105061993 A CN 105061993A CN 201510433967 A CN201510433967 A CN 201510433967A CN 105061993 A CN105061993 A CN 105061993A
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Abstract
The present invention provides an environment-friendly white epoxy molding compound, a preparation method therefor and an application thereof. The white epoxy molding compound comprises the following components in percentage by weight : 3-20% of hydantoin type epoxy resin, 0-5% of alicyclic type epoxy resin, 5-20 % of an acid anhydride curing agent, 50-80% of a silica filler, 10-30% of white pigment as well as an accelerator, an antioxidant, a release agent and the like. On the premise of guaranteeing that the prepared white epoxy molding compound has characteristics of low toxicity and environment friendliness, melt viscosity of the white epoxy molding compound can decrease sharply to below 100 mPa.s, and therefore, the white epoxy molding compound provided by the present invention has good environmental compatibility. Furthermore, the white epoxy molding compound further has heat resistance and high temperature and yellowing resistance that are superior to those in the prior art, and can be widely applied to the fields of packaging and manufacturing of microelectronic and photoelectronic devices .
Description
Technical field
The present invention relates to a kind of packaged material technology, particularly a kind of environment-friendly white epoxy plastic cement and preparation method thereof and purposes.
Background technology
The fast development taking photodiode (LED) device as the advanced display device of representative is day by day urgent for the demand of packaged material.Wherein, the white epoxy plastic cement with characteristics such as high-reflectivity, high temperature resistant, color inhibition, high pliable and tough, moisture resistance gas cut erosions is the of paramount importance integral parts of the luminescent devices such as LED.But there is stronger restricting relation between these performance requriementss, often cannot meet these performance requriementss simultaneously.Such as, the white epoxy plastic cement that can meet above-mentioned performance requirement is made up of epoxy resin, solidifying agent, curing catalyst, mineral filler, white pigment, coupling agent, releasing agent, antioxidant etc. usually.In order to the color inhibition characteristic improving white epoxy plastic cement often needs the epoxy resin adopting alicyclic structure, but therefore the resistance toheat of plastic cement can decline.For another example, in order to realize the high whiteness of white plastic cement and reflectivity, need to add heavy dose of white pigment, but therefore the snappiness of plastic cement can decline etc.Therefore, in order to realize above-mentioned performance requriements simultaneously, need to combine accurately each moiety.
FDAC changes into the preparation method disclosing a kind of white epoxy coating in US8343616, US8367153 and US8421113.This resin system adopts isocyanuric acid three-glycidyl ester (TGIC) or alicyclic epoxy 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate is epoxy resin, adopts anhydride-cured system, adds TiO 2 pigment and the composition such as oxidation inhibitor, silane coupling agent simultaneously.This resin system can be used for impregnated glass fiber cloth to manufacture the white laminated plate in LED component, and after being solidified by this resin system, obtained veneer sheet has good whiteness and heat-resistant stability.The said firm discloses a kind of preparation method of LED reflection plate white epoxy constituent in US8785525.This resin system is based on TGIC system equally, is equipped with anhydride curing agent, preparing spherical SiO 2 filler, aluminium sesquioxide white pigment and coupling agent, releasing agent etc. simultaneously.This resin system cured article has good whiteness and heat-resisting xanthochromia characteristic.Henkel Corp. discloses a kind of preparation method with good ultraviolet resistance, heat resistant type white epoxy plastic cement in US7125917.This system, also based on TGIC resin, is simultaneously curing system with acid anhydrides, and adds the components such as stearic acid, glycerine, antioxidant and phosphorus.This system cured article has good transmittance and resisting high-temperature yellowing characteristic.As can be seen here, prior art prepares LED component white epoxy mixture is substantially all adopt TGIC epoxy resin.This mainly because, TGIC is a kind of containing heterocycle trifunctional alicyclic ring epoxy compound, cured article has good thermotolerance, weathering resistance and light transmission, but because TGIC is polyfunctional group resin system, therefore be easy to generation in the curing process highly cross-linked, cause cured article volumetric shrinkage and mechanical property deterioration.Meanwhile, what is more important, the bio-toxicity problem of TGIC obtains great attention (Hu Ningxian, the toxicity of isocyanuric acid three-glycidyl ester and surrogate thereof and Study on Performance, modern coatings and application, 2011,14:10-16.) in recent years especially.Some country has started the goods prohibited containing TGIC composition and has entered its country.Therefore, the TGIC composition replaced as early as possible in prior art white epoxy plastic cement all has great importance for the health and protection of the environment ensureing operator.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, proposes a kind ofly to have that toxicity is low, Environmental compatibility good, the environment-friendly white epoxy plastic cement of resisting high-temperature yellowing excellent property.The another one technical problem that the present invention will solve there is provided a kind of preparation method and its usage of this epoxy plastic cement.
The technical problem to be solved in the present invention is achieved through the following technical solutions, and a kind of environment-friendly white epoxy plastic cement, is characterized in: the composition comprising following weight percent:
Glycolylurea type epoxy resin 3 ~ 20%;
Alicyclic type epoxy resin 0 ~ 5%;
Anhydride curing agent 5 ~ 20%;
Promotor 0.01 ~ 0.1%;
Oxidation inhibitor 0.01 ~ 0.1%;
Coupling agent 0.1 ~ 1%;
Releasing agent 0.05 ~ 1%;
Silica filler 50 ~ 80%;
White pigment 10 ~ 30%.
Described glycolylurea type epoxy resin is selected from the epoxy resin of structure as shown in I formula,
I
Wherein R
1=-C
nh
2n+1(
n=0 ~ 5) or R
1=-C
6h
6; R
2=-C
nh
2n+1(
n=0 ~ 5) or R
2=-C
6h
6; R
3=-H or R
3=-CH
3.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, and described glycolylurea type epoxy resin is specifically selected from hydantoin epoxy (R
1=R
2=-H, R
3=-H), 5,5-dimethyl hydantion epoxies, 5-methyl-5-ethylhydantoin epoxy (R
1=-CH
3, R
2=-CH
2cH
3, R
3=-H), 5-phenyl hydantoin epoxy (R
1=-C
6h
6, R
2=-H, R
3=-H), 5,5-dimethyl-Beta-methyl hydantoin epoxy (R
1=R
2=-CH
3, R
3=-CH
3) in a kind of or several arbitrarily mixing.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, and described glycolylurea type epoxy resin is 5,5-dimethyl hydantion epoxies or 5-methyl-5-ethylhydantoin epoxy or both mixing preferably.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described alicyclic type epoxy resin is selected from 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, 4, a kind of or several arbitrarily mixing of 5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described anhydride curing agent is selected from least one in phthalic anhydride, methyl phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride or norbornylene acid anhydrides or multiple mixing, at least one in preferable methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described promotor is selected from glyoxaline compound or organic phosphine compound, glyoxaline compound is selected from least one in glyoxal ethyline, 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole, at least one in preferred 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole; Described organic phosphine compound is selected from triphenylphosphine, tributylphosphine, three p-methylphenyl phosphines, three nonyl Phenylphosphines, tetraphenyl phosphine tetraphenylborate, triphenylphosphine benzoquinones adducts, the tetrabutyl-O, one or more mixing in O-diethyldithiophosphoric acid phosphine, the preferred tetrabutyl-O, O-diethyldithiophosphoric acid phosphine.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described oxidation inhibitor is selected from phosphorus-containing antioxidant, comprise 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), two 2,6-di-t-butyl-4-aminomethyl phenyl pentaerythritol diphosphate, two 2, one or more mixing in 4-di-tert-butyl-phenyl pentaerythritol diphosphate, distearyl pentaerythritol diphosphite, preferred DOPO.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described coupling agent is selected from γ-2, one or more mixing in 3-glycidoxy-propyltrimethoxy silane (KH-560), γ aminopropyltriethoxy silane (KH-550), γ-mercaptan aminopropyl trimethoxysilane (KH-580), preferred KH-560.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described releasing agent is selected from one or more the mixing in natural wax (bar wax etc.), synthetic wax (polyethylene wax etc.), stearic acid, palmitinic acid, Zinic stearas, calcium stearate, lithium stearate and Magnesium Stearate, preferred stearic acid and palmitinic acid.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, described silica filler is selected from one or both the mixing in spherical or dihedral silicon powder, silicon powder form comprises crystal type and fusion, preferred crystal type ball-shaped silicon micro powder.Silicon powder median
d 50be no more than 30 μm.
The technical problem to be solved in the present invention can also be come to realize further by the following technical programs, and described white pigment is selected from one or more the mixing in aluminium sesquioxide, titanium dioxide, zinc oxide, calcium carbonate, preferred titanium dioxide.
Another technical problem that will solve of the present invention is achieved through the following technical solutions, and described environment-friendly white epoxy plastic cement, its preparation method comprises the steps:
(1) alicyclic ring epoxide resin shown in glycolylurea epoxide resin shown in formula I, formula II, anhydride curing agent, promotor, oxidation inhibitor, coupling agent, releasing agent, silica filler and white pigment are added hot milling on conventional various ceramic materials three roller or two roller mixing rolls, mixing after mixing, described white epoxy mixture is obtained after cooling, pulverizing, in described mixing step, temperature is 20-120 DEG C; Specifically can be 20-30 DEG C, 50-80 DEG C, 90-110 DEG C or 90-120 DEG C, preferred 60-90 DEG C; Time is 0.5-3 hour, specifically can be 0.5-1.5 hour or 1-1.5 hour, preferred 0.5-1 hour.
(2) obtained white epoxy mixture is bought cake on pancake making machine, obtain the white epoxy plastic cement of desired size size.
Another technical problem that will solve of the present invention is achieved through the following technical solutions, the described application of environment-friendly white epoxy plastic cement in microelectronic device package and optoelectronic device packaging.
Described microelectronic device package is ball type array encapsulation or wafer-level package, and described optoelectronic device packaging is LED and organic LED.
The present invention is by adopting glycolylurea type epoxy resin, under the prepared white epoxy plastic cement of guarantee has the prerequisite of low toxicity, environmental friendliness feature, the melt viscosity of white epoxy plastic cement sharply can be reduced to below 100mPa.s, solidified by adding each composition and controlling certain processing temperature, namely obtained white epoxy plastic cement provided by the invention.Compared with prior art white epoxy plastic cement, epoxy plastic cement disclosed by the invention has the features such as whiteness is high, resisting high-temperature yellowing excellent property, weathering resistance are excellent, good mechanical performance, can be widely used in the manufacture of the photoelectric device parts comprising LED component, there is important using value.
Accompanying drawing explanation
Fig. 1 is the microtexture Electronic Speculum figure of white epoxy plastic cement prepared by the present invention;
Fig. 2 is that the thermal weight loss spectrogram that the present invention and comparative example prepare plastic cement contrasts;
Fig. 3 is that the reflectivity that the present invention and comparative example prepare plastic cement changes comparison diagram with digestion time.
Embodiment
A kind of environment-friendly white epoxy plastic cement, comprises the composition of following weight percent:
Glycolylurea type epoxy resin 3 ~ 20%;
Alicyclic type epoxy resin 0 ~ 5%;
Anhydride curing agent 5 ~ 20%;
Promotor 0.01 ~ 0.1%;
Oxidation inhibitor 0.01 ~ 0.1%;
Coupling agent 0.1 ~ 1%;
Releasing agent 0.05 ~ 1%;
Silica filler 50 ~ 80%;
White pigment 10 ~ 30%.
Described glycolylurea type epoxy resin is selected from the epoxy resin of structure as shown in I formula,
I
Wherein R
1=-C
nh
2n+1(
n=0 ~ 5) or R
1=-C
6h
6; R
2=-C
nh
2n+1(
n=0 ~ 5) or R
2=-C
6h
6; R
3=-H or R
3=-CH
3.
Described glycolylurea type epoxy resin is specifically selected from hydantoin epoxy (R
1=R
2=-H, R
3=-H), 5,5-dimethyl hydantion epoxies, 5-methyl-5-ethylhydantoin epoxy (R
1=-CH
3, R
2=-CH
2cH
3, R
3=-H), 5-phenyl hydantoin epoxy (R
1=-C
6h
6, R
2=-H, R
3=-H), 5,5-dimethyl-Beta-methyl hydantoin epoxy (R
1=R
2=-CH
3, R
3=-CH
3) in a kind of or several arbitrarily mixing.
Described glycolylurea type epoxy resin is 5,5-dimethyl hydantion epoxies or 5-methyl-5-ethylhydantoin epoxy or both mixing preferably.
Described alicyclic type epoxy resin is selected from such as formula 3 in II shown in a, 4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, such as formula 4 in II shown in b, 5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, a kind of or several arbitrarily mixing such as formula the tetrahydrophthalic acid 2-glycidyl ester in II shown in c.
II
Described anhydride curing agent is selected from least one in phthalic anhydride, methyl phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride or norbornylene acid anhydrides or multiple mixing, at least one in preferable methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
Described promotor is selected from glyoxaline compound or organic phosphine compound, glyoxaline compound is selected from least one in glyoxal ethyline, 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole, at least one in preferred 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole; Described organic phosphine compound is selected from triphenylphosphine, tributylphosphine, three p-methylphenyl phosphines, three nonyl Phenylphosphines, tetraphenyl phosphine tetraphenylborate, triphenylphosphine benzoquinones adducts, the tetrabutyl-O, one or more mixing in O-diethyldithiophosphoric acid phosphine, the preferred tetrabutyl-O, O-diethyldithiophosphoric acid phosphine.
Described oxidation inhibitor is selected from phosphorus-containing antioxidant, comprise 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), two 2,6-di-t-butyl-4-aminomethyl phenyl pentaerythritol diphosphate, two 2, one or more mixing in 4-di-tert-butyl-phenyl pentaerythritol diphosphate, distearyl pentaerythritol diphosphite, preferred DOPO.
Described coupling agent is selected from γ-2, one or more mixing in 3-glycidoxy-propyltrimethoxy silane (KH-560), γ aminopropyltriethoxy silane (KH-550), γ-mercaptan aminopropyl trimethoxysilane (KH-580), preferred KH-560.
Described releasing agent is selected from one or more the mixing in natural wax (bar wax etc.), synthetic wax (polyethylene wax etc.), stearic acid, palmitinic acid, Zinic stearas, calcium stearate, lithium stearate and Magnesium Stearate, preferred stearic acid and palmitinic acid.
Described silica filler is selected from one or both the mixing in spherical or dihedral silicon powder, and silicon powder form comprises crystal type and fusion, preferred crystal type ball-shaped silicon micro powder.Silicon powder median
d 50be no more than 30 μm.
Described white pigment is selected from one or more the mixing in aluminium sesquioxide, titanium dioxide, zinc oxide, calcium carbonate, preferred titanium dioxide.
Described environment-friendly white epoxy plastic cement, its preparation method comprises the steps:
(1) alicyclic ring epoxide resin shown in glycolylurea epoxide resin shown in formula I, formula II, anhydride curing agent, promotor, oxidation inhibitor, coupling agent, releasing agent, silica filler and white pigment are added hot milling on conventional various ceramic materials three roller or two roller mixing rolls, mixing after mixing, described white epoxy mixture is obtained after cooling, pulverizing
In described mixing step, temperature is 20-120 DEG C; Specifically can be 20-30 DEG C, 50-80 DEG C, 90-110 DEG C or 90-120 DEG C, preferred 60-90 DEG C; Time is 0.5-3 hour, specifically can be 0.5-1.5 hour or 1-1.5 hour, preferred 0.5-1 hour.
(2) obtained white epoxy mixture is bought cake on pancake making machine, obtain the white epoxy plastic cement of desired size size.
The described application of environment-friendly white epoxy plastic cement in microelectronic device package and optoelectronic device packaging.Described microelectronic device package is ball type array encapsulation or wafer-level package, and described optoelectronic device packaging is LED and organic LED.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.Epoxy resin purchased from American Huntsman company of glycolylurea type shown in formula I used (trade(brand)name AralditeXuAY238), Angene company of Britain, Hubei Xi Tai Chemical Co., Ltd. (fusing point: 80 ~ 90 in the present invention
oc) or other company's relative commercial products, commercialization glycolylurea type epoxy resin can be carried out decolouring purification process, to remove tramp material wherein as required; Alicyclic ring epoxide resin shown in formula II used is purchased from Japanese Daicel chemical company (trade(brand)name Celloxide2021P) or Tianjin Synthetic Material Industry Research Institute (trade(brand)name: TDE-85) or other company's relative commercial products; Anhydride curing agent used is purchased from Japanese TCI company (HHPA, methyl tetrahydro phthalic anhydride etc.); Coupling agent γ used-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) is purchased from Nanjing Lian Gui Chemical Co., Ltd. or other company's relative commercial products; Ball-type silica flour used is purchased from Wuhan Shuaier Photoelectronic Materials Co., Ltd., Japanese Admatechs company or other company's relative commercial products.
The microscopic appearance test of white epoxy plastic cement adopts HIT S-4800 scanning electronic microscope (SEM) to carry out.
The yellowness index (YI) of white epoxy plastic cement and reflectance test: use transfer moIding machine white epoxy composition to be injected mould, injection temperature: 175
oc, injection pressure: 9.6MPa, clamping time: 120s, obtains that diameter is 50mm, thickness is the print of 1mm.This print is adopted to test at U.S.'s Ai Seli X-riteColori7 color measurement instrument.
The Spiral flow length test of white epoxy plastic cement: use transfer moIding machine white epoxy composition to be injected mould, injection temperature: 175
oc, injection pressure: 7.0MPa, clamping time: 120s, test plastic cement length of flow (cm).
The thermal characteristics of white epoxy plastic cement adopts German Nai Chi company DSC204F1 calorimetric differential scanning instrument to measure.
The mechanical property of white epoxy plastic cement adopts American I nstron company 5967 type universal testing machine to measure.
embodiment 1
The preparation of white epoxy plastic cement, raw material is selected from the component of following weight percentage:
5,5-dimethyl hydantion epoxy 4.0%;
Methyl tetrahydro phthalic anhydride 5.7%;
The tetrabutyl-O, O-diethyldithiophosphoric acid phosphine 0.03%;
Oxidation inhibitor DOPO0.05%;
Coupling agent KH-5600.12%;
Releasing agent 0.1%;
Silica filler 65%;
White pigment 25%;
By said components in ceramic three roller mixing rolls in 60
othe mixing 1h of C, obtains homodisperse white mixture, cooling, pulverizing.Pancake making machine buys cake, obtains the white epoxy plastic cement of desired size size.In addition above-mentioned white mixture is made various sample in transfer moIding machine, carry out properties test, the results are shown in table 1.
The SEM spectrogram of the microscopic appearance of made white plastic cement as shown in Figure 1.Can find out, the organic constituents such as epoxy resin are together with the inorganic component such as silicon-dioxide, titanium dioxide Homogeneous phase mixing.
The thermogravimetric curve of made white plastic cement as shown in Figure 2.
The reflectivity of made white plastic cement with digestion time variation diagram as shown in Figure 3.
embodiment 2
The preparation of white epoxy plastic cement, raw material is identical with embodiment 1 with preparation method, except 5, the 5-dimethyl hydantion epoxies of 4.0% being replaced with the 5-methyl-5-ethylhydantoin epoxy of 3.0%, add the alicyclic type epoxy resin of 1.0%, properties test result lists in table 1.
The thermogravimetric curve of made white plastic cement as shown in Figure 2.Properties test result lists in table 1.
The reflectivity of made white plastic cement with digestion time variation diagram as shown in Figure 3.
embodiment 3
The preparation of white epoxy plastic cement, raw material is identical with embodiment 1 with preparation method, except 5,5-dimethyl hydantion epoxy is replaced with 5,5-dilantin epoxy.Properties test result lists in table 1.
The thermogravimetric curve of made white plastic cement as shown in Figure 2.
The reflectivity of made white plastic cement with digestion time variation diagram as shown in Figure 3.
comparative example 1
The preparation of white epoxy plastic cement, raw material is identical with embodiment 1 with preparation method, except 5,5-dimethyl hydantion epoxy is replaced with isocyanuric acid three-glycidyl ester (TGIC).Properties test result lists in table 1.
The thermogravimetric curve of made white plastic cement as shown in Figure 2.
The reflectivity of made white plastic cement with digestion time variation diagram as shown in Figure 3.
The performance of the white epoxy plastic cement that above-described embodiment and comparative example obtain is as shown in table 1.
Table 1 implementation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Spiral flow length (cm) | 108 | 112 | 116 | 118 |
| Yellowness index YI | 2.33 | 2.30 | 2.38 | 2.46 |
| Reflectivity (normal temperature, %) | 92 | 91 | 90 | 90 |
| Reflectivity (150 oC，1000h%） | 75 | 72 | 70 | 66 |
| 5% weightless temperature ( oC） | 392 | 388 | 403 | 366 |
| Flexural strength (MPa) | 135 | 135 | 132 | 123 |
| Modulus in flexure (GPa) | 25.2 | 24.3 | 24.8 | 24.0 |
| Toxicity and Environmental compatibility | Good | Good | Good | Difference |
| Comprehensive evaluation | Excellent | Excellent | Excellent | Difference |
Can find out, no matter white epoxy plastic cement provided by the invention is at toxicity and Environmental compatibility, or in resistance toheat and resisting high-temperature yellowing, be all better than prior art white epoxy plastic cement.This is extremely conducive to its application in the photoelectric device comprising LED.
Claims (15)
1. an environment-friendly white epoxy plastic cement, is characterized in that the composition comprising following weight percent:
Glycolylurea type epoxy resin 3 ~ 20%;
Alicyclic type epoxy resin 0 ~ 5%;
Anhydride curing agent 5 ~ 20%;
Promotor 0.01 ~ 0.1%;
Oxidation inhibitor 0.01 ~ 0.1%;
Coupling agent 0.1 ~ 1%;
Releasing agent 0.05 ~ 1%;
Silica filler 50 ~ 80%;
White pigment 10 ~ 30%;
Described glycolylurea type epoxy resin is selected from the epoxy resin of structure as shown in I formula,
I
Wherein R
1=-C
nh
2n+1or R
1=-C
6h
6; R
2=-C
nh
2n+1or R
2=-C
6h
6; R
3=-H or R
3=-CH
3,
n=0-5.
2. environment-friendly white epoxy plastic cement according to claim 1, it is characterized in that: described glycolylurea type epoxy resin is specifically selected from hydantoin epoxy, 5, a kind of or several arbitrarily mixing in 5-dimethyl hydantion epoxy, 5-methyl-5-ethylhydantoin epoxy, 5-phenyl hydantoin epoxy, 5,5-dimethyl-Beta-methyl hydantoin epoxy.
3. environment-friendly white epoxy plastic cement according to claim 2, is characterized in that: described glycolylurea type epoxy resin is 5,5-dimethyl hydantion epoxies or 5-methyl-5-ethylhydantoin epoxy or both mixing preferably.
4. environment-friendly white epoxy plastic cement according to claim 1, it is characterized in that: described alicyclic type epoxy resin is selected from 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, 4, a kind of or several arbitrarily mixing of 5-epoxy cyclohexane-1,2-dioctyl phthalate 2-glycidyl ester, tetrahydrophthalic acid 2-glycidyl ester.
5. environment-friendly white epoxy plastic cement according to claim 1, is characterized in that: described anhydride curing agent is selected from least one in phthalic anhydride, methyl phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride or norbornylene acid anhydrides or multiple mixing.
6. environment-friendly white epoxy plastic cement according to claim 1, it is characterized in that: described promotor is selected from glyoxaline compound or organic phosphine compound, described glyoxaline compound is selected from least one in glyoxal ethyline, 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole, at least one in preferred 2-ethyl imidazol(e) and 2-ethyl-4-methylimidazole; Described organic phosphine compound is selected from one or more the mixing in triphenylphosphine, tributylphosphine, three p-methylphenyl phosphines, three nonyl Phenylphosphines, tetraphenyl phosphine tetraphenylborate, triphenylphosphine benzoquinones adducts, the tetrabutyl-O, O-diethyldithiophosphoric acid phosphine.
7. environment-friendly white epoxy plastic cement according to claim 1, it is characterized in that: described oxidation inhibitor is selected from phosphorus-containing antioxidant, comprise 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), two 2, one or more mixing in 6-di-t-butyl-4-aminomethyl phenyl pentaerythritol diphosphate, two 2,4-di-tert-butyl-phenyl pentaerythritol diphosphate, distearyl pentaerythritol diphosphite.
8. environment-friendly white epoxy plastic cement according to claim 1, it is characterized in that: described coupling agent is selected from one or more the mixing in γ-2,3-glycidoxy-propyltrimethoxy silane, γ aminopropyltriethoxy silane, γ-mercaptan aminopropyl trimethoxysilane.
9. environment-friendly white epoxy plastic cement according to claim 1, is characterized in that: described releasing agent is selected from one or more the mixing in natural wax, synthetic wax, stearic acid, palmitinic acid, Zinic stearas, calcium stearate, lithium stearate and Magnesium Stearate.
10. environment-friendly white epoxy plastic cement according to claim 1, is characterized in that: described silica filler is selected from one or both the mixing in spherical or dihedral silicon powder, and silicon powder form comprises crystal type and fusion, silicon powder median
d 50be no more than 30 μm.
11. environment-friendly white epoxy plastic cements according to claim 1, is characterized in that: described white pigment is selected from one or more the mixing in aluminium sesquioxide, titanium dioxide, zinc oxide, calcium carbonate.
A kind of preparation method of 12. environment-friendly white epoxy plastic cements according to claim 1, is characterized in that comprising the steps:
(1) glycolylurea epoxide resin shown in formula I, alicyclic ring epoxide resin, anhydride curing agent, promotor, oxidation inhibitor, coupling agent, releasing agent, silica filler and white pigment are added hot milling on conventional various ceramic materials three roller or two roller mixing rolls, mixing after mixing, described white epoxy mixture is obtained after cooling, pulverizing, in described mixing step, temperature is 20-120 DEG C; Time is 0.5-3 hour;
(2) obtained white epoxy mixture is bought cake on pancake making machine, obtain the white epoxy plastic cement of desired size size.
The preparation method of 13. environment-friendly white epoxy plastic cements according to claim 12, is characterized in that: temperature is 60-90 DEG C; Time is 0.5-1 hour.
The purposes of 14. environment-friendly white epoxy plastic cements according to claim 1, is characterized in that: described environment-friendly white epoxy plastic cement is applied in microelectronic device package and optoelectronic device packaging.
The purposes of 15. environment-friendly white epoxy plastic cements as requested described in 14, is characterized in that: described microelectronic device package is ball type array encapsulation or wafer-level package, and described optoelectronic device packaging is LED and organic LED.
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| CN201510433967.3A Pending CN105061993A (en) | 2015-07-22 | 2015-07-22 | Environment-friendly white epoxy molding compound, preparation method therefor and application thereof |
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| CN106589836A (en) * | 2017-02-17 | 2017-04-26 | 湖北锡太化工股份有限公司 | Pouring resin having high reaction activity |
| CN106910721A (en) * | 2017-03-08 | 2017-06-30 | 东莞市佳骏电子科技有限公司 | A kind of diode and its packaging technology flow |
| CN108192285A (en) * | 2017-12-23 | 2018-06-22 | 汕头市骏码凯撒有限公司 | A kind of optics LED encapsulation bonds epoxy-plastic packaging material and preparation method thereof with high |
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| CN106589836A (en) * | 2017-02-17 | 2017-04-26 | 湖北锡太化工股份有限公司 | Pouring resin having high reaction activity |
| CN106910721A (en) * | 2017-03-08 | 2017-06-30 | 东莞市佳骏电子科技有限公司 | A kind of diode and its packaging technology flow |
| CN108192285A (en) * | 2017-12-23 | 2018-06-22 | 汕头市骏码凯撒有限公司 | A kind of optics LED encapsulation bonds epoxy-plastic packaging material and preparation method thereof with high |
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| CN112391034A (en) * | 2019-08-13 | 2021-02-23 | 北京科化新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
| CN112391034B (en) * | 2019-08-13 | 2022-12-09 | 北京科化新材料科技有限公司 | Epoxy resin composite material and preparation method and application thereof |
| CN111205796A (en) * | 2019-12-27 | 2020-05-29 | 科化新材料泰州有限公司 | Light-colored anti-yellowing epoxy resin composition for semiconductor packaging |
| CN111205796B (en) * | 2019-12-27 | 2022-08-05 | 江苏科化新材料科技有限公司 | Light-colored anti-yellowing epoxy resin composition for semiconductor packaging |
| CN116376496A (en) * | 2023-04-20 | 2023-07-04 | 瑞能半导体科技股份有限公司 | Epoxy encapsulation composition for semiconductor, preparation method thereof and semiconductor device encapsulation layer |
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Application publication date: 20151118 |