TW201728685A - Resin composition, sheet-shaped molded article of same, light-emitting device using same, and method for manufacturing same - Google Patents

Abstract

Provided are a resin composition containing at least (A) through (C) below, the resin composition having excellent heat resistance and adhesion during affixing, and a sheet-shaped molded article of the resin composition. (A) A reactive silicone resin in which 90% or more of organic groups bonded to silicon atoms are methyl groups; (B) a curing catalyst; and (C) a nonreactive silicone resin in which 90% or more of organic groups bonded to silicon atoms are methyl groups.

Description

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

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

In recent years, an amazing improvement in the luminous efficiency of a Light Emitting Diode (LED) can be seen. Moreover, it is characterized by low power consumption, long life, design, and the like, and is not only a vehicle-mounted flashlight for a mobile phone, but also a headlight for a car, and the market is rapidly expanding even for general lighting. However, in the replacement with the previous lamp, a sufficient amount of luminescence is still not obtained, and further high luminance of the LED is required.

In general, the high luminance of LEDs is a method of increasing the amount of light by causing a high current to flow into the LED elements. However, since the amount of heat generated by the LED element or the amount of stored heat of the phosphor increases, there is a problem that the sealing resin is thermally deteriorated and colored. Therefore, in order to obtain high luminous efficiency, an anthrone resin which is a main component of a ruthenium atom which bonds a methyl group to a Si—O repeating structure which is a main chain of a sealing resin (so-called methyl fluorenone resin) is often used. (for example, refer to Patent Document 1).

On the other hand, in terms of luminous efficiency and cost, a method of attaching a sheet-like molded article (hereinafter, a phosphor sheet) containing a phosphor to an LED element has been proposed (for example, refer to Patent Document 2 to Patent Document 5). Compared with a previously applied method in which a liquid resin in which a phosphor is dispersed is dispensed onto an LED element and cured, the method is easy to efficiently dispose a fixed amount of the phosphor on the LED element by the fluorescent light. The film formation of the body-containing layer is excellent in heat dissipation improvement. Further, by imparting thermal softening property and adhesion to the phosphor sheet, it is possible to directly attach the LED element to the LED element without using a previously necessary adhesive, so that heat can be efficiently dissipated. Prior art literature

Patent Document 1: Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 5: Japanese Patent Laid-Open Publication No. 2013-1791

[Problems to be Solved by the Invention] The method of directly attaching a phosphor sheet to an LED element is superior to the distribution method in heat dissipation, but the phenyl group is introduced into the molecular structure in order to impart heat fusion properties, so heat resistance is obtained. There are problems.

On the other hand, Patent Document 2 discloses a method of introducing a methyl group into a molecular structure of an anthrone resin for the purpose of improving heat resistance. However, in the method disclosed in this document, among the molecular structures of the resin, 90% or more of the side chain is a methyl group, and thus there is insufficient adhesion to the LED element, and the sheet in the continuous lighting test is detached or A gap is formed in the interface between the sheet and the element, which tends to cause a decrease in brightness. Further, since the phosphor sheet before the attachment is in an unhardened state and is semi-solid or soft, it is difficult to perform cutting or drilling with high precision.

In Patent Document 4, an anthrone resin having a softening point of 30 to 150 ° C is added in order to obtain adhesiveness. However, since the resin structure contains a cyclic ether group, it is likely to cause thermal decomposition, which causes coloring of the phosphor sheet.

In Patent Document 5, resin softening property and adhesiveness are obtained by morphological control of a phenyl group derived from a molecular structure, but a phenyl group is bonded to a ruthenium atom of a Si-O repeating structure which is a main chain of a sealing resin. The so-called phenylmethyl fluorenone resin which is a main component of the composition is insufficient in heat resistance, and coloring due to thermal deterioration is likely to occur.

As described above, a phosphor sheet excellent in heat resistance and excellent in adhesion at the time of attachment has not been obtained. An object of the present invention is to provide a resin composition and a sheet which have the above-described characteristics, a light-emitting device produced by using the same, and a method for producing the same. [Means for solving the problem]

The present invention is a resin composition containing at least the following components (A) to (C). (A) a reactive fluorenone resin in which more than 90% of the organic groups bonded to the ruthenium atom are methyl; (B) a hardening catalyst; (C) 90% of the organic groups bonded to the ruthenium atom The above is a methyl non-reactive fluorenone resin. [Effects of the Invention]

According to the resin composition of the present invention, it is possible to provide a sheet excellent in heat resistance and adhesion to the LED element. Color uniformity, heat resistance, and light resistance of a light-emitting device produced by using a phosphor-containing resin composition containing a phosphor or a sheet-like molded product containing a phosphor in a resin composition of the present invention And excellent reliability.

<Resin Composition> The resin composition of the present invention contains at least the following components (A) to (C). (A) a reactive fluorenone resin in which more than 90% of the organic groups bonded to the ruthenium atom are methyl; (B) a hardening catalyst; (C) 90% of the organic groups bonded to the ruthenium atom The above is a methyl non-reactive fluorenone resin.

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

(Component (A)) The reactive fluorenone resin of the component (A) means an organic functional group or a bond which can serve as a starting point of a condensation reaction and/or an addition reaction in a main chain terminal and/or a side chain of the resin. An anthrone resin which promotes a hardening reaction by a hydrogen atom on a ruthenium atom by heat, moisture, and ultraviolet rays.

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

[Chemical 1]

R ¹ to R ³ may be the same or different and each may be a hydrogen atom or a substituted or unsubstituted alkyl group, alkenyl group, epoxy group, alkoxy group or amine group. Among them, at least one or more of R ¹ to R ³ is an alkenyl group or a hydrogen atom. a to f are each an integer of 0 or more, and satisfy a+b=3, c+d=2, and e+f=1. 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 in the substituted or unsubstituted alkyl group bonded to the ruthenium atom is set to 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. Particularly preferred is methyl.

Examples of the alkenyl group include a vinyl group, an acrylic group, and a methacryl group.

The component (A) may be a single one or a mixture of a plurality of kinds.

In the component (A), an alkenyl group bonded to a ruthenium atom generates a hydrazine hydrogenation reaction with a hydrogen atom bonded to a ruthenium atom. Therefore, it is preferred to respectively contain a compound containing an alkenyl group bonded to a ruthenium atom and a compound containing a hydrogen atom bonded to a ruthenium atom.

Qualitative analysis and quantitative analysis of the organic group were carried out by ¹ H-nuclear magnetic resonance (NMR) measurement, ¹³ C-NMR measurement, and ²⁹ Si-NMR measurement. The ratio of the methyl group bonded to the ruthenium atom can be calculated from the average unit formula obtained from the analysis.

In the step of producing the resin composition, the component (A) is preferably liquid at 25 °C. Specifically, the viscosity at 25 ° C is preferably 10 mPa·s or more, more preferably 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.

The weight average molecular weight of the component (A) is preferably from 1,000 to 300,000, more preferably from 1,500 to 100,000, particularly preferably from 2,000 to 10,000. When the weight average molecular weight is within the above range, when the component (C) is mixed, the pulverization and mixing can be performed uniformly, and the precipitation and separation of the component (C) over time can be suppressed. Further, if it is within the above range, the phosphor can maintain good dispersion stability.

In addition, the weight average molecular weight of the component (A) is a value obtained by measuring under the following conditions using HLC-8220GPC manufactured by Tosoh Corporation. Pipe column: TSKgel Guard columnHHR-H, GMHHR-N manufactured by Tosoh (share) Development solvent: tetrahydrofuran development speed: 1.0 ml/min column temperature: 23 °C Standard sample: use order made by Tosoh (stock) The value obtained by converting the calibration curve of the dispersed polystyrene.

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

When the glass transition point of the component (A) is within the above range, it is liquid at an ambient temperature of 20 ° C or higher. Therefore, when mixed with the component (B), the component (C), and the phosphor, a uniform resin can be obtained. Composition. Therefore, color temperature unevenness of the light-emitting device produced by the resin composition can be suppressed.

The glass transition point can be measured by a commercially available measuring instrument [for example, a differential scanning calorimeter manufactured by Seiko Instruments Inc. (trade name: DSC6220, heating rate: 0.5 ° C/min)].

In the present invention, a commercially available product containing the components (A) and (B) may also be used. For example, OE-6250, JCR6115, JCR6125, JCR6126, JCR6122, JCR6101, JCR6101UP, JCR6109, JCR6110, JCR6140, OE-6351, OE-6370M, OE-6370HF, OE-6336, EG-6301 (above, Toray・Manufacture of Dow Corning (share); KER-2500, KER-2600, KER-6020F, KER-6075F, LPS-3419, LPS-3541 (above, Shin-Etsu Chemical Co., Ltd.); IVS4312, IVS4542, IVS4546, IVS4622 And IVS4632, IVS4742, IVS4752, XE14-C2042 (above, manufactured by Momentive Performance Materials Japan), but are not limited to these commercial products. These commercially available products may be used singly or in combination.

(Component (B)) The component (B) is preferably a hydrogenation reaction catalyst for promoting the hydrogenation reaction of an alkenyl group in the component (A) with a hydrogen atom bonded to a halogen atom. Specific examples thereof include a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. However, the present invention is not limited thereto as long as it promotes the curing of the composition.

In the present invention, it is preferred to use a platinum-based catalyst which is relatively easy to control the reaction. Specific examples thereof include platinum fine powder, platinum tetrachloride, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenyl alkoxylate complex, a platinum-olefin complex, and a platinum-carbonyl group. Things and so on. In particular, a platinum-alkenyl alkoxylate complex having a low chlorine component concentration is preferred. Examples of the alkenyl decane include 1,3-divinyl-1,1,3,3-tetramethyldioxane, 1,3,5,7-tetramethyl-1,3. 5,7-tetravinylcyclotetraoxane, an alkenyl oxirane obtained by substituting a part of a methyl group of the alkenyl oxirane with an ethyl group, a phenyl group or the like, using an allyl group, a hexenyl group An alkenyl alkane which is substituted with a vinyl group of the alkenyl alkane. Among these, 1,3-divinyl-1,1,3,3-tetramethyldioxane having high stability is particularly preferred.

Examples of such a reaction catalyst include "SIP6829.0" manufactured by Gelest Corporation of the United States (platinum carbonyl vinyl methyl complex, platinum 3.0% to 3.5% vinyl methyl ring). "N-oxane solution", "SIP6830.0" (platinum divinyl tetramethyl dioxane complex, platinum 3.0% to 3.5% concentration of vinyl-terminated polydimethyl siloxane solution), "SIP6831. 0" (platinum divinyltetramethyldioxane complex, platinum 2.1% to 2.4% xylene solution), "SIP6832.0" (platinum cyclovinylmethyl oxime complex, platinum 3.0% to 3.5% concentration of cyclic methylvinyl siloxane solution), "SIP6833.0" (platinum octanal/octanol complex, platinum 2.0% to 2.5% concentration octanol solution), and the like.

The content of the component (B) is preferably from 0.01 ppm to 500 ppm, more preferably from 0.1 ppm to 100 ppm, based on the total weight of the resin composition. When it is in the said range, sufficient hardening property can be acquired, and it can maintain the color-free state after hardening.

(Component (C)) The non-reactive fluorenone resin of the component (C) means an organic functional group which does not have a starting point of a condensation reaction and/or an addition reaction in the main chain terminal and/or the side chain of the resin. An anthrone resin which does not cause a hardening reaction due to heat, moisture, and ultraviolet rays.

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

[Chemical 2]

R ⁴ to R ⁶ are a substituted or unsubstituted alkyl or alkoxy group, and may be the same or different. k, p, and s are numbers indicating the proportion of constituent elements 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 of 0 or more satisfying m+n=2 and q+r=1. When the total number of methyl groups in the substituted or unsubstituted alkyl group bonded to the ruthenium atom is set to 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. Particularly preferred is methyl.

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. Particularly preferred is methoxy.

k and s are particularly good integers satisfying 0.02 ≦ k ≦ 0.40, 0.10 ≦ s ≦ 0.90.

A commercially available product can also be used as the component (C). 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, manufactured by Japan Momentive Advanced Materials Co., Ltd.); RSN-0749 resin (Resin), DC593, 670 fluid (Fluid), 680 fluid (Fluid), MQ-1600 solid resin (Solid Resin), MQ-1640 Solid Resin, AMS-C30 Cosmetic Wax, SW-8005 C30 Resin Wax, 580 Wax (above, manufactured by Toray Dow Corning (stock)) Etc., but not limited to these commercial items. These commercially available products may be used singly or in combination.

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

When the total amount of the component (A) and the component (C) is 100% by weight, the content of the component (C) in the resin composition of the present invention is preferably 0.5% by weight or more. Preferably, it is 10 wt% or more, more preferably 15 wt% or more, more preferably 20 wt% or more, and still more preferably 30 wt% or more. Further, it is preferably 70 wt% or less, more preferably 60 wt% or less, still more preferably 50 wt% or less. When the content of the component (C) is appropriate, the resin composition exhibits better adhesion upon heating.

The weight average molecular weight of the component (C) is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000, particularly preferably from 3,000 to 5,000. When the weight average molecular weight is within the above range, the glass transition point of the component (C) can be adjusted to a range of 50 to 200 °C. The weight average molecular weight of the component (C) is a value obtained by the measurement of the same weight average molecular weight as the component (A).

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

When the glass transition point of the component (C) is within the above range, when the ambient temperature is less than 50 ° C, the component (C) has a solid shape and does not exhibit adhesiveness. Therefore, when the phosphor resin composition containing the component (C) is processed into a sheet form, since it has no adhesiveness at room temperature (25 ° C), it can be easily handled. Further, when the composition is heated to a temperature higher than the glass transition point of the component (C), the component (C) is melted and exhibits a liquid property, so that the resin composition is softened and the adhesiveness is exhibited.

(Fluorescent Body) The resin composition of the present invention may contain a phosphor. The phosphor absorbs light emitted from the LED element, performs wavelength conversion, and emits light having a wavelength different from that of the LED element. Thereby, a part of the light emitted from the LED element is mixed with a part of the light emitted from the phosphor to obtain a multi-color light-emitting device including white.

The phosphor may be an organic substance or an inorganic substance as long as it can be wavelength-converted, but is preferably an inorganic substance from the viewpoint of heat resistance and light resistance. Specifically, there are a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, a phosphor that emits red light, and the like.

As the inorganic phosphor which can be preferably used in the present invention, as the phosphor which emits green light, for example, SrAl ₂ O ₄ :Eu, Y ₂ SiO ₅ :Ce, Tb, MgAl ₁₁ O ₁₉ :Ce, Tb And Sr ₇ Al ₁₂ O ₂₅ :Eu, at least one of (Mg, Ca, Sr, and Ba) Ga ₂ S ₄ :Eu, β-Sialon, or the like.

Examples of the phosphor that emits 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, or the like.

As a phosphor that emits green light to yellow light, there are at least an aluminum oxide phosphor activated by yttrium, and a lanthanum aluminum oxide phosphor activated at least by yttrium, at least by A yttrium-aluminum-garnet oxide phosphor activated by ruthenium, and a lanthanum-gallium-aluminum oxide phosphor activated by at least ruthenium (so-called YAG-based phosphor). Specifically, Ln ₃ M ₅ O ₁₂ :R (Ln is at least one selected from the group consisting of Y, Gd, and La. M includes at least one of Al and Ca. R is a lanthanoid series), (Y _{1 -x} Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : R (R is at least one selected from the group consisting of Ce, Tb, Pr, Sm, Eu, Dy, and Ho. 0<x<0.5,0 <y<0.5).

Examples of the phosphor that emits red light include 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 .} : KSF phosphor represented by Mn.

Further, examples of the phosphor that emits light corresponding to the current mainstream blue LED include 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 :Ce and other YAG-based phosphors, Tb ₃ Al ₅ O ₁₂ :Ce and other TAG-based phosphors, (Ba,Sr) ₂ SiO ₄ :Eu-based fluorescent Or Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce-based phosphor, (Sr,Ba,Mg) ₂ SiO ₄ :Eu and other citrate-based phosphors, (Ca,Sr) ₂ Si ₅ N ₈ :Eu , (Ca, Sr)AlSiN ₃ :Eu, a nitride-based phosphor such as CaSiAlN ₃ :Eu, a oxynitride-based phosphor such as Ca _x (Si,Al) ₁₂ (O,N) ₁₆ :Eu, and Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu-based phosphor, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu-based phosphor, SrAl ₂ O ₄ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, etc. Fluorescent body.

Among these, YAG-based phosphors, TAG-based phosphors, and citrate-based phosphors can be preferably used in terms of luminous efficiency, brightness, and the like. In addition to the above, a known phosphor may be used depending on the application or the intended luminescent color.

The average primary particle diameter of the phosphor in the present invention is preferably in the range of 5 μm to 40 μm. Among the above, it is preferably 8 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more. On the other hand, it is preferably 40 μm or less, more preferably 20 μm or less. When the average primary particle diameter of the phosphor is within the above range, the dispersion state in the composition becomes uniform and stable, and thus the sheet-like molded article produced from the composition (hereinafter sometimes referred to as "firefly" Light body sheet") can obtain uniform color. The phosphor preferably uses particles having a high degree of sphericity.

The average primary particle diameter of the phosphor can be obtained by the following method. According to the two-dimensional image obtained by observing the phosphor by a scanning electron microscope (SEM), the distance between the two intersections of the straight line intersecting the outer edge of the phosphor at two points is calculated to be the largest. And define it as the particle size. Further, the same measurement was performed on any of the 20 different phosphors, and the average value of the obtained particle diameters was defined as the average primary particle diameter. For example, when measuring the particle diameter of the phosphor present in the resin composition containing the phosphor, it can be mechanically ground, sliced, cross-section Polisher (CP), and focused ion. A method of processing a cross-section of a resin composition containing a phosphor, and then obtaining a two-dimensional image obtained by observing a polished cross section by a scanning electron microscope (SEM). For example, the average primary particle diameter was calculated in the same manner as the above method.

The amount of the phosphor which can be contained in the resin composition of the present invention is preferably from 20 parts by weight to 500 parts by weight per 100 parts by weight of the total of the component (A), the component (B) and the component (C). By setting the phosphor content within the above range, re-agglomeration of the phosphor can be prevented, and good dispersion stability can be obtained.

(Inorganic Particles) The resin composition of the present invention preferably contains inorganic particles and/or fluorenone fine particles. Examples of the inorganic particles include metal particles, metal nitride particles, metal oxide particles, metal salt particles, and the like, and in particular, metal oxide particles can be preferably used.

Examples of the metal oxide particles include cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, cerium oxide, magnesium oxide, zinc oxide, manganese oxide, copper oxide, iron oxide, cerium oxide, lead oxide, and oxidation. Tin or the like is preferably alumina in terms of being easily dispersed in the composition. By containing the inorganic particles in the resin composition of the present invention, the heat dissipation property of the resin composition is improved, and thermal deterioration of the resin can be suppressed. It is particularly preferably one or more selected from the group consisting of cerium oxide, aluminum oxide, titanium oxide, magnesium oxide, and aluminum nitride.

As the fluorenone fine particles, the fluorenone fine particles represented by the average unit formula (3) are preferable.

[Chemical 3]

Here, R ⁷ to R ⁹ are a substituted or unsubstituted alkyl group, and they may be the same or different. t, u, and w are numbers indicating the ratio of 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 the present invention, a commercially available product can also be used as the fluorenone fine particles. 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 Industry Co., Ltd.) Manufacturing); EP-5500, EP-2601, EP-2720, EP-2600, E-606 (above, manufactured by Toray Dow Corning (share)); MSP-N050, MSP-N080, NH-RAS06, MSP-TK04 , Silcrusta MK03, MSP-SN05, MSP-SN08, NH-RASN06, MSP-TKN04, MSP-150, MSP-200, MSP-3500 (above, Nikko Rica) Share) manufacturing); Tosporl 120, Tospearl 130, Tospearl 145, Tospearl 240 (above, Japan Momentive Advanced Materials Co., etc.), but not Limited to these commercial items. These commercially available products may be used singly or in combination.

By containing the fluorenone fine particles in the resin composition of the present invention, the dispersion stability of the phosphor is improved, so that the phosphor can be filled at a higher concentration. When the filling rate of the phosphor in the composition is increased, the thermal conductivity of the resin composition is increased. Therefore, heat storage of the phosphor can be prevented, and heat resistance of the resin composition can be improved.

The content of the inorganic particles and/or the fluorenone fine particles in the resin composition of the present invention is preferably 5 in terms of 100 wt% of the total of the components (A), (B) and (C). It is more than 10 parts by weight or more, more preferably 10 parts by weight or more. Further, the upper limit is preferably 50 parts by weight or less, more preferably 30 parts by weight or less.

By containing 5 parts by weight or more of inorganic particles, a particularly good heat dissipation effect can be obtained. On the other hand, by containing 50 parts by weight or less, aggregation of inorganic particles is suppressed. By containing 5 parts by weight or more of the fluorenone fine particles, a particularly good phosphor dispersion stabilizing effect can be obtained, and on the other hand, by containing 50 parts by weight or less, the viscosity of the resin composition is not excessively increased. .

The size of the inorganic particles and the fluorenone fine particles is not particularly limited, but in the volume-based particle size distribution obtained by the laser diffraction scattering particle size distribution measurement, the cumulative particle diameter from the small particle diameter side is 50%. The (D50) and/or the average primary particle diameter is preferably from 0.01 μm to 100 μm. 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.

The average primary particle diameter can be obtained by the following method similarly to the phosphor. According to a two-dimensional image obtained by observing inorganic particles and/or fluorenone microparticles by a scanning electron microscope (SEM), the distance between the two intersections of the straight line intersecting the outer edge of the particle at two points is calculated to be the largest. And define it as the particle size. Further, the same measurement was performed on any of the 20 different particles, and the average value of the obtained particle diameters was defined as the average primary particle diameter. For example, when measuring the particle diameter of inorganic particles and/or fluorene ketone microparticles present in the resin composition, mechanical milling, slicer method, CP method (Cross-section Polisher), and focused ion beam (FIB) can be used. In any of the processing methods, after the cross-section polishing of the resin composition, the two-dimensional image obtained by observing the obtained polishing cross section by a scanning electron microscope (SEM) is averaged once in the same manner as the above method. Particle size.

In addition to the above, the components used in the present embodiment may be arbitrarily blended with other components within the range in which the effects and effects of the present invention are not impaired. Specific examples thereof include a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone degradant, a light stabilizer, a tackifier, and a plasticizer. An antioxidant, a conductivity imparting agent, an antistatic agent, a radiation blocking agent, an organic solvent, and the like. These components may be used alone or in combination of two or more.

The resin composition of the present invention may also be a sheet-like formed article. In other words, it is a sheet-like molded article containing at least the components (A) and (B) and further containing the component (C). Since the resin composition is excellent in dispersion stability of the phosphor, even when it is formed into a sheet shape, the phosphor can be molded into a desired thickness at a uniform concentration. Specifically, the resin composition is applied onto a base substrate and dried to form a sheet.

A method of producing a phosphor sheet will be described. In the following, as an example, the method of producing the phosphor sheet is not limited thereto.

First, a resin composition containing a phosphor is prepared as a coating liquid for forming a phosphor sheet. The resin composition containing a phosphor is obtained by mixing a phosphor and a resin composition in a suitable solvent.

The solvent is not particularly limited as long as it is a viscosity of a resin in which the flow state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, etc. are mentioned.

The ingredients are blended in such a manner as to have a predetermined composition, and then uniformly mixed and dispersed by a stirring and kneading machine such as a homogenizer, a self-rotating mixer, a three-roll mill, a ball mill, a planetary ball mill, or a bead mill. A resin composition containing a phosphor is obtained. Defoaming may also preferably be carried out under vacuum or reduced pressure during mixing or dispersion or during mixing and dispersion.

Then, the resin composition containing the phosphor is applied onto the base substrate. The base substrate is not particularly limited, and aluminum (including aluminum alloy), metal plates or foils such as zinc, copper, and iron, cellulose acetate, glass, ceramics, and polyethylene terephthalate (Polyethylene) can be used. Terephthalate, PET) film, polypropylene (PP) film, polyphenylene sulfide (PPS) film, polyimide film, polyamide film, polycarbonate film, aromatic polyamide film, etc. . Among these, in terms of adhesion when the phosphor sheet is attached to the LED element, the base substrate is preferably a soft film. Further, in order to treat the film-form base substrate without breaking or the like, a film having high strength is preferable. In view of such required characteristics and economical efficiency, a resin film is preferred, and among these, a PET film is preferred in terms of economy and handleability. Further, in the case where curing of the resin or bonding of the phosphor sheet to the LED element requires a high temperature of 200 ° C or higher, a polyimide film is preferable in terms of heat resistance. In terms of easiness of peeling off the sheet, it is preferred to perform a mold release treatment on the surface of the base substrate in advance. The thickness of the base substrate is not particularly limited, and the lower limit is preferably 25 μm or more, and more preferably 40 μm or more. Further, the upper limit is preferably 5,000 μm or less, more preferably 3,000 μm or less.

As a coating method of the phosphor resin composition, a reverse roll coater, a blade coater, a kiss coater, a slit coater (a slit coater) can be used. A slit die coater, a direct gravure coater, an offset gravure coater, a natural roll coater, an air knife coater, Roll blade coater, vari-bar roll blade coater, two stream coater, rod coater , wire bar coater, applicator, dip coater, curtain coater, spin coater, screen printing, etc. To proceed, but is not limited to this. Among the above methods, in order to obtain film thickness uniformity, coating is preferably carried out by a slit die coater. The drying of the phosphor sheet can be carried out using a general heating device such as a hot air dryer or an infrared dryer. Further, as the heat curing of the sheet, a general heating device such as a hot air dryer or an infrared dryer can be used. In this case, the heat curing conditions are usually 40 ° C to 250 ° C for 1 minute to 5 hours, preferably 100 ° C to 200 ° C for 2 minutes to 3 hours.

The film thickness of the phosphor sheet is determined by the phosphor content and the desired optical characteristics. As described above, from the viewpoint of dispersion stability, the phosphor content has a limit, and therefore the film thickness is preferably 10 μm or more. The film thickness of the sheet-like molded article containing the phosphor is preferably 1000 μm or less, more preferably 200 μm or less, and still more preferably 100 μm, from the viewpoint of improving the optical characteristics and heat resistance of the phosphor sheet. the following. By setting the phosphor sheet to a film thickness of 1000 μm or less, heat generation from the LED element is efficiently dissipated, and heat storage in the sheet is reduced, so that heat resistance is improved.

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

Typically, LED lighting devices are in an environment that generates a significant amount of heat from the LED wafer. By such heat generation, the temperature of the phosphor rises and the active material in the phosphor is deactivated, whereby the total light beam of the light-emitting device is lowered. Therefore, it is important how to efficiently dissipate the generated heat. In the present invention, by setting the sheet thickness to the above range, a phosphor sheet excellent in heat resistance can be obtained.

Further, when the film thickness of the sheet is uneven, the amount of the phosphor varies in each of the LED chips, and as a result, unevenness occurs in the emission spectrum (color temperature, luminance, and chromaticity). Therefore, the unevenness of the film thickness of the sheet is preferably within ±5%, more preferably within ±3%.

In addition, the film thickness unevenness described here is based on the measurement method of the thickness of the thickness of the mechanical scanning by the method A of the plastic-film and sheet-thickness measurement method of JIS K7130 (1999), and the film thickness is used, and the following is used. Calculated by the formula shown.

More specifically, the measurement conditions of the thickness measurement method by the mechanical scanning method are used, and the film thickness is measured using a micrometer such as a commercially available contact type thickness gauge, and the maximum value of the obtained film thickness is calculated or The difference between the minimum value and the average film thickness, and the value expressed by the percentage after dividing the value by the average film thickness becomes the film thickness unevenness B (%).

Film thickness unevenness B (%) = {(maximum film thickness deviation value * - average film thickness) / average film thickness} × 100 * Maximum film thickness deviation value is selected from the maximum or minimum value of the film thickness, and the average film Thick and poor.

The phosphor sheet formed from the phosphor-containing resin composition of the present invention preferably has a storage elastic modulus of not less than 25 MPa at 25 ° C and a storage elastic modulus of less than 25 ° C when heated to 100 ° C and The respective storage elastic coefficients at 200 °C.

The storage elastic coefficient described herein refers to the storage elastic coefficient when the dynamic viscoelasticity measurement is performed. The so-called dynamic viscoelasticity refers to a method of decomposing the shear stress occurring in a steady state into a component corresponding to the strain phase when a shear strain is applied to the material at a certain sinusoidal frequency (elasticity). The composition) and the composition (viscosity component) which is 90° out of phase with the strain phase, and analyzes the dynamic mechanical properties of the material. Here, the stress component that matches the shear strain phase is divided by the shear strain to store the elastic coefficient G′, and represents the deformation and follow-up of the material with respect to the dynamic strain at each temperature. Sexuality or adhesion is closely related.

The storage elastic modulus of the phosphor sheet at 25 ° C is 0.01 MPa or more, and the storage elastic modulus when heated to 100 ° C is lower than the respective storage elastic coefficients at 25 ° C and 200 ° C, so if it is carried out from 25 ° C When heated, the storage elastic modulus of the sheet is lowered, and the shape of the object is rapidly deformed and followed, showing high adhesion. Therefore, the sheet can be directly attached to the LED element or the polyorganosiloxane layer formed on the element without using an adhesive. As long as a phosphor sheet having a storage elastic modulus of less than 0.01 MPa is obtained at 100 ° C, the adhesion is improved with temperature rise even if it is less than 100 ° C, but in order to obtain practical adhesion, Suitably it is above 80 °C. Further, when the phosphor sheet is heated to more than 100 ° C, the storage elastic modulus is further lowered, and the adhesion is improved. However, at a temperature exceeding 150 ° C, the components (A) and (B) are usually used. The heat hardening reaction, so the storage elastic modulus starts to rise and the adhesion decreases. Therefore, a suitable heating and attaching temperature is 50 ° C to 150 ° C.

The storage elastic modulus at 25° C. of the phosphor sheet is 0.01 MPa or more, and can be processed with high dimensional accuracy in the die blanking at room temperature (25° C.) or the cutting process using the cutting tool. For the purpose of the present invention, the upper limit of the storage elastic modulus at room temperature is not particularly limited, but it is preferably 1 GPa or less in consideration of the necessity of reducing the stress strain after bonding to the LED element. For the purpose of the present invention, the lower limit of the storage elastic modulus at 100 ° C is not particularly limited. However, if the fluidity is too high when attached to the LED element, the film thickness of the phosphor sheet cannot be maintained. Ideally it is 0.001 MPa or more.

The chromaticity of the phosphor sheet formed by the resin composition of the present invention after heat treatment at 150 ° C for 100 hours is preferably in the range of Clx ± 0.01 and Cly ± 0.01 as compared with that before the heat treatment.

The method of measuring the chromaticity of the sheet will be described. In the following, as an example, the method of measuring the chromaticity of the phosphor sheet is not limited thereto. Into a light-emitting device in which a phosphor sheet is attached to a blue LED element, a current of 20 mA is supplied to light the LED element, and an instantaneous multi-time measuring system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) is used. ) Perform the measurement. Then, the light-emitting device can be placed in a hot air oven in a state where the light-emitting device is turned on, and heat-treated at 150 ° C for 100 hours, and then measured again by the photometric system, and the chromaticity change before and after the heat treatment is calculated (maximum value and The difference between the minimum values).

The change in chromaticity of the light-emitting device to which the phosphor sheet is attached is mainly caused by deterioration of the phosphor due to high temperature and deterioration of the resin component. The phosphor sheet of the present invention can be thinned by the excellent dispersion stability of the phosphor, and can efficiently dissipate heat generated from the LED element, thereby suppressing deterioration of the phosphor.

Further, the resin component constituting the phosphor sheet is the component (A) and the component (C), and the substituent bonded to the oxime is an alkyl group, an alkenyl group, an epoxy group, an amine group, and a hydrogen atom. Therefore, even in a high-temperature environment of 150 ° C or higher, radicals are not generated in the resin structure, so that conjugate formation which is a cause of blue absorption (coloring) is not caused, and thermal deterioration is hard to occur. From the above viewpoints, the chromaticity change of the light-emitting device can be suppressed within the above range.

Further, in the light-emitting device in which the phosphor sheet is attached to the blue LED element, the light beam maintenance ratio is preferably 90 when the LED is continuously lit for 1000 hours at a temperature (Ta) of 100 ° C. %the above.

A method of measuring a light beam of a light-emitting device will be described. In addition, the following is an example, and the beam measuring method is not limited to this. Into a light-emitting device in which a phosphor sheet is attached to a blue LED element, a current of 20 mA is supplied to light the LED element, and an instantaneous multi-time measuring system (MCPD-300, manufactured by Otsuka Electronics Co., Ltd.) is used. ) Determine the full beam (initial value A). Then, the light-emitting device was placed in a hot air oven set at 100 ° C, left in a lighted state for 1000 hours, and then left to cool to 25 ° C, and the total light beam (measured value B) was measured again. Then, each measurement value was substituted into the following formula, and the beam maintenance rate was calculated. Beam maintenance rate = {(measured value B) / (initial value A)} × 100.

The phosphor sheet formed from the resin composition of the present invention and the phosphor can be attached as a wavelength conversion layer to the LED element or the fluorenone resin layer formed on the element, and used as a light-emitting device. Further, it may be attached not only to cover the upper side of the LED element but also to cover the side surface.

As a method of manufacturing a light-emitting device, when the phosphor sheet is attached to an enamel resin layer formed on the LED element or the element, the element is heated to a predetermined temperature and then attached. The heating temperature is 50 ° C or more and 200 ° C or less. When the component (C) is sufficiently softened by setting it to 50 ° C or more, the storage elastic modulus can be lowered to the extent that the phosphor sheet exhibits adhesion. Further, by setting it to 200 ° C or lower, the thermosetting reaction of the component (A) can be controlled, and the storage elastic modulus required for attachment is suitably ensured.

In order to improve the reliability of the LED light-emitting device of the present invention, it is preferable that there is no stress strain between the sheet-like molded article containing the phosphor and the LED element. Therefore, the bonding temperature is preferably set to be near the operating temperature of the LED light-emitting device, and preferably within ±20 °C of the operating temperature. At the time of lighting, the temperature of the LED lighting device rises to 70 ° C to 180 ° C. Therefore, the bonding temperature is preferably 50° C. or higher and 200° C. or lower in the sense that the operating temperature is close to the bonding temperature.

As a method of bonding the phosphor sheet to the fluorene-ketone resin layer formed on the LED element or the element, any conventional one can be used as long as it can be heated and pressure-bonded at a predetermined temperature. Device. As will be described later, there is a method in which the phosphor sheet is cut into a single sheet and then bonded to individual LED elements, and is uniformly bonded to a wafer on which the LED elements before cutting are mounted. A method of performing dicing of a wafer and cutting of a phosphor sheet by a method of dividing a phosphor sheet into a single sheet and bonding the same can be performed by a flip chip bonding machine. When uniformly attached to a wafer-level LED element, it is bonded by a heating crimping tool or the like having a heating portion of about 100 mm square. In either case, after the phosphor sheet is attached to the LED element at a high temperature, it is left to cool to room temperature, and then the base substrate is peeled off.

As a method of bonding the phosphor sheet to the side surface of the LED element, as in the above, a heat pressable device is used, but in this case, it is preferred to first attach the phosphor sheet to the melting point. It is on a thermoplastic resin base substrate of about 40 ° C to 100 ° C.

The attachment of the phosphor sheet onto the thermoplastic resin base substrate is performed by pressing the thermoplastic resin base substrate in a softened state. Therefore, the attachment temperature is preferably a temperature at which the thermoplastic resin base substrate softens and flows. Moreover, in order to prevent the residual of air accumulation, it is preferable to attach under pressure reduction of 0.01 MPa or less. A vacuum diaphragm laminator or the like can be exemplified as the manufacturing apparatus for performing such attachment, but the invention is not limited thereto.

Then, in order to bond the phosphor sheet to the side surface of the LED element, the phosphor sheet attached to the thermoplastic resin base substrate is heated to a temperature higher than the melting point of the thermoplastic resin for the base substrate, and the LED element is contacted. The pressure is laminated from the upper surface, whereby the phosphor sheet can be attached to the side surface of the LED element.

A method of cutting the phosphor sheet when it is bonded to the upper surface of the LED element will be described. There are the following methods: cutting a phosphor sheet into a single piece before attaching it to the LED element, and then attaching it to individual LED elements; and attaching the phosphor sheet to the wafer After the LED element of the stage, the method of uniformly cutting the phosphor sheet simultaneously with the cutting of the wafer.

When the cutting is performed before the attachment, the uniformly formed phosphor sheet is processed into a predetermined shape by the processing using the laser or the cutting by the cutting tool, and the division is performed. Since the processing using the laser imparts high energy, it is extremely difficult to avoid the burnt of the resin or the deterioration of the phosphor, and it is desirable to use the cutting of the blade.

In order to improve the workability, it is very important that the phosphor sheet is non-stick at 25 ° C in order to improve the workability. As a cutting method using a cutting tool, there are a method of pressing a simple cutting tool and cutting it, and a method of cutting by a rotating blade, and any method can be suitably used. As a device for cutting by a rotary blade, a device called a dicer for cutting (cutting) a semiconductor substrate into individual wafers can be suitably used. When the dicer is used, the width of the dividing line can be precisely controlled according to the thickness or condition setting of the rotating blade, so that higher cutting accuracy can be obtained than cutting by a simple cutting tool.

When the phosphor sheet in a state of being laminated with the base substrate is cut, it may be singulated together with the base substrate, or the phosphor sheet may be singulated without cutting the base substrate. Alternatively, it may be a so-called half cut that cuts into a slit line that does not penetrate the base substrate. The singulated phosphor sheet as described above is heat-compressed to the upper surface of the individual LED elements.

FIG. 1 shows an example of a procedure of bonding and dicing the singulation and LED elements when the phosphor sheet is singulated together with the base substrate. The step of FIG. 1 includes a step of cutting the phosphor sheet into a single sheet, and a step of heating the phosphor sheet cut into a single sheet and attaching it to the LED element.

In (a) of FIG. 1, the phosphor sheet 1 of the present invention in a state of being laminated with the base substrate 2 is fixed to the temporary fixing sheet 3. In the step shown in FIG. 1, since both the phosphor sheet 1 and the base substrate 2 are singulated, they are first fixed to the temporary fixing sheet 3 in an easy-to-handle manner.

Then, as shown in FIG. 1(b), the phosphor sheet 1 and the base substrate 2 are cut and singulated.

Then, as shown in FIG. 1(c), on the LED element 4 mounted on the mounting substrate 5, the singulated phosphor sheet 1 is aligned with the base substrate 2, and then as shown in FIG. (d) The crimping is performed by a heating crimping tool as shown. At this time, it is preferable to carry out the pressure bonding step under vacuum or under reduced pressure so that air is not mixed between the phosphor sheet 1 and the LED element 4.

After the pressure bonding, it was left to cool to room temperature, and then the base substrate 2 was peeled off as shown in FIG. 1(e).

Further, when the phosphor sheet is singulated in a state in which the base substrate is continuous, it can be directly and uniformly adhered to the wafer-level LED elements before the dicing.

FIG. 2 shows an example of a procedure of singulation and LED element bonding and dicing when the phosphor sheet is singulated in a state in which the base substrate is continuous. In the step of FIG. 2, the step of cutting the phosphor sheet into a single sheet and the step of heating the phosphor sheet cut into a single sheet and attaching to the upper surface of the LED element are also included. .

In the example of the step shown in FIG. 2, first, in the step shown in (b) of FIG. 2, when the phosphor sheet 1 is singulated, the base substrate 2 is not singulated. In FIG. 2(b), the base substrate 2 is not cut at all, but the base substrate 2 may be partially cut as long as it is continuous.

Then, as shown in FIG. 2(c), the singulated phosphor sheet 1 is aligned with the wafer 7 on the surface of which the LED element before cutting is formed, and is aligned.

In the step shown in FIG. 2(d), the phosphor sheet 1 is pressure-bonded to the wafer 7 on which the LED element before cutting is formed by a heating and pressing tool. At this time, at this time, it is preferable to carry out the pressure bonding step under vacuum or under reduced pressure so that air is not mixed between the phosphor sheet 1 and the LED element 4.

After the pressure is placed and cooled to room temperature, the base substrate 2 is peeled off as shown in FIG. 2(e), and then the wafer is diced to be singulated, and a single piece is obtained as shown in FIG. 2(f). LED elements with phosphor sheets.

When the phosphor sheet is uniformly attached to the wafer-level LED element before the dicing, the phosphor sheet can be cut together with the dicing of the LED element wafer after bonding.

FIG. 3 shows an example of a procedure when the phosphor sheet is bonded to the wafer and then collectively cut. The step of FIG. 3 includes a step of uniformly heating the phosphor sheet and attaching it to the upper surface of the plurality of LED elements, and a step of uniformly cutting the phosphor sheet and the LED element.

In the step of FIG. 3, the phosphor sheet 1 of the present invention is not subjected to cutting processing in advance, and as shown in FIG. 3(a), the side of the phosphor sheet 1 and the surface thereof are formed with LEDs before cutting. The wafer 7 of the component is aligned in the opposite direction.

Then, as shown in FIG. 3(b), the phosphor sheet 1 and the wafer 7 on which the LED element before cutting is formed are pressure-bonded by a heating and pressing tool. At this time, it is preferable to carry out the pressure bonding step under vacuum or under reduced pressure so that air is not mixed between the phosphor sheet 1 and the LED element 4.

After the pressure is placed and cooled to room temperature, the base substrate 2 is peeled off as shown in FIG. 3( c ), and the phosphor sheet 1 is cut and singulated simultaneously with the dicing of the wafer. A singulated LED element with a phosphor sheet is obtained as shown in (d) of 3 .

In the case of employing the steps of any of the above-described FIGS. 1 to 3, 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 of the electrode portion For the sheet, it is desirable that the portion is previously opened before the bonding of the phosphor sheet. A well-known method such as laser processing, die punching, and cutting by a cutting tool can be suitably used for the hole drilling, but laser processing causes burnt of the resin or deterioration of the phosphor, and therefore it is more preferable to use a mold. Punching processing.

When the punching process is performed, since the phosphor sheet cannot be punched after being attached to the LED element, it is necessary to perform punching processing on the phosphor sheet before attaching. By punching a mold, a hole having an arbitrary shape or size can be formed depending on the shape of the electrode of the LED element to be bonded or the like. As long as the mold is designed, the size or shape of the hole can be formed into any size or shape. However, in order not to reduce the area of the light-emitting surface, the electrode joint portion on the LED element of about 1 mm square is desirably 500 μm or less. It is formed in a size of 500 μm or less. In addition, the electrode for wire bonding or the like needs to have a certain size, and since it is at least about 50 μm, the hole is about 50 μm in comparison with the size. If the size of the hole is much larger than the electrode, the light-emitting surface is exposed to cause light leakage, and the color characteristics of the LED light-emitting device are lowered. Further, if it is much smaller than the electrode, the wire is contacted at the time of wire bonding to cause a joint failure. Therefore, it is necessary to process the small holes of 50 μm or more and 500 μm or less with high precision within ±10%.

Next, a cutting method when the phosphor sheet is bonded to the side surface of the LED element is exemplified. A manufacturing example is shown in FIG.

In FIG. 4(a), the LED element 4 is bonded to the package electrode 9 on the package substrate 5 via gold bumps 8.

(b) of FIG. 4 is a method in which the phosphor sheet 1 on the base substrate 2 is in contact with the LED element 4.

(c) of FIG. 4, after the laminate is placed in the lower chamber 13 of the vacuum diaphragm laminator 10, it is exhausted through the exhaust/suction port 11 while being heated, and the upper chamber 12 is exhausted. The lower chamber 13 is depressurized. After the pressure reduction heating is performed until the base substrate 2 flows, the upper chamber 12 is taken into the atmosphere through the exhaust/suction port 11, whereby the diaphragm 14 is inflated, and the phosphor sheet 1 is pressed by the base substrate 2, and It is attached so as to follow the light emitting surface of the LED element 4.

In (d) of FIG. 4, after the upper and lower chambers are returned to the atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 10, and after cooling, the base substrate 2 is peeled off. Then, the obtained coating body is cut at the position of the cut portion.

(e) in Fig. 4 is to obtain a monolithic LED element with a phosphor sheet. Example

Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited to the embodiments.

<Materials> A component <Synthesis Example 1> Synthesis of an alkenyl group-containing fluorenone resin (A1-1) A stirring apparatus and a Liebig cooler were placed in a 1 L three-necked flask, and methyltrimethoxydecane was added thereto. (KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) 136 g, dimethyldimethoxydecane (KBM-22, manufactured by Shin-Etsu Chemical Co., Ltd.) 24 g, trimethylethoxy decane (T1394, 13.6 g of dimethyl vinyl chlorodecane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 g of isobutyl alcohol were stirred at 20 ° C. Then, 60 g of a 0.05 N hydrochloric acid solution was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred while heating to 80 ° C for 1 hour. Then, the mixture was stirred for 1 hour while being heated to 105 °C. Then, the reaction solution was left to cool to 25 ° C, and 150 g of xylene was added for dilution. Thereafter, the reaction solution was added to a separatory funnel, and the washing operation was repeated 5 times with 300 g of pure water. Thereafter, the refining solution was heated to 110 ° C, and water was removed to obtain 100 g of a colorless transparent resin. As a result of structural analysis of the obtained resin, the average unit is

[Chemical 4]

. The colorless transparent resin had a weight average molecular weight of 5,000, a refractive index of 1.43, and a glass transition point of -30 °C. The methyl group in the organic group bonded to the ruthenium atom was 94%.

<Synthesis Example 2> Synthesis of an alkenyl group-containing fluorenone resin (A1-2) The synthesis was carried out in the same manner as in Synthesis Example 1 except that the time of heating and stirring to 105 ° C was 5 hours, to obtain a colorless transparent resin. 100 g.

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

[Chemical 5]

. The colorless transparent resin had a weight average molecular weight of 16,000, a refractive index of 1.43, and a glass transition point of -70 °C. The methyl group in the organic group bonded to the ruthenium atom was 91%.

<Synthesis Example 3> Synthesis of an alkenyl group-containing fluorenone resin (A1-3) In the same manner as in Synthesis Example 1, except that the heating and stirring to 105 ° C was carried out for 15 hours, a colorless transparent resin was obtained. 100 g. As a result of structural analysis of the obtained resin, the average unit is

[Chemical 6]

. The colorless transparent resin had a weight average molecular weight of 350,000, a refractive index of 1.43, and a glass transition point of -90 °C. The methyl group in the organic group bonded to the ruthenium atom is 96%.

<Synthesis Example 4> Synthesis of an oxime ketone resin (A2-1) containing a hydroquinone group, except that the raw material was changed from dimethyl vinyl decane (manufactured by Tokyo Chemical Industry Co., Ltd.) to dimethyl chlorodecane (Tokyo Chemical Industry Co., Ltd.) (manufactured by the company)) The synthesis was carried out in the same manner as in the synthesis example 1 of the polyorganosiloxane compound containing an alkenyl group, and 100 g of a colorless transparent resin was obtained. As a result of structural analysis of the obtained resin, the average unit is

[Chemistry 7]

. The colorless transparent resin had a weight average molecular weight of 4,500, a refractive index of 1.43, and a glass transition point of -90 °C. The methyl group in the organic group bonded to the ruthenium atom was 91%.

(B) component hardening catalyst B-1: platinum (1,3-divinyl-1,1,3,3-tetramethyldioxane) complex 1,3-divinyl-1, The platinum content of the 1,3,3-tetramethyldioxane solution was 5 wt%.

(C) component fluorenone resin C-1: SR-1000 (made by Japan Momentive Advanced Materials Co., Ltd.), having a glass transition point of 80 ° C and a weight average molecular weight of 3,800, bonded to an organic group on a ruthenium atom The methyl group is 92%. The average unit is

[化8]

.

Anthrone resin C-2: X-40-3237 (manufactured by Shin-Etsu Chemical Co., Ltd.), the glass transition point is 130 ° C, the weight average molecular weight is 6,000, and the methyl group bonded to the organic group on the ruthenium atom is 93. %. The average unit is

[Chemistry 9]

.

Anthrone resin C-3: CB-1002 (manufactured by Toray Dow Corning Co., Ltd.), the glass transition point is 160 ° C, the weight average molecular weight is 70,000, and the methyl group bonded to the organic group on the ruthenium atom is 97%. . The average unit is

[化10]

.

Anthrone resin C-4: MQ-1640 (manufactured by Toray Dow Corning Co., Ltd.), having a glass transition point of 250 ° C, a weight average molecular weight of 150,000, and a methyl group bonded to an organic group on a halogen atom is 91%. . The average unit is

[11]

.

Anthrone resin C-5: KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), the glass transition point is -100 ° C, the weight average molecular weight is 900, and the methyl group bonded to the organic group on the ruthenium atom is 90%. . The average unit is

[化12]

.

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 Corporation): 4.8 g/cm ³ , D50: 12 μm.

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

Inorganic particles <Inorganic particles 1> Alumina powder "Aeroxide" (manufactured by Aerosil, Japan) Average particle diameter D50: 13 nm Anthrone fine particles <Synthesis Example 5> Fine particles 1 A 3 L four-neck round bottom flask was equipped with a stirrer, a thermometer, a reflux tube, a dropping funnel, and a 1600 g of a 2.5 wt% aqueous ammonia solution having a pH of 12 (25 ° C) and a nonionic surfactant Emma were added to the flask. Emulgen 1108 (made by Kao (Stock)) 0.004 g. Stirring was carried out at 300 rpm, and 150 g of methyltrimethoxydecane was added dropwise from the dropping funnel over 20 minutes. Thereafter, the polymerization solution was heated to 50 ° C over 30 minutes, and stirring was continued for further 60 minutes. Then, after cooling the polymerization solution to room temperature, 10 g of ammonium acetate was added, and the mixture was stirred at 150 rpm for 10 minutes. Then, the polymerization solution was subdivided into eight 250 ml centrifuge bottles (manufactured by Nalgene Co., Ltd.) using a centrifugal separator (desktop centrifuge 4000, manufactured by Kubota Manufacturing Co., Ltd.) at 3000 rpm for 10 minutes. After the conditions of centrifugation, the supernatant was removed. Then, 200 g of pure water was added to the centrifuge bottle, and the mixture was stirred by a spatula, and then centrifuged again under the above conditions. Repeat the cleaning operation 5 times. Then, the cake remaining in the centrifuge bottle was transferred to a tub and dried at 100 ° C for 8 hours using a hot air oven to obtain 70 g of a white powder. The obtained powder has an average particle diameter (D50) of 0.5 μm and an average unit formula of

[Chemistry 13]

.

<Base substrate> Substrate 1: PET film with release agent "Cerapeel" BLK (manufactured by Toray Film Processing Co., Ltd.) Peeling force 5.7 N/50 mm <Measurement of storage elastic modulus> Measuring device : Viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments Japan, Ltd.) Geometry: Parallel disk type (15 mm) Strain: 1% Angular frequency: 1 Hz Temperature range: 25 °C to 200 °C Heating rate: 5 ° C / min Measurement environment: in the atmosphere.

<Measurement of Measurement Sample for Storage Viscoelasticity Measurement> Using a polyethylene container, the ratio of 70 parts by weight of the component (A), 0.005 parts by weight of the component (B), 30 parts by weight of the component (C), and 100 parts by weight of the phosphor were used. mixing. Then, using a planetary stirring/deaerator "Mazerustar KK-400" (manufactured by Kurabo Co., Ltd.), the mixture was stirred and defoamed at 1000 rpm for 20 minutes to obtain fluorescence. The resin composition of the body. The resin composition containing a phosphor was applied onto 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 of the obtained sheets were laminated and heated and pressure-bonded on a hot plate at 100 ° C to prepare an integrated film (sheet) of 600 μm or more, and cut into a diameter of 15 mm to prepare a measurement sample. The measurement samples prepared by the above operation were measured under the conditions described above, and the storage elastic coefficients at 25 ° C, 100 ° C, and 200 ° C are shown in Table 1.

<Adhesion evaluation> The phosphor sheet cut into 1 mm square was bonded to the LED element at 100 ° C and pressed for a predetermined period of time, and then returned to room temperature. When the base substrate was peeled off, the fluorescent material was irradiated. The minimum time during which the body sheets are all on the LED elements without remaining on the base substrate is set as the last time. The sheet-like molded article containing the phosphor at 100 ° C and the heat-pressing time of 3 minutes is all adhered to the LED element and does not remain on the base substrate. The adhesive property A is set to 100 ° C for 3 minutes. If it is not followed, but the follower is set to the adhesiveness B within 5 minutes, it will not be followed within 5 minutes, but within 10 minutes, the follower is set to the adhesive C, and the recipient will be set to follow at 150 ° C for 15 minutes. The property D is, if it is heated and pressure-bonded at 150 ° C for 15 minutes or more, and is not adhered to the LED element or even partially, and a part remains on the base substrate, and the adhesion E (adequate defect) is used.

<Color temperature unevenness> A current of 20 mA flows into an LED light-emitting device in which a phosphor sheet is mounted on an LED element to light an LED element, and an instantaneous multi-time measuring system (MCPD-3000, Otsuka Electronics) is used. Share) manufacturing) Determination of the relevant color temperature. Ten samples were prepared, and the difference between the maximum value and the minimum value of the measured correlated color temperature (CCT) was set as the color temperature unevenness.

<Evaluation of heat resistance> In an LED light-emitting device in which a phosphor sheet is mounted on an LED element, a current of 20 mA is supplied to light the LED element, and an instantaneous multi-time measuring system (MCPD-3000, Otsuka Electronics) is used. Share) Manufacturing) Determination of color. Then, the light-emitting device was placed in a hot air oven, and the heat treatment was performed at 150 ° C for 100 hours. Then, the chromaticity was measured again by the photometric system, and the chromaticity variation range before and after the heat treatment was calculated.

<Evaluation of LED beam maintenance rate> A current of 20 mA was flowed into an LED light-emitting device in which a phosphor sheet was mounted on an LED element to light an LED element, and an instantaneous multi-time metering system (MCPD-3000, Otsuka) was used. The electronic (manufacturing) production measures the full beam and sets it to the initial value A. Then, the light-emitting device was placed in a hot air oven set at 100 ° C, and placed in a lighted state for 1000 hours, and then taken out from the hot air oven, left to cool to 25 ° C, and measured by a photometric system. The beam is set to the measured value B. Then, each measurement value was substituted into the following formula, and the beam maintenance rate was calculated.

Beam maintenance rate = {(measured value B) / (initial value A)} × 100.

(Example 1) Using a polyethylene container, 56 parts by weight of an fluorenone resin A1-1, 14 parts by weight of an fluorenone resin A2-1, 30 parts by weight of an fluorenone resin C-1, and 0.005 parts by weight of hardening The ratio of the catalyst B-1 to 100 parts by weight of the phosphor D-1 was mixed. Then, using a planetary stirring/deaerator "Mazerustar KK-400" (manufactured by Kurashiki Textile Co., Ltd.), stirring and defoaming at 1000 rpm for 20 minutes to obtain a resin containing a phosphor Composition. The resin composition containing a phosphor was applied onto 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. The film thickness of the obtained sheet was measured and found to be 80 μm, and the film thickness difference was 1.5%. Then, the storage elastic 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, the adhesion of the sheet was evaluated, and as a result, the adhesiveness A was obtained. Then, the LED light-emitting device produced using the sheet was 10 of 10 lightings, and the color temperature was not 104 K, and the heat resistance (variation range) was ΔClx 0 and ΔCly 0, and the beam maintenance ratio was 100%.

(Examples 2 to 9) The amount of the fluorenone resin (C) component to be added is the same as in the first embodiment except that the ratio of the component (B) is not changed and the ratio of the component (A) to the component (C) is changed. The operation of the phosphor sheet was carried out, and the film thickness, storage elastic modulus, adhesion, color temperature unevenness, heat resistance, and beam maintenance ratio were evaluated. The results are shown in Table 1. Examples 2 to 3 are adhesive B, Examples 4 to 5 are adhesive C, and Examples 6 to 8 are adhesive D, but color temperature unevenness, heat resistance, and light beam maintenance ratio are good.

(Examples 10 to 11) Types of component (A) A phosphor sheet was produced in the same manner as in Example 1 except that the type of the component (A) was changed, and the film thickness and storage elastic modulus were measured. Evaluation of adhesion, color temperature unevenness, heat resistance, and beam maintenance rate. The results are shown in Table 2. It was found that the color temperature unevenness of Example 9 and Example 10 was suppressed as compared with Example 1, and the dispersion stability of the phosphor was improved. On the other hand, although the chromaticity variation range of heat resistance is larger than that of Example 1, it is relatively good.

(Examples 12 to 15) The type of the component (C) was prepared by the same operation as in Example 1 except that the type of the component (C) component to be added was changed, and the sheet was produced. Evaluation of film thickness, storage elastic modulus, adhesion, color temperature unevenness, heat resistance, and beam maintenance ratio. The results are shown in Table 2. The adhesion of Examples 12 to 15 decreased.

(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 the phosphor to be added was changed, and the sheet thickness and storage elasticity were performed. Evaluation of coefficient, adhesion, color temperature unevenness, heat resistance, and beam maintenance ratio. The results are shown in Table 3. In Examples 16 to 17, although the color temperature unevenness was large, it was a relatively good result.

(Examples 18 to 20) Addition effect of inorganic particles or fluorenone fine particles Example 18 was newly added with 5 wt% of inorganic particles 1, Example 19 was newly added with 20 wt% of inorganic particles 1, and Example 20 was newly added 20 A phosphor sheet was produced in the same manner as in Example 1 except for the fine particles 1 of wt%, and the sheet thickness, storage elastic modulus, adhesion, color temperature unevenness, heat resistance, and beam maintenance ratio were measured. Evaluation. The results are shown in Table 3. In Examples 18 to 20, the color temperature unevenness was improved as compared with Examples 1 to 17.

(Comparative Example 1) A phosphor sheet was produced in the same manner as in Example 1 except that the fluorenone resin (C) component was not added, and the sheet thickness, storage elastic modulus, adhesion, and color temperature unevenness were observed. Evaluation of heat resistance and beam maintenance rate. The results are shown in Table 4. The obtained sheet had a film thickness difference of 6%, and no adhesion was observed, and it was evaluated as the adhesiveness E. Further, since the sheet was not attached, evaluation of color temperature unevenness, heat resistance, and beam maintenance ratio could not be performed.

[Table 1] [Table 1]

[Table 2] [Table 2]

[Table 3] [Table 3]

[Table 4] [Table 4]

1‧‧‧Fuel sheet
2‧‧‧Support substrate
3‧‧‧ Temporary fixed sheets
4‧‧‧LED components
5‧‧‧Installation substrate
6‧‧‧heating crimping tool
7‧‧‧ wafers with LED components on the surface
8‧‧‧ Gold bumps
9‧‧‧Package electrode
10‧‧‧Vacuum diaphragm laminating machine
11‧‧‧Exhaust/suction port
12‧‧‧ upper chamber
13‧‧‧Lower chamber
14‧‧‧Separator

1 is a first example of a manufacturing procedure of an LED light-emitting device using a sheet-like molded article of the present invention. FIG. 2 is a second example of a manufacturing process of an LED light-emitting device using the sheet-shaped molded article of the present invention. FIG. 3 is a sheet using the present invention. Third Example of Manufacturing Step of LED Light Emitting Device of Shaped Product FIG. 4 is a fourth example of manufacturing procedure of LED light emitting device using the sheet shaped product of the present invention.

1‧‧‧Fuel sheet

2‧‧‧Support substrate

3‧‧‧ Temporary fixed sheets

4‧‧‧LED components

5‧‧‧Installation substrate

6‧‧‧heating crimping tool

Claims (17)

A resin composition comprising at least the following components (A) and (B), further comprising (C) component, and (A) component: 90% or more of the organic groups bonded to the ruthenium atom a methyl reactive fluorenone resin; (B) component: a curing catalyst; (C) component: a non-reactive fluorenone resin in which 90% or more of the organic groups bonded to the fluorene atom is a methyl group. The resin composition according to claim 1, wherein the component (C) comprises an anthrone resin represented by the average unit formula (2), R ⁴ to R ⁶ are a substituted or unsubstituted alkyl or alkoxy group, which may be the same or different, and k, p and s are numbers indicating the proportion of constituent units in each parenthesis, and satisfy 0.01. ≦k≦0.50, a positive number of k+p+s=1.0; m, n, q, and r are integers of 0 or more satisfying m+n=2, q+r=1; when substituted or unsubstituted alkyl bonded to a ruthenium atom When the total number of methyl groups in the group is M, M/{3k+2p+s}≧0.90 is satisfied. The resin composition according to claim 1 or 2, wherein the glass transition point of the component (A) in the resin composition is in the range of -100 ° C to 20 ° C, and the glass of the component (C) The transfer point is in the range of 50 ° C to 200 ° C. The resin composition according to any one of claims 1 to 3, further comprising a phosphor. The resin composition according to any one of claims 1 to 4, wherein when the total amount of the component (A) and the component (C) is 100% by weight, the resin composition The content of the component (C) is from 0.50 wt% to 70 wt%. The resin composition according to any one of the items 1 to 5, wherein the component (C) in the resin composition has a weight average molecular weight of 1,000 to 100,000. The resin composition according to any one of claims 1 to 6, which further comprises inorganic particles and/or fluorenone microparticles. The resin composition according to claim 7, wherein the resin composition contains inorganic particles, and the inorganic particles are selected from the group consisting of cerium oxide, aluminum oxide, titanium oxide, magnesium oxide, and aluminum nitride. More than one particle in the group. The resin composition according to claim 7, wherein the resin composition contains fluorenone microparticles, and the fluorenone microparticles are fluorenone microparticles represented by an average unit formula (3). R ⁷ to R ⁹ are a substituted or unsubstituted alkyl group, which may be the same or different, and t, u and w are numbers indicating the proportion of constituent units in each parenthesis, and satisfy 0.50≦t≦0.95, 0.05≦u+w≦0.50, t+u+w=1.0. The resin composition according to any one of claims 1 to 9, wherein the phosphor has an average primary particle diameter of 5.0 μm to 40 μm. A sheet-like molded article of the resin composition according to any one of claims 1 to 10, which is a sheet-like molded article. The sheet-like formed article according to claim 11, wherein the storage elastic modulus at 25 ° C is 0.010 MPa or more, and the storage elastic modulus (G') when heated to 100 ° C is lower than 25 ° C and 200 ° C. The respective storage elastic coefficients. A light-emitting device formed by attaching a sheet-like formed article according to any one of claims 11 to 12 to an enamel resin layer formed on an LED element or an LED element. The sheet-like molded article according to any one of claims 11 to 12, wherein the sheet-like molded article according to any one of claims 11 to 12 is attached to the side surface of the LED element. A method of producing a light-emitting device, comprising: heating a sheet-like formed article according to any one of claim 11 or 12, and attaching to a light-emitting surface or a light-emitting surface of the LED element The step of forming the fluorenone resin layer thereon. The manufacturing method according to claim 15, which comprises the step of cutting the sheet-like formed product according to any one of claim 11 or 12 into a single piece, and cutting the same The step of breaking the sheet-like formed article of the single sheet and heating it and attaching it to the fluorenone resin layer formed on the LED element or the LED element. The manufacturing method according to claim 15 or claim 16, wherein the sheet-like molded article according to any one of claim 11 or 12, wherein the sheet-like molded article has a temperature of 50 ° C or more and 200 Below °C.