Organic silicon resin composition, white prepreg and white laminate using same

Abstract

Provided are an organic silicon resin composition, prepreg and laminate using the same. The organic silicon resin composition glue solution contains a condensation silicon resin, a catalyst, an auxiliary agent, a white filler and a solvent as necessary components, and is impregnated in a reinforced material such as a sheet-like fiberglass fiber base material and then dried to prepare the prepreg. The prepreg has a net structure via crosslinking of the silicon resin using a condensation reaction. Since the organic silicon resin has ultrahigh heat resistance and yellowing resistance, the present invention applies the silicon resin to a white LED copper-clad laminate instead of a traditional organic resin, satisfying the demand for high heat resistance, and replacing the ceramic substrate to be a new heat-dissipating substrate base material.

Claims

1. A white prepreg comprising a reinforcing material and a silicone resin composition comprising an organosilicone resin composition, wherein the organosilicone resin composition consists of the following components: 100 parts by weight of a condensation type silicone resin; 5-60 parts by weight of a white filler; 0.0001-2 parts by weight of a catalyst; and 0.1-10 parts by weight of an adjuvant; 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), wherein the white filler is any one or a mixture of at least two of alumina, titanium dioxide, aluminum hydroxide, silica or zinc oxide, and wherein the silicone resin composition is attached to the reinforcing material after impregnation and drying.

2. The white prepreg of claim 1, wherein the catalyst is any one or a combination of at least two 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, amine, zinc caprylate, zinc isooctanoate, quaternary ammonium base, titanate or guanidine compound.

3. A white laminate, wherein the white laminate comprises at least one white prepreg according to claim 1.

4. A white copper-clad laminate, wherein the white copper-clad laminate comprises at least one laminated white prepreg according to claim 1 and a copper foil pressed on one side or both sides of the laminated prepreg.

5. The white prepreg of claim 1, wherein the adjuvant is a coupling agent and/or a dispersant, and the coupling agent is a silane coupling agent and/or a titanate coupling agent.

Description

SPECIFIC EMBODIMENTS

(1) The technical solution of the present invention will be further described below by way of specific embodiments.

Example 1

(2) 100.0 parts of methyl silicone resin with R/Si=1.1 (molar ratio) and Ph/(Ph+Me)=0 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.003 part of zinc caprylate catalyst and 0.5 part of silane coupling agent -glycidyloxypropyltrimethoxysilane (manufactured by Dow Corning Co., Ltd., U.S.A.) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 5.5 parts of white pigment rutile type titanium dioxide was added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain a white silicone resin glue solution.

(3) A glass fiber cloth having a weight of 104 g/cm.sup.2 was impregnated with this white silicone resin varnish, then dried at 110 C. for 10 minutes to obtain a prepreg having a resin content of 58%. 8 prepregs were laminated, 35 m of electrolytic copper foil was provided on the upper and lower surfaces of the laminate respectively, which was pressure-molded at 200 C., a surface pressure of 30 kgf/cm.sup.2 and 30 mmHg or less of vacuum for 120 minutes to obtain a double-sided copper-clad laminate having a thickness of 1.0 mm.

Example 2

(4) 100.0 parts of methylphenyl silicone resin with R/Si=1.5 (molar ratio) and Ph/(Ph+Me)=0.4 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.005 part of cobalt acetylacetonate catalyst and 1.2 parts of -glycidyloxypropyltrimethoxysilane (manufactured by Dow Corning Co., Ltd., U.S.A.) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 30 parts of white pigment rutile type titanium dioxide was added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(5) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Example 3

(6) 100.0 parts of methylphenyl silicone resin with R/Si=1.6 (molar ratio) and Ph/(Ph+Me)=0.8 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.1 part of aluminum naphthenate catalyst and 1.8 parts of W-903 (manufactured by BYK Company, Germany) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 25 parts of white pigment anatase type titanium dioxide and 10 parts of silica filler were added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(7) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Example 4

(8) 100.0 parts of 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 toluene solvent, after it was dissolved completely, 0.1 part of aluminum naphthenate catalyst and 6.8 parts of W-903 (manufactured by BYK Company, Germany) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 25 parts of white pigment anatase type titanium dioxide and 35 parts of alumina filler were added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(9) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Example 5

(10) 50.0 parts of methyl silicone resin with R/Si=1.1 (molar ratio) and Ph/(Ph+Me)=0 (molar ratio) and 50.0 parts of methylphenyl silicone resin with R/Si=1.7 (molar ratio) and Ph/(Ph+Me)=0.9 (molar ratio) were weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 1.8 parts of titanate catalyst and 1.8 parts of W-903 dispersant (manufactured by BYK Company, Germany) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 25 parts of white pigment anatase type titanium dioxide and 35 parts of silica filler were added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(11) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 1

(12) 100 parts of methylvinyl silicone resin (the mass fraction of vinyl of 1.0%) was weighed and dissolved into 50 parts of methyl vinyl silicone oil having a viscosity of 500 mPa.Math.s, then 2.9 parts of methyl hydrogen silicone oil (the mass fraction of the hydrogen contained therein of 1.3%) was added after uniformly dissolved, 0.001 part of hexynol was weighed after uniformly stirring under high speed, then 0.01 part of platinum-methylphenyl vinyl complex was added after stirring for 30 minutes, 30 parts of white pigment rutile type titanium dioxide was added after continuously stirring for 30 minutes, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white addition type silicone resin glue solution.

(13) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 2

(14) 100.0 parts of methyl silicone resin with R/Si=1.1 (molar ratio) and Ph/(Ph+Me)=0 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.003 part of zinc caprylate catalyst and 0.5 part of silane coupling agent -glycidyloxypropyltrimethoxysilane (manufactured by Dow Corning Co., Ltd., U.S.A.) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 2.5 parts of white pigment type rutile type titanium dioxide was added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(15) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 3

(16) 100.0 parts of methylphenyl silicone resin with R/Si=1.6 (molar ratio) and Ph/(Ph+Me)=0.8 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.1 part of aluminum naphthenate catalyst and 1.8 parts of W-903 (manufactured by BYK Company, Germany) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 65 parts of white pigment anatase type titanium dioxide and 10 parts of silica filler were added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(17) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

Comparative Example 4

(18) 100.0 parts of methylphenyl silicone resin with R/Si=1.8 (molar ratio) and Ph/(Ph+Me)=0.8 (molar ratio) was weighed and dissolved in 100.0 parts of toluene solvent, after it was dissolved completely, 0.1 part of aluminum naphthenate catalyst and 1.8 parts of W-903 (manufactured by BYK Company, Germany) were measured with a precise pipette into the silicone resin solution, after the mixture was stirred uniformly, 25 parts of white pigment anatase type titanium dioxide and 10 parts of silica filler were added, then the mixture was stirred at room temperature for 1 hour, emulsified for 20 minutes to obtain the white silicone resin glue solution.

(19) A prepreg and a double-sided copper-clad laminate having a thickness of 1.0 mm were obtained in the same manner as that in Example 1 except that the resin glue solution prepared above was used.

(20) Effect Confirmation Test:

(21) (1) Heat Discoloration Resistance

(22) The copper-clad white laminates obtained in Examples 1-5 and Comparative Examples 1-4 were cut with a dicing saw, and the double-sided copper-clad laminates were cut into a size of 100 mm100 mm and subjected to the etching treatment to obtain respective organosilicone white laminates, which were baked at 200 C. for a long period of time, the reflectivities of which were compared, and the data were as shown in the table below.

(23) (2) Heat-Resistant Stability

(24) The copper-clad laminates of Examples 1-5 and Comparative Examples 1-4 were subjected to the etching treatment to obtain respective laminates, and the thermal decomposition temperature of the laminate substrate was measured by thermogravimetric analysis (TGA), and the temperature Td (2%) at which the decomposition was 2% was shown in the table below.

(25) Test equipment: NETZSCH TG209F3

(26) Test conditions: from room temperature to 700 C., the heating rate could be controlled at 10 C.0.1 C./min, and the flow rate of nitrogen was 0.9 ml/s.

(27) (3) Peel Strength Test

(28) Test method: Method IPC-TM-6502.4.8 was used for the test, and the test data were shown in the table below.

(29) TABLE-US-00001 Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example Example Example 1 2 3 4 5 1 2 3 4 Methylphenyl 100 100 50 100 100 silicone resin Methyl silicone 100 50 100 resin Phenyl silicone 100 resin Methylvinyl 100 silicone resin R/Si 1.1 1.5 1.6 1.7 1.1/1.7 1.1 1.6 1.8 Ph/(Me + Ph) 0 0.4 0.8 1.0 0/0.9 0 0.8 0.8 Rutile type 5.5 30 30 2.5 titanium dioxide Anatase type 25 25 25 65 25 titanium dioxide Silica 10 35 10 10 Alumina 35 Test results Heat Before 88.2 89.5 88.9 89.2 90.0 88.3 79.1 88.4 88.7 discoloration baking resistance Baking 88.1 89.2 88.6 88.3 86.7 85.0 78.6 88.6 88.1 Reflectivity % for 24 h Baking 87.4 88.7 88.2 85.4 86.7 80.7 75.3 85.4 85.3 for 72 h Baking 86.6 88.1 87.3 84.9 86.2 75.5 74.5 84.8 84.6 for 120 h Heat-resistant 601.3 621.7 686.9 594.2 598.5 389.4 576.3 596.7 456.2 stability (Temperature at which the decomposition was 2%) C. Peel strength 0.58 0.61 0.65 0.56 0.56 0.41 0.54 0.27 0.50 test N/mm

(30) Analysis of physical properties: As can be seen from the data in the above table, Examples 1-5 have good optical reflectivity at room temperature and maintains very good optical reflectivity even if baked in the long term at high temperature, meanwhile they have better stability at high temperature, and higher peel strength, which can fully meet the requirements of LED white laminates. When Comparative Example 1 was compared with Example 2, since the resin was the methylvinyl silicone resin, and an addition type curing method was used, the copper-clad laminate had poor reflectivity at high temperature, poor high temperature resistance and poor peel strength; when Comparative Example 2 was compared with Example 1, since the content of the white filler is less, their reflectivities at both room temperature and high temperature were poor; when Comparative Example 3 was compared with Example 3, since the content of the white filler was out of range, the peel strength with the copper foil was lowered and it failed to be used properly; when Comparative Example 4 was compared with Example 3, R/Si was very high, resulting in the board being soft and incomplete curing, thus the heat resistance was poor.

(31) Applicant has stated that although the detailed methods of the present invention have been described by the above embodiments in the present invention, the present invention is not limited to the detailed methods described above, that is to say, it is not meant 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.