KR20180088799A - Resin composition, its sheet-like molded article, and light emitting device using the same and method of manufacturing the same - Google Patents

Abstract

A resin composition containing at least the following components (A) to (C) and having excellent heat resistance and adhesion at the time of adherence, and a sheet-like molded article thereof can be provided. (A) a reactive silicone resin in which at least 90% of organic groups bonded to silicon atoms are methyl groups; (B) a curing catalyst; (C) a non-reactive silicone resin wherein at least 90% of the organic groups bonded to silicon atoms are methyl groups.

Description

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

Light emitting diodes (LEDs) have shown remarkable improvements in their luminous efficiency in recent years. In addition, the market is rapidly expanding not only in the field of vehicles such as flashlights for mobile phones, car headlights, etc., but also for general lighting, characterized by low power consumption, high numerical value, and designability. However, in replacement with a conventional lamp, a sufficient amount of light emission can not yet be obtained, and further increase in luminance of the LED is demanded.

Generally, in order to increase the brightness of an LED, a method of increasing a light emission amount by causing a high current to flow through the LED element is taken. However, since the amount of heat generated by the LED element and the amount of accumulated heat of the phosphor are increased, there is a problem that the sealing resin is thermally deteriorated and becomes colored. In order to obtain high luminescence efficiency, a silicone resin (so-called methyl silicone resin) having a methyl group bonded to a silicon atom of a Si-O repeating structure as a main chain of a sealing resin as a main component has been widely used 1).

On the other hand, in terms of luminous efficiency and cost, there has been proposed a method of attaching a sheet-shaped molding (hereinafter referred to as a phosphor sheet) containing a phosphor on an LED element (for example, refer to Patent Documents 2 to 5). In this method, compared with a method of dispensing and curing a liquid resin in which a conventionally practiced phosphor is dispersed on an LED element, it is easy to efficiently arrange a certain amount of phosphor on the LED element, and heat dissipation due to thinning of the phosphor- Excellent for improvement. In addition, by providing the phosphor sheet with the heat-fusing property and the adhesive property, it is possible to attach the phosphor sheet directly to the LED element without using an adhesive, which is conventionally essential, so that heat can be efficiently dissipated.

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

The method of directly attaching the phosphor sheet to the LED element has a heat radiation property superior to the dispensing method, while introducing a phenyl group into the molecular structure in order to impart heat fusion property.

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 is a methyl group, the adhesiveness to the LED element is insufficient, and the sheet is separated from the continuous lighting test, There is a problem that the luminance is liable to be lowered. Further, since the phosphor sheet before attachment is in an uncured state and is in a semi-solid or soft solid state, it is difficult to perform cutting or punching with high accuracy.

In Patent Document 4, a silicone resin having a softening point of 30 to 150 캜 is added to obtain an adhesive property. However, since the resin structure contains a cyclic ether group, pyrolysis tends to occur, which causes coloring of the phosphor sheet.

In Patent Document 5, softness and tackiness of the resin are obtained by controlling the morphology caused by the phenyl group of the molecular structure. However, in the case of the so-called phenylmethyl (meth) acrylate having a silicon atom bonded to a silicon atom of a Si- The silicone resin is insufficient in heat resistance and tends to cause coloration due to thermal degradation.

As described above, a phosphor sheet excellent in heat resistance and excellent in adhesion at the time of attachment was not obtained. It is an object of the present invention to provide a resin composition and a sheet compatible with these characteristics, a light emitting device manufactured using the same, and a method of manufacturing the same.

The present invention is a resin composition containing at least the following components (A) to (C).

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

(B) a curing catalyst;

(C) a non-reactive silicone resin wherein at least 90% of the organic groups bonded to silicon atoms are methyl groups.

According to the resin composition of the present invention, it is possible to provide a sheet excellent in heat resistance and adhesion at the time of adhering to an LED element. The light-emitting device manufactured by using the phosphor-containing resin composition containing the phosphor in the resin composition of the present invention or the molded article containing the phosphor-containing sheet is excellent in chromaticity uniformity, heat resistance, light resistance, and reliability.

1 is a first example of a LED light emitting device manufacturing process using a sheet-like molded article of the present invention
Fig. 2 shows a second example of the LED light emitting device manufacturing process by the sheet-form molding of the present invention
Fig. 3 is a third example of a process of manufacturing a LED light-emitting device by the sheet-form molding of the present invention
4 is a view showing a fourth example of a LED light emitting device manufacturing process using a sheet-

<Resin composition>

The resin composition of the present invention contains at least the following components (A) to (C).

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

(B) a curing catalyst;

(C) a non-reactive silicone resin wherein at least 90% of the organic groups bonded to silicon atoms are methyl groups.

Here, the organic group bonded to the silicon atom refers to all functional groups other than hydrogen bonded to the silicon atom. Further, 90% or more means that (number of methyl groups bonded to silicon atoms) / (number of organic groups bonded to silicon atoms) is 90% or more.

(Component (A))

The reactive silicone resin as the component (A) is a resin having a hydrogen atom bonded to an organic functional group or a silicon atom which can serve as a starting point of a condensation reaction and / or an addition reaction to the main chain terminal and / or side chain of the resin, To promote the curing reaction.

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

Each of R ¹ to R ³ may be the same or different and is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an epoxy group, an alkoxy group or an amino group. Provided that at least one of R ¹ to R ³ is an alkenyl group or a hydrogen atom. each of a to f is an integer of 0 or more and satisfies a + b = 3, c + d = 2, and e + f = g to j are numbers indicating the proportion of the constituent units in the respective parentheses, and are numbers satisfying g + h + j = 1.0. When the total number of methyl groups in the substituted or unsubstituted alkyl group 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 methyl, ethyl, propyl, butyl, pentyl and hexyl. Particularly preferably a methyl group.

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

The component (A) may be a single component or a mixture of plural components.

In the component (A), an alkenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom cause a hydrosilylation reaction. Therefore, 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 the organic group are carried out by ¹ H-NMR measurement, ¹³ C-NMR measurement and ²⁹ Si-NMR measurement. The ratio of the methyl group bonded to the silicon atom can be calculated from the average unit formula obtained from the above analysis.

The component (A) is preferably a liquid at 25 占 폚 in the process of producing the resin composition. Concretely, the viscosity at 25 캜 is preferably 10 mPa ∙ s or more, and 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 1,000 to 300,000, more preferably 1,500 to 100,000, and particularly preferably 2,000 to 10,000. When the weight average molecular weight is within the above range, component (C) can be uniformly mixed and kneaded when the component (C) is mixed, and the sedimentation and separation of component (C) over time can be suppressed. Within the above range, the phosphor can maintain good dispersion stability.

The weight average molecular weight of the component (A) is a value obtained by performing measurement under the following conditions using HLC-8220GPC manufactured by TOSOH CORPORATION.

Column: TSKgel Guard columnHHR-H manufactured by Tosoh Corporation, GMHHR-N

Developing solvent: tetrahydrofuran

Evolution rate: 1.0ml / min

Column temperature: 23 ° C

Standard sample: Numerical value converted using a calibration curve by monodisperse polystyrene manufactured by TOSOH CORPORATION.

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

When the glass transition point of the component (A) is within the above range, a homogeneous resin composition can be obtained when it is mixed with the component (B), the component (C) and the phosphor because it is a liquid at an ambient temperature of 20 ° C or higher. Therefore, the color temperature fluctuation of the light emitting device made of 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 (trade name: DSC6220, temperature rise rate of 0.5 DEG C / min) manufactured by Seiko Denshi Kogyo Co., Ltd.).

In the present invention, a commercially available product containing the component (A) and the component (B) may be used. For example, OE-6250, JCR6115, JCR6125, JCR6126, JCR6122, JCR6101, JCR6101UP, JCR6109, JCR6110, JCR6140, OE-6351, OE-6370M, OE-6370HF, OE- Dow Corning Co., Ltd.);

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

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

, But are not limited thereto. These commercially available products may be used alone or in combination of plural kinds.

(Component (B)).

The component (B) is preferably a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction of the alkenyl group in the component (A) and the hydrogen atom bonded to the silicon atom. Specific examples thereof include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, but there is no limitation as long as it accelerates the curing of the composition.

In the present invention, it is preferable to use a platinum catalyst having a relatively easy reaction control. Specific examples thereof include a fine platinum powder, platinum tetrachloride, a chloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. Particularly, a platinum-alkenylsiloxane complex having a low chlorine concentration 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, Alkenylsiloxanes obtained by substituting a part of methyl groups in these alkenylsiloxanes with ethyl groups or phenyl groups, and alkenylsiloxanes obtained by substituting the vinyl groups of these alkenylsiloxanes with allyl groups or hexenyl groups. Of these, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane having particularly high stability is preferable.

Examples of such reaction catalysts include SIP6829.0 (platinum carbonylvinylmethyl complex, platinum 3.0 to 3.5% concentration vinylmethyl cyclic siloxane solution), SIP6830.0 (platinum divinyltetramethyldisiloxane complex, platinum (Platinum divinyltetramethyldisiloxane complex, platinum 2.1 to 2.4% xylene solution), "SIP6832.0" (platinum cyclovinylmethylsiloxane complex , "SIP 6833.0" (platinum octylaldehyde / octanol complex, 2.0 to 2.5% platinum octanoate solution), and the like.

The content of the component (B) is preferably 0.01 to 500 ppm, more preferably 0.1 to 100 ppm, on the basis of the weight of the metal atom based on the total weight of the resin composition. Within this range, sufficient curability can be obtained, and a state in which there is no coloration after curing can be maintained.

(Component (C)) [

The non-reactive silicone resin as the component (C) refers to a resin which does not have an organic functional group which can be 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 is cured by heat, moisture and ultraviolet rays Refers to a silicone resin that does not occur.

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

R ⁴ to R ⁶ are each a substituted or unsubstituted alkyl group or alkoxy group, and they may be the same or different. k, p and s are numbers indicating the proportion of the constituent units in the respective parentheses, and are numbers satisfying 0.01? k? 0.50 and k + p + s = 1.0. m, n, q, and r are 0 or more integers satisfying m + n = 2, q + r = When M represents the total number of methyl groups in the substituted or unsubstituted alkyl group bonded to the silicon atom, 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 preferably 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. Particularly preferably, it is a methoxy group.

k and s are particularly preferably positive integers satisfying 0.02? k? 0.40 and 0.10? s? 0.90.

A commercially available product may be used as the component (C). For example, KF-7312J, KF-9021, KF-7312K, X-21-5595, KF-7312T, X-21-5616, KF- 5249L, X-21-5250, X-21-5250L and KP-562P (all manufactured by Shin-Etsu Chemical Co., Ltd.);

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

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 (manufactured by Toray Dow Corning);

, But are not limited thereto. These commercially available products may be used alone or in combination of plural kinds.

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

The preferable content of the component (C) in the resin composition of the present invention is 0.5 wt% or more, preferably 10 wt% or more when the total amount of the component (A) and the component (C) is 100 wt% More preferably 15% by weight or more, more preferably 20% by weight or more, and still more preferably 30% by weight or more. Further, it is preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 50% by weight or less. (C) content is suitable, the resin composition exhibits good adhesiveness upon heating.

The weight average molecular weight of the component (C) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 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 controlled within the range of 50 to 200 占 폚. The weight average molecular weight of the component (C) is a value obtained by measuring the weight average molecular weight of the component (A).

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

When the glass transition point of the component (C) is within the above range, when the environmental temperature is lower than 50 占 폚, the component (C) is in a solid form and no stickiness is exhibited. For this reason, when the phosphor resin composition containing the component (C) is processed into a sheet form, it can be handled easily because it does not have adhesiveness at room temperature (25 캜). Further, when the composition is heated to the glass transition point or higher of the component (C), the component (C) melts to exhibit the properties of a liquid, so that the resin composition can be softened to exhibit adhesiveness.

(Phosphor)

The resin composition of the present invention may contain a phosphor. The phosphor is a material that 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 and a part of the light emitted from the phosphor are mixed to obtain a multicolor light emitting device including white.

The above-described phosphor may be an organic or an inorganic if it can convert wavelength, but is preferably an inorganic in view of heat resistance and light resistance. Specifically, there are a phosphor emitting green light, a fluorescent material emitting blue light, a fluorescent material emitting yellow light, and a fluorescent material emitting red light.

As the inorganic fluorescent material preferably used in the present invention, 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, and β-type sialon.

As a phosphor that emits blue light, such as _{Sr 5 (PO 4) 3 Cl} : Eu, (SrCaBa) 5 (PO 4) 3 Cl: Eu, (BaCa) 5 (PO 4) 3 Cl: Eu, (Mg, Ca, Sr, at least one of _{Ba) 2 B 5 O 9 Cl} : and the like Eu, Mn: Eu, Mn, (Mg, Ca, Sr, at least one of _{Ba) (PO 4) 6 Cl} 2.

A yttrium-aluminum-aluminum oxide phosphor activated with at least cerium, a yttrium-gadolinium-aluminum oxide phosphor enumerated with at least cerium, an yttrium-aluminum-garnet oxide phosphor activated with at least cerium, Activated yttrium-gallium-aluminum oxide phosphor (so-called YAG-base phosphor). 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 one or more selected from Ce, Tb, Pr, Sm, Eu, , 0 < y < 0.5) can be used.

As the phosphor emitting red light, 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.

Examples of the phosphor which emits light by the current corresponding to the blue LED in the _{mainstream, Y 3 (Al, Ga)} 5 O 12: Ce, (Y, Gd) 3 Al 5 O 12: Ce, Lu 3 Al 5 O 12: Ce, A YAG-based phosphor such as Y ₃ Al ₅ O ₁₂ : Ce, a TAG-based phosphor such as Tb ₃ Al ₅ O ₁₂ : Ce, a (Ba, Sr) ₂ SiO ₄ : Eu-based phosphor, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce based phosphor, (Sr, Ba, Mg) 2 SiO 4: silicate-based phosphor, (Ca, Sr), such as _{Eu 2 Si 5 N 8: Eu} , (Ca, Sr) AlSiN 3: Eu, CaSiAlN 3: Eu , etc. of (Si, Al) nitride-based _{phosphor, Cax 12 (O, N)} 16: oxynitride-based fluorescent material such as Eu, addition (Ba, Sr, Ca) Si 2 O 2 N 2: Eu type phosphor, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu-based phosphor, and SrAl ₂ O ₄ : Eu and Sr ₄ Al ₁₄ O ₂₅ : Eu.

Among them, the YAG-base phosphor, the TAG-base phosphor and the silicate-base phosphor are preferably used in terms of light emission efficiency and brightness. In addition to the above, known phosphors may be used depending on the intended luminescent color for the purpose or purpose.

The average primary particle diameter of the phosphor in the present invention is preferably in the range of 5 to 40 mu m. More preferably 10 mu m or more, and more preferably 15 mu m or more. On the other hand, it is preferably 40 탆 or less, more preferably 20 탆 or less. When the average primary particle diameter of the phosphor is within the above range, the dispersed state in the composition becomes uniform and stable, so that the sheet-like molded product (hereinafter sometimes referred to as the &quot; phosphor sheet &quot; Uniformity is obtained. It is preferable that the phosphor has high sphericity.

The average primary particle diameter of the phosphor can be obtained by the following method. From the two-dimensional image obtained by observing the phosphor with a scanning electron microscope (SEM), it is calculated that the distance between the two intersections of the straight line intersecting the outer edge of the phosphor at two points is maximum, . The same measurement is carried out for any of the other 20 phosphors, and the average value of the obtained particle diameters is taken as the average primary particle diameter. For example, in the case of measuring the particle diameter of the fluorescent substance present in the fluorescent substance-containing resin composition, the particle size of the fluorescent substance contained in the fluorescent substance-containing resin composition may be measured by any one of mechanical polishing, microtome method, CP method (cross- section polisher) and focused ion beam The average primary particle diameter can be calculated from the two-dimensional image obtained by performing the end face polishing of the resin composition and observing the obtained end face of the polishing with a scanning electron microscope (SEM) in the same manner as the above method.

The amount of the fluorescent substance that can be contained in the resin composition of the present invention is preferably 20 to 500 parts by weight based on 100 parts by weight of the total of the component (A), the component (B) and the component (C). When the content of the phosphor is within the above range, re-aggregation of the phosphor is prevented, and good dispersion stability can be obtained.

(Inorganic particles)

The resin composition of the present invention preferably contains inorganic particles and / or silicon fine particles. As the inorganic particles, metal particles, metal nitride particles, metal oxide particles, metal salt particles and the like can be mentioned, but 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 and tin oxide, Alumina is preferable from the viewpoint of easiness of making. By including the inorganic particles in the resin composition of the present invention, the heat radiation property of the resin composition is improved, and thermal degradation of the resin can be suppressed. Particularly preferred is at least one selected from the group consisting of silica, alumina, titania, magnesium oxide and aluminum nitride.

The silicon fine particles are preferably silicon fine particles represented by the average unit formula (3).

Here, R ⁷ to R ⁹ are each a substituted or unsubstituted alkyl group, and they may be the same or different. t, u and w are numbers representing the proportion of the constituent units in the respective parentheses, 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 may be used as the silicon fine particles. For example, KMP-590, KMP-597, KMP-598, KMP-594, KMP-701, X-52-854, X-52-875, X-52-1621 (subject);

EP-5500, EP-2601, EP-2720, EP-2600 and E-606 (all manufactured by Toray Dow Corning);

MSP-N050, MSP-N080, NH-RAS06, MSP-TK04, SilcrustaMK03, MSP-SN05, MSP-SN08, NH- RASN06, MSP- TKN04, MSP- )My);

Tospel 120, Tospel 130, Tospel 145, Tospel 240 (Momentive Performance Materials, Japan);

, But are not limited thereto. These commercially available products may be used alone or in combination of plural kinds.

By including the silicon fine particles in the resin composition of the present invention, the dispersion stability of the phosphor is improved, so that the phosphor can be charged at a higher concentration. The higher the filling rate of the phosphor in the composition, the higher the thermal conductivity of the resin composition, the heat accumulation of the phosphor can be prevented, and the heat resistance of the resin composition can be increased.

The content of the inorganic particles and / or silicon fine particles in the resin composition of the present invention is preferably 5 parts by weight or more as a lower limit relative to 100% by weight of the total of the component (A), the component (B) and the component (C) More preferably 10 parts by weight or more. The upper limit is preferably 50 parts by weight or less, more preferably 30 parts by weight or less.

By containing at least 5 parts by weight of the inorganic particles, a particularly good heat radiation effect can be obtained. On the other hand, aggregation of the inorganic particles is suppressed by the content of 50 parts by weight or less. In the silicon fine particles, particularly good dispersing and stabilizing effect of the phosphor is obtained by containing not less than 5 parts by weight, and on the other hand, the content of not more than 50 parts by weight does not excessively increase the viscosity of the resin composition.

The size of the inorganic particles and the silicon fine particles is not particularly limited, but the volume-based particle size distribution obtained by the laser diffraction scattering particle size distribution measurement method is preferably such that the particle diameter (D50) of 50% It is preferable that the tea particle diameter is 0.01 탆 to 100 탆. When the particle diameter is within the above range, the dispersion stability of the phosphor in the resin composition can be maintained in a favorable state.

The average primary particle diameter can be obtained by the following method in the same manner as the phosphor. From the two-dimensional image obtained by observing the inorganic particles and / or silicon fine particles with a scanning electron microscope (SEM), it is calculated that the distance between the two intersections of the straight line intersecting with the outer edge of the particle is maximum, It is defined as the particle diameter. In addition, the same measurement is carried out for arbitrary 20 other particles concerned, and the average value of the obtained particle diameters is taken as the average primary particle diameter. For example, when measuring the particle diameters of the 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) , The average primary particle diameter can be calculated from the two-dimensional image obtained by observing the cross section of the obtained polishing surface with a scanning electron microscope (SEM) in the same manner as the above method.

The composition for use in the present embodiment may optionally contain other components as long as the functions and effects of the invention are not impaired. Specific examples thereof include radical inhibitors, ultraviolet absorbers, adhesion improvers, flame retardants, surfactants, preservation stabilizers, ozone deterioration inhibitors, photostabilizers, thickeners, plasticizers, antioxidants, conductivity-imparting agents, antistatic agents, . These components may be used singly or in combination of two or more kinds.

The resin composition of the present invention may be a sheet-like molded product. This is a sheet-like molded product containing at least components (A) and (B) and further containing component (C). Since the resin composition has excellent dispersion stability of the phosphor, even when the resin composition is formed into a sheet form, the phosphor can be formed into a desired thickness at a uniform concentration. More specifically, a sheet is formed by applying and drying the resin composition on a base substrate.

A manufacturing method of the phosphor sheet will be described. The following is only an example, and the manufacturing method of the phosphor sheet is not limited to this.

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

The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a flowing state. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol and the like.

These components are combined so as to have a predetermined composition, and homogeneously mixed and dispersed by a homogenizer, a self-ballasted stirrer, three rollers, a ball mill, a planetary ball mill and a bead mill to obtain a phosphor- Loses. It is also preferable to perform degassing under vacuum or reduced pressure conditions after the mixed dispersion or the mixed dispersion.

Next, the phosphor-containing resin composition is applied to the base substrate. The base substrate is not particularly limited, but may be a metal plate such as aluminum (including aluminum alloy), zinc, copper, and iron, or a metal plate such as foil, cellulose acetate, glass, ceramic, PET film, PP film, PPS film, polyimide film, A film, a polycarbonate film, an aramid film, or the like can be used. Among them, it is preferable that the base substrate is in the form of a flexible film in view of adhesiveness when the phosphor sheet is attached to the LED element. Further, a film having high strength is preferable so that there is no possibility of breakage or the like when handling a base substrate on a film. A resin film is preferable from the viewpoints of the required characteristics and economical efficiency. Of these, a PET film is preferable from the viewpoints of economy and handleability. In addition, when curing of the resin or a high temperature of 200 DEG C or more is required when bonding the phosphor sheet to the LED element, the polyimide film is preferable in terms of heat resistance. From the easiness of peeling of the sheet, it is preferable that the surface of the base substrate is treated in advance. Although the thickness of the base substrate is not particularly limited, it is preferably 25 占 퐉 or more and more preferably 40 占 퐉 or more as the lower limit. The upper limit is preferably 5000 탆 or less, more preferably 3000 탆 or less.

As a method of applying the phosphor resin composition, a reverse roll coater, blade coater, kiss coater, slit die coater, direct gravure coater, offset gravure coater, natural roll coater, air knife coater, roll blade coater, baribar roll blade coater , A twin-stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a screen printing, and the like. Of the above-mentioned methods, in order to obtain film thickness uniformity, it is preferable to apply with a slit die coater. Drying of the phosphor sheet can be performed using a general heating apparatus such as a hot air dryer or an infrared ray dryer. For heating and curing the sheet, a general heating apparatus such as a hot-air dryer or an infrared dryer is used. In this case, the heat curing is usually carried out at 40 to 250 ° C for 1 minute to 5 hours, preferably at 100 to 200 ° C for 2 minutes to 3 hours.

The film thickness of the phosphor sheet is determined from the phosphor content and desired optical characteristics. Since the phosphor content has a limit in terms of dispersion stability as described above, the film thickness is preferably 10 mu m or more. From the viewpoint of enhancing the optical characteristics and heat resistance of the phosphor sheet, the film thickness of the phosphor-containing sheet-shaped product is preferably 1000 탆 or less, more preferably 200 탆 or less, and further preferably 100 탆 or less. By setting the phosphor sheet to a film thickness of 1000 mu m or less, the heat generated from the LED element is efficiently dissipated, and the amount of heat accumulated in the sheet is reduced, thereby improving the heat resistance.

The film thickness of the phosphor sheet in the present invention is determined by the film thickness (average film thickness) measured on the basis of the method A for measuring the thickness by mechanical scanning in the method of measuring plastic-film and sheet-thickness according to JIS K7130 (1999) .

Generally, the LED light emitting device is in an environment where a large amount of heat is generated from the LED chip. Such heat generation increases the temperature of the phosphor, and the reactant in the phosphor is deactivated, thereby lowering the total flux of the light emitting device. Therefore, it is important how to efficiently dissipate generated heat. In the present invention, by setting the thickness of the sheet to the above range, a phosphor sheet excellent in heat resistance can be obtained.

Further, if there is a variation in the sheet film thickness, there is a difference in the amount of the phosphor per LED chip, resulting in a variation in emission spectrum (color temperature, luminance, chromaticity). Therefore, the fluctuation of the sheet film thickness is preferably within ± 5%, more preferably within ± 3%.

The film thickness variation referred to herein is a film thickness measurement based on the method A for measuring the thickness by mechanical scanning in the method of measuring plastic-film and sheet-thickness according to JIS K7130 (1999) Lt; / RTI &gt;

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

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

* The maximum film thickness difference value is selected when the difference between the maximum film thickness or the minimum film thickness is larger than the average film thickness.

The phosphor sheet formed from the phosphor-containing resin composition of the present invention has a storage elastic modulus at 25 캜 of 0.01 MPa or more and a storage elastic modulus at 25 캜 and 200 캜 Low.

Here, the storage elastic modulus is a storage elastic modulus when dynamic viscoelasticity measurement is performed. Dynamic viscoelasticity refers to the shear stress that appears when a material undergoes shear deformation at a sinusoidal frequency and when it reaches a steady state with a material that is in phase with the deformation (elastic component) A viscous component) and analyzing the dynamic dynamics of the material. Here, the storage modulus G 'obtained by dividing the stress component in phase with the shear strain by the shear strain represents the strain and follow-up of the material with respect to dynamic deformation at each temperature, so that it is closely related to the workability and adhesiveness of the material. .

The phosphor sheet has a storage elastic modulus at 25 캜 of at least 0.01 MPa and a storage elastic modulus at 25 캜 and 200 캜 when heated at 100 캜 is lower than the respective storage elastic moduli at 25 캜 and 200 캜, The storage elastic modulus of the sheet is lowered, and the shape of the object is rapidly deformed to conform to the shape of the object, thereby exhibiting high tackiness. For this reason, the sheet can be directly adhered onto the LED element or the polyorganosiloxane layer formed on the element, without using an adhesive. If the phosphor sheet has a storage elastic modulus at 100 deg. C of less than 0.01 MPa, adhesion at 80 deg. C or lower is favorable with increasing temperature, but 80 deg. C or higher is preferable to obtain practical adhesion. Further, such a phosphor sheet is heated more than 100 캜, the storage elastic modulus is further lowered, and the adhesiveness is improved. However, at a temperature exceeding 150 캜, the heat curing reaction between the component (A) The storage elastic modulus starts to increase and the tackiness decreases. A suitable heating attachment temperature is therefore 50 ° C to 150 ° C.

Since the storage elastic modulus at 25 占 폚 of the phosphor sheet is 0.01 MPa or more, the phosphor sheet can be processed with high dimensional accuracy in mold punching processing at room temperature (25 占 폚) or cutting processing by heating. The upper limit of the storage elastic modulus at room temperature is not particularly limited for the purpose of the present invention, but it is preferable that the upper limit of the storage elastic modulus at room temperature is 1 GPa or less considering the necessity of reducing the stress deformation after bonding with the LED element. The lower limit of the storage elastic modulus at 100 캜 is not particularly limited for the purpose of the present invention. However, if the fluidity is too high at the time of adhering to the LED element, the film thickness of the phosphor sheet can not be maintained. Do.

The phosphor sheet formed from the resin composition of the present invention preferably has a chromaticity after heat treatment at 150 占 폚 for 100 hours is in the range of Clx 占 0.01 and Cly 占 0.01 compared with that before the heat treatment.

A method of measuring the chromaticity of the sheet will be described. The following is merely an example, and the method of measuring the chromaticity of the phosphor sheet is not limited to this. A current of 20 mA is applied to the light emitting device in which the phosphor sheet is adhered to the blue LED element and the LED element is turned on and measured using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Denshi Co., Ltd.). Subsequently, the light emitting device is turned on and heated in a hot air oven at 150 DEG C for 100 hours, and then the light is measured again by a photometry 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 caused by deterioration of the phosphor due to high temperature and deterioration of the resin component. The phosphor sheet according to the present invention can be thinned by the excellent dispersion stability of the phosphor and efficiently dissipate the heat generated from the LED element, so that deterioration of the phosphor can be suppressed.

The resin component constituting the phosphor sheet is the component (A) and the component (C), and the substituent bonded to silicon is an alkyl group, an alkenyl group, an epoxy group, an amino group and a hydrogen atom. Therefore, even under a high temperature environment of 150 占 폚 or more, radicals are not generated due to the resin structure, so that formation of a conjugated system causing blue absorption (coloring) does not occur and thermal deterioration is hardly caused. From the above viewpoint, the change in chromaticity 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, it is preferable that the light flux retention ratio when the LED is continuously lit for 1000 hours at an ambient temperature (Ta) of 100 占 폚 is 90% or more.

A method of measuring the luminous flux of the light emitting device will be described. The following is only an example, and the method of measuring the luminous flux is not limited to this. A current of 20 mA is applied to the light emitting device in which the phosphor sheet is attached to the blue LED element to light the LED element and the whole luminous flux is measured using an instantaneous multi-photometry system (MCPD-300, manufactured by Otsuka Denshi Co., Ltd.) . (Initial value A) Then, the light emitting device is placed in a hot air oven set at 100 DEG C, left in a lighting state for 1000 hours, then cooled to 25 DEG C, and the total luminous flux is measured again. (Measurement value B) Subsequently, each measurement value is substituted into the following equation to calculate the light flux retention rate.

Luminous flux maintenance rate = {(measured value B) / (initial value A)} x 100.

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

As a manufacturing method of the light emitting device, when attaching the phosphor sheet on the LED element or the silicon resin layer formed on the element, the element is heated to a predetermined temperature and attached. The heating temperature is not less than 50 ° C and not more than 200 ° C. By setting the temperature at 50 占 폚 or higher, the component (C) is sufficiently softened, and the storage modulus can be lowered to such an extent that the phosphor sheet exhibits adhesiveness. By controlling the temperature to 200 占 폚 or less, the thermosetting reaction of the component (A) can be controlled, and the storage modulus necessary for adhesion can be appropriately secured.

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 deformation between the fluorescent substance-containing sheet-like molded product and the LED element. Therefore, it is preferable that the junction temperature is set to be within the vicinity of 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. Therefore, the junction temperature is preferably not less than 50 DEG C and not more than 200 DEG C in the sense of bringing the operating temperature close to the junction temperature.

As a method of bonding the phosphor sheet onto the LED element or the silicone resin layer formed on the element, any existing apparatus can be used as long as it can be hot-pressed at a predetermined temperature. As described later, the phosphor sheet is cut into individual pieces and bonded to individual LED elements, and a method in which dicing of the wafer and cutting of the phosphor sheet are performed through a batch bonding to a wafer on which the LED element before dicing is formed A flip chip bonder can be used in the case of a method in which the phosphor sheet is divided and then bonded. When collectively attaching to wafer-level LED elements, they are bonded by a heat-pressing tool having a heating portion of about 100 mm square. In all cases, the phosphor sheet is adhered to the LED element at a high temperature, and then is cooled to room temperature, and the base substrate is peeled off.

As a method of bonding the phosphor sheet to the side surface of the LED element, the above-mentioned apparatus capable of heating and pressing can be used. In this case, however, the phosphor sheet is first attached to the thermoplastic resin base substrate having a melting point of about 40 to 100 캜 desirable.

The attachment of the phosphor sheet to the thermoplastic resin base substrate is performed by pressing under a state in which the thermoplastic resin base substrate is softened. Therefore, the attachment temperature is preferably such a temperature that the thermoplastic resin base substrate softens and flows. Further, in order to prevent the remaining air, it is preferable to carry out the adhesion under a reduced pressure of 0.01 MPa or less. A vacuum diaphragm laminator or the like is exemplified as a manufacturing apparatus for performing such attachment, but there is no limitation thereto.

Next, 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 not lower than the melting point of the thermoplastic resin used for the base substrate, The phosphor sheet can be bonded to the side surface of the LED element.

A method of cutting a phosphor sheet when it is bonded to the upper surface of the LED element will be described. The phosphor sheet is preliminarily cut into individual pieces before being attached to the LED element, and the phosphor sheet is attached to the individual LED elements. A method of attaching the phosphor sheet to the wafer level LED element is followed by cutting the phosphor sheet collectively at the same time as dicing the wafer There is a way.

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

In order to improve the workability in cutting with a blade, it is very important that there is no tag at 25 DEG C of the phosphor sheet. As a method of cutting with a blade, there are a method of cutting a simple blade by press-fitting and a method of cutting by a rotating blade, all of which can be suitably used. As a device for cutting by a rotary blade, a device used for cutting (dicing) a semiconductor substrate called a die stop into individual chips can be suitably used. By using the dicer, the width of the divided line can be precisely controlled by setting the thickness and condition of the rotary blade, so that higher processing accuracy can be obtained than when cutting is performed by simply pressing the blade.

When the base substrate and the phosphor sheet in the stacked state are cut, the base substrate may be divided into individual pieces or the base sheet may not be cut while the phosphor sheet is separated. Alternatively, the base substrate may be a so-called half cut in which a not-penetrated infeed line is inserted. The phosphor sheet thus separated is heat-pressed on the upper surface of the individual LED element.

FIG. 1 shows an example of the steps of individualization, LED element bonding and dicing when the phosphor sheet is divided into pieces per base substrate. The step of Fig. 1 includes a step of cutting the phosphor sheet with individual pieces, and a step of heating the phosphor sheet cut by the individual pieces and attaching the sheet to the LED element.

Fig. 1 (a) shows the phosphor sheet 1 of the present invention in a state of being laminated with the base substrate 2, which is fixed to the temporary fixing sheet 3. Fig. In the process shown in Fig. 1, since the phosphor sheet 1 and the base substrate 2 are both separated, they are fixed to the temporary fixing sheet 3 for easy handling.

Next, as shown in Fig. 1 (b), the phosphor sheet 1 and the base substrate 2 are cut into individual pieces.

Subsequently, as shown in Fig. 1 (c), the separated phosphor sheet 1 and the base substrate material 2 are aligned on the LED element 4 mounted on the mounting substrate 5, As shown in Fig. 1 (d). At this time, it is preferable that the pressing step is performed under vacuum or under reduced pressure so that air does not enter between the phosphor sheet 1 and the LED element 4. [

After compression, the substrate is cooled to room temperature, and the base substrate 2 is peeled off as shown in Fig. 1 (e).

In the case where the phosphor sheet is divided into pieces as the base substrate continues to be continuous, they may be adhered to the wafer level LED element before dicing as they are.

Fig. 2 shows an example of the steps of discretization, LED element bonding and dicing in the case of disposing the phosphor sheet as the base substrate is continuous. The step shown in Fig. 2 also includes a step of cutting the phosphor sheet with individual pieces, and a step of heating the phosphor sheet cut with the corresponding piece to adhere to the upper surface of the LED element.

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

Next, as shown in Fig. 2 (c), the individualized phosphor sheet 1 is positioned so as to face the wafer 7 on which the LED element before dicing is formed on the surface.

In the step shown in Fig. 2 (d), the wafer 7 having the phosphor sheet 1 and the LED element before dicing formed on the surface thereof is pressed by means of a hot press tool. At this time, it is preferable that the pressing step is performed under vacuum or under reduced pressure so that air does not enter between the phosphor sheet 1 and the LED element 4 at this time.

2 (e), the base substrate 2 is peeled off, and then the wafer is diced into individual pieces, and as shown in FIG. 2 (f) Thereby obtaining an LED element with a sheet.

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

FIG. 3 shows an example of a process in which dicing is performed collectively after bonding a phosphor sheet and a wafer. The step of Fig. 3 includes a step of heating and attaching the phosphor sheet on the upper surface of the plurality of LED elements collectively, and a step of collectively dicing the phosphor sheet and the LED element.

In the process of Fig. 3, the phosphor sheet 1 of the present invention is not subjected to cutting processing in advance, and the phosphor sheet 1 side as shown in Fig. 3 (a) 7).

Next, as shown in Fig. 3 (b), the wafer 7 having the phosphor sheet 1 and the LED element before dicing formed on the surface thereof is pressed by a hot press tool. At this time, it is preferable that the pressing step is performed under vacuum or under reduced pressure so that air does not enter between the phosphor sheet 1 and the LED element 4. [

After the base member 2 was peeled off as shown in Fig. 3 (c), the wafer was diced and the phosphor sheet 1 was cut into individual pieces, d), an LED element with a discrete phosphor sheet is obtained.

In the case where the phosphor sheet of the present invention is attached to the LED element having the electrode on the upper surface, the phosphor sheet of the electrode portion is removed before the bonding of the phosphor sheet, It is preferable to punch the portion. Known methods such as laser processing, die punching and cutting by a blade can be suitably used for punching, but laser machining causes punching of the resin and deterioration of the phosphor, and therefore punching by a die is more preferable.

In the case of performing the punching process, since the punching process can not be performed after the phosphor sheet is attached to the LED element, it is necessary to perform the punching process on the phosphor sheet before attachment. In the punching process by the mold, holes of an arbitrary shape and size can be punched by the electrode shape of the LED element to be bonded. The size and the shape of the hole can be arbitrarily determined by designing the metal mold. However, it is preferable that the electrode joint portion on the LED element of about 1 mm in each case is not larger than 500 탆 in order not to reduce the area of the light emitting surface, Depending on the size. In addition, an electrode for wire bonding or the like needs a certain size and has a size of at least about 50 mu m, so the hole is about 50 mu m depending on its size. If the size of the hole is too large as compared with 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 the electrode is too small, the wire contacts the wire at the time of wire bonding, thereby causing defective 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 accuracy within ± 10%.

Next, a cutting method for joining the phosphor sheet to the side surface of the LED element will be exemplified. A production example is shown in Fig.

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

The phosphor sheet 1 on the base substrate 2 of FIG. 4 (b) is brought into contact with the LED element 4 to be laminated.

4 (c), the laminate is placed in the lower chamber 13 of the vacuum diaphragm laminator 10 and then exhausted through the exhaust / air inlet 11 while heating to separate the upper chamber 12 and the lower chamber 13 Decompressed. The diaphragm 14 is inflated by sucking air through the exhaust / air inlet 11 to the upper chamber 12 after the reduced pressure heating is performed until the base substrate 2 flows, The sheet 1 is pressed and attached so as to follow the light emitting surface of the LED element 4. [

After returning the upper and lower chambers to the atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 10, and the base substrate 2 is peeled off after air cooling. Subsequently, the thus obtained coated body is cut at the position of the cut portion.

Fig. 4 (e) shows a disassembled LED element with a phosphor sheet.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited thereto.

<Raw materials>

Component A

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

(KBM-13, manufactured by Shinetsu Chemical Industry Co., Ltd.), 136 g of dimethyldimethoxysilane (KBM-22, available from Shin-Etsu Chemical Co., Ltd.) , 13 g of trimethylethoxysilane (T1394, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 10 g of dimethylvinylchlorosilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 120 g of isobutyl alcohol were placed, 0.0 &gt; 20 C. &lt; / RTI &gt; Subsequently, 60 g of a 0.05 N hydrochloric acid solution was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred for 1 hour while heating to 80 캜. Subsequently, the mixture was stirred for 1 hour while heating to 105 캜. Subsequently, the reaction solution was allowed to stand still at 25 DEG C and diluted with 150 g of xylene. Thereafter, the reaction solution was put into a separating funnel, and the washing operation was repeated five times with 300 g of pure water. Thereafter, the purified solution was heated to 110 DEG C and water was removed to obtain 100 g of a colorless transparent resin. As a result of the structural analysis of the obtained resin,

Respectively. 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 占 폚. Of the organic groups bonded to the silicon atom, the methyl group was 94%.

Synthesis Example 2 Synthesis of Alkenyl Group-Containing Silicone Resin (A1-2)

100 g of a colorless transparent resin was obtained by synthesizing in the same manner as in Synthesis Example 1 except that the heating and stirring at 105 DEG C were for 5 hours.

As a result of the structural analysis of the obtained resin,

Respectively. 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 占 폚. Among the organic groups bonded to the silicon atom, the methyl group was 91%.

Synthesis Example 3 Synthesis of Alkenyl Group-Containing Silicone Resin (A1-3)

100 g of a colorless transparent resin was obtained by synthesizing in the same manner as in Synthesis Example 1, except that the heating and stirring were carried out at 105 캜 for 15 hours. As a result of the structural analysis of the obtained resin,

. 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 占 폚. The methyl group bonded to the silicon atom was 96%.

SYNTHESIS EXAMPLE 4 Synthesis of Hydrosilyl Group-Containing Silicone Resin (A2-1)

Synthesis was carried out in the same manner as in Synthesis Example 1 of alkenyl group-containing polyorganosiloxane compound 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.) To obtain 100 g of a colorless transparent resin. As a result of the structural analysis of the obtained resin,

. 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 占 폚. Among the organic groups bonded to the silicon atom, the methyl group was 91%.

Component (B)

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

(C) Component

Silicone resin C-1: SR-1000 (manufactured by Momentive Performance Materials Japan), glass transition point 80 캜, weight average molecular weight 3,800, and methyl group in organic groups bonded to silicon atom was 92%. The average unit formula

.

Silicone resin C-2: X-40-3237 (manufactured by Shin-Etsu Chemical Co., Ltd.), glass transition point of 130 占 폚, weight average molecular weight of 6,000, and the methyl group bonded to the silicon atom was 93%. The average unit formula

Respectively.

Silicone resin C-3: CB-1002 (manufactured by Toray-Dow Corning Incorporated), glass transition point 160 캜, weight average molecular weight 70,000, and the methyl group bonded to the silicon atom was 97%. The average unit formula

.

Silicone resin C-4: MQ-1640 (manufactured by Toray-Dow Corning Incorporated), glass transition point 250 캜, weight average molecular weight 150,000, and the methyl group bonded to the silicon atom was 91%. The average unit formula

.

Silicone resin C-5: KR-515 (manufactured by Shin-Etsu Chemical Co., Ltd.), glass transition point -100 占 폚, weight average molecular weight 900, and the methyl group bonded to silicon atom was 90%. The average unit formula

Respectively.

Phosphor

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

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

Phosphor D-3: "EY4254" ( Intematix ( Ltd.)), specific ^{gravity: 4.7g / cm 3, D50:} 16㎛).

Inorganic particle

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

Silicon fine particles

&Lt; Synthesis Example 5 >

A stirrer, a thermometer, a reflux condenser, and a dropping funnel were placed in a 3 L four-neck round bottom flask, and 1600 g of a 2.5 wt% aqueous ammonia solution of pH 12 (25 ° C) 0.004 g) was added. 150 g of methyltrimethoxysilane was added dropwise from the dropping funnel over 20 minutes while stirring at 300 rpm. Thereafter, the polymerization solution was heated to 50 DEG C over 30 minutes, and stirring was further continued for 60 minutes. Subsequently, the polymerization solution was cooled to room temperature, 10 g of ammonium acetate was added, and the mixture was stirred at 150 rpm for 10 minutes. Subsequently, the polymerization solution was subdivided into 8 pieces of 250 ml of Myonchi (manufactured by Nalgene KK) and centrifuged at 3000 rpm for 10 minutes using a centrifugal separator (table top centrifuge 4000, manufactured by Kubota Seisakusho Co., Ltd.) After that, the supernatant was removed. Subsequently, 200 g of pure water was added to the prescription bottle, stirred with a spatula, and centrifuged again under the above conditions. The washing operation was repeated five times. Then, the remaining cake was transferred to a bucket and dried in a hot air oven at 100 DEG C for 8 hours to obtain 70 g of a white powder. The average particle diameter (D50) of the obtained powder was 0.5 mu m, and the average unit formula

.

<Base substrate>

Substrate 1: PET film with releasing agent "Serafil" BLK (manufactured by Toray Film Processing Co., Ltd.)

Peel force 5.7N / 50mm

&Lt; Measurement of storage elastic modulus &

Measuring device: Viscoelasticity measuring device ARES-G2 (TA Instrument Japan Co., Ltd.)

Geometry: Parallel disk (15mm)

Variation: 1%

Each frequency: 1Hz

Temperature range: 25 캜 to 200 캜

Heating rate: 5 ° C / min

Measuring Atmosphere: Atmosphere.

&Lt; Measurement sample adjustment of storage viscoelasticity measurement >

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 fluorescent substance were mixed using a polyethylene container. Thereafter, a phosphor-containing resin composition was obtained by using a planetary stirring and defoaming device "Mazerstar KK-400" (manufactured by Kurabo Industries, Ltd.) with stirring and degassing at 1000 rpm for 20 minutes. The phosphor-containing resin composition was coated on the substrate 1 using a slit die coater and heated at 100 占 폚 for 1 hour and dried to obtain a semi-cured phosphor sheet. Eight sheets thus obtained were laminated and heated and pressed on a hot plate at 100 占 폚 to prepare an integrated film (sheet) of 600 占 퐉 or more, and cut into a diameter of 15 mm to obtain a measurement sample. Each measurement sample produced by the above operation was measured under the above conditions, and the storage elastic modulus at 25 ° C, 100 ° C, and 200 ° C is shown in Table 1.

&Lt; Evaluation of adhesiveness &

The phosphor sheet cut at 1 mm square was bonded to the LED element at 100 ° C for a predetermined time and returned to the room temperature. When the base substrate was peeled off, the phosphor sheet adhered to the LED element and left on the base substrate The time was set as the sticking time. All of the molded articles on the fluorescent substance-containing sheet in the heat-press contact time of 100 ° C and not remaining on the base substrate are referred to as adhesiveness A, and those which are not bonded within 3 minutes at 100 ° C, Adhesion B is defined as Adhesion C, which is not adhered in 5 minutes but Adhesion C in 10 minutes, Adhesive D is adhered within 150 minutes at 15O 0 C, (Adhesion failure) in the case where a part is left on the base substrate even if it is not adhered to the base substrate or partially adhered to the base substrate.

<Color temperature variation>

A correlated color temperature was measured using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Denshi Co., Ltd.) by turning on the LED element by passing a current of 20 mA through the LED light emitting device in which the phosphor sheet was mounted on the LED element. Ten samples were made and the difference between the maximum and minimum values of the correlated color temperature (CCT) measured was regarded as the color temperature variation.

&Lt; Evaluation of heat resistance &

The LED device was turned on by flowing a current of 20 mA to the LED light emitting device in which the phosphor sheet was mounted on the LED device and the chromaticity was measured using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Denshi Co., Ltd.). Subsequently, the light emitting device was turned on and heated in a hot air oven at 150 DEG C for 100 hours. Then, the chromaticity was re-measured in the photometric system, and the fluctuation of chromaticity before and after the heat treatment was calculated.

&Lt; Evaluation of LED luminous flux maintenance rate &

The LED device was turned on by flowing a current of 20 mA to the LED light emitting device in which the phosphor sheet was mounted on the LED device and the total luminous flux was measured using an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Denshi Co., Ltd.) The initial value A was defined as this. Then, the light emitting device was placed in a hot air oven set at 100 DEG C and left in a lighting state for 1000 hours, then taken out from the hot air oven and allowed to cool to 25 DEG C, B, respectively. Next, each measured value was substituted into the following equation to calculate the light flux retention rate.

Luminous flux maintenance rate = {(measured value B) / (initial value A)} x 100.

(Example 1)

56 parts by weight of the silicone resin A1-1, 14 parts by weight of the silicone resin A2-1, 30 parts by weight of the silicone resin C-1, 0.005 parts by weight of the curing catalyst B-1, 1 were mixed at a ratio of 100 parts by weight. Thereafter, a phosphor-containing resin composition was obtained by using a planetary stirring and defoaming device "Mazerstar KK-400" (manufactured by Kurabo Industries, Ltd.) with stirring and degassing at 1000 rpm for 20 minutes. The phosphor-containing resin composition was coated on the substrate 1 using a slit die coater and heated at 100 占 폚 for 1 hour and dried to obtain a semi-cured phosphor sheet. The film thickness of the obtained sheet was measured and found to be 80 탆, and the film thickness difference was 1.5%. Then, the storage elastic modulus of the sheet at each temperature was 0.15 MPa (25 캜), 0.03 MPa (100 캜), and 0.25 MPa (200 캜). Subsequently, the adhesive property of the sheet was evaluated. As a result, the adhesive property A was obtained. Subsequently, ten LED light emitting devices manufactured using the sheet were turned on, ten color temperature fluctuations were 104 K, heat resistance (fluctuation width) was ΔClx 0, ΔCly 0, and the luminous flux retention ratio was 100%.

(Examples 2 to 9) Amount of silicone resin (C) added

A phosphor sheet was prepared in the same manner as in Example 1 except that the ratio of the component (A) to the component (C) was changed without changing the ratio of the component (B) Color temperature fluctuation, heat resistance, and luminous flux maintenance rate were evaluated. The results are shown in Table 1. The adhesiveness B in Examples 2 to 3, the adhesiveness C in Examples 4 to 5, and the adhesiveness D in Examples 6 to 8 were good, but the color temperature variation, heat resistance, and light flux retention were good.

(Examples 10 to 11) [0154]

A phosphor sheet was produced in the same manner as in Example 1 except that the kind of the component (A) was changed, and the sheet thickness, the storage elastic modulus, the adhesion, the color temperature variation, the heat resistance and the light flux retention were evaluated. The results are shown in Table 2. Compared with Example 1, the color temperature fluctuations of Examples 9 and 10 were suppressed and the dispersion stability of the phosphor was improved. On the other hand, the fluctuation range of chromaticity of the heat resistance was larger than that of Example 1, but was relatively good.

(Examples 12 to 15) (C)

A phosphor sheet was prepared in the same manner as in Example 1 except that the kind of the silicone resin (C) to be added was changed, and the sheet thickness, the storage elastic modulus, the adhesion, the color temperature variation, the heat resistance and the light flux retention were evaluated . The results are shown in Table 2. The adhesiveness of Examples 12 to 15 was lowered.

(Examples 16 to 17) Types of phosphors

A phosphor sheet was produced in the same manner as in Example 1 except that the kind of the phosphor to be added was changed, and the sheet film thickness, storage elastic modulus, adhesion, color temperature variation, heat resistance and luminous flux maintenance rate were evaluated. The results are shown in Table 3. In Examples 16 to 17, although the color temperature fluctuation was large, it was a relatively good result.

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

Example 18 was the same as Example 1 except that 5% by weight of the inorganic particles (1), 20% by weight of the inorganic particles (1) in Example 19 and 20% by weight of the fine particles (1) 1, and evaluated for sheet film thickness, storage elastic modulus, adhesive color temperature variation, heat resistance, and light flux retention ratio. The results are shown in Table 3. In Examples 18 to 20, the color temperature fluctuation was improved as compared with 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, adhesive color temperature variation, heat resistance, and light flux retention were evaluated. The results are shown in Table 4. The resulting sheet had a film thickness difference of 6% and no adhesion was exhibited. Further, since the sheet was not adhered, it was impossible to evaluate the color temperature variation, heat resistance, and light flux retention ratio.

1 phosphor sheet
2 support substrate
3 temporary fixing sheet
4 LED elements
5 mounting substrate
6 Hot pressing tool
7 Wafer formed on the surface of LED element
8 gold bump
9 package electrode
10 Vacuum Diaphragm Laminator
11 Exhaust / intake port
12 upper chamber
13 Lower chamber
14 Diaphragm

Claims (17)

A resin composition comprising at least the following components (A) and (B), and further containing a component (C).
(A): a reactive silicone resin in which at least 90% of organic groups bonded to silicon atoms are methyl groups;
Component (B): curing catalyst;
(C): a non-reactive silicone resin in which at least 90% of organic groups bonded to silicon atoms are methyl groups. The resin composition according to claim 1, wherein the component (C) comprises a silicone resin represented by the average unit formula (2).

(Wherein R ⁴ to R ⁶ are a substituted or unsubstituted alkyl group or alkoxy group, and may be the same or different), k, p and s are numbers representing the proportion of constituent units in the respective parentheses, 0.01? K? m, n, q and r are integers of 0 or more satisfying m + n = 2 and q + r = 1. The substituted or unsubstituted When the total number of methyl groups in the alkyl group is M, M / {3k + 2p + s}? 0.90 is satisfied. 3. 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 to 20 占 폚 and the glass transition point of the component (C) is in the range of 50 to 200 占 폚. The resin composition according to any one of claims 1 to 3, further comprising a phosphor. The positive resist composition according to any one of claims 1 to 4, wherein the content of the component (C) in the resin composition is 0.50 to 70% by weight when the total amount of the component (A) and the component (C) Lt; / RTI &gt; The resin composition according to any one of claims 1 to 5, wherein the weight average molecular weight of the component (C) in the resin composition is 1,000 to 100,000 in terms of polystyrene. The resin composition according to any one of claims 1 to 6, further comprising inorganic particles and / or silicon fine particles. The resin composition according to claim 7, wherein the resin composition comprises inorganic particles, and the inorganic particles are at least one particle selected from the group consisting of silica, alumina, titania, magnesium oxide and aluminum nitride. The resin composition according to claim 7, wherein the resin composition comprises silicon fine particles, and the silicon fine particles are silicon fine particles represented by an average unit formula (3).

(Wherein R ⁷ to R ⁹ are each a substituted or unsubstituted alkyl group and may be the same or different), t, u and w are numbers representing the ratio of the constituent units in the parentheses, 0.50? T? w? 0.50, and t + u + w = 1.0. 10. The resin composition according to any one of claims 1 to 9, wherein the phosphor has an average primary particle diameter of 5.0 to 40 mu m. A sheet-form molding of the resin composition according to any one of claims 1 to 10. The method according to claim 11, wherein the storage elastic modulus at 25 占 폚 is 0.010 MPa or more and the storage elastic modulus (G ') when heated at 100 占 폚 is lower than the storage elastic modulus at 25 占 폚 and 200 占 폚 Sheet - shaped moldings. A light-emitting device in which the sheet-like molded article according to claim 11 or 12 is adhered onto a LED element or a silicon resin layer formed on an LED element. 14. The light emitting device according to claim 13, wherein the sheet-like molded article according to claim 11 or 12 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 adhering a sheet-shaped molding according to claim 11 or 12 to a silicone resin layer formed on a light emitting surface or an emitting surface of an LED element. The method according to claim 15, further comprising a step of cutting the sheet-form molding according to claim 11 or 12 into individual pieces, and heating the sheet-shaped product cut with the individual pieces to adhere to the silicone resin layer formed on the LED element or the LED element &Lt; / RTI &gt; The method of manufacturing a light-emitting device according to claim 15 or 16, wherein the temperature for adhering the sheet-form molding according to claim 11 or 12 is 50 ° C or more and 200 ° C or less.

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