JP7013353B2 - Glass fiber-containing wavelength conversion silicone sheet and optical semiconductor device using it - Google Patents

Description

The present invention relates to a glass fiber-containing wavelength conversion silicone sheet and a semiconductor device using the same.

In modern society, lighting began with incandescent light bulbs, and now LEDs have become commonplace and have spread throughout the world. In addition, the demand for thinner and smaller LEDs is constantly continuing, and further advances in science and technology are expected. By the way, the manufacturing method of LED has been remarkably advanced. It has been manufactured by casting method of pouring into an inexpensive mold, potting method of sealing material to SMD, or molding, but recently, a side wall is formed around a chip called CSP (Chip Size Package). By mounting a fluorescent material layer on the top of the chip and dicing around the chip at the end, materials such as PPA, which are called conventional package materials, are no longer used, and methods such as molding, spraying, or bonding of fluorescent material layers are adopted. Things are getting more and more.
At that time, it has been found that peeling and cracking occur in various reliability tests due to the mismatch of CTE with the fluorescent layer, the white material and the chip. The most common is the peeling of the LED and the phosphor layer.

As a countermeasure, adhesion has been improved by forming a uniformly dispersed phosphor layer on the upper part of the chip by bonding using a phosphor film in which a phosphor is mixed with a silicone composition (Patent Document 1). However, this method has a problem that the fluorescent film cannot withstand the stress from the chip or the packaging material and cracks occur.

Further, a CSP material that can be collectively molded by using a transparent silicone layer as an adhesive layer under the phosphor layer has also been attempted (Patent Document 2). However, there is also a transparent layer of silicone only on the side surface of the chip, which has no reinforcing effect, and it cannot withstand the stress of the chip, which is increasing in brightness.

Further, a highly transparent substrate reinforced by impregnating a glass cloth with a silicone resin having an adjusted refractive index is also provided (Patent Document 3). However, it has been found that the color variation within a fine range becomes large because the fluorescent material layer follows the swell of the glass cloth when it is made to emit light only by putting the fluorescent material in this substrate.

Further, an LED member obtained by firing a phosphor layer into ceramics and having a hole in a gold wire joint is also disclosed (Patent Document 4), but it is expensive to produce ceramics and there is no self-adhesiveness. Therefore, a separate adhesive is required.

In addition, when cutting a multilayer wavelength conversion silicone sheet reinforced by bonding a phosphor sheet without a reinforcing layer and a diffuser-containing sheet aimed at diffusion curing, if the filler is highly filled, the sheet will be filled. Since it is fragile, cracks may occur in the cut portion, and interfacial peeling may occur between the two layers (Patent Documents 5 and 6).

Japanese Unexamined Patent Publication No. 2010-12382 Japanese Unexamined Patent Publication No. 2016-119454 Japanese Unexamined Patent Publication No. 2015-174937 Japanese Unexamined Patent Publication No. 2016-222902 Japanese Unexamined Patent Publication No. 2013-159003 Japanese Unexamined Patent Publication No. 2014-138999

The present invention has been made to solve the above problems, and is a glass fiber-containing wavelength conversion silicone sheet and the silicone sheet having good low thermal expansion, self-adhesiveness, adhesive durability, and high thermal conductivity. It is an object of the present invention to provide an optical semiconductor device using the cured product of the above as a sealing resin layer.

In order to achieve the above-mentioned problems, in the present invention, the glass fiber-containing wavelength-converting silicone sheet is a glass fiber-containing wavelength-converting silicone sheet, which comprises a resin-treated glass substrate (I) and a wavelength-converting silicone sheet (II). The resin-treated glass substrate (I) contains a organosiloxane compound having a glass fiber as a core material and having at least one aryl group in one molecule, and is plastic at 23 ° C. A heat-curable silicone resin composition in a solid state or a semi-solid state is attached to the glass fiber, and the attached resin composition is 15 to 15 to 100% by mass when the total mass after attachment is 100% by mass. The amount is 70% by mass, the wavelength conversion silicone sheet (II) contains the heat-curable silicone resin composition and a phosphor, and the resin-treated glass substrate (I) and the said. Provided is a glass fiber-containing wavelength conversion silicone sheet, characterized in that at least one layer or more of each of the wavelength conversion silicone sheet (II) is laminated.

Such a glass fiber-containing wavelength conversion silicone sheet has good low thermal expansion, self-adhesiveness, adhesive durability, and high thermal conductivity.

It is preferable that both the thermosetting silicone resin composition in the resin-treated glass substrate (I) and the wavelength-converting silicone sheet (II) are uncured.

In this case, the self-adhesiveness becomes more excellent, and the resin-treated glass substrate (I) and the wavelength-converting silicone sheet (II) can be laminated on either surface.

Further, it is preferable that the glass fiber is at least one selected from glass cloth, glass non-woven fabric, glass wool or glass chopped strand.

By containing such glass fibers, it is possible to prevent expansion and contraction in the thermal shock test and to prevent cracks and peeling.

In this case, it is preferable that the glass fiber is a quartz glass cloth.

This makes it possible to obtain a glass fiber-containing wavelength conversion silicone sheet having both low line expansion and discoloration resistance.

Further, it is preferable that the surface of the glass fiber is treated with a silane coupling agent.

This makes it possible to obtain a glass fiber-containing wavelength conversion silicone sheet having improved adhesion between the resin and the glass fiber.

Further, it is preferable that the thermosetting silicone resin composition further contains an inorganic filler.

With such a glass fiber-containing wavelength conversion silicone sheet, the coefficient of thermal expansion of the sheet can be reduced.

In this case, the primary average particle size of the inorganic filler by the laser diffraction / scattering method is preferably 0.05 to 20 μm.

With such an inorganic filler, the filling property is improved, so that the coefficient of thermal expansion of the sheet can be made more preferable.

The present invention also provides an optical semiconductor device having a resin encapsulating layer made of a cured product of the glass fiber-containing wavelength conversion silicone sheet.

Such an optical semiconductor device has low expansion and contraction even when subjected to thermal shock, is highly reliable because it does not crack or peel, and does not contain a fluorescent substance in the reinforcing layer (resin-treated glass substrate). Therefore, the color variation of the phosphor layer due to the phosphor flowing into the joint of the glass fiber is reduced.

As described above, the glass fiber-containing wavelength conversion silicone sheet of the present invention is a silicone having self-adhesiveness, low thermal expansion property, and wavelength conversion uniformity (that is, very little color variation as a wavelength conversion film). Sheets can be provided.

The glass fiber-containing wavelength-converting silicone film of the present invention, in which one or more reinforcing layers (resin-treated glass base material (I)) and a phosphor layer (wavelength-converting silicone sheet (II)) are present, is self-contained in the phosphor layer. Adhesiveness can be given, the reinforcing layer itself can be given self-adhesiveness, and both sides can be bonded together, so the diffusion state can be changed to two conditions, front and back, depending on the chip shape, so a new diffusion layer can be provided. It is possible to omit the step of producing the above. Further, by introducing the reinforcing layer, even if the filler is highly filled, it can be cut without cracking and without interfacial peeling, so that it is very easy to handle as a wavelength conversion sheet. Since there is no phosphor in the cloth, the phosphor is uniformly present in the thickness direction, so that the color variation as the wavelength conversion film is very small.

It is a schematic sectional drawing which shows an example of the glass fiber containing wavelength conversion silicone sheet of this invention. It is the schematic sectional drawing which shows the other example of the glass fiber containing wavelength conversion silicone sheet of this invention.

As described above, there has been a demand for the development of a glass fiber-containing wavelength conversion silicone sheet having good low thermal expansion, self-adhesiveness, adhesive durability, and high thermal conductivity.

As a result of diligent studies on the above problems, the present inventors have obtained a resin-treated glass substrate having a specific silicone resin composition as a reinforcing layer adhered to a glass fiber core material, and the silicone resin as a wavelength conversion layer. Due to the structure in which at least one layer or more of the wavelength conversion silicone sheet containing the composition and the phosphor is laminated, it has good low thermal expansion property, self-adhesiveness, heat resistance / light resistance, high thermal conductivity, etc. We have found that a reliable silicone sheet can be obtained, and completed the present invention.

That is, the present invention is a glass fiber-containing wavelength conversion silicone sheet, and the glass fiber-containing wavelength conversion silicone sheet is obtained by laminating a resin-treated glass base material (I) and a wavelength conversion silicone sheet (II). The resin-treated glass substrate (I) has a glass fiber as a core material, contains an organosiloxane compound having at least one aryl group in one molecule, and is in a solid or semi-solid state plastic at 23 ° C. The heat-curable silicone resin composition is attached to the glass fiber, and the attached resin composition is 15 to 70% by mass when the total mass after attachment is 100% by mass. The wavelength-converting silicone sheet (II) contains the heat-curable silicone resin composition and a phosphor, and the resin-treated glass substrate (I) and the wavelength-converting silicone sheet (II). ) Is a glass fiber-containing wavelength conversion silicone sheet, each of which is formed by laminating at least one layer or more.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. In the present specification, "Me" indicates a methyl group, "Ph" indicates a phenyl group, and "Vi" indicates a vinyl group.

1. 1. Glass fiber-containing wavelength conversion silicone sheet The glass fiber-containing wavelength conversion silicone sheet of the present invention has at least one layer each of a resin-treated glass substrate (I) as a reinforcing layer and a wavelength conversion silicone sheet (II) as a wavelength conversion layer. The above is laminated. The resin-treated glass substrate (I) has a glass fiber as a core material, contains an organosiloxane compound having at least one aryl group in one molecule, and is in a plastic solid state or a semi-solid state at 23 ° C. A thermosetting silicone resin composition is attached to the glass fiber. The wavelength conversion silicone sheet (II) contains the thermosetting silicone resin composition and a phosphor.

The glass fiber-containing wavelength conversion silicone sheet of the present invention will be described below with reference to FIG. The glass fiber-containing wavelength conversion silicone sheet 1 is a laminate of a resin-treated glass base material (I) 2 and a wavelength conversion silicone sheet (II) 3. The resin-treated glass substrate 2 has a glass fiber as a core material 4, contains an organosiloxane compound having at least one aryl group in one molecule, and is thermosetting in a plastic solid state or a semi-solid state at 23 ° C. The mold silicone resin composition 5 is attached to the glass fiber. The wavelength conversion silicone sheet 3 contains the same resin composition and phosphor as the thermosetting silicone resin composition 5.
Note that FIG. 1 shows an embodiment in which the core material 4 is layered and the resin composition 5 is attached to both sides thereof. However, in the present invention, the resin composition 5 may be attached to the core material 4. , Not limited to such embodiments. For example, the core material 4 may be impregnated with the resin composition 5 and integrally occupy the entire resin-treated glass base material 2, or the core material 4 may be dispersed in the resin composition 5 to occupy the entire resin-treated glass base material 2. 2 may be configured.

The glass fiber-containing wavelength conversion silicone sheet 1 is formed by laminating at least one layer each of the resin-treated glass base material 2 and the wavelength conversion silicone sheet 3. The mode in which the resin-treated glass base material 2 and the wavelength conversion silicone sheet 3 are laminated is not particularly limited, but in addition to the mode in which both are laminated one layer at a time as shown in FIG. 1, as shown in FIG. It is also possible to laminate the resin-treated glass base material 2 so as to sandwich it between the two wavelength-converting silicone sheets 3, or to repeat the laminated structural unit shown in FIG. 1 a plurality of times.

Hereinafter, each of the resin-treated glass substrate (I) and the wavelength-converting silicone sheet (II) will be described.

2. 2. Resin-treated glass substrate (I)
The resin-treated glass substrate (I) constituting the present invention serves as a reinforcing layer for the glass fiber-containing wavelength conversion silicone sheet. The resin-treated glass base material is a base material in which (B) glass fiber is used as a core material and (A) a heat-curable silicone resin composition which is semi-solid or solid at 23 ° C. is adhered to the glass fiber. be. In the present invention, a glass fiber (B) coated with and impregnated with a thermosetting silicone resin composition (A) and the composition in an uncured state is particularly referred to as a prepreg. Hereinafter, the constituent components and the manufacturing method will be described in detail.

<(A) Thermosetting silicone resin composition>
The thermosetting silicone resin composition which is the component (A) of the present invention is in a solid state or a semi-solid state which is plastic at 23 ° C., and contains an organosiloxane compound having at least one aryl group in one molecule. It is characterized by that. If the properties are not such, that is, if the resin composition is liquid, the workability when producing the resin-treated glass substrate is inferior, which is not preferable. The organosiloxane compound is not particularly limited as long as it has at least one aryl group in one molecule, but an addition-curable silicone resin or an organosiloxane compound constituting a condensation-curable silicone resin described later is preferable. .. The resin composition may further contain other components, if necessary.

In addition, in this specification, "semi-solid" means a state of a substance which has plasticity and can hold the shape for at least 1 hour, preferably 8 hours or more when it is formed into a specific shape. Thus, for example, a fluid material having a very high viscosity at room temperature is essentially fluid, but due to the very high viscosity it changes to the given shape in a short time of at least 1 hour (ie, collapses). ) Is not visible to the naked eye, the substance is in a semi-solid state. Since it is in a plastic solid or semi-solid state, the composition is easy to handle and has high workability.

The thermosetting silicone resin composition includes an addition-curable silicone resin composition composed of (A1), (A2), and (A3), and a condensation-curable silicone composed of (A4) and (A5). Examples include resin compositions. The organosiloxane compound constituting the thermosetting silicone resin composition comprises the components (A1) and (A2) constituting the addition-curing silicone resin composition and the condensation-curing silicone resin composition ( Examples include A4) and (A5) components.

The thermosetting silicone resin composition as the component (A) is characterized by containing an organosiloxane compound having at least one aryl group in one molecule, and will be described below (because it is characterized by containing it. Any one of the A1) or (A2) components must be an organosiloxane compound having at least one aryl group in one molecule, and any one of the (A4) or (A5) components is in one molecule. It needs to be an organosiloxane compound having at least one aryl group. It is preferable that both the components (A1) and (A2) or both the components (A4) and (A5) have at least one aryl group.

<Additional curing type silicone resin composition>
[(A1) component]
The component (A1) is the following average composition formula (1).
(R ₃ SiO _1/2 ) _a (R ₂ SiO _2/2 ) _b (RSiO _3/2 ) _c (SiO _4/2 ) _d (1)
(In the formula, R is a group independently selected from a hydroxyl group, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. At least two of R are alkenyl groups, where a, b, c, d are a ≧ 0, b ≧ 0, c ≧ 0, d ≧ 0, a + b + c + d = 1, and 0 <(c + d) <. It is an organopolysiloxane (that is, an unsaturated group-containing organopolysiloxane) having two or more alkenyl groups bonded to a silicon atom in one molecule, which is represented by (a number satisfying 1.0).

The component (A1) contains one or both of (RSiO _3/2 ) unit [T unit] and (SiO _4/2 ) unit [Q unit], and by including such a branched structure. , A silicone resin sheet having good mechanical strength can be obtained.

In the above average composition formula (1), R is independently a hydroxyl group, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and 6 to 14 carbon atoms. , Preferably 6-10, more preferably 6-8 monovalent aromatic hydrocarbon groups, and 2-10 carbon atoms, preferably 2-8 carbon atoms, more preferably 2-6 carbon atoms alkenyl groups. Is the basis for carbon. Specific examples of R include a hydroxyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group, a trill group, a xsilyl group and a naphthyl group. And the like, aryl groups such as vinyl group, propenyl group, alkenyl group such as isopropenyl group and the like can be mentioned. Among these, a methyl group, a phenyl group, and a vinyl group are particularly preferable.

Specific examples of the component (A1) include, for example, (R ₃ SiO _1/2 ) unit [M unit], (R ₂ SiO _2/2 ) unit [D unit], and (RSiO _3/2 ) unit [T. Units] include the following organopolysiloxanes.
(Me ₂ ViSiO _1/2 ) _a1 (Me ₂ SiO _2/2 ) _b1 (PhSiO _3/2 ) _c1
(Me ₂ ViSiO _1/2 ) _a2 (MeViSiO _2/2 ) _b2 (PhSiO _3/2 ) _c2
(Me ₂ ViSiO _1/2 ) _a3 (MePhSiO _2/2 ) _b3 (PhSiO _3/2 ) _c3
(Me ₂ ViSiO _1/2 ) _a4 (Ph ₂ SiO _2/2 ) _b4 (PhSiO _3/2 ) _c4
(Me ₂ ViSiO _1/2 ) _a5 (Ph ₂ SiO _2/2 ) _b5 (MeSiO _3/2 ) _c5
(Me ₂ ViSiO _1/2 ) _a6 (Me ₂ SiO _2/2 ) _b6 (MeViSiO _2/2 ) _b7 (PhSiO _3/2 ) _c6
(Me ₂ ViSiO _1/2 ) _a7 (MePhSiO _2/2 ) _b8 (MeViSiO _2/2 ) _b9 (PhSiO _3/2 ) _c7
(MeVi ₂ SiO _1/2 ) _a8 (Me ₂ SiO _2/2 ) _b10 (PhSiO _3/2 ) _c8
(MeVi ₂ SiO _1/2 ) _a9 (MePh ₂ SiO _1/2 ) _a10 (MePhSiO _2/2 ) _b11 (MeSiO _3/2 ) _c9
(In the formula, a1, a2, a3, a4, a5, a6, a7, a8, a9, a10, b1, b2, b3, b4, b5, b6, b7, b8, b9, b10, b11, c1, c2, c3, c4, c5, c6, c7, c8, and c9 are 0.01≤a1≤0.6, 0.01≤a2≤0.6, 0.01≤a3≤0.6, 0. 01 ≦ a4 ≦ 0.6, 0.01 ≦ a5 ≦ 0.6, 0.01 ≦ a6 ≦ 0.2, 0.01 ≦ a7 ≦ 0.2, 0.01 ≦ a8 ≦ 0.6, 0. 01 ≦ a9 ≦ 0.2, 0.01 ≦ a10 ≦ 0.2, 0.005 ≦ b1 ≦ 0.5, 0.005 ≦ b2 ≦ 0.5, 0.005 ≦ b3 ≦ 0.5, 0. 005 ≦ b4 ≦ 0.5, 0.005 ≦ b5 ≦ 0.5, 0.2 ≦ b6 ≦ 0.7, 0.01 ≦ b7 ≦ 0.2, 0.2 ≦ b8 ≦ 0.7, 0. 01 ≦ b9 ≦ 0.2, 0.005 ≦ b10 ≦ 0.5, 0.4 ≦ b11 ≦ 0.9, 0.24 ≦ c1 ≦ 0.9, 0.24 ≦ c2 ≦ 0.9, 0. 24 ≦ c3 ≦ 0.9, 0.24 ≦ c4 ≦ 0.9, 0.24 ≦ c5 ≦ 0.9, 0.2 ≦ c6 ≦ 0.7, 0.2 ≦ c7 ≦ 0.7, 0. 24 ≦ c8 ≦ 0.9, 0.01 ≦ c9 ≦ 0.2, and a1 + b1 + c1 = 1, a2 + b2 + c2 = 1, a3 + b3 + c3 = 1, a4 + b4 + c4 = 1, a5 + b5 + c5 = 1, a6 + b6 + b7 + c6 = 1, a7 + b8 + b9 + 1 = 1 , A9 + a10 + b11 + c9 = 1).

Further, as another specific example of the component (A1), for example, the following organopolysiloxane having only (RSiO _3/2 ) unit [T unit] can be mentioned.
(PhSiO _3/2 ) _c10 (ViSiO _3/2 ) _c11
(MeSiO _3/2 ) _c12 (ViSiO _3/2 ) _c13
(In the formula, c10, c11, c12, and c13 are 0.5 ≦ c10 ≦ 0.95, 0.05 ≦ c11 ≦ 0.5, 0.5 ≦ c12 ≦ 0.98, 0.02 ≦, respectively. It is a number that satisfies c13 ≦ 0.5 and c10 + c11 = 1 and c12 + c13 = 1).

Further, as other specific examples of the component (A1), for example, (R ₃ SiO _1/2 ) unit [M unit], (R ₂ SiO _2/2 ) unit [D unit], and (SiO _4/2 ). ) The following organopolysiloxanes having a unit [Q unit] can be mentioned.
(Me ₂ ViSiO _1/2 ) _a11 (Ph ₂ SiO _2/2 ) _b12 (SiO _4/2 ) _d1
(Me ₃ SiO _1/2 ) _a12 (Me ₂ ViSiO _1/2 ) _a13 (MePhSiO _2/2 ) _b13 (MeViSiO _2/2 ) _b14 (Ph ₂ SiO _2/2 ) _b15 (SiO _4/2 ) _d2
(In the formula, a11, a12, a13, b12, b13, b14, b15, d1 and d2 are 0.1 ≦ a11 ≦ 0.7, 0.02 ≦ a12 ≦ 0.3 and 0.05 ≦, respectively. a13 ≦ 0.4, 0.1 ≦ b12 ≦ 0.2, 0.02 ≦ b13 ≦ 0.3, 0.005 ≦ b14 ≦ 0.1, 0.1 ≦ b15 ≦ 0.5, 0.1 ≦ It is a number that satisfies d1 ≦ 0.7, 0.1 ≦ d2 ≦ 0.6, and a11 + b12 + d1 = 1, a12 + a13 + b13 + b14 + b15 + d2 = 1).

Further, as another specific example of the component (A1), for example, the following unsaturated group having (R ₃ SiO _1/2 ) unit [M unit] and (SiO _4/2 ) unit [Q unit] is contained. Organopolysiloxanes can be mentioned.
(Me ₂ ViSiO _1/2 ) _a14 (SiO _4/2 ) _d3
(Me ₃ SiO _1/2 ) _a15 (Me ₂ ViSiO _1/2 ) _a16 (SiO _4/2 ) _d4
(Me ₃ SiO _1/2 ) _a17 (MePhViSiO _1/2 ) _a18 (SiO _4/2 ) _d5
(In the formula, a14, a15, a16, a17, a18, d3, d4, and d5 are 0.01≤a14≤0.5, 0.1≤a15≤0.5, 0.05≤a16≤, respectively. 0.3, 0.1 ≤ a17 ≤ 0.5, 0.05 ≤ a18 ≤ 0.3, 0.5 ≤ d3 ≤ 0.99, 0.3 ≤ d4 ≤ 0.85, 0.3 ≤ d5 ≤ It is a number that satisfies 0.85 and a14 + d3 = 1, a15 + a16 + d4 = 1, a17 + a18 + d5 = 1).

Among them, the organopolysiloxane which requires the T unit is preferable, the organopolysiloxane which requires the T unit, the D unit and the M unit is more preferable, and it is further preferable that the D unit is continuous. Such an organopolysiloxane tends to be in a solid state or a semi-solid state at 23 ° C., and thus has good handleability.

In addition, it is preferable to have an alkenyl group (vinyl group) at the end of the molecular chain like the above (Me ₂ ViSiO _1/2 ) unit, and in addition to the above (Me ₂ ViSiO 1/2) unit, the above (MeViSiO _1/2 ) unit. It is more preferable to have an alkenyl group (vinyl group) in the side chain of the molecular chain as in the _2/2 ) unit.

The organopolysiloxane of the component (A1) is not limited to the above specific example. Further, as the component (A1), the above-mentioned organopolysiloxane can be used alone or in combination of two or more.

The weight average molecular weight of the component (A1) in terms of polystyrene is preferably in the range of 1,000 to 1,000,000.

The weight average molecular weight referred to in the present invention refers to the weight average molecular weight using polystyrene as a standard material measured by gel permeation chromatography (GPC) under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.6 mL / min
Detector: Differential Refractometer Detector (RI)
Column: TSK Guardcolomn SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5 wt%)

For the organopolysiloxane of the component (A1), the compound that is the raw material of each unit is combined so that each siloxane unit has a required molar ratio in the produced polymer, and for example, co-hydrolysis condensation is performed in the presence of an acid. Can be synthesized by.

As the raw material of each siloxane unit, chlorosilanes corresponding to each siloxane unit, alkoxysilanes such as methoxysilanes corresponding to each of these chlorosilanes, and the like can be exemplified.

[(A2) component]
The component (A2) is an organohydrogenpolysiloxane having two or more hydrogen atoms bonded to a silicon atom (hereinafter, also referred to as “SiH group”) in one molecule, and can be used as a cross-linking agent for the above-mentioned component (A1). It is a component that acts.

Specific examples of the component (A2) include the following organohydrogenpolysiloxane.
(Me ₂ HSiO _1/2 ) _e1 (Me ₂ SiO _2/2 ) _f1 (PhSiO _3/2 ) _g1
(Me ₂ HSiO _1/2 ) _e2 (Me ₂ SiO _2/2 ) _f2 (MeHSiO _2/2 ) _f3 (PhSiO _3/2 ) _g2
(Me ₂ HSiO _1/2 ) _e3 (PhSiO _3/2 ) _g3
(Me2 HSiO _1/2 ) _e4 ( _{MeSiO 3/2 ) g4}
(MeHSiO _2/2 ) _f4 (PhSiO _3/2 ) _g5
(MeHSiO _2/2 ) _f5 (MeSiO _3/2 ) _g6
(MeHSiO _2/2 ) _f6 ( _{Me2SiO 2/2} ) _f7 (PhSiO _3/2 ) _g7
(MeHSiO _2/2 ) _f8 (MePhSiO _2/2 ) _f9 (PhSiO _3/2 ) _g8
(Me ₂ HSiO _1/2 ) _e5 (Ph ₂ SiO _2/2 ) _f10
(Me ₂ HSiO _1/2 ) _e6 (Me ₂ SiO _2/2 ) _f11
(Me ₃ SiO _1/2 ) _e7 (MeHSiO _2/2 ) _f12
(Me ₃ SiO _1/2 ) _e8 (MeHSiO _2/2 ) _f13 (Ph ₂ SiO _2/2 ) _f14
(Me ₃ SiO _1/2 ) _e9 (MeHSiO _2/2 ) _f15 (Me ₂ SiO _2/2 ) _f16
(In the formula, e1, e2, e3, e4, e5, e6, e7, e8, e9, f1, f2, f3, f4, f5, f6, f7, f8, f9, f10, f11, f12, f13, f14, f15, f16, g1, g2, g3, g4, g5, g6, g7, and g8 are 0.01≤e1≤0.5, 0.01≤e2≤0.5, 0.3≤e3≤, respectively. 0.9, 0.01 ≤ e4 ≤ 0.9, 0.3 ≤ e5 ≤ 0.9, 0.05 ≤ e6 ≤ 0.7, 0.1 ≤ e7 ≤ 0.7, 0.01 ≤ e8 ≤ 0.2, 0.01 ≦ e9 ≦ 0.3, 0.09 ≦ f1 ≦ 0.75, 0.045 ≦ f2 ≦ 0.7, 0.045 ≦ f3 ≦ 0.7, 0.05 ≦ f4 ≦ 0.5, 0.05 ≦ f5 ≦ 0.5, 0.01 ≦ f6 ≦ 0.2, 0.2 ≦ f7 ≦ 0.8, 0.01 ≦ f8 ≦ 0.2, 0.2 ≦ f9 ≦ 0.8, 0.1 ≦ f10 ≦ 0.7, 0.3 ≦ f11 ≦ 0.95, 0.3 ≦ f12 ≦ 0.9, 0.3 ≦ f13 ≦ 0.9, 0.05 ≦ f14 ≦ 0.5, 0.1 ≦ f15 ≦ 0.6, 0.3 ≦ f16 ≦ 0.8, 0.24 ≦ g1 ≦ 0.9, 0.24 ≦ g2 ≦ 0.9, 0.1 ≦ g3 ≦ 0.7, 0.1 ≦ g4 ≦ 0.99, 0.5 ≦ g5 ≦ 0.95, 0.5 ≦ g6 ≦ 0.95, 0.1 ≦ g7 ≦ 0.7, 0.1 ≦ g8 ≦ 0.7 and e1 + f1 + g1 = 1, e2 + f2 + f3 + g2 = 1, e3 + g3 = 1, e4 + g4 = 1, f4 + g5 = 1, f5 + g6 = 1, f6 + f7 + g7 = 1, f8 + f9 + g8 = 1, e5 + f10 = 1, e6 + f11 = 1 = 1, a number that satisfies e9 + f15 + f16 = 1)

Among them, the organohydrogenpolysiloxane which requires the T unit is preferable, the organohydrogenpolysiloxane which requires the T unit and the D unit is more preferable, and it is further preferable that the D unit is continuous.

In addition, like the above (HMeSiO _2/2 ) unit, it is preferable to have a hydrogen atom (hydrosilyl group) directly connected to a silicon atom in the side chain of the molecular chain.

The organohydrogenpolysiloxane of the component (A2) is not limited to the above specific example. Further, as the component (A2), the above-mentioned organohydrogenpolysiloxane can be used alone or in combination of two or more.

As for the blending amount of the component (A2), the amount of the hydrogen atom (SiH group) bonded to the silicon atom in the component (A2) is 0.1 per mole of the alkenyl group bonded to the silicon atom in the component (A1). The amount is up to 5.0 mol, preferably 0.1 to 4.0 mol, more preferably 0.5 to 3.0 mol, and particularly preferably 0.8 to 2.0 mol. It is an amount that becomes a mole. If it is 0.1 mol or more, the curing reaction can be sufficiently advanced, so that a cured product can be easily obtained, and if it is 5.0 mol or less, a large amount of unreacted SiH groups remain in the cured product. Since there is no risk of this, it is possible to prevent the properties of the cured product from changing over time.

The weight average molecular weight of the component (A2) in terms of polystyrene is preferably in the range of 100 to 1,000,000.

For the organopolysiloxane of the component (A2), the compound that is the raw material of each unit is combined so that each siloxane unit has a required molar ratio in the produced polymer, and for example, co-hydrolysis condensation is performed in the presence of an acid. Can be synthesized by.

As the raw material of each siloxane unit, chlorosilanes corresponding to each siloxane unit, alkoxysilanes such as methoxysilanes corresponding to each of these chlorosilanes, and the like can be exemplified.

In the present invention, in order to impart adhesiveness, it is preferable that either or both of the above components (A1) and (A2) are polysiloxanes containing a silanol group (silicon atom-bonded hydroxyl group). In this case, the amount of the siloxane unit having a silanol group is preferably 40 mol% or less (0 to 40 mol%), more preferably 0.1 to 10 mol%, based on the total siloxane units.

Further, the components (A1) and (A2) may contain an alkoxy group due to the production method thereof. Specifically, it is an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the amount of the siloxane unit having an alkoxy group is preferably 10 mol% or less, preferably 0 to 0 to all siloxane units. It is more preferably 5 mol%.

[(A3) component]
The component (A3) is a platinum group metal-based catalyst (curing catalyst), and is a component compounded to cause an addition curing reaction of the addition-curing silicone resin composition.

As the component (A3), any conventionally known platinum group metal-based catalyst that promotes the hydrosilylation reaction can be used. Specific examples of the component (A3) include platinum-based components such as platinum, platinum black, and chloroplatinic acid from the viewpoint of cost and the like, for example, H ₂ PtCl ₆ , pH ₂ O, K ₂ PtCl ₆ , and KH PtCl 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 , Positive integers), and complexes of these with hydrocarbons such as olefins, alcohols, or vinyl group-containing organopolysiloxanes. As the component (A3), the above-mentioned catalysts can be used alone or in combination of two or more.

The blending amount of the component (A3) 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 components (A1) and (A2), particularly. It is preferably in the range of 0.5 to 100 ppm. By blending the component (A3) in the above range, a transparent resin-treated glass substrate with good productivity can be obtained.

<Condensation curing type silicone resin composition>
The condensation-curable silicone resin composition contains a component (A4) and a component (A5) (condensation accelerator). Hereinafter, (A4) and (A5) will be described in detail.

[(A4) component]
The component (A4) is the main ingredient of this composition, and has the following average composition formula (2).
( _R'3 SiO _1/2 ) _a' ( _R'2 SiO _2/2 ) _b' (R "SiO _3/2 ) _c' (SiO _4/2 ) _d' (2)
( ^R'is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms, and a', b', c', and d'are integers of 0 or more, respectively, and b'+ c'+ d'are integers of 1 or more.)
It is an organopolysiloxane represented by, and is an organopolysiloxane having at least two alkoxy groups, hydroxyl groups or hydrogen atoms in one molecule. In the above average composition formula (2), R'is an independent hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and 6 carbon atoms. It is a group selected from to 12, preferably 6 to 10, more preferably 6 to 8, a monovalent aromatic hydrocarbon group, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of R'are: hydrogen atom; alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group; cycloalkyl group such as cyclohexyl group; phenyl group, trill group, xsilyl group, Examples thereof include an aryl group such as a naphthyl group; a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group and an isopropoxy group. Among these, a hydrogen atom, a methyl group, a phenyl group, a hydroxyl group, and a methoxy group are particularly preferable.

In the preferred range of a', b', c', and d'mentioned above, a'is an integer of 0 to 5,000, further is an integer of 0 to 2,500, and b'is an integer of 10 to 5,000. An integer of 12,000, even an integer of 100 to 10,000, c'is an integer of 0 to 10,000, an integer of 0 to 8,000, and d'is an integer of 0 to 10,000. It is an integer, further an integer of 0 to 8,000, 20 ≦ c'+ d'≦ 20,000, further 50 ≦ c'+ d'≦ 15,000, and 15 ≦ b'+ c'. + D'≦ 1,500, and further 20 ≦ b'+ c'+ d'≦ 1,000.
Further, the organopolysiloxane of the component (A4) is preferably one having a polystyrene-equivalent molecular weight of 5,000 or more and 1,000,000 or less. Within this range, the properties do not become liquid or gel and lose compatibility.

As the component (A4), the component (A2) used in the addition-curable silicone resin composition may be used. In this case, the hydroxyorgan organopolysiloxane of the component (A2) to be used needs to satisfy the condition of the formula (2) when expressed as the average composition formula (2).

[(A5) component]
The component (A5) is a condensation accelerator added for the purpose of promoting the condensation reaction of this composition, has one or more hydrogen atoms bonded to a silicon atom, and is bonded to a silicon atom -OX (X). Has two or more hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 10 carbon atoms in the molecule, and has one or more hydrogen atoms and one on the same silicon atom. It is a polyorganosiloxane having one or more silicon atoms having the group represented by the above-OX (X is the same as above).

（式中、Ｘは上記と同様であり、Ｒ^１は、互いに独立に、酸素原子、ハロゲン原子、窒素原子、又は硫黄原子を含んでいてよい炭素数１～１８の一価炭化水素基であり、Ｒ^２は、互いに独立に、酸素原子、ハロゲン原子、窒素原子、又は硫黄原子を含んでいてよい炭素数１～１８の一価炭化水素基もしくは－ＯＸ’で示される基（Ｘ’は、それぞれ独立に、炭素数１～１０のアルキル基又は炭素数２～１０のアルコキシアルキル基である）である。ｄは１～３００の整数であり、ｅは０または１であり、ｄ’は、ｅ＝０のときは、ｄ’＝０であり、ｅ＝１のときは、ｄ’＝ｄである。ｐは１以上の整数である。なお、［ ］内のシロキサンはランダム構造を有してもブロック構造を有しても良い。） Specifically, it is preferably selected from at least one of the following general formula (3), the following general formula (4), and the polyorganosiloxane represented by the following general formula (5).

(In the formula, X is the same as above, and R ¹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms which may contain an oxygen atom, a halogen atom, a nitrogen atom, or a sulfur atom independently of each other. , R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms or a group represented by -OX'which may contain an oxygen atom, a halogen atom, a nitrogen atom, or a sulfur atom independently of each other (X'is a group. Each is independently an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms). D is an integer of 1 to 300, e is 0 or 1, and d'is. When e = 0, d'= 0, and when e = 1, d'= d. P is an integer of 1 or more. The siloxane in [] has a random structure. It may also have a block structure.)

（式中、Ｒ^１、Ｒ^２、及びＸは、互いに独立に、上記と同様であり、Ｑは、互いに独立に、酸素原子、ハロゲン原子、窒素原子、又は硫黄原子を含んでいてよい炭素数１～１８の一価炭化水素基、－ＯＸ’で示される基（Ｘ’は上記と同様である）、もしくは下記一般式（４’）で示される基である。但し、Ｑのうち、１つ以上は下記一般式（４’）で示される基である。ｄ^１は１～３００の整数であり、ｅ^１は１であり、ｄ^３＝ｄ^１である。ｐ’は１以上の整数である。なお、［ ］内のシロキサンはランダム構造を有してもブロック構造を有しても良い。）

（式中、Ｒ^１、Ｒ^２、及びＸは、互いに独立に、上記と同様である。ｄ^２は１～３００の整数であり、ｅ^２は０または１である。ｐ”は、１以上の整数である。なお、［ ］内のシロキサンはランダム構造を有してもブロック構造を有しても良い。）

(In the equation, R ¹ , R ² , and X are independent of each other and the same as above, and Q is the number of carbon atoms which may contain an oxygen atom, a halogen atom, a nitrogen atom, or a sulfur atom independently of each other. 1 to 18 monovalent hydrocarbon groups, groups represented by -OX'(X'is the same as above), or groups represented by the following general formula (4'), where 1 of Q is used. One or more are groups represented by the following general formula (4'). D ^{1 is an integer of 1 to 300, e 1 is} 1, and d ³ = d ^1. p'is an atom of 1 or more. The siloxane in [] may have a random structure or a block structure.)

(In the equation, R ¹ , R ² , and X are independent of each other and are the same as above. D ² is an integer of 1 to 300, e ² is 0 or 1. p "is 1 or more. The siloxane in [] may have a random structure or a block structure.)

（式中、Ｒ^１、Ｒ^２、及びＸは、互いに独立に、上記と同様であり、Ｒ^３は、互いに独立に、水素原子、メチル基、フェニル基、炭素数２～１０のアルケニル基、又は３－グリシジルオキシプロピル基である。但し、末端のケイ素原子に結合しているＲ^２のうち、１つ以上が－ＯＸ’で示される基（Ｘ’は上記と同様である）であるとき、これと同一のケイ素原子に結合しているＲ^３は水素原子ではない。ｔは０または１であり、ｓは０～３００の整数であり、ｓ’は、ｔ＝０のときはｓ’＝０であり、ｔ＝１のときはｓ’＝ｓである。ｑは１以上の整数である。なお、［ ］内のシロキサンはランダム構造を有してもブロック構造を有しても良い。）

(In the formula, R ¹ , R ² , and X are independent of each other and the same as above, and R ³ is independent of each other, a hydrogen atom, a methyl group, a phenyl group, and an alkenyl group having 2 to 10 carbon atoms. Alternatively, it is a 3-glycidyloxypropyl group, provided that one or more of the ^R2 bonded to the terminal silicon atom is a group represented by -OX'(X'is the same as above). , R ³ bonded to the same silicon atom is not a hydrogen atom. T is 0 or 1, s is an integer from 0 to 300, and s'is s'when t = 0. = 0, and s'= s when t = 1. Q is an integer of 1 or more. The siloxane in [] may have a random structure or a block structure. .)

The condensation reaction of the silicon atom-bonded hydrogen atom of the component (A4), the alkoxy group of the component (A5), and the hydrogen atom directly bonded to silicon proceeds by heat. The blending amount of (A5) with respect to (A4) is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of (A4).

Further, the addition-curable silicone resin composition and the condensation-curable silicone resin composition may be mixed and used. In this case, the component (A2) contained in the addition-curable silicone resin composition and the component (A4) contained in the condensation-curable silicone resin composition both contain hydrogen atoms directly bonded to silicon atoms. If each component is blended together, there is a risk of variation in curing. Therefore, it is possible to further mix the addition-curing composition and the premixed condensation-curing composition. preferable.

-Other additives-
In addition to the above-mentioned components, various additives known per se can be added to the composition in the present invention, if necessary. Examples of the additive include an inorganic filler, a reaction inhibitor, an adhesive aid and the like.

[Inorganic filler]
The thermosetting silicone resin composition which is the component (A) of the present invention may contain an inorganic filler. For example, silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, antimony trioxide, titanium oxide and the like can be mentioned, but silicas are preferable in order to improve transparency. Further, as these inorganic fillers, those surface-treated with a surface treatment agent such as a silane coupling agent may be used, and the wettability between the inorganic filler and the silicone resin and the glass fiber as the core material can be improved. In order to improve it, it is preferable that it is in a slurry state.

The primary average particle size of the inorganic filler is preferably 0.05 to 20 μm, more preferably 0.1 to 1 μm. The primary average particle size of the inorganic filler refers to the median diameter (d50) measured by the laser diffraction / scattering method.

The amount of the inorganic filler added is preferably 0 to 400 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the silicone resin of the component (A). If it is 400 parts by mass or less, it has sufficient strength as a sheet and has good adhesiveness.

[Reaction inhibitor]
A reaction inhibitor can be appropriately added to the composition of the present invention, if necessary. The reaction inhibitor is added for the purpose of suppressing the curing reaction due to hydrosilylation and improving the storage stability. Examples of the reaction inhibitor include vinyl group-rich organopolysiloxanes such as tetramethyltetravinylcyclotetrasiloxane, triallyl isocyanurates, alkylmalates, acetylene alcohols and silane-modified and siloxane-modified products thereof, and hydro. Examples thereof include compounds selected from the group consisting of peroxides, tetramethylethylenediamines, benzotriazoles and mixtures thereof. The reaction inhibitor is usually added in an amount of usually 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).

[Adhesive aid]
An adhesive aid (adhesive-imparting agent) can be added to the composition of the present invention, if necessary, in order to impart adhesiveness. Examples of the adhesion aid include a hydrogen atom (SiH group) bonded to a silicon atom, an alkenyl group bonded to a silicon atom (for example, Si—CH = CH ₂ groups), and an alkoxysilyl group (for example, trimethoxysilyl) in one molecule. Group), a linear or cyclic silicon atom containing at least two, preferably two or three functional groups selected from an epoxy group (eg, glycidoxypropyl group, 3,4-epoxycyclohexylethyl group). Examples thereof include an organosiloxane oligomer having a number of 4 to 50, preferably about 4 to 20, an organooxysilyl-modified isocyanurate compound and / or a hydrolyzed condensate thereof (organosiloxane-modified isocyanurate compound).

<(B) Glass fiber>
The glass fiber in the present invention may be fibrous, cloth-like called glass cloth, chopped strand, non-woven fabric, or wool. Examples of the type of glass include E glass, T glass, NE glass, S glass, quartz and the like, but T glass and quartz having both low line expansion and discoloration resistance are preferable, and quartz is more preferable. Further, it is preferable to use glass cloth as the form of the fiber because it is easy to handle. Examples of the quartz glass cloth include plain weave, satin weave, and twill weave. Plain weave and satin weave are preferable from the viewpoint of uniformity of thickness, and plain weave is more preferable from the viewpoint of thinning. For example, it is made using quartz glass strands and / or quartz glass yarn. The quartz glass strand and / or the quartz glass yarn is a bundle of 50 or more and 500 or less quartz glass fibers. In the present invention, a bundle of fibers without twisting is referred to as a strand, and a bundle of fibers twisted and bundled is referred to as a yarn.

Further, it is preferable that the surface of the glass fiber is treated with a silane coupling agent because the adhesion between the resin and the glass fiber can be improved. Examples of the silane coupling agent include trimethylmethoxysilane, trimethylethoxysilane, phenylmethylvinylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethyldimethoxysilane, and diphenyldimethyldiethoxy. Silane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, naphthylrimethoxysilane, naphthylriethoxysilane, 1,4-bis (methoxydimethylsilyl) Benzene, tetramethoxysilane, tetraethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, vinyltrimethoxysilane, vinyl Triethoxysilane, p-styryltrimethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl dimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldiethoxysilane, N- (N-vinylbenzyl)- 2-Aminoethyl-3-aminopropyltrimethoxysilane and its hydrochloride, N- (N-vinylbenzyl) -2-aminoethyl-3-aminopropylmethyldimethoxysilane and its hydrochloride, 3-Isoxypropyltriethoxysilane , Tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltriethoxysilane, 3-chloroprepyl Examples thereof include alkoxysilane compounds such as trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and bis (trisethoxysilylpropyl) tetrasulfide, which may be used alone or in admixture of two or more. Is also good. Moreover, it is not limited to these.

[Manufacturing method of resin-treated glass substrate (I)]
The method for producing the resin-treated glass substrate is not particularly limited, but a general method for treating glass fiber can be applied. For example, a general glass fiber coating method (coating method) can be exemplified. Typical coating methods include direct gravure coater, chamber doctor coater, offset gravure coater, single roll kiss coater, reverse kiss coater, bar coater, reverse roll coater, slot die, air doctor coater, forward rotation roll coater, and blade. There are coaters, knife coaters, impregnation coaters, MB coaters, MB reverse coaters, etc. Among them, the direct gravure coater, the offset coater, the impregnated coater, and the slot die coating method are preferable for the production of the resin-treated glass substrate of the present invention.

As the coating liquid used in the above coating method, the above-mentioned thermosetting silicone resin composition may be used as it is, or may be diluted with a solvent. As the solvent, organic solvents may be used alone or in combination of two or more, depending on the dissolution characteristics of the curable silicone resin composition. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethylene glycol and propylene glycol, and fats such as hexane and heptane. Examples thereof include group hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and ethers such as diethyl ether, diisopropyl ether and din-butyl ether.

The glass substrate coated with the silicone resin composition by the above coating method may be heated at 80 to 150 ° C. for 1 minute to 4 hours for the purpose of drying after coating and used as a prepreg, or 100 to 300 for the purpose of curing. A resin-treated glass base material cured by heating at ° C. for 1 minute to 24 hours may be used. In either case, a glass fiber-containing wavelength conversion silicone sheet is manufactured by laminating with (II) a wavelength conversion silicone sheet described later or a film molded product thereof, which is an uncured product thereof.

(B) The adhered amount of the curable silicone resin composition on the resin-treated glass substrate is characterized by being 15% by mass or more and 70% by mass or less when the total mass after adhesion is 100% by mass. Within this range, the ratio of the resin composition to the glass fiber is appropriate, which is preferable. If it is less than 15% by mass, the smoothness of the fiber surface cannot be maintained, and even if the phosphor layers are laminated, the wavelength-converted color variation becomes large following the unevenness of the joints of the cloth, which is not preferable. On the other hand, if it exceeds 70% by mass, the amount of resin is large, the volume to be fused of the resin portion increases when the phosphor layers are bonded, and the resin flows, resulting in large color variation, which is not preferable. The amount of adhesion referred to here refers to the mass% of the curable silicone resin composition with respect to the mass of the entire prepreg.

3. 3. Wavelength conversion silicone sheet (II)
The wavelength conversion silicone sheet (II) constituting the present invention serves as a wavelength conversion layer of the glass fiber-containing wavelength conversion silicone sheet. The wavelength conversion silicone sheet is a silicone sheet containing (A) a thermosetting silicone resin composition which is solid or semi-solid at 23 ° C. and (C) a phosphor. In the present invention, (A) a thermosetting silicone resin composition and (C) a phosphor are mixed and molded into a sheet, which may be uncured or cured. The sheet in which the sheet is in an uncured state is particularly referred to as a film molded product. Hereinafter, the constituent components and the manufacturing method will be described in detail.

<(A) Thermosetting silicone resin composition>
(A) As an example of the thermosetting silicone resin composition which is solid or semi-solid at 23 ° C., the same ones as exemplified above can be used. Since the composition of the resin composition is the same as that used in (I), it has excellent affinity when used by laminating and can reduce warpage.

<(C) Fluorescent material>
Both an inorganic fluorescent substance and an organic fluorescent substance can be used as the fluorescent substance of the component (C) contained in the wavelength conversion silicone sheet of the present invention, and a complex-formed organic fluorescent substance is used as the organic fluorescent substance. You can also do it. Inorganic phosphors are preferable from the viewpoint of reliability such as heat resistance of the fluorophore-containing silicone film.

The amount of the fluorescent substance to be blended is preferably 1 to 600 parts by mass, more preferably 10 to 400 parts by mass with respect to 100 parts by mass of the silicone resin (A). If it is 1 part by mass or more, it functions sufficiently as a wavelength conversion sheet, and if it is 600 parts by mass or less, it can be sufficiently adhered to the substrate.

[Inorganic fluorophore]
As the inorganic phosphor, for example, one that absorbs light from a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer and converts the wavelength into light having a different wavelength can be used. Examples of such an inorganic phosphor include a nitride-based phosphor mainly activated by a lanthanoid-based element such as Eu and Ce, an oxynitride-based phosphor; a lanthanoid-based element such as Eu, and a transition metal such as Mn. Alkaline earth metal halogen apatite phosphors, alkaline earth metal boron borate phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earths mainly activated by system elements Metal sulfide phosphors, rare earth sulfide phosphors, alkaline earth metal thiogalate phosphors, alkaline earth metal silicon nitride phosphors, germanate phosphors; rare earth aluminic acid mainly activated by lanthanoid elements such as Ce. Salt phosphors, rare earth silicate phosphors; Ca-Al—Si—ON oxynitride glass phosphors mainly activated by lanthanoid elements such as Eu can be mentioned. These inorganic phosphors may be used alone or in combination of two or more. Specific examples include, but are not limited to, the following inorganic phosphors.

Nitride-based phosphors mainly activated by lanthanoid-based elements such as Eu and Ce include M ₂ Si ₅ N ₈ : Eu, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M is one or more selected from Sr, Ca, Ba, Mg, and Zn) and the like can be exemplified.

As the oxynitride-based phosphor mainly activated by lanthanoid-based elements such as Eu and Ce, MSi ₂ O ₂ N ₂ : Eu (M is one selected from Sr, Ca, Ba, Mg, and Zn). The above) can be exemplified.

Alkaline earth metal halogen apatite phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₅ (PO ₄ ) ₃ X: Z (M is Sr, Ca, Ba). , And one or more selected from Mg, X is one or more selected from F, Cl, Br, and I, and Z is one or more selected from Eu, Mn, and Eu and Mn. Yes) etc. can be exemplified.

Alkaline earth metal borate halogen phosphors that are mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₂ B ₅ O ₉ X: Z (M is Sr, Ca, Ba). , And one or more selected from Mg. X is one or more selected from F, Cl, Br, and I, and Z is one or more selected from Eu, Mn, and Eu and Mn. Yes) etc. can be exemplified.

Alkaline earth metal aluminate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include SrAl ₂ O ₄ : Z, Sr ₄ Al ₁₄ O ₂₅ : Z, CaAl ₂ . O ₄ : Z, BaMg ₂ Al ₁₆ O ₂₇ : Z, BaMg ₂ Al ₁₆ O ₁₂ : Z, BaMgAl ₁₀ O ₁₇ : Z (Z is one or more selected from Eu, Mn, and Eu and Mn). Etc. can be exemplified.

Alkaline earth metal silicate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include (BaMg) Si ₂ O ₅ : Eu, (BaSrCa) ₂ SiO ₄ : Eu. , Etc. can be exemplified.

Examples of the alkaline earth metal sulfide phosphor mainly activated by a lanthanoid element such as Eu and a transition metal element such as Mn include (Ba, Sr, Ca) (Al, Ga) 2S4; Eu and the like. ..

As rare earth sulfide phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn, La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, Gd ₂ O ₂ S: Eu and the like can be exemplified.

Alkaline earth metal thiogallate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include MGa ₂ S ₄ : Eu (M is from Sr, Ca, Ba, Mg, Zn). One or more selected species) can be exemplified.

Examples of the alkaline earth metal silicon nitride phosphor that is mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include (Ca, Sr, Ba) AlSiN3: Eu, (Ca, Sr, Ba) 2Si5N8. : Eu, SrAlSi4N7: Eu and the like can be exemplified.

Examples of the germanate phosphor mainly activated by a lanthanoid element such as Eu and a transition metal element such as Mn include Zn ₂ GeO ₄ : Mn.

Rare earth aluminate phosphors mainly activated by lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce, (Y, Gd) ₃ (Al, Ga) A YAG-based phosphor such as ₅ O ₁₂ can be exemplified. Further, Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is replaced with Tb, Lu, or the like can also be used.

Examples of the rare earth silicate phosphor activated mainly by a lanthanoid element such as Ce include Y ₂ SiO ₅ : Ce, Tb and the like.

Ca-Al-Si-ON-based oxynitride glass phosphor is 20 to 50 mol% in terms of CaCO ₃ in terms of mol%, Al ₂ O ₃ is 0 to 30 mol%, and SiO. 25 to 60 mol%, AlN to 5 to 50 mol%, rare earth oxide or transition metal oxide to be 0.1 to 20 mol%, and oxynitride glass having a total of 5 components of 100 mol% as a base material. It is a phosphor. The nitrogen content of the fluorophore using oxynitride glass as the base material is preferably 15% by mass or less. Further, in addition to the rare earth oxide ion, it is preferable to contain other rare earth element ions serving as a sensitizer in the state of the rare earth oxide, and co-activation in the phosphor with a content in the range of 0.1 to 10 mol%. It is preferably contained as an agent.

Examples of other inorganic phosphors include ZnS: Eu. Examples of the silicate-based fluorophore other than the above include (BaSrMg) ₃ Si ₂ O ₇ : Pb, (BaMgSrZnCa) ₃ Si ₂ O ₇ : Pb, Zn ₂ SiO ₄ : Mn, BaSi ₂ O ₅ : Pb and the like. Be done.

Further, in the above-mentioned inorganic phosphor, one containing one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti in place of Eu or in addition to Eu. Can also be used.

Further, any fluorescent substance other than the above-mentioned inorganic fluorescent substance having the same performance and effect as the above-mentioned one can be used as the component (C) of the present invention.

The properties of the inorganic phosphor are not particularly limited, and for example, powdery ones can be used. The shape of the inorganic phosphor powder is not particularly limited, and specific examples thereof include a spherical shape and a non-spherical shape. The average particle size of the inorganic fluorescent powder is preferably 0.01 to 200 μm, more preferably 0.01 μm to 100 μm. The average particle size can be obtained as the mass average value D ₅₀ (or median diameter) in the particle size distribution measurement by the laser optical diffraction method.

[Organic fluorophore]
As the organic phosphor, for example, an organic phosphor or an organic complex phosphor mainly activated by a lanthanoid element such as Eu can be used, and a 9,10-diarylanthracene derivative, pyrene, coronene, perylene, etc. can be used. , Lubrene, 1,1,4,4-tetraphenylbutadiene, tris (8-quinolinolate) aluminum complex, tris (4-methyl-8-quinolinolate) aluminum complex, bis (8-quinolinolate) zinc complex, tris (4-quinolinolate) Methyl-5-trifluoromethyl-8-quinolinolate) aluminum complex, tris (4-methyl-5-cyano-8-quinolinolate) aluminum complex, bis (2-methyl-5-trifluoromethyl-8-quinolinolate) [4 -(4-Cyanophenyl) phenolate] aluminum complex, bis (2-methyl-5-cyano-8-quinolinolate) [4- (4-cyanophenyl) phenolate] aluminum complex, tris (8-quinolinolate) scandium complex, bis [8- (paratosyl) aminoquinoline] zinc complex and cadmium complex, 1,2,3,4-tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, poly [2,5-diheptyloxy-p-phenylenebinylene] , Cmarin-based phosphors, perylene-based phosphors, pyran-based phosphors, anthron-based phosphors, porphyrin-based phosphors, quinacridone-based phosphors, N, N'-dialkyl-substituted quinacridone-based phosphors, naphthalimide-based phosphors, N , N'-diaryl-substituted pyrolopyrrole-based phosphors, phosphorescent illuminants such as Ir complexes, and the like can be used.

[Manufacturing method of wavelength conversion silicone sheet (II)]
Examples of the method for manufacturing the wavelength conversion silicone sheet include a film coater and a heat press machine. To process the composition into a sheet using these means, for example, the composition is sandwiched between the pressurizing base film and the release film, and is usually 60 to 120 ° C., preferably 70 ° C. using a hot press. Compression molding is performed at a temperature of about 100 ° C. under a pressure of 0.5 to 10 t / cm ² , preferably 1 to 7 t / cm ² , for about 1 to about 30 minutes, preferably 2 to 10 minutes.

Examples of the pressurizing base film include PET film, fluororesin film, polyethylene film, polypropylene film and the like, and examples of the release film include fluororesin-coated PET film, silicone resin-coated PET film, fluororesin film and the like. can give.

Alternatively, it can be manufactured according to a general method for applying a silicone sheet. Typical coating methods include direct gravure coater, chamber doctor coater, offset gravure coater, single roll kiss coater, reverse kiss coater, bar coater, reverse roll coater, slot die, air doctor coater, forward rotation roll coater, and blade. There are coaters, knife coaters, impregnation coaters, MB coaters, MB reverse coaters, etc. Above all, it is preferable to dilute the curable silicone resin composition of the component (A) with a solvent and produce it with a blade coater, a knife coater, an air doctor coater or the like.

This solvent is used to improve and secure the coatability. Due to the dissolving characteristics of the curable silicone resin, an organic solvent can be used alone or in combination of two or more. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol and n-butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethylene glycol and propylene glycol, and fats such as hexane and heptane. Examples thereof include group hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and ethers such as diethyl ether, diisopropyl ether and di-n-butyl ether.

The sheet-shaped phosphor-containing curable silicone resin composition as a wavelength conversion layer produced by the above-mentioned production method is heated at 60 to 150 ° C. for 1 minute to 4 hours for the purpose of drying after coating as a film molded product. It may be used, or it may be used as a wavelength conversion silicone sheet cured by heating at 20 to 300 ° C. for 1 minute to 24 hours for the purpose of curing.

4. Method for Manufacturing Glass Fiber-Containing Wavelength Converting Silicone Sheet The glass fiber-containing wavelength-converting silicone sheet of the present invention comprises the resin-treated glass substrate (I) as a reinforcing layer and the wavelength-converting silicone sheet (II) as a wavelength conversion layer. It is obtained by laminating and. For example, a prepreg made of an uncured product of the curable silicone resin composition or a cured product thereof, and a film molded product made of an uncured product of a phosphor-containing curable silicone resin composition produced by the above-mentioned production method. , Or a cured product thereof is laminated to produce a glass fiber-containing wavelength conversion silicone sheet.

The lamination (bonding) of the resin-treated glass base material (I) (reinforcing layer) and the wavelength conversion silicone sheet (II) (wavelength conversion layer) is not particularly limited, and various methods can be mentioned. Examples include a vacuum laminator, a pressure press, a vacuum press, a roll laminator, a thermal roll laminator, and a multilayer thermal roll laminator. A thermal roll laminator, a vacuum laminator, or a vacuum press is preferable in order to improve the uniformity of thickness and fusion property, and a multilayer thermal roll laminator is preferable in consideration of mass productivity. Examples of the conditions for fusion include a method of heating at 25 ° C. to 200 ° C. for 1 second to 10 hours.

Although the conditions differ depending on the curable resin composition used, for example, a method of heating at room temperature to 200 ° C. for 1 minute to 24 hours can be mentioned. By bonding the prepreg and the film molded product before heat curing and then curing, the reinforcing layer and the wavelength conversion layer can be bonded while maintaining low thermal expansion without using an adhesive. Therefore, it is preferable.

The thickness of the glass fiber-containing wavelength conversion silicone sheet of the present invention is preferably 20 to 500 μm, and the thermal conductivity described in JIS R2616 in a thickness in this range is 0.40 to 10 W / m · K. desirable.
When the thickness is 20 μm or more, it becomes easy to produce a glass fiber-containing wavelength conversion silicone sheet. Further, if the thickness is 500 μm or less, the thickness is sufficient for mounting on an optical semiconductor device as a wavelength conversion layer.
Further, when the thermal conductivity is 0.40 W / m · K or more, heat generation during wavelength conversion is suppressed and abnormalities are less likely to occur in the device. Therefore, when it is 10 W / m · K or less, the silicone content is preferable. It is preferable because the sheet can be produced even with a limited thickness regardless of the low thermal conductivity (0.29 W / m · K).

5. Optical semiconductor device The cured product of the glass fiber-containing wavelength conversion silicone sheet can be used as a resin encapsulating layer of the optical semiconductor device. The semiconductor device to which this cured product is applied is not particularly limited, and examples thereof include LED elements. The cured product of the glass fiber-containing wavelength conversion silicone sheet of the present invention has high thermal conductivity, so that it generates little heat even when it is lit at a high temperature, and has self-adhesiveness and adhesive durability, so that it does not crack or peel. Further, since the reinforcing layer contains glass fiber, the linear expansion coefficient is also low, so that expansion and contraction are small with respect to thermal shock, and there is no cracking or peeling. Further, since the reinforcing layer does not contain the phosphor, the color variation of the phosphor layer due to the phosphor flowing into the joints of the glass fibers is very small (that is, the wavelength conversion uniformity is high). Due to these excellent characteristics of the cured product, the optical semiconductor device of the present invention using the cured product as the resin sealing layer of the optical semiconductor device is excellent in reliability and wavelength conversion uniformity.

Hereinafter, the present invention will be specifically described with reference to synthetic examples, examples and comparative examples, but the present invention is not limited thereto. The measurement conditions for the weight average molecular weight are as described above.

(A) Thermosetting Silicone Resin Composition (A1) Alkenyl Group-Containing Organopolysiloxane: (Melting Point: 80 ° C., Weight Average Molecular Weight: 20,000)
(Me ₂ ViSiO _1/2 ) _0.018 (Me ₂ SiO _2/2 ) _0.662 (MeViSiO _2/2 ) _0.018 (PhSiO _3/2 ) _0.302
(A2) Organohydrogenpolysiloxane: (weight average molecular weight: 10,000)
(MeHSiO _2/2 ) _0.036 ( _{Me2SiO 2/2} ) _0.66 (PhSiO _3/2 ) _0.304
(A3) Curing catalyst: Platinum chloride octyl alcohol solution (concentration as a simple substance of platinum metal: 1% by mass)
(A4) Organopolysiloxane: In Preparation Examples 8 to 11, the organohydrogenpolysiloxane of (A2) above was used as the (A4) organopolysiloxane.
(A5) Condensation accelerator: [HSi (OEt) ₂ ] _0.67 (Ph ₂ SiO) _0.33
(B) Glass fiber (B1) SQF1024C (plain weave quartz cloth, thickness 25 μm, manufactured by Shinetsu Quartz Co., Ltd.)
(B2) SQF2116AC (plain weave quartz cloth, thickness 95 μm, manufactured by Shinetsu Quartz Co., Ltd.)
(B3) SQMBC-00 (Quartz chopped strand, filament diameter 5 μm, aspect ratio 10, manufactured by Shinetsu Quartz Co., Ltd.)
(C) Fluorescent material (C1) NYAG4454L (YAG-based fluorescent material, manufactured by Intematics)
(D) Inorganic filler (inorganic filler)
(D1) CRB-8SE (silica: primary average particle size 10 μm, manufactured by Fumitech Co., Ltd.)
(D2) AEROSIL957L (silica: primary average particle size 0.1 μm, manufactured by Nippon Aerosil Co., Ltd.)
(D3) SO-25H (silica: primary average particle size 0.5 μm, manufactured by Admatex Co., Ltd.)

(Preparation Example 1)
100 g of alkenyl group-containing organopolysiloxane as (A1), 100 g of organohydrogenpolysiloxane as (A2), 0.2 g of octyl alcohol-modified solution of chloroplatic acid (platinum concentration 1% by mass) as (A3), acetylene. A silicone resin composition S1 was prepared by mixing 0.6 g of ethynylcyclohexanol as an alcohol-based reaction inhibitor and 6 g of an adhesion-imparting agent of the following general formula (6) as an adhesion-imparting agent (adhesive aid). The S1 was diluted with toluene to adjust the non-volatile content to 70% to form a varnish, and then the varnish was put into an impregnated bath equipped with two impregnating rolls. After that, the varnish was impregnated with glass fiber (B1), the gap between the impregnated rolls was set to 80 μm, and the varnish was dried at 100 ° C. × 10 minutes to produce a prepreg P1 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 2)
Until the varnish of the silicone resin composition S1 was prepared, the same procedure as in Preparation Example 1 was carried out, impregnated with (B2) instead of the glass fiber (B1), and coated with a gap of 200 μm of the impregnated roll. The prepreg P2 having a length of 150 mm × a width of 150 mm and a thickness of 120 μm was produced by drying under the same conditions. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 3)
The same operation as in Preparation Example 1 was carried out until the silicone resin composition S1 was prepared, and 200 g of glass fiber (B3) was added, mixed and diluted with toluene to make the non-volatile content 70% and made into a varnish, and then automatically. The film was coated with a coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and dried at 100 ° C. × 10 minutes to produce a film molded product F1 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm.

(Preparation Example 4)
100 g of alkenyl group-containing organopolysiloxane as (A1), 100 g of organohydrogenpolysiloxane as (A2), 0.2 g of octyl alcohol-modified solution of platinum chloride acid (platinum concentration 1% by mass) as (A3), acetylene alcohol A silicone resin composition S2 was prepared by mixing 0.6 g of ethynylcyclohexanol as a system reaction inhibitor, 6 g of the adhesive-imparting agent of the above general formula (6) and 200 g of the inorganic filler (D1) as an adhesive-imparting agent. The S2 was diluted with toluene to form a varnish, and the following operations were carried out in the same manner as in Preparation Example 1 to produce a prepreg P3 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 5)
100 g of alkenyl group-containing organopolysiloxane as (A1), 100 g of organohydrogenpolysiloxane as (A2), 0.2 g of octyl alcohol-modified solution of platinum chloride acid (platinum concentration 1% by mass) as (A3), acetylene. A silicone resin composition S3 was prepared by mixing 0.6 g of ethynylcyclohexanol as an alcohol-based reaction inhibitor, 6 g of the adhesive-imparting agent of the general formula (6) and 200 g of the inorganic filler (D2) as an adhesive-imparting agent. The S3 was diluted with toluene to form a varnish, and the following operations were carried out in the same manner as in Preparation Example 1 to produce a prepreg P4 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 6)
100 g of an alkenyl group-containing organopolysiloxane as the (A1), 100 g of an organohydrogenpolysiloxane as the (A2), and 0.2 g of an octyl alcohol-modified solution of platinum chloride acid (platinum concentration 1% by mass) as the (A3). A silicone resin composition S4 was prepared by mixing 0.6 g of ethynylcyclohexanol as an acetylene alcohol-based reaction inhibitor, 6 g of the adhesive-imparting agent of the above general formula (6) and 200 g of an inorganic filler (D3) as an adhesive-imparting agent. The S4 was diluted with toluene to form a varnish, and the following operations were carried out in the same manner as in Preparation Example 1 to produce a prepreg P5 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 7)
100 g of alkenyl group-containing organopolysiloxane as (A1), 100 g of organohydrogenpolysiloxane as (A2), 0.2 g of octyl alcohol-modified solution of chloroplatic acid (platinum concentration 1% by mass) as (A3), acetylene. The silicone resin composition S5 was prepared by mixing 0.6 g of ethynylcyclohexanol as an alcohol-based reaction inhibitor, 6 g of the adhesion-imparting agent of the general formula (6) as an adhesion-imparting agent, and 200 g of the phosphor (C1) as the (C). Prepared. After diluting with toluene to make the non-volatile content 70% and making it into a varnish, it is coated with an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), dried at 100 ° C for 10 minutes, and has a length of 150 mm and a width of 150 mm. , A film molded product F2 having a thickness of 40 μm was produced.

(Preparation Example 8)
As the (A4), 100 g of the organohydrogenpolysiloxane used as the component (A2), 2 g of the condensation accelerator of the component (A5), and 6 g of the adhesion-imparting agent of the general formula (6) as the adhesion-imparting agent are mixed. , Silicone resin composition S6 was prepared. The following was performed in the same manner as in Preparation Example 1 to produce a prepreg P6 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition adhering to the glass fiber at this time was 30% by mass.

(Preparation Example 9)
Until the silicone resin composition S6 is prepared, the same operation as in Preparation Example 8 is carried out, 100 g of glass fiber (B3) is added, mixed and diluted with toluene to make the non-volatile content 70% and made into a varnish, and then automatically. The film was coated with a coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) and dried at 100 ° C. × 10 minutes to produce a film molded product F3 having a length of 150 mm × width of 150 mm and a thickness of 40 μm.

(Preparation Example 10)
As the (A4), 100 g of the organohydrogenpolysiloxane used as the component (A2), 2 g of the condensation accelerator of the component (A5), 6 g of the adhesion-imparting agent of the general formula (6) and an inorganic substance as the adhesion-imparting agent. 100 g of the filler (D1) was mixed to prepare a silicone resin composition S7. The S7 was diluted with toluene to form a varnish, and the following operations were carried out in the same manner as in Preparation Example 1 to produce a prepreg P7 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Preparation Example 11)
As the (A4), 100 g of the organohydrogenpolysiloxane used as the component (A2), 2 g of the condensation accelerator of the component (A5), 6 g of the adhesive-imparting agent of the general formula (6) and the above-mentioned adhesive-imparting agent. As (C), 100 g of the phosphor (C1) was mixed to prepare a silicone resin composition S8. After diluting with toluene to make the non-volatile content 70% and making it into a varnish, it is coated with an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.), dried at 100 ° C for 10 minutes, and has a length of 150 mm and a width of 150 mm. , A film molded product F4 having a thickness of 40 μm was produced.

(Comparative Preparation Example 1)
Until the silicone resin composition S1 is prepared, the same operation as in Preparation Example 1 is performed, and a film molding having an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) having a length of 150 mm × width of 150 mm and a thickness of 40 μm is performed. The thing F5 was manufactured.

(Comparative Preparation Example 2)
Until the silicone resin composition S2 is prepared, the same operation as in Preparation Example 4 is performed, and a film molding having an automatic coating device PI-1210 (manufactured by Tester Sangyo Co., Ltd.) having a length of 150 mm × width of 150 mm and a thickness of 40 μm is performed. The thing F6 was manufactured.

(Comparative Preparation Example 3)
The same operation as in Preparation Example 7 was carried out until the silicone resin composition S5 was diluted to a non-volatile content of 70% to form a varnish, and the mixture was placed in an impregnated bath with two impregnated rolls. After that, the varnish was impregnated with glass fiber (B1), the gap between the impregnated rolls was set to 80 μm, and the varnish was dried at 100 ° C. × 10 minutes to produce a prepreg P8 having a length of 150 mm × a width of 150 mm and a thickness of 40 μm. The amount of the resin composition attached to the glass fiber at this time was 30% by mass.

(Comparative Preparation Example 4)
The same operation as in Preparation Example 1 was carried out except that the gap between the impregnated rolls was set to 30 μm, to produce a prepreg P9 having a length of 150 mm × a width of 150 mm and a thickness of 30 μm. The amount of the resin composition attached to the glass fiber at this time was 10% by mass.

(Comparative Preparation Example 5)
The same operation as in Preparation Example 1 was carried out except that the gap between the impregnated rolls was set to 150 μm, to produce a prepreg P10 having a length of 150 mm × a width of 150 mm and a thickness of 90 μm. The amount of the resin composition attached to the glass fiber at this time was 80% by mass.

(Comparative Preparation Example 6)
The same operation as in Preparation Example 1 was carried out except that LPS-3421 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 9 Pa · s), which is a liquid addition-curable polysiloxane composition, was used as the component (A). However, since the dripping was severe at the time of coating and the adhesiveness was strong even after drying, it was difficult to cut out into a sheet, so further evaluation was not performed.

＊：調製例８～１１については、（Ａ４）成分として用いたオルガノハイドロジェンポリシロキサンの配合量である。

Tables 1A and 1B show the blending amounts of each component used in the preparation examples and the comparative preparation examples. The unit of the components (A), (C) and (D) in the table is "g".

*: Preparation Examples 8 to 11 are the blending amount of the organohydrogenpolysiloxane used as the component (A4).

[Examples and Comparative Examples]
As shown in Tables 2A and 2B, the reinforcing layer and the fluorescent material layer prepared in the preparation example and the comparative preparation example were bonded together at a roll temperature of 80 ° C. using a thermal laminator. The following physical properties and characteristics were measured for the laminated laminated sheets. Examples 1 to 13 are the glass fiber-containing wavelength conversion silicone sheets of the present invention, and have a two-layer structure (Examples 1, 3 to 8, 10, 11) shown in FIG. 1 or a three-layer structure shown in FIG. It is the one of Examples 2 and 9), or the one in which the laminated structural units shown in FIG. 1 are repeatedly laminated a plurality of times (Examples 12 and 13). On the other hand, in Comparative Examples 1 to 4, the reinforcing layer did not contain glass fiber, in Comparative Examples 5 to 8, the amount of the resin composition adhered to the reinforcing layer was out of the range of the present invention, and in Comparative Example 10, the reinforcing layer was only glass fiber. In Comparative Example 9, the reinforcing layer contained a phosphor.

<Line expansion coefficient (TMA)>
In a laminated sheet of 0.08 to 0.5 mm, heat and cure at 150 ° C. for 4 hours to prepare a test piece of 5 mm × 4 cm, and increase the linear expansion coefficient in the XY directions by the TMA method at a temperature rise rate of 5 ° C./. The temperature range was measured in minutes from −100 ° C. to 200 ° C., and the linear expansion coefficient of −50 ° C. to 0 ° C. was measured.

<Thermal conductivity>
It was cured by heating at 150 ° C. for 4 hours, and the thermal conductivity of each laminated sheet was measured using a thermal conductivity measuring device (QTM-500, manufactured by Kyoto Electronics).

<Making CSP>
The uncured wavelength conversion sheet was die-attached to a CSP (Chip Size Package) substrate on which an LED chip using an InGaN semiconductor having a main emission peak of 460 nm was mounted, and heated at 150 ° C. for 4 hours to be cured. .. Then, dicing was performed to 5 mm × 5 mm to obtain a CSP having a thickness of 300 μm.

<Saturation coordinate evaluation>
50 of each of the manufactured optical semiconductor devices (CSPs) were turned on, and the variation in chromaticity coordinates was measured by an LED optical characteristic monitor (LE-3400) manufactured by Otsuka Electronics to obtain an average value. The standard deviations of u'and v'are indicated by Δu'and Δv', respectively.
(Note: u', v': CIE1976 chromaticity coordinates. According to the method described in JIS Z 8726: 1990.)

<Thermal impact test>
Each of the 20 optical semiconductor devices (CSPs) produced was subjected to a thermal shock test at −40 ° C. to 120 ° C. for 2,000 cycles, and the number of cracks and peelings was confirmed.

<High temperature lighting test>
Twenty of each of the manufactured optical semiconductor devices (CSPs) were subjected to a high-temperature lighting test at 120 ° C./200 mA for 1,000 hours, and the number of cracks and peelings was confirmed.

As shown in Tables 2A and 2B, a two-layer structure in which a reinforcing layer and a phosphor layer are laminated (Examples 1, 3 to 8, 10, 11: see FIG. 1), or a reinforcing layer is sandwiched between them. The glass fiber-containing wavelength conversion silicone sheet of the present invention having a three-layer structure in which two phosphor layers are laminated (Examples 2 and 9: see FIG. 2) has high thermal conductivity, so that heat generation in a high-temperature lighting test is generated. There are few cracks and peeling because it has self-adhesiveness and adhesive durability. Further, since the reinforcing layer contains the glass fiber, the linear expansion coefficient is low, so that it is possible to provide a highly reliable optical semiconductor device having less expansion and contraction in the thermal shock test and no cracks or peeling. Further, the present invention provides an optical semiconductor device in which the color variation of the phosphor layer due to the phosphor flowing into the joints of the glass fibers is very small (that is, the wavelength conversion uniformity is high) because the reinforcing layer does not contain the phosphor. be able to. Even if the unit having the above two-layer structure is repeatedly laminated a plurality of times to increase the thickness of the silicone sheet, high reliability without cracks and peeling and high wavelength conversion uniformity can be maintained and compatible (Example 12, Example 12). 13) It is possible to easily produce a silicone sheet having a thickness sufficient for mounting on an optical semiconductor device as a wavelength conversion layer and having excellent characteristics as described above.

On the other hand, in Comparative Examples 1 to 4 in which the reinforcing layer does not contain glass fiber, the linear expansion coefficient of the reinforcing layer is not lowered, so that the expansion and contraction in the thermal impact test are large, cracks and peeling occur, and the reliability is increased. Inferior to. In Comparative Examples 5, 6 and 10 in which the amount of the curable silicone resin composition adhered to the resin-treated glass substrate is less than 15% by mass when the total mass after adhesion is 100% by mass, the wavelength-converted color is used. The variation becomes large because it follows the unevenness of the glass fiber, and in Comparative Examples 7 and 8 in which it exceeds 70% by mass, the amount of resin is large and the resin portion is fused when the phosphor layers are bonded. As the volume increases and the resin flows, the color variation becomes large. In Comparative Example 9 in which the reinforcing layer contains the phosphor, the phosphor flows into the joints of the glass fibers, so that the color variation of the phosphor layer becomes large (that is, the wavelength conversion uniformity is low).

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and the present invention can be anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same function and effect. Is included in the technical scope of.

1 ... Glass fiber-containing wavelength conversion silicone sheet, 2 ... Resin-treated glass substrate,
3 ... Wavelength conversion silicone sheet, 4 ... Core material, 5 ... Thermosetting silicone resin composition.

Claims (8)

It is a glass fiber-containing wavelength conversion silicone sheet.
The glass fiber-containing wavelength conversion silicone sheet is obtained by laminating a resin-treated glass base material (I) and a wavelength conversion silicone sheet (II).
The resin-treated glass substrate (I) has a glass fiber as a core material, contains an organosiloxane compound having at least one aryl group in one molecule, and is plastic solid or semi-solid at 23 ° C. The thermosetting silicone resin composition is attached to the glass fiber, and the attached resin composition is 15 to 70% by mass when the total mass after attachment is 100% by mass. ,
The wavelength conversion silicone sheet (II) contains the thermosetting silicone resin composition and a phosphor, and
The resin-treated glass substrate (I) and the wavelength-converting silicone sheet (II) are each laminated with at least one layer .
(I) The resin-treated glass base material (I) and the wavelength conversion silicone sheet (II) are laminated in a two-layer structure.
(Ii) The laminated structural unit having the two-layer structure is repeatedly laminated a plurality of times, or
(Iii) A glass fiber-containing wavelength conversion silicone sheet, wherein two wavelength conversion silicone sheets (II) are laminated in a three-layer structure so as to sandwich the resin-treated glass substrate (I) . The glass fiber-containing product according to claim 1, wherein the heat-curable silicone resin composition in the resin-treated glass substrate (I) and the wavelength-converted silicone sheet (II) is both uncured. Wavelength conversion silicone sheet. The glass fiber-containing wavelength conversion silicone sheet according to claim 1 or 2, wherein the glass fiber is at least one selected from glass cloth, glass non-woven fabric, glass wool or glass chopped strand. The glass fiber-containing wavelength conversion silicone sheet according to claim 3, wherein the glass fiber is a quartz glass cloth. The glass fiber-containing wavelength conversion silicone sheet according to any one of claims 1 to 4, wherein the surface of the glass fiber is treated with a silane coupling agent. The glass fiber-containing wavelength conversion silicone sheet according to any one of claims 1 to 5, wherein the thermosetting silicone resin composition further contains an inorganic filler. The glass fiber-containing wavelength conversion silicone sheet according to claim 6, wherein the primary average particle size of the inorganic filler is 0.05 to 20 μm by a laser diffraction / scattering method. An optical semiconductor device comprising a resin encapsulating layer made of a cured product of the glass fiber-containing wavelength conversion silicone sheet according to any one of claims 1 to 7.

Images