JPWO2016002584A1 - Laminated body and method of manufacturing light emitting device using the same - Google Patents

Abstract

A laminate having a phosphor layer containing a phosphor and a resin and a support substrate, the storage elastic modulus of the support substrate measured by a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% G ′ and the loss elastic modulus G ″ satisfy the relational expression of G ′ <G ″ (Formula 1) and 10 Pa <G ′ <105 Pa (Formula 2) in all or part of the temperature range of 10 ° C. to 100 ° C. Provided is a laminate in which a phosphor sheet is formed with good followability on a light extraction surface of an LED chip, in particular, a side surface light extraction surface in a flip chip type LED.

Description

  The present invention relates to a laminate of a phosphor layer containing a phosphor and a resin and a support substrate. The present invention also relates to a method for manufacturing a light emitting device including a step of covering the upper light emitting surface and the side light emitting surface of the LED chip using the laminate.

  Light-emitting diodes (LEDs) have a remarkable improvement in light-emitting efficiency, and feature low power consumption, long life, and design, in addition to liquid crystal display (LCD) backlights. The market is rapidly expanding in the automotive field such as lights and general lighting.

  The LEDs are classified into a lateral type, a vertical type, and a flip chip type depending on the mounting type, but the flip chip type LED has attracted attention because it can increase the light emitting area and has excellent heat dissipation. However, in conventional flip-chip type LED sealing, it is impossible to equalize the thickness of the phosphor layer between the top surface and the side surface of the chip, resulting in the problem of uneven azimuth of the emitted color. It was.

  In order to solve this problem, a technique has been proposed in which a phosphor layer containing a phosphor and a resin and processed into a sheet shape is uniformly attached to the periphery of the chip with good followability (see, for example, Patent Documents 1 and 2). Patent Document 1 is a method of attaching a phosphor layer to a side surface of an LED chip using a pressure member in which a recess that is slightly larger than the LED chip is formed. In Patent Document 2, a laminated body including a supporting base material and a phosphor layer is placed on an LED chip, and a first-stage sticking process is performed in which this is pressurized with a diaphragm film in a vacuum state, and thereafter the supporting base material is removed. Further, the phosphor layer is pasted on the side surface of the LED chip through a second stage pasting step by non-contact pressure with compressed air.

JP 2011-138831 A International Publication No. 2012/023119

  However, the method described in Patent Document 1 is not economical because it is necessary to remake a mold as a pressure member every time the type of LED changes. Further, since the pressing member is brought into contact with the phosphor layer to pressurize, there is a problem that the sheet is damaged or the pressing member is contaminated, resulting in poor productivity.

  In addition, the method described in Patent Document 2 is such that the phosphor layer cannot follow the side surface of the chip due to insufficient flexibility of the support base material only in the first stage of the diaphragm pressurization step. After that, the second non-contact pressure process was performed, and there was a problem in terms of productivity.

  An object of the present invention is to provide means for forming a phosphor layer with a uniform film thickness on the upper and side surfaces of an LED chip by a simple method. Moreover, it aims at providing the manufacturing method of the light emitting element using this laminated body.

The present invention is a laminate having a phosphor layer containing a phosphor and a resin and a supporting base material, wherein the supporting base material is measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0%. G ′ and loss elastic modulus G ″ are all or part of the temperature range from 10 ° C. to 100 ° C. G ′ <G ″ (Formula 1)
And 10 Pa <G ′ <10 ⁵ Pa (Formula 2)
It is a laminated body that satisfies the following relational expression.

  ADVANTAGE OF THE INVENTION According to this invention, a fluorescent substance layer can be affixed on a LED chip upper light emission surface and a side light emission surface with sufficient tracking property by the method excellent in productivity. This also provides a light-emitting device that is free from uneven azimuth of emitted color.

An example of a light emitting device structure manufactured using the laminate of the present invention An example of the LED package which covered the fluorescent substance layer using the layered product of the present invention An example of the LED package which covered the fluorescent substance layer using the layered product of the present invention An example of a method for attaching a phosphor layer using the laminate of the present invention An example of a method for attaching a phosphor layer using the laminate of the present invention An example of a manufacturing process of a light emitting device using the laminate of the present invention An example of a manufacturing process of a light emitting device using the laminate of the present invention An example of a manufacturing process of a light emitting device using the laminate of the present invention An example of a manufacturing process of a light emitting device using the laminate of the present invention Side view and top view of light emitting device coated with phosphor layer (explanation of film thickness measurement) Side view of light emitting device coated with phosphor layer (explanation of side dihedral angle)

The laminate of the present invention is a laminate having a phosphor layer containing a phosphor and a resin and a support substrate, and the support substrate is measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0%. The storage elastic modulus G ′ and the loss elastic modulus G ″ when Gd <G ″ in the whole or part of the temperature range of 10 ° C. to 100 ° C. (Formula 1)
And 10 Pa <G ′ <10 ⁵ Pa (Formula 2)
It is a laminated body that satisfies the following relational expression.

<Phosphor layer>
The phosphor layer contains at least a phosphor and a resin and is formed into a sheet shape. Other components may be included as necessary.

(Phosphor)
The phosphor absorbs blue light, violet light, and ultraviolet light emitted from the LED chip, converts the wavelength, and emits red, orange, yellow, green, and blue light with wavelengths different from those of the LED chip. To be released. 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 method of emitting white light by optically combining a blue LED with a phosphor that emits a yellow emission color by light from the LED is exemplified.

  The phosphors as described above include various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific phosphors used in the present invention include known phosphors such as organic phosphors and inorganic phosphors. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes, perylene phosphors, pyromethene phosphors, anthracene phosphors, and pyrene phosphors. 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 Ce, And at least one selected from Tb, Pr, Sm, Eu, Dy, and Ho.), (Y _1-x Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : R (R is Ce, At least one selected from Tb, Pr, Sm, Eu, Dy, and Ho. 0 <x <0.5 and 0 <y <0.5.) Can be used.

Examples of phosphors that emit red light include sulfide-based phosphors such as Y ₂ O ₂ S: Eu, La ₂ O ₂ S: Eu, Y ₂ O ₃ : Eu, and Gd ₂ O ₂ S: Eu, or CaSiAlN ₃ : There are nitride phosphors such as Eu (called CASN).

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, Y 3 Al 5 O 12: YAG phosphor such as Ce, Lu ₃ Al ₅ O ₁₂ : LAG phosphor such as Ce, TAG phosphor such as Tb ₃ Al ₅ O ₁₂ : Ce, (Ba, Sr) ₂ SiO ₄ : Eu fluorescence Body, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce phosphor, (Sr, Ba, Mg) ₂ SiO ₄ : Eu and other silicate phosphors, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, (Ca , Sr) AlSiN ₃ : Eu, CaSiAlN ₃ : Eu, etc., nitride phosphors, Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu, etc., oxynitride phosphors, ZnS: Cu, Al, (Ca, S r) sulfide phosphor such as S: Eu, (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu phosphor, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu phosphor, SrAl ₂ O ₄ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, and phosphors such as sialon phosphors.

  Among these, YAG-based phosphors, LAG-based phosphors, TAG-based phosphors, silicate-based phosphors, sialon-based phosphors, and nitride phosphors are preferably used in terms of luminous efficiency, luminance, and color rendering properties. .

  In addition, so-called quantum dot phosphors whose color is controlled by the particle size have been developed, and can be used for the phosphor layer of the present invention.

  In addition to the above, known phosphors can be used according to the intended use and the intended emission color.

  The particle size of the phosphor is not particularly limited, but preferably has a D50 of 0.05 μm or more, more preferably 3 μm or more. Further, those having a D50 of 50 μm or less are preferred, those having a D50 of 30 μm or less are more preferred, and those having a D50 of 20 μm or less are more preferred. Here, D50 refers to the particle size when the accumulated amount from the small particle size side is 50% in the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method. When D50 is in the above range, the dispersibility of the phosphor in the phosphor layer is good, and stable light emission can be obtained.

  One type of phosphor may be used, or a plurality of types may be mixed and used. For example, when used for a blue light emitting LED, there is a method in which one type of yellow phosphor is dispersed to emit pseudo white light from the viewpoint of economy and simplicity. On the other hand, in order to emit white light with good color rendering, there is also a method of mixing and dispersing a green phosphor or a yellow phosphor and a red phosphor.

  In the present invention, the phosphor content is not particularly limited, but from the viewpoint of increasing the wavelength conversion efficiency of light emission from the LED chip, it is preferably 10% by weight or more of the entire phosphor layer, and 40% by weight or more. More preferably. Although the upper limit of the phosphor content is not particularly defined, it is preferably 95% by weight or less, preferably 90% by weight or less of the entire phosphor layer from the viewpoint that a phosphor layer excellent in workability can be easily produced. Is more preferably 85% by weight or less, further preferably 80% by weight or less, and particularly preferably 70% by weight or less.

  The phosphor layer of the present invention is particularly preferably used for light emitting surface coating applications of LED chips. In that case, the LED light-emitting device which shows the outstanding performance can be obtained because content of the fluorescent substance in a fluorescent substance layer is the said range.

(resin)
The resin contained in the phosphor layer of the present invention may be any resin as long as the phosphor can be uniformly dispersed therein and can form a sheet.

  Specifically, silicone resin, epoxy resin, polyarylate resin, PET modified polyarylate resin, polycarbonate resin, cyclic olefin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, modified acrylic, polystyrene resin, and acrylonitrile / styrene Examples include copolymer resins. In the present invention, a silicone resin or an epoxy resin is preferably used from the viewpoint of transparency. Furthermore, a silicone resin is particularly preferably used from the viewpoint of heat resistance.

  The silicone resin used in the present invention is preferably polydimethylsiloxane having a dimethylsiloxane structure as the main chain, or polyphenylmethylsiloxane obtained by converting a part of methyl groups into phenyl groups. The former is excellent in heat resistance and light resistance, while the latter has a high refractive index and high light extraction efficiency, and is therefore suitably used as an LED sealing material. In order to further increase the refractive index and improve the light extraction efficiency, a polyorganosiloxane introduced with a condensed polycyclic aromatic functional group such as a naphthyl group can also be suitably used. Any of these may be used, particularly polyphenylmethylsiloxane because the storage elastic modulus G ′ and the loss elastic modulus G ″ are lowered and softened by heating, and the effect of having heat-fusibility is great. It is more preferable.

  The silicone resin used in the present invention is preferably a curable silicone resin. The curable silicone resin is a silicone that is cured by causing a crosslinking reaction by heating, and is hereinafter referred to as a crosslinking reaction type silicone resin. Either one liquid type or two liquid type (three liquid type) liquid structure may be used.

  The crosslinking reaction type silicone resin includes a condensation reaction type and an addition reaction type. The condensation reaction type is a type that is crosslinked and cured by causing a condensation reaction with moisture in the air or a catalyst, and includes a dealcoholization type, a deoxime type, a deacetic acid type, and a dehydroxylamine type. On the other hand, the addition reaction type is a type that causes a hydrosilylation reaction with a catalyst. By causing a transition metal catalyst such as platinum to act on a mixture of an alkenyl group-containing polysiloxane having an alkenyl group bonded to a silicon atom and a hydrolyzed polysiloxane having a hydrogen atom bonded to a silicon atom to cause a hydrosilylation reaction There are types that are crosslinked and cured.

  Any of these types of cross-linking silicone resins may be used. In particular, the addition reaction type silicone resin is more preferable in that it has no by-products associated with the curing reaction, has a small curing shrinkage, and can be easily accelerated by heating.

  Alkenyl group-containing polysiloxanes are dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane. Silane compounds that are the main components of polysiloxane such as phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornene Condensation polymerization of silane compounds containing an alkenyl group bonded to a silicon atom such as nyltrimethoxysilane and octenyltrimethoxysilane Ri is synthesized.

  Hydropolysiloxane is obtained by condensation polymerization of the above silane compound, which is the main component of polysiloxane, and hydrogenated silane compounds such as dimethylmethoxysilane, diphenylmethoxysilane, methylphenylmethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Synthesized.

  As such an example, a well-known thing as described in Unexamined-Japanese-Patent No. 2010-159411 can be utilized. Preferred examples of the hydrosilylation catalyst include platinum-based catalysts, rhodium-based catalysts, iridium-based catalysts, and iron-based catalysts. Of these, platinum-based catalysts are preferred because of their high reactivity. In particular, a platinum-alkenylsiloxane complex having a low chlorine content is preferred. Examples of the alkenyl siloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples include alkenyl siloxanes in which a part of the methyl groups of these alkenyl siloxanes are substituted with groups such as ethyl groups and phenyl groups, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with groups such as allyl groups and hexenyl groups. . In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because of its good stability.

  Furthermore, it is preferable that a hydrosilylation reaction retarder is contained in the silicone resin for the purpose of suppressing an excessive hydrosilylation reaction and extending the pot life. As hydrosilylation reaction retarders, acetylene group-containing alcohol derivatives, benzotriazole derivatives, cyclic vinylsiloxane derivatives, ethylenediamine derivatives, and the like are known, but acetylene group-containing alcohol derivatives are the most in terms of pot life extension and heat-curing properties. Are better. Examples of acetylene group-containing alcohol derivatives include 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1-pentyne- Examples include 3-ol, 3-phenyl-1-butyn-3-ol, but are not limited thereto.

  By appropriately designing the molecular weight and the degree of crosslinking of these resins, the storage elastic modulus at room temperature (25 ° C.) and the storage elastic modulus at high temperature (100 ° C.) can be controlled, and a resin useful in the practice of the present invention can be obtained. It is done.

  The silicone resin used in the present invention can be selected from those having a suitable storage elastic modulus among general silicone encapsulants for LED applications. As specific examples, as polyphenylmethylsiloxane, OE-6630, OE-6635, OE-6665, OE-6520 (manufactured by Toray Dow Corning), KER-6110, ASP-1031 (manufactured by Shin-Etsu Chemical), IVS5332, XE14-C6091 (made by Momentive Performance Materials Japan), OE-6336, OE-6351 (made by Toray Dow Corning), KER2500, KER6075 (made by Shin-Etsu Chemical), IVS4632 (momentive performance made by Polydimethylsiloxane) Materials Japan). All of these are two-liquid mixed types, for example, OE-6630 is a mixed type of liquid A and liquid B (OE-6630A / B).

(Silicone adhesive)
For the purpose of controlling the thermoplasticity of the phosphor layer in the present invention and enhancing the adhesion to the LED chip, the phosphor layer may contain a non-crosslinked reactive silicone resin as a silicone adhesive. The non-crosslinking reaction type silicone resin refers to a polyorganosiloxane that does not contain a crosslinking agent or a catalyst and does not crosslink at a temperature of 150 ° C. or lower.

  The non-crosslinking reactive silicone resin in the present invention preferably has a glass transition temperature in the range of 50 to 150 ° C. More preferably, it is 70-120 degreeC. When the glass transition temperature is within these ranges, appropriate tackiness (tackiness) can be expressed in the temperature range where the phosphor layer is applied, and adhesion to the LED chip can be enhanced.

  In addition, the glass transition point in this invention is a value measured with a commercially available measuring device [For example, the differential scanning calorimeter (brand name DSC6220 temperature rising rate 0.5 degree-C / min) by Seiko Electronic Industry Co., Ltd.]. By adding such a non-crosslinking reaction type silicone compound to a polysiloxane having a large storage elastic modulus G ′ even during heating, the storage elastic modulus G ′ during heating is lowered to impart thermoplasticity (thermosoftening property). It is possible.

  The non-crosslinking reaction type silicone resin in the present invention preferably has a structure represented by the following general formula (1).

  In the formula, R is an alkyl or cycloalkyl group having 1 to 6 carbon atoms, Ph is a phenyl group, Me is a methyl group, a, b, c, d, e, f, and g are 0 <a ≦ 10, 20 ≦ b ≦ 40, 10 ≦ c ≦ 35, 1 ≦ d ≦ 15, 10 ≦ e ≦ 35, 5 ≦ f ≦ 30, 0 <g ≦ 10, and a + b + c + d + e + f + g = 100.

  By using the non-crosslinking reaction type silicone resin having the structure as described above, the storage elastic modulus G ′ at 25 ° C. and 100 ° C. of the phosphor layer can be adjusted to a preferable range, and the phosphor-containing resin composition It becomes possible to suppress aggregation and sedimentation of the phosphor inside, and it is possible to produce a phosphor-containing resin composition having a small variation in color temperature when the phosphor layer is produced.

  In the structure represented by the general formula (1), R is an alkyl group or cycloalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and an octyl group, and a methyl group is more preferable. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, and a cyclohexyl group is more preferable.

  In the structure represented by the general formula (1), a, b, c, d, e, f and g are positive numbers, and 0 <a ≦ 10, 20 ≦ b ≦ 40, 10 ≦ c ≦. 35, 1 ≦ d ≦ 15, 10 ≦ e ≦ 35, 5 ≦ f ≦ 30, 0 <g ≦ 10, and a + b + c + d + e + f + g = 100. Further, 0 ≦ a ≦ 5, 25 ≦ b ≦ 35, 15 ≦ c ≦ 30, 5 ≦ d ≦ 15, 20 ≦ e ≦ 35, 5 ≦ f ≦ 30, and 0 <g ≦ 5 are more preferable.

Presence of such bonds includes structural analysis by solid state NMR of ¹ H-NMR and ¹³ C-NMR, copolymerization composition by decomposition by tetraethoxysilane in the presence of alkali and GC / MS measurement of the decomposition product, cross-linking point Analysis, FT-IR, etc.

  The weight average molecular weight of the non-crosslinking reaction type silicone resin in the present invention is preferably 1,000 to 10,000. By being in the said range, the dispersion stability effect of fluorescent substance becomes higher.

  The weight average molecular weight in the present invention is a value measured by a commercially available measuring instrument [for example, a multi-angle light scattering detector (trade name DAWN HELEOS II) manufactured by Shoko Scientific Co., Ltd.].

  As the non-crosslinking reaction type silicone resin in the present invention, it is possible to select and use a general resin as it is commercially available. Specific examples include KR-100, KR-101-10, KR-130 manufactured by Shin-Etsu Chemical Co., Ltd., SR-1000, YR3340, YR3286, PSA-610SM, XR37-B6722 manufactured by Momentive Performance Materials. Etc.

  In the present invention, it is not essential to add a non-crosslinking reaction type silicone resin, but by appropriately designing the mixing ratio of the crosslinking reaction type silicone resin and the non-crosslinking reaction type silicone resin, heating for pasting can be performed even after curing. Sometimes appropriate softness and tackiness can be imparted, resulting in a resin useful in the practice of the invention. In this case, a suitable ratio of the non-crosslinked reactive silicone resin to the crosslinked reactive silicone resin is 0.5 to 100 parts by weight, more preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the crosslinked reactive silicone resin. Part.

(Silicone fine particles)
The phosphor layer in the present invention may contain silicone fine particles in order to suppress sedimentation of the phosphor and improve the fluidity of the resin composition for producing a phosphor layer to improve the coating property. The silicone fine particles 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-proxysilane, methyltri-iso-proxysilane, methyltri-n-butoxysilane, methyltri-iso-butoxysilane, methyltri-s-butoxy Silane, methyltri-t-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-butyltributoxysilane, iso-butyltributoxysilane, s-butyltrimethoxysilane, t -Butyltributoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane Are illustrated.

  Organodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, and phenylmethyldiethoxysilane. Diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N -Ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, vinylmethyldiethoxysilane and the like are exemplified.

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

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

  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 Japanese Unexamined Patent Publication No. 63-77940, Japanese Unexamined Patent Publication No. 6-248081, Japanese Unexamined Patent Publication No. 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, in order to hydrolyze and condense organosilane and / or its partial hydrolyzate to produce spherical silicone fine particles, polymer dispersants such as water-soluble polymers and surfactants are added to the reaction solution. It is preferable to obtain the silicone fine particles by the method. The water-soluble polymer can be either a synthetic polymer or a natural polymer as long as it acts as a protective colloid in a solvent. Specific examples include water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone. Any surfactant may be used as long as it has a hydrophilic site and a hydrophobic site in the molecule, thereby acting as a protective colloid. Specifically, anionic surfactants such as sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, etc. Cationic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene distyrenated phenyl ethers, polyoxyalkylene alkenyl ethers, ether-based or ester-based nonionic surfactants such as sorbitan monoalkylates, polyether-modified poly Silicone surface activity such as dimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polyalkylsiloxane , And fluorine-based surfactants such as perfluoroalkyl group-containing oligomers, and acrylic surfactants. Among these, polyvinyl alcohol, polyoxyethylene alkyl ether, polyether-modified polydimethylsiloxane, and perfluoroalkyl group-containing oligomer are preferable from the viewpoint of improving dispersibility in the reaction solution and the silicone composition.

The dispersant may be added in advance to the reaction initial solution, in addition to the organotrialkoxysilane and / or its partial hydrolysate, or in the organotrialkoxysilane and / or its partial hydrolyzate. A method of adding after partial condensation can be exemplified, and any of these methods can be selected. The addition amount of the dispersant is preferably in the range of 5 × 10 ^{−7 to} 0.1 part by weight with respect to 1 part by weight of the reaction solution. When the lower limit is exceeded, the particles tend to aggregate and form a lump. On the other hand, if the upper limit is exceeded, the amount of dispersant residue in the particles increases, causing coloring.

  These silicone particles may have a particle surface modified with a surface modifier for the purpose of controlling dispersibility in a matrix component, wettability, and the like. The surface modifier may be modified by physical adsorption or may be modified by a chemical reaction. Specifically, a silane coupling agent, a thiol coupling agent, a titanate coupling agent, an aluminate coupling agent, Although a fluorine-type coating agent etc. are mentioned, since it is strong in heat resistance and there is no hardening inhibition, the modification by a silane coupling agent is especially preferable.

  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. From this viewpoint, the difference between the refractive index d1 of the silicone fine particles and the refractive index d2 of the 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 within such a range, reflection / scattering at the interface between the silicone fine particles and the silicone composition can be reduced, high transparency and light transmittance can be obtained, and the brightness of the LED light emitting device can be reduced. There is no.

  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.

  The means for controlling the refractive index difference can be adjusted by changing the amount ratio of the raw materials constituting the silicone fine particles. That is, for example, by adjusting the mixing ratio of methyltrialkoxysilane and phenyltrialkoxysilane, which are raw materials, and increasing the composition ratio of methyl groups, it is possible to achieve a refractive index close to 1.40. On the contrary, it is possible to increase the refractive index to 1.50 or more by increasing the composition ratio of the phenyl group.

  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 layer are improved. Moreover, the fluidity improvement effect of the resin liquid for fluorescent substance layer 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, that is, the median diameter (D50) and the particle size distribution of the silicone fine particles contained in the phosphor layer 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.

  The content of the silicone fine particles is preferably 1 part by weight or more and more preferably 2 parts by weight or more as a lower limit with respect to 100 parts by weight of the silicone resin. Further, the upper limit is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, further preferably 40 parts by weight or less, and particularly preferably 25 parts by weight or less. By containing 1 part by weight or more of silicone fine particles, a particularly good phosphor dispersion stabilization effect can be obtained. On the other hand, the intensity | strength of a fluorescent substance sheet can be maintained by setting it as 100 parts weight or less, and stable film formation is possible, without making the viscosity of a silicone composition excessively set as 25 parts weight or less. It becomes.

(Metal oxide fine particles)
The phosphor layer in the present invention may further contain metal oxide fine particles as an inorganic fine particle filler in order to impart effects such as viscosity adjustment, light scattering, and coating property improvement. Examples of these metal oxide fine particles include silica, alumina, titania, zirconia, barium titanate, and zinc oxide. Particularly preferred are silica fine particles and alumina fine particles. Examples of these include aerosil and aeroxide (both manufactured by Nippon Aerosil). The average particle diameter of these fine particles is preferably selected from the range of 5 nm to 10 μm. In addition, these fine particles may be used alone or in combination. As content of microparticles | fine-particles, 0.5-30 weight part is preferable with respect to 100 weight part of silicone resins, and 1-10 weight part is further more preferable. If it is this range, the effect of light scattering and an improvement in applicability | paintability can be shown in the state in which stable film formation is possible, without raising the viscosity of a silicone composition excessively.

(Other ingredients)
The phosphor layer of the present invention may contain nano-sized high refractive index inorganic fine particles for the purpose of improving the refractive index. Examples of such inorganic fine particles include alumina, titania, zirconia, and aluminum nitride. The particle diameter is preferably 50 nm or less, and more preferably 20 nm or less so that visible light is not scattered. Further, a method of modifying the particle surface is used to prevent such aggregation of fine particles and improve dispersibility.

  The silicone resin composition for producing the phosphor layer in the present invention may contain an adhesive component in order to enhance the adhesion to the LED chip or the substrate. Examples of such adhesive components include thermoplastic silicone resins, silane monomers, and siloxane oligomers. Further, it preferably has a reactive functional group such as a silanol group or an epoxy group.

  Furthermore, the silicone resin composition for preparing the phosphor layer in the present invention is a leveling agent for stabilizing the coating film, and a silane coupling such as epoxy modification, acrylic modification, carboxyl modification, and amino modification as a sheet surface modifier. An agent may be contained.

(Method for producing phosphor layer)
A method for manufacturing the phosphor layer will be described. In addition, the following is an example and the preparation method of a fluorescent substance layer is not limited to this. First, a composition in which a phosphor is dispersed in a resin is prepared as a coating liquid for forming a phosphor layer. At this time, when the resin is a silicone resin, a silicone adhesive material may be included. Silicone fine particles are preferably added for the purpose of suppressing sedimentation of the phosphor, and other additives such as metal oxide fine particles, leveling agents and adhesion aids may be added. In addition, when an addition reaction type silicone resin is used as the resin, it is possible to extend the pot life by additionally blending a hydrosilylation reaction retarder. If necessary to make fluidity appropriate, a solvent can be added to form a solution. A solvent will not be specifically limited if the viscosity of resin of a fluid state can be adjusted. Examples thereof include glycol ether solvents or glycol ester solvents such as toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, and PGMEA.

  After preparing these components to have a predetermined composition, the phosphor is mixed and dispersed homogeneously with a stirrer / kneader such as a homogenizer, self-revolving stirrer, three roller mill, ball mill, planetary ball mill, or bead mill. A layer-forming composition is obtained. Defoaming is preferably performed after mixing and dispersing or in the process of mixing and dispersing under vacuum or a reduced pressure condition of 0.01 MPa or less.

  Next, the phosphor layer preparation composition is applied onto a second substrate (hereinafter referred to as a substrate to be coated) different from the supporting substrate claimed in the present application, and dried and cured. The substrate to be coated is not particularly limited, and a known metal, film, glass, ceramic, paper or the like can be used. In order to produce a phosphor layer with high film thickness accuracy, it is preferable that the elongation at break of the substrate to be coated is less than 200% or the Young's modulus is more than 600 MPa at 23 ° C., and the Young's modulus is particularly 4000 MPa or more. Is more preferable. Further, a material having a high melting point that is less deformed at a temperature of 150 ° C. or higher at which the resin curing reaction proceeds rapidly is preferable.

  Specifically, the substrate to be coated is a metal plate or foil such as aluminum (including aluminum alloy), zinc, copper, iron, cellulose acetate, polyethylene terephthalate (PET), polyolefin, polyester, polyamide, polyimide, polyphenylene sulfide, Resin film such as polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid, paper laminated with the resin, or paper coated with the resin, paper laminated with the metal, or laminated or vapor-deposited with the metal Resin film etc. are mentioned. Among these, a resin film is preferable in terms of the required characteristics and economy, and a PET film or a polyphenylene sulfide film is particularly preferable. Moreover, when a high temperature of 200 ° C. or higher is required when the resin is cured or the phosphor layer is attached to the LED, a polyimide film is preferable in terms of heat resistance.

  Moreover, it is preferable that the surface of the substrate to be coated is subjected to a mold release treatment in advance so that the phosphor layer can be easily peeled off. Examples of the release treatment method include a silane coupling agent coat, a fluororesin coat, a silicone resin coat, a melamine resin coat, and a paraffin resin coat. Examples of such a substrate to be coated include a peeled PET film “Therapel” (manufactured by Toray Film Processing Co., Ltd.) and the like.

  Although there is no restriction | limiting in particular in the thickness of a to-be-coated base material, As a minimum, 25 micrometers or more are preferable and 50 micrometers or more are more preferable. Moreover, as an upper limit, 5000 micrometers or less are preferable, 1000 micrometers or less are more preferable, and also 100 micrometers or less are preferable.

  Application is blade coater, slit die coater, direct gravure coater, offset gravure coater, air knife coater, roll blade coater, variver roll blade coater, two stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater. , Spin coater, knife coater and the like. In order to obtain the uniformity of the phosphor layer thickness, it is preferable to apply with a slit die coater. The phosphor layer of the present invention can also be produced by using a printing method such as screen printing, gravure printing, or lithographic printing. The printing shape may be a solid film or a pattern shape. When using a printing method, screen printing is particularly preferably used. In addition, a resin molding method such as press molding can be used.

  A general heating device such as a hot air dryer or an infrared dryer is used for drying and heat-curing the applied phosphor layer. The heat-curing conditions are usually 80 ° C. to 200 ° C. for 2 minutes to 3 hours. However, in order to obtain a so-called semi-cured B-stage state that can be softened by heating and exhibit adhesiveness, the temperature is 15 ° C. Heating for minutes to 2 hours is preferable, and heating for 30 minutes to 2 hours is more preferable.

  The phosphor layer thus produced is transported and stored together with the substrate to be coated from the viewpoint of handling, and is used after peeling the substrate to be coated and transferring it to the support substrate in the present invention immediately before use. be able to. Further, it may be used after being cut into a size corresponding to the LED chip covering the phosphor layer.

(Physical properties of phosphor layer)
The phosphor layer preferably has high elasticity near room temperature from the viewpoint of storage, transportability and processability. On the other hand, from the viewpoint of deforming and adhering to the LED chip, the elasticity becomes low under certain conditions, and flexibility and adhesiveness or tackiness (hereinafter collectively referred to as “adhesiveness”). It is preferable to express From these viewpoints, it is preferable that the phosphor layer is softened by heating at 60 ° C. or more and exhibits adhesiveness.

Such a phosphor layer has a storage elastic modulus of 1.0 × 10 ⁵ Pa or more at 25 ° C. when a phosphor layer having a frequency of 1.0 Hz, a maximum strain of 1% and a film thickness of 400 μm is measured using a rheometer. It is preferably less than 1.0 × 10 ⁵ Pa at 100 ° C., more preferably 5.0 × 10 ⁵ Pa or more at 25 ° C., and less than 5.0 × 10 ⁴ Pa at 100 ° C.

  Here, the storage elastic modulus of the phosphor layer means that only the sheet-like phosphor layer is measured with a rheometer, the film thickness of the phosphor layer is 800 μm, the frequency is 1.0 Hz, the maximum strain is 1.0%, and the temperature range is 25 to 200 ° C. , Storage elastic modulus when dynamic viscoelasticity measurement is performed at a heating rate of 5 ° C./min. Dynamic viscoelasticity means that when shear strain is applied to a material at a sinusoidal frequency, the shear stress that appears when a steady state is reached is divided into a component (elastic component) whose strain and phase match, and the strain and phase are This is a technique for analyzing the dynamic mechanical properties of a material by decomposing it into components (viscous components) delayed by 90 °. Here, what is obtained by dividing the stress component whose phase coincides with the shear strain by the shear strain is the storage elastic modulus, which indicates the following property of the material against the dynamic strain at each temperature. It is closely related to adhesion. On the other hand, the loss elastic modulus is obtained by dividing the shear stress and the stress component whose phase is delayed by 90 ° by the shear strain, and represents the fluidity of the material.

In the case of the phosphor layer according to the present invention, it has a storage elastic modulus of 1.0 × 10 ⁵ Pa or more at 25 ° C., so that it can be used against a high shear stress such as cutting with a blade at room temperature (25 ° C.). Since the sheet is cut without surrounding deformation, workability with high dimensional accuracy can be obtained. The upper limit of the storage elastic modulus at room temperature is not particularly limited for the purpose of the present invention, but is preferably 1.0 × 10 ⁹ Pa or less in consideration of the stress strain after being bonded to the LED element. Moreover, when the storage elastic modulus is less than 1.0 × 10 ⁵ Pa at 100 ° C., if the heat pasting at 60 ° C. to 150 ° C. is performed, the shape of the LED chip surface is quickly deformed and followed, High adhesive strength can be obtained. If the phosphor layer has a storage elastic modulus of less than 1.0 × 10 ⁵ Pa at 100 ° C., the storage elastic modulus decreases as the temperature is increased from room temperature. In order to obtain particularly practical sticking, 60 ° C. or higher is preferable. Further, when such a phosphor layer is heated to over 100 ° C., the storage elastic modulus further decreases and the sticking property becomes good. However, at a temperature exceeding 150 ° C., the resin is not sufficiently relaxed in stress. Curing of the resin proceeds rapidly, and cracks and peeling easily occur. Therefore, a suitable heat pasting temperature is 60 ° C to 150 ° C, more preferably 60 ° C to 120 ° C, and particularly preferably 70 ° C to 100 ° C. The lower limit of the storage elastic modulus at 100 ° C. is not particularly limited for the purpose of the present invention, but if the fluidity is too high at the time of heating and pasting on the LED element, the shape processed by cutting or punching before pasting Since it becomes impossible to hold | maintain, it is desirable that it is 1.0 * 10 < ³ > Pa or more.

  If the above storage elastic modulus can be obtained as the phosphor layer, the resin contained therein may be in an uncured state, but it is included in consideration of the handleability and storage stability of the sheet as follows. The resin to be cured is preferably after curing. If the resin is in an uncured state, the curing reaction proceeds at room temperature during storage of the phosphor layer, and the storage elastic modulus may be out of the proper range. In order to prevent this, it is desirable that the resin has been cured or is in a semi-cured state in which the curing has progressed to the extent that the storage elastic modulus does not change for a long period of time of 1 month or longer after storage at room temperature.

(Film thickness)
The film thickness of the phosphor layer of the present invention is determined from the phosphor content, desired optical characteristics, and the height of the LED chip to be coated. As described above, since there is a limit to increasing the concentration of the phosphor from the viewpoint of workability, the film thickness is preferably 10 μm or more, more preferably 30 μm or more, and further preferably 40 μm or more. On the other hand, from the viewpoint of improving the optical properties and heat dissipation of the phosphor layer, the thickness of the phosphor layer is preferably 1000 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. Further, when the LED chip to be coated has a side light emitting surface with a height of 30 μm or more, the viewpoint that the phosphor layer covers the side light emitting surface with good followability, and the change in color seen from above and the color seen from diagonally From the viewpoint of reducing the light distribution shown, the thickness of the phosphor layer is preferably equal to or less than the height of the LED chip, and more preferably equal to or less than ½.

  In addition, when the sheet thickness varies, the amount of phosphor varies for each LED chip, and as a result, the emission spectrum (color temperature, luminance, chromaticity) varies. Therefore, the variation in sheet thickness is preferably within ± 5%, more preferably within ± 3%.

  The film thickness of the phosphor layer 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. ). Moreover, the film thickness variation of a fluorescent substance layer is computed based on the following numerical formula using the said average film thickness. 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, and the value expressed in 100 minutes is 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.

<Support base material>
The supporting base material in the present invention can take a state of flowing when the phosphor layer is attached to the light emitting surface of the LED chip. By applying pressure from the support substrate side in a state where the support substrate flows, the pressure is uniformly transmitted to the phosphor layer through the support substrate, and the phosphor layer is attached to the light emitting surface of the LED chip. . Since the support base material flows, the pressure can be transmitted uniformly in all directions, and the support base material can be freely deformed to be able to go into the details. It enables pasting with good followability.

  The support base material may have fluidity without giving any particular stimulus, or may exhibit fluidity by some kind of stimulus. Here, some kind of stimulation is exemplified by mechanical stimulation such as heating, humidification, solvent addition, pressurization, or vibration. However, since fluidity is most easily managed, expression of fluidity due to heating and pressurization is achieved. preferable.

  In order to prevent the support base material from wrapping around between the phosphor layer and the light emitting surface of the LED chip before pressurization, it keeps a solid shape when not pressurized, for example, clay or plastic resin It is preferable to flow when pressurized.

  From the viewpoint of expressing the tackiness of the phosphor layer in the pressurizing step, the state in which the supporting base material flows exists at 10 ° C. or higher. Furthermore, since it is preferable that it is a solid state at room temperature from a handling viewpoint, it is preferable that the state which a support base material flows exists in 40 degreeC or more, Furthermore, it exists in 50 degreeC or more. Further, from the viewpoint of preventing the resin of the phosphor layer from being cured, the state in which the supporting base material flows is present at 150 ° C. or lower, and more preferably 100 ° C. or lower. Here, the state in which the supporting base material flows includes a case in which the supporting base material flows only during pressurization.

(Rheological properties of support substrate)
The state in which the supporting substrate flows in the present invention is defined by dynamic viscoelasticity measurement using a rheometer. Specifically, the dynamic viscoelasticity measurement method is as follows: a material is sandwiched between parallel disk plates, and the shear strain is applied at a sine frequency of 1.0 Hz and a maximum strain of 1.0% while changing the temperature. Method of measuring shear stress and strain when applied, and calculating storage elastic modulus G ′ indicating deformation followability of the material against dynamic strain, loss elastic modulus G ″ indicating fluidity of the material, and viscosity from the measured values The thickness of the supporting base material used as a sample is 1 mm, and the temperature change is typically from 25 ° C. to 200 ° C. at a temperature rising rate of 5 ° C./min.

Here, the storage elastic modulus G ′ and the loss elastic modulus G ″ measured at a frequency of 1.0 Hz and a maximum strain of 1.0% using a rheometer in a state where the supporting base material of the present invention flows are 10 ° C. In the whole or part of the temperature range above 100 ° C
G ′ <G ”(Formula 1)
Relationship, and
10 Pa <G ′ <10 ⁵ Pa (Formula 2)
It is a relationship. In Formula 2, the lower limit is more preferably 10 ² Pa <G ′, and the upper limit is more preferably G ′ <10 ⁴ Pa. Moreover, it is more preferable that these relationships are satisfied in all or part of the temperature range of 40 ° C. or higher and 100 ° C. or lower, and it is more preferable that the relationship is satisfied in the entire temperature range of 70 ° C. or higher and 100 ° C. or lower.

  As shown in Equation 1, the supporting substrate can flow when G ″ indicating the viscous component is larger than G ′ indicating the elastic component.

  As shown in Equation 2, if the storage elastic modulus G ′ is larger than the lower limit, it is possible to transmit the pressure to the phosphor layer without causing the supporting base material to flow out. Further, if the storage elastic modulus G ′ is smaller than the upper limit, the support base material is likely to be fluidly deformed, so that the followability to the coating becomes high.

The viscosity of the state in which the supporting base material to flow, from the viewpoint of pressure transmission to the phosphor layer, preferably at least 10 Pa · s at all or part of the temperature range of 10 ° C. or higher 100 ° C. or less, 10 2 ^Pa · s The above is more preferable. Further, from the viewpoint of followability to the coating, 10 ⁵ Pa · s or less is preferable in all or part of the temperature range of 10 ° C. or more and 100 ° C. or less, and 10 ⁴ Pa · s or less is more preferable. Furthermore, from the viewpoint of maintaining the thickness of the phosphor layer, it is preferable that the viscosity of the support substrate is lower than the viscosity of the phosphor layer at the temperature at the time of pressurization.

  The physical properties are more preferably satisfied in all or part of the temperature range of 40 ° C. or higher and 100 ° C. or lower, particularly preferably 70 ° C. or higher and 100 ° C. or lower.

(Vicat softening temperature)
It is more preferable that the supporting base material is hard to be deformed so that it can be easily handled at room temperature, and the supporting base material softens at a temperature at which the curing of the phosphor layer does not proceed rapidly. From this viewpoint, the Vicat softening temperature of the supporting substrate is preferably 25 ° C. or higher and 100 ° C. or lower, and more preferably 25 ° C. or higher and 50 ° C. or lower. Here, the Vicat softening temperature is a temperature at which the supporting base material softens, and is measured according to a method defined in JIS K 7206 (1999) A50. Specifically, a test piece is placed on the heat transfer medium, and the temperature of the heat transfer medium is increased with the end face of the load rod (cross-sectional area 1 mm ² ) pressed against the upper surface of the center of the test piece. The temperature (° C.) when the bar enters the test piece by 1 mm is defined as the Vicat softening temperature.

(Melting point)
This supporting substrate is solid at room temperature, and is preferably melted and fluidized by heating. From this point of view, the melting point of the supporting substrate is preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 40 ° C. or higher and 70 ° C. or lower. The melting point is measured according to the method defined in JIS K 7121 (1987). Specifically, the temperature at which the phase transition from a solid to a liquid is measured when the temperature is raised at 10 ° C./min by differential thermal analysis (DTA) or differential scanning calorimetry (DSC). Of melting point.

(Melt flow rate)
The fluidity of the supporting substrate after melting can be expressed by a melt flow rate (MFR) measured according to a method defined in JIS K7210 (1999). From the viewpoint of adhering the phosphor layer to the coating with good followability, the MFR at a measurement temperature of 190 ° C. and a load of 21.2 N is preferably 1 (g / 10 minutes) or more, more preferably 10 (g / 10 minutes) or more. preferable. Further, from the viewpoint of preventing the fluidized support substrate from entering between the phosphor layer and the coating, it is preferably 500 (g / 10 minutes) or less, more preferably 200 (g / 10 minutes) or less, and 100 (g / 10 minutes) or less is more preferable.

(Thickness of support substrate)
Although the film thickness of a holding base material is not specifically limited, A suitable film thickness is dependent on the height of the target object to coat | cover.
For example, when considering the case of covering the LED chip, from the viewpoint of followability to the side surface of the LED chip, it is preferably at least the height of the LED chip to be coated, more preferably at least twice the height of the LED chip. . If the film thickness is within this range, the supporting base material that has flowed during pressurization can easily wrap around the side surface of the chip, and the phosphor layer can be attached with good followability. Moreover, it is preferable that the film thickness of a support base material is 10 times or less of LED chip height from a viewpoint of economical efficiency and the viewpoint which the whole support base material fluidizes by heating.

  Considering that the height of the LED chip that is normally used is 100 to 300 μm, the thickness of the support substrate is preferably 300 μm or more, and more preferably 500 μm or more. Moreover, 2000 micrometers or less are preferable and 1000 micrometers or less are more preferable.

  From the viewpoint of uniformly transmitting the pressure at the time of pressurization to the phosphor layer, the film thickness of the supporting substrate is preferably in the range of the average film thickness ± 10%.

(Surface condition)
The surface shape of the surface of the support substrate that contacts the phosphor layer is transferred to the phosphor layer surface during pressurization, and affects the appearance and color variation of the emitted color. Therefore, it is preferable that the surface of the support base on the phosphor layer side is a smooth surface, that is, a mirror surface. Furthermore, the surface roughness Ra of the smooth surface is preferably 10 μm or less.

(Material)
The material of the supporting substrate is not particularly limited as long as it can take the above-described fluid state. Moreover, a single substance or a mixture may be sufficient. However, the main component is preferably a plastic material, and the content thereof is preferably 50% by weight or more, more preferably 80% by weight or more, from the viewpoint of covering the phosphor layer with good followability. Specific examples of such a plastic material include a plastic resin, rubber, clay, and the like, and a thermoplastic resin is preferable from the viewpoints of moldability and handleability.

  Here, the thermoplastic resin refers to a resin having a region in which plastic deformation is possible by heating (hereinafter referred to as “thermoplastic region”). It is preferable that plastic deformation is possible at a part or all of 40 ° C. or more and 100 ° C. or less. Further, the curing reaction may proceed by heating at a temperature higher than the temperature range in which plastic deformation occurs. The region where the curing reaction proceeds is preferably 100 ° C. or higher, and more preferably 150 ° C. or higher.

  The Vicat softening temperature of the thermoplastic resin is preferably 25 ° C. or higher and 100 ° C. or lower, and more preferably 25 ° C. or higher and 50 ° C. or lower. The melting point of the thermoplastic resin is preferably 40 ° C. or higher and 100 ° C. or lower, and more preferably 40 ° C. or higher and 70 ° C. or lower. The MFR at a measurement temperature of 190 ° C. and a load of 21.2 N of the thermoplastic resin is preferably 1 (g / 10 minutes) or more, and more preferably 10 (g / 10 minutes) or more. Moreover, 500 (g / 10min) or less is preferable, 200 (g / 10min) or less is preferable, and 100 (g / 10min) or less is more preferable. Vicat softening temperature, melting point, and MFR are all measured by the same method as that for the support substrate.

  Specific examples of such thermoplastic resins include polyethylene resins, polypropylene resins, poly-α-olefin resins (sometimes referred to as α-polyolefin resins), cyclic polyolefin resins, polycaprolactone resins, urethane resins, acrylic resins. (Including methacrylic resins), epoxy resins, silicone resins and copolymers thereof.

  Here, the poly-α-olefin resin refers to a polymer having a side chain functional group having 2 or more carbon atoms obtained by addition polymerization of an α-olefin. Examples of the side chain functional group include a linear alkyl group. Specific examples of the poly-α-olefin resin include polymer compounds obtained by addition polymerization of 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and mixtures thereof. The Among these, a poly-α-olefin resin, a polycaprolactone resin, an acrylic resin, a silicone resin, and one or two or more resins selected from the group consisting of one or more of these and a copolymer resin of ethylene are included. Is preferred. The support base material of the present invention includes a “peelable support base material” that peels the support base material from the phosphor layer after the phosphor layer is coated on an object (for example, an LED chip), and remains attached to the phosphor layer. There are two types of “non-peeling support substrate” incorporated in the light emitting device.

  The material used for the “peelable support substrate” has an important balance between adhesion to the phosphor layer and peelability, and adhesion to the LED chip. On the other hand, since the material used for the “non-peelable support substrate” is incorporated in the light emitting device, it is important that the material has excellent light extraction properties, heat resistance, and light resistance.

  As a method for producing a light emitting device using the laminate of the invention, any of a process using a “peelable support substrate” and a process using a “non-peelable support substrate” can be suitably used. However, since the degree of freedom with which an optical member such as a lens structure can be precisely designed after the support substrate is peeled off is high, a process using a “peelable support substrate” is more preferable.

(Peelable support substrate)
It is important that the peelable support substrate can be easily peeled off after the phosphor layer is coated. Particularly preferable properties are fluidity when heated and properties of being hardened and peeled off after cooling to room temperature. Examples of thermoplastic resins having such properties include polypropylene resins, poly-α-olefin resins, cyclic polyolefin resins, polycaprolactone resins, and copolymer resins of these with ethylene, among which Vicat softening temperature or melting point. Copolymer resin (ethylene-α-olefin copolymer resin) of poly-α-olefin resin and ethylene is more preferable, and ethylene-1-hexene copolymer resin is particularly preferable. .

  Also, if the adhesion between the support substrate and the phosphor layer is weak and the phosphor layer is difficult to hold on the support substrate, a highly adhesive thermoplastic resin is mixed with the ethylene-α-olefin copolymer resin. A supporting substrate may be manufactured. Examples of the thermoplastic resin having high adhesiveness include urethane resins, acrylic resins, epoxy resins, and copolymer resins of these with ethylene. From the viewpoint of low Vicat softening temperature or melting point, ethylene-acrylic (methacrylic) copolymer resins. It is preferable that

  The mixing ratio of the ethylene-α-olefin copolymer resin and the highly adhesive thermoplastic resin is determined by the balance between adhesiveness and peelability. As a ratio for taking such a balance, it is preferable to contain 0.01 to 10 parts by weight of a thermoplastic resin having high adhesiveness with respect to 100 parts by weight of the ethylene-α-olefin copolymer resin. It is more preferable to contain parts by weight.

  Examples of the peelability index include the adhesive strength of the support substrate. Here, as a first method for measuring the adhesive strength of the supporting substrate, there is a 90 degree peel test defined in JIS Z 0237 (2009). In the measurement by this method, the adhesive strength of the supporting substrate is 0. 0 from the viewpoint of achieving both the adhesiveness for holding the phosphor sheet and the releasability for peeling the supporting substrate after being attached to the LED chip. It is preferable that it is the range of 05-2.0N / 20mm, and 0.1-1.5N / 20mm is more preferable.

  Furthermore, as a second method for directly measuring the adhesive strength between the phosphor layer and the supporting substrate, there is a method of measuring by the following peel test (this is referred to as “phosphor layer: supporting substrate adhesive strength evaluation test”). Can be mentioned. “Phosphor layer: support substrate adhesive strength evaluation test” includes a first step of preparing a laminate sample in which a phosphor layer having a size of 50 mm × 50 mm is bonded to a support substrate, and the surface of the phosphor layer A product name: Circuit tape 647 0.12, Adhesive strength 15 N / 50 mm (manufactured by Teraoka Seisakusho) is applied to the phosphor directly above the phosphor with a length of 50 mm. A force gauge (trade name: Digital Force Gauge ZTS-20N, Imada Co., Ltd.) required for the process and pulling the tape in a direction of 90 degrees with respect to the laminate sample to peel off the phosphor layer from the support substrate Product). In the measurement by this method, the adhesive strength of the supporting substrate is preferably in the range of 0.001 to 1.0 N / 50 mm, and more preferably 0.01 to 0.5 N / 50 mm. In addition, in this method, when a fluorescent substance layer does not peel from a support base material, it is evaluated that it is 15 N / 50mm or more.

  As for the method of peeling off the peeling type support substrate, after cooling to 30 ° C. or lower, one end of the support substrate is gripped with tweezers or the like or peeled, or the support substrate is adhered to the adhesive tape and peeled off. Although illustrated, it is not limited to these methods.

  Specific examples of the ethylene-α-olefin copolymer resin include “Tuffmer” (Mitsui Chemicals) and “Excellen” (Sumitomo Chemical). Specific examples of the cyclic olefin resin include “ZEONOR” and “ZEONEX” (manufactured by Nippon Zeon). Specific examples of the polycaprolactone resin include “Placcel H” (manufactured by Daicel). Further, as a thermoplastic resin for improving adhesiveness, ethylene-methacrylic acid ester resin “Akulift” (manufactured by Sumitomo Chemical) can be mentioned.

(Non-peelable support substrate)
Since a non-peelable support substrate is incorporated in a light emitting device, transparency and heat resistance are required. A thermoplastic resin having such properties exhibits plasticity in the temperature range (50 to 150 ° C.) to be coated, but a resin that undergoes a irreversible curing reaction and is completely cured when heated to a temperature higher than that is preferable. Here, the completely cured state refers to a state in which the storage elastic modulus G ′ and the loss elastic modulus are cured until the range where G ″ satisfies G ′ <G ″ disappears in the rheometer test. Specific examples of such thermoplastic resins include acrylic resins (including methacrylic resins), epoxy resins, silicone resins, and copolymer resins of these with ethylene. A silicone resin is particularly preferable from the viewpoint of heat resistance and light resistance.

  A specific example of the acrylic resin is “ACRlift” (manufactured by Sumitomo Chemical). Specific examples of the epoxy resin include those obtained by mixing Epicoat 157S70 and Epicoat 828 (Japan Epoxy Resin) with 2-phenylimidazole as a curing accelerator, and specific examples of the silicone resin include those having a thermoplastic region as OE- 6450, OE6635 (manufactured by Dow Corning Toray) and the like.

  The adhesive strength of the non-peelable support substrate is preferably 0.05 N / 20 mm or more and 50 N / 20 mm or less in the first method required by the 90-degree peel test specified in JIS Z 0237 (2009). In the “phosphor layer: support base material adhesive strength evaluation test”, 1.0 N / 50 mm or more is preferable and 5.0 N / 50 mm from the viewpoint of sufficient adhesion between the phosphor layer and the support base material. The above is more preferable, and 15 N / 50 mm or more, that is, it is further preferable that the phosphor layer is not peeled off from the support substrate.

  Since it is important that the non-peelable support substrate has a high light extraction effect in order to obtain high luminance, it is preferable that the non-peeling support substrate has high transparency. Here, it is desirable to evaluate the transparency with transmittance including diffused light (hereinafter referred to as diffused light transmittance), and a transmission absorption measurement system using an integrating sphere (manufactured by Otsuka Electronics) is exemplified as this measurement method. . Here, when a support substrate (fully cured product) having a thickness of 0.5 mm is used as a sample, the diffused light transmittance at 450 nm is preferably 50% or more, more preferably 70% or more, and 90%. The above is more preferable.

The heat resistance of the non-peelable support substrate is evaluated by the rate of change of the diffuse transmittance after heating at a constant temperature. Specifically, with respect to a support substrate (fully cured product) having a thickness of 0.5 mm, the initial diffused light transmittance (450 nm) and the diffused light transmittance after continuous heating for 1000 hours in a hot air dryer at 150 ° C. (450 nm) )
"Transmittance change rate" = (diffuse light transmittance after 1000 hours) / (initial diffuse light transmittance)
It is evaluated by calculating based on the following formula. The “heat transmittance change rate” is preferably 0.7 or more, and more preferably 0.8 or more.

Manufacturing method of supporting substrate)
The supporting base material is not particularly limited as long as the above-mentioned material can be molded so as to have the above-described film description and surface state. Examples of the production method include methods such as extrusion molding, mold press molding, injection molding, and roll stretch molding. From the viewpoint of productivity, it is preferable that the film is manufactured by extrusion molding on a peeled film.

  Here, it is preferable to process so that at least one surface becomes a smooth surface (mirror surface). The smooth surface processing is performed by extruding a resin onto a smooth release film with Ra of 10 μm or less and cooling.

  As an example of a specific production method, the raw material of the supporting substrate is put into an extruder kneader heated to 150 ° C. or higher and kneaded, and then the raw material melted from the slit die is extruded onto a peeled PET to form a sheet, and wound up And a method of manufacturing as a roll product.

<Laminated body>
The laminate of the present invention is produced by stacking the phosphor layer and a supporting substrate. Here, after manufacturing and manufacturing the laminated body from the phosphor layer and the supporting base material in advance, it may be used for coating the LED chip. Or you may manufacture as a laminated body just before the coating | covering process to a LED chip, after storing and conveying a fluorescent substance layer and a support base material separately.

  The laminate is stacked so that the phosphor layer prepared on the substrate to be coated and the smooth surface of the supporting substrate are aligned, and bonded together while heating at a temperature of 40 ° C. or more and 120 ° C. or less, and then the coating is performed. It is preferable to manufacture by peeling the substrate. Although it does not specifically limit as an apparatus used for bonding, A roll laminator, a vacuum roll laminator, a vacuum diaphragm laminator, etc. are illustrated. Moreover, as a laminated body manufacturing temperature, it is more preferable to carry out at 70 to 100 degreeC.

  The laminate of the present invention may have a layer other than the phosphor layer and the supporting substrate in order to add some function. For example, a film layer may be provided between the phosphor layer and the support substrate for the purpose of protecting the phosphor layer, or a transparent resin layer for the purpose of a diffusion effect or a light extraction effect may be provided. Furthermore, you may provide an adhesive layer in the surface on the opposite side to the support base material side of a fluorescent substance layer in order to improve adhesiveness with an LED chip.

  The laminate of the present invention may be provided with a cover film on both the phosphor layer side and the support substrate side from the viewpoints of handleability, storage, and surface protection during transportation. The cover film on the phosphor layer side is preferably a peelable film so as not to damage the phosphor layer in the B stage state. Specifically, a polydimethylsiloxane coating PET film, a fluororesin film (PFA, ETFE, etc.), a polyurethane film, etc. are illustrated. As the cover film on the support substrate side, a peelable film of the same type as the cover film on the phosphor layer side can be used. When a non-peelable film is used, the cover film can be peeled from the phosphor layer together with the support substrate after the phosphor layer is coated on the object. Examples of such non-peelable films include PET films and PP films.

<Light emitting device>
Next, the light emitting device will be described. In the light emitting device of the present invention, a wiring pattern is formed by an LED chip having a light emitting surface covered with a phosphor layer, a package substrate to which the LED chip is fixed and electrically joined, and a conductor such as a metal foil. A circuit board or the like on which the package board is mounted is formed.

(LED chip)
The LED chip preferably emits blue light or ultraviolet light. As such an LED chip, a gallium nitride LED chip is particularly preferable. A gallium nitride LED chip is formed by providing a gallium nitride buffer layer on a sapphire wafer, silicon carbide wafer, gallium nitride wafer or silicon wafer, laminating a gallium nitride light emitting layer by MOCVD, and then dicing the gallium nitride LED chip. Manufactured by separating. Examples of the light emitting layer of gallium nitride include a light emitting layer in which an n-type GaN layer, an InGaN layer, and a p-type GaN layer are sequentially stacked.

  There are three types of LED chip types: a lateral type, a vertical type, and a flip chip type. Either one can be used, but it has high luminance and high power from the viewpoint that the light emitting area can be increased, there is no risk of failure due to wire breakage, and the heat emitting layer and the circuit board are close to each other and the heat dissipation is good. The flip-chip type is particularly preferable for the type LED.

  Moreover, the light emitting surface from the LED chip may be a single plane or not a single plane. In the case of a single plane, there are mainly those having only the upper light emitting surface. Specifically, a vertical type LED, a flip chip type LED whose side surface is covered with a white resin as a reflection layer and light is extracted only from the upper surface are exemplified. When the laminate of the present invention is used for a single planar light emitting LED, the support base material is fluidized, and the phosphor layer is pressurized uniformly and gently so that the film thickness change and the film are covered in the phosphor layer coating. It becomes easy to suppress thickness unevenness.

  On the other hand, when it is not a single plane, an LED chip having an upper light emitting surface and a side light emitting surface and an LED chip having a curved light emitting surface can be mentioned. It is preferable that the light emitting surface is not a single plane because the light emitting area can be increased by utilizing the light emitted from the side portion and the color orientation is less uneven and the light distribution characteristics are excellent. In particular, a flip chip type LED chip having an upper light emitting surface and a side light emitting surface is preferable because the light extraction area can be increased and the chip manufacturing process is easy.

  Further, in order to improve the light extraction efficiency, the light emitting surface may be processed into a concavo-convex structure like PSS (Pattern Sapphire Substrate) based on an optical design.

  The film thickness of the LED chip is not particularly limited, but the upper limit of the film thickness is preferably 500 μm or less from the viewpoint of reducing the pressure applied to the phosphor layer on the upper surface and corners of the LED chip and maintaining the film thickness uniformity. More preferably, it is 300 micrometers or less, More preferably, it is 200 micrometers or less. Moreover, the minimum of a film thickness should just have a light emitting layer, and it is preferable that it is 1 micrometer or more. Furthermore, it is preferable that the total thickness of the connection portion between the LED chip and the substrate and the thickness of the phosphor layer satisfy the following relational expression.

  1 ≦ (total film thickness of connection part with LED chip and substrate / film thickness of phosphor layer) ≦ 10.

  If it is at least the lower limit, it is easy to suppress the uneven orientation of the emitted color. Moreover, it is easy to maintain phosphor layer film thickness uniformity below the upper limit. From this viewpoint, the lower limit is preferably 2 or more. The upper limit is preferably 5 or less, and more preferably 4 or less.

(Package substrate)
The package substrate fixes and electrically bonds the LED chip and mounts it on the circuit substrate. The material of the substrate is not particularly limited, but polyphthalamide (PPA), liquid crystal polymer, resin such as silicone, aluminum nitride (AlN), alumina (Al ₂ O ₃ ), ceramic such as boron nitride (BN), copper, etc. Examples thereof include metals such as aluminum. In particular, in the case of a high-brightness high-power LED, a ceramic substrate such as an aluminum nitride substrate or an alumina substrate is preferable from the viewpoint of heat dissipation.

  On the package substrate, an electrode pattern may be formed of gold, silver, copper, aluminum, or the like in order to energize the LED chip. It is preferable that a heat dissipation mechanism is provided. Further, a reflector made of resin or metal may be provided on the substrate.

(Circuit board)
The circuit board refers to a printed wiring board for mounting a package board in which an LED chip is bonded to a wiring pattern formed of a conductor and incorporating the package board in an electronic device. As the substrate, a paper-phenol resin plate, a glass epoxy resin plate, or a copper-clad substrate in which a copper foil is stacked on a metal plate such as aluminum is generally used. In some cases, an LED chip is directly bonded to a circuit board as in a Chip on Board (COB type) described later.

(Configuration of light emitting device)
The LED chip and the substrate are bonded by a metal wire such as gold in the lateral type or the vertical type. On the other hand, with respect to the flip chip type LED, a method of bonding the LED chip and the electrode by solder bonding using gold bumps, eutectic bonding of gold and tin, or conductive paste bonding is exemplified.

  As the type of the structure of the light emitting device, as shown in FIG. 1A, after the LED chip 7 is bonded to the package electrode 9, it is mounted on the circuit wiring 2 on the circuit board 1, and the surface mounting type (SMD), An example is a Chip on Board type (COB) that is directly mounted on the circuit wiring 2 on the circuit board 1 as shown in FIG. The SMD of (a) is obtained by bonding the LED chip 7 via the gold bump 8 to the individual package substrate 10 on which the reflector 4 and the package electrode 9 are formed, and further covering the LED chip 7 with the phosphor layer 6. The LED package 3 sealed with the transparent resin 5 is first manufactured, and this is joined so that the circuit wiring 2 formed on the circuit board 1 and the package electrode 9 are energized. On the other hand, the COB of (b) is obtained by mounting the LED chip 7 directly on the circuit wiring 2 formed on the circuit board 1 via the gold bumps 8 and further covering the LED chip 7 with the phosphor layer 6, and then transparent resin. This is a structure sealed with 5. In any case, the light emitting surface of the LED chip 7 has an upper light emitting surface and a side light emitting surface, all of which are covered with the phosphor layer 6. In COB, in order to prevent the transparent resin 5 from flowing out, a dam 11 made of white resin may be formed around the periphery.

  Only one LED chip 7 may be mounted on the package substrate 10 or the circuit substrate 1, or a plurality of LED chips 7 may be mounted.

  2 and 3 show an example of an LED package in which the LED chip 7 is covered with the laminate of the present invention. The phosphor layer 6 may be installed in direct contact with the light emitting surface of the LED chip 7, or may be installed indirectly with the transparent resin 5 sandwiched between the LED chip 7 as shown in FIG. From the viewpoint of reducing the amount of phosphor, it is preferable to install the LED chip 7 in direct contact with the light emitting surface.

  In this light emitting device, the LED chip 7 bonded on the package substrate 10 may be coated only with the phosphor layer 6, and the LED chip 7 may be coated for the purpose of protecting the phosphor layer as shown in FIG. An overcoat layer made of a transparent resin 5 may be provided on the outer periphery of the phosphor layer 6, and a lens formed of the transparent resin 5 is provided for the purpose of improving light extraction as shown in FIG. Also good.

(Method for manufacturing light emitting device)
A method for manufacturing a light emitting device includes a step of bonding an LED chip to a package substrate, a step of coating a phosphor layer on the LED chip, a step of sealing with a transparent resin or installing a lens, and a step of mounting the package substrate on a circuit board including. However, in the case of COB, the LED chip is mounted directly on the circuit board. The present invention is characterized in the process of coating the phosphor layer on the LED chip.

The step of attaching the phosphor layer is a step of covering the light emitting surface of the LED chip with the phosphor layer using the above-described laminate. In this step, the above-described laminate is stacked on the light emitting surface of the LED chip so that the phosphor layer is on the light emitting surface side of the LED chip, and then a rheometer is used with a frequency of 1.0 Hz and a maximum strain of 1.0%. The storage elastic modulus G ′ and loss elastic modulus G ″ of the supporting substrate when measured are
G ′ <G ”(Formula 1)
And 10 Pa <G ′ <10 ⁵ Pa (Formula 2)
It is preferable to carry out by applying pressure while satisfying the following relational expression.

  The step of attaching the phosphor layer may be performed before or after the bonding step of the LED chip to the package substrate.

  The phosphor layer is attached by applying pressure while the supporting base material is softened and fluidized. In particular, when a heat-fusible phosphor layer is used, the sticking temperature is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of enhancing adhesiveness. In addition, the heat-fusible resin used for the phosphor layer has a property that the viscosity is temporarily lowered by heating, and is further thermally cured when the heating is continued. Therefore, the temperature of the attaching step is preferably 150 ° C. or lower from the viewpoint of maintaining adhesiveness, and more preferably 120 ° C. or lower from the viewpoint of maintaining the shape of the phosphor layer at a certain level or higher. 100 ° C. or less is preferable. Moreover, in order to prevent the remaining of an air pocket, it is preferable to stick on under reduced pressure of 0.01 MPa or less. Examples of the manufacturing apparatus for performing such attachment include a vacuum attaching machine such as a vacuum diaphragm laminator, a vacuum roll laminator, a vacuum hydraulic press, a vacuum servo press, a vacuum electric press, and a TOM molding machine. Among these, a vacuum diaphragm muraminator is preferable because a large number of treatments can be performed at one time, and pressure can be applied without deviation from directly above. V-130, V-160 (made by Nikko Materials) etc. are illustrated as such a vacuum diaphragm muraminator.

  As a method of attaching the phosphor layer to the LED chip, as shown in FIG. 4, the laminated body 12 composed of the phosphor layer 6 and the support base 13 is individualized for each LED chip 7 one by one. As shown in FIG. 5, a method of pasting and laminating the laminated body 12 on a plurality of LED chips 7 as shown in FIG. 5, and a method of cutting and individualizing may be used. Any method may be used. 4 (1) and 5 (1) show the state before pasting, and FIGS. 4 (2) and 5 (2) show the state after pasting.

  Below, four methods are illustrated about the manufacturing process of a light-emitting device. The first and second production examples are examples of a production process using a “peelable support substrate”, and the third and fourth production examples are production processes using a “non-peelable support substrate”. It is an example. Note that the manufacturing process of the light-emitting device is not limited to these examples.

  A first production example is shown in FIG. (A) The LED chip 7 is temporarily fixed on the base 15 via the adhesive tape 14. Here, the adhesive tape 14 is not particularly limited as long as the LED chip can be temporarily fixed and can withstand the application temperature, but a tape whose adhesive strength is reduced by UV irradiation (hereinafter referred to as UV peeling tape), heating Thus, either a tape whose adhesive strength is reduced (hereinafter referred to as a heat release tape) or a tape whose adhesive strength is as weak as 2 N / 20 mm or less (hereinafter referred to as a slightly adhesive tape) is preferably used.

  (B) The laminated body 12 is laminated so that the phosphor layer 6 is in contact with the LED chip 7.

  (C) After the laminate of (b) is put into the lower chamber 19 of the vacuum diaphragm muraminator 16, the upper chamber 18 and the lower chamber 19 are decompressed by heating and exhausting through the exhaust / intake port 17. After heating until the support base material 13 flows, the diaphragm film 20 is expanded by sucking the air into the upper chamber 18 through the exhaust / intake port 17, and the phosphor layer 6 is pressurized through the support base material 13. The LED chip 7 is pasted so as to follow the light emitting surface.

  (D) After returning the upper and lower chambers 18 to atmospheric pressure, the load consisting of the pedestal 15, the adhesive tape 14, the LED chip 7 and the laminated body 12 is taken out from the vacuum diaphragm muraminator 16, and the support base material 13 is peeled off after being allowed to cool. . The obtained covering is cut with a dicing cutter or the like at a cutting position 21 to produce individual phosphor layer-covered LED chips 22.

  (E) When the pressure-sensitive adhesive tape 14 is a UV peeling tape, a UV irradiation step is performed; It is removed and bonded to the package electrode 9 formed on the package substrate 10 via the gold bumps 8.

  (F) The LED package 23 is manufactured by the above process. The LED package 23 is mounted on the circuit wiring 2 on the circuit board 1 to manufacture the light emitting device 24. If necessary, an overcoat layer, a lens, or the like made of the transparent resin 5 is installed.

  A second production example is shown in FIG. (A) The LED chip 7 is bonded to the package electrode 9 formed on the package substrate 10 via the gold bumps 8.

  (B) The stacked body 12 is stacked so that the phosphor layer 6 is in contact with the LED chip 7.

  (C) After the load of (b) is placed in the lower chamber 19 of the vacuum diaphragm muraminator 16, the phosphor layer 6 is attached to the light emitting surface of the LED chip 7 by the same method as in the first manufacturing example.

  (D) After returning the lower chamber 19 to atmospheric pressure, the load is taken out of the vacuum diaphragm muraminator 16 and allowed to cool, and then the support substrate 13 is peeled off. Subsequently, the obtained covering is cut into pieces by cutting at a cutting position 21.

  (E) The LED package 23 is manufactured by the above process. The LED package 23 is mounted on the circuit wiring 2 on the circuit board 1 to manufacture the light emitting device 24. If necessary, an overcoat layer, a lens, or the like made of the transparent resin 5 is installed.

  A third production example is shown in FIG. (A)-(c) performs operation similar to a 1st manufacture example. (D) After returning the upper and lower chambers 18 and 19 to atmospheric pressure, the load is taken out from the vacuum diaphragm mura terminator 16, and the load obtained after being allowed to cool is cut with the dicing cutter together with the support base 13 at the cutting position 21. Then, the phosphor layer-covered LED chip 25 with the supporting base material separated into individual pieces is produced. (E) The LED package 26 with a supporting base material is formed by the same process as the first manufacturing method. (F) The LED package 26 with the supporting base material is mounted on the circuit wiring 2 formed on the circuit board 1 to manufacture the light emitting device 24.

  A fourth production example is shown in FIG. (A)-(c) performs operation similar to a 1st manufacture example. (D) After the upper and lower chambers 18 and 19 are returned to atmospheric pressure, the load is taken out from the vacuum diaphragm muraminator 16, and the load obtained after standing to cool is cut into individual pieces by cutting together with the support base 13 at the cutting position 21. Then, the LED package 26 with a supporting substrate is manufactured. (E) The light emitting device 24 is manufactured by mounting the LED package 26 with a supporting base material on the circuit wiring 2 formed on the circuit board 1.

(Evaluation of pasteability)
By using the laminate of the present invention, a light emitting device in which the phosphor layer attached from the laminate is coated in direct contact with 90% or more of the upper light emitting surface area and 70% or more of the side light emitting area of the LED chip. It is also possible to produce it.

  Here, the direct contact refers to a state in which the phosphor sheet and the upper light emitting surface or the side light emitting surface of the LED chip are bonded without any voids. In covering the LED chip upper light emitting surface, when the directly adhered portion is less than 90% of the LED chip upper light emitting surface area, the phosphor sheet is easily peeled off, which causes a failure of the light emitting device. From this viewpoint, it is more preferable that 99% or more of the LED chip upper light emitting surface is directly adhered and covered.

  Further, in covering the LED chip side light emitting surface, if the direct contact portion is less than 70% of the side light emitting area of the LED chip, the light emission efficiency from the side surface of the LED chip is lowered and the luminance is lowered. In addition, peeling from the non-adhered portion is likely to occur and reliability is lowered. From this viewpoint, it is more preferable that the direct contact portion is 90% or more of the LED chip side light emitting area, and it is further more preferable that it is 99% or more.

  Evaluation of adhesion is a method of observing with a SEM (hereinafter referred to as a cross-sectional SEM method) after cutting a cross section by a cross section polisher method (CP method) or the like, or a method of observing a cross section with an X-ray CT image analyzer It can be evaluated from a cross-sectional photograph by (hereinafter, X-ray CT method).

  When the laminate of the present invention is used, it is preferable that the change in the thickness of the phosphor layer covering the LED chip is small in any part from the viewpoint of suppressing the uneven orientation of light emission. From this point of view, a method of obtaining the film thickness ratio between the upper surface portion and the side surface portion of the phosphor layer coated on the LED chip will be described with reference to FIG.

  FIG. 10A is a top view of the LED package 23. Reference numeral 27 denotes an upper surface portion of the phosphor layer coated with the LED chip, reference numeral 28 denotes a side surface portion of the phosphor layer coated with the LED chip, and reference numeral 29 denotes a phosphor layer coated on the package substrate. FIG. 10B is a cross-sectional view taken along the line I-I ′ in FIG. I-I 'passes through substantially the center of the LED chip as shown in FIG.

  In this specification, in this cross section, a distance A [μm] from the upper surface of the LED chip to the outer surface of the phosphor layer in a portion where the LED chip and the phosphor layer are in contact with each other on the upper surface of the LED chip is defined as follows. In a region where the upper surface of the LED chip 7 and the phosphor layer 6 are in contact with each other, a position that is almost equally divided from the left end of the upper surface, that is, a position that satisfies L1≈L2≈L3≈L4 is extracted. The distances between the LED chip 7 and the outer surface of the phosphor layer 6 at the remaining three points excluding both ends are A1 to A3 [μm], respectively. The average value of these three points is defined as A [μm].

  Further, in the I-I ′ sectional view, a distance B [μm] from the LED chip side surface to the phosphor layer outer surface in a portion where the LED chip and the phosphor layer are in contact with each other on the side surface of the LED chip is defined as follows. In the region where the left side surface of the LED chip 7 and the phosphor layer 6 are in contact with each other, when the thickness of the LED chip 7 from the package electrode 9 on the package substrate 10 is t1, the LED chip 7 at half the height t2 The distance to the outer surface of the phosphor layer 6 is B1 [μm]. Similarly, the same distance on the right side surface of the LED chip 7 is defined as B2 [μm]. The average value of B1 and B2 is defined as B [μm].

  When defined as described above, it is preferable that the relationship of 0.70 ≦ A / B ≦ 1.50 is satisfied, and 0.80 ≦ A / B ≦ 1.20 is more preferable, from the viewpoint of suppressing light emission unevenness. .

From the viewpoint of controlling the emission color, it is preferable that the film thickness of the phosphor layer before the coating step is maintained. When the average film thickness of the phosphor layer before the coating step is C [μm], the film thickness retention rate is
Film thickness retention (%) = distance A [μm] / film thickness C [μm] × 100
It can be obtained from the following formula. The film thickness retention is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more.

  Moreover, in the light-emitting device obtained using the laminated body of this invention, it is preferable that the fluorescent substance layer is installed following the side surface of a LED chip from a viewpoint of suppressing the azimuth | direction nonuniformity of light emission. The followability of the phosphor layer can be evaluated by comparing the inclination of the side surface of the LED chip with the inclination of the phosphor layer covering the side surface portion. Thus, as shown in FIG. 11, the dihedral angle between the substrate upper surface and the LED chip side surface is a (°), and is opposite to the LED chip coating surface of the phosphor layer covering the substrate upper surface and the LED chip side surface light emitting portion. When the dihedral angle with the side surface is b (°), the relationship of a−30 ≦ b ≦ a is preferably satisfied, and the relationship of a−20 ≦ b ≦ a is more satisfied. preferable.

  Thus, in the light-emitting device using the laminated body of this invention, the effect excellent in suppression of the light emitting orientation nonuniformity is shown. Here, the uneven azimuth of light emission means that the light appearance of the light emitting device varies depending on the angle. Such orientation unevenness is caused by a color temperature at a distance 10 cm vertically away from the upper surface of the LED chip of the light emitting device (hereinafter referred to as a vertical color temperature) and a color temperature at a distance 10 cm above obliquely 45 ° (hereinafter referred to as 45 °). It can be determined by the absolute value of the difference in color temperature. In the present invention, the smaller the absolute value of the difference, the smaller the uneven azimuth of light emission, which is preferable.

  The laminate of the present invention is suitably used when a high-power type flip-chip type LED is used, and a light-emitting device manufactured using the same is particularly used for illumination from the viewpoint of high luminance and high heat dissipation. preferable. As an illumination application, for example, it is suitable for use in a flash light of a portable terminal such as a smart phone by taking advantage of a feature that enables a compact design. In addition, because of excellent color light distribution characteristics, general lighting for home use and industrial lighting for use in industrial facilities and public facilities are also preferable usage methods. Furthermore, from the viewpoint of excellent heat dissipation, use for in-vehicle lighting such as a headlamp and DRL (Daytime Running Light) is also suitable.

  The lighting application as described above is a particularly preferable usage method, but it does not limit the use to other applications such as a backlight.

  Hereinafter, the present invention will be described specifically by way of examples.

<Phosphor layer>
The composition and characteristics of the phosphor layer are summarized in Table 1. Details will be described below.

(Raw material for phosphor layer)
(1) Silicone resin Silicones 1 to 3 are polyphenylmethylsiloxane, and silicones 4 to 5 are polydimethylsiloxane.

-Silicone 1;
A resin composition obtained by mixing the following components was used.

Resin main component: (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.3 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.03 75 parts by weight Hardness modifier: ViMe ₂ SiO (MePhSiO) _17.5 SiMe ₂ Vi 10 parts by weight Crosslinking agent: (HMe ₂ SiO) ₂ SiPh ₂ 25 parts by weight * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group Reaction inhibitor: 1-ethynyl-1-hexanol 0.025 part by weight Platinum catalyst: Platinum (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) complex 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution [platinum content 5 weight %] 0.01 parts by weight Silicone 2; “OE6630” (manufactured by Toray Dow Corning)
・ Silicone 3; “XE14-C6091” (made by Momentive Performance Materials Japan) / “Non-crosslinking reactive silicone” = 8/2
* "Non-crosslinking reactive silicone": Solid siloxane represented by the following average composition formula

・ Silicone 4; “OE6336” (manufactured by Dow Corning Toray)
Silicone 5: “KER6075” (manufactured by Shin-Etsu Chemical)

(2) Silicone fine particles-Particle 1;
What was manufactured according to the following synthesis examples was used.

[Synthesis example]
A 3L four-necked round bottom flask was equipped with a stirrer, thermometer, reflux tube, and dropping funnel, and 1600 g of 2.5 wt% aqueous ammonia solution at pH 12 (25 ° C.) and nonionic surfactant “BYK-333” (BIC Chemi) -0.002g (made by Corporation | KK) was added. While stirring at 300 rpm, a mixture of 130 g of phenyltrimethoxysilane and 30 g of methyltrimethoxysilane was added dropwise from a dropping funnel over 20 minutes. Thereafter, the temperature was raised to 50 ° C. over 30 minutes, and stirring was further stopped for 60 minutes, and then stirring was stopped. After cooling to room temperature, 20 g of ammonium acetate was added and stirred at 150 rpm for 10 minutes, and then the reaction solution was divided into 8 250 ml centrifuge bottles (manufactured by Nalgen Co., Ltd.) and centrifuged (table top centrifuge 4000, ) And then centrifuged at 3000 rpm for 10 minutes. After removing the supernatant, 200 g of pure water was added to each centrifuge bottle, the mixture was stirred with a spatula, and then the washing operation for centrifugation under the above conditions was repeated three times. The cake remaining in the centrifuge bottle was transferred to a vat and dried at 100 ° C. for 8 hours in a blower oven to obtain 70 g of white powder. As a result of measuring the obtained particle powder using a particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., Microtrac 9320HRA), the particle diameter (D50) of 50% integrated from the small particle diameter side is 0.5 μm. The monodispersed spherical fine particles. As a result of measuring the refractive index of this fine particle by the immersion method, it was 1.55.

  Particle 2; “Tospearl 120” (polymethylsilsesquioxane) (D50) 2.0 μ (made by Momentive Performance Materials Japan).

(3) Fine metal oxide particles ・ Oxide 1; fumed alumina particles “Aeroxide AluC” D50 13 nm (manufactured by Aerosil Japan).

(4) Phosphor Phosphor 1: “NYAG-02” Ce-doped YAG phosphor, specific gravity: 4.8 g / cm ³ , D50: 7 μm (manufactured by Intematix)
Phosphor 2; “YAG450” YAG phosphor, specific gravity: 5.0 g / cm ³ , D50: 20 μm (manufactured by Nemoto Lumi Material)
Phosphor 3; two-color mixed phosphor (mixture of (i) / (ii) = 3/1);
(I) “BY102” YAG phosphor, specific gravity: 5.5 g / cm ³ , D50: 17 μm (manufactured by Mitsubishi Chemical)
(Ii) “BR-101” CASN phosphor, specific gravity: 3.7 g / cm ³ , D50: 10 μm (manufactured by Mitsubishi Chemical).

(Method for producing phosphor layer)
[Production Example of Phosphor Layer 1]
Using a polyethylene container having a capacity of 300 ml, 28% by weight of silicone 1, 7% by weight of particles 1 and 65% by weight of phosphor 1 were mixed. Thereafter, using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming were carried out at 1000 rpm for 20 minutes to obtain a phosphor dispersion for sheet preparation. Using a slit die coater, the phosphor dispersion for sheet preparation is applied to the peeled surface of the substrate to be coated “Therapyl” WDS (manufactured by Toray Film Processing Co., Ltd .; film thickness 50 μm, elongation at break 115%, Young's modulus 4500 MPa). It was applied, heated at 120 ° C. for 1 hour, and dried to obtain a phosphor layer 1 having a thickness of 50 μm and a 100 mm square. The storage elastic modulus of this phosphor layer was 1.0 × 10 ⁶ Pa at 25 ° C. and 3.0 × 10 ³ Pa at 100 ° C. The composition and film thickness are shown in Table 1.

[Example of production of phosphor layer 2]
Using a polyethylene container having a capacity of 300 ml, 30% by weight of silicone 1, 8% by weight of particles 1, 2% by weight of oxide 1, and 60% by weight of phosphor 1 were mixed. Thereafter, using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming were carried out at 1000 rpm for 20 minutes to obtain a phosphor dispersion for sheet preparation. A phosphor dispersion liquid for sheet preparation is applied on the release surface of the substrate to be coated “Therapy” WDS using a slit die coater, heated at 120 ° C. for 20 minutes, and dried to give a phosphor film having a thickness of 50 μm and a 100 mm square. Layer 2 was obtained. The storage elastic modulus of this phosphor layer was 1.0 × 10 ⁶ Pa at 25 ° C. and 1.0 × 10 ⁴ Pa at 100 ° C. The composition and film thickness are shown in Table 1.

[Production example of phosphor layers 3 to 12]
A phosphor layer was produced in the same manner as the phosphor layer 2 except that the composition or film thickness was changed to those shown in Table 1. The composition and film thickness are shown in Table 1.

(Method for measuring storage elastic modulus of phosphor layer)
Measuring device: Viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments)
Geometry: Parallel disk type (15mm)
Maximum strain: 1.0%
Angular frequency: 1.0 Hz
Temperature range: 25 ° C to 200 ° C
Temperature increase rate: 5 ° C./min Measurement atmosphere: In air.

  Sixteen phosphor layers having a thickness of 50 μm were stacked, and heat-pressed on a 100 ° C. hot plate to produce an integrated film (sheet) having a thickness of 800 μm, and cut into a diameter of 15 mm to obtain a measurement sample. This sample was measured under the above conditions, and the storage elastic modulus at 25 ° C. and 100 ° C. was measured. The results are shown in Table 1.

<Support base material>
(Supporting base resin)
Support base materials of the materials shown in Table 2 were prepared. The following resins are listed in the resin type column.
A-1: Ethylene-α-olefin copolymer resin “Toughmer” DF640 (Mitsui Chemicals)
A-2: Ethylene-α-olefin copolymer resin “Toughmer” DF7350 (Mitsui Chemicals)
A-3: Ethylene-α-olefin copolymer resin “Toughmer” DF8200 (manufactured by Mitsui Chemicals)
A-4: Ethylene-α-olefin copolymer resin “Toughmer” DF9200 (Mitsui Chemicals)
A-5: Ethylene-α-olefin copolymer resin “Toughmer” XM7090 (Mitsui Chemicals)
A-6: Ethylene-α-olefin copolymer resin “Toughmer” PN2070 (Mitsui Chemicals)
A-7: Ethylene-α-olefin copolymer resin “Tuffmer” prototype A (Mitsui Chemicals)
B-1: Polycaprolactone resin “Placcel” H1P (Daicel)
C-1: Ethylene-methyl methacrylate copolymer resin (ethylene-acrylic copolymer resin) “ACRLIFT” WK402 (manufactured by Sumitomo Chemical)
C-2: Ethylene-methyl methacrylate copolymer resin (ethylene-acrylic copolymer resin) “ACRLIFT” CM5021 (manufactured by Sumitomo Chemical)
D-1: Ethylene-α-olefin copolymer resin “Tuffmer” DF7350 / Ethylene-methyl methacrylate copolymer resin “Aclift” CM5021 = 99.9 parts by weight / 0.1 part by weight D-2: Ethylene-α-olefin copolymer Polymerization resin “Tuffmer” DF7350 / ethylene-methyl methacrylate copolymer resin “Acrylift” CM5021 = 99 parts by weight / 1 part by weight D-3: Ethylene-α-olefin copolymer resin “Toughmer” DF7350 / ethylene-methyl methacrylate copolymer resin "Aclift" CM5021 = 98 parts by weight / 2 parts by weight E-1: Silicone resin OE-6450 (manufactured by Toray Dow Corning)
* 2 liquids (A liquid / B liquid) are mixed and cured. A / B = 1 part by weight / 1 part by weight E-2: Silicone resin OE-6635 (manufactured by Dow Corning Toray)
* 2 liquids (A liquid / B liquid) are mixed and cured. A / B = 1 part by weight / 3 parts by weight F-1: Polyethylene resin “NOVATEC” LL (manufactured by Japan Epoxy Resin)
G-1: Fluororesin “Neofluon” ETFE (manufactured by Daikin).

(Method for producing support substrate)
[Production Example of Support Substrate 1]
After the resin A-1 pellets were put into a kneader of an extruder heated to 150 ° C. and melted, a release-treated PET film “Celapeel” BX9 (manufactured by Toray Film Processing Co., Ltd .; film thickness 50 μm, surface roughness (Ra ) 8 μm), a molten resin was extruded from a slit of an extruder to form a film, and a sheet-like molded product having a thickness of 500 μm was produced. This was cut into an appropriate size to obtain a support substrate 1. Table 2 shows the resin type and film thickness.

[Production Examples of Supporting Substrate 2-8 and Supporting Substrate 11-13]
The resin was produced in the same manner as the supporting substrate 1 except that the resin type and film thickness were changed as described in Table 2. Table 2 shows the resin type and film thickness.

[Production Example of Support Substrate 9]
The resin A-6 pellets were placed in an extruder kneader heated to 200 ° C. and melted. Then, a release-treated PET film “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd .; film thickness 50 μm, surface roughness (Ra ) 8 μm), a molten resin was extruded from a slit of an extruder to form a film, and a sheet-like molded product having a thickness of 500 μm was produced. This was cut into an appropriate size to obtain a supporting substrate 9. Table 2 shows the resin type and film thickness.

[Example of production of supporting substrate 10]
After the resin A-7 pellets were put into a kneader of an extruder heated to 100 ° C. and melted, a release-treated PET film “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd .; film thickness 50 μm, surface roughness (Ra ) 8 μm), the molten resin was extruded from the slit of the extrusion molding machine, and then cooled to a film by a delivery machine to form a sheet-like molded product having a film thickness of 500 μm. This was cut into an appropriate size, and further cooled in a refrigerator (internal temperature 5 ° C.) to obtain a supporting substrate 10. Table 2 shows the resin type and film thickness.

[Production Example of Support Substrate 14]
Resin D-2 was prepared by mixing 99.9 parts by weight of resin A-2 pellets and 0.1 part by weight of pellets of resin C-2 as an adhesive component. This was put into a kneader of an extruder heated to 150 ° C. and melted, and then a sheet-like molded product having a film thickness of 500 μm was produced in the same manner as the supporting substrate 1. This was cut into an appropriate size to obtain a support substrate 14. Table 2 shows the resin type and film thickness.

[Production Example of Support Base Material 15]
A resin D-2 was prepared by mixing 99 parts by weight of the resin A-2 pellets and 1 part by weight of the pellets of the resin C-2 as an adhesive component. A sheet-like molded product having a film thickness of 500 μm was produced in the same manner as the support substrate 14. This was cut into an appropriate size to obtain a support base material 15. Table 2 shows the resin type and film thickness.

[Production Example of Support Base 16]
Resin A-2 was mixed with 98 parts by weight of pellets of resin A-2 and 2 parts by weight of pellets of resin C-2 as an adhesive component to obtain resin D-3. A sheet-like molded product having a film thickness of 500 μm was produced in the same manner as the support substrate 14. This was cut into an appropriate size to obtain a support substrate 16. Table 2 shows the resin type and film thickness.

[Example of production of support substrate 17]
A mold in which 1 part by weight of liquid A and 1 part by weight of liquid B of resin E-1 are mixed, and this is a 4 cm square size, a depth of 500 μm, and a bottom surface is peeled mirror-finished (surface roughness (Ra) 10 μm) And heated at 80 ° C. for 15 minutes with a hot press. After standing to cool, a sheet-like molded product having a film thickness of 500 μm was taken out from the mold and used as a support base material 17. Table 2 shows the resin type and film thickness.

[Example of production of support substrate 18]
A mold in which 1 part by weight of A liquid and 3 parts by weight of B liquid of resin E-2 are mixed, and this is a 4 cm square size, a depth of 500 μm, and a bottom surface is peeled mirror-finished (surface roughness (Ra) 10 μm) And heated at 100 ° C. for 15 minutes with a hot press. After standing to cool, a sheet-like molded product having a film thickness of 500 μm was taken out from the mold and used as the support base material 18. Table 2 shows the resin type and film thickness.

[Production Example of Support Base Material 19]
After the resin F-1 pellets were put into a kneader of an extruder heated to 230 ° C. and melted, a release-treated PET film “Therapel” BX9 (manufactured by Toray Film Processing Co., Ltd .; film thickness 50 μm, surface roughness (Ra ) 8 μm), a molten resin was extruded from a slit of an extruder to form a film, and a sheet-like molded product having a thickness of 500 μm was produced. This was cut into an appropriate size to obtain a support base material 19. Table 2 shows the resin type and film thickness.

[Supporting substrate 20]
A 50 μm-thick film (commercial product) formed with the resin G-1 was cut into an appropriate size to obtain a support substrate 20. Table 2 shows the resin type and film thickness.

(Measurement method of the storage elastic modulus G ′ and loss elastic modulus G ″ of the supporting substrate)
The storage elastic modulus G ′ and loss elastic modulus G ″ of the supporting substrate were measured under the following conditions.

Measuring device: Viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments)
Geometry: Parallel disk type (15mm)
Maximum distortion: 1.0%
Angular frequency: 1.0 Hz
Temperature range: 10 ° C to 200 ° C
Temperature increase rate: 5 ° C./min Measurement atmosphere: In air.

  A sheet-like molded product having a film thickness of 1 mm was prepared in accordance with the above (Manufacturing method of support substrate), and cut into a diameter of 15 mm to obtain a measurement sample. This sample was measured under the above-mentioned conditions, and the storage elastic modulus G ′ and the loss elastic modulus G ″ at 10 ° C. to 200 ° C. were measured. From the obtained data, the relationship of G ′ <G ″ was obtained at 10 to 100 ° C. A temperature range satisfying the equation and a temperature range where the storage elastic modulus G ′ satisfies the relational expressions shown in (1) to (4) were determined. The results are shown in Table 2.

(1) 10 Pa <G ′ <10 ⁵ Pa
(2) 10 ² Pa <G ′ <10 ⁵ Pa
(3) 10 Pa <G ′ <10 ⁴ P
(4) 10 ² Pa <G ′ <10 ⁴ Pa.

(Vicat softening temperature)
The Vicat softening temperature of the supporting substrate is in accordance with JIS K 7206 (1999) A50 (load 10 N, heating rate 50 ° C./hour), using a Vicat softening point tester “TP-102” (manufactured by Tester Sangyo) with a pressure needle ( The temperature when the cross-sectional area 1 mm ² ) bites into the resin piece by 1 mm was measured as the Vicat softening temperature. The results are shown in Table 2.

(Melting point)
The melting point of the supporting substrate was measured according to JIS K 7121 (1987) using a differential scanning calorimeter “DSC-60 Plus” (manufactured by Shimadzu Corp.) at a heating rate of 10 ° C./min. The results are shown in Table 2.

(Melt flow rate; MFR)
The melt flow rate of the supporting substrate was measured according to JIS K7210 (1999) using a melt indexer G-01 (manufactured by Toyo Seiki Seisakusho) under the conditions of a measurement temperature of 190 ° C. and a load of 21.2 N. The results are shown in Table 2.

(transparency)
The transparency of the supporting substrate was measured using a transmission absorption measurement system (manufactured by Otsuka Electronics Co., Ltd.) by producing a sheet-like molded product having a film thickness of 0.5 mm according to the above (Manufacturing method of supporting substrate). The determination was made according to the following criteria using a diffuse transmittance (% T) of 450 nm. The results are shown in Table 2.
A: 90 ≦% T
B: 70 ≦% T <90
C: 50 ≦% T <70
D:% T <50

<Laminated body>
(Laminate manufacturing method)
A phosphor layer with a substrate to be coated cut to an appropriate size of 5 cm square or more and a support substrate cut to a size equal to or larger than the phosphor layer were prepared. Next, a smooth surface is exposed, and this is overlaid so that the phosphor layer side is in contact with the smooth surface of the support substrate, and then a dry film laminator heated to 80 ° C. is used to prevent bubbles from entering 1 m / min. Pasting was performed at a speed. After cooling to 30 ° C. or lower, the coated substrate of the phosphor layer was peeled off to obtain a predetermined laminate.

<Manufacturing and Evaluation of Phosphor Layer Covering LED Chip Mounted on Package Substrate and Light-Emitting Device Obtained thereby>
(Manufacturing method of package substrate)
A package electrode pattern was formed by silver plating on an aluminum nitride substrate (size 5 cm square, film thickness 1.5 mm) so that the size of each light emitting device was 10 mm long and 5 mm wide. Next, the flip chip type LED chip “B3838FCM” (manufactured by Genelight, size 1000 μm square, film thickness 150 μm, dominant emission wavelength 450 nm) was bonded onto the package electrode using gold bumps by a flip chip method. By repeating this bonding, a package substrate in which 50 LED chips were bonded on a 5 cm square aluminum nitride plate was produced.

(Method of coating phosphor layer on LED chip on package substrate)
Vacuum chamber of V-130 (manufactured by Nikko Materials) with a lower platen connected to a heater in the vacuum chamber and a pressing mechanism comprising a diaphragm film made of flexible fluorosilicone rubber on the upper platen The inside was heated to a predetermined pasting temperature. Next, a laminate that is cut into a 5 cm square is overlaid on the package substrate so that the phosphor layer side is in contact with the LED chip, and the load is sandwiched between the upper and lower sides with a peeled PET film “Therapy” WDS (film thickness 50 μm). Installed on the lower platen. Subsequently, the vacuum chamber was sealed while heating at a predetermined pasting temperature, and then evacuation was performed for 30 seconds under a reduced pressure of 0.5 kPa or less. Subsequently, the diaphragm film was expanded by introducing air to the upper platen side, and the load was pressurized at atmospheric pressure (0.1 MPa) for 30 seconds. Thereafter, air was introduced into the lower platen side to break the decompression state, and then the vacuum chamber was opened to take out the substrate and laminate stack. When a peelable support substrate was used, after cooling to 30 ° C. or lower, the end of the support substrate was gripped and peeled off.

(Method for manufacturing light emitting device)
The LED chip coated with the phosphor layer was cut based on the pattern of the package electrode by dicing to produce a package substrate having a size of 10 mm in length and 5 mm in width. This package substrate was mounted on a circuit substrate on which a wiring pattern was formed with a conductor to obtain a light emitting device.

<Evaluation of light emitting device>
(Appearance evaluation)
The 50 light-emitting devices obtained were visually evaluated using a 20-fold magnifier, and the appearance of the phosphor layer was determined based on the following criteria.
A: Appearance defects (peeling, cracking, wrinkles) are not observed in the phosphor layer with respect to the entire LED chip.
B: Appearance defects are observed in 10% or less of the entire LED chip.
C: Appearance defects are observed at 10% to 50% of the entire LED chip.
D: Appearance defects are observed in 50% or more of the entire LED chips.

(Evaluation of phosphor layer thickness uniformity)
About the obtained light-emitting device, X-ray CT measurement was performed and the cross-sectional image of the center part was obtained (II 'sectional drawing in Fig.10 (a)). From this image, the distance A [μm] from the upper surface of the LED chip to the outer surface of the phosphor layer at the portion where the LED chip and the phosphor layer are in contact with each other as defined in this specification, and the ED chip and the phosphor layer are LEDs The distance B [μm] from the side surface of the LED chip to the outer surface of the phosphor layer in the portion in contact with the side surface of the chip was measured.

  That is, in the region where the upper surface of the LED chip 7 and the phosphor layer 6 are in contact with each other, a position that is almost equally divided from the left end of the upper surface, that is, a position where L1≈L2≈L3≈L4 is extracted, The distance from the LED chip 7 to the outer surface of the phosphor layer 6 at the remaining three points was measured as A1 to A3 [μm], and the average value of these three points was A [μm].

  Further, when the thickness of the LED chip 7 is t1 in a region where the left side surface of the LED chip 7 and the phosphor layer 6 are in contact with each other, the distance from the LED chip 7 to the outer surface of the phosphor layer 6 at the half height t2. B1 [μm], similarly, in the region where the right side surface of the LED chip 7 and the phosphor layer 6 are in contact with each other up to the outer surface of the LED chip 7 and the phosphor layer 6 at a height t2 that is half the thickness t1 of the LED chip 7. The distance was measured as B2 [μm], and the average value of B1 and B2 was defined as B [μm].

  From this value, the phosphor layer thickness ratio (A / B) between the upper surface and the side surface was determined. The results are shown in Tables 3-5.

(Phosphor layer thickness retention rate evaluation)
Using the distance A [μm] obtained from the X-ray CT cross-sectional image and the average film thickness of the phosphor layer before the coating step, C [μm]
Film thickness retention (%) = distance A [μm] / film thickness C [μm] × 100
The film thickness retention rate was calculated by the following formula. The results are shown in Tables 3-5.

(Evaluation of dihedral angle of side part)
About the obtained light-emitting device, X-ray CT measurement was performed and the cross-sectional image was obtained. From this image, the angle a (°) between the upper surface of the substrate and the side surface of the LED chip in the cross section, and the upper surface of the substrate and the surface opposite to the LED chip covering surface of the phosphor layer covering the LED chip side surface light emitting portion The angle b (°) was measured as shown in FIG. The same operation was performed by changing the location of the cross section, and the average value of the angles of a and b in 10 cross sections with respect to one LED chip was defined as the dihedral angle of the side surface portion. The results are shown in Tables 3-5.

(Phosphor layer: support substrate adhesive strength evaluation)
A laminate sample in which a phosphor layer was bonded to a supporting substrate with a size of 50 mm × 50 mm was produced. Next, a tape (product name: circuit tape 647 0.12, adhesive strength 15 N / 50 mm, manufactured by Teraoka Seisakusho) with a 50 mm width applied to the surface of the phosphor layer is pasted to a length of 50 mm. The contact portion between the layer and the supporting substrate was set to 50 mm × 50 mm. One end of the pressure-sensitive adhesive tape thus produced is attached to a force gauge (trade name: Digital Force Gauge ZTS-20N, manufactured by Imada Co., Ltd.), and the tape is pulled in a direction of 90 degrees with respect to the laminate sample to phosphor layer. The force required to peel from the support substrate was measured. The unit of adhesive force was expressed as N / 50 mm. In addition, when the adhesive tape and the phosphor layer are peeled off without peeling off the phosphor layer and the supporting substrate, it is judged that the adhesive force between the phosphor layer and the supporting substrate is stronger than the adhesive force of the adhesive tape, Expressed as> 15 N / 50 mm. The results are shown in Tables 3-5.

(Evaluation of peelability of support substrate after coating)
After the coating process of the phosphor layer, it was cooled to 30 ° C. or lower, and then the end of the supporting substrate was grasped and peeled off. Peeling from the phosphor layer at this time A: The phosphor layer is completely moved from the supporting base material side to the LED chip side.
B: The ratio of the phosphor layer moving from the support base material side to the LED chip side is 90% or more and less than 100% of the entire LED chip.
C: The ratio of the phosphor layer moving from the support base material side to the LED chip side is 50% or more and less than 90% of the entire LED chip.
D: The ratio of the phosphor layer moving from the support base material side to the LED chip side is less than 50% of the entire LED chip.
Non-peeling: The supporting substrate is not peeled off from the phosphor layer-covered LED chip.

(Evaluation of light appearance of light emitting device)
The difference between the color temperature at a distance 10 cm vertically away from the upper surface of the LED chip of the light emitting device (hereinafter referred to as “vertical color temperature”) and the color temperature at a distance 10 cm above obliquely 45 ° (hereinafter referred to as “45 ° color temperature”). It was determined as follows.
A: | (Vertical color temperature)-(45 ° color temperature) | <250K
B: 250K ≦ | (vertical color temperature) − (45 ° color temperature) | <500K
C: 500K ≦ | (vertical color temperature) − (45 ° color temperature) | <1000K
D: 1000K ≦ | (vertical color temperature) − (45 ° color temperature) |.

[Examples 1-14 and Comparative Examples 1-3]
Using various laminates 1 to 16 manufactured using the phosphor layer 1 and coating the phosphor layer at the attaching temperature shown in Table 3, a light emitting device is manufactured by the above-described method, Appearance evaluation, phosphor layer film thickness uniformity evaluation, phosphor layer film thickness retention rate evaluation, dihedral angle evaluation of side surfaces, phosphor layer: support substrate adhesive strength evaluation, peelability evaluation of support substrate after coating Table 3 shows the evaluation results of the light appearance of the light emitting device.

[Examples 15 to 25 and Comparative Examples 4 to 5]
Using various laminates 17 to 29 manufactured using the phosphor layer 2 and coating the phosphor layer at the attaching temperature shown in Table 4, a light emitting device is manufactured by the above-described method, Various evaluation was performed about the obtained light-emitting device. The evaluation results are shown in Table 4.

[Examples 26 to 38]
Using the various laminates 30 to 42 manufactured by the combination of the phosphor layer and the support substrate described in Table 5, the phosphor layer was coated at an application temperature of 80 ° C. A light emitting device was manufactured, and various evaluations were performed on the obtained light emitting device. The evaluation results are shown in Table 5.

From these results, when the LED chip is coated using the laminate of the present invention, the storage elastic modulus G ′ and the loss elastic modulus G ″ of the supporting substrate are G ′ <G ″ and 10 Pa <G ′ < It was found that the phosphor layer can be coated with good followability on the side surface of the LED chip by applying pressure in a state satisfying the relationship of 10 ⁵ Pa. Moreover, it was shown that the light emitting device in which the phosphor layer is coated on the light emitting surface of the LED chip with good followability can suppress the unevenness of the emitted color.

<Coating process of phosphor layer on LED chip fixed on adhesive tape> Production and evaluation of light emitting device using phosphor layer-covered LED chip obtained thereby>
(Adhesive tape used)
About the adhesive tape of Table 6 which fixes LED chip temporarily, the following adhesive tapes were used.
・ UV release tape: “Elegrip tape” UV1005M3 (manufactured by Denki Kagaku Kogyo, UV irradiation condition 150 mJ / cm2 or more, adhesive strength; before UV irradiation: 12 N / 20 mm, after UV irradiation: 0.2 N / 20 mm)
・ Thermal peeling tape: “Riva Alpha” 31950 (manufactured by Nitto Denko, heat peeling condition 200 ° C., adhesive strength; before heating, 4.5 N / 20 mm, after heating, 0.03 N / 20 mm)
・ Slight adhesive tape: “Adwill” C-902 (Lintec, adhesive strength: 0.9 N / 20 mm)
(Method of coating phosphor layer on LED chip fixed on adhesive tape)
The pressure-sensitive adhesive tape shown in Table 6 was mounted without wrinkles on a metal frame provided with a 5 cm square opening at the center of a SUS plate having a thickness of 0.3 mm and a size 9 cm square. Next, 64 pieces (8 × 8 pieces) of flip chip type LED chip “B3838FCM” (manufactured by Genelight, size 1000 μm square, film thickness 150 μm, dominant emission wavelength 450 nm) at a chip interval of 1 mm so that the electrode part is in contact with the adhesive part. ) Was temporarily fixed to the adhesive part. Subsequently, the laminated body cut into a 2 cm square is temporarily stacked on the temporarily fixed LED chip so that the phosphor layer side is in contact with the LED chip, and the upper and lower sides are sandwiched by the peeled PET film “Therapel” WDS (film thickness 50 μm). A product was made.

  This load was placed on the lower platen of the vacuum diaphragm muraminator V-130 (Nikko Materials) heated in the vacuum chamber to a predetermined application temperature. Subsequently, the vacuum chamber was sealed while heating at a predetermined pasting temperature, and then evacuation was performed for 30 seconds under a reduced pressure of 0.5 kPa or less. Subsequently, the diaphragm film was expanded by introducing air to the upper platen side, and the load was pressurized at atmospheric pressure (0.1 MPa) for 30 seconds. After that, air was introduced into the lower platen side to break the decompression state, the vacuum chamber was opened, and the load was taken out. After cooling to 30 ° C. or lower, the end of the supporting substrate was grasped and peeled off.

(Method for manufacturing light emitting device)
According to the kind of adhesive tape, the peeling process of Table 6 was performed with respect to the load which coat | covered the fluorescent substance layer on the LED chip with the said method. Thereafter, the chip was cut with a dicing cutter, and the phosphor layer-covered LED chip was picked up.

  Subsequently, the picked-up phosphor layer-covered LED chip was bonded to the package electrode of an aluminum nitride substrate (size 5 mm square, film thickness 1.5 mm) on which a package electrode pattern was formed by silver plating by gold bumps. By repeating this bonding, a package substrate on which 64 phosphor layer-covered LED chips were mounted was produced. This package substrate was mounted on a circuit substrate on which a wiring pattern was formed with a conductor to obtain a light emitting device.

[Example 39 and Comparative Example 6]
A light emitting device was manufactured by the above method except that the laminate described in Table 6 was used, a UV release tape was used as the adhesive tape, and UV (365 nm) 500 mJ / cm ² was applied as the release treatment. The evaluation results are shown in Table 6.

[Example 40 and Comparative Example 7]
A light emitting device was manufactured by the above method except that the laminate shown in Table 6 was used, a heat peeling tape was used as an adhesive tape, and a heating (200 ° C., 10 minutes heating) treatment was performed as a peeling treatment. The evaluation results are shown in Table 6.

[Example 41]
A light emitting device was manufactured by the above-described method except that the laminate 18 was used, a fine adhesive tape was used as the adhesive tape, and the peeling treatment was not performed. The evaluation results are shown in Table 6.

  From the above results, it was found that if the laminate of the present invention is used, the phosphor layer can be coated on the light emitting surface of the LED chip with good followability, and thereby a light emitting device with suppressed color azimuth unevenness can be manufactured. On the other hand, when a known fluororesin film is used as a comparative example, it is found that the phosphor layer comes into contact with the adhesive portion before sufficiently following the air, and the LED chip cannot be coated on the side surface. It was.

<Productivity evaluation of phosphor layer coating process using laminate of the present invention>
When the phosphor layer is coated by the process of the present invention using the laminate 18 (one-step method), fluorescence is obtained by a two-step method described in the publicly known (Patent Document 2; International Publication No. 2012/023119). The case where the body layer was coated was compared.

(Evaluation of processing time of phosphor layer coating)
The common conditions are as follows.
・ Equipment; Vacuum diaphragm muraminator V-130 1 unit ・ Worker; 2 persons (preparation and machine operation 1 person, peeling and storage operation 1 person)
Processing substrate: Package substrate obtained by bonding 33 × 33 LED chips to a 10 cm × 10 cm ceramic substrate. Number of batches processed: Four substrates were coated by one operation of a laminator.
・ Total number of sheets processed: 40 sheets (10 batches)
The time required for the process of coating 40 substrates was defined as “10 batch processing time”. In addition, the characteristics of the light-emitting device were evaluated, and conditions were selected such that the light appearance was A evaluation.

[Example 47]
The laminated body 18 was coated by a one-step coating method including the following steps.

  (I) Preparatory process: Four pieces of the laminated body placed on a ceramic substrate were prepared and set in a vacuum diaphragm muraminator. Since the second and subsequent batches are performed simultaneously with the coating step, only the preparation time of the first batch was added to the processing time. The time required was 1 minute.

  (Ii) Coating step: Coating was performed by starting a laminator (evacuation time: 0.5 minutes, pressurization time: 0.5 minutes, handling time: 0.5 minutes).

  At the same time, the next batch was prepared in parallel. The time required was 1.5 minutes for 1 batch and 15 minutes for 10 batches.

  (Iii) Cooling and peeling process: After the coating process, the film was allowed to cool for 3 minutes, and then the support substrate was peeled and stored in a case. Since the work can be performed in parallel with the coating step, only the time required for the 10th batch cooling release step was added. The time required was 4 minutes.

  From the above, 10 batch processing time = 1 + 15 + 4 = 20 minutes. The results are shown in Table 7.

[Comparative Example 8]
Based on the method shown by the method of patent document 2 using the laminated body 29, it coat | covered with the two-step coating method which consists of the following processes.

  (I) Preparatory process: Four pieces of the laminated body placed on a ceramic substrate were prepared and set in a vacuum diaphragm muraminator. Since the second and subsequent batches are performed simultaneously with the coating step, only the preparation time of the first batch was added to the processing time. The time required was 1 minute.

  (Ii) First stage of coating process: The laminator was started and pressure was applied with a diaphragm membrane (evacuation time: 0.5 minutes, pressure time: 0.1 minutes, handling time: 0.5 minutes). The time required was 1 batch of 1.1 minutes and 10 batches of 11 minutes.

  (Iii) Cooling and peeling step: After the coating step, the substrate was allowed to cool for 3 minutes, and then the support substrate was peeled off. Since the process can proceed simultaneously with the first stage of the coating process, the time required was substantially 0 minutes.

  (Iv) Setting change: After all the diaphragm membrane pressurization steps were completed, the setting was changed so as to pressurize only with compressed air. The time required was 1 minute.

  (V) 2nd stage of coating process: 4 substrates each from which the supporting base material was peeled were set and pressurized with compressed air (evacuation time: 1 minute, air pressure time: 0.5 minutes, Handling time: 0.5 minutes). The time required was 1 batch 2 minutes and 10 batches 20 minutes.

  (Vi) Cooling step: After the covering step, the plate was allowed to cool for 3 minutes and then stored in a case. Since work can be performed in parallel with the coating step, only the time required for the 10th batch cooling step was added.

  The time required was 3 minutes.

  From the above, 10 batch processing time = 1 + 111 + 1 + 20 + 3 = 36 minutes. The results are shown in Table 7.

  From the above results, it was shown that the processing time can be shortened to 5/9 compared with the known method, and the productivity is greatly improved.

DESCRIPTION OF SYMBOLS 1 Circuit board 2 Circuit wiring 3 LED package 4 Reflector 5 Transparent resin 6 Phosphor layer 7 LED chip 8 Gold bump 9 Package electrode 10 Package board 11 Dam 12 Laminated body 13 Support base material 14 Double-sided adhesive tape 15 Base 16 Vacuum diaphragm mura terminator 17 Exhaust / intake port 18 Upper chamber 19 Lower chamber 20 Diaphragm film 21 Cutting position 22 Phosphor layer-covered LED chip 23 LED package 24 Light-emitting device 25 Phosphor layer-covered LED chip with support base 26 LED package with support base 27 LED chip The upper surface portion 28 of the phosphor layer coated with the LED The side surface portion 29 of the phosphor layer coated with the LED chip The phosphor layer coated on the package substrate

Claims (12)

A laminate having a phosphor layer containing a phosphor and a resin and a support substrate, the storage elastic modulus of the support substrate measured by a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% G ′ and loss elastic modulus G ″ are all or part of the temperature range from 10 ° C. to 100 ° C. G ′ <G ″ (Formula 1)
And 10 Pa <G ′ <10 ⁵ Pa (Formula 2)
A laminate that satisfies the relational expression The laminate according to claim 1, wherein the support base material includes a thermoplastic resin. The laminated body according to claim 1 or 2, wherein the support substrate has a Vicat softening temperature of 25C or higher and 100C or lower. The laminate according to any one of claims 1 to 3, wherein the support base has a melting point of 40 ° C or higher and 100 ° C or lower. The thermoplastic resin is one or two or more resins selected from the group consisting of poly-α-olefin resins, polycaprolactone resins, acrylic resins, silicone resins and copolymer resins of one or more of these with ethylene. The laminated body in any one of Claim 2 to 4 containing. The manufacturing method of the light-emitting device including the process of coat | covering the light emission surface of a LED chip with a fluorescent substance layer using the laminated body in any one of Claim 1 to 5 with respect to the light emission surface of a LED chip. The method of manufacturing a light emitting device according to claim 6, wherein the light extraction surface of the LED chip is not a single plane. The distance A [μm] from the upper surface of the LED chip to the outer surface of the phosphor layer in the portion where the LED chip and the phosphor layer are in contact with each other on the upper surface of the LED chip, and the portion where the LED chip and the phosphor layer are in contact with the side surface of the LED chip The distance B [μm] from the LED chip side surface to the phosphor layer outer surface in FIG.
0.70 ≦ A / B ≦ 1.50
The manufacturing method of the light-emitting device in any one of Claim 6 to 7 satisfy | filling these relationships. The dihedral angle between the upper surface of the substrate and the side surface of the LED chip is a (°), and the upper surface of the substrate and the surface opposite to the LED chip coating surface of the phosphor layer covering the LED chip side surface light emitting portion are two. When the surface angle is b (°),
a-30 ≦ b ≦ a
The manufacturing method of the light-emitting device in any one of Claim 6 to 8 including the process of coat | covering a fluorescent substance layer on the light emission surface of an LED chip so that the relationship may be satisfy | filled. A light-emitting device obtained by the manufacturing method according to claim 6. A flashlight comprising the light emitting device according to claim 10. A portable terminal comprising the flashlight according to claim 11.

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