WO2013089075A1 - Laminate, and method for producing light-emitting diode provided with wavelength conversion layer - Google Patents

Abstract

Provided are: a laminate which does not undergo the formation of fisheyes or the unevenness in coating in a step of coating a resin solution for sheet production purposes onto a base of the laminate, and in which the base and a phosphor sheet can be delaminated easily in a delamination step; and a method for producing a light-emitting diode provided with a wavelength conversion layer. The laminate according to the present invention is characterized by comprising: a base which comprises polyphenylenesulfide; and a phosphor sheet which is laminated on the base and contains at least a silicone resin and a phosphor.

Description

Laminated body and method for manufacturing light emitting diode with wavelength conversion layer

The present invention relates to a laminate which is a sheet-like material for converting the emission wavelength of an LED chip and a method for producing a light emitting diode with a wavelength conversion layer.

Light-emitting diodes (LEDs, light emitting diodes) are used for backlights of liquid crystal displays (LCDs), car headlights, etc. due to their remarkable improvement in luminous efficiency and low power consumption, long life, and design. The market is rapidly expanding not only in the automotive field but also for general lighting.

Since the emission spectrum of an LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain white light for LCD backlight or general illumination using LEDs, it is necessary to arrange phosphors suitable for the respective chips on the LED chips and convert the emission wavelength. Specifically, a method of installing a yellow phosphor on an LED chip that emits blue light, a method of installing red and green phosphors on an LED chip that emits blue light, and red, green, and blue on an LED chip that emits ultraviolet light A method of installing a phosphor is proposed. Among these, the method of installing a yellow phosphor on a blue LED and the method of installing red and green phosphors on a blue LED are currently most widely adopted in terms of the luminous efficiency and cost of the LED chip. .

As a specific method of installing a phosphor on an LED chip, a method of bonding a silicone resin sheet containing phosphor particles (hereinafter referred to as a phosphor sheet) on the LED chip has been proposed ( For example, see Patent Documents 1 to 4). This method is easier to dispose a certain amount of phosphor on the LED chip than the conventional method of dispensing and curing a liquid resin in which the phosphor is dispersed on the LED chip. The resulting white LED is excellent in that the color and brightness can be made uniform.

JP 2009-235368 A JP 2010-123802 A Japanese Patent No. 2011-102004 JP 2010-159411 A

The method of attaching the phosphor sheet to the LED chip is a better method for stabilizing the color and brightness than using the liquid phosphor resin as described above, but a resin in which phosphor particles are dispersed is used. It is difficult to make a uniform sheet. Moreover, such a sheet | seat is normally formed by apply | coating on the film-form base material which consists of polyethylene terephthalate etc. Since the elastic modulus of the phosphor sheet itself containing silicone resin as a main component is not so high, it may be deformed or damaged during handling. Therefore, the phosphor sheet is handled in a state of a laminated body integrated with the base material until it is applied to the LED chip after being applied onto the base material. The phosphor sheet laminated on the substrate peels off the substrate after being bonded to the LED chip. However, if the adhesion strength between the substrate and the phosphor sheet is high, the phosphor sheet may be damaged at the time of peeling. was there.

In order to prevent the phosphor sheet from being damaged when the substrate is peeled off, a treatment called mold release treatment is generally applied to the substrate. In the mold release treatment, a thin film of a material having a very low surface energy such as a silicone-based organic compound or a fluorine-based organic compound is applied to the substrate surface, and the phosphor sheet formed thereon is easily peeled off. However, the silicone resin used for the phosphor sheet has poor coatability, and when applied to a surface treated with such a low surface energy chemical, repelling and unevenness occur, so it is very difficult to apply uniformly. there were.

Furthermore, the laminated body in which the phosphor sheet is formed is cut to the size of the LED chip before being attached to the LED chip, or the portion of the laminated body that contacts the electrode connection pad of the LED chip is punched, etc. May be subjected to mechanical processing. When mechanical processing is performed on a laminate in which a phosphor sheet containing a silicone resin and a phosphor is formed on a base material that has been subjected to a release treatment, the phosphor sheet may be peeled off from the base material and damaged. It was a challenge.

The present invention has been made in view of the above, and in the case where a phosphor sheet is formed by applying a silicone resin sheet-forming resin solution having poor applicability to a base material, the application step is for sheet preparation. The present invention provides a laminate and a method for producing a light emitting diode with a wavelength conversion layer, in which no repellency or unevenness of the resin liquid occurs and the substrate and the phosphor sheet can be easily separated in the peeling step.

The laminate of the present invention comprises a base material containing polyphenylene sulfide and a phosphor sheet containing at least a silicone resin and a phosphor laminated on the base material.

The laminate of the present invention can obtain a phosphor sheet having a uniform film thickness because a good coating property can be obtained when a sheet-forming resin solution containing a phosphor is applied to a substrate. The material and the phosphor sheet can be easily peeled off, and the phosphor sheet can be prevented from being damaged.

The phosphor sheet in the present invention is not particularly limited as long as it mainly contains a silicone resin and a phosphor, and various sheets can be used. Other components may be included as necessary.

The silicone resin used in the present invention is a binder resin that contains a phosphor inside, and is a component that forms the form of the phosphor sheet. Therefore, there is no particular limitation as long as the phosphor can be uniformly dispersed inside and can be formed into a sheet shape. Moreover, the thing excellent in mechanical strength, transparency, heat resistance, and light resistance is requested | required from durability and reliability at the time of using for an LED light-emitting device. Further, the silicone resin used in the present invention is preferably a curable silicone rubber. Either one liquid type or two liquid type (three liquid type) liquid structure may be used. Examples of the curable silicone rubber include a dealcohol-free type, a deoxime type, a deacetic acid type, and a dehydroxylamine type that cause a condensation reaction with moisture in the air or a catalyst. Moreover, there is an addition reaction type as a type that causes a hydrosilylation reaction with a catalyst. Any of these types of curable silicone rubber may be used. In particular, addition-reactive silicone rubber has no by-products associated with the curing reaction, is not easily affected by moisture, has low curing shrinkage, and is easy to accelerate curing by heating. More preferred.

For example, the addition reaction type silicone rubber is formed by a hydrosilylation reaction between a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom. Such materials contain alkenyl groups bonded to silicon atoms such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane, etc. And hydrogen atoms bonded to silicon atoms such as methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, methylhydrogenpolysiloxane-CO-methylphenylpolysiloxane, etc. Examples thereof include those formed by hydrosilylation reaction of the compounds having them.

Further, as the silicone resin used in the present invention, for example, those described in JP 2010-159411 A can be used. The silicone resin described in Japanese Patent Application Laid-Open No. 2010-159411 is a silicone resin that cures by a condensation reaction and an addition reaction, and has a silicon compound having a substituent capable of condensation reaction and a substituent capable of addition reaction. It can be obtained by subjecting a silicone resin composition containing a silicon compound to a condensation reaction.

Examples of the silicon compound having a substituent capable of a condensation reaction include silicon compounds having a substituent such as a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, an ester group, and a halogen atom. Preferably, a silicon compound having a hydroxyl group or an alkoxy group is used. There is no particular limitation on the number of substituents contained in one molecule.

As the silicon compound having a substituent capable of condensation reaction, for example, a both-end silanol type silicon compound represented by the following formula (1) is preferable.

In the formula, R ¹ is a monovalent hydrocarbon group, for example, a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a naphthyl group, a cyclohexyl group, and a cyclopentyl group. Of these, a methyl group is preferred from the viewpoints of transparency and light resistance. In formula (1), all R ¹ groups may be the same or different, but all R ¹ groups are preferably methyl groups.

In the above formula (1), n is an integer of 1 or more, and from the viewpoint of stability and handleability, n is an integer of 1 to 10000, more preferably 1 to 1000.

Examples of the compound represented by the formula (1) include both-end silanol-type polydimethylsiloxane, both-end silanol-type polymethylphenylsiloxane, and both-end silanol-type polydiphenylsiloxane. These may be used alone or in combination of two or more. Can be used. Among these, compounds in which R ¹ is all a methyl group and n is an integer of 1 to 1000 are preferable.

The content of the compound represented by the formula (1) in the condensation reaction monomer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The proportion of the condensation reaction monomer in the silicone resin is preferably 1 to 99% by mass, more preferably 50 to 99% by mass, and still more preferably 80 to 99% by mass.

Examples of the silicon compound having a substituent capable of addition reaction (hereinafter also referred to as addition reaction monomer) include, for example, alkenyl group, hydrogen atom, alkynyl group, carbonyl group, thiol group, epoxy group, amino group, hydroxyl group, sulfide. The silicon compound which has substituents, such as group, is illustrated, Preferably it is a silicon compound which has a hydrogen atom and an alkenyl group. There is no restriction | limiting in particular in the number of the substituents contained in 1 molecule.

Examples of the silicon compound having a hydrogen atom or an alkenyl group include compounds having an alkenyl group bonded to a silicon atom or compounds having a hydrogen atom bonded to a silicon atom, exemplified as the above addition reaction type silicone rubber. It is done.

The content of the addition reaction monomer in the silicone resin is preferably 0.1 to 99% by mass, more preferably 0.1 to 90% by mass, and further preferably 0.1 to 80% by mass.

Further, the blending ratio of the condensation reaction system monomer and the addition reaction system monomer (condensation reaction system monomer / addition reaction system monomer) is 99.9 / 0.1 to 1/99 from the viewpoint of viscoelasticity when formed into a sheet. It is preferably 99.9 / 0.1 to 50/50, more preferably 99.9 / 0.1 to 90/10.

In addition to the condensation reaction system monomer and the addition reaction system monomer, the silicone resin described in Japanese Patent Application Laid-Open No. 2010-159411 further includes a compound that can react with both the condensation reaction system monomer and the addition reaction system monomer (hereinafter referred to as “reaction monomer”). , Also referred to as a condensation / addition monomer).

The condensation / addition monomer has a functional group capable of reacting with the condensation reaction system monomer and a functional group capable of reacting with the addition reaction system monomer in one molecule. Examples of the functional group capable of reacting with the condensation reaction monomer include the same substituents as those described above that can undergo the condensation reaction, and the number of functional groups in one molecule is not particularly limited. Examples of the functional group capable of reacting with the addition reaction monomer include the same substituents as those described above that can undergo the addition reaction, and the number of functional groups in one molecule is not particularly limited.

As such a compound, for example, an alkenyl group-containing trialkoxysilane is preferable. In the above compound, an alkenyl group undergoes an addition reaction with an addition reaction monomer, and an alkoxy group undergoes a condensation reaction with a condensation reaction monomer.

The alkenyl group of the alkenyl group-containing trialkoxysilane has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and specifically includes a vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group. Group, octenyl group, norbornenyl group, cyclohexenyl group and the like are exemplified. Among these, a vinyl group is preferable from the viewpoint of reactivity with respect to the hydrosilylation reaction.

The alkoxy group of the alkenyl group-containing trialkoxysilane is an alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms, and specifically includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyl group. An oxy group etc. are illustrated. Of these, a methoxy group is preferred from the viewpoint of reactivity to the condensation reaction. All alkoxy groups may be the same or different, but all are preferably methoxy groups.

Examples of the alkenyl group-containing trialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane, and the like. Alternatively, two or more kinds can be used in combination. Of these, vinyltrimethoxysilane is preferred.

The content of the alkenyl group-containing trialkoxysilane in the condensation / addition monomer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The content of the condensation / addition monomer in the silicone resin is preferably 0.01 to 90% by mass, more preferably 0.01 to 50% by mass, and still more preferably 0.01 to 10% by mass.

In addition, when the both-end silanol type silicone oil represented by the formula (1) is used as the condensation reaction monomer and the alkenyl group-containing trialkoxysilane is used as the condensation / addition monomer, the blending ratio of both is the silanol type at both ends. From the viewpoint of reacting the silanol group of the silicone oil and the alkoxy group of the alkenyl group-containing trialkoxysilane without excess or deficiency, the molar ratio of the functional groups (silanol group / alkoxy group) is preferably 20/1 to 0.2 / 1. 10/1 to 0.5 / 1 is more preferable, and it is more preferable that it is substantially equivalent (1/1).

In the case of using the silicone resin described in JP 2010-159411 A, the silicone resin is cured in two steps, so that it is not necessary to form an adhesive layer on the phosphor sheet.

The phosphor absorbs light emitted from the LED chip, converts the wavelength, and emits light having a wavelength different from that of the LED chip. Thereby, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor are mixed to obtain a multicolor LED including white. Specifically, a white LED is caused to emit light using a single LED chip by optically combining a blue LED and a phosphor that emits a yellow emission color by light from the blue LED. Can do.

The phosphors as described above include various phosphors such as a phosphor emitting green, a phosphor emitting blue, a phosphor emitting yellow, and a phosphor emitting red. Specific phosphors used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, fluorescent pigments, and fluorescent dyes. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes and perylene phosphors. Perylene phosphors are preferably used because they can be used for a long period of time. Examples of the fluorescent material that is particularly preferably used in the present invention include inorganic phosphors. The inorganic phosphor used in the present invention is described below.

Examples of phosphors that emit green light include SrAl ₂ O ₄ : Eu, Y ₂ SiO ₅ : Ce, Tb, MgAl ₁₁ O ₁₉ : Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ : Eu, (Mg, Ca, Sr , At least one of Ba) and Ga ₂ S ₄ : Eu.

Examples of phosphors that emit blue light include Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrCaBa) ₅ (PO ₄ ) ₃ Cl: Eu, (BaCa) ₅ (PO ₄ ) ₃ Cl: Eu, (Mg, ₂ B ₅ O ₉ Cl: Eu, Mn, (Mg, Ca, Sr, Ba, at least one) (PO ₄ ) ₆ Cl ₂ : Eu, Mn, etc. .

As phosphors emitting green to yellow, at least cerium-activated yttrium / aluminum oxide phosphors, at least cerium-enriched yttrium / gadolinium / aluminum oxide phosphors, at least cerium-activated yttrium / aluminum There are garnet oxide phosphors and at least cerium activated yttrium gallium aluminum oxide phosphors (so-called YAG phosphors). Specifically, Ln ₃ M ₅ O ₁₂ : R (Ln is at least one selected from Y, Gd, and La. M includes at least one of Al and Ca. R is a lanthanoid series. ), (Y _1-x Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : R (R is at least one selected from Ce, Tb, Pr, Sm, Eu, Dy, Ho) 0 <x <0.5, 0 <y <0.5) can be used.

Examples of phosphors that emit red light include Y ₂ O ₂ S: Eu, La ₂ O ₂ S: Eu, Y ₂ O ₃ : Eu, and Gd ₂ O ₂ S: Eu.

As the phosphor corresponding to the current mainstream of the blue LED _{emission, Y 3 (Al, Ga)} 5 O 12: Ce, (Y, Gd) 3 Al 5 O 12: Ce, Lu 3 Al 5 O 12: Ce, Y ₃ Al ₅ O ₁₂ : YAG phosphor such as Ce, TAG phosphor such as Tb ₃ Al ₅ O ₁₂ : Ce, (Ba, Sr) ₂ SiO ₄ : Eu phosphor and Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce phosphor, silicate phosphor such as (Sr, Ba, Mg) ₂ SiO ₄ : Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, (Ca, Sr) AlSiN ₃ : Eu, CaSiAlN ₃ : Nitride phosphor such as Eu, Cax (Si, Al) ₁₂ (O, N) ₁₆ : Oxynitride phosphor such as Eu, and (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : E Examples include phosphors such as u-based phosphors, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu-based phosphors, SrAl ₂ O ₄ : Eu, and Sr ₄ Al ₁₄ O ₂₅ : Eu.

Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used in terms of light emission efficiency and luminance.
In addition to the above, known phosphors can be used according to the intended use and the intended emission color.

The average particle diameter of the phosphor used in the present invention is not particularly limited, but is preferably 1 μm or more. Moreover, an average particle diameter of 20 micrometers or less is preferable. Here, in the present invention, the average particle diameter means a median diameter, that is, D50. The D50 of the phosphor contained in the phosphor sheet is obtained by subjecting a measurement image of a cross section of the sheet with a scanning electron microscope (SEM) to image processing to obtain a particle size distribution, and in the volume-based particle size distribution obtained therefrom, Is measured by a method in which the particle diameter of 50% of the accumulated amount from is set to the median diameter D50. The value of D50 obtained by this method is smaller than that obtained by directly observing the phosphor powder, but the average particle diameter of the phosphor in the present invention is defined as the value obtained by the above measurement method. When the average particle diameter is in the above range, the phosphor in the phosphor sheet has good dispersibility and stable light emission can be obtained.

The reason why the value of D50 is smaller than that obtained when the phosphor powder is directly observed is that the diameter is correctly measured when the powder is directly observed, but the fluorescence existing in the cross section of the phosphor sheet. This is because when the particle diameter of the body is measured, the phosphor particles are not always cut at the equator plane. Assuming that the phosphor particles are spherical and are cut at any location, the apparent diameter is theoretically 78.5% of the true diameter (the area of a circle with a diameter of 1 and one side of 1 Equivalent to the square area ratio). Actually, since the phosphor particles are not true spheres, it is empirically about 70% to 85%.

In the present invention, the phosphor content is preferably 53% by mass or more of the entire phosphor sheet, more preferably 57% by mass or more, and further preferably 60% by mass or more. By setting the phosphor content in the phosphor sheet within the above range, the light resistance of the phosphor sheet can be improved. In addition, from the viewpoint of workability that the phosphor sheet is easy to create, it is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less of the entire phosphor sheet. More preferably, it is particularly preferably 80% by mass or less.

The phosphor sheet in the present invention is formed by applying a sheet preparation resin solution for forming a phosphor sheet on a substrate containing polyphenylene sulfide, and then thermally drying and curing the applied sheet preparation resin solution. Is done. Polyphenylene sulfide is a polymer containing a structure represented by the following general formula (2) as an essential repeating unit.

The polyphenylene sulfide used in the present invention is a polymer containing the repeating unit represented by the general formula (2), preferably 70 mol% or more, more preferably 90 mol% or more. When polyphenylene sulfide contains 70 mol% or more of the repeating unit represented by the general formula (2), heat resistance is excellent, which is preferable.

In addition, the polyphenylene sulfide used in the present invention can be composed of a repeating unit represented by the following structural formula at 30 mol% or less of the repeating unit. The polyphenylene sulfide used in the present invention comprises a random copolymer composed of a repeating unit represented by the general formula (2) and at least one repeating unit represented by the following structural formula, a block copolymer Or a mixture of a polymer having a repeating unit represented by the general formula (2) and a polymer having at least one repeating unit represented by the following structural formula. Good.

Moreover, as the polyphenylene sulfide of the present invention, in addition to the linear polyphenylene sulfide composed of the above repeating units, a crosslinked polyphenylene sulfide can be used, but the base material used in the present invention has flexibility. Since it is desirable to have a film shape, a film shape made of linear polyphenylene sulfide is preferably used.

As long as the effects of the present invention are not impaired, the substrate may contain components other than polyphenylene sulfide. For example, a resin component other than polyphenylene sulfide or an inorganic component may be included. Resin components other than polyphenylene sulfide include polyolefins such as polyethylene, polypropylene and ethylene copolymer resins, styrene resins such as polystyrene and ABS resin, polyvinyl chloride, vinylidene chloride, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly Examples thereof include thermoplastic resins such as tetrafluoroethylene, and high heat resistant resins such as polyacrylate resin, polyoxybenzoyl, polycarbonate, polyacetal, polyphenylene ether, and polyimide. As a method of mixing polyphenylene sulfide and another resin, there are a method of mixing and alloying at the time of film formation, and a method of dispersing fine particles of other resin in the polyphenylene sulfide matrix. In the use of a molded article, polytetrafluoroethylene and alloyed polyphenylene sulfide are known for improving the sliding performance.

Examples of the inorganic component include glass fiber and inorganic fine particles. By including these, it is possible to improve mechanical properties such as reduction of thermal expansion coefficient, improvement of toughness, and improvement of elastic modulus. Any glass fiber can be used, but those made of alkali-free glass such as quartz glass and E glass and low alkali glass are preferred from the viewpoint of hardly causing deterioration of mechanical properties. For example, inorganic oxide fine particles such as silica, alumina, calcium oxide, boron oxide, zinc oxide, titanium oxide, zirconia, glass powder, quartz powder, barium titanate, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, etc. Examples include inorganic compound powders other than these oxides, and inorganic fine particles derived from natural products such as talc, montmorillonite, and mica. These inorganic fine particles may be subjected to a surface treatment if necessary. Specific examples of the surface treatment include water repellency treatment using silicone oil and the like, hydrophobization treatment using a surface treatment agent such as a silane coupling agent, hydrophilization treatment, or hydroxyl group, amino group on the surface of fine particles, Examples include the introduction of organic functional groups such as carboxyl, epoxy, acrylic, vinyl, alkyl, and aryl groups, which improve affinity with the resin used, adhesion at the interface, and dispersibility. Is selected as appropriate.

Even if the base material according to the present invention contains any of the above-described components, it contains polyphenylene sulfide as a main component, so that a coating film free from repellency or unevenness when applying a resin liquid for preparing a phosphor sheet described below. Further, after the phosphor sheet is attached to the LED chip, it can be easily peeled off when the substrate is peeled off.

The base material according to the present invention may be a laminate having a polyphenylene sulfide layer. For example, a laminate in which a layer mainly composed of polyphenylene sulfide is laminated on one side or both sides of a polyolefin-based resin layer having a heat distortion temperature of 70 to 150 ° C. disclosed in Japanese Patent Application Laid-Open No. 2006-21372 is also disclosed. It can be used as a substrate of the invention.

The phosphor sheet in the present invention may contain silicone fine particles in order to improve the fluidity of a resin liquid for producing a phosphor sheet, which will be described later, and to improve the coating property. The silicone fine particles to be contained are preferably fine particles comprising a silicone resin and / or silicone rubber. In particular, silicone fine particles obtained by a method in which organosilane such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane are hydrolyzed and then condensed are obtained. preferable.

Examples of the organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-i-butoxysilane, methyltri-s-butoxy Silane, methyltri-t-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, n-butyltributoxysilane, i-butyltributoxysilane, s-butyltrimethoxysilane, t -Butyltributoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, etc. It is.

Organodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, vinylmethyl Examples include diethoxysilane.

Examples of organotriacetoxysilane include methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, and the like.

Examples of organodiacetoxysilane include dimethyldiacetoxysilane, methylethyldiacetoxysilane, vinylmethyldiacetoxysilane, and vinylethyldiacetoxysilane.

Examples of the organotrioxime silane include methyl trismethyl ethyl ketoxime silane, vinyl trismethyl ethyl ketoxime silane, and examples of the organodioxime silane include methyl ethyl bismethyl ethyl ketoxime silane.

Specifically, such particles are reported in the method reported in JP-A-63-77940, the method reported in JP-A-6-248081, and in JP-A-2003-342370. Or a method reported in JP-A-4-88022. In addition, organosilane such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane and / or a partial hydrolyzate thereof are added to an alkaline aqueous solution, Hydrolysis / condensation to obtain particles, or addition of organosilane and / or partial hydrolyzate thereof to water or acidic solution to obtain hydrolyzed partial condensate of organosilane and / or partial hydrolyzate thereof Thereafter, a method in which an alkali is added to proceed with a condensation reaction to obtain particles, an organosilane and / or a hydrolyzate thereof is used as an upper layer, an alkali or a mixed solution of an alkali and an organic solvent is used as a lower layer, and the organosilane at these interfaces. And / or hydrolyzate thereof · Polycondensation engaged with is also known a method of obtaining a particle, In any of these methods, it is possible to obtain the particles used in the present invention.

Among these, the reaction as reported in Japanese Patent Application Laid-Open No. 2003-342370 is carried out in the production of spherical organopolysilsesquioxane fine particles by hydrolyzing and condensing organosilane and / or a partial hydrolyzate thereof. It is preferable to use silicone fine particles obtained by a method of adding a polymer dispersant in the solution.

In the production of particles, organosilane and / or a partial hydrolyzate thereof are hydrolyzed / condensed in the presence of a polymer dispersant and a salt that act as a protective colloid in a solvent in an acidic aqueous solution. Silicone fine particles produced by adding a silane and / or a hydrolyzate thereof to obtain a hydrolyzate and then adding an alkali to advance the condensation reaction can also be used.

The polymer dispersant is a water-soluble polymer, and any synthetic polymer or natural polymer can be used as long as it acts as a protective colloid in a solvent. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be used. It can be illustrated. As a method for adding the polymer dispersant, a method of adding in advance to the reaction initial solution, a method of adding organotrialkoxysilane and / or a partial hydrolyzate thereof simultaneously, an organotrialkoxysilane and / or a partial hydrolyzate thereof, The method of adding after hydrolyzing partial condensation can be illustrated, and any of these methods can be selected. Here, the addition amount of the polymer dispersant is preferably in the range of 5 × 10 ⁻⁷ to 10 ⁻² parts by mass with respect to 1 part by mass of the reaction solution, and in this range, aggregation of particles hardly occurs.

The organic substituent contained in the silicone fine particles is preferably a methyl group or a phenyl group, and the refractive index of the silicone fine particles can be adjusted by the content of these substituents. In order not to reduce the luminance of the LED light-emitting device, when it is desired to use the light passing through the silicone resin as the binder resin without scattering, the refractive index d1 of the silicone fine particles and the refractive index due to components other than the silicone fine particles and the phosphor A smaller refractive index difference of d2 is preferable. The difference in refractive index between the refractive index d1 of the silicone fine particles and the refractive index d2 due to components other than the silicone fine particles and the phosphor is preferably less than 0.10, and more preferably 0.03 or less. By controlling the refractive index of the silicone resin and the silicone fine particles so as to be in such a range, reflection / scattering at the interface between the silicone fine particles and the silicone resin is reduced, and high transparency and light transmittance are obtained. The brightness of the LED light emitting device is not lowered.

For the measurement of the refractive index, Abbe refractometer, Pulfrich refractometer, immersion type refractometer, immersion method, minimum declination method, etc. are used as the total reflection method, but for the refractive index measurement of the silicone composition, The immersion method is useful for measuring the refractive index of Abbe refractometer and silicone fine particles.

Further, as a means for controlling the refractive index difference, it can be adjusted by changing the blending ratio of raw materials constituting the silicone fine particles. That is, for example, when a mixture of methyltrialkoxysilane and phenyltrialkoxysilane is used as a raw material, it is close to 1.4 by increasing the composition ratio of methyl groups, that is, by increasing the amount of methyltrialkoxysilane. It is possible to reduce the refractive index. Conversely, a relatively high refractive index can be achieved by increasing the proportion of phenyl groups, that is, by increasing the amount of phenyltrialkoxysilane.

In the present invention, the average particle diameter of the silicone fine particles is represented by a median diameter (D50), and the average particle diameter is preferably 0.01 μm or more and more preferably 0.05 μm or more as a lower limit. The upper limit is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle size is 0.01 μm or more, it is easy to produce particles with a controlled particle size, and when the average particle size is 2.0 μm or less, the optical properties of the phosphor sheet are improved. Moreover, the fluidity improvement effect of the resin liquid for fluorescent substance sheet manufacture is fully acquired because an average particle diameter is 0.01 micrometer or more and 2.0 micrometers or less. Moreover, it is preferable to use monodispersed true spherical particles. In the present invention, the average particle diameter of the silicone fine particles contained in the phosphor sheet, that is, the median diameter (D50) and the particle size distribution can be measured by SEM observation of the sheet cross section. A particle size distribution is obtained by performing image processing on a measurement image obtained by SEM, and in the particle size distribution obtained therefrom, the particle diameter of 50% of the accumulated portion from the small particle diameter side is obtained as the median diameter D50. In this case as well, as in the case of the phosphor particles, the average particle size of the silicone fine particles obtained from the cross-sectional SEM image of the phosphor sheet is theoretically 78.5% compared to the true average particle size, and is actually approximately Although the value is 70% to 85%, the average particle size of the silicone fine particles in the present invention is defined as a value obtained by the above-described measuring method.

In the phosphor sheet according to the present invention, the content of the silicone fine particles is preferably 0.5% by mass or more as a lower limit with respect to the total amount of the silicone resin and the silicone fine particles, and is 1% by mass or more. More preferred is 2% by mass or more. Moreover, as an upper limit, it is preferable that it is 20 mass parts or less, and it is more preferable that it is 10 mass parts or less. By containing 1% by mass or more of silicone fine particles, a particularly good phosphor dispersion stabilizing effect can be obtained. On the other hand, the content of 20% by mass or less does not excessively increase the viscosity of the resin liquid for sheet preparation. .

In the resin liquid for producing a phosphor sheet in the present invention, as other components, a hydrosilylation reaction retarder such as acetylene alcohol is blended to suppress the curing of the resin liquid for producing a sheet at room temperature and lengthen the pot life. It is preferable to do.

Further, within the range in which the effect of the present invention is not impaired, the resin liquid for sheet preparation may contain fine particles such as fumed silica, glass powder, and quartz powder as necessary, titanium oxide, zirconia oxide, barium titanate, zinc oxide, etc. Inorganic fillers, pigments, flame retardants, heat-resistant agents, antioxidants, dispersants, solvents, adhesiveness-imparting agents such as silane coupling agents and titanium coupling agents may be blended.

In particular, from the viewpoint of the surface smoothness of the phosphor sheet, it is preferable to add a low molecular weight polydimethylsiloxane component, silicone oil or the like to the resin liquid for producing the phosphor sheet. Such a component is preferably added in an amount of 100 to 2,000 ppm, more preferably 500 to 1,000 ppm in the resin liquid for sheet preparation (excluding the amount of the solvent when a solvent is included).

The film thickness of the phosphor sheet in the present invention is determined from the phosphor content and desired optical characteristics. In order to obtain desired optical characteristics, the phosphor sheet needs to contain a predetermined amount of phosphor. However, if the amount of the phosphor in the phosphor sheet is excessively high, there is a limit from the viewpoint of workability. Therefore, the thickness of the phosphor sheet is preferably 10 μm or more. Moreover, since the phosphor sheet in the present invention has a large phosphor content, it is excellent in light resistance even when the film thickness is large. On the other hand, from the viewpoint of improving the optical properties and heat resistance of the phosphor sheet, the thickness of the phosphor sheet is preferably 200 μm or less, and more preferably 100 μm or less. By making the phosphor sheet have a thickness of 200 μm or less, light absorption and light scattering by the binder resin can be proposed, so that the phosphor sheet is optically excellent.

The film thickness of the phosphor sheet in the present invention is a film thickness (average film thickness) measured based on the method A of measuring thickness by mechanical scanning in JIS K7130 (1999) plastic-film and sheet-thickness measurement method. ).

The LED is in an environment where a large amount of heat is generated in a small space, and particularly in the case of a high power LED, heat generation is significant. Due to such heat generation, the temperature of the phosphor increases, and the luminance of the LED decreases. Therefore, it is important how efficiently the generated heat is radiated. In this invention, the fluorescent substance sheet excellent in heat resistance can be obtained by making the film thickness of a fluorescent substance sheet into the said range. In addition, if there is a variation in the thickness of the phosphor sheet, a difference occurs in the amount of phosphor for each LED chip, and as a result, a variation occurs in the emission spectrum (color temperature, luminance, chromaticity). Therefore, the variation in sheet thickness is preferably within ± 5%, more preferably within ± 3%. The film thickness variation referred to here is a film thickness measured by the method A of measuring thickness by mechanical scanning in JIS K7130 (1999) plastic-film and sheet-thickness measuring method, and is shown below. Calculated by the formula.

More specifically, it is obtained by measuring the film thickness using a micrometer such as a commercially available contact-type thickness meter using the measurement conditions of the method A of measuring the thickness by mechanical scanning. The difference between the maximum value or the minimum value of the film thickness and the average film thickness is calculated, and this value is divided by the average film thickness to express the percentage as the film thickness variation B (%).
Film thickness variation B (%) = {(maximum film thickness deviation value * −average film thickness) / average film thickness} × 100
* For the maximum film thickness deviation value, the one with the larger difference from the average film thickness is selected from the maximum value or the minimum value.

Hereinafter, a method for producing the laminate according to the present invention will be described with specific examples. In addition, the following is an example and the manufacturing method of the laminated body concerning this invention is not limited to this.

First, as a coating liquid for producing a phosphor sheet, a resin liquid (hereinafter referred to as “sheet producing resin liquid”) in which phosphor particles and silicone fine particles used as necessary are dispersed in a silicone resin material is produced. The resin liquid for sheet preparation can be obtained by mixing phosphor particles, silicone resin material and, if necessary, silicone fine particles in a solvent-free or suitable solvent. When an addition reaction type silicone resin is used, a curing reaction starts even at room temperature when a compound containing an alkenyl group bonded to a silicon atom, which is a silicone resin material, and a compound having a hydrogen atom bonded to a silicon atom are mixed. Therefore, it is also possible to improve the storage stability by further adding a hydrosilylation reaction retarder such as an acetylene compound to the resin liquid for sheet preparation. In addition, the compound having an alkenyl group bonded to a silicon atom, the compound having a hydrogen atom bonded to a silicon atom, and the addition reaction catalyst (platinum catalyst) are not mixed and separated into two liquids. Is effective in terms of storage stability. For example, a siloxane compound having an alkenyl group bonded to a silicon atom and a platinum-based catalyst are set as liquid A, a compound having a hydrogen group bonded to a silicon atom is set as liquid B, and phosphor particles and silicone fine particles are dispersed in liquid A. B liquid is mixed just before making into a sheet.

It is also possible to mix a dispersing agent or leveling agent for stabilizing the coating film as an additive, an adhesion aid such as a silane coupling agent as a sheet surface modifier, and the like into the resin liquid for sheet preparation.

When the solvent is added to adjust the viscosity of the resin liquid for sheet preparation, the type of the solvent is not particularly limited as long as the viscosity of the resin in a fluid state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexane, acetone, terpineol, butyl carbitol, butyl carbitol acetate, glyme, diglyme and the like can be mentioned.

After these components are prepared to have a predetermined composition, a sheet is obtained by uniformly mixing and dispersing in a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, a bead mill, or a kneader. A resin solution for preparation is obtained. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing.

Next, the resin liquid for sheet preparation is applied on the polyphenylene sulfide resin film substrate and dried. Application is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, reverse roll coater, blade coater, kiss coater, screen printing, natural roll coater, air knife coater, roll blade coater, varibar roll blade. A coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used. In order to obtain the uniformity of the sheet thickness, it is preferable to apply with a slit die coater. The phosphor sheet according to the present invention can also be produced by using a printing method such as screen printing, gravure printing, and lithographic printing. In particular, screen printing is preferably used.

The film thickness of the substrate used in the present invention is not particularly limited, but the lower limit is preferably 40 μm or more, more preferably 60 μm or more. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.

Heat-curing of the sheet-forming resin liquid applied to the substrate can be performed using a general heating device such as a hot air dryer or an infrared dryer. The heating and curing conditions for the resin liquid for sheet preparation are generally 40 ° C. to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 hours. Min to 3 hours.

In the laminate according to the present invention, a pressure-sensitive adhesive layer may be provided on the phosphor sheet side in order to improve the adhesiveness with the LED chip. The material for the adhesive layer is not particularly limited, and examples thereof include general rubber-based, acrylic-based, urethane-based, and silicone-based adhesives. Any adhesive may be used, but a silicone-based adhesive is useful as an adhesive suitable for heat resistance, insulation, and transparency.

Also, in the laminate according to the present invention, a protective film may be provided on the phosphor sheet side. The material for the protective film is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, cellophane, and polyphenylene sulfide. Further, the protective film may be subjected to a release treatment with a known release agent such as a silicone type or a fluorine type.

Examples of the LED chip to which the phosphor sheet according to the present invention can be applied include a face-up type LED chip and a flip chip type LED chip, and a flip chip type LED chip is particularly preferable. The flip chip type LED chip has high luminous efficiency and high heat dissipation. Therefore, the use of the phosphor sheet according to the present invention facilitates the production of a high-power LED for illumination use having excellent light resistance.

The phosphor sheet in the present invention can be used by being mounted on a LED element as a wavelength conversion sheet. The current mainstream white LED for illumination uses a phosphor material to convert a part of the blue light of the blue light into yellow, green, or red, and mixes it with the blue light of the blue LED element. It has gained. As a method of attaching the phosphor material to the blue LED element, a method of incorporating the phosphor into a liquid transparent sealing material used when the blue LED element is resin-sealed is mainly used. Although this method is simple, it is difficult to precisely apply a certain amount of phosphor-containing liquid sealing resin onto individual blue LED elements, which causes color unevenness. In contrast, according to the present invention, since a phosphor sheet having a uniform film thickness is obtained, it is possible to easily attach a phosphor sheet having a constant thickness on the blue LED element, and thus on the blue LED element. The amount of phosphor can be made constant. By mounting the phosphor sheet according to the present invention and converting the wavelength of the blue LED element, an excellent white LED light-emitting device free from color unevenness and luminance unevenness can be obtained.

Next, a method for manufacturing an LED light emitting device using the laminate according to the present invention will be described. In addition, the following description is an example and the sealing manufacturing method is not restricted to these.

When applying the laminate of the present invention to a flip chip type LED chip, first, the laminate is made into small pieces according to the size of the LED chip to be sealed. The fragmentation can be performed by dicing. When a laminated body has a protective film, after peeling, it may be fragmented, and the whole protective film may be fragmented. In addition, when the LED chip has an electrode pad on the light emitting surface (light extraction surface) side, it is desirable to process the laminated body and make a hole in a portion corresponding to the electrode pad before bonding.

Next, when the protective film is provided, the protective film is peeled off, and then the laminated body that has been cut into pieces is bonded to the light emitting surface of the LED chip. At this time, the phosphor sheet of the laminate may be in a semi-cured state or may be cured in advance. It is preferable to use an adhesive for pasting, and known die bond agents and adhesives, such as acrylic resin, epoxy resin, urethane resin, silicone resin, modified silicone resin, phenol resin, polyimide, Polyvinyl alcohol, polymethacrylate resin, melamine resin, and urea resin adhesives can be used. When the phosphor sheet itself has adhesiveness or has an adhesive layer, it may be used. In the case of a semi-cured phosphor sheet, curing by heating may be used. In addition, when the phosphor sheet has heat softening properties after curing, it can be bonded by heat fusion.

Next, the polyphenylene sulfide resin film substrate is peeled from the laminate. If the base material is polyphenylene sulfide, the base material can be easily removed without causing damage to the phosphor sheet or peeling from the LED chip. It is possible to stick the phosphor sheet to the LED chip after peeling off the base material in advance with the timing to peel off the protective film, but if the strength of the phosphor sheet is weak, the base material will be peeled off first Since there is a possibility that the phosphor sheet may be damaged, it is preferable that the substrate is peeled off after being attached to the LED chip.

Then, the light emitting device can be obtained by electrically connecting the electrode of the LED chip and the wiring of the circuit board by a known method. When the LED chip has an electrode on the light emitting surface side, the LED chip is fixed to the circuit board with a die bonding material or the like with the light emitting surface facing up, and then the wire on the upper surface of the LED chip and the circuit board are connected by wire bonding To do. Further, when the LED chip is a flip chip type having an electrode pad on the opposite surface of the light emitting surface, the electrode surface of the LED chip is opposed to the wiring of the circuit board and connected by batch bonding. When the phosphor sheet is bonded to the LED chip in a semi-cured state, it can be cured at a suitable timing before or after this electrical connection. For example, in the case where the flip chip type is collectively bonded, when the thermocompression bonding is performed, the phosphor sheet may be simultaneously cured by the heating. Further, in the case where a package in which an LED chip and a circuit board are connected is surface-mounted on a larger circuit board, the phosphor sheet may be cured simultaneously with soldering by solder reflow.

The phosphor sheet may serve as a sealing agent for the LED chip, but the LED chip to which the phosphor sheet is attached can be further sealed using a known silicone resin or the like as a light-transmitting sealing material. Moreover, after sealing an LED chip with a translucent sealing material, it is also possible to use a phosphor sheet on the sealing material.

It is also possible to attach a non-separated laminate to a semiconductor wafer with LED chips formed on the surface, and then singulate the semiconductor wafer and the laminate together (dicing).

The light emitting device to which the LED chip obtained by using the phosphor sheet in the present invention can be applied is not particularly limited, and the backlight of a display used in a television, a personal computer, a mobile phone, a game machine, etc. Widely applicable to general lighting of fields and buildings.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

<Film thickness measurement>
The film thickness of a predetermined position of the base material on which the phosphor sheet was formed was measured in advance with a micrometer and marked. After laminating the phosphor sheet, the marking portion was measured again with a micrometer, and the film thickness of the phosphor sheet was obtained by subtracting the film thickness of the base material previously measured from the film thickness obtained. The film thickness was measured at 100 points in a grid pattern with a 110 mm square sheet as a measurement sample, the maximum value, the minimum value, and the average value of each sample were determined, and the film thickness variation B was determined by the following formula. .
Film thickness variation B (%) = {(maximum film thickness deviation value * −average film thickness) / average film thickness} × 100
* For the maximum film thickness deviation value, the one with the larger difference from the average film thickness is selected from the maximum value or the minimum value.

<Correlated color temperature variation>
Correlation color immediately after the start of the test using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) by turning on the LED chip by applying a current of 400 mA to a light emitting device in which each phosphor sheet is mounted on a blue LED element. The temperature was measured. 100 LED light-emitting devices were produced separately for each type of phosphor sheet, and an average value, maximum value, and minimum value in 100 pieces were obtained, and variations were evaluated from the following formulas.
Correlated color temperature variation (K) = correlated color temperature maximum deviation value−average correlated color temperature * correlated color temperature maximum deviation value is selected from the maximum value or the minimum value of the correlated color temperature that has a larger difference from the average.

<Synthesis Example of Silicone Fine Particle: Silicone Fine Particle 1>
Attach a stirrer, thermometer, reflux tube, and dropping funnel to a 2 L four-necked round bottom flask, and put 2 L of 2.5% aqueous ammonia containing 1 ppm of polyether-modified siloxane “BYK333” as a surfactant into the flask. The temperature was raised in an oil bath while stirring at. When the internal temperature reached 50 ° C., 200 g of a mixture of methyltrimethoxysilane and phenyltrimethoxysilane (23/77 mol%) was dropped from the dropping funnel over 30 minutes. Stirring was continued for 60 minutes at the same temperature, then about 5 g of acetic acid (special grade reagent) was added, mixed with stirring, and then filtered. 600 mL of water was added twice to the produced particles on the filter and 200 mL of methanol was added once, followed by filtration and washing. The cake on the filter was taken out, crushed, and freeze-dried over 10 hours to obtain 60 g of white powder. The obtained particles were monodispersed spherical fine particles having a median diameter (D50) of 0.5 μm. As a result of measuring the refractive index of this fine particle by the immersion method, it was 1.54. As a result of observing the particles with a cross-sectional TEM, it was confirmed that the particles had a single structure.

Example 1
Using a polyethylene container with a volume of 300 ml, “OE-6630A / B” (made by Toray Dow Corning Co., Ltd., refractive index 1.53) as a silicone resin is 40.0% by mass, and “NYAG-02” as a phosphor ( Manufactured by Intematix: Ce-doped YAG phosphor, specific gravity: 4.8 g / cm ³ , D50: 7 μm) was mixed at a ratio of 60.0% by mass.
Thereafter, using a planetary stirring and defoaming apparatus “Mazerustar (registered trademark)” KK-400 (manufactured by Kurabo Industries), stirring and defoaming were carried out at 1000 rpm for 20 minutes to obtain a phosphor sheet preparation liquid. Using a slit die coater, a sheet-forming resin solution is applied onto a polyphenylene sulfide film “Torelina (registered trademark)” (manufactured by Toray Industries, Inc.), heated at 130 ° C. for 2 hours, and dried to give an average film thickness of about 100 μm The laminated body in which the body sheet was formed was obtained. In the obtained laminate, the phosphor sheet was uniformly applied on the base film, pinholes were not observed, and the film thickness uniformity was also good.

On the phosphor sheet, “SD4580” (a silicone adhesive manufactured by Toray Dow Corning) was applied and dried by heating at 100 ° C. for 15 minutes to obtain an adhesive layer.
On the adhesive layer, “Celapeel (registered trademark)” BLK (manufactured by Toray Film Processing Co., Ltd.) was laminated at room temperature as a cover film.
Next, in order to test the substrate peelability of the obtained laminate, transfer lamination onto a glass substrate was performed.
The laminate was cut into 100 mm × 50 mm, and the cover film was peeled off. Next, the cover film was peeled off and the surface on which the adhesive layer was exposed was brought into contact with the glass substrate, and the surface was brought into close contact with a rubber hand roller so that air bubbles would not enter. Thereafter, when the “Torelina (registered trademark)” film of the base material was peeled off, only the base material film could be peeled easily without peeling off or damaging the phosphor sheet in close contact with the glass substrate.
Similarly, when a phosphor sheet was pasted on the LED element, and the luminescent color was measured by lighting, a good white LED with small variation in correlated color temperature was obtained.

(Examples 2 to 4)
The same procedure as in Example 1 was conducted, except that silicone fine particles 1 were added so as to have the amounts shown in Table 1, and the amount of each component was adjusted so that the phosphor particle content in the phosphor sheet was maintained at 60.0% by mass. Thus, a phosphor sheet was prepared. On the phosphor sheet, “SD4580” (a silicone adhesive manufactured by Toray Dow Corning) was applied and dried by heating at 100 ° C. for 15 minutes to obtain an adhesive layer.
On the adhesive layer, “Celapeel (registered trademark)” BLK (manufactured by Toray Film Processing Co., Ltd.) was laminated at room temperature as a cover film.
Next, in order to test the substrate peelability of the obtained laminate, transfer lamination onto a glass substrate was performed.
The laminate was cut into 100 mm × 50 mm, and the cover film was peeled off. Next, the cover film was peeled off and the surface on which the adhesive layer was exposed was brought into contact with the glass substrate, and the surface was brought into close contact with a rubber hand roller so that air bubbles would not enter. Thereafter, when the “Torelina (registered trademark)” film of the base material was peeled off, only the base material film could be peeled easily without peeling off or damaging the phosphor sheet in close contact with the glass substrate.
Similarly, when a phosphor sheet was pasted on the LED element, and the emission color was measured by lighting, a good white LED with very little variation in correlated color temperature was obtained.

(Comparative Example 1)
A laminate was prepared in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film “Lumirror (registered trademark)” (manufactured by Toray Industries, Inc.). The sex was confirmed. A phosphor sheet having good coating properties, no pinholes, and good film thickness uniformity was obtained. However, after transferring the laminate to a glass substrate, the substrate film was peeled off to remove the phosphor sheet. The part was attached to the base film side and was not peeled off, and was damaged and peeled off from the glass substrate.
Similarly, when the laminate was attached on the LED element and the substrate was peeled off, most of the phosphor sheets were peeled off from the LED element, and it was not possible to turn on and measure the emission color.

(Comparative Example 2)
A phosphor sheet was produced in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film with a release treatment “Therapy (registered trademark)” HP2 (manufactured by Toray Film Processing Co., Ltd.). The coating property and the substrate peelability were confirmed. At the time of application, repelling of the resin liquid for producing the phosphor sheet occurred, and the film thickness of the phosphor sheet obtained by heating and curing became non-uniform. When the base material film was peeled off after transferring the laminate to the glass substrate, the phosphor sheet could be easily peeled off without being peeled or damaged while being in close contact with the glass substrate.
Similarly, when a phosphor sheet is pasted on the LED element, and the emission color is measured by lighting, the variation in the correlated color temperature is larger than that in Examples 1 to 4 due to the large variation in film thickness. Sufficient uniformity was not obtained.

(Comparative Examples 3 and 4)
In the same manner as in Comparative Example 2, except that the silicone fine particles 1 were added so as to have the amounts shown in Table 1, and the amount of each component was adjusted so that the content of the phosphor particles in the phosphor sheet was maintained at 60.0% by mass. Thus, a phosphor sheet was prepared, and the applicability of the resin liquid for sheet preparation and the substrate peelability were confirmed. At the time of application, repelling of the resin liquid for producing the phosphor sheet occurred, and the film thickness of the phosphor sheet obtained by heating and curing became non-uniform. When the base material film was peeled off after transferring the laminate to the glass substrate, the phosphor sheet could be easily peeled off without being peeled or damaged while being in close contact with the glass substrate.
Similarly, when a phosphor sheet is pasted on the LED element, and the emission color is measured by lighting, the variation in the correlated color temperature is larger than that in Examples 1 to 4 due to the large variation in film thickness. Sufficient uniformity was not obtained.

(Comparative Example 5)
A phosphor sheet was prepared in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film with a release treatment “Therapy (registered trademark)” BLK (manufactured by Toray Film Processing Co., Ltd.). The coating property and the substrate peelability were confirmed. The repelling of the resin liquid for producing the phosphor sheet was generated at the time of coating, pinholes were frequently generated, and the thickness of the phosphor sheet obtained by heating and curing became non-uniform. When the base material film was peeled off after transferring the laminate to the glass substrate, the phosphor sheet could be easily peeled off without being peeled or damaged while being in close contact with the glass substrate.
Similarly, when a phosphor sheet is pasted on the LED element, and the emission color is measured by lighting, the variation in the correlated color temperature is very large compared to Examples 1 to 4 due to the large variation in film thickness. As a result, sufficient uniformity could not be obtained.

(Comparative Example 6)
In the same manner as in Comparative Example 5, except that the silicone fine particles 1 were added so as to have the amounts shown in Table 1, and the amount of each component was adjusted so that the content of the phosphor particles in the phosphor sheet was maintained at 60.0% by mass. Thus, a phosphor sheet was prepared, and the applicability of the resin liquid for sheet preparation and the substrate peelability were confirmed. At the time of application, repelling of the resin liquid for producing the phosphor sheet occurred, and the film thickness of the phosphor sheet obtained by heating and curing became non-uniform. When the base material film was peeled off after transferring the laminate to the glass substrate, the phosphor sheet could be easily peeled off without being peeled or damaged while being in close contact with the glass substrate.
Similarly, when a phosphor sheet is pasted on the LED element, and the emission color is measured by lighting, the variation in the correlated color temperature is larger than that in Examples 1 to 4 due to the large variation in film thickness. Sufficient uniformity was not obtained.

Claims (10)

1. A substrate containing polyphenylene sulfide;
   A phosphor sheet containing at least a silicone resin and a phosphor laminated on the substrate;
   A laminate comprising:
2. The silicone resin is an addition-curable silicone resin formed by a hydrosilylation reaction between a compound containing an alkenyl group bonded to at least a silicon atom and a compound having a hydrogen atom bonded to a silicon atom. The laminate according to claim 1.
3. The laminate according to claim 1 or 2, wherein the phosphor sheet further contains silicone fine particles.
4. The laminate according to claim 3, wherein the silicone fine particles are a silicone resin obtained by condensing organosilane.
5. The laminate according to claim 3 or 4, wherein the amount of the silicone fine particles is 1% by mass or more and 20% by mass or less based on the total amount of the silicone resin and the silicone fine particles.
6. The laminate according to any one of claims 1 to 5, wherein the content of the phosphor particles is 53% by mass or more based on the phosphor sheet.
7. The laminate according to any one of claims 1 to 6, wherein the phosphor sheet has a thickness of 10 to 200 µm.
8. The laminate according to any one of claims 1 to 7, wherein a variation in film thickness of the phosphor sheet is within ± 5%.
9. The laminate according to any one of claims 1 to 8, wherein the phosphor sheet is used as a wavelength conversion sheet of a light emitting diode element.
10. A method for producing a light-emitting diode with a wavelength conversion layer, comprising: a step of bonding the laminate according to any one of claims 1 to 9 to an LED element; and a step of peeling a substrate from the laminate. .