KR102460162B1 - Resin composition, sheet-like molded product thereof, light emitting device using same, and manufacturing method thereof - Google Patents

Abstract

It is a resin composition containing at least the following components (A) - (C), and it is excellent in heat resistance and adhesiveness at the time of adhesion, and its sheet-like molded object can be provided. (A) reactive silicone resin in which 90% or more of organic groups bonded to silicon atoms are methyl groups; (B) a curing catalyst; (C) A non-reactive silicone resin in which 90% or more of the organic groups bonded to silicon atoms are methyl groups.

Description

Resin composition, sheet-like molded product thereof, light emitting device using same, and manufacturing method thereof

The present invention relates to a resin composition, a sheet-like molded product thereof, a light emitting device using the same, and a method for manufacturing the same.

A light emitting diode (LED, Light Emitting Diode) has seen a remarkable improvement in its luminous efficiency in recent years. And, characterized by low power consumption, long life, designability, etc., it is suitable for not only in-vehicle fields such as mobile phone flashlights and car headlights, but also general lighting, and the market is rapidly expanding. However, in replacement with a conventional lamp, a sufficient amount of light emission has not yet been obtained, and further higher luminance of the LED is demanded.

In general, in order to increase the luminance of the LED, a method has been taken to increase the amount of light emitted by flowing a high current through the LED element. However, since the calorific value of an LED element and the heat storage amount of a fluorescent substance increase, there existed a subject that the sealing resin thermally deteriorated and colored. Therefore, in order to obtain high luminous efficiency, a silicone resin (so-called methyl silicone resin) having as a main component a methyl group bonded to a silicon atom having a Si-O repeating structure, which is the main chain of the sealing resin, has been widely used (for example, Patent Documents) see 1).

On the other hand, from the viewpoint of luminous efficiency and cost, a method of adhering a sheet-like molded product (hereinafter referred to as a phosphor sheet) containing a phosphor on an LED element has been proposed (for example, refer to Patent Documents 2 to 5). In this method, it is easy to efficiently arrange a certain amount of phosphor on the LED element, and heat dissipation due to thinning of the phosphor-containing layer, compared to the conventional method of dispensing and curing a liquid resin in which a phosphor is dispersed on the LED element, which has been put into practical use. Excellent for improvement In addition, by imparting thermal softening properties and adhesive properties to the phosphor sheet, it can be directly attached to the LED element without using an adhesive, which is conventionally essential, so that heat can be efficiently dissipated.

Japanese Patent Laid-Open No. 2014-34679 Japanese Patent Laid-Open No. 2013-177553 Japanese Patent Laid-Open No. 2011-107717 Japanese Patent Laid-Open No. 2009-84511 Japanese Patent Laid-Open No. 2013-1791

The method of directly attaching the phosphor sheet to the LED element has better heat dissipation than the dispensing method, but has a problem in heat resistance because a phenyl group is introduced into the molecular structure to impart heat-sealability.

On the other hand, Patent Document 2 discloses a method of introducing a methyl group into the molecular structure of a silicone resin for the purpose of improving heat resistance. However, in the method disclosed herein, since 90% or more of the side chains in the molecular structure of the resin are methyl groups, the adhesiveness to the LED element is not sufficient, and there is no sheet detachment in the continuous lighting test or voids at the interface between the sheet and the element. , and there is a problem in that it is easy to cause a decrease in luminance. Moreover, since the fluorescent substance sheet before attachment is in an uncured state, and since it is a semi-solid state or a soft solid state, it is difficult to perform a cutting|disconnection or punching process with high precision.

In patent document 4, in order to acquire adhesiveness, the silicone resin whose softening point is 30-150 degreeC is added. However, since a cyclic ether group is included in a resin structure, it is easy to raise|generate thermal decomposition, and it becomes a cause of coloring of a fluorescent substance sheet.

In Patent Document 5, resin softening and adhesiveness are obtained by controlling the morphology resulting from the phenyl group in the molecular structure, but so-called phenylmethyl, which has as a main component that a phenyl group is bonded to a silicon atom of the Si-O repeating structure, which is the main chain of the encapsulating resin, is In the silicone resin, heat resistance is insufficient, and coloration due to thermal deterioration tends to occur.

As mentioned above, the fluorescent substance sheet which was excellent in heat resistance and excellent also in the adhesiveness at the time of attachment was not obtained. An object of the present invention is to provide a resin composition and a sheet that make these characteristics compatible, a light emitting device produced using them, and a method for manufacturing the same.

This invention is a resin composition containing at least following (A)-(C) component.

(A) reactive silicone resin in which 90% or more of organic groups bonded to silicon atoms are methyl groups;

(B) a curing catalyst;

(C) A non-reactive silicone resin in which 90% or more of the organic groups bonded to silicon atoms are methyl groups.

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, the sheet|seat excellent in heat resistance and adhesiveness at the time of attachment to an LED element can be provided. A light-emitting device produced by using the phosphor-containing resin composition or the phosphor-containing sheet-like molded article in which the phosphor is contained in the resin composition of the present invention is excellent in chromaticity uniformity, heat resistance, light resistance and reliability.

1 is a first example of a process for manufacturing an LED light emitting device using a sheet-like molding of the present invention;
2 is a second example of the manufacturing process of the LED light emitting device by the sheet-like molding of the present invention;
3 is a third example of the manufacturing process of the LED light emitting device by the sheet-like molding of the present invention;
4 is a fourth example of the manufacturing process of the LED light emitting device by the sheet-like molding of the present invention;

<Resin composition>

The resin composition of this invention contains the following (A)-(C) component at least.

(A) reactive silicone resin in which 90% or more of organic groups bonded to silicon atoms are methyl groups;

(B) a curing catalyst;

(C) A non-reactive silicone resin in which 90% or more of the organic groups bonded to silicon atoms are methyl groups.

Here, the organic group couple|bonded with the silicon atom means all the functional groups couple|bonded with the silicon atom other than hydrogen. In addition, 90 % or more means that (the number of the methyl groups couple|bonded with the silicon atom)/(the number of the organic groups couple|bonded with the silicon atom) is 90 % or more.

((A) component)

The reactive silicone resin of component (A) has, in the main chain terminal and/or side chain of the resin, a hydrogen atom bonded to an organic functional group or silicon atom that can serve as a starting point of a condensation reaction and/or an addition reaction, heat, moisture and ultraviolet rays It refers to a silicone resin whose curing reaction is accelerated by

A silicone resin preferable as the component (A) is a reactive silicone resin represented by the average unit formula (1).

R ¹ to R ³ may be the same or different, respectively, and represent a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, epoxy group, alkoxy group or amino group. However, at least one of R ¹ to R ³ is an alkenyl group or a hydrogen atom. a to f is an integer of 0 or more, respectively, and a+b=3, c+d=2, and e+f=1 are satisfied. g to j are numbers indicating the ratio of constituent units in each parenthesis, and are positive numbers satisfying g+h+j=1.0. When the total number of methyl groups among the substituted or unsubstituted alkyl groups bonded to the silicon atom is M, M/{3g+2h+j}≥0.90 is satisfied.

Examples of the alkyl group represented by R ¹ to R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Especially preferably, it is a methyl group.

As an alkenyl group, a vinyl group, an acryl group, methacryl group, etc. are mentioned.

(A) Single 1 type may be sufficient as a component, and multiple types of mixture may be sufficient as it.

In component (A), the alkenyl group couple|bonded with the silicon atom and the hydrogen atom couple|bonded with the silicon atom raise|generate a hydrosilylation reaction. Accordingly, it is preferable to include a compound containing an alkenyl group bonded to a silicon atom and a compound containing a hydrogen atom bonded to a silicon atom, respectively.

Qualitative analysis and quantitative analysis of organic groups are performed by ¹ H-NMR measurement, ¹³ C-NMR measurement, and ²⁹ Si-NMR measurement. The ratio of the methyl group couple|bonded with the silicon atom can be computed from the average unit formula obtained from the said analysis.

It is preferable that (A) component is liquid at 25 degreeC on the process of producing a resin composition. Specifically, it is preferable that the viscosity in 25 degreeC is 10 mPa*s or more, and it is more preferable that it is 50 mPa*s or more. When the viscosity of the resin composition is within the above range, a phosphor-containing resin composition having excellent dispersibility of the phosphor can be obtained.

(A) 1,000-300,000 are preferable, as for the weight average molecular weight of component, 1,500-100,000 are more preferable, 2,000-10,000 are especially preferable. When (C)component is mixed as a weight average molecular weight is in the said range, pulverization and kneading|mixing can be carried out uniformly, and sedimentation and separation|separation with time of (C)component can be suppressed. In addition, within the above range, the phosphor can maintain good dispersion stability.

In addition, the weight average molecular weight of (A) component is a value obtained when measuring on the following conditions using Tosoh Co., Ltd. product HLC-8220GPC.

Column: Tosoh Co., Ltd. TSKgel Guard columnHHR-H, GMHHR-N

Developing solvent: tetrahydrofuran

Deployment rate: 1.0ml/min

Column temperature: 23°C

Standard sample: A value converted using a calibration curve using monodisperse polystyrene manufactured by Tosoh Corporation.

The glass transition point of component (A) is preferably in the range of -100 to 20°C, more preferably in the range of -80 to 10°C, still more preferably in the range of -50 to 0°C.

If the glass transition point of component (A) is within the above range, it is liquid at an environmental temperature of 20°C or higher, and therefore, when mixed with component (B), component (C), and a phosphor, a uniform resin composition can be obtained. Therefore, the color temperature fluctuation|variation of the light emitting device produced with the said resin composition can be suppressed.

The glass transition point can be measured with a commercially available measuring instrument (for example, a differential scanning calorimeter manufactured by Seiko Denshi Kogyo Co., Ltd. (trade name: DSC6220 temperature increase rate of 0.5°C/min)).

In this invention, you may use the commercial item containing (A) component and (B) component. For example, OE-6250, JCR6115, JCR6125, JCR6126, JCR6122, JCR6101, JCR6101UP, JCR6109, JCR6110, JCR6140, OE-6351, OE-6370M, OE-6370HF, OE-6336, EG-6301 (or higher, Toray · Dow Corning Co., Ltd.);

KER-2500, KER-2600, KER-6020F, KER-6075F, LPS-3419, LPS-3541 (above, manufactured by Shin-Etsu Chemical Co., Ltd.);

IVS4312, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, XE14-C2042 (above, Momentive Performance Materials Japan Co., Ltd.);

etc. are mentioned, but it is not limited to these. These commercial items may be used independently and multiple types may be mixed.

((B) component)

It is preferable that component (B) is a hydrosilylation reaction catalyst for accelerating|stimulating the hydrosilylation reaction of the hydrogen atom couple|bonded with the alkenyl group in (A) component and the silicon atom. Specific examples include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, but there is no limitation thereto as long as it promotes curing of the present composition.

In the present invention, it is preferable to use a platinum-based catalyst whose reaction control is relatively easy. Specific examples thereof include fine platinum powder, platinum tetrachloride, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex having a low chlorine content is preferable. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane; and alkenylsiloxane in which a part of the methyl group of these alkenylsiloxanes is substituted with an ethyl group, a phenyl group, or the like, and an alkenylsiloxane in which the vinyl group of these alkenylsiloxanes is substituted with an allyl group, a hexenyl group, or the like. Among these, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with particularly high stability is preferable.

As such a reaction catalyst, "SIP6829.0" (platinum carbonylvinylmethyl complex, platinum 3.0-3.5% concentration vinylmethyl cyclic siloxane solution) manufactured by Gelest, USA, "SIP6830.0" (platinum divinyltetramethyldisiloxane complex, platinum) 3.0-3.5% concentration vinyl-terminated polydimethylsiloxane solution), "SIP6831.0" (platinum divinyltetramethyldisiloxane complex, platinum 2.1-2.4% concentration xylene solution), "SIP6832.0" (platinum cyclovinylmethylsiloxane complex) , platinum 3.0-3.5% concentration cyclic methylvinylsiloxane solution), "SIP6833.0" (platinum octylaldehyde/octanol complex, platinum 2.0-2.5% concentration octanol solution), etc. are mentioned.

(B) It is preferable that it is 0.01-500 ppm in weight conversion of a metal atom with respect to the total weight of a resin composition, and, as for content of component, it is more preferable that it is 0.1-100 ppm. If it is in the said range, sufficient sclerosis|hardenability is acquired, and the state without coloring can be maintained after hardening.

((C) component)

(C) The non-reactive silicone resin of the component does not have an organic functional group that can serve as a starting point of a condensation reaction and/or an addition reaction in the main chain terminal and/or side chain of the resin, and the curing reaction is prevented by heat, moisture and ultraviolet rays. It is a silicone resin that does not occur.

A silicone resin preferable as the component (C) is a non-reactive silicone resin represented by the average unit formula (2).

R ⁴ to R ⁶ are a substituted or unsubstituted alkyl group or alkoxy group, and may be the same or different from each other. k, p and s are numbers indicating the ratio of constituent units in each parenthesis, and are positive numbers satisfying 0.01≤k≤0.50 and k+p+s=1.0. m, n, q and r are integers greater than or equal to 0 satisfying m+n=2 and q+r=1. When the total number of methyl groups among the substituted or unsubstituted alkyl groups bonded to the silicon atom is M, M/{3k+2p+s}≥0.90 is satisfied.

Examples of the alkyl group represented by R ⁴ to R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Especially preferably, it is a methyl group.

Examples of the alkoxy group represented by R ⁴ to R ⁶ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Especially preferably, it is a methoxy group.

It is particularly preferable that k and s are positive integers satisfying 0.02≤k≤0.40 and 0.10≤s≤0.90.

(C) You may use a commercial item as a component. For example, KF-7312J, KF-9021, KF-7312K, X-21-5595, KF-7312T, X-21-5616, KF-7312L, KF-9021L, X-21-5249, X-21- 5249L, X-21-5250, X-21-5250L, KP-562P (above, manufactured by Shin-Etsu Chemical Co., Ltd.);

SilForm Flexible resin, SR1000, SS4230, SS4267, XS66-B8226, XS66-C1191, XS66-B8636 (above, Momentive Performance Materials Japan (manufactured);

RSN-0749 Resin, DC593, 670Fluid, 680Fluid, MQ-1600 Solid Resin, MQ-1640 Solid Resin, AMS-C30 Cosmetic Wax, SW-8005 C30 Resin Wax, 580 Wax (above, manufactured by Toray Dow Corning Co., Ltd.);

etc. are mentioned, but it is not limited to these. These commercial items may be used independently and multiple types may be mixed.

In this invention, since softening property at the time of heating can be controlled by appropriately designing the mixing ratio of (A) component and (C)component, this resin composition can acquire adhesiveness.

When the total amount of (A) component and (C)component is 100 weight%, suitable content of (C)component in the resin composition of this invention is 0.5 weight% or more, It is preferable that it is 10 weight% or more More preferably, it is more preferable that it is 15 weight% or more, It is more preferable that it is 20 weight% or more, It is still more preferable that it is 30 weight% or more. Moreover, it is preferable that it is 70 weight% or less, It is more preferable that it is 60 weight% or less, It is still more preferable that it is 50 weight% or less. (C) When component content is suitable, this resin composition expresses favorable adhesiveness at the time of heating.

(C) 1,000-100,000 are preferable, as for the weight average molecular weight of component, 2,000-50,000 are more preferable, 3,000-5,000 are especially preferable. The glass transition point of (C)component as a weight average molecular weight is in the said range can be adjusted in the range of 50-200 degreeC. (C) The weight average molecular weight of component is a value obtained by the same measurement as the weight average molecular weight of (A) component.

The glass transition point of component (C) is preferably in the range of 50 to 200°C, more preferably in the range of 60 to 150°C, still more preferably in the range of 70 to 120°C.

(C) When the glass transition point of component is in the said range, when the environmental temperature is less than 50 degreeC, (C)component is a solid form, and adhesiveness is not expressed. For this reason, when the fluorescent substance resin composition containing (C)component is processed into a sheet form, since it does not have adhesiveness under room temperature (25 degreeC), it can handle easily. In addition, when the composition is heated above the glass transition point of the component (C), the component (C) melts and exhibits liquid properties, so that the resin composition can soften and exhibit tackiness.

(phosphor)

The resin composition of the present invention may contain a phosphor. A phosphor is a substance that absorbs light emitted from the LED element, then converts the wavelength, and emits light having a wavelength different from the emission wavelength of the LED element. Thereby, a part of the light emitted from the LED element and a part of the light emitted from the phosphor are mixed, and a multicolor light emitting device containing white is obtained.

As long as wavelength conversion is possible, an organic substance or an inorganic substance may be sufficient as the above-mentioned fluorescent substance, However, From a viewpoint of heat resistance and light resistance, an inorganic substance is preferable. Specifically, there are a phosphor that emits light in green, a phosphor that emits light in blue, a phosphor that emits light in yellow, and a phosphor that emits light in red.

The inorganic fluorescent substance preferably used in the present invention is a fluorescent substance emitting green light, for example, SrAl ₂ O ₄ :Eu, Y ₂ SiO ₅ :Ce, Tb, MgAl ₁₁ O ₁₉ :Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ :Eu, (at least one of Mg, Ca, Sr, and Ba) Ga ₂ S ₄ :Eu, β-sialon, and the like.

As a fluorescent substance emitting blue light, for example, 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.

A phosphor emitting from green to yellow, comprising at least a yttrium aluminum oxide phosphor activated with cerium, a yttrium gadolinium aluminum oxide phosphor activated with at least cerium, a yttrium aluminum garnet oxide phosphor activated with at least cerium, and at least cerium There are activated yttrium/gallium/aluminum oxide phosphors and the like (so-called YAG-based phosphors). Specifically, Ln ₃ M ₅ O ₁₂ :R (Ln is at least one selected from Y, Gd, and La. M includes at least one of Al and Ca. R is a lanthanoid system.), ( Y _1-x Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ :R (R is at least 1 selected from Ce, Tb, Pr, Sm, Eu, Dy, Ho. 0<x<0.5 , 0 < y < 0.5) can be used.

As a red light-emitting phosphor, for example, Y ₂ O ₂ S:Eu, La ₂ O ₂ S:Eu, Y ₂ O ₃ :Eu, Gd ₂ O ₂ S:Eu, and K ₂ SiF ₆ :Mn KSF phosphors are mentioned.

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In addition, as a fluorescent substance emitting light corresponding to the current mainstream blue LED, Y ₃ (Al,Ga) ₅ O ₁₂ :Ce, (Y,Gd) ₃ Al ₅ O ₁₂ :Ce, Lu ₃ Al ₅ O ₁₂ :Ce, Y ₃ Al ₅ O ₁₂ : YAG-based phosphor such as Ce, TAG-based phosphor such as Tb ₃ Al ₅ O ₁₂ :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 :Eu, etc. Silicate-based phosphor, (Ca,Sr) ₂ Si ₅ N ₈ :Eu, (Ca,Sr)AlSiN ₃ :Eu, CaSiAlN ₃ :Eu, etc. Nitride-based phosphors of, Cax(Si,Al) ₁₂ (O, N) ₁₆ :Eu and other oxynitride-based phosphors, and further (Ba,Sr,Ca)Si ₂ O ₂ N ₂ :Eu-based phosphors, Ca ₈ Phosphors, such as _MgSi4O16Cl2 :Eu _- type fluorescent substance, _{SrAl2O4 : Eu} , and _{Sr4Al14O25 : Eu} , are mentioned.

Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used from the viewpoints of luminous efficiency and luminance. In addition to the above, a well-known phosphor can be used according to the use or the desired luminescent color.

It is preferable that the average primary particle diameter of the fluorescent substance in this invention is the range of 5-40 micrometers. It is preferable that it is 8 micrometers or more in the said range, The thing of 10 micrometers or more is more preferable, and the thing of 15 micrometers or more is still more preferable. On the other hand, the thing of 40 micrometers or less is preferable, and the thing of 20 micrometers or less is more preferable. If the average primary particle diameter of the phosphor is within the above range, the dispersion state in the composition becomes uniform and stable, so that the sheet-like molded article produced from the composition (hereinafter, sometimes referred to as “phosphor sheet”) has a chromaticity. A uniform one is obtained. It is preferable to use particles with a high sphericity as the phosphor.

The average primary particle diameter of a phosphor can be calculated|required by the following method. From the two-dimensional image obtained by observing the phosphor with a scanning electron microscope (SEM), calculate that the distance between the outer edge of the phosphor and the two intersection points of the straight line intersecting at two points becomes the maximum, and calculates the particle diameter define it as Moreover, the same measurement is performed about 20 arbitrary other phosphors, and let the average value of the obtained particle diameters be an average primary particle diameter. For example, when measuring the particle size of the phosphor present in the phosphor-containing resin composition, any one of a mechanical polishing method, a microtome method, a CP method (cross-section polisher), and a focused ion beam (FIB) processing method, After performing cross-section grinding|polishing of a resin composition, from the two-dimensional image obtained by observing the obtained grinding|polishing cross section with a scanning electron microscope (SEM), it carries out similarly to the said method, and can compute an average primary particle diameter.

It is preferable that the amount of fluorescent substance which can be contained in the resin composition of this invention is 20-500 weight part with respect to 100 weight part which summed up (A) component, (B) component, and (C) component. By making the phosphor content within the above range, re-aggregation of the phosphor can be prevented and good dispersion stability can be obtained.

(inorganic particles)

It is preferable that the resin composition of this invention contains an inorganic particle and/or silicone microparticles|fine-particles. Examples of the inorganic particles include metal particles, metal nitride particles, metal oxide particles, and metal salt particles, and metal oxide particles are particularly preferably used.

Examples of the metal oxide particles include silica, alumina, titania, zirconia, yttria, ceria, magnesia, zinc oxide, manganese oxide, copper oxide, iron oxide, holmium oxide, lead oxide, tin oxide, etc., especially dispersed in the composition Alumina is preferable from the point which it is easy to make. By including an inorganic particle in the resin composition of this invention, the heat dissipation property of this resin composition improves, and thermal deterioration of resin can be suppressed. Particularly preferably, it is at least one selected from the group consisting of silica, alumina, titania, magnesium oxide and aluminum nitride.

It is preferable that they are silicone microparticles|fine-particles represented by an average unit formula (3) as a silicon microparticles|fine-particles.

Here, R ⁷ to R ⁹ are substituted or unsubstituted alkyl groups, and may be the same or different from each other. t, u, and w are numbers indicating the ratio of the constituent units in each parenthesis, and satisfy 0.50≤t≤0.95, 0.05≤u+w≤0.50, and t+u+w=1.0.

In this invention, you may use a commercial item as a silicone microparticle. For example, KMP-590, KMP-597, KMP-598, KMP-594, KMP-701, X-52-854, X-52-875, X-52-1621 (above, Shin-Etsu Chemical High School) (topic);

EP-5500, EP-2601, EP-2720, EP-2600, E-606 (above, manufactured by Toray Dow Corning Co., Ltd.);

MSP-N050, MSP-N080, NH-RAS06, MSP-TK04, SilcrustaMK03, MSP-SN05, MSP-SN08, NH-RASN06, MSP-TKN04, MSP-150, MSP-200, MSP-3500 (or above, Nikko Rica) (topic);

Tospearl 120, Tospearl 130, Tospearl 145, Tospearl 240 (above, Momentive Performance Materials Japan (manufactured by);

etc. are mentioned, but it is not limited to these. These commercial items may be used independently and multiple types may be mixed.

By including silicone microparticles|fine-particles in the resin composition of this invention, since dispersion stability of a fluorescent substance improves, fluorescent substance can be filled with a higher concentration. Since the thermal conductivity of the said resin composition will become high when the fluorescent substance filling rate in a composition becomes high, it can prevent that a fluorescent substance is heat-storage, and the heat resistance of this resin composition can be improved.

The content of the inorganic particles and/or silicone fine particles in the resin composition of the present invention is preferably 5 parts by weight or more as the lower limit, relative to 100 parts by weight of the total of the component (A), component (B) and component (C), It is more preferable that it is 10 weight part or more. Moreover, as an upper limit, it is preferable that it is 50 weight part or less, and it is more preferable that it is 30 weight part or less.

By containing 5 parts by weight or more of inorganic particles, a particularly favorable heat dissipation effect is obtained. On the other hand, the aggregation of inorganic particles is suppressed by containing 50 parts by weight or less. In silicone microparticles|fine-particles, the especially favorable fluorescent substance dispersion stabilization effect is acquired by containing 5 weight part or more, On the other hand, the viscosity of this resin composition is not raised excessively by containing 50 weight part or less.

The size of the inorganic particles and the silicon fine particles is not particularly limited, but in the volume-based particle size distribution obtained by the laser diffraction scattering particle size distribution measurement method, the particle diameter (D50) and/or average 1 of 50% of the cumulative passing fraction from the small particle diameter side It is preferable that the primary particle diameter is 0.01 micrometer - 100 micrometers. When the particle diameter is within the above range, the dispersion stability of the phosphor in the resin composition can be maintained in a good state.

An average primary particle diameter can be calculated|required by the following method similarly to a fluorescent substance. From a two-dimensional image obtained by observing inorganic particles and/or silicon fine particles with a scanning electron microscope (SEM), calculate that the distance between the two intersections of the two points of the straight line intersecting at two points with the outer edge of the particle is the maximum, It is defined as the particle diameter. Moreover, the same measurement is performed with respect to arbitrary 20 other said particle|grains, and let the average value of the obtained particle diameter be an average primary particle diameter. For example, when measuring the particle size of inorganic particles and/or silicon fine particles present in the resin composition, any one of a mechanical polishing method, a microtome method, a cross-section polisher (CP) method, and a focused ion beam (FIB) processing method After performing cross-sectional polishing of the resin composition with the above method, the average primary particle size can be calculated from the two-dimensional image obtained by observing the obtained polished cross-section with a scanning electron microscope (SEM) in the same manner as described above.

In the composition used for this embodiment, other components can be arbitrarily mix|blended with the range which does not impair the effect|action and effect of invention other than the above. Specifically, radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, surfactants, storage stability improvers, ozone deterioration inhibitors, light stabilizers, thickeners, plasticizers, antioxidants, conductivity imparting agents, antistatic agents, radiation blockers, organic solvents, etc. can be heard These components may be used individually by 1 type, or may use 2 or more types together.

The resin composition of the present invention may be a sheet-like molded product. That is, it is a sheet-like molded product containing at least the components (A) and (B), and further containing the component (C). Since the said resin composition is excellent in dispersion stability of a fluorescent substance, even when it shape|molds into a sheet form, the fluorescent substance can be shape|molded to a desired thickness with uniform density|concentration. Specifically, the sheet is formed by coating and drying the resin composition on the base substrate.

The manufacturing method of a fluorescent substance sheet is demonstrated. In addition, the following is an example, and the manufacturing method of a fluorescent substance sheet is not limited to this.

First, a fluorescent substance containing resin composition is produced as a coating liquid for fluorescent substance sheet formation. The phosphor-containing resin composition is obtained by mixing the phosphor and the resin composition in a suitable solvent.

A solvent will not be specifically limited, if the resin viscosity of a fluidized state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, etc. are mentioned.

After combining these components to a predetermined composition, homogeneously mixing and dispersing with a stirrer/kneader such as a homogenizer, a self-rotating stirrer, three rollers, a ball mill, a planetary ball mill, and a bead mill, a phosphor-containing resin composition is obtained lose Degassing is also preferably performed under vacuum or reduced pressure conditions after mixing and dispersing or in the course of mixing and dispersing.

Next, the phosphor-containing resin composition is applied to the base substrate. The base substrate is not particularly limited, but metal plates such as aluminum (including aluminum alloy), zinc, copper, and iron, foil, cellulose acetate, glass, ceramic, PET film, PP film, PPS film, polyimide film, polyamide A film, a polycarbonate film, an aramid film, etc. can be used. Among these, it is preferable that a base substrate is in the form of a flexible film from the adhesiveness at the time of making a fluorescent substance sheet adhere to an LED element. In addition, a film with high strength is preferable so that there is no fear of breakage or the like when the film-form base substrate is handled. A resin film is preferable from the point of those required characteristics and economical efficiency, and among these, the point of economical efficiency and handleability to a PET film is preferable. Moreover, when high temperature 200 degreeC or more is required when hardening of resin or bonding a fluorescent substance sheet to an LED element, a polyimide film is preferable from a heat resistant point. From the viewpoint of the ease of peeling the sheet, it is preferable that the surface of the base substrate is previously subjected to a release treatment. Although there is no restriction|limiting in particular as for the thickness of a base substrate, As a minimum, 25 micrometers or more are preferable and 40 micrometers or more are more preferable. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.

As a method of applying the phosphor resin composition, a reverse roll coater, a blade coater, a kiss coater, a slit die coater, a direct gravure coater, an offset gravure coater, a natural roll coater, an air knife coater, a roll blade coater, a baribar roll blade coater , two stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, screen printing, etc., but are not limited thereto. Among the above methods, in order to obtain film thickness uniformity, it is preferable to apply with a slit die coater. Drying of a fluorescent substance sheet can be performed using general heating apparatuses, such as a hot air dryer and an infrared dryer. In addition, general heating apparatuses, such as a hot air dryer and an infrared dryer, are used for heat-hardening of a sheet|seat. In this case, the heat curing conditions are usually 1 minute to 5 hours at 40 to 250°C, preferably 2 minutes to 3 hours at 100°C to 200°C.

The film thickness of a fluorescent substance sheet is determined from fluorescent substance content and desired optical characteristic. Since the phosphor content has a limit from the viewpoint of dispersion stability as described above, the film thickness is preferably 10 µm or more. From a viewpoint of improving the optical characteristic and heat resistance of a fluorescent substance sheet, it is preferable that the film thickness of a fluorescent substance containing sheet-like molded object is 1000 micrometers or less, It is more preferable that it is 200 micrometers or less, It is still more preferable that it is 100 micrometers or less. By making the phosphor sheet into a film thickness of 1000 µm or less, heat from the LED element is efficiently dissipated and the amount of heat stored in the sheet is reduced, so that heat resistance is improved.

The film thickness of the fluorescent substance sheet in this invention is the film thickness (average film thickness) measured based on the measuring method A method of thickness by mechanical scanning in JIS K7130 (1999) plastic-film and sheet-thickness measuring method (average film thickness) say

In general, the LED light emitting device is in an environment in which a large amount of heat is generated from the LED chip. Due to such heat generation, the temperature of the phosphor rises and the activator in the phosphor is deactivated, thereby reducing the total luminous flux of the light emitting device. Therefore, it is important to efficiently dissipate the generated heat. In this invention, the fluorescent substance sheet excellent in heat resistance can be obtained by making a sheet|seat film thickness into the said range.

Moreover, if there is a fluctuation|variation in the sheet film thickness, a difference arises in the amount of phosphors for each LED chip, and, as a result, the fluctuation|variation generate|occur|produces in the emission spectrum (color temperature, luminance, chromaticity). Accordingly, the variation in the sheet film thickness is preferably within ±5%, more preferably within ±3%.

In addition, the film thickness fluctuations here are measured based on the method A of thickness measurement by mechanical scanning in JIS K7130 (1999) plastics-film and sheet-thickness measurement method, and the formula shown below is is calculated by

More specifically, the film thickness is measured using a commercially available micrometer such as a contact thickness meter using the measurement conditions of the method A method for measuring the thickness by mechanical scanning, and the maximum or minimum value of the obtained film thickness and The difference in the average film thickness is calculated, and this value is divided by the average film thickness, and the value expressed in 100 parts becomes the film thickness variation B (%).

Film thickness variation B (%) = {(maximum film thickness difference value * - average film thickness) / average film thickness} x 100

* For the maximum film thickness difference value, the larger difference from the average film thickness is selected among the maximum value or the minimum value of the film thickness.

The phosphor sheet molded from the phosphor-containing resin composition of the present invention has a storage elastic modulus at 25°C of 0.01 MPa or more, and a storage elastic modulus when heated at 100°C is higher than the storage elastic modulus at 25°C and 200°C, respectively. Low is preferable.

The storage elastic modulus here is a storage elastic modulus at the time of performing a dynamic viscoelasticity measurement. Dynamic viscoelasticity refers to the shear stress that appears when a steady state is reached when a material is subjected to shear deformation at a certain sinusoidal frequency; It is a method to analyze the dynamic mechanical properties of materials by decomposing them into viscous components). Here, the storage modulus G' is the storage modulus G', which divides the stress component whose phase coincides with the shear strain by the shear strain, and is closely related to the workability and adhesiveness of the material because it represents the strain and follow-up of the material with respect to the dynamic strain at each temperature. has been

When the phosphor sheet has a storage elastic modulus at 25°C of 0.01 MPa or more, and a storage elastic modulus when heated at 100°C is lower than the respective storage modulus at 25°C and 200°C, when heated from 25°C, The storage elastic modulus of the sheet is lowered, and it deforms rapidly to follow the shape of the object, thereby exhibiting high adhesiveness. For this reason, the sheet can be directly attached on the LED element or on the polyorganosiloxane layer formed on the element without using an adhesive. If it is a fluorescent substance sheet from which the storage elastic modulus of less than 0.01 MPa is obtained at 100 degreeC, although adhesiveness becomes favorable with a temperature rise even at less than 100 degreeC, 80 degreeC or more is suitable for obtaining practical adhesiveness. Further, when such a phosphor sheet is heated above 100°C, the storage elastic modulus further decreases and adhesion becomes good, but at a temperature exceeding 150°C, the thermosetting reaction between component (A) and component (B) is usually As this progresses, the storage elastic modulus starts to rise, and the adhesiveness decreases. Therefore, a suitable heat attachment temperature is 50° C. to 150° C.

When the storage elastic modulus in 25 degreeC is 0.01 MPa or more in a fluorescent substance sheet, it is the metal mold|die punching process in room temperature (25 degreeC), or the cutting process by a blade body, and can process with high dimensional accuracy. Although the upper limit of the storage modulus at room temperature is not particularly limited for the purpose of the present invention, it is preferably 1 GPa or less in consideration of the necessity to reduce the stress strain after bonding to the LED element. The lower limit of the storage elastic modulus at 100°C is not particularly limited for the purpose of the present invention, but if the fluidity is too high at the time of heating and attaching onto the LED element, the film thickness of the phosphor sheet cannot be maintained, so it is preferably 0.001 MPa or more do.

It is preferable that the chromaticity of the fluorescent substance sheet shape|molded from the resin composition of this invention after heat processing at 150 degreeC for 100 hours is in the range of Clx+/-0.01 and Cly+/-0.01 compared with before heat processing.

A method for measuring the chromaticity of a sheet will be described. In addition, the following is an example, and the chromaticity measuring method of a fluorescent substance sheet is not limited to this. A current of 20 mA is passed through a light emitting device in which a phosphor sheet is attached to a blue LED element to light the LED element, and measurement is made using an instantaneous multi-metering system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). Then, with the light emitting device turned on, put it in a hot air oven and heat-treat at 150° C. for 100 hours, then measure again with a photometric system, and the chromaticity change (difference between the maximum value and the minimum value) before and after the heat treatment can be calculated.

The change in chromaticity of the light emitting device to which the phosphor sheet is attached is mainly due to deterioration of the phosphor due to high temperature and deterioration of the resin component. Since the phosphor sheet according to the present invention can be thinned due to the excellent dispersion stability of the phosphor and can efficiently radiate heat from the LED element, deterioration of the phosphor can be suppressed.

In addition, the resin component which comprises a fluorescent substance sheet is (A) component and (C) component, and the substituent couple|bonded with a silicon atom are an alkyl group, an alkenyl group, an epoxy group, an amino group, and a hydrogen atom. For this reason, even in a high-temperature environment of 150°C or higher, since radicals are not generated on the resin structure, the formation of a conjugated system that causes blue absorption (coloring) does not occur, and thermal deterioration is unlikely to occur. In view of the above, the change in chromaticity of the light emitting device can be suppressed within the above range.

Moreover, in the light emitting device which made the fluorescent substance sheet affixed to the blue LED element, it is preferable that the luminous flux maintenance factor at the time of 1000 hours of continuous lighting at 100 degreeC of LED ambient temperature (Ta) is 90 % or more.

A method of measuring the luminous flux of the light emitting device will be described. In addition, the following is an example, and the luminous flux measuring method is not limited to this. A current of 20 mA flows through a light emitting device in which a phosphor sheet is attached to a blue LED element to light the LED element, and the total luminous flux is measured using an instantaneous multi-metering system (MCPD-300, manufactured by Otsuka Denshi Co., Ltd.). (initial value A). Next, the light emitting device is placed in a hot-air oven set at 100°C, left lit for 1000 hours, then allowed to cool to 25°C, and the total luminous flux is measured again (measured value B). Next, each measured value is substituted into the following formula|equation, and the luminous flux retention is computed.

Luminous flux retention = {(measured value B)/(initial value A)}×100.

The phosphor sheet molded from the resin composition and phosphor of the present invention can be affixed as a wavelength conversion layer on an LED element or on a silicone resin layer formed on the element, and can be used as a light emitting device. Moreover, you may attach and use so that it may cover the side surface as well as just above the LED element.

As a method of manufacturing a light emitting device, when the phosphor sheet is attached on the LED element or on the silicone resin layer formed on the element, the element is attached by heating it to a predetermined temperature. Heating temperature is 50 degreeC or more and 200 degrees C or less. By setting it as 50 degreeC or more, (C)component fully softens and the storage elastic modulus can be lowered|hung to such an extent that this fluorescent substance sheet expresses adhesiveness. Moreover, by setting it as 200 degrees C or less, the thermosetting reaction of (A) component can be controlled and the storage elastic modulus required for adhesion can be ensured suitably.

In order to improve the reliability of the LED light emitting device according to the present invention, it is preferable that there is no stress strain between the phosphor-containing sheet-like molded article and the LED element. Therefore, the junction temperature is preferably around the operating temperature of the LED light emitting device, preferably within ±20°C of the operating temperature. The temperature of the LED light-emitting device rises from 70°C to 180°C at the time of lighting. Accordingly, the bonding temperature is preferably 50°C or more and 200°C or less also in the sense of bringing the operating temperature and the bonding temperature close to each other.

As a method for bonding the phosphor sheet on the LED element or on the silicone resin layer formed on the element, any existing apparatus can be used as long as it can be thermocompressed at a predetermined temperature. As will be described later, the method of cutting the phosphor sheet into individual pieces and then bonding them to individual LED elements, and collectively bonding the LED elements before dicing to the pasted wafer, dicing the wafer and cutting the phosphor sheet Although there is a method of performing collectively, in the case of the method of joining, after dividing|segmenting a fluorescent substance sheet into individual pieces, a flip-chip bonder can be used. When sticking together to a wafer level LED element, it joins by the thermocompression-bonding tool etc. which have a heating part of about 100 mm square. In all cases, the phosphor sheet is adhered on the LED element at a high temperature, then allowed to cool to room temperature, and the base substrate is peeled off.

As a method of bonding the phosphor sheet up to the side surface of the LED element, the same apparatus capable of thermal compression as described above is used, but in that case, first, the phosphor sheet is attached to a thermoplastic resin base substrate having a melting point of about 40 to 100°C. desirable.

The phosphor sheet is attached to the thermoplastic resin base substrate by pressing while the thermoplastic resin base substrate is softened and flowed. Therefore, the adhesion temperature is preferably a temperature at which the thermoplastic resin base substrate softens and flows. In addition, in order to prevent residual air stasis, it is preferable to perform adhesion under reduced pressure of 0.01 MPa or less. Although a vacuum diaphragm laminator etc. are illustrated as a manufacturing apparatus which performs this attachment, there is no restriction|limiting there.

Next, in order to bond the phosphor sheet up to the side surface of the LED element, the phosphor sheet adhered to the thermoplastic resin base substrate is heated above the melting point of the thermoplastic resin used for the base substrate, and is pressed and laminated from the upper surface so as to be in contact with the LED element. By doing so, the phosphor sheet can be bonded to the side surface of the LED element.

The method of cutting at the time of bonding a fluorescent substance sheet to the upper surface of an LED element is demonstrated. A method of cutting a phosphor sheet into pieces in advance before attachment to an LED element and attaching it to an individual LED element, and a method of attaching a phosphor sheet to a wafer level LED element and then cutting the phosphor sheet simultaneously with dicing of the wafer There is a way.

In the case of cutting in advance before attaching, the uniformly formed phosphor sheet is processed and divided into a predetermined shape by processing with a laser or cutting with a blade. Since high energy is imparted to the processing by laser, it is very difficult to avoid burning of the resin or deterioration of the phosphor, and cutting with a blade is preferable.

In cutting with a blade, in order to improve workability, it is very important that there is no tack at 25 degreeC of a fluorescent substance sheet. As a cutting method with a blade, there exist a method of cutting by press-fitting a simple blade, and a method of cutting with a rotary blade, all of which can be used suitably. As an apparatus for cutting with a rotary blade, an apparatus used for cutting (dicing) a semiconductor substrate called a dicer into individual chips can be suitably used. When a dicer is used, since the width of a dividing line can be precisely controlled by the thickness of a rotary blade and condition setting, higher processing precision is obtained than cutting by a simple press-fitting of a blade.

In the case of cutting the phosphor sheet in a laminated state with the base substrate, it may be separated for each base substrate, or the base substrate may not be cut while the phosphor sheet is separated into individual pieces. Alternatively, the base substrate may be a so-called half-cut in which a non-pierced cut-out line enters. The phosphor sheet thus separated into pieces is heat-bonded on the upper surface of each LED element.

An example of the process of singulation|segmentation, LED element bonding, and dicing in the case of separating a fluorescent substance sheet into individual pieces for every base board|substrate is shown in FIG. The process of FIG. 1 includes the process of cutting|disconnecting the fluorescent substance sheet into individual pieces, and the process of heating the fluorescent substance sheet cut|disconnected into the said individual piece, and making it adhere to an LED element.

Fig. 1 (a) shows a base substrate 2 and a laminated state phosphor sheet 1 of the present invention fixed to a temporary fixing sheet 3 . In the process shown in FIG. 1, since both the fluorescent substance sheet 1 and the base board|substrate 2 are divided into pieces, it is fixed to the temporary fixing sheet 3 so that handling may be easy.

Next, as shown in FIG.1(b), the fluorescent substance sheet 1 and the base board|substrate 2 are cut|disconnected and separated into individual pieces.

Then, as shown in FIG. As shown to (d) of 1, it crimps|compresses with the hot-bonding tool 6. At this time, it is preferable to perform the crimping|compression-bonding process under vacuum or reduced pressure so that air may not enter between the fluorescent substance sheet 1 and the LED element 4 .

After crimping, it is allowed to cool to room temperature, and the base substrate 2 is peeled off as shown in Fig. 1E.

In addition, when the phosphor sheet is separated into pieces as the base substrate is continuous, it may be attached to the LED element at the wafer level before dicing as it is collectively.

An example of the process of singulation|segmentation, LED element bonding, and dicing in the case of dividing a phosphor sheet into pieces as it is a base board continuous is shown in FIG. The process of FIG. 2 also includes the process of cutting|disconnecting the fluorescent substance sheet into individual pieces, and the process of heating the fluorescent substance sheet cut into the said individual piece and making it adhere to the upper surface of an LED element.

In the example of the process shown in FIG. 2, when the phosphor sheet 1 is first divided into pieces in the step shown in FIG. 2B, the base substrate 2 is not divided into pieces. Although the base board|substrate 2 is not cut|disconnected at all in FIG.2(b), as long as the base board|substrate 2 is continuous, you may cut|disconnect partially.

Next, as shown in FIG.2(c), the phosphor sheet 1 divided into pieces is made to face the wafer 7 in which the LED element before dicing was formed on the surface, and position alignment is performed.

In the process shown in FIG.2(d), the fluorescent substance sheet 1 and the wafer 7 which formed the LED element before dicing on the surface are crimped|bonded with the hot-bonding tool 6 by the process. At this time, it is preferable that the pressing step is performed under vacuum or under reduced pressure so that no air enters between the phosphor sheet 1 and the LED element.

After crimping, it was allowed to cool to room temperature and the base substrate 2 was peeled off as shown in FIG. A sheet-attached LED element is obtained.

When bonding a fluorescent substance sheet collectively to the LED element of the wafer level before dicing, a fluorescent substance sheet can also be cut|disconnected with dicing of an LED element wafer after bonding.

An example of the process in the case of collectively dicing a phosphor sheet and a wafer after bonding is shown in FIG. The process of FIG. 3 includes the process of heating and collectively attaching a fluorescent substance sheet to the upper surface of several LED element, and the process of dicing a fluorescent substance sheet and an LED element collectively.

In the process of Fig. 3, the phosphor sheet 1 of the present invention is not cut in advance, and as shown in Fig. 3(a), the phosphor sheet 1 side is a wafer ( 7) and align the position opposite to the

Next, as shown in FIG.3(b), the fluorescent substance sheet 1 and the wafer 7 which formed the LED element before dicing on the surface are crimped|bonded with the hot crimping|compression-bonding tool 6. As shown in FIG. At this time, it is preferable that the pressing step is performed under vacuum or under reduced pressure so that no air enters between the phosphor sheet 1 and the LED element.

After crimping, it was allowed to cool to room temperature, and the base substrate 2 was peeled off as shown in Fig. 3(c), the wafer was diced, and the phosphor sheet 1 was cut into individual pieces, as shown in Fig. 3(c). As shown to d), the individualized LED element with a fluorescent substance sheet is obtained.

Even in the case of employing any of the steps of FIGS. 1 to 3 described above, when the phosphor sheet of the present invention is attached to an LED element having an electrode on its upper surface, in order to remove the phosphor sheet of the electrode portion, the phosphor sheet is attached in advance. It is preferable to give a punching process to the part. For the punching process, a known method such as laser processing, die punching, or cutting with a blade body can be suitably used, but laser processing causes scorching of the resin or deterioration of the phosphor, so punching processing with a mold is more preferable.

When performing a punching process, since a punching process is impossible after attaching a fluorescent substance sheet to an LED element, it becomes essential to give a punching process to a fluorescent substance sheet before attachment. The punching process with a metal mold|die can punch a hole of arbitrary shape and size by the electrode shape etc. of the LED element to be joined. Any size or shape of the hole can be formed as long as the mold is designed. However, the electrode bonding portion on the LED element of about 1 mm square is preferably 500 µm or less in order not to reduce the area of the light emitting surface, and the hole is It is formed to be less than 500㎛ depending on the size. In addition, since the electrode which performs wire bonding etc. needs a certain size and becomes a size of at least about 50 micrometers, the hole is about 50 micrometers depending on the size. If the size of the hole is too larger than that of the electrode, the light emitting surface is exposed, light leakage occurs, and the color characteristic of the LED light emitting device is deteriorated. In addition, if it is too small than the electrode, the wire is contacted during wire bonding, causing poor bonding. Therefore, in the punching process, it is necessary to process small holes of 50 µm or more and 500 µm or less with high precision within ±10%.

Next, the cutting method at the time of bonding a fluorescent substance sheet to the side surface of an LED element is illustrated. A manufacturing example is shown in FIG.

In FIG. 4A , the LED element 4 is bonded to the package electrode 9 on the mounting substrate 5 through the gold bump 8 .

Fig. 4 (b) is laminated so that the phosphor sheet 1 on the base substrate 2 is in contact with the LED element 4 .

4(c) After putting the laminate in the lower chamber 13 of the vacuum diaphragm laminator 10, it is exhausted through the exhaust/intake port 11 while heating, and the upper chamber 12 and the lower chamber 13 are separated. depressurize. After heating under reduced pressure until the base substrate 2 flows, the diaphragm 14 is expanded by sucking the air through the exhaust/intake port 11 into the upper chamber 12, and the phosphor is passed through the base substrate 2 The sheet 1 is pressed and attached so as to follow the light emitting surface of the LED element 4 .

4(d) After returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 10, and the base substrate 2 is peeled off after cooling. Then, the obtained covering body is cut|disconnected at the position of a cut|disconnection part.

Fig. 4(e) An LED element with a phosphor sheet divided into pieces is obtained.

Example

Hereinafter, the present invention will be specifically described by way of Examples. However, the present invention is not limited thereto.

<Raw material>

A component

<Synthesis Example 1> Synthesis of alkenyl group-containing silicone resin (A1-1)

A stirring device and a Liebig condenser were installed in a 1-L 3-neck flask, and 136 g of methyltrimethoxysilane (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), dimethyldimethoxysilane (KBM-22, Shin-Etsu) Chemicals Co., Ltd. 24 g, trimethylethoxysilane (T1394, Tokyo Kasei Kogyo Co., Ltd.) 13.6 g, dimethylvinyl chlorosilane (Tokyo Kasei Kogyo Co., Ltd.) 10 g, isobutyl alcohol 120 g, Stirred at 20°C. Then, 60 g of a 0.05 N hydrochloric acid solution was dripped over 30 minutes. After completion|finish of dripping, it stirred for 1 hour, heating at 80 degreeC. Then, it stirred for 1 hour, heating to 105 degreeC. Next, the reaction solution was allowed to cool to 25°C, and 150 g of xylene was added thereto to dilute. Thereafter, the reaction solution was placed in a separatory funnel, and the washing operation was repeated 5 times with 300 g of pure water. Then, the purification solution was heated to 110 degreeC, water was removed, and 100 g of colorless transparent resin was obtained. As a result of structural analysis of the obtained resin, the average unit formula

it was The weight average molecular weight of this colorless transparent resin was 5,000, the refractive index was 1.43, and the glass transition point was -30 degreeC. Among the organic groups bonded to the silicon atom, methyl groups were 94%.

<Synthesis Example 2> Synthesis of alkenyl group-containing silicone resin (A1-2)

It synthesized in the same manner as in Synthesis Example 1, except that the heating and stirring time at 105°C was set to 5 hours to obtain 100 g of a colorless and transparent resin.

As a result of structural analysis of the obtained resin, the average unit formula

it was The weight average molecular weight of this colorless transparent resin was 16,000, the refractive index was 1.43, and the glass transition point was -70 degreeC. Among the organic groups bonded to the silicon atom, 91% of the methyl groups were.

<Synthesis Example 3> Synthesis of alkenyl group-containing silicone resin (A1-3)

It synthesized in the same manner as in Synthesis Example 1, except that the heating and stirring time at 105°C was set to 15 hours to obtain 100 g of a colorless and transparent resin. As a result of structural analysis of the obtained resin, the average unit formula

It was. The weight average molecular weight of this colorless transparent resin was 350,000, the refractive index was 1.43, and the glass transition point was -90 degreeC. Among the organic groups bonded to the silicon atom, 96% of the methyl groups were.

<Synthesis Example 4> Synthesis of hydrosilyl group-containing silicone resin (A2-1)

Synthesis in the same manner as in Synthesis Example 1 of the polyorganosiloxane compound containing an alkenyl group except that the raw material was changed from dimethylvinylsilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) to 15 g of dimethylchlorosilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Thus, 100 g of a colorless transparent resin was obtained. As a result of structural analysis of the obtained resin, the average unit formula

It was. The weight average molecular weight of this colorless transparent resin was 4,500, the refractive index was 1.43, and the glass transition point was -90 degreeC. Among the organic groups bonded to the silicon atom, 91% of the methyl groups were.

(B) component

Curing catalyst B-1: Platinum (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) complex 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution platinum Content 5% by weight.

(C) component

Silicone resin C-1: SR-1000 (manufactured by Momentive Performance Materials Japan), a glass transition point of 80°C, a weight average molecular weight of 3,800, and 92% of methyl groups among organic groups bonded to silicon atoms. average unit formula

It was.

Silicone resin C-2: X-40-3237 (manufactured by Shin-Etsu Chemical Co., Ltd.), a glass transition point of 130°C, a weight average molecular weight of 6,000, and 93% of methyl groups among organic groups bonded to silicon atoms. average unit formula

it was

Silicone resin C-3: CB-1002 (manufactured by Toray Dow Corning Co., Ltd.), a glass transition point of 160°C, a weight average molecular weight of 70,000, and 97% of methyl groups among organic groups bonded to silicon atoms. average unit formula

It was.

Silicone resin C-4: MQ-1640 (manufactured by Toray Dow Corning Co., Ltd.), a glass transition point of 250°C, a weight average molecular weight of 150,000, and 91% of methyl groups among organic groups bonded to silicon atoms. average unit formula

It was.

Silicone resin C-5: KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), a glass transition point of -100°C, a weight average molecular weight of 900, and 90% of methyl groups among organic groups bonded to silicon atoms. average unit formula

it was

phosphor

Phosphor D-1: "NYAG-02" (manufactured by Intematix Co., Ltd.) Specific gravity: 4.8 g/cm ³ , D50: 8 µm.

Phosphor D-2: "BY-202/A" (manufactured by Mitsubishi Chemical Co., Ltd.) Specific gravity: 4.8 g/cm ³ , D50: 12 µm.

Phosphor D-3: "EY4254" (manufactured by Intematix Co., Ltd.) Specific gravity: 4.7 g/cm ³ , D50: 16 µm.

inorganic particles

<Inorganic particle 1> Alumina powder "Aeroxide" (manufactured by Nippon Aerosil Co., Ltd.) Average particle diameter D50: 13 nm

Silicon fine particles

<Synthesis Example 5> Particulate 1

A stirrer, thermometer, reflux tube, and dropping funnel were installed in a 3L 4-necked round-bottom flask, and 1600 g of a 2.5wt% aqueous ammonia solution at pH 12 (25°C) and 1600 g of a nonionic surfactant Emalgen 1108 (Gao Co., Ltd.) ) 0.004 g was added. 150 g of methyltrimethoxysilane was dripped over 20 minutes from the dropping funnel, stirring at 300 rpm. Then, the polymerization solution was heated up to 50 degreeC over 30 minutes, and stirring was continued for further 60 minutes. Next, after cooling the polymerization solution to room temperature, 10 g of ammonium acetate was added, followed by stirring at 150 rpm for 10 minutes. Next, the polymerization solution was subdivided into 8 250 ml centrifugal bottles (Nargen Co., Ltd.), and centrifuged at 3000 rpm with a centrifuge (Table Top Centrifuge 4000, manufactured by Kubota Seisakusho Co., Ltd.) at 3000 rpm for 10 minutes. Then, the supernatant was removed. Then, 200 g of pure water was added to the centrifugal bottle, stirred with a spatula, and centrifuged again under the above conditions. The washing operation was repeated 5 times. Next, the cake remaining in the centrifugal bottle was transferred to a bucket and dried in a hot air oven at 100°C for 8 hours to obtain 70 g of white powder. The average particle diameter (D50) of the obtained powder was 0.5 µm, and the average unit formula was

It was.

<Base board>

Base 1: PET film "Cerafil" BLK with mold release agent (manufactured by Toray Film Processing Co., Ltd.)

Peel force 5.7N/50mm

<Measurement of storage modulus>

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

Geometry: Parallel Disc (15mm)

Deformation: 1%

Angular frequency: 1Hz

Temperature range: 25°C to 200°C

Temperature increase rate: 5°C/min

Measurement Atmosphere: Atmospheric.

<Preparation of measurement sample for storage viscoelasticity measurement>

Using a polyethylene container, 70 parts by weight of component (A), 0.005 parts by weight of component (B), 30 parts by weight of component (C), and 100 parts by weight of phosphor were mixed. Then, using the planetary stirring and defoaming apparatus "Mazerstar KK-400" (manufactured by Kurabo Co., Ltd.), stirring and defoaming were performed at 1000 rpm for 20 minutes to obtain a phosphor-containing resin composition. The phosphor-containing resin composition was applied on the substrate 1 using a slit die coater, and heated and dried at 100° C. for 1 hour to obtain a semi-cured phosphor sheet. Eight sheets obtained were laminated and thermocompressed on a hot plate at 100°C to prepare an integrated film (sheet) of 600 µm or more, cut out to a diameter of 15 mm, and used as a measurement sample. Each measurement sample produced by the above operation was measured under the above conditions, and the storage modulus at 25°C, 100°C, and 200°C is shown in Table 1.

<Adhesiveness evaluation>

A phosphor sheet cut to 1 mm square is bonded to the LED element at 100° C., returned to room temperature after compression for a predetermined time, and when the base substrate is peeled off, all the phosphor sheets are adhered to the LED element and remain on the base substrate. Time was made into adhesion-capable time. When the heat-pressing time is 100° C., the sheet-like molded material containing the phosphor is all adhered to the LED element within 3 minutes and does not remain on the base substrate is referred to as Adhesive A, and does not adhere within 3 minutes at 100° C., but adheres within 5 minutes It is called adhesiveness B, what does not adhere in 5 minutes but adheres in 10 minutes is called adhesiveness C, what adheres within 15 minutes at 150°C is called adhesiveness D, In the case where a part remained on the base substrate even if it was not adhered to or partially adhered to, it was referred to as adhesion E (defective adhesion).

<Color temperature fluctuation>

A current of 20 mA was passed to an LED light emitting device in which a phosphor sheet was mounted on the LED element to light the LED element, and the correlated color temperature was measured using an instantaneous multi-metering system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). Ten samples were produced, and the difference between the maximum value and the minimum value of the measured correlated color temperature (CCT) was made into color temperature fluctuation|variation.

<Heat resistance evaluation>

A current of 20 mA was passed to an LED light emitting device in which a phosphor sheet was mounted on the LED element to light the LED element, and the chromaticity was measured using an instantaneous multi-metering system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). Next, the light emitting device was placed in a hot air oven with the light on and heat-treated at 150° C. for 100 hours, and then the chromaticity was measured again in the photometric system, and the chromaticity fluctuation range before and after the heat treatment was calculated.

<Evaluation of LED luminous flux retention rate>

A current of 20 mA is passed to an LED light emitting device in which a phosphor sheet is mounted on an LED element to light the LED element, and the total luminous flux is measured using an instantaneous multi-metering system (MCPD-3000, manufactured by Otsuka Denshi Co., Ltd.), This was set as the initial value A. Next, the light emitting device is placed in a hot air oven set at 100° C., left on for 1000 hours in a lit state, and then taken out from the hot air oven, allowed to cool to 25° C., and the total luminous flux is measured in a photometric system, and this is the measured value. It was set to B. Next, each measured value was substituted into the following formula|equation, and the luminous flux retention was computed.

Luminous flux retention = {(measured value B)/(initial value A)}×100.

(Example 1)

Using a polyethylene container, 56 parts by weight of silicone resin A1-1, 14 parts by weight of silicone resin A2-1, 30 parts by weight of silicone resin C-1, 0.005 parts by weight of curing catalyst B-1, phosphor D- 1 was mixed in a proportion of 100 parts by weight. Then, using the planetary stirring and defoaming apparatus "Mazerstar KK-400" (manufactured by Kurabo Co., Ltd.), stirring and defoaming were performed at 1000 rpm for 20 minutes to obtain a phosphor-containing resin composition. The phosphor-containing resin composition was applied on the substrate 1 using a slit die coater, and heated and dried at 100° C. for 1 hour to obtain a semi-cured phosphor sheet. As a result of measuring the film thickness of the obtained sheet|seat, 80 micrometers and the film thickness difference were 1.5 %. Subsequently, the storage modulus at each temperature of the sheet was 0.15 MPa (25° C.), 0.03 MPa (100° C.), and 0.25 MPa (200° C.). Then, as a result of evaluating the adhesiveness of the sheet, it was adhesive A. Next, in the LED light emitting device produced using the sheet, 10 out of 10 were lit, the color temperature fluctuation was 104K, the heat resistance (variation width) was ΔClx 0, ΔCly 0, and the luminous flux retention was 100%.

(Examples 2 to 9) Addition amount of silicone resin (C) component

A phosphor sheet was prepared in the same manner as in Example 1, except that the ratio of the component (B) was not changed and the ratio of the component (A) and the component (C) was changed, and the sheet film thickness, storage elastic modulus, adhesiveness, Color temperature fluctuation, heat resistance, and luminous flux retention were evaluated. The results are shown in Table 1. In Examples 2-3, adhesiveness B, Examples 4-5 were adhesiveness C, Examples 6-8 were adhesiveness D, but color temperature fluctuation|variation, heat resistance, and luminous flux retention were favorable.

(Examples 10 to 11) (A) Kind of component

(A) A phosphor sheet was produced by the same operation as in Example 1 except that the kind of component was changed, and the sheet film thickness, storage elastic modulus, adhesiveness, color temperature fluctuation, heat resistance, and luminous flux retention were evaluated. The results are shown in Table 2. It can be seen that the color temperature fluctuation of Examples 9 and 10 is suppressed, and dispersion stability of the phosphor is improved as compared with Example 1. On the other hand, although the chromaticity fluctuation range of heat resistance became larger than Example 1, it was comparatively favorable.

(Examples 12 to 15) (C) Kind of component

Except for changing the type of the silicone resin (C) component to be added, a phosphor sheet was prepared in the same manner as in Example 1, and the sheet film thickness, storage elastic modulus, adhesiveness, color temperature fluctuation, heat resistance and luminous flux retention were evaluated. . The results are shown in Table 2. The adhesive properties of Examples 12 to 15 were lowered.

(Examples 16 to 17) Types of phosphors

A phosphor sheet was produced in the same manner as in Example 1 except that the type of phosphor to be added was changed, and the sheet film thickness, storage elastic modulus, adhesiveness, color temperature fluctuation, heat resistance, and luminous flux retention were evaluated. The results are shown in Table 3. Examples 16 to 17 exhibited large color temperature fluctuations, but were relatively good results.

(Examples 18 to 20) Effect of adding inorganic particles or silicon particles

Example 18 is Example 1, except that 5 parts by weight of the inorganic particles (1), Example 19, 20 parts by weight of the inorganic particles (1), and Example 20, 20 parts by weight of the fine particles (1) are additionally added. A phosphor sheet was produced by the same operation as described above, and the sheet film thickness, storage elastic modulus, adhesive color temperature fluctuation, heat resistance, and luminous flux retention were evaluated. The results are shown in Table 3. In Examples 18 to 20, the color temperature fluctuation was improved compared to Examples 1 to 17.

(Comparative Example 1)

A phosphor sheet was prepared in the same manner as in Example 1 except that the silicone resin (C) component was not added, and the sheet film thickness, storage elastic modulus, adhesiveness, color temperature fluctuation, heat resistance, and luminous flux retention were evaluated. The results are shown in Table 4. In the obtained sheet, the film thickness difference was 6%, adhesiveness was not expressed, and evaluation was adhesiveness E. In addition, since the sheet was not adhered, evaluation of color temperature fluctuation, heat resistance, and luminous flux retention could not be performed.

1 phosphor sheet
2 base board
3 Temporary fixed seat
4 LED element
5 Mounting board
6 Heat crimping tool
7 Wafer with LED elements formed on the surface before dicing
8 gold bump
9 package electrode
10 vacuum diaphragm laminator
11 Exhaust/Intake
12 upper chamber
13 lower chamber
14 diaphragm

Claims (17)

It contains at least the following components (A) and (B), further contains component (C), further comprising inorganic particles and silicone particles, wherein the silicone particles are represented by the average unit formula (3) A sheet-like molded product of a resin composition to be used.
Component (A): a reactive silicone resin in which (the number of methyl groups bonded to silicon atoms)/(the number of organic groups bonded to silicon atoms) is 90% or more;
(B) component: curing catalyst;
Component (C): A non-reactive silicone resin in which (the number of methyl groups bonded to silicon atoms)/(the number of organic groups bonded to silicon atoms) is 90% or more, including the silicone resin represented by the average unit formula (2).

(R ⁴ to R ⁶ are a substituted or unsubstituted alkyl group or alkoxy group, and may be the same or different, respectively. k, p and s are numbers representing the ratio of structural units in each parenthesis, 0.01≤k≤0.50, k A positive number satisfying +p+s=1.0 m, n, q and r are integers greater than or equal to 0 satisfying m+n=2, q+r=1 Substituted or unsubstituted bonded to a silicon atom If the total number of methyl groups among the alkyl groups is M, M/{3k+2p+s}≥0.90 is satisfied.)

(R ⁷ to R ⁹ are substituted or unsubstituted alkyl groups, and may be the same or different, respectively. t, u and w are numbers representing the ratio of structural units in each parenthesis, 0.50≤t≤0.95, 0.05≤u+ It satisfies w≤0.50, t+u+w=1.0.) The sheet-like molded article according to claim 1, wherein the glass transition point of component (A) in the resin composition is in the range of -100 to 20°C, and the glass transition point of component (C) is in the range of 50 to 200°C. The sheet-like molded article according to claim 1 or 2, further comprising a phosphor. The sheet-like molded product according to claim 1 or 2, wherein the content of component (C) in the resin composition is 0.50 to 70% by weight when the total amount of component (A) and component (C) is 100% by weight. . The sheet-like molded product according to claim 1 or 2, wherein the weight average molecular weight of component (C) in the resin composition is 1,000 to 100,000 in terms of polystyrene. The sheet-like molded article according to claim 1 or 2, wherein the resin composition contains inorganic particles, and the inorganic particles are one or more particles selected from the group consisting of silica, alumina, titania, magnesium oxide and aluminum nitride. The sheet-like molded article according to claim 3, wherein the average primary particle diameter of the phosphor is in the range of 5.0 to 40 mu m. The storage elastic modulus at 25 degreeC is 0.010 MPa or more, and the storage elastic modulus (G') at the time of heating to 100 degreeC is lower than the storage elastic modulus at 25 degreeC and 200 degreeC, respectively. A sheet-like molded article, characterized in that. A light-emitting device in which the sheet-like molded product according to claim 1 or 2 is adhered on an LED element or on a silicone resin layer formed on the LED element. The light emitting device according to claim 9, wherein the sheet-like molded article is attached to the side surface of the LED element. A method for manufacturing a light emitting device comprising at least a step of heating and attaching the sheet-like molded product according to claim 1 or 2 to at least the light emitting surface or the silicone resin layer formed on the light emitting surface of the LED element. The light emitting device according to claim 11, comprising a step of cutting the sheet-like molding into pieces, and a step of heating the sheet-like molding cut into the pieces and attaching it to an LED element or a silicone resin layer formed on the LED element. manufacturing method. The method for manufacturing a light emitting device according to claim 11, wherein the temperature at which the sheet-like molded article is adhered is 50°C or more and 200°C or less. delete delete delete delete

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