TWI686963B - Laminate, light-emitting device and manufacturing method thereof, flash lamp and mobile terminal - Google Patents

Abstract

Provides a laminate with the following structure to provide a light emitting surface of an LED chip, especially a side light emitting surface of a flip chip type LED, with good followability, which includes a phosphor The phosphor layer of the body and the resin, and the laminate of the supporting substrate, the storage elastic modulus G'and the loss elastic modulus when measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% The number G" satisfies G'<G" in all or part of the temperature range of 10°C or more and 100°C or less (Equation 1)

And 10Pa<G'<10 ⁵ Pa (Formula 2)

Relationship.

Description

Laminated body, light-emitting device and manufacturing method thereof, flash lamp, and Mobile terminal

The present invention relates to a laminate including a phosphor layer containing a phosphor and a resin, and a supporting base material. Furthermore, it relates to a method of manufacturing a light-emitting device including the step of covering the upper light-emitting surface and the side light-emitting surface of an LED wafer using this laminate.

Light emitting diode (LED, Light Emitting Diode) is based on the significant improvement of its luminous efficiency, with low power consumption, long life, design and other characteristics as a backlight for liquid crystal displays (LCD), in addition to cars The headlamps and other automotive fields or general lighting are rapidly expanding the market.

LEDs are classified into lateral type, vertical type, and flip chip type according to their mounting modes. Flip chip type LEDs have attracted attention because they can increase the light emitting area and have excellent heat dissipation. However, there is a problem in flip chip type LEDs: by using the existing distribution method of sealing, the thickness of the phosphor layer cannot be made uniform between the top surface and the side surface of the chip, resulting in uneven luminous color orientation .

For this problem, a technique of uniformly attaching a phosphor layer containing a phosphor and a resin and processed into a sheet shape with good followability around the wafer (for example, refer to Patent Document 1 to Patent Document 2). Patent Document 1 uses a pressing member formed with a concave portion that is larger than the LED chip to attach a phosphor layer on the side of the LED chip Methods. Furthermore, Patent Document 2 is a first-stage attaching step of placing a laminate including a supporting base material and a phosphor layer on an LED chip and pressing it with a separator film in a vacuum state. After that, the supporting base material is removed, and a method of attaching the phosphor layer on the side of the LED chip is further passed through the second-stage attaching step of non-contact pressurization with compressed air.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-138831

[Patent Document 2] International Publication No. 2012/023119

However, the method described in Patent Document 1 requires a new mold to be a pressurizing member when changing the type of LED, which is inefficient. In addition, there is a problem in that the pressing member is brought into contact with the phosphor layer and pressurized. Therefore, the sheet is damaged, the pressing member is contaminated, and the productivity is poor.

In addition, if the method described in Patent Document 2 is only the first step of pressing the separator, the phosphor layer cannot follow the side of the wafer due to insufficient flexibility of the supporting base material. After the support substrate is removed, the second-step non-contact pressing step is performed, which is problematic from the viewpoint of productivity.

An object of the present invention is to provide a method for forming a phosphor layer with a uniform thickness on the upper surface and side surface of an LED chip by a simple method with good followability. Moreover, the objective is to provide the manufacturing method of the light emitting element using this laminated body.

The present invention is a laminate including a phosphor layer containing a phosphor and a resin and a supporting base material, the storage elasticity of the supporting base material is measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% The modulus G'and the loss elastic modulus G" satisfy G'<G" in all or part of the temperature range of 10°C or more and 100°C or less (Equation 1)

And 10Pa<G'<10 ⁵ Pa (Formula 2)

Relationship.

According to the present invention, the phosphor layer can be attached to the upper light emitting surface and the side light emitting surface of the LED chip with good followability by a method with excellent productivity. Furthermore, by this, a light-emitting device having no unevenness in luminous color can be provided.

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 substrate

11: Barrier

12: laminate

13: Support substrate

14: Double-sided adhesive tape

15: Pedestal

16: Vacuum separator laminator

17: Exhaust/suction port

18: upper chamber

19: Lower chamber

20: separator membrane

21: Cutting position

22: Phosphor coated LED chip

23: LED package

24: Light emitting device

25: Phosphor layer with supporting substrate coated LED chip

26: LED package with supporting substrate

27: The upper surface of the phosphor layer covered with the LED chip

28: Side part of phosphor layer covered with LED chip

29: phosphor layer covered on the package substrate

t1, t2: thickness

A1~A3: Distance

B1, B2: distance

L1~L4: location

a(°): angle

b(°): angle

i, ii: length

1(a) and 1(b) are examples of the structure of a light-emitting device manufactured using the laminate of the present invention

2(a) and 2(b) are an example of an LED package using the laminate of the present invention to cover the phosphor layer

3 is an example of an LED package using a laminate of the present invention to cover a phosphor layer

4(1) and 4(2) are stickers of the phosphor layer using the laminate of the present invention An example of the attached method

5(1) and 5(2) are examples of a method of attaching a phosphor layer using the laminate of the present invention

FIG. 6(a), FIG. 6(b), FIG. 6(c), FIG. 6(d), FIG. 6(e), and FIG. 6(f) are examples of the manufacturing process of the light-emitting device using the laminate of the present invention

7(a), 7(b), 7(c), 7(d), and 7(e) are examples of manufacturing processes of a light-emitting device using the laminate of the present invention

8(a), 8(b), 8(c), 8(d), 8(e), and 8(f) are examples of manufacturing processes of a light-emitting device using the laminate of the present invention

9(a), 9(b), 9(c), 9(d), and 9(e) are examples of manufacturing processes of a light-emitting device using the laminate of the present invention

10(a) and 10(b) are a side view and a plan view of a light-emitting device covering a phosphor layer (explanation of film thickness measurement)

FIG. 11 is a side view of a light-emitting device covering a phosphor layer (explanation of the dihedral angle of the side)

The laminate of the present invention includes a phosphor layer containing a phosphor and a resin, and a supporting base material, the storage elastic modulus of the supporting base material when measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% G'and the loss elastic modulus G" satisfy G'<G" in all or part of the temperature range of 10°C or more and 100°C or less (Equation 1)

And 10Pa<G'<10 ⁵ Pa (Formula 2)

Relationship.

<Phosphor layer>

The phosphor layer contains at least phosphor and resin, and is formed into a sheet shape. Other ingredients may also be included as needed.

(Phosphor)

The phosphor absorbs blue light, purple light, and ultraviolet light emitted from the LED chip to convert wavelengths, and emits light with wavelengths in the red, orange, yellow, green, and blue regions at different wavelengths from the light of the LED chip. By this, part of the light emitted from the LED chip and part of the light emitted from the phosphor are mixed to obtain a multi-color LED including white. Specifically, a method of emitting white light by optically combining blue-type LEDs with phosphors that emit yellow-based luminescent colors due to light from the LEDs is exemplified.

The phosphors 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 allylsulfonamide-melamine formaldehyde co-condensation dyes, perylene-based phosphors, pyrrole-methylene-based phosphors, anthracene-based phosphors, and pyrene-based phosphors. Examples of the fluorescent substance particularly preferably used in the present invention include inorganic phosphors. Hereinafter, the inorganic phosphor used in the present invention will be described.

For example, 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) Ga ₂ S ₄ : Eu, etc.

For example, 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, At least one of Ca, Sr, and Ba) ₂ B ₅ O ₉ Cl: Eu, Mn, (at least one of Mg, Ca, Sr, and Ba) (PO ₄ ) ₆ Cl ₂ : Eu, Mn, and the like.

Phosphors that emit green to yellow light have yttrium activated by at least cerium. Aluminum oxide phosphor, yttrium activated by at least cerium.釓. Aluminum oxide phosphor, yttrium activated by at least cerium. aluminum. Garnet oxide phosphor, and at least yttrium activated by cerium. gallium. Aluminum oxide phosphors (so-called YAG phosphors). Specifically, Ln ₃ M ₅ O ₁₂ can be used: R (Ln is at least one selected from Y, Gd, and La. M contains at least any one of Al and Ca. R is selected from Ce, Tb, Pr, and Sm , At least one of Eu, Dy, Ho), (Y _1-x Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : R (R is selected from Ce, Tb, Pr, Sm, Eu, Dy At least one of Ho. 0<x<0.5, 0<y<0.5).

Phosphors that emit red light include, for example, sulfide-based phosphors such as Y ₂ O ₂ S: Eu, La ₂ O ₂ S: Eu, Y ₂ O ₃ : Eu, Gd ₂ O ₂ S: Eu, or CaSiAlN ₃ : Eu (referred to as CASN) and other nitride-based phosphors.

In addition, phosphors that emit light corresponding to current mainstream blue LEDs include Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Y ₃ Al ₅ O ₁₂ : YAG-based phosphors such as Ce, Lu ₃ Al ₅ O ₁₂ : LAG-based phosphors such as Ce, Tb ₃ Al ₅ O ₁₂ : TAG-based phosphors such as Ce, (Ba,Sr) ₂ SiO ₄ : Eu-based Phosphor or Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce-based phosphor, (Sr, Ba, Mg) ₂ SiO ₄ : silicate-based phosphor such as Eu, (Ca, Sr) ₂ Si ₅ N ₈ : Eu, (Ca, Sr) AlSiN ₃ : Eu, CaSiAlN ₃ : Eu and other nitride-based phosphors, Cax(Si, Al) ₁₂ (O, N) ₁₆ : Eu and other oxynitride-based phosphors, ZnS : Cu, Al, (Ca, Sr) S: Eu and other sulfide-based phosphors, further exemplified by (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu-based phosphors, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu-based phosphor, SrAl ₂ O ₄ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, Sialon-based phosphor and other phosphors.

Among these phosphors, YAG-based phosphors, LAG-based phosphors, TAG-based phosphors, and silicate-based phosphors can be preferably used in terms of luminous efficiency, brightness, color rendering, etc. , Sialon phosphors, nitride phosphors.

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

In addition to the above, a well-known phosphor can also be used according to the use or target emission color.

The particle size of the phosphor is not particularly limited, and D50 is preferably 0.05 μm or more, and more preferably 3 μm or more. Furthermore, D50 is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. Here, the D50 refers to the particle size when the cumulative component from the small particle size side becomes 50% in the volume-based particle size distribution measured by the laser diffraction scattering particle size distribution measurement method. When D50 is within the above range, the phosphor in the phosphor layer has good dispersibility and stable light emission is obtained.

One type of phosphor may be used, or a mixture of multiple types may be used. For example, in the case of using blue-emitting LEDs, from the viewpoint of economy and convenience, There is a method of dispersing a yellow phosphor to make it emit white light. On the other hand, in order to perform white light emission 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 content of the phosphor is not particularly limited. From the viewpoint of improving the wavelength conversion efficiency of light emitted from the LED chip, it is preferably 10% by weight or more of the entire phosphor layer, and more preferably 40 More than% by weight. The upper limit of the phosphor content is not particularly limited. From the viewpoint of easily making a phosphor layer with excellent workability, it is preferably 95% by weight or less of the entire phosphor layer, more preferably 90% by weight or less, further More preferably, it is 85% by weight or less, even more preferably 80% by weight or less, and particularly preferably 70% by weight or less.

The phosphor layer of the present invention can be used particularly well in the application of coating the light emitting surface of LED chips. At this time, by setting the content of the phosphor in the phosphor layer to the above range, an LED light-emitting device exhibiting excellent performance can be obtained.

(Resin)

The resin contained in the phosphor layer of the present invention is a resin in which phosphors are uniformly dispersed in the interior, and it can be any resin if a sheet can be formed.

Specific examples include silicone resin, epoxy resin, polyarylate resin, PET modified polyarylate resin, polycarbonate resin, cyclic olefin, polyethylene terephthalate resin, polymethacrylate Ester resin, polypropylene resin, modified acrylic resin, polystyrene resin and acrylonitrile-styrene copolymer resin, etc. In the present invention, from the viewpoint of transparency, silicone resin or epoxy resin can be preferably used. In addition, from the viewpoint of heat resistance, a silicone resin can be particularly preferably used.

The silicone resin used in the present invention is preferably polydimethylsiloxane with a dimethylsiloxane structure as the main chain, or polyphenylmethylsilicon which converts a part of the methyl group into a phenyl group Oxane. The former is excellent in heat resistance and light resistance. On the other hand, the latter has a high refractive index and high light emission efficiency, so it can be suitably used as a sealing material for LEDs. In addition, in order to further increase the refractive index and improve the light emission efficiency, a polyorganosiloxane into which a condensed polycyclic aromatic functional group such as a naphthyl group can be suitably used. Any of these can be used, in particular, it is free from heating to reduce and soften the storage elastic modulus G'and the loss elastic modulus G". Considering that the effect of thermal fusion is large, polyphenyl is more preferable. Methyl silicone.

The silicone resin used in the present invention is preferably a hardened silicone resin. The so-called hardening type silicone resin is a silicone that hardens due to a crosslinking reaction due to heating, and is hereinafter referred to as a crosslinking type silicone resin. Any liquid composition of one-liquid type or two-liquid type (three-liquid type) can also be used.

There are condensation reaction type and addition reaction type in the crosslinking reaction type silicone resin. The condensation reaction type is a type in which condensation reaction occurs due to moisture or catalyst in the air, thereby crosslinking and hardening it. There are a dealcohol type, a deoxime type, a deacetic acid type, and a dehydroxylamine type. On the other hand, the addition reaction type is a type in which a hydrosilylation reaction occurs due to a catalyst. There is a mixture of an alkenyl group-containing polysiloxane having an alkenyl group bonded to a silicon atom, and a hydrogenated polysiloxane having a hydrogen atom bonded to a silicon atom, with a transition metal catalyst such as platinum The type of cross-linking caused by the hydrosilation reaction and hardening.

These arbitrary types of crosslinking type silicone resins can be used. Especially in Addition-reactive silicone resins are more preferable in that there are no by-products associated with the hardening reaction and the hardening shrinkage is small, and the hardening is accelerated by heating.

Polysiloxanes containing alkenyl groups can be obtained by using dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyl Methyldimethoxysilane, phenylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc. become poly Silane compound, the main component of siloxane, and vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl methyl diethoxy silane, allyl trimethoxy Silane compounds containing an alkenyl group bonded to a silicon atom, such as a silane group, acryl trimethoxy silane, norbornenyl trimethoxy silane, octenyl trimethoxy silane, etc., are synthesized by condensation polymerization.

Hydrogenated polysiloxane can be made by making the silane compound that is the main component of polysiloxane, and dimethyl methoxy silane, diphenyl methoxy silane, methyl phenyl methoxy silane, methyl Hydrogenated silane compounds such as dimethoxysilane and phenyldimethoxysilane are synthesized by condensation polymerization.

As such an example, a well-known example described in Japanese Patent Laid-Open No. 2010-159411 can be used. Further, as the hydrosilation catalyst, platinum-based catalysts, rhodium-based catalysts, iridium-based catalysts, iron-based catalysts, etc. can be cited as preferred examples. In view of high self-reactivity, the platinum catalyst is preferred among these. Particularly preferred is a platinum-alkenyl siloxane complex with a low chlorine concentration. Examples of the alkenyl siloxane are 1,3-divinyl-1,1,3,3-tetramethyldisilaxane, 1,3,5,7-tetramethyl-1,3,5, 7-Tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl group of these alkenylsiloxanes are substituted with ethyl, phenyl and other groups, these An alkenyl siloxane in which the vinyl group of an alkenyl siloxane is substituted with an allyl group, a hexenyl group and the like. Especially considering good self-stability, 1,3-divinyl-1,1,3,3-tetramethyldisilaxane is preferred.

In addition, in order to suppress the excess hydrosilation reaction and extend the pot life, it is preferred that the silicone resin contains a hydrosilation reaction retarder. Hydrosilylation reaction retarders are known as alcohol derivatives containing ethynyl groups, benzotriazole derivatives, cyclic vinylsiloxane derivatives, ethylenediamine derivatives, etc. Alcohol derivatives containing ethynyl groups are in use The elongation and heat hardenability are the most excellent. Examples of alcohol derivatives containing an ethynyl group include 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol , 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, etc., but not limited to these compounds.

By appropriately designing the molecular weight or 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 to obtain resins useful in the practice of the present invention .

The silicone resin used in the present invention can also be used by selecting a resin having a suitable storage elastic modulus from silicone sealing materials for general LED applications. As specific examples, there are OE-6630, OE-6635, OE-6665, OE-6520 (manufactured by Toray Dow Corning), KER-6110, and ASP-1031 (manufactured by Shin-Etsu Chemical Co., Ltd.). ), IVS5332, XE14-C6091 (manufactured by Mitu Hi-Tech Materials Japan Co., Ltd.); polydimethylsiloxane exists OE-6336, OE-6351 (manufactured by Toray Dow Corning), KER2500, KER6075 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), IVS4632 (Mituto High-tech Materials Japan Co., Ltd.), etc. These are two-liquid mixed type, For example, OE-6630 is a mixed type of liquid A and liquid B (OE-6630A/B).

(Silicone adhesive material)

In order to control the thermoplasticity of the phosphor layer in the present invention and improve the adhesion to the LED chip, the phosphor layer may also contain a non-crosslinking reaction type silicone resin as a silicone adhesive material. The so-called non-crosslinking reaction type silicone resin refers to a polyorganosiloxane that does not contain a crosslinking agent or catalyst and does not crosslink at a temperature below 150°C.

The non-crosslinking reaction type silicone resin in the present invention preferably has a glass transition point temperature in the range of 50°C to 150°C. Even better is 70℃~120℃. If the temperature of the glass transition point is within these ranges, it exhibits suitable adhesion (tackiness) in the temperature range of attachment of the phosphor layer, which can improve the adhesion to the LED chip.

In addition, the glass transition point in the present invention is a value measured by a commercially available measuring instrument [for example, a differential scanning thermal analyzer manufactured by Seiko Instruments Inc. (trade name: DSC6220, temperature increase rate of 0.5° C./min)]. By adding such a non-crosslinking reaction type silicone compound to a polysiloxane that has a large storage elastic modulus G'even when heated, the storage elastic modulus G'when heated can be reduced to impart thermoplasticity ( Heat softening).

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

[Chem 1](R ₃ SiO _1/2 ) _a (PhSiO _3/2 ) _b (MeSiO _3/2 ) _c (MeOHSiO _2/2 ) _d (Me ₂ SiO _2/2 ) _e (PhOHSiO _2/2 ) _f (SiO ₂ ) _g

In the formula, R is an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, Ph is a phenyl group, Me is a methyl group, and a, b, c, d, e, f, and g satisfy 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 = A number of 100.

By using the non-crosslinking reaction type silicone resin having the structure as described above, the storage elastic modulus G′ of the phosphor layer at 25° C. and 100° C. can be adjusted to a preferable range, and the content can be suppressed. Agglomeration and sedimentation of the phosphor in the resin composition of the phosphor can produce a phosphor-containing resin composition with a small color temperature unevenness when the phosphor layer is produced.

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

Moreover, in the structure represented by the general formula (1), a, b, c, d, e, f, and g are positive numbers, and satisfy 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. Furthermore, it is more preferable that 0≦a≦5, 25≦b≦35, 15≦c≦30, 5≦d≦15, 20≦e≦35, 5≦f≦30, and 0<g≦5.

The existence of such a bond can be determined by the structural analysis of solid NMR using ¹ H-NMR or ¹³ C-NMR, the decomposition of tetraethoxysilane in the presence of a base, and GC/MS of the resulting decomposition product. The copolymer composition, cross-linking point analysis, FT-IR, etc. were analyzed.

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 making it within the above range, the dispersion and stabilization effect of the phosphor can be further increased.

In addition, 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 Zhaoguang Technology Co., Ltd.].

The non-crosslinking reaction type silicone resin in the present invention can also be selected and used as a general resin commercially available. Specific examples include KR-100, KR-101-10, KR-130 manufactured by Shin-Etsu Chemical Co., Ltd., or SR-1000, YR3340, YR3286, PSA-610SM, XR37-B6722, etc. manufactured by Meitu High-Tech Materials Co., Ltd.

In the present invention, it is not necessary 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, even after hardening for adhesion When heated, suitable softness and adhesiveness can also be imparted, thereby obtaining a resin useful in the practice of the present invention. In this case, a suitable ratio of the non-crosslinking reaction type silicone resin to the crosslinking reaction type silicone resin is 0.5 to 100 parts by weight relative to 100 parts by weight of the crosslinking reaction type silicone resin. More preferably, it is 10-50 parts by weight.

(Silicone microparticles)

The phosphor layer in the present invention may contain silicone fine particles in order to suppress the sedimentation of the phosphor and improve the fluidity of the resin composition for phosphor layer production to improve the coating property. The contained silicone fine particles preferably contain silicone resin and/or silicone rubber Gum particles. It is particularly preferable to hydrolyze organosilanes such as organotrialkoxysilane or organodialkoxysilane, organotriethoxysilane, organodiacetoxysilane, organotrioxane silane, organodioxane silane, etc. , Followed by the method of condensing the resulting silicone microparticles.

The organic trialkoxysilane can be exemplified by methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-isopropoxysilane, methyltri-n-butoxy Silane, methyltri-isobutoxysilane, methyltri-second-butoxysilane, methyltri-third-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, Isopropyltrimethoxysilane, n-butyltributoxysilane, isobutyltributoxysilane, second butyltrimethoxysilane, third butyltributoxysilane, N-β-( (Aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, etc.

Examples of organic dialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, and diethyldimethoxysilane. Ethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxy Silane, 3-aminopropylmethyl diethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl )-3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyl diethoxysilane, (phenylaminomethyl)methyldimethoxysilane, vinylmethyl Diethoxysilane etc.

The organic triethoxysilane can be exemplified by methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, and the like.

Examples of organic diacetoxysilanes include dimethyldiethoxysilane, methylethyldiethoxysilane, vinylmethyldiethoxysilane, and vinylethyldiethoxysilane. Silane, etc.

Examples of organic trioxime silanes include methyl tri (methyl ethyl ketone) oxime silanes, vinyl tri (methyl ethyl ketone) oxime silanes, and organic dioxime silanes can exemplify methyl ethyl bis (methyl ethyl ketone). Oxime silane etc.

Specifically, such particles can be obtained by the method reported in Japanese Patent Laid-Open No. 63-77940, the method reported in Japanese Patent Laid-Open No. 6-248081, and the Japanese Patent Laid-Open No. 2003-342370 The reported method and the method reported in Japanese Patent Laid-Open No. 4-88022 are obtained. In addition, organic silanes such as organic trialkoxysilane or organic dialkoxysilane, organic triethoxysilane, organic diethoxysilane, organic trioxime silane, organic dioxime silane, etc. are also known And/or its partial hydrolysate is added to an alkaline aqueous solution to hydrolyze and condense it to obtain particles; or an organosilane and/or its partial hydrolysate is added to water or an acidic solution to obtain the organosilane and/or After the partial hydrolyzate is hydrolyzed by a partial condensate, a method of obtaining a particle by adding a base to perform a condensation reaction; making the organic silane and/or its hydrolysate as the upper layer, and making the mixed liquid of the base or the alkali and the organic solvent as the lower layer, among these The method of obtaining particles by hydrolyzing and polycondensing the organosilane and/or its hydrolyzate at the interface can be obtained by any of these methods.

Among these methods, it is preferred that when spherical silicone fine particles are produced by hydrolyzing and condensing organosilane and/or its partial hydrolysate, the reaction solution The method of adding a polymer dispersant such as a water-soluble polymer or a surfactant to obtain silicone fine particles. If the water-soluble polymer functions as a protective colloid in the solvent, any of a synthetic polymer and a natural polymer can be used. Specific examples include water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone. The surfactant only needs to function as a protective colloid by having a hydrophilic part and a hydrophobic part in the molecule. Specific examples include anionic surfactants such as sodium dodecylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, etc., Lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride and other cationic activators, polyoxyethylene ethyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyalkylene Ether-based or ester-based nonionic surfactants such as alkenyl ethers, sorbitan monoalkylates, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aromatic Silicone-based surfactants such as alkyl-modified polyalkylsiloxanes, fluorine-based surfactants such as oligomers containing perfluoroalkyl groups, and acrylic-based surfactants. From the viewpoint of improving the dispersibility in the reaction solution and the silicone composition, preferred among these are polyvinyl alcohol, polyoxyethylene alkyl ether, and polyether-modified polydimethylsiloxane And oligomers containing perfluoroalkyl groups.

The method of adding the dispersant can be exemplified by a method of adding to the reaction preliminary liquid in advance, a method of adding simultaneously with the organic trialkoxysilane and/or its partial hydrolysate, and hydrolyzing the organic trialkoxysilane and/or its partial As for the method of adding after partial condensation of the hydrolyzed substance, any of these methods can be selected. The added amount of the dispersant is preferably in the range of 5×10 ^-7 parts by weight to 0.1 parts by weight with respect to 1 part by weight of the reaction liquid. If the lower limit is exceeded, the particles are likely to aggregate with each other and form a mass. Furthermore, if the upper limit is exceeded, the residue of the dispersant in the particles increases, which causes coloration.

In order to control the dispersibility or wettability of the matrix components, these silicone particles may also be modified with a surface modifier. The surface modifier can be modified by physical adsorption or by chemical reaction. Specific examples include silane coupling agent, thiol coupling agent, titanate coupling agent, aluminate coupling agent, and fluorine system. Coating agents, etc., have high self-heat resistance and are not considered to be hardening inhibitors. The most preferred is modification using a silane coupling agent.

The organic substituents contained in the silicone fine particles are preferably methyl and phenyl groups, and the refractive index of the silicone fine particles can be adjusted by the content of these substituents. In order to reduce the brightness of the LED light-emitting device and not use the light passing through the silicone resin as the adhesive resin to scatter the light, it is preferable that the refractive index d1 of the silicone fine particles and the silicone fine particles and The refractive index d2 of the components other than the phosphor has a small refractive index difference. From this viewpoint, the refractive index 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 to such a range, the reflection and scattering at the interface of 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 is not reduced.

As for the measurement of the refractive index, the total reflection method uses Abbe refractometer, Pulfrich refractometer, liquid immersion refractometer, liquid immersion method, minimum declination method, etc. An Abbe refractometer is used for refractive index measurement, and a liquid immersion method is used for refractive index measurement of silicone fine particles.

Moreover, as a means for controlling the refractive index difference, it can be changed by changing The volume ratio of the raw materials constituting the silicone fine particles is adjusted. That is, for example, by adjusting the mixing ratio of methyltrialkoxysilane and phenyltrialkoxysilane as raw materials, by increasing the composition ratio of methyl groups, the refractive index can be reduced to approximately 1.40. On the contrary, by The composition ratio of the phenyl group is increased, and the refractive index can be increased to 1.50 or more.

In the present invention, the average particle diameter of the silicone fine particles represents the median particle diameter (D50), and the lower limit of the average particle diameter is preferably 0.01 μm or more, and more preferably 0.05 μm or more. Moreover, the upper limit is preferably 2.0 μm or less, and more preferably 1.0 μm or less. If the average particle diameter is 0.01 μm or more, it is easy to produce particles with a controlled particle size, and if it is 2.0 μm or less, the optical characteristics of the phosphor layer become good. Moreover, if the average particle diameter is 0.01 μm or more and 2.0 μm or less, the effect of improving the fluidity of the resin liquid for phosphor layer production can be sufficiently obtained. Furthermore, it is preferable to use spherical particles in a monodisperse manner. In the present invention, the average particle diameter of the silicone fine particles contained in the phosphor layer, that is, the median particle diameter (D50) and the particle size distribution can be measured by SEM observation of the cross section of the sheet. The particle size distribution is obtained by performing image processing on the measurement image of the SEM, and in the particle size distribution thus obtained, the particle diameter at which 50% of the cumulative components from the small particle diameter side is obtained is obtained as the median diameter D50.

The content of the silicone fine particles is preferably 1 part by weight or more relative to 100 parts by weight of silicone resin, and more preferably 2 parts by weight or more. Moreover, the upper limit is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, still more 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 is obtained. On the other hand, by setting it to 100 parts by weight or less, the phosphor sheet can be guaranteed By setting the strength to 25 parts by weight or less, the film can be formed stably without excessively increasing the viscosity of the silicone composition.

(Metal oxide 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 improvement. Examples of these metal oxide fine particles include silica, alumina, titania, zirconia, barium titanate, and zinc oxide. Particularly preferred are silica particles and alumina particles. Examples of these include Aerosil and Aerooxide (both manufactured by Aerosil Corporation of Japan). The average particle diameter of these fine particles is preferably selected from the range of 5 nm to 10 μm. Moreover, these fine particles may be used alone or in combination. The content of the fine particles is preferably 0.5 to 30 parts by weight relative to 100 parts by weight of the silicone resin, and more preferably 1 to 10 parts by weight. Within this range, it is possible to exhibit the effects of light scattering and improvement in coatability without causing the viscosity of the silicone composition to rise excessively and stably form a film.

(Other ingredients)

The phosphor layer of the present invention may contain nano-sized high-refractive-index inorganic fine particles in order to increase the refractive index. Examples of the material of such inorganic fine particles include alumina, titania, zirconia, and aluminum nitride. Furthermore, as the particle size, in order to prevent visible light from scattering, the particle size is preferably 50 nm or less, and more preferably 20 nm or less. In addition, in order to prevent the aggregation of such fine particles and improve the dispersibility, a method of modifying the surface of the particles is used.

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

In addition, the silicone resin composition for phosphor layer preparation in the present invention may contain a leveling agent for stabilizing the coating film, an epoxy modification or acrylic modification as a surface modifier, and a carboxyl group Silane coupling agent for modification and amine modification.

(Manufacturing method of phosphor layer)

The method of manufacturing the phosphor layer will be described. In addition, the following is an example, and the method of manufacturing the phosphor layer is not limited to this. First, a composition in which phosphor is dispersed in a resin is prepared as a coating liquid for phosphor layer formation. At this time, when the resin is a silicone resin, a silicone adhesive material may also be included. It is preferable to add silicone fine particles in order to suppress the sedimentation of the phosphor, and other additives such as metal oxide fine particles, leveling agents, and adhesion aids may also be added. In addition, when an addition reaction type silicone resin is used as the resin, a hydrosilation reaction retarder may be additionally added to extend the pot life. In order to make the fluidity suitable, if necessary, a solvent can also be added to make a solution. The solvent is not particularly limited as long as the viscosity of the resin whose flow state can be adjusted. For example, glycol ethers such as toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, rosin alcohol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, PGMEA, etc. System or glycol ester system solvent.

After blending these ingredients in such a way as to have a prescribed composition, by means of a homogenizer, a rotating revolution mixer, a three-roll mill, a ball mill, a planetary ball mill, Stirring with a bead mill or the like. Mixing and dispersing with a kneading machine to obtain a composition for making a phosphor layer. After mixing and dispersing, or in the process of mixing and dispersing, defoaming can also be preferably performed under vacuum or under a reduced pressure of 0.01 MPa or less.

Next, the composition for preparing a phosphor layer is coated on a second substrate (hereinafter referred to as a coated substrate) different from the supporting substrate applied in the invention of the present application, and dried and hardened. The substrate to be coated is not particularly limited, and known metals, films, glass, ceramics, paper, etc. can be used. In order to produce a phosphor layer with high film thickness accuracy, it is preferable that the breaking elongation of the coated substrate at 23° C. is less than 200%, or the Young’s modulus is greater than 600 MPa, and it is particularly preferable that the Young’s modulus is Above 4000MPa. Furthermore, a high-melting-point material with little deformation at a temperature of 150° C. or higher, which rapidly undergoes a hardening reaction of the resin, is preferable.

Specific examples of the coated substrate include metal plates or foils such as aluminum (including aluminum alloys), zinc, copper, and iron, cellulose acetate, polyethylene terephthalate (PET), polyolefin, Resin films of polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polyaramide, etc., paper laminated with the resin , Or paper coated with the resin, paper laminated or vapor-deposited with the metal, resin film laminated or vapor-deposited with the metal, and the like. Among these, in terms of the required characteristics or economy, resin films are preferred, and PET films or polyphenylene sulfide films are particularly preferred. In addition, in the case where a high temperature of 200° C. or higher is required when curing the resin or attaching the phosphor layer to the LED, a polyimide film is preferred in terms of heat resistance.

Moreover, in order to easily peel off the phosphor layer, the coated substrate is preferably First demold the surface. Examples of the mold release treatment method include silane coupling agent coating, fluororesin coating, silicone resin coating, melamine resin coating, and paraffin resin coating. Examples of such a coated substrate include a peeling PET film "Cerapeel" (manufactured by Toray Film Processing Co., Ltd.) and the like.

The thickness of the coated substrate is not particularly limited, and the lower limit is preferably 25 μm or more, and more preferably 50 μm or more. Moreover, the upper limit is preferably 5000 μm or less, more preferably 1000 μm or less, and still more preferably 100 μm or less.

Coating can be done by blade coater, slot die coater, direct gravure coater, indirect gravure coater, air knife coater, roller blade coater, baribar roller blade coater, double flow Coater, bar coater, wire bar coater, applicator, dip coater, curtain coater, rotary coater, blade coater, etc. In order to obtain the uniformity of the thickness of the phosphor layer, it is preferably coated by a slot die coater. Furthermore, the phosphor layer of the present invention can also be produced using printing methods such as screen printing, gravure printing, and lithography. The printed shape may be a monolithic film or a pattern shape. When the printing method is used, screen printing is particularly preferably used. In addition to this, resin molding methods such as press molding can also be used.

For drying or heat curing of the applied phosphor layer, a general heating device such as a hot air dryer or an infrared dryer is used. The heating hardening condition is usually at 80° C. to 200° C. for 2 minutes to 3 hours. In order to make it a so-called semi-hardened B-stage state that is softened by heating and exhibits adhesion, it is preferably at 80° C.~ Heating at 120°C for 15 minutes to 2 hours, preferably 30 minutes to 2 hours.

As for the phosphor layer manufactured as described above, from the viewpoint of handling, it can be transported and stored together with the coated substrate, and the coated substrate is peeled off and transferred to the support base of the present invention shortly before use Use after material. Furthermore, the phosphor layer may be cut to a size corresponding to the covered LED chip and used.

(Physical properties of phosphor layer)

The phosphor layer preferably has high elasticity in the vicinity of room temperature from the viewpoint of storage properties, transportability, and processability. On the other hand, from the viewpoint of deforming and adhering to follow the LED chip, it is preferable that the elasticity becomes low under certain conditions, and exhibit flexibility, adhesiveness, or adhesiveness (hereinafter these are collectively referred to as " Continuity"). From these viewpoints, it is preferable that the phosphor layer is softened by heating at 60° C. or higher and exhibits adhesion.

Such a phosphor layer preferably uses a rheometer to measure a phosphor layer with a film thickness of 400 μm at a frequency of 1.0 Hz and a maximum strain of 1%. The storage elastic modulus is 1.0×10 ⁵ at 25° C. Pa or higher, less than 1.0×10 ⁵ Pa at 100°C, more preferably 5.0×10 ⁵ Pa or higher at 25°C, and less than 5.0×10 ⁴ Pa at 100°C.

The storage elastic modulus of the phosphor layer here is that the thickness of the phosphor layer on the phosphor layer by the rheometer is 800 μm, the frequency is 1.0 Hz, the maximum strain is 1.0%, the temperature range is 25° C. to 200° C., and the heating rate is At 5°C/min, the storage elastic modulus in the case where only the sheet-like phosphor layer is subjected to dynamic viscoelasticity measurement. The so-called dynamic viscoelasticity means that when a shear strain is applied to a material at a certain sinusoidal frequency, when the fixed state is reached, the strain that decomposes into the shear stress exhibited is consistent with the phase (elastic component), and the difference between the strain and the phase is 90 ° The composition (viscous composition) of the analysis material Dynamic mechanical characteristics. Here, the storage elastic modulus is one in which the stress component of the shear strain and the phase is removed by the shear strain, which indicates the followability of the dynamic strain of the material with respect to each temperature, and therefore is closely related to the workability or adhesiveness of the material. On the other hand, the loss elastic modulus is obtained by removing the stress component whose shear strain differs from the phase by 90° by shear strain, and indicates the fluidity of the material.

In the case of the phosphor layer of the present invention, it has a storage elastic modulus of 1.0×10 ⁵ Pa or more at 25° C. Therefore, even at room temperature (25° C.), the cutting process such as the cutting process using the blade edge is fast. Due to stress, the periphery of the sheet is cut without deformation, so that high dimensional accuracy workability is obtained. The upper limit of the storage elastic modulus at room temperature is not particularly limited for the purpose of the present invention, and considering the stress and strain after bonding to the LED element, it is preferably 1.0×10 ⁹ Pa or less. Moreover, since the storage elastic modulus at 100°C is less than 1.0×10 ⁵ Pa, if heating and bonding is performed at 60°C to 150°C, the shape of the surface of the LED chip is rapidly deformed to follow and obtain a high adhesion force. If the phosphor layer has a storage elastic modulus of less than 1.0×10 ⁵ Pa at 100° C., as the temperature increases from room temperature, the storage elastic modulus decreases, so even if it is less than 100° C., the adhesiveness It also becomes good, especially in order to obtain a practical attachment, preferably 60° C. or higher. Furthermore, if such a phosphor layer is heated above 100°C, the storage elastic modulus is further lowered, and the adhesion is improved; if it is above 150°C, the resin is rapidly performed before the stress relaxation is insufficient. The hardening becomes easy to crack or peel. Therefore, the suitable heating and attaching temperature is 60°C to 150°C, further 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 due to the purpose of the present invention. If the fluidity is too high when it is attached to the LED element by heating, it becomes impossible to maintain it by cutting or opening before attaching Since the hole is processed into a shape, it is preferably 1.0×10 ³ Pa or more.

As the phosphor layer, if the storage elastic modulus can be obtained, the resin contained therein may also be in an uncured state. If the operability and storage properties of the sheet are considered as described below, the resin contained The best is the cured resin. If the resin is in an uncured state, there is a possibility that the curing reaction proceeds at room temperature during storage of the phosphor layer, and the storage elastic modulus deviates from an appropriate range. In order to prevent this phenomenon, it is desirable that the resin is completely cured or hardened to a semi-hardened state where the storage elastic modulus does not change to a long time when stored at room temperature for more than 1 month.

(Film thickness)

The thickness of the phosphor layer of the present invention is determined by the phosphor content, desired optical characteristics, and the height of the covered LED chip. As the phosphor content, as described above, from the viewpoint of workability, there is a limit to increase the concentration. Therefore, the film thickness is preferably 10 μm or more, more preferably 30 μm or more, and still more preferably 40 μm or more. On the other hand, from the viewpoint of improving the optical characteristics and heat dissipation of the phosphor layer, the film thickness of the phosphor layer is preferably 1000 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less. Further, in the case where the coated LED chip has a side light emitting surface with a height of 30 μm or more, the viewpoint of covering the side light emitting surface with good followability from the phosphor layer, and showing the color and From the viewpoint that the change in color seen from the oblique side becomes smaller, the thickness of the phosphor layer is preferably the height of the LED chip or less, and more preferably 1/2 or less.

Moreover, if there is unevenness in the film thickness of the sheet, the amount of phosphor produced in each LED chip is different, and as a result, unevenness occurs in the emission spectrum (color temperature, brightness, chromaticity). Therefore, the unevenness of the sheet thickness is preferably within ±5%, and more preferably within ±3%.

The film thickness of the phosphor layer in the present invention refers to the film thickness (average film thickness) measured based on the thickness measurement method A by mechanical scanning in the JIS K7130 (1999) Plastic-Film and Sheet-Thickness Measurement Method. The uneven thickness of the phosphor layer is calculated based on the following formula using the average thickness. More specifically, using the measurement conditions of the thickness measurement method A by mechanical scanning, the film thickness is measured using a micrometer such as a commercially available contact thickness meter, and the maximum or minimum value of the obtained film thickness and the average film are calculated The difference in thickness, the value of which is divided by the average film thickness and expressed as a percentage of 100, becomes the film thickness unevenness B (%).

Uneven film thickness B(%)={(Maximum film thickness shift value*-average film thickness)/average film thickness}×100

*The maximum film thickness deviation value is a value where the difference between the maximum value and the minimum value of the film thickness is larger than the average film thickness.

<support substrate>

The supporting base material in the present invention may adopt a state of flowing when the phosphor layer is attached to the light emitting surface of the LED chip. By pressurizing from the supporting substrate side while the supporting substrate is flowing, the pressure is uniformly transmitted to the phosphor layer through the supporting substrate, and the phosphor layer is attached to the light emitting surface of the LED chip. Because the supporting substrate flows, the pressure can be universally transmitted in all directions, and the supporting substrate deforms freely, even in small parts Since it can also be wound back, the shape of the light-emitting surface of the covered LED chip can be adhered extremely well.

The supporting base material has fluidity even if no stimulation is specifically given, and can also exhibit fluidity due to certain stimulations. Here, some of the stimuli may include mechanical stimuli such as heating, humidification, adding a solvent, pressurization, or vibration. Self-liquidity management is easiest to consider, and it is preferable to exhibit fluidity by heating and pressurization.

In addition, in order to prevent the support base material from wrapping between the phosphor layer and the light emitting surface of the LED chip before being pressed, it is preferable to maintain the shape of a solid shape such as clay or plastic resin when it is not pressurized. Flow when pressurized.

From the viewpoint of showing the adhesion of the phosphor layer in the pressing step, the state where the supporting base material flows exists at 10° C. or higher. Further from the viewpoint of operation, it is preferable to be in a solid state at room temperature, so it is preferable that the state in which the supporting substrate flows exists at 40°C or higher, and more preferably exists at 50°C or higher. Furthermore, from the viewpoint of preventing the resin of the phosphor layer from hardening, it is more preferable that the state where the supporting base material flows exists at 150°C or lower and at 100°C or lower. Here, the state where the supporting base material flows also includes a case where it flows only when pressurized.

(Rheological properties of supporting substrate)

The state in which the supporting base material flows in the present invention is specified by dynamic viscoelasticity measurement using a rheometer. Here, the method of dynamic viscoelasticity measurement is specifically to sandwich the material in a parallel disc-shaped plate, while changing the temperature, while measuring and applying shear at a sinusoidal frequency with a frequency of 1.0 Hz and a maximum strain of 1.0% The shear stress and strain at the time of strain are calculated according to their values The method of storing the elastic modulus G', the loss elastic modulus G" representing the fluidity of the material, and the viscosity. The film thickness of the supporting substrate to be the sample is 1 mm, and the standard for temperature change is 5°C/min The rate of temperature increase from 25°C to 200°C.

Here, the storage elastic modulus G'and the loss elastic modulus G" when measured at a frequency of 1.0 Hz and a maximum strain of 1.0% using a rheometer in the state where the supporting base material of the present invention flows are 10° C. or higher , In all or part of the temperature range below 100°C is G'<G" (Equation 1)

The relationship is 10Pa<G'<10 ⁵ Pa (Formula 2)

Relationship. In addition, in Formula 2, the lower limit is more preferably 10 ² Pa<G′, and the upper limit is more preferably G′<10 ⁴ Pa. Furthermore, it is more preferable to satisfy these relationships in all or part of the temperature range of 40°C or more and 100°C or less, and it is more preferable to satisfy these relationships in all the temperature ranges of 70°C or more and 100°C or less.

As shown in Formula 1, by making G” representing the viscosity component larger than G′ representing the elastic component, the supporting base material becomes fluid.

As shown in Equation 2, if the storage elastic modulus G'is greater than the lower limit, the substrate can be supported without transmitting pressure to the phosphor layer. Moreover, if the storage elastic modulus G'is smaller than the upper limit, the supporting base material is liable to flow and deform, so the followability to the covering becomes high.

Moreover, from the viewpoint of the pressure transmission to the phosphor layer, the viscosity of the state in which the supporting substrate flows is preferably 10 Pa in all or part of the temperature range of 10°C or more and 100°C or less. Above s, the better is 10 ² Pa. s or more. Moreover, from the viewpoint of followability to the covering, it is preferably 10 ⁵ Pa in all or part of the temperature range of 10°C or more and 100°C or less. Below s, the better is 10 ⁴ Pa. s below. Further from the viewpoint of maintaining the film thickness of the phosphor layer, it is preferable that the viscosity of the supporting base material is lower than the viscosity of the phosphor layer at the temperature during pressurization.

More preferably, the physical properties are satisfied in all or a part of the temperature range of 40° C. or more and 100° C. or less, and it is particularly preferable that the physical properties are satisfied in all the parts of 70° C. or more and 100° C. or less.

(Vicat softening temperature)

More preferably, the support base material is difficult to deform for easy operation at room temperature, and the support base material is softened at a temperature at which the phosphor layer is not hardened abruptly. From this viewpoint, the Vicat softening temperature of the supporting base material 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 the temperature at which the supporting base material softens, and can be measured according to the method specified in JIS K 7206 (1999) A50. Specifically, a test piece is provided on the heat transfer medium, and the heat transfer medium is heated in a state where the end surface of the load bar (cross-sectional area is 1 mm ² ) is pressed to the upper surface of the central portion of the test piece, and the load bar is put into the test The temperature (°C) at 1 mm of the sheet is regarded as the Vicat softening temperature.

(Melting point)

The supporting base material is preferably solid at room temperature, and melts and flows by heating. From this viewpoint, the melting point of the supporting base material is preferably 40°C or higher and 100°C or lower, and more preferably 40°C or higher and 70°C or lower. Melting point can be based on JIS K 7121 (1987) Determined by the method specified in. Specifically, by means of differential thermal analysis (DTA) or differential scanning calorimetry (DSC), the temperature at which the temperature is changed from the solid phase to the liquid when the temperature is raised at 10° C./min is used as the supporting base The melting point of the wood.

(Melt flow rate)

The fluidity of the support base material after melting can be expressed in accordance with the melt flow rate (MFR) measured according to the method specified in JIS K7210 (1999). From the viewpoint of attaching the phosphor layer to the covering with good followability, the MFR at a measurement temperature of 190° C. and a load of 21.2 N is preferably 1 (g/10 min) or more, and more preferably 10 ( g/10min) or more. In addition, the self-flowing supporting substrate does not wrap around between the phosphor layer and the coating, but it is preferably 500 (g/10min) or less, more preferably 200 (g/10min) or less, and further Preferably, it is 100 (g/10min) or less.

(Film thickness of supporting substrate)

The film thickness of the supporting base material is not particularly limited, and the appropriate film thickness depends on the height of the coated object.

For example, when considering coating on an LED wafer, from the viewpoint of followability to the side of the LED wafer, the height of the coated LED wafer is preferably more than the height, and more preferably twice the height of the LED wafer the above. When the film thickness is in this range, the supporting base material that flows during pressurization is easily wrapped around the side surface of the wafer, and the phosphor layer can be attached with good followability. In addition, from the viewpoint of economic efficiency and the viewpoint that the entire support base material is fluidized by heating, the film thickness of the support base material is preferably ten times or less the height of the LED wafer.

If the height of commonly used LED chips is considered to be 100μm~300μm, then The thickness of the supporting substrate is preferably 300 μm or more, and more preferably 500 μm or more. Moreover, it is preferably 2000 μm or less, and more preferably 1000 μm or less.

In addition, from the viewpoint that the pressure at the time of pressurization is uniformly transmitted to the phosphor layer, the film thickness of the supporting base material is preferably in the range of ±10% of the average film thickness.

(surface condition)

The surface shape of the surface of the supporting base material that is in contact with the phosphor layer is transferred to the surface of the phosphor layer under pressure, which affects the visual effect of the luminescent color or the unevenness of the color. Therefore, the surface of the support substrate on the phosphor layer side is preferably 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 base material is not particularly limited as long as it can adopt the above-mentioned flowing state. Moreover, it may be a single substance or a mixture. Among them, it is preferable that the main component is a plastic material, and from the viewpoint of covering the phosphor layer with good followability, its content is preferably 50% by weight or more of the weight of the supporting substrate, and more preferably 80% by weight or more . Specific examples of such a plastic material include plastic resin, rubber, and clay. From the viewpoint of formability and handleability, a thermoplastic resin is preferred.

Here, the thermoplastic resin refers to a resin having a region that can be plastically deformed by heating (hereinafter referred to as "thermoplastic region"). It is preferable to be plastically deformable in part or all of 40°C or more and 100°C or less. Furthermore, the hardening reaction may be performed by heating at a temperature higher than the temperature range where plastic deformation occurs. The area where the hardening 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 of the thermoplastic resin at a measurement temperature of 190° C. and a load of 21.2 N is preferably 1 (g/10 min) or more, and more preferably 10 (g/10 min) or more. Moreover, it is preferably 500 (g/10 min) or less, more preferably 200 (g/10 min) or less, and even more preferably 100 (g/10 min) or less. Vicat softening temperature, melting point, and MFR are all measured by the same method as the measurement method in the supporting base material.

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, and amine groups. Formate resin, acrylic resin (including methacrylic resin), epoxy resin, silicone resin and copolymers of these.

Here, the poly-α-olefin resin refers to a polymer having a C 2 or more side chain functional group obtained by addition polymerization of α-olefin. Examples of the side chain functional group include linear alkyl groups. The poly-α-olefin resin can be specifically exemplified by the addition polymerization of 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and a mixture of these. Molecular compound. Among these, it is preferable to include one or more than two selected from the group consisting of poly-α-olefin resin, polycaprolactone resin, acrylic resin, silicone resin, and one or more copolymerized resins with ethylene Resin. The support substrate of the present invention has the following two types: a "peel-type support substrate" that peels the support substrate from the phosphor layer after coating the phosphor layer on the object (such as an LED chip), which is attached to the phosphor layer The "non-stripping type" incorporated directly into the light-emitting device in the state of Support substrate."

As the material used in the "peelable support substrate", it is important to balance the adhesion and peelability of the phosphor layer and the adhesion to the LED chip. On the other hand, as a material used in the “non-peelable supporting substrate”, in order to be incorporated into a light-emitting device, it is important that the light exit property, heat resistance, and light resistance are excellent.

As a method for manufacturing a light-emitting device using the laminate of the invention, any one of a process using a "peel-type support substrate" and a process using a "non-peel-type support substrate" can be suitably used to peel from the support substrate It is possible to precisely design the lens structure and other optical components with high degrees of freedom, and it is better to use the "peel-type supporting substrate" process.

(Releasable support substrate)

It is important that the peeling type supporting base material can be easily peeled off after coating the phosphor layer. A particularly good property is that it fluidizes when heated, hardens after cooling to room temperature, and easily peels off. Examples of thermoplastic resins having such properties include polypropylene resins, poly-α-olefin resins, cyclic polyolefin resins, polycaprolactone resins, and copolymer resins of these resins with ethylene, in which the Vicat softening temperature or melting point In terms of low and excellent releasability, the copolymer resin of poly-α-olefin resin and ethylene (ethylene-α-olefin copolymer resin) is more preferable, and the ethylene-1-hexene copolymer resin is even more particularly preferable. .

Furthermore, in the case where the adhesion between the support substrate and the phosphor layer is weak and the phosphor layer is difficult to be held on the support substrate, a thermoplastic resin with high adhesiveness may be mixed with the ethylene-α-olefin copolymer resin to manufacture the support Substrate. Examples of thermoplastic resins with high adhesiveness include urethane resins, acrylic resins, epoxy resins, and these resins and The copolymer resin of ethylene is preferably an ethylene-acrylic acid (methacrylic acid) copolymer resin from the viewpoint of low Vicat softening temperature or melting point.

The mixing ratio of the ethylene-α-olefin copolymer resin and the thermoplastic resin having high adhesiveness is determined by the balance of adhesiveness and peelability. The ratio to obtain such a balance is preferably 0.01 parts by weight to 10 parts by weight of a thermoplastic resin with high adhesion relative to 100 parts by weight of the ethylene-α-olefin copolymer resin, and more preferably 0.1 parts by weight~ 1 part by weight.

These peelability indicators can exemplify the adhesive force of the supporting substrate. Here, the first method for measuring the adhesive force of the supporting base material may include a 90-degree peel test specified in JIS Z 0237 (2009). In the measurement of this method, the adhesive force of the support substrate is considered from both the viewpoint of maintaining the adhesion of the phosphor sheet and the peelability of the support substrate after being attached to the LED chip It is preferably in the range of 0.05N/20mm to 2.0N/20mm, and more preferably 0.1N/20mm to 1.5N/20mm.

Furthermore, the second method for directly measuring the adhesion between the phosphor layer and the supporting substrate can be exemplified by the peeling test shown below (referred to as "phosphor layer: supporting substrate adhesion evaluation test"). Method of determination. "Phosphor layer: evaluation test for the adhesion of the supporting substrate" includes: the first step is to produce a laminate sample with a phosphor layer with a size of 50 mm × 50 mm attached to the supporting substrate; the second step is to On the surface of the body layer, a tape coated with a silicone adhesive material with a width of 50 mm (trade name: circuit tape 647 0.12, adhesive force of 15 N/50 mm (manufactured by Teraoka Manufacturing Co., Ltd.)) is attached to the phosphor with a length of 50 mm. Directly above; the third step, with a dynamometer (trade name: digital dynamometer ZTS-20N, manufactured by Yida Motor Co., Ltd. (Making) The force required when the tape is stretched in the direction of 90 degrees with respect to the laminate sample to peel off the phosphor layer from the supporting substrate. In the measurement by this method, the adhesive force of the supporting substrate is preferably in the range of 0.001 N/50 mm to 1.0 N/50 mm, and more preferably 0.01 N/50 mm to 0.5 N/50 mm. In addition, in this method, when the phosphor layer is not peeled off from the supporting substrate, it is evaluated to be 15 N/50 mm or more.

The method of peeling off the peeling type supporting base material can be exemplified by, after cooling to 30° C. or less, sandwiching one end of the supporting base material with tweezers and the like, or peeling the supporting base material and the adhesive tape to peel it off, etc. , But not limited to these methods.

Specific examples of the ethylene-α-olefin copolymer resin include "TAFMER" (manufactured by Mitsui Chemicals) and "EXCELLEN" (manufactured by Sumitomo Chemicals). Specific examples of the cyclic olefin resin include "ZEONOR" and "ZEONEX" (manufactured by Japan Zeon Corporation). Specific examples of the polycaprolactone resin include "Placcell H" (made by Daicel Corporation). Moreover, the thermoplastic resin which improves adhesiveness may include an ethylene-methacrylate resin "ACRYFT" (made by Sumitomo Chemical Co., Ltd.).

(Non-peelable support substrate)

The non-peelable supporting substrate requires transparency and heat resistance in order to be incorporated into the light-emitting device. The thermoplastic resin having such properties preferably exhibits plasticity in the coating temperature range (50° C. to 150° C.), but if heated to a temperature above it, it irreversibly undergoes a hardening reaction to completely harden the resin. Here, the fully hardened state refers to a state in which the range where the storage elastic modulus G'and the loss elastic modulus G" become G'<G" becomes zero in the rheometer test. This type of thermoplastic resin Specific examples include acrylic resins (including methacrylic resins), epoxy resins, silicone resins, and copolymerized resins of these resins with ethylene. Especially from the viewpoint of heat resistance and light resistance, silicone resin is particularly preferable.

Specific examples of acrylic resins include "ACRYFT" (made by Sumitomo Chemical Co., Ltd.). Specific examples of epoxy resins include those in which Epikote 157S70 and Epikote 828 (Japan Epoxy Resin Co.) are mixed with 2-phenylimidazole as a hardening accelerator, and silicone Specific examples of the resin include OE-6450 and OE6635 (manufactured by Toray Dow Corning) having a thermoplastic region.

As the adhesive force of the non-peelable support substrate, in the first method determined by the 90-degree peel test specified in JIS Z 0237 (2009), it is preferably 0.05 N/20 mm or more and 50 N/20 mm or less. Moreover, in the "phosphor layer: evaluation test of adhesion of the supporting substrate", from the viewpoint of sufficient adhesion between the phosphor layer and the supporting substrate, it is preferably 1.0 N/50 mm or more, and more preferably 5.0N/50mm or more, more preferably 15N/50mm or more, that is, the phosphor layer does not peel off the self-supporting substrate.

In order to obtain high brightness for the non-peelable support substrate, it is important that the light exit effect is high, and therefore it is preferable that the transparency is high. Here, the transparency is ideally evaluated by including the transmittance of diffused light (hereinafter referred to as diffused light transmittance), and the measurement method thereof can be exemplified by a transmission absorption measurement system (manufactured by Otsuka Electronics Co., Ltd.) using an integrating sphere. Here, in the case where a supporting substrate (fully cured product) with a thickness of 0.5 mm is used as a sample, the transmittance of diffused light at 450 nm is preferably 50% or more, more preferably 70% or more, and still more preferably Is over 90%.

The heat resistance of the non-peelable supporting base material is evaluated by the rate of change of the diffuse transmittance after heating at a constant temperature. Specifically, the evaluation was performed by measuring the initial diffuse light transmittance (450 nm) of the supporting base material (completely cured product) with a thickness of 0.5 mm, and performing it with a hot air dryer at 150° C. for 1,000 hours. The diffuse light transmittance (450nm) after continuous heating is based on the transmittance change rate = (diffuse light transmittance after 1000 hours)/(initial diffuse light transmittance)

Calculation. The "transmittance change rate" is preferably 0.7 or more, and more preferably 0.8 or more.

(Manufacturing method of supporting base material)

The supporting base material is not particularly limited as long as the material can be shaped so as to have the film thickness and surface state. Examples of the production method include extrusion molding, die press molding, injection molding, and roll stretch molding. From the viewpoint of productivity, it is preferably produced by performing extrusion molding on the film subjected to the peeling process.

Here, it is preferable to perform processing so that at least one surface becomes a smooth surface (mirror surface). The smooth surface can be processed by extruding the resin on a smooth peeling film with Ra of 10 μm or less and cooling it.

Specific examples of the manufacturing method include: putting the raw materials of the supporting base material in an extruding and kneading machine heated to 150° C. or more and kneading, extruding the molten raw materials from the slit die onto the peeled PET to make a sheet In the form of a coil Method of shaped products.

<Laminate>

The layered body of the present invention can be manufactured by loading the phosphor layer and the supporting substrate. Here, the phosphor layer and the supporting base material may be pre-manufactured as a laminate and used for coating on the LED chip after storage and transportation. Alternatively, the phosphor layer and the supporting substrate may be separately stored and transported, and then manufactured as a laminate shortly before the step of coating on the LED wafer.

The laminate is preferably manufactured by mounting the phosphor layer produced on the coated substrate so as to overlap with the smooth surface of the supporting substrate, while the temperature is 40°C or more and 120°C or less After heating under one side to bond it, the coated substrate is peeled off. The device used for bonding is not particularly limited, and examples thereof include a roll laminator, a vacuum roll laminator, and a vacuum separator laminator. Furthermore, the manufacturing temperature of the laminate is more preferably 70°C or higher and 100°C or lower.

In order to add some functions, the laminate of the present invention may include a layer other than the phosphor layer and the supporting substrate. For example, between the phosphor layer and the supporting substrate, a thin film layer may be provided for the purpose of protecting the phosphor layer, and a transparent resin layer may also be provided for the purpose of diffusion effect or light emission effect. In addition, an adhesive layer may be provided on the surface opposite to the support substrate side of the phosphor layer to improve the adhesion to the LED chip.

From the viewpoint of operability or surface protection during storage and transportation, the laminate of the present invention may include a cover film on both sides of the phosphor layer side and the supporting base material side. As the cover film on the phosphor layer side, in order not to cause damage to the phosphor layer in the B-stage state The damage is preferably a peelable film. Specifically, a polydimethylsiloxane coated PET film, a fluororesin film (PFA, ETFE, etc.), a polyurethane film, etc. can be exemplified. As the cover film on the support substrate side, the same peelable film as the cover film on the phosphor layer side can be used. Furthermore, when a non-releasing film is used, after covering the object with the phosphor layer, the cover film and the supporting base material can be peeled off from the phosphor layer. Examples of such non-peelable films include PET films and PP films.

<Lighting device>

Next, the light-emitting device will be described. The light-emitting device of the present invention includes: an LED chip covering a light-emitting surface with a phosphor layer; a package substrate to which the LED chip is fixed for electrical bonding; and a wiring pattern formed by a conductor such as metal foil, to which the package substrate is mounted Circuit board, etc.

(LED chip)

The LED chip preferably emits blue light or ultraviolet light. This type of LED chip is particularly preferably a GaN-based LED chip. GaN-based LED chips can be manufactured as follows: a buffer layer of gallium nitride is provided on a sapphire wafer, a silicon carbide wafer, a gallium nitride wafer, or a silicon wafer, and a layer is deposited thereon by MOCVD After the light emitting layer of gallium nitride is cut, it is singulated. 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 chips: lateral, vertical, and flip-chip. Any mode can be used, but it has high brightness and high brightness from the viewpoints that the light-emitting area can be increased, there is no wire, and there is little concern about defects due to disconnection, and the light-emitting layer of the heat source is close to the circuit board and the heat dissipation is good. The best among power LEDs is inverted Load wafer type.

Furthermore, there is a case where there is a single plane and a case where there is not a single plane on the light emitting surface from the LED wafer. The case of a single plane mainly includes the case where only the upper light-emitting surface is included. Specifically, a vertical type LED, or a flip chip type LED that covers the side surface with white resin as a reflective layer and emits only light from the upper surface, etc. can be exemplified. When the laminate of the present invention is used in a single planar light-emitting LED, the support substrate is fluidized to uniformly and slowly pressurize the phosphor layer, thereby making it easier to control the film in the coating of the phosphor layer Thickness changes and uneven film thickness.

On the other hand, when it is not a single plane, an LED chip including an upper light-emitting surface and a side light-emitting surface or an LED chip having a curved light-emitting surface can be cited. By using the light emitted from the side portion, the light emitting area can be increased, the color orientation unevenness can be reduced, and the light distribution characteristics are excellent. Therefore, it is preferable that the light emitting surface is not a single plane. In particular, since the light output area can be increased and the wafer manufacturing process can be easily considered, a flip-chip LED chip including an upper light-emitting surface and a side light-emitting surface is preferable.

Furthermore, in order to improve the light emission efficiency, the light emitting surface may be processed into a concave-convex structure based on optical design, such as a patterned sapphire substrate (Patterned Sapphire Substrate, PSS).

The film thickness of the LED chip is not particularly limited. From the viewpoint of reducing the pressure applied to the phosphor layer on the upper surface or corner of the LED chip and maintaining the uniformity of the film thickness, the upper limit of the film thickness is preferably 500 μm or less. It is more preferably 300 μm or less, and still more preferably 200 μm or less. Moreover, as the lower limit of the film thickness, if there is a The optical layer may be sufficient, preferably 1 μm or more. It is further preferred that the total film thickness of the LED chip and the connection portion with the substrate and the film thickness of the phosphor layer satisfy the following relationship.

1≦(Total film thickness of the LED chip and the connection portion with the substrate/film thickness of the phosphor layer)≦10.

If it is more than the lower limit, it is easy to suppress the azimuth unevenness of the emission color. Moreover, if it is below the upper limit, it is easy to maintain the uniformity of the thickness of the phosphor layer. From this viewpoint, the lower limit is preferably 2 or more. Moreover, the upper limit is preferably 5 or less, and more preferably 4 or less.

(Package substrate)

The package substrate is a fixed and electrically bonded LED chip, and is mounted on the circuit substrate. The material of the substrate is not particularly limited, and examples include resins such as polyphthalamide (PPA), liquid crystal polymer, silicone, aluminum nitride (AlN), aluminum oxide (Al ₂ O ₃ ), and boron nitride ( BN) and other ceramics, copper, aluminum and other metals. In particular, in the case of a high-brightness and high-power LED, a ceramic substrate such as an aluminum nitride substrate or an aluminum oxide substrate is preferable from the viewpoint of self-heat dissipation.

On the package substrate, in order to energize the LED chip, electrode patterns can also be formed by gold, silver, copper, aluminum, or the like. Moreover, it is preferable to include a heat dissipation mechanism. Furthermore, a resin or metal reflector may be provided on the substrate.

(Circuit board)

The circuit board refers to a printed circuit board in which an LED chip is mounted on a wiring pattern formed by a conductor and is bonded to an LED chip for integration into an electronic device. The substrate is generally a paper-phenol resin board, a glass epoxy board, and a metal plate such as aluminum is superimposed Copper clad copper substrate. In addition, there are also cases where the LED chip is directly bonded to the circuit board like 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 a lateral type or a vertical type. On the other hand, as a flip-chip type LED, there can be exemplified a method of bonding an LED chip and an electrode by solder bonding using gold bumps, eutectic bonding using gold and tin, and bonding by conductive paste.

As the type of the structure of the light emitting device, the following can be cited as an example: As shown in FIG. 1(a), the LED chip 7 and the package electrode 9 are joined, and then mounted on the surface of the circuit wiring 2 on the circuit board 1 Mounted type (SMD); as shown in FIG. 1(b), a chip on board (COB) type directly mounted on the circuit wiring 2 on the circuit board 1. The SMD of FIG. 1( a) is formed by bonding the LED chip 7 via the gold bumps 8 on 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 First, an LED package 3 sealed with a transparent resin 5 is fabricated, and a structure in which the circuit wiring 2 formed on the circuit board 1 and the package electrode 9 are energized is energized. On the other hand, the COB of FIG. 1(b) is to directly mount the LED chip 7 on the circuit wiring 2 formed on the circuit board 1 through the gold bumps 8, and further coat the LED chip 7 with the phosphor layer 6 The structure is sealed by transparent resin 5. All of the LED chips 7 have a light-emitting surface having an upper light-emitting surface and a side light-emitting surface, and all of them are covered by the phosphor layer 6. In the COB, in order to prevent the transparent resin 5 from flowing out, a barrier 11 of white resin may be formed around it.

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(a), 2(b), and 3 are examples of LED packages that cover the LED chip 7 using the laminate of the present invention. The phosphor layer 6 can be provided in direct contact with the light-emitting surface of the LED chip 7, and can also be provided indirectly with the transparent resin 5 interposed between the LED chip 7 as shown in FIG. 3, but it can reduce fluorescence From the viewpoint of volume, it is preferable to directly install the LED chip 7 in close contact with it.

This light-emitting device may be a device that covers only the phosphor layer 6 on the LED chip 7 bonded to the package substrate 10, and may also use the LED chip 7 for the purpose of protecting the phosphor layer as shown in FIG. 2(a). A protective layer of the transparent resin 5 is provided on the outer periphery of the phosphor layer 6 coated thereon, and as shown in FIG. 2( b ), a lens formed of the transparent resin 5 may be provided for the purpose of improving light emission.

(Manufacturing method of light-emitting device)

The manufacturing method of the light emitting device includes the steps of bonding the LED chip to the package substrate, the step of coating the phosphor layer on the LED chip, the step of sealing with a transparent resin or providing a lens, and the step of mounting the package substrate on the circuit substrate . Among them, in the case of COB, the LED chip is directly mounted on the circuit board. The invention has features in the step 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 laminate. This step is preferably carried out by mounting the laminate on the light emitting surface of the LED chip so that the phosphor layer becomes the light emitting surface side of the LED chip, and then using a rheometer at a frequency of 1.0 The storage elastic modulus G'and the loss elastic modulus G" of the supporting base material when measured at Hz and a maximum strain of 1.0% satisfy G'<G" (Equation 1)

And 10Pa<G'<10 ⁵ Pa (Formula 2)

Pressure in the state of the relationship.

Furthermore, the step of attaching the phosphor layer may be performed before the step of bonding the LED chip to the package substrate, or may be performed afterwards.

The phosphor layer can be applied under pressure while the supporting base material is softened and flowing. In particular, when a thermally fusible phosphor layer is used, from the viewpoint of strengthening the adhesiveness, the adhesion temperature is preferably 50° C. or higher, and more preferably 60° C. or higher. Moreover, the thermally fusible resin used in the phosphor layer has a property that the viscosity temporarily decreases due to heating, and if further heating is continued, it is thermosetting. Therefore, the temperature in the attaching step is preferably 150° C. or less from the viewpoint of maintaining the adhesiveness, and more preferably 120° C. or less from the viewpoint of keeping the viscosity of the phosphor layer above a certain level and maintaining the shape. More preferably, it is below 100°C. In addition, in order to prevent the residual gas from accumulating, it is preferable to perform the attachment under a reduced pressure of 0.01 MPa or less. Examples of manufacturing apparatuses that perform such attachment include vacuum separator laminators, vacuum roll laminators, vacuum hydraulic presses, vacuum servo presses (servo presses), vacuum electric presses, and TOM forming machines. Machine etc. Among them, considering that there are a large number of disposables that can be processed at one time and can be pressurized from above without offset, a vacuum separator laminator is preferred. This type of vacuum separator laminator can be exemplified by V-130 and V-160 (Rising Materials Materials company) etc.

The method of attaching the phosphor layer to the LED chip may include: as shown in FIG. 4, the laminate 12 including the phosphor layer 6 and the supporting substrate 13 is individualized and attached to each LED chip 7 one by one Method; and as shown in FIG. 5, after the laminated body 12 is collectively attached to the plurality of LED wafers 7, a method of cutting off and individualizing can be used, and any method can be used. In addition, FIGS. 4(1) and 5(1) respectively show before attachment, and FIGS. 4(2) and 5(2) respectively show after attachment.

Hereinafter, four methods will be exemplified regarding the manufacturing process of the light-emitting device. The first manufacturing example and the second manufacturing example are examples of the manufacturing process using the "peel-type supporting substrate", and the third manufacturing example and the fourth manufacturing example are examples of the manufacturing process using the "non-peeling supporting substrate". In addition, the manufacturing process of the light emitting device is not limited to these examples.

The first manufacturing example is shown in FIG. 6(a), FIG. 6(b), FIG. 6(c), FIG. 6(d), FIG. 6(e), and FIG. 6(f). FIG. 6( a) temporarily fixes the LED chip 7 on the pedestal 15 via the adhesive tape 14. Here, the adhesive tape 14 is not particularly limited as long as it can temporarily fix the LED chip and can withstand the attachment temperature, and it is preferable to use an adhesive tape (hereinafter referred to as UV peeling) that reduces the adhesive force by UV irradiation Tape), any of tapes (hereinafter referred to as thermal peeling tapes) whose adhesive force is reduced by heating or tapes whose adhesive force is weak to 2 N/20 mm or less (hereinafter referred to as micro-adhesive tapes).

FIG. 6(b) laminates the laminate 12 so that the phosphor layer 6 and the LED chip 7 are in contact with each other.

6(c) After putting the laminate of FIG. 6(b) into the lower chamber 19 of the vacuum separator laminator 16, it is heated while passing through the exhaust/suction port 17 The exhaust is performed to decompress the upper chamber 18 and the lower chamber 19. After heating until the support substrate 13 flows, the upper chamber 18 is sucked into the atmosphere through the exhaust/suction port 17, thereby expanding the separator film 20, and pressurizing the phosphor layer 6 through the support substrate 13 Affixed so as to follow the light emitting surface of the LED wafer 7.

6(d) After returning the upper chamber 18 and the lower chamber 19 to atmospheric pressure, the load including the pedestal 15, the adhesive tape 14, the LED wafer 7 and the laminate 12 is taken out from the vacuum separator laminator 16, After leaving to cool, the supporting base material 13 is peeled off. At the cutting position 21, the obtained coating body is cut by a dicing machine or the like to produce a singulated phosphor layer-covered LED chip 22.

6(e) When the adhesive tape 14 is a UV peeling tape, a step of reducing the adhesive force by a UV irradiation step is performed, and in the case of a thermal peeling tape, a step of reducing the adhesive force by heating is performed Then, the phosphor layer-covered LED chip 22 is taken out from the adhesive tape 14 and bonded to the package electrode 9 formed on the package substrate 10 through the gold bumps 8.

FIG. 6(f) manufactures the LED package 23 through the above steps. 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, a protective layer or lens of the transparent resin 5 is provided.

The second manufacturing example is shown in FIGS. 7(a), 7(b), 7(c), 7(d), and 7(e). 7( a ), the LED chip 7 is bonded to the package electrode 9 formed on the package substrate 10 via the gold bump 8.

7( b ), the laminate 12 is stacked so that the phosphor layer 6 and the LED chip 7 are in contact with each other.

7(c) After placing the load shown in FIG. 7(b) into the lower chamber 19 of the vacuum separator laminator 16, the phosphor layer 6 is attached to the phosphor layer 6 by the same method as the first manufacturing example. The light emitting surface of the LED chip 7.

7(d) After the lower chamber 19 is restored to atmospheric pressure, the load is taken out of the vacuum separator laminator 16, and after being left to cool, the supporting base 13 is peeled off. Next, the obtained covering body is cut at the cutting position 21 to be singulated.

FIG. 7(e) manufactures the LED package 23 through the above steps. 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, a protective layer or lens of the transparent resin 5 is provided.

The third manufacturing example is shown in Figs. 8(a), 8(b), 8(c), 8(d), 8(e), and 8(f). 8(a) to 8(c) perform the same operation as the first manufacturing example. 8(d) After returning the upper and lower chambers 18 and 19 to atmospheric pressure, the load is taken out of the vacuum separator laminator 16, and the cutting position 21 is carried out by a cutter or the like for each supporting substrate 13 After the placement and cooling, the resulting load was cut to produce a single-piece phosphor layer-coated LED chip 25 with a supporting base material. FIG. 8(e) forms the LED package 26 with the supporting base material in the same steps as the first manufacturing method. FIG. 8(f) mounts the LED package 26 with a supporting base material on the circuit wiring 2 formed on the circuit board 1 to manufacture the light-emitting device 24.

The fourth manufacturing example is shown in FIGS. 9(a), 9(b), 9(c), 9(d), and 9(e). 9(a) to 9(c) perform the same operation as the first manufacturing example. 9(d) After the upper and lower chambers 18 and 19 are restored to atmospheric pressure, the load is taken out from the vacuum separator laminator 16, and each support base is cut at the cutting position 21 The material 13 is cut and left to stand, and the resulting load is singulated to produce an LED package 26 with a supporting base material. 9(e), the LED package 26 with a supporting base material is mounted on the circuit wiring 2 formed on the circuit board 1, and the light emitting device 24 is manufactured.

(Evaluation of adhesion)

If the laminate of the present invention is used, a light-emitting device in which the phosphor layer attached by the laminate is directly in contact with and covered with 90% or more of the upper light-emitting surface area of the LED chip and 70% or more of the side light-emitting area can be produced.

Here, the direct adhesion refers to a state where there is no gap or the like between the phosphor sheet and the upper light-emitting surface or the side light-emitting surface of the LED chip, and then the state is followed. In the coating of the upper light emitting surface of the LED chip, when the direct contact portion is less than 90% of the area of the upper light emitting surface of the LED chip, the phosphor sheet easily peels off, which causes a defect of the light emitting device. From this point of view, it is more preferable that the light-emitting surface on the upper part of the LED chip is directly covered with more than 99% and covered.

In addition, in the coating of the side light emitting surface of the LED wafer, if the direct contact portion is less than 70% of the side light emitting area of the LED wafer, the light emitting efficiency from the side surface of the LED wafer becomes low, resulting in a decrease in brightness. Moreover, peeling from its non-adherent portion becomes easy, and reliability is reduced. From this point of view, it is more preferable that the direct contact portion is more than 90% of the light emitting area on the side of the LED chip, and even more preferably 99% or more.

The evaluation of the adhesion is performed by cutting the profile by the profile polisher method (CP method) or the like, and then performing the profile by a method using SEM observation (hereinafter referred to as a profile SEM method) or using an X-ray CT image analysis device The partial observation method (hereinafter referred to as X-ray CT method) is evaluated from a cross-sectional photograph.

In the case of using the layered product of the present invention, from the viewpoint of suppressing uneven orientation of light emission, it is preferable that the film thickness of the phosphor layer covering the LED chip changes little at any locations. From this point of view, a method of obtaining the film thickness ratio of the upper surface portion and the side surface portion of the phosphor layer coated on the LED chip will be described with reference to FIGS. 10(a) and 10(b).

FIG. 10( a) is a plan view of the LED package 23. Reference numeral 27 refers to the upper surface portion of the phosphor layer covering the LED chip, reference numeral 28 refers to the side surface portion of the phosphor layer covering the LED chip, and reference numeral 29 refers to the phosphor layer covering the package substrate. 10(b) is a cross-sectional view taken along line II' of FIG. 10(a). As shown in FIG. 10(a), II' passes through the substantially center of the LED wafer.

In this specification, in this section, 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 the upper surface of the LED chip is as follows definition. In a region where the upper surface of the LED chip 7 is in contact with the phosphor layer 6, a position approximately four quarters from the left end of the upper surface, that is, a position L1≒L2≒L3≒L4 is extracted. Among these, the distance between the remaining three points of the LED chip 7 excluding the two ends and the outer surface of the phosphor layer 6 is defined as A1 to A3 [μm], respectively. The average value of these 3 points is defined as A [μm].

Furthermore, in the II′ cross-sectional view, the distance B [μm] from the side 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 the side surface of the LED chip is defined as follows . In the area where the left side of the LED chip 7 is in contact with the phosphor layer 6, when the thickness of the LED chip 7 from the package electrode 9 on the package substrate 10 is taken as t1, the LED chip 7 and the fluorescent chip whose half height is t2 Light The distance of the outer surface of the bulk layer 6 is referred to as B1 [μm]. Similarly, the same distance in the right side surface of the LED wafer 7 is referred to as B2 [μm]. The average value of B1 and B2 is defined as B [μm].

In the case of being defined as described above, from the viewpoint of suppressing uneven light emission, it is preferable to satisfy the relationship of 0.70≦A/B≦1.50, and more preferably 0.80≦A/B≦1.20.

From the viewpoint of controlling the emission color, it is preferable to maintain the thickness of the phosphor layer before the coating step. If the average film thickness of the phosphor layer before the coating step is C[μm], the film thickness retention rate can be determined by the film thickness retention rate (%)=distance A[μm]/film thickness C[μm]×100

The formula is calculated. The film thickness retention rate is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

In addition, in the light-emitting device obtained by using the laminate of the present invention, from the viewpoint of suppressing uneven orientation of light emission, it is preferable to provide the phosphor layer following the side of the LED chip. The compliance of the phosphor layer can be evaluated by comparing the slope of the side surface of the LED chip with the slope of the phosphor layer covering the side surface. Thus, as shown in FIG. 11, the dihedral angle between the upper surface of the substrate and the side surface of the LED chip is defined as a (°), and the surface of the substrate and the phosphor layer covering the light emitting portion of the side surface of the LED chip and the coated surface of the LED chip are When the dihedral angle of the surface on the opposite side is b (°), it is preferable to satisfy the relationship of a-30≦b≦a, and more preferably to satisfy the relationship of a-20≦b≦a.

As described above, the light-emitting device using the layered product of the present invention has an excellent effect of suppressing uneven orientation of light emission. Here, the so-called luminous orientation is not All of them indicate that the visual effect of the light of the light emitting device differs depending on the angle. Such an orientation cannot be determined by the color temperature at a distance of 10 cm (hereinafter referred to as vertical color temperature) vertically above the upper surface of the LED chip of the light-emitting device, and the color temperature at a distance of 10 cm above 45° (hereinafter below) The absolute value of the difference is called 45° color temperature. In the present invention, the smaller the absolute value of the difference, the smaller the unevenness of the azimuth of light emission, which is preferable.

The laminate of the present invention is suitably used when a high-power type flip chip LED is used, and the light-emitting device manufactured using the same is particularly preferably used for lighting from the viewpoint of high brightness and high heat dissipation . As a lighting application, for example, it is suitable for making use of features that can simplify the design and use it in a flash of a mobile terminal such as a smartphone. In addition, considering the excellent light distribution characteristics of colors, general lighting for household use and industrial lighting used in industrial equipment or public facilities are also preferred methods of utilization. Furthermore, from the viewpoint of excellent heat dissipation, it can also be suitably used for automotive lighting such as headlamps or daytime running lights (DRLs).

The lighting application described above is a particularly good use method, but it does not limit the use of the backlight and the like in other practical applications.

[Example]

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

<Phosphor layer>

The composition and characteristics of the phosphor layer are summarized in Table 1. The details will be described below.

(Raw material for phosphor layer)

(1) Silicone resin

Silicone 1~silicone 3 is polyphenylmethylsiloxane, and silicone 4~silicone 5 is polydimethylsiloxane.

. Silicone 1:

The resin composition obtained by mixing the following components was used.

. Silicone 2: "OE6630" (manufactured by Toray Dow Corning Corporation)

. Silicone 3: "XE14-C6091" (Mituto High-Tech Materials Japan) / "Non-crosslinking reactive silicone" = 8/2

※ "Non-crosslinking reactive silicone": solid silicone represented by the following average composition formula

[Chem 2] (Me ₃ SiO _1/2 ) ₁ (PhSiO _3/2 ) ₃₁ (MeSiO _3/2 ) ₂₈ (MeOHSiO _2/2 ) ₁₀ (Me ₂ SiO _2/2 ) ₂₁ (PhOHSiO _2/2 ) ₈ (SiO _4/2 ) ₁

. Silicone 4: "OE6336" (manufactured by Toray Dow Corning Corporation)

. Silicone 5: "KER6075" (manufactured by Shin-Etsu Chemical Co., Ltd.).

(2) Silicone particles

. Particle 1:

Use the manufacturer according to the following synthesis example.

[Synthesis example]

Install a stirrer, thermometer, reflux tube, and dropping funnel on a 3L four-necked round-bottom flask, add 1600g of 2.5wt% aqueous ammonia solution with a pH of 12 (25°C) and 0.002g of nonionic surfactant to the flask. BYK-333" (Bike Chemical Co., Ltd.). While stirring at 300 rpm, a mixture of 130 g of phenyltrimethoxysilane and 30 g of methyltrimethoxysilane was added dropwise from the dropping funnel over 20 minutes. Thereafter, the temperature was raised to 50° C. in 30 minutes, and after further stirring for 60 minutes, the stirring was stopped. After cooling to room temperature, 20 g of ammonium acetate was added and stirred at 150 rpm for 10 minutes, the reaction solution was divided into eight 250 ml centrifuge bottles (made by Nalgen Co., Ltd.), and placed in a centrifuge (table) After the upper centrifuge 4000, Kubota Manufacturing Co., Ltd.) was put on, it was centrifuged at 3000 rpm for 10 minutes. The following washing operation was repeated three times: after the supernatant was removed, 200 g of pure water was added to each centrifuge bottle, and after stirring with a spatula, centrifugal separation was performed under the conditions. Transfer the filter cake remaining in the centrifuge bottle Into the tank, drying was carried out at 100°C for 8 hours in a blower-type oven to obtain 70 g of white powder. The obtained particle powder was measured using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., Microtrac 9320HRA). As a result, the particle size of the passing component from the small particle size side was 50% (D50) Monodisperse spherical fine particles of 0.5 μm. The refractive index of the fine particles was measured by liquid immersion method and found to be 1.55.

. Particle 2: "Tospearl (Tospearl 120)" (polymethylsilsesquioxane) (D50) 2.0μm (made by Meitu High-Tech Materials Japan).

(3) Metal oxide particles

. Oxide 1: Smoked alumina particles "Aeroxide AluC" D50 13nm (manufactured by Japan Aerosil).

(4) Phosphor

. Phosphor 1: "NYAG-02" Ce-doped YAG phosphor, specific gravity: 4.8g/cm ³ , D50: 7μm (made by Intematix)

. Phosphor 2: "YAG450" YAG phosphor, specific gravity: 5.0 g/cm ³ , D50: 20 μm (manufactured by Basic Special Chemicals)

. Phosphor 3: Two-color mixed phosphor ((i)/(ii)=3/1 mixture);

(i) "BY102" YAG phosphor, specific gravity: 5.5 g/cm ³ , D50: 17 μm (manufactured by Mitsubishi Chemical Corporation)

(ii) "BR-101" CASN phosphor, specific gravity: 3.7 g/cm ³ , D50: 10 μm (manufactured by Mitsubishi Chemical Corporation).

(Manufacturing method of phosphor layer)

[Production example of phosphor layer 1]

A polyethylene-made container with a volume of 300 ml was used and mixed at a ratio of silicone 1 to 28% by weight, particles 1 to 7% by weight, and phosphor 1 to 65% by weight. After that, a planetary stirring and defoaming device "Mazerustar (KK-400)" (manufactured by Kurabo) was used to stir and defoam at 1000 rpm for 20 minutes to obtain a sheet. Use phosphor dispersion. Using a slot die coater, apply a phosphor dispersion to the coated substrate "Cerapeel" WDS (manufactured by Toray Film Processing Co., Ltd.; film thickness 50 μm, broken The elongation was 115% and the Young's modulus was 4500 MPa). The heated and dried at 120° C. for 1 hour obtained a phosphor layer 1 with a film thickness of 50 μm and 100 mm square. The storage elastic modulus of this phosphor layer is 1.0×10 ⁶ Pa at 25° C. and 3.0×10 ³ Pa at 100° C. Table 1 shows the composition and film thickness.

[Production example of phosphor layer 2]

A polyethylene container having a volume of 300 ml was used and mixed at a ratio of 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. After that, a planetary stirring and defoaming device "Mazerustar (KK-400)" (manufactured by Kurabo) was used to stir and defoam at 1000 rpm for 20 minutes to obtain a sheet. Use phosphor dispersion. Using a slot die coater, the sheet material was coated with a phosphor dispersion on the peeling surface of the coated substrate "Cerapeel" WDS, and heated and dried at 120°C for 20 minutes A phosphor layer 2 having a film thickness of 50 μm and a square of 100 mm was obtained. Storage elastic modulus of the phosphor layer at 25 deg.] C of 1.0 × 10 ⁶ Pa, at 100 deg.] C of 1.0 × 10 ⁴ Pa. Table 1 shows the composition and film thickness.

[Production Examples of Phosphor Layer 3 to Phosphor Layer 12]

The phosphor layer was manufactured in the same manner as the phosphor layer 2 except that the composition or film thickness shown in Table 1 was changed. Table 1 shows the composition and film thickness.

(Measurement method of storage elastic modulus of phosphor layer)

Measuring device: Viscoelastic measuring device ARES-G2 (manufactured by TA Instruments)

Geometric shape: parallel disc type (15mm)

Maximum strain: 1.0%

Angular frequency: 1.0Hz

Temperature range: 25℃~200℃

Heating rate: 5℃/min

Measurement environment: in the atmosphere.

Sixteen phosphor layers with a film thickness of 50 μm were laminated, heated and pressure-bonded on a 100° C. hot plate to produce an 800 μm integrated film (sheet), and cut out to a diameter of 15 mm to be a measurement sample. The sample was measured under the conditions described above, and the storage elastic modulus at 25°C and 100°C was measured. The results are shown in Table 1.

<support substrate>

(Resin supporting substrate)

Prepare the supporting base material of the material shown in Table 2. Here, the following resins are described in the column of resin type.

A-1: Ethylene-α-olefin copolymer resin "TAFMER" DF640 (Mitsui Chemical Co., Ltd.)

A-2: Ethylene-α-olefin copolymer resin "TAFMER" DF7350 (Mitsui Chemical Co., Ltd.)

A-3: Ethylene-α-olefin copolymer resin "TAFMER" DF8200 (Mitsui Chemical Co., Ltd.)

A-4: Ethylene-α-olefin copolymer resin "TAFMER" DF9200 (Mitsui Chemical Co., Ltd.)

A-5: Ethylene-α-olefin copolymer resin "TAFMER" XM7090 (Mitsui Chemical Co., Ltd.)

A-6: Ethylene-α-olefin copolymer resin "TAFMER" PN2070 (Mitsui Chemical Co., Ltd.)

A-7: Trial product A of ethylene-α-olefin copolymer resin "TAFMFR" (Made by Mitsui Chemicals)

B-1: Polycaprolactone resin "PLACCEL" H1P (made by Daicel)

C-1: Ethylene-methyl methacrylate copolymer resin (ethylene-acrylic copolymer resin) "ACRYFT" WK402 (made by Sumitomo Chemical Co., Ltd.)

C-2: Ethylene-methyl methacrylate copolymer resin (ethylene-acrylic acid copolymer resin) "ACRYFT" CM5021 (made by Sumitomo Chemical Co., Ltd.)

D-1: ethylene-α-olefin copolymer resin "TAFMER" DF7350/ethylene-methyl methacrylate copolymer resin "ACRYFT" CM5021=99.9 parts by weight/0.1 parts by weight

D-2: ethylene-α-olefin copolymer resin "TAFMER" DF7350/ethylene-methyl methacrylate copolymer resin "ACRYFT" CM5021=99 parts by weight/1 part by weight

D-3: Ethylene-α-olefin copolymer resin "TAFMER" DF7350/ethylene-methyl methacrylate copolymer resin "ACRYFT" CM5021=98 parts by weight/2 parts by weight

E-1: Silicone resin OE-6450 (manufactured by Toray Dow Corning Corporation)

※Two liquids (A liquid/B liquid) are mixed and hardened. A/B=1 part by weight/1 part by weight

E-2: Silicone resin OE-6635 (manufactured by Toray Dow Corning Corporation)

※Two liquids (A liquid/B liquid) are mixed and hardened. A/B=1 weight part/3 weight part

F-1: Polyethylene resin "NOVATEC" LL (made by Japan Epoxy Resin)

G-1: Fluororesin "NEOFLON" ETFE (made by Daikin).

(Manufacturing method of supporting base material)

[Production Example of Support Base 1]

After putting the pellets of resin A-1 into the kneading machine of an extruder heated at 150°C and melting it, the PET film "Cerapeel" BX9 (Toray Film Processing Co., Ltd.) is peeled off Manufactured by the company; on a film thickness of 50 μm and a surface roughness (Ra) of 8 μm), a molten resin is extruded from a slit of an extrusion molding machine to form a film, and a sheet-shaped molded product with a film thickness of 500 μm is manufactured. This is cut into an appropriate size and used as the supporting base 1. Table 2 shows the resin types and film thicknesses.

[Production Examples of Support Base 2 to Support Base 8 and Support Base 11 to Support Base 13]

As described in Table 2, the resin type and film thickness were changed, and otherwise the manufacturing was performed in the same manner as the support base 1. Table 2 shows the resin types and film thicknesses.

[Production Example of Support Base 9]

After putting the pellets of resin A-6 into the kneading machine of an extruder heated at 200°C and melting them, the PET film "Cerapeel" BX9 (Toray Film Processing Co., Ltd.) is peeled off Manufactured by the company; on a film thickness of 50 μm and a surface roughness (Ra) of 8 μm), a molten resin is extruded from a slit of an extrusion molding machine to form a film, and a sheet-shaped molded product with a film thickness of 500 μm is manufactured. This is cut into an appropriate size and used as the supporting base 9. Table 2 shows the resin types and film thicknesses.

[Manufacturing example of support base 10]

After putting the pellets of resin A-7 into the kneading machine of an extruder heated at 100°C and melting them, the PET film "Cerapeel" BX9 (Toray Film Processing Co., Ltd.) is peeled off Manufactured by the company; with a film thickness of 50 μm and a surface roughness (Ra) of 8 μm), the molten resin is extruded from the slit of the extruder and cooled by a blower to form a film, and a sheet with a film thickness of 500 μm is produced Moldings. This was cut into an appropriate size, and further cooled in the refrigerator compartment (refrigerator compartment temperature 5° C.) to serve as the supporting base 10. Table 2 shows the resin types and film thicknesses.

[Manufacturing example of support base 14]

99.9 parts by weight of particles of Resin A-2 and 0.1 parts by weight of particles of Resin C-2 as an adhering component were mixed to prepare Resin D-1. After putting this into the kneading machine of the extrusion molding machine heated to 150 degreeC and melting it, it carried out similarly to the support base material 1, and produced the sheet-shaped molded object with a film thickness of 500 micrometers. This is cut into an appropriate size and used as the supporting base 14. Table 2 shows the resin types and film thicknesses.

[Manufacturing example of support base 15]

99 parts by weight of particles of Resin A-2 and 1 part by weight of particles of Resin C-2 as an adhering component were mixed to prepare Resin D-2. This was carried out in the same manner as the support base 14 to produce a sheet-shaped molded product having a film thickness of 500 μm. This is cut into an appropriate size and used as the supporting base 15. Table 2 shows the resin types and film thicknesses.

[Production Example of Support Base 16]

98 parts by weight of particles of Resin A-2 and 2 parts by weight of particles of Resin C-2 as an adhering component were mixed to prepare Resin D-3. This is carried out in the same manner as the support substrate 14 On the other hand, a sheet-shaped molded product with a film thickness of 500 μm is produced. This is cut into an appropriate size and used as the supporting base 16. Table 2 shows the resin types and film thicknesses.

[Production Example of Support Base 17]

1 part by weight of resin A liquid A was mixed with 1 part by weight of liquid B, which was poured into a size of 4 cm square, a depth of 500 μm, and the bottom surface was peeled off mirror surface processing (surface roughness (Ra) is 10 μm) The frame of the mold is heated at 80°C for 15 minutes by a hot press. After being left to cool, a sheet-shaped molded product having a film thickness of 500 μm was taken out of the mold frame as the support base 17. Table 2 shows the resin types and film thicknesses.

[Manufacturing example of support base material 18]

1 part by weight of Resin E-2 liquid A and 3 parts by weight of liquid B were mixed and injected into a size of 4 cm square, a depth of 500 μm, and the bottom surface was peeled off mirror surface treatment (surface roughness (Ra) is 10 μm) The frame of the mold is heated at 100°C for 15 minutes by a hot press. After being left to cool, a sheet-shaped molded product with a film thickness of 500 μm was taken out of the mold frame as the supporting base material 18. Table 2 shows the resin types and film thicknesses.

[Production Example of Support Base 19]

After putting the pellets of resin F-1 into the kneading machine of an extruder heated at 230°C and melting it, the PET film "Cerapeel" BX9 (Toray Film Processing Co., Ltd.) is peeled off Manufactured by the company; on a film thickness of 50 μm and a surface roughness (Ra) of 8 μm), a molten resin is extruded from a slit of an extrusion molding machine to form a film, and a sheet-shaped molded product with a film thickness of 500 μm is manufactured. Cut it to a suitable size Instead, as a support substrate 19. Table 2 shows the resin types and film thicknesses.

[Support base material 20]

A film (commercially available product) with a film thickness of 50 μm formed by using resin G-1 was cut to a suitable size and used as the supporting base 20. Table 2 shows the resin types and film thicknesses.

(Measurement method of storage elastic modulus G'and loss elastic modulus G" of supporting substrate)

The storage elastic modulus G'and the loss elastic modulus G" of the supporting base material were measured under the following conditions.

Measuring device: Viscoelastic measuring device ARES-G2 (manufactured by TA Instruments)

Geometric shape: parallel disc type (15mm)

Maximum strain: 1.0%

Angular frequency: 1.0Hz

Temperature range: 10℃~200℃

Heating rate: 5℃/min

Measurement environment: in the atmosphere.

According to the above (manufacturing method of a supporting base material), a sheet-shaped molded product with a film thickness of 1 mm was produced, and the cut-out was 15 mm in diameter as a measurement sample. The sample is measured under the above conditions, and the storage elastic modulus G'and the loss elastic modulus G" at 10°C to 200°C are measured. Based on the obtained data, it is determined that G'satisfies G'at 10°C to 100°C The temperature range of the relationship of <G" and the storage elastic modulus G'satisfy (1)~ (4) The temperature range of the relationship shown. The results are shown in Table 2.

(1)10Pa<G'<10 ⁵ Pa

(2)10 ² Pa<G'<10 ⁵ Pa

(3)10Pa<G'<10 ⁴ P

(4) 10 ² Pa<G'<10 ⁴ Pa.

(Vicat softening temperature)

The Vicat softening temperature of the supporting base material is in accordance with JIS K 7206 (1999) A50 (load 10N, heating rate 50°C/hr), using a Vicat softening point test machine "TP-102" (manufactured by Test Machine Industry Corporation) The temperature at which the pressurized needle (cross-sectional area is 1 mm ² ) sinks to 1 mm of the resin sheet is measured as the Vicat softening temperature. The results are shown in Table 2.

(Melting point)

The melting point of the supporting base material was measured at a temperature increase rate of 10° C./min using a differential scanning calorimeter “DSC-60Plus” (manufactured by Shimadzu Corporation) in accordance with JIS K 7121 (1987). The results are shown in Table 2.

(Melt flow rate; MFR)

The melt flow rate of the supporting base material was measured in accordance with JIS K7210 (1999) using a melt index measuring instrument G-01 (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a measurement temperature of 190°C and a load of 21.2N. The results are shown in Table 2.

(Transparency)

The transparency of the supporting base material is based on the above (manufacturing method of supporting base material) to produce a sheet-shaped molded product having a film thickness of 0.5 mm, using a transmission absorption measurement system (Otsuka (Made by an electronics company). Using the diffuse transmittance (%T) of 450 nm, the determination was made based on the following criteria. The results are shown in Table 2.

A: 90≦%T

B: 70≦%T<90

C: 50≦%T<70

D: %T<50

<Laminate>

(Manufacturing method of laminate)

A phosphor layer with a coated substrate cut to a suitable size of 5 cm square or more, and a supporting substrate cut to a size equal to or larger than the phosphor layer are prepared. Next, the smooth surface was exposed, and the phosphor layer was superimposed on the smooth surface of the supporting substrate, and then a dry film laminator heated to 80°C was used. Attach at a speed of min. After cooling to 30° C. or lower, the substrate to be coated of the phosphor layer is peeled off to obtain a predetermined laminate.

<The procedure of coating the phosphor layer on the LED chip mounted on the package substrate and the manufacturing and evaluation of the resulting light-emitting device>

(Manufacturing method of package substrate)

On an aluminum nitride substrate (size 5 cm square, film thickness 1.5 mm), a pattern of package electrodes was produced by silver plating so that the average size of each light-emitting device was 10 mm in length and 5 mm in width. Next, on the package electrode, flip chip type LED chip "B3838FCM" (manufactured by Genelight, size 1000 μm square, film thickness 150 μm, main emission wavelength 450 nm) using gold bumps was used to flip LED The wafer is joined to the electrode. By repeatedly performing this bonding, a package substrate in which 50 LED chips were bonded to a 5 cm square aluminum nitride plate was produced.

(Method of coating phosphor layer on LED chip on package substrate)

The vacuum separator laminator V-130 (manufactured by Nisshin Materials) will have a clamping mechanism containing a flexible fluorosilicone rubber separator film clamping mechanism on the lower platform and the upper platform connected to the heater in the vacuum chamber The vacuum chamber is heated to the specified attachment temperature. Secondly, On the package substrate, the laminate layer cut into 5cm square was overlapped so that the phosphor layer side was in contact with the LED chip, and the upper and lower layers were sandwiched with the peeling PET film "Cerapeel" WDS (film thickness 50μm) The resulting stowage is set on the lower platform. Next, after heating at a predetermined sticking temperature to seal the vacuum chamber, the vacuum is evacuated for 30 seconds under a reduced pressure of 0.5 kPa or less. Then, the atmosphere was introduced on the upper platform side to expand the separator membrane, and the load was pressurized at atmospheric pressure (0.1 MPa) for 30 seconds. After that, the atmosphere was also introduced on the lower platform side, and after the decompressed state was disconnected, the vacuum chamber was opened to take out the substrate and the laminate. In the case of using a peelable supporting base material, after cooling to 30° C. or lower, one end of the supporting base material is pinched to peel it off.

(Manufacturing method of light-emitting device)

By cutting and cutting based on the pattern of the package electrode, the person covered with the phosphor layer on the LED chip is cut to produce a package substrate of 10 mm in length and 5 mm in width. The package substrate was mounted on a circuit board formed with wiring patterns by conductors to obtain a light-emitting device.

<Evaluation of light-emitting device>

(Outside evaluation)

The 50 light-emitting devices obtained were visually evaluated using a 20-fold magnifying glass, and the appearance of the phosphor layer was determined based on the following criteria.

A: For the entire LED chip, no defective appearance (peeling, breakage, wrinkles) was observed in the phosphor layer.

B: Defective appearance was observed at 10% or less of the entire LED wafer.

C: Defective appearance was observed in 10% or more and 50% or less of the entire LED chip.

D: Defective appearance was observed in 50% or more of the entire LED chip.

(Evaluation of thickness uniformity of phosphor layer)

About the obtained light-emitting device, X-ray CT measurement was performed, and the cross-sectional image of the center part (I'I cross-sectional view in FIG. 10(a)) was obtained. Based on this image, 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 on the upper surface defined in this specification are in contact with each other, and the LED chip and the fluorescent light are measured The distance B [μm] from the side surface of the LED chip to the outer surface of the phosphor layer in the portion where the body layer is in contact with the side surface of the LED chip.

That is, in a region where the upper surface of the LED chip 7 is in contact with the phosphor layer 6, a position roughly divided into four parts from the left end of the upper surface, that is, a position L1≒L2≒L3≒L4 is extracted, and these The distance between the remaining three points of the LED chip 7 and the outer surface of the phosphor layer 6 except for the two points in each is measured as A1 to A3 [μm], and the average of these three points is taken as A [μm].

In the area where the left side surface of the LED chip 7 is in contact with the phosphor layer 6, when the thickness of the LED chip 7 is t1, the distance between the LED chip 7 at half the height t2 and the outer surface of the phosphor layer 6 is measured as B1 [μm], similarly, the distance between the LED chip 7 and the outer surface of the phosphor layer 6 at the half-thickness t1 of the thickness t1 of the LED chip 7 and the outer surface of the phosphor layer 6 are measured in the region where the right side of the LED chip 7 is in contact with the phosphor layer 6 As B2 [μm], the average value of B1 and B2 is defined as B [μm].

From this value, the thickness ratio (A/B) of the phosphor layer on the upper surface and the side surfaces was determined. The results are described in Tables 3 to 5.

(Evaluation of Phosphor Layer Thickness Retention Rate)

Using the distance A [μm] obtained from the X-ray CT cross-sectional image and the average film thickness C [μm] of the phosphor layer before the coating step, the film thickness retention rate (%) = distance A [μm] /Film thickness C[μm]×100

Calculate the film thickness retention rate. The results are described in Tables 3 to 5.

(Evaluation of dihedral angle of side surface)

The obtained light-emitting device was subjected to X-ray CT measurement to obtain a cross-sectional image. Based on this image, the angle a (°) of 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 LED chip coating surface covering the phosphor layer covering the light emitting portion of the LED chip side surface are measured as shown in FIG. 11 The angle b (°) of the surface on the opposite side. The same operation is performed by changing the position of the cross section. For one LED wafer, the average value of the angles a and b of the ten cross sections is used as the dihedral angle of the side surface. The results are described in Tables 3 to 5.

(Phosphor layer: Evaluation of support base adhesion)

A sample of a laminate in which a phosphor layer was bonded to a support substrate with a size of 50 mm×50 mm. Next, on the surface of the phosphor layer, a tape coated with silicone adhesive material (trade name: circuit tape 6470.12, adhesive force 15N/50mm, manufactured by Teraoka Manufacturing Co., Ltd.) is attached with a length of 50 mm and a width of 50 mm. The contact portion of the phosphor layer and the supporting base material becomes 50 mm×50 mm. Attach one end of the adhesive tape produced as described above to a dynamometer (trade name: digital dynamometer ZTS-20N, manufactured by Yida Motor Co., Ltd.) in a direction of 90 degrees relative to the laminate sample Apply a tensile tape and measure the force required to peel the phosphor layer from the self-supporting substrate. Stick The unit of force is expressed as N/50mm. Moreover, in the case where the adhesive layer and the phosphor layer are peeled without peeling off the phosphor layer and the supporting base material, it is determined that the adhesive force between the phosphor layer and the supporting base material is stronger than the adhesive force of the adhesive tape, expressed as >15N/50mm. The results are described in Tables 3 to 5.

(Removability evaluation of the supporting substrate after coating)

After the coating step of the phosphor layer, it is cooled to below 30°C, and then one end of the supporting substrate is pinched and peeled off in a peeling manner. At this time, peeling off from the phosphor layer.

A: The phosphor layer completely moves from the supporting substrate side to the LED chip side.

B: The proportion of the phosphor layer moving from the supporting substrate side to the LED chip side is 90% or more and less than 100% of the entire LED chip.

C: The proportion of the phosphor layer moving from the supporting substrate side to the LED chip side is 50% or more and less than 90% of the entire LED chip.

D: The proportion of the phosphor layer moving from the supporting substrate side to the LED chip side is less than 50% of the entire LED chip.

No peeling: The supporting substrate does not peel off from the phosphor layer coated LED chip.

(Evaluation of visual efficacy of light of light-emitting device)

Calculate the color temperature at a distance of 10 cm vertically above the top surface of the LED chip of the light-emitting device (hereinafter referred to as vertical color temperature) and the color temperature at a distance of 10 cm above the inclined 45° (hereinafter referred to as 45° color temperature) The difference is determined as described below.

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)|.

[Example 1 to Example 14 and Comparative Example 1 to Comparative Example 3]

After using various laminates 1 to 16 manufactured using the phosphor layer 1 to coat the phosphor layer at the attachment temperature described in Table 3, a light-emitting device was manufactured by the method described above, and the appearance was evaluated , Evaluation of the uniformity of the thickness of the phosphor layer, evaluation of the retention of the thickness of the phosphor layer, evaluation of the dihedral angle of the side surface, phosphor layer: evaluation of the adhesion of the supporting substrate, evaluation of the peelability of the supporting substrate after coating, and luminescence The results of the visual efficacy evaluation of the light of the device are shown in Table 3.

[Examples 15 to 25 and Comparative Examples 4 to 5]

After using various laminates 17 to 29 manufactured using the phosphor layer 2 and coating the phosphor layer at the attachment temperature described in Table 4, a light-emitting device was manufactured by the method described above. Device for various evaluations. The evaluation results are shown in Table 4.

[Example 26 to Example 38]

Using various laminates 30 to 42 manufactured by the combination of the phosphor layer and the supporting substrate described in Table 5, the phosphor layer was coated at an attachment temperature of 80° C. Method to produce a light-emitting device, and various evaluations were performed on the obtained light-emitting device. The evaluation results are shown in Table 5.

From these results, it can be seen that 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 base material satisfy "G'<G" and 10 Pa When the pressure is applied in the state of <G'<10 ⁵ Pa, the phosphor layer can be covered with good followability to the side surface of the LED chip. In addition, it has been shown that in a light-emitting device in which a phosphor layer is covered with good followability to the light-emitting surface of an LED chip, it is possible to suppress azimuth unevenness of light-emitting colors.

<Manufacturing and evaluation of the step of coating the phosphor layer on the LED chip fixed on the adhesive tape and the light emitting device using the phosphor layer thus coated on the LED chip>

(Adhesive tape used)

For the adhesive tape described in Table 6 for temporarily fixing the LED chip, the following adhesive tape was used.

. UV peeling tape: "ELEGRIP TAPE" UV1005M3 (manufactured by Electrochemical Industry Corporation, UV irradiation conditions: 150mJ/cm ² or more, adhesion: 12N/20mm before UV irradiation, 0.2N after UV irradiation) /20mm)

. Hot peeling tape: "REVALPHA" 31950 (manufactured by Nitto Denko Corporation, heating peeling conditions: 200°C, adhesion: 4.5N/20mm before heating, 0.03N/20mm after heating)

. Micro-adhesive tape: "Adwill" C-902 (made by LINTEC, adhesion: 0.9N/20mm)

(Method of coating phosphor layer on the LED chip fixed on the adhesive tape)

At the center of the SUS plate with a thickness of 0.3mm and a size of 9cm square The adhesive tape described in Table 6 was assembled without wrinkles in a metal frame with an opening of 5 cm square. Next, the flip chip type LED chip "B3838FCM" (manufactured by Genelight, with a size of 1000 μm square, a film thickness of 150 μm, and a main emission wavelength of 450 nm) was connected with the electrode part and the adhesive part at a chip interval of 1 mm. 64 (8×8) were temporarily fixed to the adhesive part. Then, on the temporarily fixed LED chip, a laminate of 2 cm square was superimposed so that the phosphor layer side was in contact with the LED chip, and a PET film "Cerapeel" WDS (film) was produced by peeling the PET film up and down (50 μm thick) sandwiched load.

The load was placed on the lower platform of the vacuum separator laminator V-130 (manufactured by Nissin Materials) that heated the vacuum chamber to a predetermined sticking temperature. After heating at a predetermined sticking temperature to seal the vacuum chamber, vacuum was applied for 30 seconds under a reduced pressure of 0.5 kPa or less. Then, the atmosphere was introduced on the upper platform side to expand the separator membrane, and the load was pressurized at atmospheric pressure (0.1 MPa) for 30 seconds. After that, the atmosphere was also introduced on the lower platform side, and after the decompression state was turned off, the vacuum chamber was opened to take out the load. After cooling to below 30°C, pinch one end of the supporting substrate and peel it off.

(Manufacturing method of light-emitting device)

For the load covered with the phosphor layer on the LED chip by the above method, the peeling treatment described in Table 6 was performed according to the type of the adhesive tape. Thereafter, the wafer is cut by a dicing machine, and the phosphor layer is picked up to cover the LED chip.

Then, on the package electrode of the aluminum nitride substrate (size 5 mm square, film thickness 1.5 mm) with the package electrode pattern made by silver plating, by gold bumps The LED chip is covered with the picked phosphor layer in a block. By repeating this bonding, a package substrate mounted with 64 phosphor layer-covered LED chips is fabricated. The package substrate was mounted on a circuit board formed with wiring patterns by conductors to obtain a light-emitting device.

[Example 39 and Comparative Example 6]

The laminate described in Table 6 was used, and a UV peeling tape was used as the adhesive tape, and 500 mJ/cm ² of UV (365 nm) was irradiated as the peeling treatment. Other than that, a light-emitting device was manufactured by the above method. The evaluation results are shown in Table 6.

[Example 40 and Comparative Example 7]

The laminate described in Table 6 was used, and a thermal peeling tape was used as an adhesive tape, followed by heat (200° C., 10 minutes heating) treatment as a peeling treatment, and otherwise a light-emitting device was manufactured by the above method. The evaluation results are shown in Table 6.

[Example 41]

The laminate 18 is used, and a micro-adhesive tape is used as the adhesive tape, and the peeling treatment is not performed. Otherwise, the light-emitting device is manufactured by the method described above. The evaluation results are shown in Table 6.

From the above results, it can be seen 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 thus a light-emitting device with suppressed color orientation unevenness can be manufactured. On the other hand, it can be seen that in the case of using a known fluororesin film as a comparative example, the phosphor layer is in contact with the adhesive portion before sufficient follow-up, so that air remains and cannot cover the side surface of the LED chip.

<Productivity evaluation of phosphor layer coating process using the laminate of the present invention>

Regarding the use of the laminate 18, the case of coating the phosphor layer by the process of the present invention (one-stage method) and the two-stage method described in the well-known (Patent Document 2: International Publication No. 2012/023119) In comparison, the coating of the phosphor layer is compared.

(Evaluation of the processing time of the phosphor layer coating)

The sharing conditions are as follows.

. Device: Vacuum separator laminator V-130 1 set

. Operator: 2 people

(1 person for preparation and mechanical operations, 1 person for peeling and storage operations)

. Processing substrate: a package substrate with 33×33 LED chips bonded to a 10cm×10cm ceramic substrate

. Number of batches in one batch: 4 substrates are covered by one laminator operation.

. Total number of processed pieces: 40 pieces (10 batches)

The time required for the step of coating 40 substrates was taken as "10 batch processing time". In addition, the characteristics of the light-emitting device were evaluated, and the visual efficacy of the selected light became the condition for the A evaluation.

[Example 47]

The laminated body 18 is coated by a one-step coating method including the following steps.

(i) Preparation steps: 4 pieces of laminate are placed on a ceramic substrate Otherwise, place it in a vacuum separator laminator. Since the second batch and the coating step are performed simultaneously, only the preparation time and the processing time of the first batch are added. The time required is 1 minute.

(ii) Coating step: Start the laminator to perform coating (vacuum extraction time: 0.5 minutes, pressurization time: 0.5 minutes, operation time: 0.5 minutes).

Simultaneously prepare for the next batch in parallel. The time required is 1.5 minutes for 1 batch and 15 minutes for 10 batches.

(iii) Stand cooling and peeling step: After the covering step is completed, after standing and cooling for 3 minutes, the supporting substrate is peeled off and stored in a box. The operation is performed in parallel with the coating step, so only the time consumed by the 10th batch of the cooling and peeling step is added. The time required is 4 minutes.

Based on the above, the processing time for 10 batches = 1 + 15 + 4 = 20 minutes. The results are shown in Table 7.

[Comparative Example 8]

The laminated body 29 is coated by a two-stage coating method including the following steps based on the method described in Patent Document 2.

(i) Preparatory steps: 4 pieces are prepared by placing a laminate on a ceramic substrate and placing them in a vacuum separator laminator. Since the second batch and the coating step are performed simultaneously, only the preparation time and the processing time of the first batch are added. The time required is 1 minute.

(ii) The first step of the coating step: start the laminator and pressurize the separator film (vacuum extraction time: 0.5 minutes, pressurization time: 0.1 minutes, operation) Time: 0.5 minutes). The time required is 1.1 minutes for 1 batch and 11 minutes for 10 batches.

(iii) Stand cooling and peeling step: After the covering step is completed, after standing and cooling for 3 minutes, the supporting base material is peeled off. It can be performed simultaneously with the first stage of the coating step, so the time required is essentially 0 minutes.

(iv) Setting change: After all the separator membrane pressing steps are completed, the setting is changed to pressurize only with compressed air. The time required is 1 minute.

(v) The second step of the coating step: placing four substrates with the support substrate peeled off, and pressurizing with compressed air (vacuuming time: 1 minute, air pressure time: 0.5 minutes, operation time: 0.5 minutes) . The time required is 1 batch for 2 minutes and 10 batches for 20 minutes.

(vi) Placement cooling step: After the covering step, leave it to cool for 3 minutes and store it in a box. Since the operation is performed in parallel with the coating step, only the time consumed by the 10th batch of the cooling step is added.

The time required is 3 minutes.

Based on the above, the processing time for 10 batches = 1 + 11 + 1 + 20 + 3 = 36 minutes. The results are shown in Table 7.

The above results show that the processing time can be shortened to five-ninth compared with the known method, and the productivity is greatly improved.

1: Circuit board

2: Circuit wiring

6: phosphor layer

7: LED chip

8: Gold bump

9: package electrode

10: package substrate

12: laminate

13: Support substrate

16: Vacuum separator laminator

17: Exhaust/suction port

18: upper chamber

19: Lower chamber

20: separator membrane

21: Cutting position

23: LED package

24: Light emitting device

Claims (10)

A laminate including a phosphor layer and a supporting substrate for coating a phosphor layer on a light emitting surface of an LED chip, the phosphor layer containing a phosphor and a resin, the supporting substrate covering the phosphor layer After the light emitting surface of the LED chip is peeled off by the phosphor layer, the storage elastic modulus G'and the loss elastic modulus G of the supporting substrate are measured with a rheometer at a frequency of 1.0 Hz and a maximum strain of 1.0% "The relationship between G'<G" (Equation 1) and 10Pa<G'<10 ⁵ Pa (Equation 2) is satisfied in all or a part of the temperature range of 10°C or more and 100°C or less, wherein the support base The material includes a thermoplastic resin including one or more than two selected from the group consisting of poly-α-olefin resins, polycaprolactone resins, acrylic resins, and copolymerized resins of one or more of these resins and ethylene Of resin. The laminate according to item 1 of the patent application range, wherein the Vicat softening temperature of the support base material is 25°C or higher and 100°C or lower. The laminate as described in the first or second patent application, wherein the melting point of the supporting base material is 40°C or higher and 100°C or lower. A method for manufacturing a light-emitting device, comprising: the step of coating the light-emitting surface of an LED chip with a phosphor layer on the light-emitting surface of an LED chip using the laminate as described in any one of claims 1 to 3 . The method for manufacturing a light-emitting device as described in item 4 of the patent application, wherein the light exit surface of the LED wafer is not a single plane. The method for manufacturing a light-emitting device according to claim 4 or 5, wherein the portion of the LED chip and the phosphor layer that are in contact with the upper surface of the LED chip is from the upper surface of the LED chip to the outside of the phosphor layer The surface distance A [μm] and the distance B [μm] from the side 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 the side surface of the LED chip satisfy 0.70≦A/B≦1.50 Relationship. The method for manufacturing a light-emitting device as described in item 4 or 5 of the patent application scope includes the steps of setting the dihedral angle of the upper surface of the substrate and the side surface of the LED wafer to a (°), and setting When the dihedral angle of the upper surface of the substrate and the phosphor layer covering the LED chip side light-emitting portion and the surface opposite to the LED chip coating surface is set to b (°), a mode satisfying the relationship of a-30≦b≦a , The phosphor layer is coated on the light emitting surface of the LED chip. A light-emitting device obtained by the method of manufacturing a light-emitting device as described in any one of claims 4 to 7. A flash lamp including the light-emitting device as described in item 8 of the patent application scope. A mobile terminal including the flash as described in item 9 of the patent application scope.

Images