JP6720470B2 - Method for producing phosphor-containing silicone sheet - Google Patents

Description

The present invention relates to a silicone sheet containing a phosphor, which can be suitably used for a light emitting device that emits white or other colors by wavelength-converting part or all of the light emitted from a light emitting diode (LED), and particularly, The present invention relates to a phosphor-containing silicone sheet which has excellent brightness and utilization efficiency of the phosphor by having an uneven portion on the sheet.
The present invention also relates to a light emitting device including a phosphor-containing silicone sheet.

Taking advantage of the features of high brightness, high luminous efficiency, low power consumption, and long life, LEDs make use of numeric keypad lighting and backlights for mobile phones, liquid crystal display backlights, car headlights,
Widely used for vehicle lighting and general lighting applications.

In order to obtain white light for a backlight of a liquid crystal display or general illumination using an LED, it is necessary to use a combination of an LED chip and a phosphor that converts the wavelength of the emitted light of the LED, which is suitable for the emission wavelength. .. For example, in a blue LED, a combination of a yellow phosphor and a combination of red and green phosphors has been performed in order to further enhance the color rendering of light. Further, in order to further improve color rendering properties, near-ultraviolet LEDs are combined with red, green, and blue phosphors.

Conventionally, as a method of arranging a phosphor on an LED, a lead frame package (Pkg) or a chip-on-board (COB) substrate has been previously prepared with an encapsulating resin (epoxy resin, silicone resin, etc.) for encapsulating the LED. A method has been adopted in which a fixed amount of phosphor is added, kneaded, and sealed with a dispenser. However, according to this method, the content of the fluorescent material is likely to vary within the sealing portion, and when the white LED light emitting device is used, variation in emission color between devices is a problem.

Therefore, in recent years, a method has been used in which a molded body containing a phosphor is prepared in advance as a wavelength conversion member, and this member is mounted on an LED element. Specifically, a resin composition obtained by adding a predetermined amount of a phosphor to a thermoplastic resin or a thermosetting resin in advance and kneading the resin composition is molded into a sheet or a cap, and is placed in Pkg or COB directly or through a space. Is the way. With this method, it is possible to obtain white light with less variation in phosphor content and less variation in chromaticity. Further, the phosphor arrangement portion can be separated from the LED, and the deterioration of the characteristics of the phosphor due to heat generation of the LED can be prevented.

In the phosphor-containing sheet used in this method, a silicone resin having high heat resistance and high light resistance has come to be used as a resin serving as a sheet base material with an increase in brightness of LEDs.
Generally, when curing a silicone resin, a crosslinking method by heating is used. For example, Patent Document 1 proposes a sheet obtained by dispersing a phosphor in a silicone elastomer and crosslinking it by heat.
Further, Patent Document 2 proposes to coat the surface of the phosphor in order to suppress the curing failure of the silicone resin composition containing the sulfide phosphor, however, it includes a phosphor-containing molded body using a silicone resin. In the light emitting device, there are problems to be improved such as (1) suppressing total reflection and increasing total luminous flux (brightness), and (2) increasing utilization efficiency of expensive phosphor. ..

Japanese Patent No. 4937966 International Publication No. 2013/021990

Therefore, an object of the present invention is to provide a silicone sheet containing a phosphor, which is preferably used in a light emitting device that emits white or other colors by wavelength conversion of a part or all of the light emitted from an LED, and the brightness as described above. It is an object of the present invention to provide a phosphor-containing silicone sheet and a light-emitting device including the phosphor-containing silicone sheet, which can solve the problems of increasing the thickness and increasing the utilization efficiency of the phosphor.

As a result of intensive studies to solve the above problems, the present inventors solve the conventional problems by providing at least one surface irregularity portion on a sheet formed by mixing a polyorganosiloxane with a phosphor. I found that I can.
The present invention has been achieved based on such findings, and the gist is as follows.

[1] A sheet containing an organosiloxane and a phosphor is molded in a state of being sandwiched between two cover sheets having an average surface roughness (Ra) of 0.10 to 10 μm, and the obtained laminated sheet is crosslinked. A method for producing a phosphor-containing silicone sheet , characterized in that, after curing, the cover sheet is peeled off , and at least one surface has an uneven portion having the following feature (1) .
(1) Average surface roughness (Ra) is 0.30 to 10 μm

[2] The method for producing a phosphor-containing silicone sheet according to [1], wherein the phosphor-containing silicone sheet has a thickness of 3 μm to 1000 μm.

[3] The method for producing a phosphor-containing silicone sheet according to [1] or [2], wherein the laminated sheet is a three- layer laminated sheet of cover sheet/phosphor-containing silicone sheet/cover sheet.

[4] The method for producing a phosphor-containing silicone sheet according to [1] or [2], wherein the laminated sheet includes an adhesive or pressure-sensitive adhesive sheet between the phosphor-containing silicone sheet and the cover sheet.

[5] The method for producing a phosphor-containing silicone sheet according to any one of [1] to [4], wherein the cover sheet is PET.

[6] The method for producing a phosphor-containing silicone sheet according to [5], wherein the cover sheet has a thickness of 5 to 500 μm.

[7] The method for producing a phosphor-containing silicone sheet according to any one of [1] to [6], wherein the cover sheet is obtained by a blast method.

[8] The method for producing a phosphor-containing silicone sheet according to any one of [1] to [6], wherein the cover sheet is obtained by a chemical method.

[9] The method for producing a phosphor-containing silicone sheet according to any one of [1] to [8], wherein the organosiloxane is a millable polyorganosiloxane.

According to the present invention, it is possible to manufacture a phosphor-containing silicone sheet having increased brightness and increased utilization efficiency of the phosphor as compared with the conventional case.

1 is a cross-sectional view showing an example of an embodiment of a phosphor-containing silicone sheet with a protective sheet and a protective sheet/phosphor-containing silicone sheet with an adhesive or pressure-sensitive adhesive sheet of the present invention. It is a typical sectional view showing an example of a Pkg type light emitting device. It is a typical sectional view showing an example of a COB type light emitting device. It is a schematic diagram which shows an example of the manufacturing method of the light-emitting device of this invention. It is a schematic diagram which shows the other example of the manufacturing method of the light-emitting device of this invention.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments unless the gist thereof is exceeded.

In the present invention, when expressed as “X to Y” (X and Y are arbitrary numbers), the meaning is “X or more and Y or less”, “preferably larger than X” and “preferably more than Y” unless otherwise specified. "Small" is included. Further, in the present invention, when expressed as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and “Y or less” (
When Y is expressed as an arbitrary number, it means "preferably smaller than Y" unless otherwise specified.

The phosphor-containing silicone sheet of the present invention is characterized in that a concavo-convex portion is provided on at least one surface of a pre-crosslinking sheet containing polyorganosiloxane and a phosphor (hereinafter, simply referred to as “pre-crosslinking sheet”). More specifically, first, a phosphor-containing polyorganosiloxane composition (hereinafter sometimes referred to as “sheet composition”) containing a polyorganosiloxane and a phosphor is prepared, and this sheet is prepared. When the composition for a sheet is formed into a sheet, the composition is formed by being sandwiched between two cover sheets, and the cover sheet is peeled off.

[Explanation of terms]
Generally, "sheet" means a flat product whose thickness is small in terms of length and width according to the definition in JIS, and "film" is generally thicker than length and width. Is a thin flat product with a very small thickness and an arbitrarily limited maximum thickness, which is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900). In terms of thickness, in the narrow sense, a film having a thickness of 100 μm or more may be referred to as a sheet, and a film having a thickness of less than 100 μm may be referred to as a film. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish between the two in the present invention in terms of the wording, in the present invention, the term “sheet” is included even when the term “film” is included, and is referred to as “sheet”. Even in this case, "film" is included.

[Polyorganosiloxane]
The polyorganosiloxane used in the present invention has a siloxane skeleton represented by the following formula (1) and can cause a crosslinking reaction by radiation.

In the formula (1), n is an integer of 2 or more, R is a hydrogen atom, an oxetanyl group, an alkyl group such as a methyl group or an ethyl group, a hydrocarbon group such as a vinyl group or a phenyl group, or a fluoroalkyl group. It is a halogen-substituted hydrocarbon group. The plurality of Rs may be the same as or different from each other. Specifically, polydialkylsiloxanes such as polydimethylsiloxane in which all Rs in the formula (1) are alkyl groups such as methyl groups, or a part of the methyl groups of polydimethylsiloxane are hydrocarbon groups or halogen-substituted carbons. Examples include various polyorganosiloxanes substituted with one kind or two or more kinds such as a hydrogen group. Among these, many polyorganosiloxanes having a crosslinkable group such as carbon-carbon unsaturated bond (particularly vinyl group), silicon-hydrogen bond, and oxetanyl group in the molecule are commercially available, but they do not have a crosslinkable group. It may be a non-polyorganosiloxane. In the present invention, one kind of these polyorganosiloxanes may be used alone, or two or more kinds may be mixed and used.

The molecular weight of the polyorganosiloxane used in the present invention is usually 10,000 to 700,000, and a low molecular weight one called silicone oil can be used according to the classification. However, when the molecular weight of polyorganosiloxane is small (for example, liquid silicone), when the fluorescent substance is kneaded with the polyorganosiloxane, the fluorescent substance precipitates and the content may vary within the sheet when it is formed into a sheet. Therefore, it is preferable to use a millable polyorganosiloxane having a molecular weight of about 400,000 to 700,000, which has a somewhat high viscosity before uncrosslinking and has a molecular weight.

[Phosphor]
The type of the phosphor used in the present invention is appropriately selected, but it is preferably an inorganic phosphor, and as the red (orange), green, blue, and yellow phosphors, the following are typical phosphors. Can be mentioned.
The phosphors may be used alone or in combination of two or more. By using two or more kinds of phosphors, the color temperature can be lowered and the color rendering properties can be improved.

In particular, in order to effectively obtain the effect of preventing deterioration of the phosphor due to moisture in the atmosphere by enabling the application of the cover sheet described below by performing radiation crosslinking, as the phosphor used in the present invention, moisture Examples of such a phosphor include phosphors that are easily deteriorated by the following, and among such phosphors illustrated below, phosphors that contain an alkaline earth metal and that easily form an alkaline earth metal carbonate due to moisture (specifically, Specifically, the phosphor described in JP-A 2007-314626) or a phosphor containing sulfur and easily generating hydrogen sulfide gas due to humidity (specifically, described in WO 2013/021990). Fluorescent substance) and the like.

<Red phosphor>
The emission peak wavelength of the red phosphor is usually 565 nm or more, preferably 575 nm or more, more preferably 580 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. ..

The full width at half maximum of the emission peak of the red phosphor is usually in the range of 1 nm to 120 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. It is preferably 30 μm or less, more preferably 20 μm or less.

As such a red phosphor, for example, CaAlSiN ₃ :Eu (hereinafter, may be abbreviated as “CASN”) described in JP-A-2006-008721 and JP-A-2008-7751 are described. has been is (Sr, Ca) AlSiN3: Eu , JP _Ca 1 _-xAl disclosed in 2007-231245 JP _{1 -xSi 1 + xN 3 -xOx:} Eu -activated oxide such as Eu, nitride or acid It is also possible to use a nitride phosphor or the like, or JP 2008-38081 A (Sr, Ba, Ca) ₃ SiO ₅ :Eu (hereinafter sometimes abbreviated as “SBS phosphor”).

Among the above, as the red phosphor, a phosphor having high wavelength conversion efficiency even at high temperature is preferable, and CASN phosphor, SCASN phosphor, CASON phosphor, and SBS phosphor are preferable.
Any one of the red phosphors exemplified above may be used, or two or more thereof may be used in any combination and ratio.

<Green phosphor>
The emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 540 nm or less, further preferably 535 nm or less. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and in either case, the characteristics as green light may deteriorate.

The full width at half maximum of the emission peak of the green phosphor is usually in the range of 1 nm to 80 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. It is preferably 30 μm or less, more preferably 20 μm or less.

As such a green phosphor, for example, (Ba,Ca,Sr,Mg) ₂ SiO ₄ :Eu (hereinafter, may be abbreviated as “BSS phosphor”) described in International Publication WO2007-091687. ). Eu-activated alkaline earth silicate-based phosphors represented by.

In addition, as the green phosphor, for example, Si _6- zAlzN ₈ -zOz:Eu (where 0<z≦4.2. In the following, “β-SiAlON” is described in Japanese Patent No. 3921545. . sometimes abbreviated as phosphor ") phosphor and Eu Tsukekatsusan nitride such, WO WO2007-088966 No. are described in _{M 3 Si 6 O 12 N 2} : Eu ( where, M is represents an alkaline earth metal element. hereinafter sometimes abbreviated as "BSON phosphor".) Eu Tsukekatsusan nitride phosphor such as and, BaMgAl ₁₀ O as described in JP-a-2008-274254 It is also possible to use ₁₇ :Eu,Mn activated aluminate phosphor (hereinafter sometimes abbreviated as “GBAM phosphor”).

Among the above, BSS phosphor, β-SiAlON phosphor, and BSON phosphor are preferable as the green phosphor. Further, a phosphor having a high wavelength conversion efficiency even at a high temperature is preferable, and as such a phosphor, a Ce-activated aluminate phosphor such as Lu ₃ Al ₅ O ₁₂ :Ce or a β-SiAlON phosphor is preferable.
Any one of the green phosphors exemplified above may be used, or two or more thereof may be used in any combination and ratio.

<Blue phosphor>
The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more and usually less than 500 nm, preferably 490 nm or less, more preferably 480 nm or less, further preferably 470 nm or less, particularly preferably 460 nm. The wavelength ranges are as follows.

The full width at half maximum of the emission peak of the blue phosphor is usually in the range of 10 nm to 100 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. It is preferably 30 μm or less, more preferably 20 μm or less.

Examples of such a blue phosphor include a europium-activated calcium halophosphate-based phosphor represented by (Ca,Sr,Ba) ₅ (PO ₄ ) ₃ Cl:Eu, (Ca,Sr,Ba) ₂ B ₅ O Europium-activated alkaline earth chloroborate-based phosphor represented by ₉ Cl:Eu, (Sr,Ca,Ba)Al ₂ O ₄ :Eu or (Sr,Ca,Ba) ₄ Al ₁₄ O ₂₅ :Eu The europium-activated alkaline earth aluminate-based phosphors and the like that can be mentioned.

Any one of the blue phosphors exemplified above may be used, or two or more thereof may be used in any combination and ratio.

<Yellow phosphor>
The emission peak wavelength of the yellow phosphor is usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less.

The full width at half maximum of the emission peak of the yellow phosphor is usually in the range of 80 nm to 130 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. It is preferably 30 μm or less, more preferably 20 μm or less.

Examples of such a yellow phosphor include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, RE ₃ M ₅ O ₁₂ :Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc). And at least one element selected from the group consisting of: Ma ₃ Mb ₂ Mc ₃ O ₁₂ :Ce (wherein Ma is a divalent metal element, Mb is a trivalent metal element, and Mc is a tetravalent metal). garnet phosphor having a garnet structure represented by the representative of the metal element) or the _{like, AE 2 MdO 4:. Eu} ( where, AE is selected Ba, Sr, Ca, Mg, and from the group consisting of Zn An orthosilicate-based phosphor represented by at least one kind of element, Md represents Si and/or Ge, etc., and a part of oxygen of the constituent elements of the phosphor of these systems is replaced with nitrogen. And a CaAlSiN ₃ structure such as AEAlSiN ₃ :Ce (where AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg and Zn). A phosphor obtained by activating a nitride phosphor with Ce, La ₃ Si ₆ N ₁₁ :Ce, Ca _1.5 xLa ₃ -xSi ₆ N ₁₁ :Ce (where x is 0≦x≦1), etc. Examples of the phosphor include a lanthanum silicon nitride crystal as a matrix.

Among these, the garnet-based phosphor is preferably used, and among them, Y ₃ Al ₅ O ₁₂ :Ce (hereinafter sometimes abbreviated as “YAG”) is particularly preferably used.
Further, a phosphor having a high wavelength conversion efficiency even at a high temperature is preferable, and as such a phosphor, La ₃ Si ₆ N ₁₁ :Ce, Ca _1.5 xLa ₃ -xSi ₆ N ₁₁ :Ce (where x is 0 A phosphor having a lanthanum silicon nitride crystal as a host (hereinafter, may be abbreviated as “LSN”) such as ≦x≦1 is preferable.

The yellow phosphors exemplified above may be used alone or in any combination of two or more at any ratio.

<Average particle size>
The average particle size of the phosphor used in the present invention is preferably 5 μm or more, more preferably 8 μm or more. By setting the average particle diameter of the phosphor to be the above lower limit or more, it is possible to suppress a decrease in wavelength conversion efficiency when the wavelength conversion member is used. The average particle size of the phosphor is preferably 30 μm or less, and more preferably 20 μm or less. When the average particle diameter of the phosphor is not more than the above upper limit, the phosphor particles do not aggregate, and coating unevenness and clogging of a dispenser are less likely to occur, which is preferable.
Here, the average particle diameter is an average particle diameter of primary particles and is a value measured by a laser granulometer.

<Surface treatment>
The phosphor used in the present invention may be surface-treated.
As the surface treatment agent, siloxane compounds such as polydimethylsiloxane and methylhydrogenpolysiloxane, alkyltrimethoxysilane such as methyltrimethoxysilane and ethyltrimethoxysilane, silane compounds such as dialkyldimethoxysilane and glycidyltrimethoxysilane, and titanate. A coupling agent or the like can be preferably used. Of these, alkyltrimethoxysilanes such as methylhydrogenpolysiloxane, methyltrimethoxysilane, and ethyltrimethoxysilane are particularly preferable, and methylhydrogenpolysiloxane is most preferable. These can be used singly or in combination of two or more, and can enhance the transparency of the obtained phosphor-containing silicone sheet and prevent coloring.

<Content>
Regarding the content of the phosphor, the content of the phosphor in the composition for a sheet, that is, the content of the sheet before crosslinking is 100 parts by weight of polyorganosiloxane. 0.2 parts by weight or more is preferable, 0.5 parts by weight or more is more preferable, and 1 part by weight or more is most preferable. On the other hand, the upper limit of the phosphor content is usually 80 parts by weight or less based on 100 parts by weight of polyorganosiloxane, preferably 75 parts by weight or less, and more preferably 67 parts by weight or less. Within this range, the thickness of the sheet composition when formed into a sheet is likely to be in an appropriate range, and variation in chromaticity of the white LED light-emitting device using this sheet can be suppressed.

[silica]
The composition for a sheet according to the present invention contains 5 to 100 parts by mass, preferably 10 to 50 parts by mass, and more preferably 20 to 30 parts by mass of silica with respect to 100 parts by mass of polyorganosiloxane. Good. By containing silica in such a range, not only the mechanical properties of the obtained crosslinked sheet but also the light diffusion property and gas barrier property of the LED can be further improved.

[Inorganic filler]
The composition for a sheet according to the present invention may contain an inorganic filler in order to improve light diffusivity, thermal conductivity, gas barrier properties and mechanical properties. Examples of the inorganic filler include talc, mica, mica, glass flakes, boron nitride (BN), calcium carbonate, aluminum hydroxide, silica, titanates (potassium titanate, etc.), barium sulfate, alumina, kaolin, clay, Examples thereof include titanium oxide, zinc oxide, zinc sulfide, lead titanate, zircon oxide, antimony oxide and magnesium oxide. These may be added alone or in combination of two or more.

For the inorganic filler, in order to improve the dispersibility in polyorganosiloxane, the surface of the inorganic filler is treated with a silicone compound, a polyhydric alcohol compound, an amine compound, a fatty acid, a fatty acid ester, or the like. Good. Among them, those treated with a silicone compound (siloxane, silane coupling agent, etc.) can be preferably used.

The particle size of the inorganic filler is preferably 0.05 μm or more and 100 μm or less, more preferably 0.1 μm or more and 50 μm or less, and further preferably 0.05 μm or more and 15 μm or less. When the particle size of the inorganic filler is 0.05 μm or more and 15 μm or less, dispersibility in polyorganosiloxane can be maintained and a homogeneous sheet can be obtained.

The content of the inorganic filler in the composition for a sheet is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, with respect to 100 parts by mass of polyorganosiloxane. Further, it is preferably 1 to 20 parts by mass. By setting the content of the inorganic filler within the above range, the dispersibility in the polyorganosiloxane can be maintained, and a homogeneous sheet can be obtained even if the thickness of the obtained crosslinked sheet is thin.

[Other additives]
In the composition for a sheet according to the present invention, polyorganosiloxane, phosphor, silica, resins other than inorganic fillers and various additives, for example, heat stabilizers and ultraviolet absorbers, to the extent that the properties are not impaired. , Light stabilizers, nucleating agents, coloring agents, lubricants, flame retardants and the like may be appropriately mixed.
In the present invention, since the polyorganosiloxane is cross-linked by radiation, a cross-linking agent is not required, but if necessary, the cross-linking agent is contained in the sheet composition in an amount of 5% by mass or less. It may be. Examples of the cross-linking agent include peroxides (for example, benzoyl peroxide) and hydrogenorganosiloxane (catalyst of platinum compound).

[Method for preparing sheet composition]
The method for preparing the sheet composition containing the polyorganosiloxane and the phosphor is not particularly limited, and a known method can be used. For example, a polyorganosiloxane, a phosphor, and a method of mixing silica, an inorganic filler and other additives to be blended as necessary, and mechanically blending using a kneader or an extruder, a phosphor, Separately prepare a master batch of polyorganosiloxane containing other compounding materials at a high concentration, mix this with the rest of the polyorganosiloxane and other compounding materials by adjusting the concentration, and then use a kneader or extruder. And a method of mechanically blending.

[Cover sheet]
When the phosphor-containing silicone sheet of the present invention is produced, the pre-crosslinking sheet is molded between two cover sheets to form a three-layer laminated sheet, and the three-layer laminated sheet is irradiated with radiation. Crosslinking and curing are preferable in terms of fixing and maintaining the shape of the sheet before crosslinking and preventing deterioration of the phosphor in the sheet due to moisture in the atmosphere during crosslinking. Further, the productivity can be improved by forming the pre-crosslinking sheet between the two cover sheets and subjecting it to radiation irradiation as it is.
As will be described later, the phosphor-containing silicone sheet of the present invention has irregularities on the surface, but the degree of surface irregularity of the cover sheet used to impart the irregularities of the silicone sheet is the average surface roughness (Ra). Is preferably about 0.10 to 10 μm, more preferably about 0.30 to 5 μm, and particularly preferably 0.50 to 1 μm. When Ra is less than 0.10 μm, it becomes difficult to form surface irregularities on the phosphor-containing silicone sheet, which is not preferable. When Ra exceeds 10 μm, the composition composed of polyorganosiloxane and the phosphor does not enter into the concave portion of the cover sheet when the sheet is sandwiched between the cover sheets to be molded into a three-layer laminated sheet, so that unevenness is satisfactorily formed. It is not preferable because it may not be formed.
As a method of forming the surface irregularities of the cover sheet, a conventionally known blast method or a chemical method can be used.

As the cover sheet, the shape of the sheet before cross-linking is fixed, radiation cross-linking is performed as it is, the sheet after cross-linking is protected from external force and contamination, and the handling property during transportation, winding, storage, and further sheet use It is preferable to use those which are non-adhesive (the sheets do not stick to each other), have high strength, and have the property of not impairing the practically required physical properties under crosslinking conditions.

It is also necessary that this cover sheet does not absorb radiation. However, when γ-rays are used as the radiation, there is no problem in practical use because the transparency is high.

The surface characteristics of the cover sheet, particularly the characteristics of the surface in contact with the pre-crosslinking sheet, can be set according to the purpose. For example, when the cover sheet is used after peeling from the crosslinked sheet after crosslinking, a material that is not adhesive to the polyorganosiloxane before crosslinking and is easily peeled off is selected. Specifically, a plastic film such as polyethylene terephthalate (PET) or a metal foil such as an aluminum foil or a copper foil is suitable, and one having excellent surface smoothness is generally used. For the purpose of improving releasability, it is possible to provide a release layer such as fluorine on the surface of these films or metal foils. Among these, the cover sheet is preferably polyethylene terephthalate (PET) from the viewpoint of good handleability in the case of a laminated structure because of its high rigidity and from the viewpoint of economy.

On the contrary, when the cover sheet is used in a laminated state even after crosslinking, the cover sheet may be subjected to a treatment for improving the adhesiveness. As the method, the cover sheet itself may be made of an adhesive material, or an ordinary film or sheet may be laminated and applied with an adhesive material (primer).
Examples of the adhesive material include those grafted with silicone, block copolymerized, blended with a silane coupling agent, and those having a radiation-polymerizable functional group (for example, vinyl group, acryloyl group). These improve the adhesive force at their interface due to the chemical bond generated by radiation crosslinking.
In this case, when a gas barrier film is used as the cover sheet, deterioration of the phosphor due to moisture in the atmosphere of the phosphor-containing silicone sheet after production is suppressed, and silver plating of the conductor mounting the chip is suppressed. Discoloration can be suppressed.

Examples of the silane coupling agent include those having vinyl groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropyr groups, mercapto groups, sulfide groups, isocyanate groups and the like as functional groups. Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxypropyl)tetrasulfide, 3-isocyanatopropyltri Examples thereof include ethoxysilane.
These can be appropriately selected according to the polyorganosiloxane and one or more kinds of silane coupling agents can be used.

When a surface-roughened film is used as the cover sheet, the surface property of the surface-roughened film is transferred to the surface of the resulting phosphor-containing silicone sheet when the cover sheet is peeled off and used after radiation crosslinking. Unevenness can be formed. The degree of surface irregularity of the phosphor-containing silicone sheet on at least one surface is 0.30 to 10 μm in average surface roughness (Ra), preferably 0.40 to 5 μm, and 0.50 to 1 μm. More preferably. When Ra is less than 0.30 μm, the surface of the sheet is sticky and the handling property is poor, and the effect of suppressing total reflection on the surface of the sheet decreases, which is not preferable. When Ra exceeds 10 μm, the strength of the silicone sheet may be reduced and the light diffusivity may be reduced, which is not preferable.
By forming the surface irregularities on the phosphor-containing silicone sheet in this way, it is possible to suppress stickiness of the sheet surface, and it is easy to adsorb by air adsorption, etc., which improves the handleability in terms of the light emitting device manufacturing process, Improves the light diffusion of the LED, improves the utilization efficiency of the phosphor by suppressing the total reflection of light on the sheet surface, and attaches it to the surface of Pkg or COB using an adhesive such as epoxy resin or silicone resin. At the time of application, the advantage that the air of the adhesive can be easily removed can be obtained.

The thickness of the cover sheet is appropriately determined depending on its material, purpose of use, etc. For example, a plastic film such as a PET film has a thickness of about 5 to 500 μm, and a metal foil such as an aluminum foil or a copper foil. It is preferably about 5 to 100 μm.

[Molding method of pre-crosslinking sheet]
As a method for forming the pre-crosslinking sheet, an extrusion method, a calendar method, a pressing method, a solution coating method, or a method combining these can be preferably used.
The same forming method can be used also when forming a sheet with both sides sandwiched by two cover sheets.

For example, in the case of the extrusion method, a cover sheet is extrusion-molded on one or both sides at the same time as the extrusion of the pre-crosslinking sheet, or a pre-manufactured cover sheet is prepared, and the composition for sheet is extruded to form a cover sheet from a die. It is possible to use various methods such as a method of discharging a sheet in the meantime and laminating a cover sheet at the same time. In the case of the calendering method, two cover sheets are passed through two calender rolls, the composition for a sheet is supplied therebetween, a bank is formed in the calender rolls, and a pre-crosslinking sheet is laminated between the two cover sheets at the same time. Any method can be used.

In the case of the pressing method, it is possible to use a method in which the sheet composition is supplied between two cover sheets and pressed by a press machine, or a method of continuously pressing between two endless belts.
In the case of the solution coating method, it is possible to use a method in which a cover sheet is coated with a solution of a sheet composition and dried, and then another cover sheet is laminated from the sheet composition side.

[Crosslinking method by radiation irradiation]
In the present invention, it is preferable to cure the polyorganosiloxane by irradiating the pre-crosslinking sheet obtained as described above with radiation to crosslink the polyorganosiloxane.

As the radiation used for radiation crosslinking, electron beams, X-rays, γ-rays, etc. can be used. These radiations are widely used industrially, are easily available, and are energy efficient methods. Among them, γ-rays are particularly preferable because they have high transparency and almost no absorption loss. Further, even after being wound into a roll in a state of being sandwiched between two cover sheets, it is possible to crosslink a long roll as it is because it has excellent permeability. Therefore, as compared with irradiating the manufactured sheet as it is while traveling or rewinding the once-wound sheet, there is a great practical advantage that the conveying device and the like can be simplified and there is no trouble. There is no limitation on the size of the winding roll, and the final product (winding roll) with various winding lengths can be freely obtained.

The cumulative irradiation dose of γ-rays is preferably 10 kGy to 300 kGy, more preferably 20 kGy to 200 kGy, and particularly preferably 50 kGy to 150 kGy, depending on the type of radiation source.
In addition to the crosslink density of the polyorganosiloxane, it is preferable to take into consideration the radiation resistance of the plastic film used as the cover sheet and the deterioration of the phosphor in the selection of the cumulative irradiation dose.

[Fluorescent substance-containing silicone sheet/Fluorescent substance-containing silicone sheet with protective sheet]
The thickness of the phosphor-containing silicone sheet of the present invention is preferably 3 μm to 1000 μm, more preferably 10 μm to 500 μm, and further preferably 30 μm to 300 μm. When the thickness of the phosphor-containing silicone sheet is within such a range, when used in a light-emitting device that emits white or another color by wavelength-converting part or all of the light emission of the LED, white or other colors with little variation are used. It is possible to realize light, and it is possible to meet the demand for thinning with a Pkg or COB substrate.

FIG. 1(a) is a three-layer laminated sheet of cover sheet/phosphor-containing silicone sheet/cover sheet obtained by sheet-molding in the cover sheet and then performing radiation crosslinking as described above. 2 is a cross-sectional view showing the sheet-containing phosphor-containing silicone sheet 1, 2 is a phosphor-containing silicone sheet, and 3 is a cover sheet, that is, a protective sheet.
The phosphor-containing silicone sheet and the phosphor-containing silicone sheet with a protective sheet of the present invention obtained by radiation cross-linking have uniform film thickness of the phosphor-containing silicone sheet and excellent uniform dispersibility of the phosphor. It is possible to obtain uniform light emission over the entire surface of the sheet.

[Protective sheet/Silicone sheet containing phosphor with adhesive or adhesive sheet]
The phosphor-containing silicone sheet of the present invention is sometimes referred to as an adhesive or pressure-sensitive adhesive sheet (hereinafter referred to as “adhesive (adhesive) sheet”) between the phosphor-containing silicone sheet and the cover sheet in order to manufacture a light emitting device described later. .) may be provided.

1B and 1C are cross-sectional views showing a protective sheet/adhesive (adhesive) sheet-containing phosphor-containing silicone sheet 1A, 1B having such an adhesive (adhesive) sheet 4, and FIG. The protective sheet/adhesive (adhesive) sheet-containing phosphor-containing silicone sheet 1A of b) is a four-layer laminated sheet of cover sheet 3/phosphor-containing silicone sheet 2/adhesive (adhesive) sheet 4/cover sheet 3, The protective sheet/adhesive (adhesive) sheet-attached phosphor-containing silicone sheet 1B of 1(c) is a cover sheet 3/adhesive (adhesive) sheet 4/phosphor-containing silicone sheet 2/adhesive (adhesive) sheet 4/cover sheet 3 Is a 5-layer laminated sheet.

The resin used for the adhesive (adhesive) sheet 4 is not particularly limited, and examples thereof include polyester resins, acrylic resins, fluorine resins, epoxy resins, silicone resins and the like. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio. Among these resins, the silicone-based resin is preferable because it has light transmittance, heat resistance, and light resistance.

There are dimethyl type and methyl phenyl type silicone resins, but considering adhesiveness, the silicone resin used for the phosphor-containing silicone sheet 2 and the adhesive (adhesive) sheet 4 is preferably the same type. When a silicone-based resin is used as a sealing resin for a light-emitting device that mounts the phosphor-containing silicone sheet with a protective sheet/adhesive (adhesive) sheet of the present invention, it is more preferable that the sealing resin is the same type of resin. preferable. Further, in order to suppress a decrease in light extraction efficiency due to total reflection at the interface between the phosphor-containing silicone sheet and the adhesive sheet after mounting and the adhesive (adhesive) sheet and the sealing resin, the phosphor sheet-containing silicone sheet It is preferable that the silicone-based resin used for 2, the adhesive (adhesive) sheet resin 4, and the sealing resin have the same refractive index.

The thickness of the adhesive (adhesive) sheet 4 is preferably 0.1 μm to 200 μm, more preferably 1 μm to 100 μm, and particularly preferably 10 μm to 50 μm. Within such a range, when the phosphor-containing silicone sheet is mounted on the light emitting device, even if the mounting surface has irregularities, it can be sufficiently absorbed and installed in the light emitting device without a gap. Therefore, it is possible to prevent performance degradation of the light emitting device due to light leakage.

There is no particular limitation on the method for producing the protective sheet/adhesive (adhesive) sheet-attached phosphor-containing silicone sheet having such an adhesive (adhesive) sheet, and known methods can be employed. For example, a phosphor-containing silicone sheet with a protective sheet is produced by the above-mentioned method, and separately, a three-layer laminated sheet of cover sheet/adhesive (adhesive) sheet/cover sheet is produced by an ordinary method, and these laminated sheets are The protective sheet/adhesive (adhesive) sheet having a four-layer laminated structure shown in FIG. 1(b) is obtained by adhering the phosphor-containing silicone sheet surface and the adhesive (adhesive) sheet surface while peeling off one of the cover sheets. The fluorescent substance-containing silicone sheet 1A can be used. Alternatively, a phosphor-containing silicone sheet with a protective sheet is manufactured, one of the cover sheets is peeled off, an adhesive (adhesive) resin is coated in-line, and then the cover sheets are stuck together, as shown in FIG. 1(b). A phosphor-containing silicone sheet 1A with a protective sheet/adhesive sheet having a four-layer laminated structure can be used.
Further, in the case of the phosphor-containing silicone sheet 1B with a protective sheet/adhesive (adhesive) sheet having a five-layer laminated structure of FIG. 1(c), the above-mentioned four-layer laminated sheet and cover sheet/adhesive (adhesive) sheet/cover It can be manufactured by using a three-layer laminated sheet of sheets and similarly adhering the phosphor-containing silicone sheet surface and the adhesive (adhesive) sheet surface while peeling off one of the cover sheets. Alternatively, a phosphor-containing silicone sheet with a protective sheet is produced, the cover sheets on both sides are peeled off, an adhesive (adhesive) resin is coated in-line, and then the cover sheets are attached to each other, as shown in FIG. 1(c). A phosphor-containing silicone sheet 1B with a protective sheet/adhesive (adhesive) sheet having a five-layer laminated structure can be used.

[Light emitting device]
The light emitting device of the present invention uses the phosphor-containing silicone sheet of the present invention, and can be applied to a Pkg type light emitting device as shown in FIG. 2 and a COB type light emitting device as shown in FIG. ..

The Pkg type light emitting device 10 shown in FIG. 2 has a package 11 and a light emitting element (LED) 12 mounted on the package 11. The package 11 has a first lead electrode 13, a second lead electrode 14, and a resin molded body 15 molded so as to be integrated with the lead electrodes 13, 14. The resin molded body 15 has a ring shape having a cup portion 15a having a recessed hole shape, and its outer peripheral shape is a substantially square shape. After mounting the light emitting element 12, the thermosetting sealing resin (16) is filled in the cup portion 15a. This sealing resin is formed by filling an uncured resin into the cup portion 15a and then curing the resin.

The light emitting element 12 such as an LED is fixed on the lead electrode 14 in the cup portion 15a. The light emitting element 12 is connected to the lead electrodes 13 and 14 by thin metal wires 17 and 18 formed by wire bonding. A bridge portion 15b made of resin is filled between the opposing edges of the lead electrodes 13 and 14. The bridge portion 15b is integrated with the resin molded body 15.
A phosphor-containing sheet 19 is provided so as to cover the upper surfaces of the resin molded body 15 and the sealing resin 16.

The COB type light emitting device 20 shown in FIG. 3 includes an aluminum substrate 21, an insulating film 22 formed on the aluminum substrate 21, wirings 23 and 24 formed on the insulating film 22, and wirings 23 and 24. The light emitting element (LED) 25 installed on the insulating film 22 between, the thin metal wires 26 and 27 by wire bonding for connecting the light emitting element 25 and the wirings 23 and 24, the wirings 23 and 24 and the light emitting element 25. It is composed of an annular spacer 28 that surrounds the spacer 28, a sealing resin 29 filled in the inner region of the spacer 28, and a phosphor-containing sheet 30 that covers the spacer 28 and the upper surface of the sealing resin 29.

In the light emitting device of the present invention, as the phosphor-containing sheets 19 and 30 of FIGS. 2 and 3, the phosphor-containing silicone sheet of the present invention, the phosphor-containing silicone sheet of the present invention, or the protection sheet of the present invention. A phosphor-containing silicone sheet with an adhesive (adhesive) sheet is used.

[Method of manufacturing light emitting device]
The light emitting device of the present invention comprises, as a phosphor-containing sheet, a phosphor-containing silicone sheet of the present invention, a phosphor-containing silicone sheet with a protective sheet of the present invention, or a phosphor with a protective sheet/adhesive (adhesive) sheet of the present invention. A silicone sheet (hereinafter, sometimes referred to as “phosphor sheet of the present invention”) can be used without particular limitation.
Specifically, the phosphor sheet of the present invention, a cutting step of cutting the phosphor sheet into small pieces with a cutter, dicing, a mold, and the like, by a surface mounting device, etc., of the sealing resin filled in the package or the bridge portion. It includes a mounting step of installing on the upper surface and fixing by adhesion or adhesion.
Each step will be described below.

<Cutting process>
The means for cutting the phosphor sheet of the present invention is not particularly limited, and examples thereof include a cutter, dicing, a mold and the like. A cutter is preferable, and a commercially available product (for example, Super Cutter (manufactured by Ogino Seiki Co., Ltd.)) can be preferably used.

The method of cutting the phosphor sheet of the present invention into small pieces is not particularly limited, but for example, the phosphor-containing silicone sheet with a protective sheet of the present invention or the phosphor-containing silicone sheet with a protective sheet/adhesive (adhesive) sheet In that case, the method of cutting so that the small pieces exist in a sea-island shape on the cover sheet is a way to secure the escape of the stress applied to the sheet at the time of cutting, and suppress the peeling between the cover sheet and the fluorescent-containing silicone sheet at the time of cutting. It is preferable in that In this case, as the cutting method, as described above, it is preferable to use a cutter, and when a cutter is used, it is easier to secure the escape area of the stress applied to the sheet at the time of cutting, as compared with the case where a mold is used. It is possible to narrow the gap between each other. Further, in particular, in the case of a protective sheet having an adhesive (adhesive) sheet/a phosphor-containing silicone sheet with an adhesive (adhesive) sheet, by cutting the cover sheet so that small pieces are present in a sea-island shape, It is possible to prevent the adhesion (adhesion) sheets from sticking to each other, and it is possible to suppress problems when picking up small pieces in the mounting process.

The size of the small piece can be appropriately adjusted according to the size of the light emitting device.

Further, it is preferable not to completely cut the cover sheet on the back side (opposite side) with respect to the cutting device at the time of cutting, from the viewpoint of improving the handleability of the small pieces. The cover sheet on the upper side (front side) of the cutting device may be peeled off before cutting, or may be peeled off for each small piece after cutting. It is preferable that after cutting, the adhesive sheet is adhered to the upper part of the small piece, and the entire cover sheet of the small piece is adhered to the adhesive sheet and then peeled off at once, because the steps described later are simplified. At that time, the adhesive strength between the adhesive sheet and the upper cover sheet is preferably weaker than the adhesive strength between the lower cover sheet and the phosphor-containing silicone sheet.

<Mounting process>
In the mounting step, the small piece obtained in the cutting step is transported by a known method (for example, a surface mounting device, a mounter, etc.) and placed on the upper surface of the sealing resin which is a part of the light emitting device. As the surface mounting device, for example, those commercially available from Panasonic Factory Solutions, Yamaha Motor, AI Tech, Fuji Machine Manufacturing, I-Pulse, Sony EMCS, Micronic MyData, JUKI, etc. can be used.

With such a surface mounting device, small pieces cut into reel shapes or sea-island shapes arranged in trays are picked up by air suction nozzles and placed on the upper surface of the Pkg or the sealing resin of the COB type light emitting device. The light emitting device shown in FIGS.

In order to bond the small piece and the sealing resin, the small piece is set in a state where the sealing resin is uncured (B stage), and then the sealing resin is cured, or the sealing resin is cured (C stage). In the case of (1), the adhesive sheet is laminated on the small piece of the phosphor-containing silicone sheet in advance (for example, the small piece of the protective sheet/adhesive sheet-containing phosphor-containing silicone sheet of the present invention is used), or the small piece is used. There is a method in which an adhesive resin is applied to the upper surface of the sealing resin before the installation, a small piece is placed and then the adhesive resin is cured. When the sealing resin is in a cured (C stage) state, an adhesive sheet is preliminarily laminated on the phosphor-containing sheet (for example, a small piece of the protective sheet/adhesive sheet-containing phosphor-containing silicone sheet of the present invention is used. Alternatively, it is also possible to apply an adhesive resin on the upper surface of the sealing resin before installing the small pieces.

The adhesive resin is not particularly limited, but an epoxy resin or a silicone resin is preferably used, and a silicone resin is preferably used from the viewpoint of light transmittance, heat resistance, and light resistance. The silicone-based resin includes dimethyl-based and methylphenyl-based, but considering adhesiveness, it is preferable that the phosphor-containing silicone sheet of the present invention and the silicone-based resin used as the adhesive are of the same type. When a silicone-based resin is used as the sealing resin, it is more preferable that the sealing resin is a resin of the same type. Further, in order to suppress a decrease in light extraction efficiency due to total reflection at the interface, it is preferable that the phosphor-containing silicone sheet, the adhesive resin, and the silicone resin used for the sealing resin have the same refractive index.

A silicone resin is also preferable as the adhesive resin, and as described above, it is preferable that the refractive index thereof is equal to that of the phosphor-containing silicone sheet and the sealing resin.

Since the phosphor-containing silicone sheet of the present invention is preferably obtained by radiation crosslinking, it can be crosslinked even if it does not contain a crosslinking agent. It is possible to ensure good adhesiveness without causing curing inhibition of the adhesive (adhesive) sheet or sealing resin using a resin. It is also good in that the adhesive (adhesive) sheet and the sealing resin are not obstructed by the bleeding of the cross-linking agent when heat is applied such as when the adhesive sheet or the sealing resin is cured or when the light emitting device is used. It is possible to secure adhesiveness.

In order to enhance the adhesive strength and adhesive strength between the small piece and the sealing resin, the surface of the small piece or the sealing resin may be subjected to surface treatment such as corona treatment, ultraviolet ray irradiation treatment, and surface plasma treatment. The surface treatment of the small pieces is not particularly limited, but the method of transferring the surface property of the surface-roughened film described above is preferable from the viewpoint of operability. As described above, when the sealing resin contains an epoxy resin, a layer containing a release agent, a silane coupling agent such as aminosilane is provided as the surface layer of the surface-roughened film. It is preferable because it can be easily adhered to the resin.

Hereinafter, the method for manufacturing the light emitting device of the present invention will be described more specifically with reference to FIGS. 4 and 5, the same members as those shown in FIGS. 1 to 3 are designated by the same reference numerals.

<Method of manufacturing light emitting device using phosphor-containing silicone sheet with protective sheet of the present invention>
With reference to FIG. 4, a method of manufacturing the light emitting device of the present invention by cutting and mounting the phosphor-containing silicone sheet 1 with a protective sheet of the present invention shown in FIG. 1A into small pieces will be described.

First, the phosphor-containing silicone sheet 1 with a protective sheet is cut at a predetermined interval in one direction with a cutter or the like, and divided into strips. At this time, only the upper cover sheet 3 and the phosphor-containing silicone sheet 2 are cut, and the lower cover sheet 3 is not cut (FIG. 4A).
Next, the cut portion is partially peeled and removed to leave the strip 1a on the lower cover sheet 3 (FIG. 4B).
Next, a predetermined interval is provided in the direction orthogonal to the cutting direction, and the same cutting is performed to divide it into a lattice shape (FIG. 4C).
Similarly, the cut portion is partially peeled and removed to leave the small piece 1b on the lower cover sheet 3 (FIG. 4D).
The cover sheet 3 on the small piece 1b is peeled off and removed, and the small piece (chip) 1c of only the phosphor-containing silicone sheet 2 is divided and formed on the cover sheet 3 (FIG. 4(e)).
After that, the chip 1c is sucked and picked up by the air suction nozzle 9 of the surface mounting device by the surface mounting device (FIG. 4(f)) and placed on the sealing resin 16 of the package 11 of the Pkg type light emitting device (FIG. 4 (g)). Then, the encapsulating resin 16 is cured by heating and the chip 1c and the encapsulating resin 16 are adhered.
At this time, the lower surface of the chip 1c and/or the upper surface of the sealing resin 16 may be subjected to a pretreatment for bonding the above-mentioned small piece and the sealing resin.
Although FIG. 4 shows the method for manufacturing the Pkg type light emitting device, the COB type light emitting device can be manufactured by similarly mounting and adhering the chip 1c on the sealing resin of the COB type light emitting device. it can.

<Method for producing light emitting device using phosphor-containing silicone sheet with protective sheet/adhesive sheet of the present invention>
With reference to FIG. 5, the protective sheet/adhesive (adhesive) sheet-containing phosphor-containing silicone sheet 1A of the present invention shown in FIG. 1(b) is cut into small pieces and mounted to manufacture the light emitting device of the present invention. How to do it is explained.

First, the phosphor-containing silicone sheet 1A with a protective sheet/adhesive (adhesive) sheet is cut at a predetermined interval in one direction with a cutter or the like, and divided into strips. At this time, only the upper cover sheet 3, the phosphor-containing silicone sheet 2 and the adhesive (adhesive) sheet 4 are cut, and the lower cover sheet 3 is not cut (FIG. 5A).
Next, the cut portion is partially peeled and removed to leave the strip-shaped piece 1a′ on the lower cover sheet 3 (FIG. 5(b)).
Next, a predetermined interval is provided in the direction orthogonal to the cutting direction, and the same cutting is performed to divide it into a lattice shape (FIG. 5C).
Similarly, the cut portion is partially peeled and removed to leave the small piece 1b′ on the lower cover sheet 3 (FIG. 5D).
The cover sheet 3 on the small piece 1b' is peeled off and removed, and the small piece (chip) 1c' having only the phosphor-containing silicone sheet 2 and the adhesive (adhesive) sheet 4 is dividedly formed on the cover sheet 3. (FIG.5(e)).
After that, the chip 1c′ is sucked and picked up by the air suction nozzle 9 of the surface mounting device by the surface mounting device (FIG. 5(f)) and placed on the sealing resin 16 of the package 11 of the Pkg type light emitting device ( FIG. 5(g)). After that, in the case of an adhesive sheet, the chip 1c and the sealing resin 16 are adhered by heating.
At this time, since the lower surface side of the chip 1c′ is the adhesive (adhesive) sheet 4, the chip 1c′ can be fixed to the sealing resin 16 only by placing it on the sealing resin 16. The above-mentioned pretreatment may be performed on the upper surface of the sealing resin 16.
Although FIG. 5 shows the manufacturing method of the Pkg type light emitting device, the COB type light emitting device can be manufactured by similarly mounting and adhering the chip 1c on the sealing resin of the COB type light emitting device. it can.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
In the following examples and comparative examples, various measured values and evaluations of the obtained phosphor-containing silicone sheet were obtained as follows.

<Example 1>
100 parts by mass of a polysiloxane resin (“TSE2571-5U” manufactured by Momentive) and 36.4 parts by mass of a yellow phosphor (YAG, BY-102D manufactured by Mitsubishi Chemical Corporation, average particle diameter 17 μm) are mixed with a planetary mixer to form a sheet. A resin composition for use was obtained.
Two sheets of the biaxially stretched PET film that had been chemically treated and were supplied along a two-calender with a diameter of 100 mm (“Chemical Mat 75LM” manufactured by Kimoto Co., Ltd., average surface roughness) were obtained. (Ra)=0.948 μm), and a bank was formed on the roll at a roll temperature of 80° C. at room temperature of 25° C. to form a sheet having a thickness of 300 μm and simultaneously laminated to obtain a three-layer laminated sheet. This laminated sheet was irradiated with γ-rays so that the integrated irradiation dose was 50 kGy to crosslink the polyorganosiloxane, thereby obtaining a phosphor-containing silicone sheet with a protective sheet.

<Example 2>
In Example 1, one of the two cover sheets was a biaxially stretched PET film (“T100” manufactured by Mitsubishi Plastics Co., Ltd., average surface roughness (Ra)=0.279 μm) which was not surface-treated. A phosphor-containing silicone sheet with a protective sheet was obtained in the same manner except that it was used.

<Example 3>
Protecting in the same manner as in Example 1 except that two cover sheets were blast-treated and a biaxially stretched PET film (Lumimat 50S manufactured by Toray Industries, Inc., average surface roughness (Ra)=0.660 μm) was used. A phosphor-containing silicone sheet with a sheet was obtained.

<Example 4>
A phosphor-containing silicone sheet with a protective sheet was obtained in the same manner as in Example 3 except that one of the two cover sheets was a biaxially stretched PET film which was not surface-treated.

<Comparative Example 1>
A phosphor-containing silicone sheet with a protective sheet was obtained in the same manner as in Example 1 except that a biaxially stretched PET film (“T100” manufactured by Mitsubishi Plastics, Inc.) was used for both of the two cover sheets.

<Comparative example 2>
A phosphor-containing silicone sheet with a protective sheet was obtained in the same manner as in Example 1 except that the gamma ray was not irradiated.

<Reference example 1>
A phosphor-containing silicone sheet with a protective sheet was obtained in the same manner as in Example 1, except that 34.5 parts by mass of the yellow phosphor (YAG, BY-102D manufactured by Mitsubishi Chemical Corporation, average particle size 17 μm) was used.

<Evaluation of peelability>
When the PET films on both sides of the phosphor-containing silicone sheet with a protective sheet of Examples 1 to 4 were peeled off, a single-layer phosphor-containing silicone sheet was easily obtained. These were evaluated as good peelability (◯).
Moreover, the PET film was peeled off from the three-layer laminated sheet of Comparative Example 2 and an evaluation was tried.
Since the adhesive strength of the phosphor-containing silicone sheet portion of the intermediate layer to the film was strong and there was no sheet strength, the sheet was destroyed when the PET film was peeled off, and evaluation could not be made. This laminated sheet was evaluated as poor peelability (x).

<Evaluation of light emission characteristics>
The single-layer phosphor-containing silicone sheet obtained by peeling off the PET film in Examples 1 to 4, Comparative Example 1 and Reference Example 1 is irradiated with blue light emitted from the LED chip (peak wavelength 450 nm). Thus, a light emitting device capable of obtaining white light was manufactured. The emission spectrum of the device was observed using a 20-inch integrating sphere manufactured by SphereOptics and a spectroscope USB2000 manufactured by OceanOptics, and the measurement results of measuring the luminance (lumen) are shown in Table 1 together with the evaluation results of PET peeling property.
<Surface roughness measurement>
The average surface roughness (Ra) was measured using a contact type surface roughness meter (“Surf Coder ET4000A” manufactured by Kosaka Laboratory Ltd.). The measurement sample length was 8 mm, the measurement speed was 0.2 mm/s, and the measurement force was 100 μN.

As is clear from Table 1, in Examples 1 to 4, it was confirmed that the brightness was improved as compared with Comparative Example 1. By roughening the surface of the phosphor-containing silicone sheet, total reflection was suppressed, and white light extraction efficiency was improved.
Further, it is understood that, in Reference Example 1 in which the roughness of the silicone sheet after peeling is small, it is necessary to increase the amount of phosphor in order to obtain the brightness as in Example 1. Considering that phosphors are expensive, the present invention is useful in that the effect of brightness can be obtained by reducing the amount of phosphors by embossing.

1 Fluorescent substance-containing silicone sheet with protective sheet 1A, 1B Fluorescent substance-containing silicone sheet with protective sheet/adhesive (adhesive) sheet 2 Fluorescent substance-containing silicone sheet 3 Cover sheet 4 Adhesive (adhesive) sheet 9 Air suction nozzle 10 Pkg type light emitting device 11 Package 12,25 Light emitting device (LED)
15 resin molded body 16,29 sealing resin 19,30 phosphor-containing sheet 20 COB type light emitting device 21 aluminum substrate 22 insulating film 28 spacer

Claims (9)

A sheet containing a millable polyorganosiloxane and a phosphor is molded in a state of being sandwiched between two cover sheets having an average surface roughness (Ra) of 0.10 to 10 μm, and the obtained laminated sheet is crosslinked. A method for producing a phosphor-containing silicone sheet, characterized in that, after curing, the cover sheet is peeled off, and at least one surface has an uneven portion having the following feature (1).
(1) Average surface roughness (Ra) is 0.30 to 10 μm The method for producing a phosphor-containing silicone sheet according to claim 1, wherein the phosphor-containing silicone sheet has a thickness of 3 μm to 1000 μm. The method for producing a phosphor-containing silicone sheet according to claim 1, wherein the laminate sheet is a three-layer laminate sheet of cover sheet/phosphor-containing silicone sheet/cover sheet. The method for producing a phosphor-containing silicone sheet according to claim 1, wherein the laminated sheet comprises an adhesive or pressure-sensitive adhesive sheet between the phosphor-containing silicone sheet and the cover sheet. The said cover sheet is PET, The manufacturing method of the fluorescent substance containing silicone sheet in any one of Claims 1-4 characterized by the above-mentioned. The method for producing a phosphor-containing silicone sheet according to claim 5, wherein the cover sheet has a thickness of 5 to 500 μm. The method for producing a phosphor-containing silicone sheet according to claim 1, wherein the cover sheet is obtained by a blast method. The method for producing a phosphor-containing silicone sheet according to claim 1, wherein the cover sheet is obtained by a chemical method. The method for producing a phosphor-containing silicone sheet according to claim 1, wherein (1) the average surface roughness (Ra) is 0.30 to 1 μm.

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