Organic Silicone Resin Composition and Pre-preg, Laminate, Copper-clad Laminate, and Aluminum Substrate that Use the Composition

Abstract

The present invention relates to an organic silicone resin composition and a prepreg, a laminate, and an aluminum substrate that use the composition. The organic silicone resin composition comprises in terms of parts by weight: 100 parts of a condensation-type silicone resin, 0.0001-2 parts of a catalyst, and 0.001-10 parts of an additive. The organic silicone resin composition has the advantages of high heat resistance, halogen-free and phosphorus-free flame retardancy, improved peel strength with copper foil, and low coefficient of expansion, and is applicable in manufacturing the pre-preg, the laminate, and the aluminum substrate for used in a high-performance printed circuit.

Claims

1. An organosilicone resin composition, wherein the organosilicone resin composition comprises in parts by weight: 100 parts of a condensation type silicone resin; 0.0001-2 parts of a catalyst; and 0.001-10 parts of an adjuvant.

2. The organosilicone resin composition according to claim 1, wherein the condensation type silicone resin is any one selected from the group consisting of a methyl silicone resin, a methylphenyl silicone resin, and a phenyl silicone resin, or a mixture of at least two selected therefrom.

3. The organosilicone resin composition according to claim 1, wherein the condensation type silicone resin is any one selected from the group consisting of a methyl silicone resin, a methylphenyl silicone resin and a phenyl silicone resin with R/Si=1.0-1.7 (molar ratio) and Ph/(Me+Ph)=0-1.0 (molar ratio), or a mixture of at least two selected therefrom, wherein Ph represents a phenyl group, Me represents a methyl group, and R represents an organic functional group selected from —CH.sub.3, -Ph, —OCH.sub.3, —OCH.sub.2CH.sub.3, —H or —OH.

4. The organosilicone resin composition according to claim 1, wherein the condensation type silicone resin is a methylphenyl silicone resin with R/Si=1.2-1.7 (molar ratio) and Ph/(Me+Ph)=0.2-0.6 (molar ratio).

5. The organosilicone resin composition according to any one of claim 1, wherein the catalyst is any one selected from the group consisting of zinc naphthenate, tin naphthenate, cobalt naphthenate, iron naphthenate, cerium naphthenate, zinc carboxylate, tin carboxylate, cobalt carboxylate, iron carboxylate, cerium carboxylate, perfluorosulfonic acid, phosphonitrilic chloride, amines, quaternary ammonium bases, zinc caprylate, zinc isooctanoate, titanates and guanidine compounds, or a combination of at least two selected therefrom.

6. The organosilicone resin composition according to claim 1, wherein the organosilicone resin composition further comprises a filler.

7. The organosilicone resin composition according to claim 1, wherein the organosilicone resin composition comprises in parts by weight: 100 parts of a condensation type silicone resin; 0.0001-2.0 parts of a catalyst; 0.001-10 parts of an adjuvant; and 0-60 parts of a filler.

8. (canceled)

9. A prepreg, wherein it comprises a reinforcing material and the organosilicone resin composition according to claim 1 attached to the reinforcing material after impregnation and drying.

10. A laminate, wherein the laminate comprises at least one prepreg according to claim 9.

11. A copper-clad laminate, wherein the copper-clad laminate comprises at least one laminated prepreg according to claim 9 and a copper foil pressed on one side or both sides of the laminated prepreg.

12. An aluminum-based copper-clad laminate comprising a copper foil layer and an aluminum-based layer with an insulation layer being coated between the copper foil layer and the aluminum-based layer, wherein the insulation layer is prepared from the silicone resin composition according to claim 1 with addition of a thermal conductive filler.

13. (canceled)

14. The organosilicone resin composition according to claim 1, wherein the adjuvant comprises any one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and a dispersant, or a mixture of at least two selected therefrom.

15. The organosilicone resin composition according to claim 6, wherein the filler comprises any one selected from the group consisting of silica, alumina, aluminum hydroxide, boron nitride, aluminum nitride, barium sulfate, mica powder, zinc borate, titanium dioxide, talc powder, silicon nitride and silicon carbide, or a mixture of at least two selected therefrom.

16. The organosilicone resin composition according to claim 6, wherein the content of the filler is 0-60 parts by weight.

17. The organosilicone resin composition according to claim 1, wherein the organosilicone resin composition comprises in parts by weight: 100 parts of a condensation type silicone resin; 0.0005-1.5 parts of a catalyst; 0.005-5 parts of an adjuvant; and 0-50 parts of a filler.

Description

EMBODIMENTS

[0048] The technical solution of the present invention will be further described below by way of specific embodiments.

Example 1

[0049] 100.0 parts of a methyl silicone resin with R/Si=1.1 (molar ratio) and Ph/(Ph+Me)=0 (molar ratio) was weighed and dissolved in 60.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 0.0001 parts of zinc isooctanoate, and 0.001 parts of a silane coupling agent γ-(2,3-epoxypropoxy) propyltrimethoxysilane (supplied by Dow Corning Corporation, U.S.A.) were added, and stirred to be mixed well so that a glue solution was obtained. A smooth and glabrous E-glass fiber cloth with a thickness of 0.1 mm was selected, evenly coated with the glue solution obtained above, and baked in the oven at 170° C. for 5 minutes to obtain a prepreg. 8 sheets of prepregs obtained above were laminated and 35 μm of copper foils were attached to the upper and lower surfaces, then placed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. to be pressed for 3 hours to obtain a laminate.

Example 2

[0050] 100.0 parts of a methylphenyl silicone resin with R/Si=1.4 (molar ratio) and Ph/(Ph+Me)=0.5 (molar ratio) was weighed and dissolved in 70.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 23.0 parts of silica fine powder, 0.1 parts of cobalt acetylacetonate, 1.5 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane coupling agent (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0051] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Example 3

[0052] 100.0 parts of a phenyl silicone resin with R/Si=1.7 (molar ratio) and Ph/(Ph+Me)=1.0 (molar ratio) was weighed and dissolved in 100.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 50.0 parts of alumina, 1.5 parts of titanate, and 8.7 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0053] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Example 4

[0054] 60.0 parts of a methyl silicone resin with R/Si=1.1 (molar ratio) and Ph/(Ph+Me)=0 (molar ratio) and 40.0 parts of a methylphenyl silicone resin with Ph/(Ph+Me)=0.9 (molar ratio) were weighed and dissolved in 85.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 25.0 parts of alumina, 10.0 parts of silica fine powder, 0.08 parts of cobalt acetylacetonate, and 1.5 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane coupling agent (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0055] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 1

[0056] 100 parts of a methylphenylvinyl silicone resin (the content of vinyl being 1.0%) was weighed and dissolved into 70 parts of a solvent, 3.1 parts of a methylphenyl hydrogen-containing silicone oil (the content of the hydrogen contained therein being 1.2%) was added after uniformly dissolved, 0.001 parts of hexynol was weighed after uniformly stirring under high speed, then 0.01 parts of platinum-methylphenylvinyl complex was added after stirring for 30 minutes, and 1.5 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane coupling agent (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) and 23.0 parts of silica fine powder were added after continuously stirring for 30 minutes, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain a silicone resin glue solution.

[0057] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 2

[0058] 100.0 parts of a methylphenyl silicone resin with R/Si=1.4 (molar ratio) and Ph/(Ph+Me)=0.5 (molar ratio) was weighed and dissolved in 70.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 70.0 parts of silica fine powder, 0.1 parts of cobalt acetylacetonate, and 1.5 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane coupling agent (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0059] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 3

[0060] 100.0 parts of a phenyl silicone resin with R/Si=1.7 (molar ratio) and Ph/(Ph+Me)=1.0 (molar ratio) was weighed and dissolved in 100.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 50.0 parts of alumina, 1.5 parts of titanate, and 12.0 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0061] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 4

[0062] 100.0 parts of a phenyl silicone resin with R/Si=1.9 (molar ratio) and Ph/(Ph+Me)=1.0 (molar ratio) was weighed and dissolved in 100.0 parts of a toluene solvent, then stirred to dissolve it completely. After the silicone resin was dissolved completely, 50.0 parts of alumina, 1.5 parts of titanate, and 8.7 parts of a silane coupling agent γ-methylacryloyloxypropyltrimethoxysilane (supplied by Hubei WuDa Silicone New Materials Co., Ltd.) were added, and stirred to be mixed well so that a glue solution was obtained.

[0063] A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manners as those in Example 1 except that the resin glue solution prepared above was used.

[0064] Effect Confirmation:

[0065] (1) Test for Z-Expansion Coefficient (CTE) (Thermal Mechanical Analysis Method)

[0066] Test method: IPC-TM-650 2.4.24 was used, and the test data were shown in the table below.

[0067] (2) Thermal Delamination Time (T300) (Thermal Mechanical Analysis Method)

[0068] Test method: IPC-TM-650 2.4.24.1 was used, and the test data were shown in the table below.

[0069] (3) Flame Rating

[0070] Test method: Reference to the United States UL94 standard was made, and the test data were shown in the table below.

[0071] (4) Peel Strength Test

[0072] Test method: Method IPC-TM-650 2.4.8 was used to test, and the test data were shown in the table below.

TABLE-US-00001 Compar- Compar- Compar- Compar- Test Example Example Example Example ative ative ative ative items 1 2 3 4 Example 1 Example 2 Example 3 Example 4 Methylphenyl — 100 — 40 — 100 — — silicone resin Methyl 100 — — 60 — — — — silicone resin Phenyl — — 100 — — — 100 100 silicone resin Methylvinyl — — — — 100 — — — silicone resin R/Si 1.1 1.4 1.7 1.1/1.7 — 1.4 1.7 1.9 Ph/ 0 0.5 1.0  0/0.9 — 0.5 1.0 1.0 (Me + Ph) Silane 0.001 1.5 8.7 1.5 1.5 1.5 12.0 8.7 coupling agent Silica — 23 — 10 23 70 — — fine powder Alumina — — 50 25 — — 50 50 Test results CTE (%) 0.7451 0.9007 0.9201 0.9114 5.6473 0.9156 1.6425 2.5214 T300 >60 >60 >60 >60 23.1 56.2 45.7 51.2 (min) Flame UL UL UL UL UL UL UL UL rating V-0 V-0 V-0 V-0 V-1 V-0 V-0 V-0 Peel 0.56 0.62 0.58 0.59 0.39 0.37 0.58 0.50 strength test N/mm

[0073] Analysis of Physical Properties:

[0074] As can be seen from the data in the above table, Examples 1-4 had very low thermal expansion coefficient, high thermal delamination time, halogen-free and phosphorus-free flame retardancy and better peel strength, which can satisfy the requirements of copper-clad laminates. When Comparative Example 1 was compared with Example 2, since the silicone resin was a methylphenylvinyl silicone resin, and an addition type curing method was used, the laminate had great expansion coefficient, low peel strength and less prominent flame retardancy effect after curing; when Comparative Example 2 was compared with Example 2, the content of filler was out of range, resulting in a decrease in peel strength with copper foil and a decrease in thermal delamination time; when Comparative Example 3 was compared with Example 3, the used amount of the adjuvant was not within the protection scope, and since most of the adjuvants were small molecules, the laminate would release more small molecules at high temperatures if the added amount of the adjuvants was too large, so that the thermal expansion coefficient was increased and the delamination time was shortened at the same time; and when Comparative Example 4 was compared with Example 3, the R/Si value was out of range, the greater the R/Si value was, the lower the crosslinking density of resin was, and the more the resin tended to thermoplastic resin, so that the thermal expansion coefficient was increased, the stability at high temperatures was lowered, and the thermal delamination time was reduced.

[0075] Applicant stated that although the detailed methods of the present invention have been described by the above examples in the present invention, the present invention is not limited to the detailed methods described above, that is to say, it does not mean that the present invention has to be implemented depending on the above detailed methods. It will be apparent to those skilled in the art that any improvements made to the present invention, equivalent replacements to the raw materials of the products of the present invention and addition of adjuvant ingredients, and selections of the specific implementations, etc., all fall within the protection scope and the disclosure scope of the present invention.