CN102660027B - Polysiloxane curing agent - Google Patents
Polysiloxane curing agent Download PDFInfo
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- CN102660027B CN102660027B CN201210134487.3A CN201210134487A CN102660027B CN 102660027 B CN102660027 B CN 102660027B CN 201210134487 A CN201210134487 A CN 201210134487A CN 102660027 B CN102660027 B CN 102660027B
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- polysiloxane
- phenyltrimethoxysila
- oil phase
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Abstract
The invention relates to a semiconductor packaging adhesive, in particular to a polysiloxane curing agent for the semiconductor packaging adhesive. Each molecule of the polysiloxane curing agent at least contains two hydrogen atoms bonded to silicon and oxysilane of aryl. The curing agent has a structural formula as follows: (R1R4SiO1/2) O . (R12SiO2/2) p . ( R1R4SiO2/2) q . (R3SiO2/2) r . (R3SiO3/2) s, wherein R1 is alkyl, R3 is aryl, R4 is an H atom or alkyl, o + p + q + r + s is equal to 100, o is 1 to 20, p is 10 to 20, q is 0 to 20, r is 0 to 10, and s is 30 to 60. The organic silicone semiconductor packaging adhesive cured by the product provided by the invention has the characteristics of high refractive index, high light transmittance, high physical strength, resistance to yellowing, and resistance to ultraviolet and thermal aging.
Description
Technical field
The present invention relates to a kind of semiconductor packages glue, relate in particular to a kind of semiconductor packages glue polysiloxane solidifying agent.
Background technology
Traditional semiconductor element epoxy encapsulation, but in use can there is xanthochromia, thus making translucidus variation, in Reusability, epoxy resin easily becomes fragile, strength degradation.For addressing the above problem, adopt again modifying epoxy resin by organosilicon composition, silica gel etc. as the packaged material of semiconductor element, resistance to ultraviolet and heat aging performance have been improved like this, but along with improving constantly of semiconductor element power, organic-silicon-modified epoxy resin encapsulating material still can not meet the requirement of semiconductor components and devices, has introduced phenyl and solved preferably the problems referred to above in the semiconductor packages collagen material the present invention relates to.For LED lamp, because GaN chip has high specific refractory power, in order effectively to reduce the light loss that interfacial refraction brings, improve and get optical efficiency as far as possible, require the specific refractory power of silica gel and lens material high as far as possible.Traditional silica gel or the refractive index of silicone material are only 1.41 left and right, and the refractive index of desirable packaged material should approach the refractive index of GaN as much as possible.
Summary of the invention
In order to solve above-mentioned technical problem, an object of the present invention is to provide a kind of polysiloxane solidifying agent, another object of the present invention is to provide the preparation method of above-mentioned polysiloxane, this polysiloxane and a kind of solidifying agent have high refractive index after solidifying, high-transmittance, high physical strength, anti-yellowing change, the characteristic of resistance to ultraviolet and thermal ageing.
In order to realize first above-mentioned object, the present invention has adopted following technical scheme:
Polysiloxane solidifying agent, at least contains the TMOS of two hydrogen atoms that are connected with silicon and aromatic base in per molecule in this polysiloxane solidifying agent, structural formula is as follows:
(R
1R
4SiO1/2)o·(R
12SiO2/2)p·(R
1R
4SiO2/2)q·(R
3SiO2/2)r·(R
3SiO3/2)s
R wherein
1for alkyl, R
3for aromatic base, R
4for H atom or alkyl, described o+p+q+r+s=100, o=1 ~ 20, p=10 ~ 20, q=0 ~ 20, r=0 ~ 10, s=30 ~ 60;
As preferably, R
1for methyl, ethyl, propyl group or butyl, be preferably methyl; R
3for phenyl, tolyl or naphthyl, be preferably phenyl; R
4for H atom or methyl, ethyl, propyl group or butyl.
As preferably, the viscosity of described polysiloxane solidifying agent is 50 ~ 50000mPa, and the best is 100 ~ 5000mPa.
In order to realize second above-mentioned object, the present invention has adopted following technical scheme:
A preparation method who prepares above-mentioned polysiloxane solidifying agent, the method comprises the following steps:
1) catalyzer, solvent, end-capping reagent, methylsiloxane, methyl hydrogen siloxane, phenyl siloxane are dripped while stirring to phenyl trialkoxy silane under room temperature or heating, under room temperature or heating, react 3 ~ 18 hours after dripping off phenyl trialkoxy silane;
2) static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, and oil phase is washed to neutrality, then at 140 ~ 160 ℃, takes out low component under-0.099Mpa, obtains water white transparency product.
As preferably, above-mentioned catalyzer is one or more in hydrochloric acid, sulfuric acid and trifluoromethayl sulfonic acid.
As preferably, above-mentioned solvent is one or more in toluene, dimethylbenzene and cyclohexane.
As preferably, above-mentioned end-capping reagent is that end-capping reagent is hexamethyldisiloxane, tetramethyl disiloxane or dimethyltetraphenyldisiloxane.
As preferably, above-mentioned methylsiloxane is one or more in octamethylcyclotetrasiloxane, dimethyldimethoxysil,ne and dimethyldiethoxysilane.
As preferably, above-mentioned methyl hydrogen siloxane is one or more in tetramethyl-ring tetrasiloxane, methyl hydrogen dimethoxy silane and methyl hydrogen diethoxy silane.
As preferably, above-mentioned phenyl siloxane is one or more in dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e and phenyl triethoxysilane.
Polysiloxane solidifying agent of the present invention (hereinafter referred to as polysiloxane B) can be used as the solidifying agent of semiconductor packages glue composition.As preferably, the host of semiconductor packages glue composition can be another polysiloxane A.Polysiloxane A, polysiloxane A, at least contains the polysiloxane of an alkylene being connected with silicon and aromatic base in per molecule, and structural formula is as follows:
(R
1R
22SiO1/2)a·(R
12SiO2/2)b·(R
1R
2SiO2/2)c·(R
3SiO2/2)d·(R
3SiO3/2)e
R wherein
1for alkyl, R
2for alkylene, R
3for aromatic base, described a+b+c+d+e=100, a=1 ~ 20, b=10 ~ 20, c=10 ~ 20, d=0 ~ 10, e=30 ~ 60;
By weight, described polysiloxane A is 30 ~ 70 weight parts, and polysiloxane B is 30 ~ 70 weight parts.
In semiconductor packages glue composition, polysiloxane A is as host, and polysiloxane B is as solidifying agent.A, B mixture also can comprise that adhesion promoters is to improve adhesiveproperties, and mixture also can add other optional component, as silicon-dioxide, and the non-organic filler such as aluminum oxide.In A, B mixture, the amount of A and B is without strict restriction, but the amount of B should be lower than mixture solidified is limited, best for A:B be 1:1.
As preferably, above-mentioned semiconductor packages glue composition also comprises one or both in curing catalyst C and curing inhibitors D, and curing catalyst C is 0.001 ~ 0.003 weight part, and curing inhibitors D is 0.001 ~ 0.003 weight part.Curing catalyst C can be used as the catalyzer that promotes A, B mixture solidified, and curing inhibitors D has been the effect that suppresses A, B mixture solidified.The consumption of curing catalyst C is without strict restriction, but should be lower than impelling mixture solidified to be limited.
As preferably, above-mentioned curing catalyst C selects the title complex of platinum and organo-siloxane oligopolymer.As preferred again, in curing catalyst C, with respect to total composition platinum content, be 1 ~ 100ppm, the best is 5 ~ 50ppm.
As preferably, above-mentioned curing inhibitors D is the title complex of alkynol or alkynol and organo-siloxane oligopolymer.
As preferably, the viscosity of above-mentioned polysiloxane B is 50 ~ 50000mPa, and the best is 100 ~ 5000mPa.
As preferably, above-mentioned polysiloxane A is no less than 40mol% with the total group of fragrant fiduciary point being connected with silicon in polysiloxane B, and the best is no less than 45mol%.
As preferably, above-mentioned semiconductor packages glue composition can also add non-organic filler, as silicon-dioxide or aluminum oxide etc.
Adopt the composition of polysiloxane B of the present invention generally under heating, to solidify, Heating temperature is at 50 ℃ ~ 200 ℃, and the best is 100 ℃ ~ 180 ℃.The refractive index that semiconductor packages glue composition of the present invention solidifies rear 25 ℃ of visible rays is not less than 1.5, and light permeable rate is not less than 90%, has high refractive index, high-transmittance, high physical strength, anti-yellowing change, the feature of resistance to ultraviolet and thermal ageing.
Embodiment
One, the preparation of polysiloxane A
The general structure that the present invention relates to polysiloxane A is:
R wherein
1for alkyl, as methyl, ethyl, propyl group, butyl etc., preferable methyl; R
2for alkyl or alkenyl, as methyl, vinyl, allyl group, butenyl etc., preferred vinyl; R
3for aryl, as phenyl, tolyl, naphthyl etc., preferably phenyl.a+b+c+d+e=100，a=1~20，b=0~20，c=0~20，d=0~20,e=30~60。
The preparation method who the present invention relates to polysiloxane A is: catalyzer, solvent, end-capping reagent, methylsiloxane, ethylene methacrylic radical siloxane, phenyl siloxane are dripped while stirring to phenyl trialkoxy silane under room temperature or heating, after dripping off phenyl trialkoxy silane, under room temperature or heating, react 3 ~ 18 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, and oil phase is washed to neutrality, then at 150 ℃, under-0.099Mpa, take out low component, obtain water white transparency products A.
Described catalyzer is one or more in hydrochloric acid, sulfuric acid and trifluoromethayl sulfonic acid.
Described solvent is one or more in toluene, dimethylbenzene and cyclohexane.
Described end-capping reagent is one or more in hexamethyldisiloxane, tetramethyl divinyl disiloxane and tetraphenyl dimethyl sily oxide.
Described methylsiloxane is one or more in octamethylcyclotetrasiloxane, dimethyldimethoxysil,ne and dimethyldiethoxysilane.
Described ethylene methacrylic radical siloxane is one or more in tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, methyl ethylene dimethoxy silane and methyl ethylene diethoxy silane.
Described phenyl siloxane is one or more in dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e and phenyl triethoxysilane.
embodiment 1
The sulfuric acid of 20g 30%, 54g toluene, 40g hexamethyldisiloxane, 22g octamethylcyclotetrasiloxane and 26g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane are dropped in four-hole bottle, open stirring, slowly drip phenyltrimethoxysila,e, at room temperature react 18 hours after dripping off 178g phenyltrimethoxysila,e, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, and oil phase is washed to neutrality, then at 150 ℃, under-0.099Mpa, take out low fraction, obtain water white transparency products A 1.
embodiment 2
The sulfuric acid of 25g 30%, 107g toluene, 30g hexamethyldisiloxane, 88g dimethyldimethoxysil,ne and 49g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane are dropped in four-hole bottle, load onto return line, open stirring, start slowly to drip phenyltrimethoxysila,e, drip off after 400g phenyltrimethoxysila,e, at room temperature stir after 16 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, and oil phase is washed to neutrality, then at 150 ℃, under-0.099Mpa, take out low fraction, obtain water white transparency products A 2.
embodiment 3
The sulfuric acid of 20g 30%, 66g toluene, 37g tetramethyl divinyl disiloxane, 37g octamethylcyclotetrasiloxane and 218g phenyltrimethoxysila,e are dropped in four-hole bottle, open stirring, at room temperature stir after 16 hours, static, after minute disacidify water, wash with water, to oil phase, be neutral, at 150 ℃, steam toluene and water after minute anhydrating mutually, then-0.099Mpa, set aside low component for 150 ℃, obtain water white transparency products A 3.
embodiment 4
The sulfuric acid of 25g 30%, 60g toluene, 20g tetramethyl divinyl disiloxane, 39g octamethylcyclotetrasiloxane, 54g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 180g dimethoxydiphenylsilane are dropped in four-hole bottle, open stirring, at room temperature react 18 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, oil phase is washed to neutrality, at 150 ℃, under-0.099Mpa, take out low fraction again, obtain water white transparency products A 4.
Two, the preparation of polysiloxane B
The general structure that the present invention relates to polysiloxane B is:
R wherein
1for alkyl, as methyl, ethyl, propyl group, butyl etc.; R
3for aryl, as phenyl, tolyl, naphthyl etc.; R
4for H atom or methyl, ethyl, propyl group, butyl etc., o+p+q+r+s=100, o=1 ~ 20, p=0 ~ 20, q=0 ~ 20, r=0 ~ 10, s=30 ~ 60.
The preparation method of polysiloxane B is: catalyzer, solvent, end-capping reagent, methylsiloxane, methyl hydrogen siloxane, phenyl siloxane are dripped while stirring to phenyl trialkoxy silane under room temperature or heating, after dripping off phenyl trialkoxy silane, under room temperature or heating, react 3 ~ 18 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, and oil phase is washed to neutrality, then at 150 ℃, under-0.099Mpa, take out low component, obtain water white transparency product B.
In preparation method, catalyzer is hydrochloric acid, sulfuric acid, trifluoromethayl sulfonic acid etc.
Solvent is toluene, dimethylbenzene, cyclohexane etc.
End-capping reagent is hexamethyldisiloxane, tetramethyl disiloxane or dimethyltetraphenyldisiloxane.
Methylsiloxane is octamethylcyclotetrasiloxane, dimethyldimethoxysil,ne, dimethyldiethoxysilane etc.
Methyl hydrogen siloxane is tetramethyl-ring tetrasiloxane, methyl hydrogen dimethoxy silane, methyl hydrogen diethoxy silane etc.
Phenyl siloxane is dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane etc.
embodiment 5
The sulfuric acid of 20g 30%, 53g toluene, 40g hexamethyldisiloxane, 18g tetramethyl-ring tetrasiloxane, 26g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 18g phenyltrimethoxysila,e are dropped in four-hole bottle, load onto return line, open stirring, be warmed up to 60 ℃ of beginnings and slowly drip phenyltrimethoxysila,e, drip off after 178g phenyltrimethoxysila,e at 70 ~ 75 ℃ back flow reaction 8 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, oil phase is washed to neutrality, at 150 ℃, under-0.099Mpa, take out low fraction again, obtain water white transparency product B 5.
embodiment 6
The sulfuric acid of 25g30%, 104g toluene, 16g hexamethyldisiloxane, 30g octamethylcyclotetrasiloxane, 18g tetramethyl-ring tetrasiloxane, 218g phenyltrimethoxysila,e are dropped in four-hole bottle, open stirring, at room temperature stir after 16 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, oil phase is washed to neutrality, at 150 ℃, under-0.099Mpa, take out low fraction again, obtain water white transparency product B 6.
embodiment 7
The sulfuric acid of 30g30%, 54g tetramethyl disiloxane, 144g tetramethyl-ring tetrasiloxane, 195g dimethoxydiphenylsilane and 80g toluene are dropped in four-hole bottle, open stirring, at room temperature stir after 16 hours, static, after minute disacidify water, lower floor's oil phase adds water washing, oil phase is washed to neutrality, at 150 ℃, under-0.099Mpa, take out low fraction again, obtain water white transparency product B 7.
Three, the preparation of semiconductor packages glue
Host is polysiloxane A, and solidifying agent is polysiloxane B, and accelerant C is that curing catalyst C selects the title complex of platinum and organo-siloxane oligopolymer, as platinum one vinylsiloxane as the catalyzer that promotes A, B mixture solidified; Curing inhibitors D has been the effect that suppresses A, B mixture solidified, and curing inhibitors D is the title complex of alkynol or alkynol and organo-siloxane oligopolymer.In addition, A, B mixture also can comprise that adhesion promoters is to improve adhesiveproperties, and mixture also can add other optional component, as silicon-dioxide, and the non-organic filler such as aluminum oxide.
Get products A and add respectively curing catalyst C to stir, obtain component P.Get product B and add respectively or do not add curing inhibitors D and stir, obtain component Q.After component P and component Q mix by 1:1, under vacuum, after row's bubble, obtain semiconductor packages glue.
| Index | Packaging plastic I | Packaging plastic II |
| 25 ℃ of cp of viscosity | 5882 | 2361 |
| Specific refractory power, 25 ℃ | 1.5206 | 1.5210 |
| After solidifying, hardness is 150 ℃, 3h | D50 | D68 |
| Cured strength MPa | 4.5MPa | 1.3MPa |
| Transparency@400nm after solidifying | 95.7% | 94.3% |
Claims (1)
1. polysiloxane solidifying agent, it is characterized in that this polysiloxane solidifying agent is prepared by following method: by the sulfuric acid of 20g 30%, 53g toluene, 40g hexamethyldisiloxane, 18g tetramethyl-ring tetrasiloxane, 26g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 18g phenyltrimethoxysila,e drop in four-hole bottle, load onto return line, open stirring, be warmed up to 60 ℃ of beginnings and slowly drip phenyltrimethoxysila,e, drip off after 178g phenyltrimethoxysila,e at 70 ~ 75 ℃ back flow reaction 8 hours, static, divide and remove upper strata sour water, lower floor's oil phase adds water washing, oil phase is washed to neutrality, again at 150 ℃, under-0.099Mpa, take out low fraction, obtain water white transparency product.
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| CN201210134487.3A CN102660027B (en) | 2012-05-04 | 2012-05-04 | Polysiloxane curing agent |
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| CN102660027B true CN102660027B (en) | 2014-09-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105567155B (en) * | 2016-03-02 | 2018-12-07 | 广东杰果新材料有限公司 | The preparation method of sulfuration resistant paster LED packaging plastic |
| CN109705351B (en) * | 2018-12-28 | 2022-04-05 | 广州市白云化工实业有限公司 | Dendritic polysiloxane and preparation method thereof, addition type liquid organosilicon plane sealant and preparation method thereof |
| CN112358847B (en) * | 2020-10-31 | 2023-11-24 | 武汉双键新材料股份有限公司 | Organopolysiloxane composition resistant to UV light |
| CN115353857B (en) * | 2022-07-11 | 2023-06-27 | 武汉飞恩微电子有限公司 | Packaging medium for pressure sensor chip and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
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