JP5650092B2 - Silicone prepreg, silicone resin plate, silicone metal-clad laminate, silicone metal base substrate and LED mounting substrate using the same - Google Patents

Description

  The present invention relates to a prepreg, a silicone resin plate using the prepreg, a silicone metal-clad laminate, a silicone metal base substrate, and an LED mounting substrate.

  A white glass epoxy base material in which a glass cloth is impregnated with an epoxy resin is widely used as a mounting substrate for electric / electronic components and LEDs (hereinafter also referred to as light emitting diodes). However, there is a problem that lead-free solder having a high melting point is employed, or that the epoxy resin is deteriorated due to heat generation of parts or light. As a base material for heat dissipation, metal base circuit boards using epoxy resin with high filling of inorganic filler in the insulating layer are also used due to good heat dissipation, but deterioration of epoxy resin and solder connection of mounted parts A major issue remains in reliability.

Ceramics have also been used as mounting substrates that require heat resistance, but they are expensive and cannot accommodate large substrates. Therefore, it has excellent characteristics such as weather resistance and heat resistance, and prepregs, laminates and metal-clad laminates, and metal base substrates that are used for various applications such as LED mounting boards or electrical / electronic components Use as a mounting substrate is under consideration.
However, prepregs produced using conventional condensation varnishes and additional varnishes have problems that they are inconvenient to handle and complicated in production method, and have a weak adhesive force such as copper foil.

  With the recent progress in energy saving activities aimed at solving global environmental problems, LED demands for blue and white LEDs have been increasing, and the brightness of LEDs has further increased along with technological advances. Has been.

  In addition, as a prior art regarding this invention, what is described in the following patent document is mentioned, for example.

JP 2008-213426 A JP 2011-127074 A JP 2010-89493 A

  In general, when using an addition-curing type silicone varnish composition for the production of a silicone prepreg, it is common to prepare a metal-clad laminate with a hot press after the composition is B-staged with a precure. However, there are disadvantages that handling of the prepreg is inconvenient and sufficient characteristics and processability cannot be obtained.

  The present invention is a substrate material that has a high reflectance in the visible light region, is less susceptible to deterioration due to heating and ultraviolet rays, discoloration, and a decrease in reflectance, and has high heat resistance and heat dissipation, and high reliability of solder connection of mounted components. An object of the present invention is to provide a silicone prepreg that is easy to handle, a silicone resin plate, a silicone metal-clad laminate, a silicone metal base substrate, and an LED mounting substrate using the same.

In order to solve the above problems, according to the present invention, quartz glass cloth,
(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (where R ¹ , R ² and R ³ are independent) Represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ independently represents a vinyl group or an allyl group, a is 0, 1 or 2, and b is 1 or 2 And a + b is 2 or 3.)
An organopolysiloxane having a resin structure including a structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetitions thereof is 5 to 50;
(B) R ¹ SiO _1.5 units, R ² ₂ SiO units and R ³ _c H _d SiO _{(4-cd) / 2} units (where R ¹ , R ² and R ³ are independently As described above, c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3.)
Organohydrogenpolysiloxane having a resin structure including a structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetition is 5 to 50: vinyl group and allyl in component (A) An amount of hydrogen atoms bonded to silicon atoms in the component (B) relative to the total of the groups in a molar ratio of 0.1 to 4.0,
(C) platinum group metal catalyst: effective amount, and (D) filler: 900 parts by mass or less with respect to a total of 100 parts by mass of components (A) and (B),
A silicone prepreg characterized by being impregnated and dried with a silicone resin composition comprising

  By using such a silicone prepreg of the present invention, the reflectance in the visible light region is high, and there is little deterioration due to heating or ultraviolet rays, discoloration, and a decrease in reflectance, and further high heat resistance and heat dissipation, high solder connection of mounted components. A substrate having reliability can be obtained, and in particular, it can be suitably used as a base material for an LED mounting substrate.

  According to the present invention, there is provided a silicone resin plate characterized by being manufactured by heating and press-molding one or more of the silicone prepregs, and having a thermal conductivity of 0.8 W / mK or more. provide.

  Thus, a silicone resin plate (hereinafter also referred to as a silicone laminate) obtained by heat-pressing one or a plurality of the silicone prepregs of the present invention achieves a thermal conductivity of 0.8 W / mK or more. It becomes a silicone resin plate excellent in heat dissipation.

  In this case, the silicone resin plate preferably has a linear expansion coefficient in a direction parallel to the silicone resin plate of 30 ppm / ° C. or less over a range of −100 to 100 ° C.

  Thus, the silicone resin plate obtained by heating and press-molding one or a plurality of the silicone prepregs of the present invention is excellent in heat resistance.

  Moreover, in this invention, it is produced using the said silicone resin board, The LED mounting board characterized by the above-mentioned is provided.

  As described above, the silicone prepreg of the present invention is excellent in processability and can be suitably used as various high-brightness LED mounting substrate materials. The LED mounting substrate manufactured using the silicone resin plate of the present invention has heat resistance and heat dissipation. , Discoloration resistance and solder connection reliability of mounted parts, LED brightness is also long life.

  According to the present invention, there is provided a silicone metal-clad laminate characterized by being manufactured by stacking metal foils on both sides of one or a plurality of the above-described silicone prepregs, and heating and pressing. provide.

  As described above, the silicone prepreg of the present invention has good adhesion to a metal foil, and can be suitably used for producing a mounting substrate such as an electronic / electrical component.

  Moreover, in this invention, it is produced using the said silicone metal clad laminated board, The LED mounting board characterized by the above-mentioned is provided.

  As described above, the silicone metal-clad laminate in which the adhesiveness to the metal foil is maintained can be suitably used for producing an LED mounting substrate.

  In the present invention, the silicone prepreg is produced by heating and pressing with a metal foil on one side and a metal plate on the other side of one or more of the silicone prepregs. A silicone metal base substrate is provided.

  Thus, the silicone prepreg of the present invention has good adhesion to metal foils and metal plates, and can be suitably used for production of mounting substrates such as electronic / electrical components.

  Moreover, it is preferable that the said metal plate is what was processed with the adhesion | attachment adjuvant previously.

  Thus, it is preferable to use a metal plate that has been treated with an adhesion aid in advance, because the adhesion to the silicone prepreg can be improved.

  According to the present invention, there is provided an LED mounting substrate manufactured using the silicone metal base substrate.

  Thus, the silicone metal base substrate in which the adhesiveness with the metal foil and the metal plate is maintained can be suitably used for the production of the LED mounting substrate.

By using the addition-curable silicone prepreg of the present invention that can be easily molded with conventional molding equipment, a new LED base material with excellent heat resistance, heat dissipation, and discoloration resistance that did not exist before Can be easily obtained, and a high-luminance LED mounting substrate can be easily obtained.
The silicone prepreg of the present invention is excellent in flexibility and easy to handle despite the prepreg obtained by impregnating a quartz glass cloth with a hard silicone resin. In particular, after the silicone resin composition is impregnated into a quartz glass cloth in a state dissolved and dispersed in a solvent and the solvent is removed by evaporation from the glass cloth, the composition is a plastic solid or semi-solid. Therefore, even in the A stage state, it can be handled as a prepreg, the prepreg impregnated with the composition can be easily stored, and there is an advantage that molding by hot pressing can be easily performed. Furthermore, since the silicone prepreg of the present invention is excellent in processability, it can be suitably used for production of various high-brightness LED mounting substrates. Further, the produced LED mounting substrate is excellent in heat resistance, heat dissipation, discoloration resistance, and solder connection reliability of mounted components, and the LED brightness is also long-lived.

It is sectional drawing which shows an example of the LED mounting board of this invention.

  Hereinafter, the present invention will be described in more detail. In the present specification, “room temperature” means a temperature of 15 to 30 ° C. “Semi-solid” means having a property of having plasticity but not fluidity and exhibiting liquid or solid properties due to external stress such as temperature, stress, and strain. Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, and Vi represents a vinyl group.

[Silicone resin composition]
The silicone resin composition of the present invention contains the following components (A) to (D) and is preferably used for manufacturing the silicone resin plate of the present invention, and particularly preferably used for manufacturing an LED mounting board. Is done. The composition of the present invention is preferably a plastic solid or semi-solid at room temperature, and more preferably a plastic solid at room temperature.
Hereinafter, each component contained in the silicone resin composition of the present invention will be described.

Hereinafter, the present invention will be described in more detail.
-(A) Organopolysiloxane with resin structure-
The component (A), which is one of the important components of the composition of the present invention, includes R ¹ SiO _1.5 units, R ² ₂ SiO units and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units (wherein R ¹ , R ² and R ³ independently represent a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group, and R ⁴ independently represents a vinyl group or an allyl group. A is 0, 1 or 2, b is 1 or 2, and a + b is 2 or 3.)
At least a part of the above R ² ₂ SiO unit is continuously repeated, and partially contains a structure having a repetition number of 5 to 50, preferably 8 to 40, more preferably 10 to 35. It is an organopolysiloxane having a resin structure (that is, a three-dimensional network structure).

（ここで、ｍは５〜５０の整数）
で表される直鎖状ジオルガノポリシロキサン連鎖構造を意味する。 The structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetitions thereof is 5 to 50 is the following general formula (1):

(Where m is an integer from 5 to 50)
The linear diorganopolysiloxane chain structure represented by these is meant.

(A) At least a part of the entire R ² ₂ SiO unit present in the organopolysiloxane of the component, preferably 50 mol% or more (50 to 100 mol%), particularly 80 mol% or more (80 to 100 mol%) However, it is preferable to form a chain structure represented by the general formula (1) in the molecule.

In the molecule of the component (A), the R ² ₂ SiO unit works to stretch the polymer molecule in a straight line, and the R ¹ SiO _1.5 unit branches the polymer molecule or forms a three-dimensional network. R ³ _a R ⁴ _b SiO _{(4-ab) / 2} R ⁴ (independently a vinyl group or an allyl group) in the unit is R ³ _c H _d SiO _(4- It serves to cure the composition of the present invention by hydrosilylation addition reaction with hydrogen atoms (ie, SiH groups) bonded to silicon atoms of _{cd) / 2} units.

(A) Molar ratio of three essential siloxane units constituting the component, that is, R ¹ SiO _1.5 units: R ² ₂ SiO units: R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units The molar ratio of 90 to 24:75 to 9:50 to 1 (provided that the total is 100), particularly 70 to 28:70 to 20:10 to 2 (provided that the total is 100). It is preferable from the characteristics of the product.

  When the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of this component (A) is in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000, the polymer It is solid or semi-solid and is suitable from the viewpoint of workability and curability.

  Organopolysiloxane with such a resin structure is a combination of compounds that are raw materials for each unit such that the three siloxane units in the resulting polymer have the required molar ratio, for example, cohydrolytic condensation in the presence of an acid. Can be synthesized.

Here, as raw materials for R ¹ SiO _1.5 unit, MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ , chlorosilanes such as propyltrichlorosilane, cyclohexyltrichlorosilane, and alkoxy such as methoxysilane corresponding to each of these chlorosilanes Silanes etc. can be illustrated.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _j SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ Cl,
(HO) Me ₂ SiO (Me ₂ SiO) _j SiMe ₂ (OH),
(HO) Me ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ (OH),
(HO) Me ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ (OH),
(MeO) Me ₂ SiO (Me ₂ SiO) _j SiMe ₂ (OMe),
(MeO) Me ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ (OMe),
(MeO) Me ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ (OMe)
(Where j = an integer of 3 to 48 (average value), an integer of k = 0 to 47 (average value), an integer of L = 1 to 48 (average value), and an integer of k + L = 3 to 48 (average value))
Etc. can be illustrated.

R ³ _a R ⁴ _b SiO _{(4-ab) / 2} units are R ³ R ⁴ SiO units, R ³ ₂ R ⁴ SiO _0.5 units, R ⁴ ₂ SiO units and R ³ R ⁴ _2. 1 type of siloxane units selected from _0.5 units of SiO or a combination of two or more types of siloxane units. Examples of the raw material include chlorosilanes such as Me ₂ ViSiCl, MeViSiCl ₂ , Ph ₂ ViSiCl, and PhViSiCl ₂ , and alkoxysilanes such as methoxysilane corresponding to each of these chlorosilanes.

In the present invention, when the organopolysiloxane of component (A) is produced by cohydrolysis and condensation of the above raw material compounds, R ¹ SiO _1.5 units, R ² ₂ SiO units, R ³ _a R A siloxane unit having a silanol group is contained in ⁴ _b SiO 2 _{(4-ab) / 2} units or a combination of two or more thereof. The organopolysiloxane of component (A) usually contains about 10 mol% or less (0 to 10 mol%) of such silanol group-containing siloxane units with respect to the total siloxane units. Examples of the silanol group-containing siloxane unit include (HO) SiO _1.5 unit, R ^{2 ′} (HO) SiO unit, (HO) ₂ SiO unit, R ⁴ (HO) SiO unit, and R ⁴ ₂ (HO). SiO _0.5 unit, R ^{3 ′} R ⁴ (HO) SiO _0.5 unit, R ⁴ (HO) ₂ SiO _0.5 unit (where R ^{2 ′} and R ^{3 ′} are R ² other than a hydroxyl group, And R ^{3 is} as defined above, and R ⁴ is as defined above. Note that the hydroxyl groups in R ^1, R ² and R ^3, means a hydroxyl group in the silanol-containing siloxane units.

-(B) Organohydrogenpolysiloxane with resin structure-
(B) component which is one of the important components of the composition of the present invention includes R ¹ SiO _1.5 unit, R ² ₂ SiO unit and R ³ _c H _d SiO _{(4-cd) / 2.} Consisting of units (wherein R ¹ , R ² and R ³ are independently as described above, c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3). ,
A linear siloxane structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetitions is 5 to 50, preferably 8 to 40, more preferably 10 to 35. It is an organohydrogenpolysiloxane having a partially contained resin structure (that is, a three-dimensional network structure).

The structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetitions is 5 to 50 is present in the component (B) as described above with respect to the component (A). At least a part of the R ² ₂ SiO units, preferably 50 mol% or more (50 to 100 mol%), particularly 80 mol% or more (80 to 100 mol%) is the above-mentioned general formula in the molecule of the component (B). It means that the linear diorganopolysiloxane chain structure represented by (1) is formed.

Also in the molecule of the component (B), the R ² ₂ SiO unit works so as to extend the polymer molecule in a straight line, and the R ¹ SiO _1.5 unit branches the polymer molecule or forms a three-dimensional network. The hydrogen atom bonded to silicon in the R ³ _c H _d SiO _{(4-cd) / 2} unit undergoes a hydrosilylation addition reaction with the alkenyl group of the component (A) described above, whereby the composition of the present invention. Plays a role in curing.

(B) The molar ratio of the three essential siloxane units constituting the component, that is, R ¹ SiO _1.5 units: R ² ₂ SiO units: R ³ _c H _d SiO _{(4-cd) / 2} units The molar ratio is preferably 90 to 24:75 to 9:50 to 1, particularly 70 to 28:70 to 20:10 to 2 (however, a total of 100) in view of the properties of the cured product.

  Further, the weight average molecular weight in terms of polystyrene by GPC of the component (B) is in the range of 3,000 to 1,000,000, particularly 10,000 to 100,000, in terms of workability and cured product characteristics. To preferred.

  The organohydrogenpolysiloxane having such a resin structure is obtained by combining the compounds used as raw materials for each unit so that the above three types of siloxane units have a required molar ratio in the produced polymer, for example, in the presence of an acid. It can be synthesized by decomposing.

Here, as raw materials for R ¹ SiO _1.5 unit, MeSiCl ₃ , EtSiCl ₃ , PhSiCl ₃ , chlorosilanes such as propyltrichlorosilane, cyclohexyltrichlorosilane, and alkoxy such as methoxysilane corresponding to each of these chlorosilanes A silane etc. can be illustrated.

As a raw material of the R ² ₂ SiO unit,
ClMe ₂ SiO (Me ₂ SiO) _j SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ Cl,
ClMe ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ Cl,
(HO) Me ₂ SiO (Me ₂ SiO) _j SiMe ₂ (OH),
(HO) Me ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ (OH),
(HO) Me ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ (OH),
(MeO) Me ₂ SiO (Me ₂ SiO) _j SiMe ₂ (OMe),
(MeO) Me ₂ SiO (Me ₂ SiO) _k (PhMeSiO) _L SiMe ₂ (OMe),
(MeO) Me ₂ SiO (Me ₂ SiO) _k (Ph ₂ SiO) _L SiMe ₂ (OMe)
(Where j = an integer of 3 to 48 (average value), an integer of k = 0 to 47 (average value), an integer of L = 1 to 48 (average value), and an integer of k + L = 3 to 48 (average value))
Etc. can be illustrated.

The R ³ _c H _d SiO _{(4-cd) / 2} unit is selected from R ³ HSiO units, R ³ ₂ HSiO _0.5 units, H ₂ SiO units, and R ³ H ₂ SiO _0.5 units. 1 type of siloxane units or a combination of two or more types of siloxane units. Examples of the raw material include chlorosilanes such as Me ₂ HSiCl, MeHSiCl ₂ , Ph ₂ HSiCl, and PhHSiCl ₂ , and alkoxysilanes such as methoxysilanes corresponding to each of these chlorosilanes.

In the present invention, when the organohydrogenpolysiloxane of component (B) is produced by co-hydrolysis and condensation of the above raw material compounds, R ¹ SiO _1.5 units, R ² ₂ SiO units, R ³ A siloxane unit having a silanol group is contained in _c H _d SiO _{(4-cd) / 2} unit or a combination of two or more thereof. The organohydrogenpolysiloxane as the component (B) may usually contain about 10 mol% or less (0 to 10 mol%) of such silanol group-containing siloxane units with respect to the total siloxane units. Examples of the silanol group-containing siloxane unit include (HO) SiO _1.5 unit, R ^{2 ′} (HO) SiO unit, (HO) ₂ SiO unit, H (HO) SiO unit, and H ₂ (HO) SiO _{0. .5 ^{units, R 3 'H (HO)}} SiO 0.5 _units, H (HO) _{2 SiO 0.5} units (wherein, R ^2' for and R ^{3 'R 2} and ^{R 3} in the non-hydroxyl Group as defined). Note that the hydroxyl groups in R ^1, R ² and R ^3, means a hydroxyl group in the silanol-containing siloxane units.

  The blending amount of the organohydrogenpolysiloxane of component (B) is such that the hydrogen atoms (SiH groups) bonded to silicon atoms in component (B) with respect to the total of vinyl groups and allyl groups in component (A) are in molar ratio. It is preferable that the amount is 0.1 to 4.0, particularly preferably 0.5 to 3.0, and more preferably 0.8 to 2.0. If it is less than 0.1, the curing reaction does not proceed and it is difficult to obtain a silicone cured product. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product. Causes changes over time.

  In the present invention, it is preferable that one or both of the components (A) and (B) contain a silanol group for imparting adhesion. The amount of the silanol group may be about 10 mol% or less (0 to 10 mol%) based on the total siloxane units in the organopolysiloxane of component (A) or the organohydrogenpolysiloxane of component (B). .

-(C) Platinum group metal catalyst-
This catalyst component is blended in order to cause an addition curing reaction of the composition of the present invention, and there are platinum-based, palladium-based, and rhodium-based ones. As the catalyst, any conventionally known catalyst for promoting the hydrosilylation reaction can be used. In consideration of cost and the like, platinum-based materials such as platinum, platinum black, and chloroplatinic acid, such as H ₂ PtCl ₆ · pH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · pH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · pH ₂ O, PtO ₂ · pH ₂ O, PtCl ₄ · pH ₂ O, PtCl ₂ , H ₂ PtCl ₄ · pH ₂ O (where p is a positive integer), etc. And a complex with a hydrocarbon such as olefin, alcohol, or vinyl group-containing organopolysiloxane. These catalysts can be used singly or in combination of two or more.

  The compounding amount of the component (C) may be an effective amount for curing, and is usually 0.1 to 500 ppm in terms of mass as a platinum group metal with respect to the total amount of the component (A) and the component (B). Preferably it is the range of 0.5-100 ppm.

-(D) Filler-
The filler of component (D) is added to the composition of the present invention for the purpose of lowering the linear expansion coefficient of the silicone laminate of the present invention and improving the thermal conductivity and strength of the laminate. The component (D) may be any known filler, for example, silicas such as precipitated silica, fumed silica, fused silica, fused spherical silica, crystalline silica, fumed titanium dioxide. , Calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, aluminum oxide, zinc oxide, silicon nitride, aluminum nitride, boron nitride, antimony trioxide, zircon oxide, zinc sulfide, magnesium oxide, barium sulfate Etc. Examples of the reinforcing inorganic filler include calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide. Component (D) can be used alone or in combination of two or more.

  The blending amount of the component (D) is 900 parts by mass or less (0 to 900 parts by mass) per 100 parts by mass in total of the components (A) and (B) from the viewpoint of the linear expansion coefficient and heat dissipation characteristics of the resulting silicone laminate. It is more preferable that it is the range of 600 mass parts or less (0-600 mass parts).

When the silicone prepreg of the present invention is used for the production of an LED mounting substrate, the following (D1) and optionally a filler containing a component (D2) are preferably used as the component (D).
-(D1) Inorganic filler The (D1) component is an inorganic filler other than the (D2) component, for the purpose of lowering the linear expansion coefficient of the LED mounting substrate of the present invention and improving the thermal conductivity of the substrate. Added to the composition of the present invention. As the component (D1), those blended in a silicone resin can be used, and any known inorganic filler may be used. For example, fused silica, fused spherical silica, crystalline Examples thereof include silicas such as silica, aluminum oxide, silicon nitride, aluminum nitride, boron nitride, antimony trioxide, and the like, and fused silica, fused spherical silica, crystalline silica, and aluminum oxide are particularly preferable. The component (D1) can be used alone or in combination of two or more. The average particle diameter and shape of the component (D1) are not particularly limited. The average particle diameter of the component (D1) is usually 0.5 to 50 μm, preferably 1 to 10 μm, more preferably 1 to 5 μm, from the viewpoint of moldability and fluidity of the resulting silicone resin composition. In addition, an average particle diameter can be calculated | required as mass average value D50 (or median diameter) in the particle size distribution measurement by a laser beam diffraction method.
The inorganic filler as component (D1) may be surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to increase the bond strength between the resin and the inorganic filler. Examples of such a coupling agent include epoxy functional groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Alkoxyfunctional silanes; amino-functional alkoxysilanes such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-mercaptopropyl It is preferable to use a mercapto functional alkoxysilane such as trimethoxysilane. The amount of coupling agent used for the surface treatment and the surface treatment method are not particularly limited.
Moreover, the inorganic filler of the component (D1) can be added to the composition of the present invention even in a slurry state in which the inorganic filler is dispersed in an organic solvent.

  The blending amount of the component (D1) is 600 parts by mass or less (0 to 600 parts by mass) per 100 parts by mass in total of the components (A) and (B) from the viewpoint of the linear expansion coefficient and the thermal conductivity of the obtained LED mounting substrate. ), Preferably 10 to 600 parts by mass, more preferably 50 to 500 parts by mass.

-(D2) White pigment (D2) A component is a white pigment, and is used as a white coloring agent for making the hardened | cured material obtained white. The component (D2) is added to the composition of the present invention for the purpose of increasing the light reflectivity of the silicone mounting substrate when the obtained LED mounting substrate needs to reflect light. In particular, when obtaining an LED mounting substrate that does not need to reflect light, it may not be added to the composition of the present invention. Here, “the silicone mounting substrate needs to reflect light” means that, as described later, the silicone mounting substrate preferably has a light reflectance of 80% or more over the entire visible light region (that is, 80 to 100). %). As the component (D2), any known white pigment that has been conventionally used can be used without limitation, but preferably titanium dioxide, zircon oxide, zinc sulfide, zinc oxide, magnesium oxide, barium sulfate or A combination of two or more of these is used. Examples of the combination include a combination of titanium dioxide and at least one other white pigment specifically exemplified. Of these, titanium dioxide and magnesium oxide are more preferred, and titanium dioxide is even more preferred. The crystal form of titanium dioxide may be any of the rutile type, anatase type, and brookite type, but the rutile type is preferably used.
The white pigment preferably has an average particle size of 0.05 to 10.0 μm, more preferably 0.1 to 5.0 μm. In order to improve the mixing and dispersibility of the white pigment of component (D2), the resin component of components (A) and (B) and the inorganic filler of component (D1), the white pigment of component (D2) Surface treatment may be performed in advance with a hydroxide such as Al hydroxide or Si hydroxide. In addition, as above-mentioned, an average particle diameter can be calculated | required as the mass average value D50 (or median diameter) in the particle size distribution measurement by a laser beam diffraction method. The component (D2) can be used alone or in combination of two or more.

  The amount of component (D2) is preferably 1 to 300 parts by weight, more preferably 3 to 200 parts by weight, and more preferably 10 to 150 parts by weight per 100 parts by weight of the total of components (A) and (B). Part is particularly preferred. When the blending amount is less than 1 part by mass, the whiteness of the obtained cured product may not be sufficient. When the blending amount exceeds 300 parts by mass, the total inorganic content of the inorganic filler of component (D1) added for the purpose of lowering the linear expansion coefficient of the LED mounting substrate of the present invention and improving the heat dissipation characteristics of the substrate. The proportion of the filler may be too low. In addition, it is preferable that the quantity of the white pigment of (D2) component is the range of 1-50 mass% in the whole silicone resin composition, It is more preferable that it is the range of 5-30 mass%, 10-30 mass Even more preferably, it is in the range of%.

―Other ingredients―
In addition to the components (A) to (D) described above, various additives known per se can be blended with the composition of the present invention as necessary.

-Adhesion aid An adhesive aid (adhesion imparting agent) can be added to the composition of the present invention as necessary in order to impart adhesiveness. The adhesion assistant can be used alone or in combination of two or more. Examples of the adhesion assistant include a hydrogen atom (SiH group) bonded to a silicon atom in one molecule, an alkenyl group (for example, Si—CH═CH ₂ group) bonded to a silicon atom, and an alkoxysilyl group (for example, trimethoxysilyl). Group) and an epoxy group (for example, glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) a linear or cyclic silicon atom containing at least two, preferably two or three functional groups 4 to 50, preferably about 4 to 20 organosiloxane oligomers, organooxysilyl-modified isocyanurate compound represented by the following general formula (2), hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) and these Or a combination of two or more thereof.

（式中、Ｒ^５は、下記式（３）

(In the formula, R ⁵ represents the following formula (3)

（ここで、Ｒ^６は水素原子又は炭素原子数１〜６の一価炭化水素基であり、ｖは１〜６、特に１〜４の整数である。）
で表される有機基、又は脂肪族不飽和結合を含有する一価炭化水素基であるが、Ｒ^５の少なくとも１個は式（３）の有機基である。）

(Here, R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and v is an integer of 1 to 6, particularly 1 to 4.)
Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of R ⁵ is an organic group of the formula (3). )

Examples of the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R ⁵ in the general formula (2) include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group. And a cycloalkenyl group having 6 to 8 carbon atoms, such as an alkenyl group having 2 to 6 carbon atoms, particularly a cyclohexenyl group, and the like. Examples of the monovalent hydrocarbon group for R ⁶ in the formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. C 1-8, especially 1-6 monovalent hydrocarbon groups such as alkyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups and cycloalkenyl groups exemplified for R ⁵ above, and aryl groups such as phenyl groups. And preferably an alkyl group.

  Furthermore, examples of the adhesion assistant include 1,5-bis (glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane and compounds represented by the following formula.

（式中、ｇ及びｈは各々０〜５０の範囲の整数であって、しかもｇ＋ｈが２〜５０、好ましくは４〜２０を満足するものである。）

(In the formula, g and h are each integers in the range of 0 to 50, and g + h satisfies 2 to 50, preferably 4 to 20.)

  Among the above-mentioned organosilicon compounds, compounds that provide particularly good adhesion to the resulting cured product are organic compounds having a silicon atom-bonded alkoxy group and an alkenyl group or silicon atom-bonded hydrogen atom (SiH group) in one molecule. It is a silicon compound.

  The compounding amount of the adhesion assistant is usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0.1 to 8 parts by mass, more preferably 0.2 to 100 parts by mass of the component (A). About 5 parts by mass. If the amount is too large, the hardness of the cured product may be adversely affected or surface tackiness may be increased.

-Cure inhibitor A cure inhibitor can be suitably mix | blended with the silicone resin composition used by this invention as needed. The curing inhibitor can be used singly or in combination of two or more. Examples of the curing inhibitor include, for example, organopolysiloxanes having a high vinyl group such as tetramethyltetravinylcyclotetrasiloxane, triallyl isocyanurate, alkyl maleate, acetylene alcohols and their silane-modified products and siloxane-modified products, Examples thereof include compounds selected from the group consisting of oxide, tetramethylethylenediamine, benzotriazole, and mixtures thereof. The curing inhibitor is usually added in an amount of 0.001 to 1.0 part by mass, preferably 0.005 to 0.5 part by mass, per 100 parts by mass of the component (A).

-Preparation-
The silicone resin composition used in the present invention is prepared by uniformly mixing required components. Usually, it is stored in two liquids so that the curing does not proceed, and the two liquids are mixed and cured at the time of use. Of course, a small amount of the above-mentioned curing inhibitor such as acetylene alcohol can be added and used as one liquid. In addition, the silicone resin composition of the present invention is obtained by uniformly mixing the components (A) to (C) to obtain a base composition, and adding a solvent such as toluene, xylene, heptane to the base composition, Furthermore, you may prepare as a solution or a dispersion liquid by adding (D) component.

[Silicone prepreg]
The silicone prepreg of the present invention is impregnated into a quartz glass cloth in a state where the silicone resin composition containing the components (A) to (D) is dissolved and dispersed in a solvent. Upon drying, the solvent can be removed by evaporation.

-Solvent-
The solvent is not particularly limited as long as it can dissolve and disperse the above-described silicone resin composition and can be evaporated at a temperature at which the composition is maintained in an uncured or semi-cured state. For example, the solvent whose boiling point is 50-200 degreeC, Preferably it is 80-150 degreeC is mentioned. When the prepreg for an LED device of the present invention is produced, the above-described silicone resin composition can be dissolved and dispersed and evaporated at a temperature at which the composition is maintained in an uncured or semi-cured state. The solvent is not particularly limited as long as it can be used, and examples thereof include a solvent having a boiling point of 50 to 150 ° C, preferably 60 to 100 ° C. Specific examples of the solvent include hydrocarbon nonpolar solvents such as toluene, xylene, hexane, and heptane; ethers and the like. The amount of the solvent used is not particularly limited as long as the above-described silicone resin composition can be dissolved and dispersed and the obtained solution or dispersion can be impregnated into quartz glass cloth, and the silicone resin composition is not limited. Preferably it is 10-200 mass parts with respect to 100 mass parts, More preferably, it is 20-100 mass parts. When producing a silicone prepreg for an LED device, there is no particular limitation as long as the above-described silicone resin composition can be dissolved and dispersed and the obtained solution or dispersion can be impregnated into quartz glass cloth. The amount is preferably 10 to 200 parts by mass, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the silicone resin composition.

  Then, the silica glass cloth is impregnated with the above-described solution or dispersion of the silicone resin composition, and the solvent is removed preferably in a drying furnace at 50 to 150 ° C., more preferably 60 to 120 ° C. obtain. The silicone prepreg of the present invention is excellent in flexibility and easy to handle despite the prepreg obtained by impregnating a quartz glass cloth with a hard silicone resin. In particular, the silicone prepreg after impregnating quartz glass cloth with the silicone resin composition dissolved and dispersed in a solvent and evaporating and removing the solvent from the glass cloth is easy to store and hot press There is an advantage that molding can be easily performed. The silicone prepreg of the present invention is excellent in processability and can be suitably used as various high-brightness LED mounting substrates. Moreover, this LED mounting board is excellent in heat resistance, heat dissipation, discoloration resistance, and solder connection reliability of mounted components, and the LED brightness is also long-lived.

  Further, the silicone resin composition containing the components (A) to (D) is impregnated with alkali glass cloth and high tensile strength T glass cloth by impregnating quartz glass and drying. Since there is no elution of the minute, the siloxane bond in the silicone resin is not impaired, and thereby the adhesion between the silicone prepreg and the metal is not lowered. Therefore, since a prepreg having excellent adhesion to the metal foil can be obtained, a silicone metal-clad laminate or a silicone metal base substrate that maintains the adhesion to the metal foil can be obtained. In addition, quartz glass has a small coefficient of thermal expansion, high heat resistance, and good thermal conductivity, so that an extremely high quality silicone prepreg can be formed.

[Silicone resin plate]
The silicone resin plate of the present invention is prepared by heating one or a plurality of laminated silicone prepregs impregnated with quartz glass cloth and dried with the silicone resin composition having the components (A) to (D) described above. It is pressure-molded.

  The silicone resin plate of the present invention preferably has a linear expansion coefficient in a direction parallel to the silicone resin plate (hereinafter referred to as XY axis direction) in the range of −100 to 100 ° C., preferably 30 ppm / ° C. or less, more preferably 20 ppm / It is below ℃. Further, the silicone resin plate of the present invention can achieve a thermal conductivity of 0.8 W / mK or more (25 ° C.), and becomes a silicone resin plate excellent in heat dissipation.

-Manufacturing method of silicone resin plate-
The silicone resin plate of the present invention is
A quartz glass cloth is impregnated with the silicone resin composition containing the components (A) to (D) dissolved and dispersed in a solvent,
Next, the solvent is evaporated and removed from the quartz glass cloth to obtain a prepreg, and then the obtained prepreg is stacked in a number corresponding to the thickness of the insulating layer and cured by heating and pressing (molding). Can be obtained. Here, as the component (D), the component (D1) of 600 parts by mass or less (0 to 600 parts by mass) with respect to a total of 100 parts by mass of the components (A) and (B), and optionally (A) and ( By using a filler containing 1 to 300 parts by mass of the component (D2) with respect to 100 parts by mass of the total component B), the silicone resin plate for an LED mounting substrate of the present invention can be obtained.

[Silicone metal-clad laminate]
In addition, the present invention provides a silicone metal-clad laminate obtained by heating and pressing a metal foil on both sides of one or a plurality of the above-described silicone prepregs. Specifically, one or a plurality of the above-mentioned silicone prepregs are laminated with metal foil on both sides, and heated with a vacuum press or the like at a pressure of 5 to 50 MPa and a temperature of 70 to 180 ° C. A metal-clad laminate is produced by pressure forming.
Although it does not specifically limit as metal foil, Copper foil is used preferably electrically and economically. A printed wiring board can be obtained by processing this metal-clad laminate by a commonly used method such as subtracting or drilling.

[Silicone metal base substrate]
Moreover, in the present invention, one or more of the silicone prepregs are stacked, and the metal foil is stacked on one side, and the metal plate is stacked on the other side, and is manufactured by heating and pressing. A silicone metal base substrate is provided.
The metal base substrate of the present invention includes a metal foil such as a copper foil, an insulating layer formed from a prepreg, and a metal plate. As the insulating layer according to the required thickness between the copper foil and the metal plate, the number of prepregs is stacked and manufactured by the same heat and pressure as described above.
The metal plate is not particularly limited, but aluminum, copper, iron, zinc, nickel and alloys thereof are preferably selected from the viewpoint of heat dissipation and adhesion to the insulating layer, and aluminum and copper are considered from the viewpoint of thermal conductivity, weight and price. Aluminum alloys are preferably used. Furthermore, if necessary, a surface treatment for improving the adhesion to the insulating layer can be applied to the metal plate in advance. Although the thickness of a metal plate is not specifically limited, 0.3-4.0 mm is used preferably.

  In the silicone resin plate, silicone metal-clad laminate, and silicone metal base substrate of the present invention, the thickness of the insulating layer made of quartz glass cloth and silicone resin formed from the prepreg is the same as that of the silicone resin plate, silicone of the present invention. What is necessary is just to select suitably according to the use etc. of a metal foil tension laminated board and a silicone metal base board, Although it does not specifically limit, Preferably it is 20-2,000 micrometers, More preferably, it is 50-1,000 micrometers.

[LED mounting board]
The present invention also provides an LED mounting substrate produced by using the above-described silicone resin plate, silicone metal-clad laminate, and silicone metal base substrate as LED base materials.
Such an LED mounting substrate of the present invention includes an LED base material and an LED chip mounted on the base material. The thickness of the substrate for LED may be appropriately selected according to the use of the substrate for high-brightness LED, the thickness of the quartz glass cloth used for the production of the prepreg, and the like. ˜2,000 μm, more preferably 60 to 1,000 μm.

  FIG. 1 is a cross-sectional view showing an example of an LED mounting substrate using the silicone resin plate of the present invention. In the LED mounting substrate 1 shown in FIG. 1, an electrode pattern 3 composed of an anode and a cathode is formed on a silicone resin plate (silicone resin laminate) 2 of the present invention, and a die bonding paste is applied to one electrode of the electrode pattern 3. LED chip 5 is die-bonded via 4. A bonding wire 6 is connected between the LED chip 5 and the other electrode of the electrode pattern 3. A part of the electrode pattern 3, the LED chip 5 and the bonding wire 6 are sealed with a transparent sealing body 7.

  What is necessary is just to produce the electrode pattern 3 by a well-known method. For example, by performing etching or the like on a copper-clad laminated substrate manufactured by heating and press-molding a copper foil on one side or both sides of one or a plurality of silicon prepregs of the present invention, which are laminated. The electrode pattern 3 can be produced on the silicone resin plate 2 (insulating layer). Examples of the die bonding paste 4 include a silver paste. An example of the bonding wire 6 is a gold wire. The transparent sealing body 7 can be provided by, for example, forming a known sealing agent such as a silicone sealing agent or an epoxy sealing agent into a desired shape and curing it.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

(Synthesis Example 1)
-Vinyl group-containing organopolysiloxane resin (A1)-
Organosilane represented by PhSiCl ₃ : 1142.1 g (87.1 mol%), ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), MeViSiCl ₂ : 84.6 g (9. 7 mol%) was dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, and the solvent was stripped to synthesize a vinyl group-containing resin (A1). This resin was a solid having a weight average molecular weight of 62,000 and a melting point of 60 ° C. The vinyl group content of this product is 0.05 mol / 100 g.

(Synthesis Example 2)
-Hydrosilyl group-containing organopolysiloxane resin (B1)-
Organosilane represented by PhSiCl ₃ : 1142.1 g (87.1 mol%), ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), MeHSiCl ₂ : 69 g (9.7 mol) %) Was dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, and then the solvent was stripped to synthesize a hydrosilyl group-containing resin (B1). This resin was a solid having a weight average molecular weight of 58,000 and a melting point of 58 ° C. The hydrosilyl group content of this product is 0.05 mol / 100 g.

(Synthesis Example 3)
-Vinyl group-containing organopolysiloxane resin (A2)-
Organosilane represented by PhSiCl ₃ : 1142.1 g (87.1 mol%), ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), Me ₂ ViSiCl: 72.3 g (9 0.7 mol%) was dissolved in a toluene solvent, dropped into water, cohydrolyzed, neutralized by water washing and alkali washing, dehydrated, and then the solvent was stripped to synthesize a vinyl group-containing resin (A2). . This resin was a solid having a weight average molecular weight of 63,000 and a melting point of 63 ° C. The vinyl group content of this product is 0.05 mol / 100 g.

(Synthesis Example 4)
-Hydrosilyl group-containing organopolysiloxane resin (B2)-
Organosilane represented by PhSiCl ₃ : 1142.1 g (87.1 mol%), ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl: 529 g (3.2 mol%), Me ₂ HSiCl: 56.7 g (9 0.7 mol%) was dissolved in a toluene solvent, dropped into water, co-hydrolyzed, neutralized by water washing and alkali washing, dehydrated, stripped of the solvent, and a hydrosilyl group-containing resin (B2) was synthesized. . This resin was a solid having a weight average molecular weight of 57,000 and a melting point of 56 ° C. The hydrosilyl group content of this product is 0.05 mol / 100 g.

Example 1
Vinyl group-containing resin (A1) obtained in Synthesis Example 1: 189 g, hydrosilyl group-containing resin (B1) obtained in Synthesis Example 2: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, A 1 mass% octyl alcohol solution of chloroplatinic acid: 0.1 g was added, and the mixture was thoroughly stirred with a planetary mixer heated to 60 ° C. to obtain a base composition. To this base composition, 6 g of an adhesion assistant represented by the following formula and 400 g of toluene as a solvent were added, and alumina (trade name: Admafine AO-502, average particle size: about 0.6 μm, Admatechs Co., Ltd.) 473 g of titanium oxide (trade name: PF-691, average particle size: about 0.2 μm, manufactured by Ishihara Sangyo) was added to prepare a toluene dispersion of the silicone resin composition.

  After impregnating this toluene dispersion with quartz glass cloth (made by Shin-Etsu quartz, thickness: 100 μm), toluene was evaporated by a hot air dryer at 110 ° C. for 10 minutes to obtain a prepreg 1 of quartz glass cloth. The prepreg was subjected to pressure molding at 150 ° C. for 30 minutes with a hot press, and then secondarily cured at 150 ° C. for 1 hour to obtain a silicone laminate.

1. Mechanical properties The obtained silicone laminate was measured for tensile strength (0.2 mm thickness) according to JIS K 6251.

2. Thermal conductivity was measured by a laser flash method using a xenon flash analyzer (LFA447 manufactured by NETZSCH).

3. Linear expansion coefficient With respect to the obtained silicone laminate (0.2 mm thickness), a direction parallel to the laminate over a range of −100 to 100 ° C. by a thermomechanical analysis (TMA) measurement method according to JIS K 7197 ( The linear expansion coefficient in the XY axis direction) was measured.

4). IR reflow test In the same manner as described above, the toluene dispersion was impregnated into the quartz glass cloth, and toluene was evaporated. The prepreg after evaporation of toluene was sandwiched between two copper foils (Fukuda Metal, thickness: 35 μm) and molded by pressing at 150 ° C. for 30 minutes with a hot press to obtain a molded product. Was secondarily cured at 150 ° C. for 1 hour to obtain a copper-clad laminate (0.3 mm thick). The copper-clad laminate is subjected to an IR reflow treatment at 260 ° C. for 10 seconds using an IR reflow device (trade name: Reflow Soldering Device, manufactured by Tamura Corporation) to confirm whether the copper foil has peeled off. did.

5. Light reflectivity The light reflectivity of the obtained silicone laminated substrate was measured over the entire visible light region. Moreover, after performing IR reflow processing for 60 seconds and 260 degreeC with respect to the obtained silicone laminated substrate with the said IR reflow apparatus, the light reflectivity was measured over all visible light area | regions. Furthermore, after irradiating the obtained silicone laminated substrate with ultraviolet rays having a wavelength of 365 nm and an intensity of 30 mW / cm ² at 120 ° C. for 24 hours, the light reflectance was measured over the entire visible light region. The light reflectivity was measured using a light reflectometer X-rite 8200 (integral sphere spectrophotometer, manufactured by X-rite (US)).

These measurement results are shown in Table 1.

(Example 2)
In Example 1, instead of the vinyl group-containing resin (A1) obtained in Synthesis Example 1 and the hydrosilyl group-containing resin (B1) obtained in Synthesis Example 2, the vinyl group-containing resins obtained in Synthesis Example 3 respectively. A quartz glass prepreg 2 was produced in the same manner as in Example 1 except that the hydrosilyl group-containing resin (B2) obtained in (A2) and Synthesis Example 4 was used, and a silicone laminated substrate and a copper clad laminated substrate were obtained. ,evaluated. The results are shown in Table 1.

Example 3
When the prepreg 1 and prepreg 2 obtained in Example 1 and Example 2 were sandwiched between a copper foil (made by Fukuda Metal Co., Ltd., thickness: 35 μm) and an aluminum plate and molded by heating and pressing, an aluminum plate (Al5052- H34) was applied in advance with a 10% toluene solution of an adhesion assistant represented by the following formula, and a dried aluminum plate was used. The pressing conditions were the same as in Example 1 and pressure molded at 150 ° C. for 30 minutes to obtain a molded product, which was further secondarily cured at 150 ° C. for 1 hour to obtain a metal base substrate. The adhesion between the aluminum plate and the silicone prepreg was good, and the base material was destroyed at the prepreg portion.

(Comparative Example 1)
In Example 1, glass cloth WEA-116E (manufactured by Nittobo, thickness: 100 μm, E glass) was used instead of the quartz glass cloth (made by Shin-Etsu quartz, thickness: 100 μm). After impregnating the glass cloth with a toluene dispersion, toluene was evaporated by a hot air dryer at 110 ° C. for 10 minutes to prepare prepreg 3. The prepreg was subjected to pressure molding at 150 ° C. for 30 minutes with a hot press, and then secondarily cured at 180 ° C. for 1 hour to obtain a silicone resin plate.
In the same manner as in Example 1, a silicone resin plate and a copper clad laminated substrate were obtained and evaluated. The results are shown in Table 1.

(note)
* 1: Molar ratio of silicon-bonded hydrogen atoms in hydrosilyl group-containing resin to silicon-bonded vinyl groups in vinyl group-containing resin

Example 4
Using the metal base substrate manufactured in Example 3 and using an aluminum plate (Al5052-H34) that is not treated with an adhesion aid, press conditions are the same as in Example 1 and pressurized at 150 ° C. for 30 minutes. Molding was performed to obtain a molded product, which was then secondarily cured at 150 ° C. for 1 hour to obtain a metal base substrate. The adhesion state of the aluminum plate and the silicone prepreg was inferior to that of Example 3, and interface peeling sometimes occurred.

(Example 5)
Vinyl group-containing resin (A1) obtained in Synthesis Example 1: 189 g, hydrosilyl group-containing resin (B1) obtained in Synthesis Example 2: 189 g, acetylene alcohol-based ethynylcyclohexanol as a reaction inhibitor: 0.2 g, A 1% by mass octyl alcohol solution of chloroplatinic acid: 0.1 g, an adhesion assistant represented by the following formula: 6 g was added, and the mixture was stirred well with a planetary mixer heated to 60 ° C. to obtain a base composition. To this base composition, 400 g of toluene was added as a solvent, and 378 g of silica (trade name: Admafine E5 / 24C, average particle size: about 3 μm, manufactured by Admatechs) and titanium oxide (trade name: PF-691). , Average particle size: about 0.2 μm, manufactured by Ishihara Sangyo Co., Ltd.) was added to prepare a toluene dispersion of the silicone resin composition. After impregnating this toluene dispersion with quartz glass cloth (made by Shin-Etsu quartz, thickness: 100 μm), toluene was evaporated by a hot air dryer at 110 ° C. for 10 minutes to obtain a prepreg of the quartz glass cloth. The prepreg was subjected to pressure molding at 150 ° C. for 30 minutes with a hot press, and then secondarily cured at 150 ° C. for 1 hour to obtain a silicone laminate.

The measurement of thermal conductivity, linear expansion coefficient, IR reflow test, and light reflectance measurement were performed in the same manner as in Example 1. In addition, a solder connection test was performed as follows. These measurement results are shown in Table 2 together with the results of the white epoxy aluminum plate of Comparative Example 2 described later.
6). Solder connection test The LED package was solder-connected to the substrate, a temperature cycle test was performed, and a solder connection state and a crack generation state of the solder were observed every 500 cycles in a cross-sectional photograph.
Temperature cycle condition is held at -40 ° C for 15 minutes, then raised to 125 ° C and held for 15 minutes
Did. An acceleration acceleration test was performed by a continuous operation temperature cycle in which -40 ° C to 125 ° C is one cycle.

(note)
* 1: Molar ratio of silicon-bonded hydrogen atoms in hydrosilyl group-containing resin to silicon-bonded vinyl groups in vinyl group-containing resin

(Comparative Example 2)
An LED mounting substrate was prepared using a white epoxy aluminum plate with a high filler added, which is a commercially available metal base substrate, and a lighting test was performed as follows. The results are shown in Table 3 together with the lighting test results of the metal base substrate prepared in Example 3.

7). Lighting test The LED device shown in FIG. 1 was produced and a lighting test was performed. In FIG. 1, the electrode pattern 3 was produced by etching the copper-clad laminate produced as described above. The blue LED chip 5 (wavelength 450 nm) was die-bonded using KJR-632DA-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the die-bonding paste 4. A gold wire was used as the bonding wire 6. The transparent encapsulant 7 was prepared by casting a part of the electrode pattern 3, the LED chip 5 and the bonding wire 6 with a silicone resin coating agent (trade name: KJR-9022, manufactured by Shin-Etsu Chemical Co., Ltd.) ( Curing conditions: 150 ° C., 4 hours). The lighting test was performed by continuously lighting the LED device thus obtained at an input current of 150 mA and observing whether the silicone laminated substrate was discolored. The results are shown in Table 3.

  When the silicone prepreg of the present invention is used, the reflectance in the visible light region is high, there is little deterioration due to heating or ultraviolet rays, discoloration, and a decrease in reflectance, and further high heat resistance and heat dissipation, and high reliability of solder connection of mounted components. It was found that the substrate material can be obtained, and in particular, it can be suitably used as an LED base material for an LED mounting substrate.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

  DESCRIPTION OF SYMBOLS 1 ... LED mounting board, 2 ... Silicone resin board. DESCRIPTION OF SYMBOLS 3 ... Electrode pattern, 4 ... Die bonding paste, 5 ... LED chip, 6 ... Bonding wire, 7 ... Transparent sealing body.

Claims (9)

To quartz glass cloth,
(A) R ¹ SiO _1.5 unit, R ² ₂ SiO unit and R ³ _a R ⁴ _b SiO _{(4-ab) / 2} unit (where R ¹ , R ² and R ³ are independent) Represents a hydroxyl group, a methyl group, an ethyl group, a propyl group, a cyclohexyl group or a phenyl group, R ⁴ independently represents a vinyl group or an allyl group, a is 0, 1 or 2, and b is 1 or 2 And a + b is 2 or 3.)
An organopolysiloxane having a resin structure including a structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetitions thereof is 5 to 50;
(B) R ¹ SiO _1.5 units, R ² ₂ SiO units and R ³ _c H _d SiO _{(4-cd) / 2} units (where R ¹ , R ² and R ³ are independently As described above, c is 0, 1 or 2, d is 1 or 2, and c + d is 2 or 3.)
Organohydrogenpolysiloxane having a resin structure including a structure in which at least a part of the R ² ₂ SiO unit is continuously repeated and the number of repetition is 5 to 50: vinyl group and allyl in component (A) An amount of hydrogen atoms bonded to silicon atoms in the component (B) relative to the total of the groups in a molar ratio of 0.1 to 4.0,
(C) Platinum group metal catalyst: 0.1 to 500 ppm in terms of mass as a platinum group metal with respect to the total amount of the components (A) and (B) , and (D) fillers: (A) and ( B) 900 parts by mass or less with respect to 100 parts by mass in total of the components,
A silicone prepreg obtained by impregnating and drying a silicone resin composition comprising   A silicone resin plate produced by heating and press-molding one or more of the silicone prepregs according to claim 1 and having a thermal conductivity of 0.8 W / mK or more.   It is a silicone resin board of Claim 2, Comprising: The linear expansion coefficient of the direction parallel to this silicone resin board is 30 ppm / degrees C or less over the range of -100-100 degreeC, The silicone resin board characterized by the above-mentioned.   An LED mounting substrate, which is manufactured using the silicone resin plate according to claim 2 or 3.   A silicone metal-clad laminate, wherein one or more of the silicone prepregs according to claim 1 are laminated and metal foil is laminated on both sides and heated and pressed.   6. An LED mounting board produced using the silicone metal-clad laminate according to claim 5.   One or more of the silicone prepregs according to claim 1 are laminated, and a metal foil is laminated on one side, and a metal plate is laminated on the other side, and is produced by heating and pressing. Silicone metal base substrate.   The silicone metal base substrate according to claim 7, wherein the metal plate is previously treated with an adhesion aid. 9. An LED mounting substrate produced using the silicone metal base substrate according to claim 7 or 8.

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