ORGANOPOLYSILOXANE COMPOSITION, PREPARATION METHOD THEREFOR, AND SEMICONDUCTOR COMPONENT

Abstract

The disclosed embodiments include an organopolysiloxane composition, a preparation method therefor, and a semiconductor component. The shore hardness of the cured product thereof is greater than A30 and less than A65. The composition comprises: (A1) solid 3D organopolysiloxane having an R.sup.1.sub.3SiO.sub.1/2 unit and an SiO.sub.4/2 unit; (A2) liquid straight-chain organopolysiloxane having an R.sup.1.sub.3SiO.sub.1/2 unit and an R.sup.2.sub.2SiO.sub.2/2 unit; the mixing viscosity of component (A1) and (A2) is between 6,000 and 20,000 mPa.Math.s; (B) liquid straight-chain polyorganohydrosiloxane having an R.sup.3.sub.3SiO.sub.1/2 unit and an R.sup.4.sub.2SiO.sub.2/2 unit; (C) an organosiloxane tackifier in which one molecule has on average at least one epoxy group; (D) a hydrosilylation catalyst of a volume enough to promote the curing of the composition. The composition of the present invention and the cured semiconductor component thereof have good heat resistance, good adhesiveness with aluminum having a mirror finish and ceramic substrate, and good resistance to humidity.

Claims

1. A organopolysiloxane composition, wherein, in its cured state, a cured product thereof has a shore hardness greater than A30 and less than A65, and the composition comprises: (A1) solid three-dimensional structured organopolysiloxane comprising an R.sup.1.sub.3SiO.sub.1/2 unit and a SiO.sub.4/2 unit, wherein R.sup.1 is selected from similar or different alkenyl groups, univalent substituted or unsubstituted hydrocarbyls which do not contain any aromatic hydrocarbon and aliphatic unsaturated bond; wherein the number-average molecular weight of organopolysiloxane is 2500-3500; (A2) liquid straight-chain organopolysiloxane comprising an R′.sub.3SiO.sub.1/2 unit and an R.sup.2.sub.2SiO.sub.2/2 unit, wherein R.sup.1 and R.sup.2 are selected from similar or different alkenyl groups, univalent substituted or unsubstituted hydrocarbyls which do not contain any aromatic hydrocarbon and aliphatic unsaturated bond; wherein component (A1) and (A2) have a mixing viscosity of 6000 to 20000 mPa.Math.s; (B) liquid straight-chain polyorganohydrosiloxane comprising an R.sup.3.sub.3SiO.sub.1/2 unit and an R.sup.4.sub.2SiO.sub.2/2 unit, wherein R.sup.3 and R.sup.4 are selected from similar or different, univalent substituted or unsubstituted hydrocarbyls and hydrogen atoms, which do not contain any aromatic hydrocarbon and aliphatic unsaturated bond; wherein the molar ratio of silicon-bonded hydrogen atoms in the component (B) to the alkenyl groups in the component (A1) and (A2) is 1.1-2.0; (C) an organosiloxane tackifier in which one molecule has on average at least one epoxy group; (D) a hydrosilylation catalyst of a volume enough to promote the curing of the composition.

2. The organopolysiloxane composition according to claim 1, wherein, the viscosity of component (A2) is 5000 to 22000 mPa.Math.s, and the content of the alkenyl groups is 0.0001-0.01.

3. The organopolysiloxane composition according to claim 1, wherein, the sum of the weight of the component (A1) and (A2) represents 70 wt %-95 wt % of the total weight of the composition, the component (B) represents 5 wt %-30 wt % of the total weight of the composition, and component (C) represents 0.01 wt %-10 wt % of the total weight of the composition.

4. The organopolysiloxane composition according to claim 1, wherein, the component (A1) and (A2) have a mixing viscosity of 6000 to 18000 mPa.Math.s.

5. The organopolysiloxane composition according to claim 1, wherein, the weight ratio of the component (A1) to the component (A2) ranges from 10:100 to 150:100.

6. The organopolysiloxane composition according to claim 1, wherein, the component (A1) has the following average unit formula,
(SiO.sub.4/2).sub.a1(R.sup.5R.sup.6.sub.2SiO.sub.1/2).sub.a2, wherein R.sup.5 is selected from similar or different alkenyl groups, the content of the alkenyl groups is 0.01-0.30 mol/100 g, R.sup.6 is selected from alkenyl groups and similar or different alkyl groups that are univalent substituted or unsubstituted, wherein 0.5<a1<0.99, 0.01<a2<0.5, and a1+a2=1.

7. The organopolysiloxane composition according to claim 1, wherein, the component (A2) has the following average unit formula,
R.sup.5R.sup.6.sub.2SiO(R.sup.6.sub.2SiO).sub.a3SiR.sup.6.sub.2R.sup.5, wherein R.sup.5 is selected from similar or different alkenyl groups, the content of the alkenyl groups is 0.0001-0.01 mol/100 g, R.sup.6 is selected from similar or different alkyl groups that are univalent substituted or unsubstituted, wherein 10<a3<10000.

8. The organopolysiloxane composition according to claim 1, wherein, the component (B) has the following average unit formula,
R.sup.8.sub.3SiO(R.sup.8.sub.2SiO).sub.b1(R.sup.8HSiO).sub.b2SiR.sup.8.sub.3, Wherein, R.sup.8 is selected from similar or different alkyl groups that are univalent substituted or unsubstituted, wherein 0.2<b1<0.8, 0.2<b2<0.8, and b1+b2=1.

9. The organopolysiloxane composition according to claim 1, wherein, the component (C) has the following average unit formula: ##STR00005## wherein, the R represents ##STR00006## or a hydrogen atom.

10. A preparation method for an organopolysiloxane composition of claim 1, comprising the following steps: blending the components (A1) and (A2) to obtain a mixed solution having a mixing viscosity of 6000 to 20000 mPa.Math.s; blending the components (B), (C) and (D) with the mixed solution; and obtaining the composition.

11. A semiconductor component comprising a light-emitting component and a support configured to fix the light-emitting component, wherein the support is any one of a copper support, a mirror finish aluminum support, a ceramic substrate support, a COB support or an integrated support, and wherein the light-emitting component is coated with the cured substance of the organopolysiloxane composition of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG. 1 is a cross-sectional schematic view of a packaged semiconductor unit provided by an embodiment of the present invention;

[0041] The reference signs in the drawings are as follows: [0042] 1—LED support; 2—light-emitting component; 3—electrode; 4—wire; 5—cured body of a curable organopolysiloxane composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0043] In order to make the purposes, technical solutions, and advantages of the present invention be clearer, the present invention will be further described in detail hereinafter with reference to accompany embodiments. It should be understood that the specific embodiments described here are only intended to illustrate the present invention, but not to limit the present invention.

[0044] In the following description, Vi refers to a vinyl group, and Me represents a methyl group.

Synthesis Example 1

[0045] Ethyl orthosilicate (10.9 g) is added into a flask, absolute ethyl alcohol (30 g) and concentrated hydrochloric acid having a concentration of 37% by mass (15 g) are added successively, and a reaction is performed at 70° C. for 5 min; Tetramethyldivinyltetramethyldisiloxane (1.7 g) is added and refluxing is further performed for 60 min. The reactants are transferred into a separatory funnel, an acid layer is removed, the organic layer is washed with water into a neutral pH, and then transferred to a flask; deionized water (1 g) is added, refluxing is performed at 70° C. for 60 min, and the pressure is reduced by a pump. A MQ resin with the following structure is obtained:

The average formula (ViMe.sub.2SiO.sub.0.5).sub.0.07(SiO.sub.2).sub.0.93  (A1-1)

[0046] The component is solid at 25° C., has a number average molecular weight of 3000, and a vinyl content of 0.10 mol/100 g.

Synthesis Example 2

[0047] Ethyl orthosilicate (10.4 g) is added into a flask, absolute ethyl alcohol (30 g) and concentrated hydrochloric acid having a concentration of 37% by mass (15 g) are added successively, and a reaction is performed at 70° C. for 5 min; Tetramethyldivinyltetramethyldisiloxane (1.8 g) and Hexamethyldisiloxane (0.5 g) are added and refluxing is further performed for 60 min. The reactants are transferred into a separatory funnel, an acid layer is removed, the organic layer is washed with water into a neutral pH, and then transferred to a flask; deionized water (1 g) is added, refluxing is performed at 70° C. for 60 min, and the pressure is reduced by a pump. A MQ resin with the following structure is obtained:

The average formula (ViMe.sub.2SiO.sub.0.5).sub.0.07(Me.sub.3SiO.sub.0.5).sub.0.04(SiO.sub.2).sub.0.89  (A1-2)

[0048] The component is solid at 25° C., has a number average molecular weight of 2500, and a vinyl content of 0.11 mol/100 g.

Synthesis Example 3

[0049] Ethyl orthosilicate (10.4 g) is added into a flask, absolute ethyl alcohol (30 g) and concentrated hydrochloric acid having a concentration of 37% by mass (15 g) are added successively, and a reaction is performed at 70° C. for 10 min; Tetramethyldivinyltetramethyldisiloxane (1.6 g) is added and refluxing is further performed for 180 min. The reactants are transferred into a separatory funnel, an acid layer is removed, the organic layer is washed with water into a neutral pH, and then transferred to a flask; deionized water (1 g) is added, refluxing is performed at 70° C. for 60 min, and the pressure is reduced by a pump. A MQ resin with the following structure is obtained:

The average formula (ViMe.sub.2SiO.sub.0.5).sub.0.06(SiO.sub.2).sub.0.94  (A1-3)

[0050] The component is solid at 25° C., has a number average molecular weight of 3500, and a vinyl content of 0.09 mol/100 g.

Synthesis Example 4

[0051] Ethyl orthosilicate (10.6 g) is added into a flask, absolute ethyl alcohol (30 g) and concentrated hydrochloric acid having a concentration of 37% by mass (15 g) are added successively, and a reaction is performed at 70° C. for 10 min; Tetramethyldivinyltetramethyldisiloxane (1.7 g) is added and refluxing is further performed for 240 min. The reactants are transferred into a separatory funnel, an acid layer is removed, the organic layer is washed with water into a neutral pH, and then transferred to a flask; deionized water (1 g) is added, refluxing is performed at 70° C. for 60 min, and the pressure is reduced by a pump. A MQ resin with the following structure is obtained:

The average formula (ViMe.sub.2SiO.sub.0.5).sub.0.07(SiO.sub.2).sub.0.93  (A1-4)

[0052] The component is solid at 25° C., has a number average molecular weight of 3700, and a vinyl content of 0.10 mol/100 g.

Synthesis Example 5

[0053] Ethyl orthosilicate (10.4 g) is added into a flask, absolute ethyl alcohol (30 g) and concentrated hydrochloric acid having a concentration of 37% by mass (15 g) are added successively, and a reaction is performed at 70° C. for 5 min; Tetramethyldivinyltetramethyldisiloxane (1.8 g) is added and refluxing is further performed for 45 min. The reactants are transferred into a separatory funnel, an acid layer is removed, the organic layer is washed with water into a neutral pH, and then transferred to a flask; deionized water (1 g) is added, refluxing is performed at 70° C. for 60 min, and the pressure is reduced by a pump. A MQ resin with the following structure is obtained:

The average formula (ViMe.sub.2SiO.sub.0.5).sub.0.07(SiO.sub.2).sub.0.93  (A1-5)

[0054] The component is solid at 25° C., has a number average molecular weight of 2200, and a vinyl content of 0.10 mol/100 g.

Synthesis Example 6

[0055] Octamethylcyclotetrasiloxane (52.6 g) and Tetramethyldivinyltetramethyl-disiloxane (2.5 g) are added into a flask and stirred well, tetramethylammonium hydroxide (2.5 g) is added successively, the temperature is raised to 120° C. and reaction is performed for 18 h, then the temperature is further raised to 180° C. and reaction is performed for 2 h, then the temperature is raised to 200° C. and substances with low boiling points are removed under a reduced pressure, a resin with the following structure is obtained:

CH.sub.2═CH(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.341Si(CH.sub.3).sub.2CH═CH.sub.2  (A2-1)

[0056] The component is an organosilicon compound has a viscosity of 6000 mPa.Math.s at 25° C., and a vinyl content of 0.007 mol/100 g.

Synthesis Example 7

[0057] Octamethylcyclotetrasiloxane (63.2 g) and Tetramethyldivinyltetramethyl-disiloxane (1.1 g) are added into a flask and stirred well, tetramethylammonium hydroxide (2.5 g) is added successively, the temperature is raised to 120° C. and reaction is performed for 18 h, then the temperature is further raised to 180° C. and reaction is performed for 2 h, then the temperature is raised to 200° C. and substances with low boiling points are removed under a reduced pressure, a resin with the following structure is obtained:

CH.sub.2═CH(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.823Si(CH.sub.3).sub.2CH═CH.sub.2  (A2-2)

[0058] The component is an organosilicon compound has a viscosity of 15000 mPa.Math.s at 25° C., and a vinyl content of 0.003 mol/100 g.

Synthesis Example 8

[0059] 15 parts by mass of Me.sub.3SiOSiMe.sub.3, 60 parts by mass of (Me.sub.2SiO).sub.4 and 40 parts by mass of Me.sub.3SiO(MeHSiO).sub.mSiMe.sub.3 (From Chengdu Chenguang Chemical Research Institute) are blended, and seven parts by mass of concentrated sulfuric acid having a concentration of 98% by mass is added as catalyst, the mixture is equilibrated at room temperature for 5 h, the layers are allowed to stand, then an acid layer is removed, and an oil layer is neutralized with Na.sub.2CO.sub.3 for 30 min, a product with a yield up to 95% by mass fraction is obtained after filtration as follows:

Me.sub.3SiO(MeHSiO).sub.5(Me.sub.2SiO).sub.10SiMe.sub.3  (B)

[0060] The component is an organosilicon compound has a viscosity of 56 mPa.Math.s at 25° C., and a hydrogen content of 0.5 mol/100 g.

Synthesis Example 9

[0061] Tetramethylcyclotetrasiloxane (60 g), allyl glycidyl ether (200 g) and ethyl acetate (50 g) are added into a flask and stirred well, chloroplatinic acid in octanol solution (a platinum concentration of 5 wt %) is added dropwise, the temperature is raised to 80° C. and reaction is performed for 10 h, vacuumed to −0.095 MPa, then the temperature is raised to 170° C. and substances with low boiling points are removed under a reduced pressure, a resin with the following structure is obtained:

##STR00003##

wherein, the R represents

##STR00004##

[0062] The component is an organosilicon compound has a viscosity of 30 mPa.Math.s at 25° C.

Practical Examples 1-6 and Comparative Examples 1-6

[0063] The resins (A1-1)-(A1-5), (A2-1), (A2-2), (B), (C) as prepared by the synthesis example 1-10, a catalyst for the addition reaction (D): chloroplatinic acid in octanol solution (a platinum concentration of 5 wt %), and (E) an inhibitor: 2-Phenyl-3-butyn-2-ol are mixed; according to the combination as shown in Table 1, the components (A1) and (A2) are mixed at first, and the obtained mixture are mixed with the components (B), (C), (D) and (E), all components are calculated as parts by mass, and the compositions of the present invention are obtained.

[0064] The semiconductor device LED light shown in FIG. 1 is packaged in the following manner a LED support 1 (a 100 W integrated support) where a light-emitting component 2 is fixed is provided, wherein the light-emitting component 2 (S-23BBMUP-455 Chip from San'an) is connected with an electrode 3 by a wire 4 (23 μm gold wire from Beijing Dabo nonferrous metal solder limited liability company); by a dispenser, the deformed aforementioned curable organopolysiloxane composition 5 of the present invention is coated on the LED support 1 where a light-emitting component 2 is fixed and then cured, and thus an integrated package is obtained.

[0065] The physical and chemical properties of the obtained compositions are measured by the following means, and the results are recorded in Table 1.

[0066] The organopolysiloxane mixture is poured into a mold, heated and cured and made into a film, curing condition is as follows: cured at 100° C. for 1 h and then cured at 150° C. for 3 h. The physical properties of the film are measured, and the testing results are recorded in Table 1.

Hardness

[0067] The obtained composition is defoamed and 10 g of the defoamed composition is kept at 100° C. for 1 h, and then cured at 150° C. for 3 h; at 25° C. and 60% RH, the hardness thereof is measured at three points using a Shore A hardness tester, and the average value is recorded.

Tensile Strength and Elongation at Break

[0068] The obtained composition is defoamed and made into a sheet with a thickness of 2 mm, which is held at 100° C. for 1 h and then cured at 150° C. for 3 h; the sheet is then processed into a dumbbell-shape, and the tensile strength and elongation at break thereof are measured at 25° C. and 60% RH by a universal materials tester.

Heat Resistance

[0069] The obtained composition is defoamed and 0.7 g of the defoamed composition is dispensed on a 100 W integrated support, the dispensed composition is held at 100° C. for 1 h and then cured at 150° C. for 3 h, after cooling, it is then placed onto a 230° C. heating platform and heated for different time and then placed under room temperature, and the time the gel cracks is recorded.

TABLE-US-00001 TABLE 1 Practical Practical Practical Practical Practical Practical Parts by mass Example1 Example2 Example3 Example4 Example5 Example6 A1-1 40 35 A1-2 8.2 6.6 A1-3 51 52 A1-4 A1-5 A2-1 40 82 83 43.2 A2-2 34 30.6 B 17.9 7.8 12.9 8.3 15.3 19.7 C 2 1.9 2 2 2 2 D 0.1 0.1 0.1 0.1 0.1 0.1 E 0.02 0.02 0.02 0.02 0.02 0.02 Mixing viscosity of 13000 7000 18000 6000 20000 11000 resin A1 and A2 Si—H/Si—Vi 1.68 1.10 1.16 1.18 1.50 2.00 (molar ratio) Evaluation Result Hardness (25° C.) A50 A30 A60 A30 A60 A45 Tensile strength Mpa 2.1 3.2 4.2 3.2 5.2 3.0 Elongation at break % 160 150 120 150 110 150 Heat resistance time 30 32 30 20 20 30 Before crack

TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Comparative Comparative Comparative Parts by mass Example1 Example2 Example3 Example4 Example5 Example6 A1-1 35 A1-2 5 8 A1-3 55 A1-4 23 A1-5 40 A2-1 62 43 83 83 40 A2-2 30 B 12.9 14.9 9.9 12.9 6.9 22.9 C 2 2 2 2 2.0 2 D 0.1 0.1 0.1 0.1 0.1 0.1 E 0.02 0.02 0.02 0.02 0.02 0.02 Mixing viscosity of 9000 11000 4000 23000 6000 18000 resin A1 and A2 Si—H/Si—Vi 1.57 1.20 1.51 1.21 0.97 2.15 (molar ratio) Evaluation Result Hardness (25° C.) A70 A48 A35 A70 A40 A60 Tensile strength Mpa 6.2 1.9 3.2 7.8 2.1 2.5 Elongation at break % 75 160 150 80 130 120 Heat resistance time 6 8 7 6 7 7 Before crack

[0070] As can be seen from Table 1, the hardness is A30-A60 for practical examples 1-6, and the heat resistance time before crack is 20-32 h; as can be seen from Table 2, the heat resistance time before crack of comparative examples 1-6 is only 6-8 h. Thus, the embodiments of the present invention have excellent heat resistance.

[0071] As can be seen from Table 1, the MQ resins of practical examples 1-6 have a molecular weight range from 2500 to 3500 (component A1-1 to A1-3) and have excellent heat resistance; as can be seen from Table 2, component A1-4 of comparative example 1 has a number average molecular weight of 3700, whereas component A1-5 of comparative example 2 has a number average molecular weight of 2200, both of which have poor heat resistance.

[0072] As can be seen from Table 1, the mixing viscosity of component A1 and A2 of practical examples 1-6 is between 6000 and 20000, and have excellent heat resistance; as can be seen from Table 2, the mixing viscosity of component A1 and A2 from comparative example 3 is 4000, whereas the mixing viscosity of component A1 and A2 from comparative example 4 is 23000, both of which have poor heat resistance.

[0073] As can be seen from Table 1, the molar ratio of Si—H/Si-Vi in practical examples 1-6 is between 1.1 and 2, the composition is fully cured and has excellent heat resistance; as can be seen from Table 2, the molar ratio of Si—H/Si-Vi in comparative example 5 is 0.97, whereas, the molar ratio of Si—H/Si-Vi in comparative example 6 is 2.15, both of which have poor heat resistance.

[0074] The advantageous effects of the present invention: comparing with the prior art, the composition of the present invention and the cured semi-conductive component thereof not only have good heat resistance, but also have good adhesiveness with aluminum having a mirror finish and ceramic substrates, and good resistance to humidity.

[0075] The above contents are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.