CN104910829A - Tackifying agent for LED sealed packaging adhesive and preparation method thereof - Google Patents
Tackifying agent for LED sealed packaging adhesive and preparation method thereof Download PDFInfo
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- CN104910829A CN104910829A CN201510225282.XA CN201510225282A CN104910829A CN 104910829 A CN104910829 A CN 104910829A CN 201510225282 A CN201510225282 A CN 201510225282A CN 104910829 A CN104910829 A CN 104910829A
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Abstract
The invention discloses a tackifying agent for an LED sealed packaging adhesive and a preparation method thereof. The tackifying agent is prepared by the steps: carrying out a condensation reaction on polyborosiloxane, a siloxane prepolymer, a silane coupling agent and an end-capping agent in a water and organic solvent environment and under the action of an acid catalyst, then washing with water to neutral, carrying out reduced pressure distillation to remove an organic solvent and a low-boiling-point substance, and thus obtaining the colorless transparent viscous tackifying agent. The polyborosiloxane is obtained by carrying out a reaction of boric acid and phenyl chlorosilane under a reduced pressure condition, and the siloxane prepolymer is obtained by dehydration condensation of phenyl siloxane under the action of an acid catalyst. The tackifying agent used for the LED sealed packaging adhesive and prepared by the method has good adhesion ability on PPA and a silver plated layer of an aluminum base plate simultaneously, and has the advantages of high refractive index and yellowing resistance.
Description
Technical field
The present invention relates to LED glue technical field, particularly relate to a kind of LED glue tackifier and preparation method thereof.
Background technology
The advantages such as the internal characteristics of photodiode (LED) is as little in volume, current consumption is low, long service life, high brightness, low in calories, environmental protection, sturdy and durable, changeable, determine LED to occupy an important position at the lighting field in future, current LED is rapid to be used widely in fields such as illumination, backlight, display screens.
Phenyl addition type polysiloxane is due to its high refractive index, high-low temperature resistant, ultraviolet aging resistance, insulation, hydrophobic, anti-aging, the performances such as sulfuration resistant, become the development trend of LED gradually, but phenyl addition type polysiloxane is owing to its molecular weight there being a large amount of nonpolar phenyl groups, cause the metal base of phenyl addition type polysiloxane and support and polar plas PPA adhesiveproperties poor, phenyl addition type polysiloxane is easily peeled off from support, chip is made to lose protection, this is mainly because addition-type silicon rubber molecule itself is in nonpolar, as embedding, coating, when inserts injecting forming material uses, cementability is very poor.At present, it is process substrate surface with silane coupling agent that the method for the cementability of raising packaging plastic and various material mainly contains three kinds: one, and this method adds production process and production time, reduces production efficiency, silane coupling agent many uses flammable solvent, causes peril of transportation and environmental pollution simultaneously; Two is strengthen cementability by changing base xanthan molecule structure, but this method is due to actual production process more complicated, and cost is relatively high; Three is improve cementability by adding tackifier, and this method is easy to operate, so synthesizing new tackifier become study hotspot.
Publication number is CN103275325A, name is called the Chinese patent application of " Borosiloxane and preparation method thereof ", utilize the cementability of boron and metal, a kind of polyborosiloxane tackifier are prepared, but due to the character of boron, boron is excellent to metal sticking power in LED support, but more weak to the PPA plastic bonding power on support, and packaging plastic is easily peeled off with PPA in hot environment, make oxygen G&W enter support, cause the inefficacy of LED.Publication number is CN1993427A, name is called the Chinese patent application of " curable organopolysiloxane composition, its curing, semiconducter device and adhesion promotor ", prepare a kind of polymkeric substance comprising epoxide group and ester group, but these type of tackifier are after joining packaging plastic, through long-time weathering test, often easily turn to be yellow, cause LED lamp bead light decay serious.
Summary of the invention
The invention provides and a kind ofly have tackifier of excellent bonds ability and preparation method thereof to PPA, aluminium base silvered film simultaneously, these tackifier possess the advantage of high refractive index and anti-yellowing change simultaneously.
According to a first aspect of the invention, the invention provides a kind of LED glue tackifier, these tackifier be polyborosiloxane, siloxane prepolymer, silane coupling agent and end-capping reagent in water, organic solvent environment under the effect of an acidic catalyst, carry out condensation reaction, then neutrality is washed to, and underpressure distillation removes organic solvent and low-boiling-point substance, and the tackifier that the water white transparency obtained is thick; Wherein above-mentioned polyborosiloxane is that boric acid and phenyl chlorosilane are obtained by reacting at reduced pressure conditions, and above-mentioned siloxane prepolymer is that phenyl siloxane is obtained by dehydrating condensation under the effect of an acidic catalyst.
As preferred version of the present invention, above-mentioned phenyl chlorosilane be selected from diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI one or more, preferred diphenyl dichlorosilane.
As preferred version of the present invention, above-mentioned phenyl siloxane be selected from dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and triphenylmethoxy silane one or more, preferred phenyltrimethoxysila,e.
As preferred version of the present invention, above-mentioned silane coupling agent is selected from 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and 3-(2,3 epoxy third oxygen) one or more in hydroxypropyl methyl diethoxy silane, preferred 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
As preferred version of the present invention, above-mentioned end-capping reagent be selected from tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane one or more, preferred tetramethyl disiloxane.
According to a second aspect of the invention, the invention provides a kind of preparation method of LED glue tackifier, the method comprises the steps:
(1) boric acid and phenyl chlorosilane is made to be obtained by reacting polyborosiloxane at reduced pressure conditions;
(2) phenyl siloxane is made to obtain siloxane prepolymer by dehydrating condensation under the effect of an acidic catalyst;
(3) above-mentioned polyborosiloxane and above-mentioned siloxane prepolymer, silane coupling agent, end-capping reagent, water, organic solvent are carried out condensation reaction under the effect of an acidic catalyst, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains the LED glue tackifier that water white transparency is thick.
As preferred version of the present invention, aforesaid method comprises the steps:
(1) at 80-100 DEG C, make the phenyl chlorosilane of the boric acid of 50-80 mass parts and 200-300 mass parts react 8-12h at reduced pressure conditions and obtain polyborosiloxane;
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts dehydration condensation 3-5h under the effect of an acidic catalyst of 1-2 mass parts is made to obtain siloxane prepolymer;
(3) at 50-80 DEG C, make the above-mentioned polyborosiloxane of 5-8 mass parts and above-mentioned siloxane prepolymer, the silane coupling agent of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, organic solvent condensation reaction 10-15h under the effect of an acidic catalyst of 0.1-1 mass parts of 100-150 mass parts of 30-50 mass parts, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains tackifier.
As preferred version of the present invention, above-mentioned phenyl chlorosilane be selected from diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI one or more, preferred diphenyl dichlorosilane.
As preferred version of the present invention, the situation of above-mentioned reduced pressure to be vacuum tightness be-0.075MPa to-0.096MPa.
As preferred version of the present invention, above-mentioned phenyl siloxane be selected from dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and triphenylmethoxy silane one or more, preferred phenyltrimethoxysila,e.
As preferred version of the present invention, above-mentioned an acidic catalyst be selected from hydrochloric acid, sulfuric acid, trifluoromethayl sulfonic acid, Zeo-karb SK1BH, phosphoric acid and phosphonitrilic chloride one or more, preferred trifluoromethayl sulfonic acid.
As preferred version of the present invention, above-mentioned silane coupling agent is selected from 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and 3-(2,3 epoxy third oxygen) one or more in hydroxypropyl methyl diethoxy silane, preferred 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
As preferred version of the present invention, above-mentioned end-capping reagent be selected from tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane one or more, preferred tetramethyl disiloxane.
As preferred version of the present invention, above-mentioned organic solvent be selected from toluene, dimethylbenzene, normal hexane, hexanaphthene, tetracol phenixin and ethyl acetate one or more, preferred toluene or dimethylbenzene.
The LED glue tackifier that method of the present invention prepares have excellent bonds ability to PPA, aluminium base silvered film simultaneously, possess the advantage of high refractive index and anti-yellowing change simultaneously.
Embodiment
Below by embodiment, the present invention is described in further detail.
The present inventor is by being obtained by reacting polyborosiloxane at reduced pressure conditions by (1) boric acid and phenyl chlorosilane; (2) phenyl siloxane is obtained siloxane prepolymer by dehydrating condensation under the effect of an acidic catalyst; (3) polyborosiloxane and siloxane prepolymer, silane coupling agent, end-capping reagent, water, organic solvent are carried out condensation reaction under the effect of an acidic catalyst, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains a kind ofly having excellent bonds ability to PPA, aluminium base silvered film simultaneously and possessing the thick LED glue tackifier of the water white transparency of high refractive index and anti-yellowing change advantage simultaneously.
The present inventor have been surprisingly found that, use the LED glue tackifier that prepared by aforesaid method as the composition of packaging plastic, packaging plastic can be made to improve 10-20 doubly to the adhesive capacity of PPA, aluminium base silvered film, greatly exceed the expectation of those skilled in the art.
It should be noted that, the order of above-mentioned steps (1) and (2) is also unrestricted, first can carry out step (1) and carry out step (2) again, also first can carry out step (2) and carry out step (1) again, because these two steps are independently.Although marked in claim (1) and (2), be to be understood that the scope of claim not only comprises and first carry out the situation that step (1) carries out step (2) again, also comprise and first carry out the situation that step (2) carries out step (1) again.
On the basis of such scheme of the present invention, the present inventor has carried out further optimization to the raw material dosage in reaction, temperature of reaction and reaction times, obtains a kind of preferred technical scheme.By the composition of the tackifier obtained by this preferred technical scheme as LED glue, unexpectedly can improve the adhesiveproperties of packaging plastic to PPA, aluminium base silvered film, and possess the advantage of high refractive index and anti-yellowing change simultaneously.
This preferred technical scheme is as follows:
(1) at 80-100 DEG C, make the phenyl chlorosilane of the boric acid of 50-80 mass parts and 200-300 mass parts react 8-12h at reduced pressure conditions and obtain polyborosiloxane;
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts dehydration condensation 3-5h under the effect of an acidic catalyst of 1-2 mass parts is made to obtain siloxane prepolymer;
(3) at 50-80 DEG C, make the above-mentioned polyborosiloxane of 5-8 mass parts and above-mentioned siloxane prepolymer, the silane coupling agent of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, organic solvent condensation reaction 10-15h under the effect of an acidic catalyst of 0.1-1 mass parts of 100-150 mass parts of 30-50 mass parts, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains tackifier.
In certain embodiments of the present invention, above-mentioned phenyl chlorosilane is selected from diphenyl dichlorosilane, dichloromethyl phenylsilane and α, one or more in ω-dichloro PSI, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of diphenyl dichlorosilane and dichloromethyl phenylsilane, diphenyl dichlorosilane and α, the mixing of ω-dichloro PSI, dichloromethyl phenylsilane and α, the mixing of ω-dichloro PSI, the mixing of diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI.Preferred diphenyl dichlorosilane.
In certain embodiments of the present invention, the situation of above-mentioned reduced pressure to be vacuum tightness be-0.075MPa to-0.096MPa, such as vacuum tightness-0.080MPa ,-0.082MPa ,-0.085MPa ,-0.087MPa ,-0.090MPa ,-0.092MPa ,-0.095MPa ,-0.096MPa ,-0.080 ~-0.092MPa or-0.082 ~-0.090MPa.
In certain embodiments of the present invention, above-mentioned phenyl siloxane be selected from dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and triphenylmethoxy silane one or more, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of dimethoxydiphenylsilane and diphenyl diethoxy silane, the mixing of dimethoxydiphenylsilane and aminomethyl phenyl dimethoxysilane, the mixing of diphenyl diethoxy silane and aminomethyl phenyl dimethoxysilane, the mixing of dimethoxydiphenylsilane, diphenyl diethoxy silane and aminomethyl phenyl dimethoxysilane.Preferred phenyltrimethoxysila,e.
In certain embodiments of the present invention, above-mentioned an acidic catalyst be selected from hydrochloric acid, sulfuric acid, trifluoromethayl sulfonic acid, Zeo-karb SK1BH, phosphoric acid and phosphonitrilic chloride one or more, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of sulfuric acid and trifluoromethayl sulfonic acid, the mixing of sulfuric acid and phosphonitrilic chloride, the mixing of trifluoromethayl sulfonic acid and phosphonitrilic chloride, the mixing of sulfuric acid, trifluoromethayl sulfonic acid and phosphonitrilic chloride.Preferred trifluoromethayl sulfonic acid.
In certain embodiments of the present invention, above-mentioned silane coupling agent is selected from 3-(2, 3-epoxy third oxygen) propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane (KH-540), γ-aminopropyl triethoxysilane (KH550) and 3-(2, 3 epoxy third oxygen) one or more in hydroxypropyl methyl diethoxy silane, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of KH560 and KH570, the mixing of KH570 and vinyltrimethoxy silane, the mixing of vinyltrimethoxy silane and KH-540, the mixing of KH-540 and 3-(2,3 epoxy third oxygen) hydroxypropyl methyl diethoxy silane.Preferred KH560 and KH570.
In certain embodiments of the present invention, above-mentioned end-capping reagent be selected from tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane one or more, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of tetramethyl disiloxane and tetramethyl divinyl disiloxane, the mixing of tetramethyl disiloxane and hexamethyldisiloxane, the mixing of tetramethyl divinyl disiloxane and hexamethyldisiloxane, the mixing of tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane.Preferred tetramethyl disiloxane.
In certain embodiments of the present invention, above-mentioned organic solvent be selected from toluene, dimethylbenzene, normal hexane, hexanaphthene, tetracol phenixin and ethyl acetate one or more, that is can be used alone wherein a kind of, also can used in combination two or more, and the present invention does not limit for blending ratio used in combination.Typical case but the example used in combination of indefiniteness such as: the mixing of toluene and dimethylbenzene, the mixing of toluene and normal hexane, the mixing of dimethylbenzene and normal hexane, the mixing of toluene, dimethylbenzene and normal hexane, the mixing of hexanaphthene and tetracol phenixin, the mixing of tetracol phenixin and ethyl acetate, the mixing of hexanaphthene, tetracol phenixin and ethyl acetate.Preferred toluene or dimethylbenzene.
In above-mentioned preferred technical scheme, raw material dosage, temperature of reaction and reaction times, all further optimization obtained.
Wherein, the temperature of reaction 80-100 DEG C in step (1), such as 82 DEG C, 85 DEG C, 87 DEG C, 89 DEG C, 91 DEG C, 93 DEG C, 95 DEG C, 96 DEG C, 98 DEG C, 99 DEG C, 82-95 DEG C, 85-90 DEG C, 88-95 DEG C or 90-98 DEG C; The consumption 50-80 mass parts of boric acid, such as 52 mass parts, 55 mass parts, 58 mass parts, 62 mass parts, 64 mass parts, 67 mass parts, 69 mass parts, 71 mass parts, 73 mass parts, 75 mass parts, 78 mass parts, 60-75 mass parts or 65-70 mass parts; The consumption 200-300 mass parts of phenyl chlorosilane, such as 200 mass parts, 220 mass parts, 235 mass parts, 250 mass parts, 270 mass parts, 280 mass parts, 285 mass parts, 295 mass parts, 220-270 mass parts or 230-250 mass parts; Reaction times 8-12h, such as 8.5h, 8.8h, 9.2h, 9.5h, 9.7h, 10h, 10.5h, 10.8h, 11h, 11.25h, 11.5h, 11.7h, 11.9h, 8.5-11h or 9-10h.
Temperature of reaction 50-80 DEG C in step (2), such as 52 DEG C, 54 DEG C, 56 DEG C, 59 DEG C, 61 DEG C, 65 DEG C, 68 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 60-75 DEG C or 65-70 DEG C; The consumption 100-200 mass parts of phenyl siloxane, such as 110 mass parts, 120 mass parts, 130 mass parts, 150 mass parts, 160 mass parts, 180 mass parts, 190 mass parts, 195 mass parts, 120-180 mass parts or 130-150 mass parts; The consumption 1-2 mass parts of an acidic catalyst, such as 1.1 mass parts, 1.2 mass parts, 1.3 mass parts, 1.5 mass parts, 1.7 mass parts, 1.8 mass parts, 1.9 mass parts, 1.2-1.8 mass parts or 1.3-1.5 mass parts; Dehydration condensation 3-5h, such as 3.2h, 3.5h, 3.8h, 4.1h, 4.3h, 4.5h, 4.7h, 4.9h, 3.5-4.8h or 3.8-4.2h.
Temperature of reaction 50-80 DEG C in step (3), such as 52 DEG C, 54 DEG C, 56 DEG C, 59 DEG C, 61 DEG C, 65 DEG C, 68 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 60-75 DEG C or 65-70 DEG C; The consumption 5-8 mass parts of polyborosiloxane, such as 5.5 mass parts, 5.8 mass parts, 6.2 mass parts, 6.7 mass parts, 7.3 mass parts, 7.5 mass parts, 7.7 mass parts, 7.8 mass parts, 5.5-7.5 mass parts or 6.0-7.0 mass parts; The consumption 30-50 mass parts of siloxane prepolymer, such as 33 mass parts, 35 mass parts, 37 mass parts, 41 mass parts, 43 mass parts, 45 mass parts, 48 mass parts, 35-45 mass parts or 38-42 mass parts; The consumption 30-50 mass parts of silane coupling agent, such as 33 mass parts, 35 mass parts, 37 mass parts, 41 mass parts, 43 mass parts, 45 mass parts, 48 mass parts, 35-45 mass parts or 38-42 mass parts; The consumption 2-5 mass parts of end-capping reagent, such as 2.1 mass parts, 2.3 mass parts, 2.5 mass parts, 2.8 mass parts, 3.2 mass parts, 3.5 mass parts, 3.8 mass parts, 4.2 mass parts, 4.5 mass parts, 4.8 mass parts, 2.5-4.5 mass parts or 3-4 mass parts; The consumption 5-10 mass parts of deionized water, such as 5.2 mass parts, 5.5 mass parts, 6 mass parts, 6.5 mass parts, 7 mass parts, 7.5 mass parts, 8 mass parts, 8.5 mass parts, 9 mass parts, 9.5 mass parts, 9.8 mass parts, 6-9 mass parts or 7-8 mass parts; The consumption 100-150 mass parts of organic solvent, such as 110 mass parts, 115 mass parts, 120 mass parts, 130 mass parts, 135 mass parts, 140 mass parts, 145 mass parts, 110-140 mass parts or 120-130 mass parts; The consumption 0.1-1 mass parts of an acidic catalyst, such as 0.1 mass parts, 0.2 mass parts, 0.3 mass parts, 0.4 mass parts, 0.5 mass parts, 0.6 mass parts, 0.7 mass parts, 0.8 mass parts, 0.9 mass parts, 0.95 mass parts, 0.2-0.8 mass parts or 0.4-0.6 mass parts; Condensation reaction 10-15h, such as 11h, 11.5h, 12h, 12.5h, 13.5h, 14h, 14.5h, 15h, 13-14.5h or 13.5-14h.
Below by way of specific embodiment, LED glue tackifier of the present invention and preparation method thereof are described in detail.Should be appreciated that following examples are only exemplary, the present invention is not limited to following examples.
The tackifier prepared in following examples are used as the composition of LED glue, the measuring method of its cured body bond strength is as follows: use Vinylphenyl silicon resin RH-SP605-3 (Zhejiang Run He new chemical materials company limited) and Silicon Containing Hydrogen resin RH-SP303 (Zhejiang Run He new chemical materials company limited) to obtain base glue according to the proportions of vinyl (RH-SP605-3 provides) molar weight/si-h bond (RH-SP303 provides) molar weight=1.3, and add the ethynylcyclohexanol (Aladdin Reagent Company) of 0.5% base glue mass parts and Andisil 785Catalyst (the extraordinary organosilicon company of the An Biya) catalyzer of 0.5% base glue mass parts successively, then the LED glue tackifier adding the high refractive index of each embodiment synthesis of 1% base glue mass parts are mixed with packaging plastic to be tested.
According to the testing method of GB/T13936-1992, at two silver-plated aluminium sheet (or PPA plate) (width: 25mm; Length: 50mm; Thickness: 1mm) between fill gaps packaging plastic obtained above.In the hot air circulate formula baking oven of 150 DEG C, keep this packaging plastic to solidify.After being cooled to room temperature, in tensile testing machine, measured the bond strength of cured body by the obtained sample that stretches in horizontal direction relative to each other.
Embodiment 1
Under the condition of 80 DEG C, the dichloromethyl phenylsilane of the boric acid of 50 mass parts (Aladdin Reagent Company) and 200 mass parts (Dalian Yuan Yong organosilicon factory) is used to be react 8h under the reduced pressure of-0.096MPa to obtain a kind of polyborosiloxane in vacuum tightness;
Under the condition of 50 DEG C, the phenyl triethoxysilane of 100 mass parts (Dalian Yuan Yong organosilicon factory) dehydrating condensation 3h under the effect of the Zeo-karb SK1BH (Mitsubishi KCC) of 1 mass parts is used to obtain a kind of siloxane prepolymer;
The polyborosiloxane of 5 mass parts and the siloxane prepolymer of 30 mass parts that obtain will be synthesized, the 3-(2 of 15 mass parts, 3 epoxy third oxygen) hydroxypropyl methyl diethoxy silane (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei), the KH570 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 15 mass parts, the tetramethyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 2 mass parts, the deionized water of 5 mass parts, the ethyl acetate (Xilong Chemical Co., Ltd) of 100 mass parts is under 50 DEG C of conditions, condensation 10h under the effect of the Zeo-karb SK1BH of 1 mass parts, then neutrality is washed to, underpressure distillation removes ethyl acetate and low-boiling-point substance, obtain the high refractive index LED glue tackifier that a kind of water white transparency is thick.
Embodiment 2
Under the condition of 90 DEG C, the diphenyl dichlorosilane of the boric acid of 60 mass parts (Aladdin Reagent Company) and 240 mass parts (Dalian Yuan Yong organosilicon factory) is used to be react 9h under the reduced pressure of-0.096MPa to obtain a kind of polyborosiloxane in vacuum tightness;
Under the condition of 60 DEG C, the phenyltrimethoxysila,e of 100 mass parts (Dalian Yuan Yong organosilicon factory) dehydrating condensation 4h under the effect of the phosphonitrilic chloride (Aladdin Reagent Company) of 1 mass parts is used to obtain a kind of siloxane prepolymer;
The polyborosiloxane of 6 mass parts and the siloxane prepolymer of 40 mass parts that obtain will be synthesized, the KH540 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 20 mass parts, the KH550 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 20 mass parts, the tetramethyl divinyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 3 mass parts, the deionized water of 6 mass parts, the hexanaphthene (Xi Long Chemical Co., Ltd.) of 120 mass parts is under 60 DEG C of conditions, condensation 12h under the effect of the phosphonitrilic chloride of 0.1 mass parts, then neutrality is washed to, underpressure distillation removes hexanaphthene and low-boiling-point substance, obtain the high refractive index LED glue tackifier that a kind of water white transparency is thick.
Embodiment 3
Under the condition of 85 DEG C, the dichloromethyl phenylsilane of the boric acid of 70 mass parts (Aladdin Reagent Company) and 250 mass parts (Dalian Yuan Yong organosilicon factory) is used to be react 10h under the reduced pressure of-0.096MPa to obtain a kind of polyborosiloxane in vacuum tightness;
Under the condition of 70 DEG C, the phenyltrimethoxysila,e of 150 mass parts (Dalian Yuan Yong organosilicon factory) dehydrating condensation 4h under the effect of the trifluoromethayl sulfonic acid (Aladdin Reagent Company) of 1.5 mass parts is used to obtain a kind of siloxane prepolymer;
The polyborosiloxane of 7 mass parts and the siloxane prepolymer of 40 mass parts that obtain will be synthesized, the KH560 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 25 mass parts, the KH570 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 25 mass parts, the hexamethyldisiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 4 mass parts, the deionized water of 7 mass parts, the normal hexane (Xilong Chemical Co., Ltd) of 130 mass parts is under 80 DEG C of conditions, condensation 13h under the effect of the trifluoromethayl sulfonic acid of 0.5 mass parts, then neutrality is washed to, underpressure distillation removes normal hexane and low-boiling-point substance, obtain the high refractive index LED glue tackifier that a kind of water white transparency is thick.
Embodiment 4
Under the condition of 100 DEG C, the dichloromethyl phenylsilane of the boric acid of 80 mass parts (Aladdin Reagent Company) and 270 mass parts (Dalian Yuan Yong organosilicon factory) is used to be react 11h under the reduced pressure of-0.096MPa to obtain a kind of polyborosiloxane in vacuum tightness;
Under the condition of 70 DEG C, use 50 mass parts aminomethyl phenyl diethoxy silanes (Dalian Yuan Yong organosilicon factory), 150 mass parts phenyltrimethoxysila,e (Dalian Yuan Yong organosilicon factory) dehydrating condensation 5h under the effect of 2 mass parts sulfuric acid (concentration 98%, Xilong Chemical Co., Ltd) obtains a kind of siloxane prepolymer;
The polyborosiloxane of 8 mass parts and the siloxane prepolymer of 50 mass parts that obtain will be synthesized, the KH570 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 50 mass parts, the tetramethyl disiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 3 mass parts, the hexamethyldisiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 2 mass parts, the deionized water of 10 mass parts, the dimethylbenzene (Xilong Chemical Co., Ltd) of 150 mass parts is under 80 DEG C of conditions, condensation 15h under the effect of the sulfuric acid of 0.5 mass parts, then neutrality is washed to, underpressure distillation removes dimethylbenzene and low-boiling-point substance, obtain the high refractive index LED glue tackifier that a kind of water white transparency is thick.
Embodiment 5
Under the condition of 95 DEG C, the diphenyl dichlorosilane of the boric acid of 75 mass parts (Aladdin Reagent Company) and 280 mass parts (Dalian Yuan Yong organosilicon factory) is used to be react 12h under the reduced pressure of-0.075MPa to obtain a kind of polyborosiloxane in vacuum tightness;
At 75 DEG C, phenyltrimethoxysila,e (Dalian Yuan Yong organosilicon factory) the dehydrating condensation 4.5h under the effect of 2 mass parts hydrochloric acid (concentration 36%, Xilong Chemical Co., Ltd) of the dimethoxydiphenylsilane of 100 mass parts (Dalian Yuan Yong organosilicon factory) and 100 mass parts is used to obtain a kind of siloxane prepolymer;
The polyborosiloxane of 8 mass parts and the siloxane prepolymer of 45 mass parts that obtain will be synthesized, the KH560 (Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei) of 45 mass parts, the hexamethyldisiloxane (Quzhou Ruilijie Chemical Co., Ltd.) of 4 mass parts, the deionized water of 10 mass parts, the toluene (Xilong Chemical Co., Ltd) of 150 mass parts is under 80 DEG C of conditions, condensation 15h under the effect of the hydrochloric acid of 1 mass parts, then neutrality is washed to, underpressure distillation removes toluene and low-boiling-point substance, obtain the high refractive index LED glue tackifier that a kind of water white transparency is thick.
The tackifier that above-described embodiment 1-5 obtains are used as the composition of LED glue, the specific refractory power recorded, high bake performance and as shown in table 1 with the performance data of the cured body bonding force of aluminium sheet silvered film and PPA plastics.Use do not add tackifier and containing other all the components base glue as a comparison case.
The test data of the LED tackifier that table 1 embodiment 1-5 obtains
Result shows: the tackifier using embodiments of the invention 1-5 to obtain are as the added ingredients of LED glue, the cured body bonding force of packaging plastic to aluminium sheet silvered film and PPA plastics can be significantly improved, adhesive capacity even improves 10-20 doubly, far exceeds the expectation of those skilled in the art.
Above content is in conjunction with concrete embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made.
Claims (10)
1. LED glue tackifier, it is characterized in that, described tackifier be polyborosiloxane, siloxane prepolymer, silane coupling agent and end-capping reagent in water, organic solvent environment under the effect of an acidic catalyst, carry out condensation reaction, then neutrality is washed to, and underpressure distillation removes organic solvent and low-boiling-point substance, and the tackifier that the water white transparency obtained is thick; Wherein said polyborosiloxane is that boric acid and phenyl chlorosilane are obtained by reacting at reduced pressure conditions, and described siloxane prepolymer is that phenyl siloxane is obtained by dehydrating condensation under the effect of an acidic catalyst.
2. tackifier according to claim 1, is characterized in that, described phenyl chlorosilane be selected from diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI one or more, preferred diphenyl dichlorosilane;
Preferably, described phenyl siloxane be selected from dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and triphenylmethoxy silane one or more, preferred phenyltrimethoxysila,e;
Preferably, described silane coupling agent is selected from 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and 3-(2,3 epoxy third oxygen) one or more in hydroxypropyl methyl diethoxy silane, preferred 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane;
Preferably, described end-capping reagent be selected from tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane one or more, preferred tetramethyl disiloxane.
3. a preparation method for LED glue tackifier, is characterized in that, described method comprises the steps:
(1) boric acid and phenyl chlorosilane is made to be obtained by reacting polyborosiloxane at reduced pressure conditions;
(2) phenyl siloxane is made to obtain siloxane prepolymer by dehydrating condensation under the effect of an acidic catalyst;
(3) described polyborosiloxane and described siloxane prepolymer, silane coupling agent, end-capping reagent, water, organic solvent are carried out condensation reaction under the effect of an acidic catalyst, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains the LED glue tackifier that water white transparency is thick.
4. method according to claim 3, is characterized in that, described method comprises the steps:
(1) at 80-100 DEG C, make the phenyl chlorosilane of the boric acid of 50-80 mass parts and 200-300 mass parts react 8-12h at reduced pressure conditions and obtain described polyborosiloxane;
(2) at 50-80 DEG C, the phenyl siloxane of 100-200 mass parts dehydration condensation 3-5h under the effect of an acidic catalyst of 1-2 mass parts is made to obtain described siloxane prepolymer;
(3) at 50-80 DEG C, make the described polyborosiloxane of 5-8 mass parts and described siloxane prepolymer, the silane coupling agent of 30-50 mass parts, the end-capping reagent of 2-5 mass parts, the deionized water of 5-10 mass parts, organic solvent condensation reaction 10-15h under the effect of an acidic catalyst of 0.1-1 mass parts of 100-150 mass parts of 30-50 mass parts, then neutrality is washed to, underpressure distillation removes organic solvent and low-boiling-point substance, obtains described tackifier.
5. the method according to claim 3 or 4, is characterized in that, described phenyl chlorosilane be selected from diphenyl dichlorosilane, dichloromethyl phenylsilane and α, ω-dichloro PSI one or more, preferred diphenyl dichlorosilane;
Preferably, the situation of described reduced pressure to be vacuum tightness be-0.075MPa to-0.096MPa.
6. the method according to claim 3 or 4, it is characterized in that, described phenyl siloxane be selected from dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane and triphenylmethoxy silane one or more, preferred phenyltrimethoxysila,e.
7. the method according to claim 3 or 4, is characterized in that, described an acidic catalyst be selected from hydrochloric acid, sulfuric acid, trifluoromethayl sulfonic acid, Zeo-karb SK1BH, phosphoric acid and phosphonitrilic chloride one or more, preferred trifluoromethayl sulfonic acid.
8. the method according to claim 3 or 4, it is characterized in that, described silane coupling agent is selected from 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, 3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and 3-(2,3 epoxy third oxygen) one or more in hydroxypropyl methyl diethoxy silane, preferred 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
9. the method according to claim 3 or 4, is characterized in that, described end-capping reagent be selected from tetramethyl disiloxane, tetramethyl divinyl disiloxane and hexamethyldisiloxane one or more, preferred tetramethyl disiloxane.
10. the method according to claim 3 or 4, is characterized in that, described organic solvent be selected from toluene, dimethylbenzene, normal hexane, hexanaphthene, tetracol phenixin and ethyl acetate one or more, preferred toluene or dimethylbenzene.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105131291A (en) * | 2015-09-29 | 2015-12-09 | 肇庆皓明有机硅材料有限公司 | Tackifier and preparation thereof as well as adhesion addition type liquid silicone rubber and preparation thereof |
| CN105504833A (en) * | 2016-01-22 | 2016-04-20 | 蒋柱明 | Single-component power-type organosilicon insulation paste for LED (light-emitting diode) packaging and preparation method thereof |
| CN105524281A (en) * | 2016-01-25 | 2016-04-27 | 广东恒大新材料科技有限公司 | Boron silane modified silicon resin, addition type resin composition and application |
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| CN106008983A (en) * | 2016-07-11 | 2016-10-12 | 广州双桃精细化工有限公司 | Silicon-boron tackifier and preparation method and application thereof |
| CN106543957A (en) * | 2016-10-14 | 2017-03-29 | 沈阳理工大学 | The poly- diphenyl Borosiloxane adhesive of bi-component toughening type and its methods for making and using same |
| CN106800655A (en) * | 2015-11-26 | 2017-06-06 | 比亚迪股份有限公司 | A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of silica-gel composition |
| CN107275465A (en) * | 2017-06-29 | 2017-10-20 | 华中科技大学鄂州工业技术研究院 | LED encapsulation and preparation method thereof |
| CN107312496A (en) * | 2017-05-14 | 2017-11-03 | 杭州师范大学 | A kind of cementability add-on type liquid silicon rubber |
| CN108047449A (en) * | 2017-12-30 | 2018-05-18 | 汕头市骏码凯撒有限公司 | A kind of synthetic method of boracic tackifier |
| CN111154453A (en) * | 2020-01-19 | 2020-05-15 | 厦门艾贝森电子有限公司 | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739848A (en) * | 2013-12-25 | 2014-04-23 | 北京化工大学 | Tackifier for addition type organosilicone packaging glue and preparation method thereof |
| CN103755964A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane tackifying resin and preparation method thereof |
-
2015
- 2015-05-05 CN CN201510225282.XA patent/CN104910829B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739848A (en) * | 2013-12-25 | 2014-04-23 | 北京化工大学 | Tackifier for addition type organosilicone packaging glue and preparation method thereof |
| CN103755964A (en) * | 2013-12-27 | 2014-04-30 | 深圳市安品有机硅材料有限公司 | Polysiloxane tackifying resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴艳金等: "聚硼硅氧烷的制备及应用研究进展", 《高分子通报》 * |
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