CN105765744B

CN105765744B - Fluorescencer composition, fluorophor sheet material, fluorophor sheet material lamilate and the LED chip, LED package and its manufacturing method that have used them

Info

Publication number: CN105765744B
Application number: CN201480057773.1A
Authority: CN
Inventors: 石田丰; 重田和树; 诹访充史
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2013-10-24
Filing date: 2014-10-21
Publication date: 2019-01-22
Anticipated expiration: 2034-10-21
Also published as: CN105765744A; JPWO2015060289A1; KR20160075495A; TWI657599B; KR102035511B1; WO2015060289A1; TW201521238A

Abstract

The present invention relates to a kind of fluorescencer compositions, it contains fluorophor, matrix resin and metallic compound particle, it is characterized in that, the refractive index of the metallic compound particle is 1.7 or more, and average grain diameter is 1~50nm, the refractive index N2 of the mean refractive index N1 of the metallic compound particle and described matrix resin and the fluorophor meets following relationship, being grafted of metallic compound particle.Pass through above-mentioned fluorescencer composition etc., it is possible to provide sheet material can be made by a coating process and can be improved the fluorescencer composition for applying the brightness of LED package of the fluorescencer composition.0.20 >=| N1-N2 |.

Description

Fluorescencer composition, fluorophor sheet material, fluorophor sheet material lamilate and them are used LED chip, LED package and its manufacturing method

Technical field

The present invention relates to fluorescencer composition, fluorophor sheet material, fluorophor sheet material lamilate and the LED cores for having used them Piece, LED package and its manufacturing method.

Background technique

For light emitting diode (LED), with significantly improving as background for luminous efficiency, with low-power consumption, the high life, set Meter property etc. is liquid crystal display (LCD) backlight, the car-mounted head (headlight), spotlight, general illumination of advantage With on the way, sharply expand its market.

Since the luminescent spectrum of LED depends on being formed the material of LED, so its luminescent color is limited.Therefore, in order to use LED obtains the white light of LCD backlight, general illumination, needs to configure the fluorescence matched with each chip on LED chip Body, conversion emission wavelength is to obtain white light.Specifically, it has been proposed that configure yellow on the LED chip for the coloured light that turns blue The method of fluorophor, is emitting ultraviolet light at the method that red and green fluorophor is configured on the LED chip for the coloured light that turns blue Red, green, method of fluorophor of blue etc. are configured on LED chip.In these methods, from the luminous efficiency of LED chip, at Present aspect considers, the method for yellow fluorophor is configured on blue LED die and is configured on blue LED die red and green The method of the fluorophor of color is most widely used at present.

As one of the specific method for configuring fluorophor on LED chip, high concentration will be evenly distributed with by proposing The resin preforming of fluorophor be sheet and carry out using method (fluorophor sheet material method) (for example, with reference to patent document 1). In this method, by being sheet by the resin preforming containing the fluorophor of high concentration, uniform film thickness and glimmering can be obtained Body of light concentration distribution and light resistance.Therefore, when being attached at LED package, LED chip, it is able to suppress the face of LED package Colo(u)r bias.But since the refractive index of LED chip, resin of the refractive index than containing in fluorophor sheet material of fluorophor is high, because This, the reflection of LED chip, phosphor interfaces causes the light for failing to generate in LED chip fully to extract to outside.

In order to inhibit the reflection as caused by refringence, it is investigated the sequence by the different film of refractive index by refractive index Scheme that is laminated, making refractive index consecutive variations.Such as, it has been proposed that following proposal: by be formed with refractive index it is different 2~20 The sealant of layer, the refractive index n of undermost sealant (the 1st sealant)₁In the range of 1.55~1.85, top layer it is close The refractive index n of sealing (the n-th sealant, n=2~20)_nIn the range of 1.30~1.65, at least 2 layers or more of refractive index is not Same sealant is laminated by the sequence of refractive index height, and each sealant includes hydrophobic zirconium particle and/or hydrophobicity titanium dioxide Silicon systems hollow-particle and matrix resin, to form refractive index gradient (for example, with reference to patent document 2).

In addition, also disclosing following the description: making to configure the conversion layer on LED chip and contain fluorescer, adhesive material With multiple nanoparticles, in such a way that the refractive index with fluorescer particle is closely coordinated by nanoparticle dispersion (for example, with reference to Patent document 3).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 5-152609 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2012-121941 bulletin

Patent document 3: No. 5227252 bulletins of Japan Patent

Summary of the invention

Problems to be solved by the invention

But due in the above-mentioned methods, it is etched on LED chip using dry ecthing etc. or repeatedly laminated refraction The different thin layer etc. of rate, technique number increases, so there are the projects of increased costs.In addition, there is also the brightness of LED package not The project of raising.

Brightness especially for LED package does not improve this point, the inventor of the present application discovered that it is by following 2 originals Because caused by.(1) using the conversion layer for being dispersed with multiple nanoparticles in adhesive material when, nanoparticle agglomerates. (2) due to the hole, crackle etc. of generation air etc. between the light-emitting surface of LED chip and fluorophor sheet material, LED chip and fluorescence The adaptation of body sheet material reduces, and reduces so as to cause the light extraction efficiency for extracting light from LED chip.

Currently invention addresses the above subject, it is therefore intended that can cut down the manufacturing process of LED package, and improve LED The brightness of packaging body.

Means for solving the problems

A feature of the present invention is following fluorescencer compositions, contains fluorophor, matrix resin and metallic compound Particle, which is characterized in that the refractive index of the metallic compound particle is 1.7 or more, and average grain diameter is 1~50nm, described The refractive index N2 of the mean refractive index N1 of metallic compound particle and described matrix resin and the fluorophor meets following relationship, Being grafted of metallic compound particle.

0.20≥|N1-N2|。

In addition, another feature of the present invention is following fluorophor sheet materials, contain fluorophor, matrix resin and metal compound Object particle, which is characterized in that the refractive index of the metallic compound particle is 1.7 or more, and average grain diameter is 1~50nm, institute State metallic compound being grafted of particle, the mean refractive index N1 of the metallic compound particle and described matrix resin with it is described The refractive index N2 of fluorophor meets following relationship (i), and the viscoelastic sexual behaviour of sheet material meets following relationship (ii), (iii) and (iv).

(i)0.20≥|N1-N2|

(ii) when temperature is 25 DEG C, store elastic modulus G ' meets 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and tan δ < 1；

(iii) when temperature is 100 DEG C, store elastic modulus G ' meets 1.0 × 10²Pa≤G ' < 1.0 × 10⁴Pa, and tanδ≥1；

(iv) when temperature is 200 DEG C, store elastic modulus G ' meets 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and tan δ < 1.

The effect of invention

In accordance with the invention it is possible to provide the LED package that brightness is improved by easy technique.

Detailed description of the invention

The section SEM photograph of the cured film of the fluorescencer composition of [Fig. 1] embodiment 10 (multiplying power is 50,000 times)

The section SEM photograph of the cured film of the fluorescencer composition of [Fig. 2] embodiment 10 (multiplying power is 100,000 times)

The section SEM photograph of the cured film of the fluorescencer composition of [Fig. 3] comparative example 8 (multiplying power is 50,000 times)

The section SEM photograph of the cured film of the fluorescencer composition of [Fig. 4] comparative example 8 (multiplying power is 100,000 times)

The section SEM photograph of the fluorophor sheet material of [Fig. 5] embodiment 19 (multiplying power is 50,000 times)

The section SEM photograph of the fluorophor sheet material of [Fig. 6] embodiment 19 (multiplying power is 100,000 times)

The section SEM photograph of the fluorophor sheet material of [Fig. 7] comparative example 12 (multiplying power is 50,000 times)

The section SEM photograph of the fluorophor sheet material of [Fig. 8] comparative example 13 (multiplying power is 50,000 times)

[Fig. 9] has used an example of the LED chip with fluorophor sheet material of fluorophor sheet material lamilate of the invention.

[Figure 10 A] has used an example of the LED package of fluorophor sheet material lamilate of the invention.

[Figure 10 B] has used an example of the LED package of fluorophor sheet material lamilate of the invention.

The schematic diagram of [Figure 11] illumination photometry system.

[Figure 12] has used an example of the manufacturing method of the LED package of fluorescencer composition of the invention.

[Figure 13] has used an example of the manufacturing method of the LED package of fluorophor sheet material lamilate of the invention.

[Figure 14] has used the manufacturer of the LED chip with fluorophor sheet material of fluorophor sheet material lamilate of the invention An example of method.

[Figure 15] has used the manufacturer of the LED chip with fluorophor sheet material of fluorophor sheet material lamilate of the invention An example of method.

An example of the attaching method of fluorophor sheet material lamilate [Figure 16] of the invention

An example of the attaching method of fluorophor sheet material lamilate [Figure 17] of the invention

[Figure 18] has used an example of the manufacturing method of the LED package of fluorophor sheet material lamilate of the invention.

[Figure 19] has used an example of the manufacturing method of the LED package of fluorophor sheet material lamilate of the invention.

Specific embodiment

It is containing fluorophor, matrix resin and metallic compound as the fluorescencer composition of a feature of the present invention The fluorescencer composition of particle, which is characterized in that the refractive index of the metallic compound particle is 1.7 or more, and average grain diameter For 1~50nm, the mean refractive index N1 of the metallic compound particle and described matrix resin and the refractive index of the fluorophor N2 meets following relationship, being grafted of metallic compound particle.

0.20≥|N1-N2|。

So-called fluorescencer composition in the present invention refers to containing fluorophor, matrix resin and metallic compound particle Composition.

For fluorescencer composition of the invention, the mean refractive index N1 of metallic compound particle and matrix resin with The refractive index N2 of fluorophor meets following relationship.

0.20≥|N1-N2|。

It, can will be from LED chip as a result, when fluorescencer composition of the invention to be set to the light-emitting surface of LED chip The light efficiency of extraction is irradiated on fluorophor well, and the light extraction of LED chip improves, as a result, LED is encapsulated The brightness of body improves.

Speculate that its reason is as follows.By making matrix resin contain metallic compound particle, being mixed into for they can be reduced Divide the refringence with fluorophor.Thereby, it is possible to inhibit light in fluorophor and the matrix resin containing metallic compound particle The reflection of interface, scattering, therefore, from LED chip to the light of fluorescencer composition incidence can efficiency be radiated at well it is glimmering In body of light.In addition, the refractive index of fluorescencer composition entirety can be made to connect by making matrix resin contain metallic compound particle The refractive index of nearly LED chip.Thus, it is also possible to inhibit the total reflection inside LED chip, the light that light is extracted from LED chip is improved Extractability.As above two effect as a result, the brightness of LED package can be improved.

In the present invention, refringence | N1-N2 | preferred upper limit value be 0.20, further preferably 0.10, it is especially excellent It is selected as 0.05.By for the upper limit value hereinafter, can get said effect, the brightness of LED package can be improved.It needs to illustrate It is refringence | N1-N2 | smaller, said effect is higher, and therefore, lower limit is not particularly limited, but preferably | N1-N2 | >= 0.02。

The mean refractive index N1 of matrix resin containing metallic compound particle, by metallic compound particle refractive index and The product of volume fraction is indicated with the sum of the refractive index of matrix resin and the product of volume fraction.

Refractive index film thickness measuring device " Prism Coupler MODEL2010/M " (Metricon can be used in refractive index Corporation) it is measured.Specifically, production metallic compound particle is dispersed in matrix resin obtained by composition it is saturating Bright film measures the refractive index in the direction vertical with film surface at 633nm (use of He-Ne laser) in 25 DEG C of measuring temperature (TE), mean refractive index N1 is thus found out.

The refractive index N2 of fluorophor can be found out using Becke-line method (Becke-line method), immersion method, extrapolation.

The refractive index of metallic compound particle used in the present invention is 1.7 or more, and average grain diameter is 1~50nm.Hereinafter, Such metallic compound particle is known as " high refractive index nanoparticles ".

High refractive index nanoparticles are sufficiently smaller than the wavelength of visible light, therefore, can by being dispersed in matrix resin It is considered as optically homogeneous.Further, since the refractive index of high refractive index nanoparticles is different from the refractive index of matrix resin, so containing Have average grain diameter be 1~50nm metallic compound particle matrix resin mean refractive index by metallic compound particle folding It penetrates the product of rate and volume fraction, indicated with the sum of the refractive index of matrix resin and the product of volume fraction.That is, comparing matrix for refractive index When the big metallic compound particle of resin, mean refractive index can be improved.

(partial size)

For metallic compound particle, if average grain diameter is less than 1nm, it is difficult to exist as particle；If more than 50nm, then becoming easy scatters light, and light transmittance reduces.From inhibit light scattering from the viewpoint of, preferably average grain diameter be 1~ 30nm。

The average grain diameter of so-called metallic compound particle herein is the average value of the partial size found out by the following method. The two dimensional image obtained from particle from using scanning electron microscope (SEM), what calculating was intersected with the outer rim of particle with 2 points Distance between this 2 intersection points of straight line becomes maximum distance, is defined as partial size.For 200 particles observed into Row measurement, using the average value of obtained partial size as average grain diameter.For example, the metallization being present in fluorophor sheet material in measurement When the partial size of polymer particle, using mechanical milling method, microtomy (microtome method), CP method (Cross-sect (I) On Pol (I) sher, section polishing) and focused ion beam (F (I) B) processing method in any means ground so that fluorescence The section of body sheet material can be observed, and obtained section then be observed using scanning electron microscope (SEM), from obtained X-Y scheme As calculating average grain diameter.

(composition)

As metallic compound particle, can enumerate titanium dioxide, zirconium oxide, aluminium oxide, cerium oxide (ceria), tin oxide, Indium oxide, zircon, iron oxide, zinc oxide, niobium oxide, silicon nitride, boron nitride, aluminium nitride, silicon carbide, aluminium hydroxide, barium titanate Diamond etc., these metallic compound particles can be used alone, can also be used in combination of two or more.From high refractive index, the easy journey obtained From the viewpoint of degree, preferably using selected from by aluminium compound particle, tin compound particle, titanium compound particle, zirconium compounds It is particle, at least one kind of in molecular group of niobium compound grain.Specifically, the oxide of aluminium, tin, titanium or zirconium, vulcanization can be enumerated Object, hydroxide etc., wherein from the viewpoint of the refractive index for adjusting film, cured film, preferably use Zirconia particles And/or Titanium particles.

If metallic compound particle is high refractive index, mean refractive index when being dispersed in matrix resin can be improved, because This, can reduce the refringence with LED chip as already mentioned above, mention to improve from the light that LED chip extracts light Take efficiency.As the metallic compound particle being commercially available, stannic oxide-titanium oxide compound particle " opt-Lake TR- can be enumerated 502 ", " opt-Lake TR-504 ", " opt-Lake TR-520 ", silica-titania compound particle " opt-Lake TR- 503”、“opt-Lake TR-527”、“opt-Lake TR-528”、“opt-Lake TR-529”、“opt-Lake TR-513”、 Titanium particles " opt-Lake TR-505 " (the above are trade name, catalyst chemical conversion industry (strain) systems), Zirconia particles ((strain) High-purity chemical research it is made), tin oxide-zirconium oxide compound particle (catalyst chemical conversion industry (strain) system), tin oxide particles ((strain) High-purity chemical research is made) etc..For these metallic compound particles, in order to improve the dispersibility with matrix resin, preferably Implement aftermentioned grafting and uses.

(grafting)

In the present invention, so-called being grafted of metallic compound particle refers to, using hydroxyl existing for particle surface, makes to polymerize Object is chemically bonded (grafting) in particle surface.By metallic compound being grafted of particle, can be obtained closely sealed with LED chip etc. The excellent fluorescencer composition of property, fluorophor sheet material.

The adaptation of the light-emitting surface of fluorescencer composition and LED chip is for improving the important of the brightness of LED package Element.If due to air etc. is generated between the light-emitting surface of LED chip and fluorescencer composition, fluorophor sheet material hole, The reasons why crackle or the like, and to reduce with the adaptation of LED chip, then light extraction efficiency reduces.

If metallic compound being grafted of particle, dispersibility of the metallic compound particle in matrix resin becomes good Good, the compatibility of metallic compound particle and matrix resin improves.Become not allowing to be also easy to produce matrix resin and metal compound as a result, The interface of object particle.Therefore, it when fluorescencer composition, fluorophor sheet material are set to LED chip light-emitting surface, is able to suppress Fluorescencer composition, fluorophor sheet material solidification when the hole, the crackle that generate.Therefore, in the hair that they are set to LED chip When smooth surface, the adaptation of they and light-emitting surface becomes well, the light extraction raising of light to be extracted from LED chip, as a result, The brightness of LED package improves.

The example for not generating the state at the interface of matrix resin and metallic compound particle is shown in Fig. 1 and Fig. 2, produces boundary The example of the state in face is shown in Fig. 3, Fig. 4.Fig. 1 and Fig. 2 is to cut out the solidification of the fluorescencer composition of aftermentioned embodiment 10 The section of film and the photo obtained by scanning electron microscope (SEM) observation, Fig. 3 and Fig. 4 are to cut out aftermentioned comparative example 8 The section of the cured film of fluorescencer composition and photo obtained by being observed with SEM.

In the state of not generating the interface of matrix resin and metallic compound particle, as shown in Figures 1 and 2, metallization Polymer particle is homogeneously dispersed in matrix resin, and the boundary part of metallic compound particle and matrix resin becomes unclear. In contrast, it in the case where producing the interface of matrix resin and metallic compound particle, as shown in Figures 3 and 4, forms Therefore aggregation made of metallic compound particle aggregates with one another can be clearly observed the aggregation of metallic compound particle 102 The boundary part of body and matrix resin 101.

It should be noted that in fluorescencer composition contain organic silicone microparticle in the case where, observe sometimes and this Different complexions.The point will be described hereinafter.

In the present invention, for the type of the polymer used in the grafting in metallic compound particle, as long as can It is chemically bound in the surface of metallic compound particle, is not particularly limited.It can be that (for example, poly-, (N- is different for water-soluble polymer Propylacrylamide), polyethylene glycol, polyacrylamide, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, Resoles Initial condensates such as resin, urea resin, melamine resin etc.), or non-soluble polymer is (for example, poly- silicon oxygen Alkane, cis--Isosorbide-5-Nitrae-isoprene, isoprene elastomer, polystyrene, polybutadiene, polyisoprene, polymethylacrylic acid Methyl esters, polyacrylic acid n-butyl, polyvinyl chloride, polyacrylonitrile, polylactic acid etc.).Aftermentioned alkoxy can particularly preferably be enumerated Condensation product, that is, polysiloxanes of silane.

In the present invention, for particle surface whether grafting, can be by using scanning electron microscope (hereinafter referred to as SEM), transmission electron microscope (hereinafter referred to as TEM) is observed the boundary part of metallic compound particle and matrix resin and is obtained Know.In the case where being grafted, it is dispersed in matrix resin to metallic compound uniform particle, metallic compound particle and base The boundary part of body resin becomes unclear, and in the case where not being grafted, since metallic compound particle aggregates with one another, So the boundary part of metallic compound particle and matrix resin can be observed clearly.It should be noted that as it was noted above, In the case where containing organic silicone microparticle in fluorescencer composition, complexion unlike this is observed sometimes.

Polymer is not particularly limited to the method that metallic compound particle surface is grafted, and is expected that by siliconization Close the polycondensation of object and by particle surface grafting.Particularly preferred following methods: in the presence of metallic compound particle, in solvent After middle utilization acid catalyst hydrolyzes alkoxysilane compound containing trialkylsilyl group in molecular structure, the hydrolysate is made to carry out condensation reaction.

(polysiloxanes)

Polysiloxanes is the condensation product of alkoxy silane, can be obtained by following manner: utilizing acid catalyst in a solvent Alkoxysilane compound containing trialkylsilyl group in molecular structure is hydrolyzed, after silanol compound is consequently formed, the silanol compound is made to carry out condensation reaction.Make For alkoxysilane compound containing trialkylsilyl group in molecular structure, be preferably selected from a kind in the alkoxysilane compound containing trialkylsilyl group in molecular structure of the following general formula (1)~(3) expression with On alkoxysilane compound containing trialkylsilyl group in molecular structure.

R¹Si(OR⁴)₃ (1)

R¹Indicate hydrogen, alkyl, alkenyl, aryl or their substituent.From it is resistance to it is anti-thread breakage from the viewpoint of, it is preferable to use With methyl or phenyl as R¹Alkoxysilane compound containing trialkylsilyl group in molecular structure.R⁴Indicate methyl, ethyl, propyl, isopropyl or butyl, respectively It can be the same or different.R⁴More preferably methyl or ethyl.

R²R³Si(OR⁵)₂ (2)

R²And R³Respectively indicate hydrogen, alkyl, alkenyl, aryl or their substituent.R⁵Indicate methyl, ethyl, propyl, Isopropyl or butyl, respectively can be the same or different.R5 is more preferably methyl or ethyl.

Si(OR⁶)₄ (3)

R⁶It indicates methyl or ethyl, respectively can be the same or different.

The concrete example for the alkoxysilane compound containing trialkylsilyl group in molecular structure that general formula (1)~(3) described below indicate.

As trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure that general formula (1) indicates, for example, methyl trimethoxy oxygroup silicon can be enumerated Alkane, methyltriethoxysilane, methyl tripropoxy silane, three isopropoxy silane of methyl, three butoxy silane of methyl, ethyl Trimethoxy silane, ethyl triethoxysilane, hexyl trimethoxysilane, octadecyl trimethoxysilane, octadecyl Triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, three isopropoxy silane of phenyl, 3- aminopropyl Triethoxysilane, N- (2- amino-ethyl) -3- TSL 8330,3- r-chloropropyl trimethoxyl silane, 3- (N, N- diglycidyl) TSL 8330,3- glycidoxypropyltrime,hoxysilane, vinyl trimethoxy Base silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy Propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N- β-(amino second Base)-gamma-amino propyl trimethoxy silicane, beta-cyano ethyl triethoxysilane, glycidyl oxy methyl trimethoxy silicon Alkane, glycidyl oxy methyl triethoxysilane, α-glycidoxyethyl trimethoxy silane, α-glycidoxyethyl three Ethoxysilane, beta epoxide Among trimethoxy silane, beta epoxide Among triethoxysilane, α-epoxy third Oxygroup propyl trimethoxy silicane, α-epoxy propoxy propyl triethoxysilane, beta epoxide propoxypropyl trimethoxy silicon Alkane, beta epoxide propoxypropyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy third Ethyl triethoxy silicane alkane, γ-glycidoxypropyl group tripropoxy silane, three isopropoxy silane of γ-glycidoxypropyl group, Three butoxy silane of γ-glycidoxypropyl group, γ-glycidoxypropyltrime,hoxysilane, α-glycidoxy butyl Trimethoxy silane, α-glycidoxy butyl triethoxysilane, beta epoxide propyloxybutyl trimethoxy silane, beta epoxide Propyloxybutyl triethoxysilane, γ-glycidoxy butyl trimethoxy silane, γ-three ethoxy of glycidoxy butyl Base silane, δ-glycidoxy butyl trimethoxy silane, δ-glycidoxy butyl triethoxysilane, (3,4- epoxide rings Hexyl) methyltrimethoxysilane, (3,4- epoxycyclohexyl) methyltriethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl Tripropoxy silane, three butoxy silane of 2- (3,4- epoxycyclohexyl) ethyl, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy Base silane, 2- (3,4- epoxycyclohexyl) ethyl triethoxysilane, 3- (3,4- epoxycyclohexyl) propyl trimethoxy silicane, 3- (3,4- epoxycyclohexyl) propyl-triethoxysilicane, 4- (3,4- epoxycyclohexyl) butyl trimethoxy silane, 4- (3,4- Epoxycyclohexyl) butyl triethoxysilane, trifluoromethyl trimethoxy silane, trifluoromethyl triethoxysilane, trifluoropropyl Base trimethoxy silane, trifluoro propyl triethoxysilane, perfluoro propyl ethyl trimethoxy silane, three second of perfluoro propyl ethyl Oxysilane, perfluoropentyl ethyl trimethoxy silane, perfluoropentyl ethyl triethoxysilane, ten trifluoro octyl trimethoxies Silane, tridecafluoro-n-octyltriethoxysilane, ten trifluoro octyl tripropoxy silane, ten trifluoro octyls, three isopropoxy silane, 17 fluorine ruthenium trimethoxysilanes, heptadecafluorodecyl triethoxysilane etc..Wherein, it is examined from the viewpoint of the easiness obtained Consider, preferably methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysila,e and phenyl triethoxysilane.

As the two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure that general formula (2) indicate, for example, dimethylformamide dimethyl oxygroup silicon can be enumerated Alkane, dimethyl diethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxy Silane, methylvinyldimethoxysilane, methyl vinyl diethoxysilane, γ-glycidoxypropyl diformazan Oxysilane, gamma-amino hydroxypropyl methyl dimethoxysilane, gamma-amino hydroxypropyl methyl diethoxy silane, N- (2- amino second Base) -3- aminopropylmethyldimethoxysilane, γ-methacryloxypropylmethyl dimethoxysilane, γ-methyl Acryloyloxy propyl methyl diethoxysilane, glycidyl oxy methyl dimethoxysilane, glycidyl oxy methyl methyl Diethoxy silane, α-glycidoxyethyl methyl dimethoxysilane, α-glycidoxyethyl methyl diethoxy silicon Alkane, beta epoxide Among methyl dimethoxysilane, beta epoxide Among methyldiethoxysilane, α-epoxy third Oxygroup hydroxypropyl methyl dimethoxysilane, α-glycidoxypropyl diethoxy silane, beta epoxide propoxypropyl first Base dimethoxysilane, beta epoxide propoxypropyl methyldiethoxysilane, γ-glycidoxypropyl dimethoxy Silane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl dipropoxy silane, β-ring Oxygen propoxypropyl methyl dibutoxy silane, γ-glycidoxypropyl methoxy-ethoxy-silane, γ-epoxy third Oxygroup ethyl dimethoxysilane, γ-glycidoxypropyl group ethyl diethoxy silane, γ-glycidoxypropyl group Vinyl dimethoxysilane, γ-glycidoxypropyl group methylvinyldiethoxysilane, trifluoro propyl methyl dimethoxy oxygroup silicon Alkane, trifluoro propyl methyldiethoxysilane, trifluoro propyl ethyldimethoxysilane, trifluoro propyl ethyl diethoxy silicon Alkane, trifluoro propyl vinyl dimethoxysilane, trifluoro propyl methylvinyldiethoxysilane, 17 fluorine decyl methyl dimethoxy oxygen Base silane, 3- chloropropylmethyldimethoxysilane, 3- chloropropyl diethoxy silane, cyclohexyl methyl dimethoxy silicon Alkane, octadecyl methyl dimethoxysilane etc..Wherein, from the viewpoint of the easiness obtained, dimethyl is preferably used Dialkoxy silicane.

As the 4 functionality alkoxysilane compound containing trialkylsilyl group in molecular structure that general formula (3) indicate, for example, tetramethoxy-silicane, tetrem can be enumerated Oxysilane etc..

The alkoxysilane compound containing trialkylsilyl group in molecular structure that these general formula (1)~(3) indicate can be used alone, and can also combine two or more It uses.

, it is preferable to use alkoxysilane compound containing trialkylsilyl group in molecular structure and methylic alkoxysilane compound containing trialkylsilyl group in molecular structure containing phenyl in the present invention. As a result, when matrix resin is organic siliconresin, is improved with the compatibility of matrix resin, the fluorophor of excellent adhesion can be obtained Composition, fluorophor sheet material.

In addition, in the present invention, it is expected that trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure is used only, or by trifunctional's alkoxy Silane compound is used in mixed way with two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure.More specifically, 100~70 moles of % are preferably comprised Trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure, 0~30 mole of % two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure, further preferably 90 Two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure of trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure of~80 moles of %, 10~20 moles of %. In this way, curability, the hardness when solidifying the fluorescencer composition containing metallic compound particle can be adjusted, from And the operability of the fluorophor sheet material containing metallic compound particle can be improved.

Herein, the operability of so-called fluorophor sheet material indicates that the operation of sheet material when sheet material to be attached to LED chip is easy Property.Operability is related to the hardness of fluorophor sheet material.When the hardness of sheet material is really up to the mark, is using tweezers, heating crimping tool to piece It when material is operated, cracks, or ruptures on sheet material.In addition, when sheet material is excessively soft, with tweezers, heating crimping tool When lifting sheet material, shape is collapsed, and is adhered to tweezers, is heated on crimping tool, becomes to be not easy to be pasted on LED chip.

In addition, above-mentioned trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably trifunctional's alkoxyl silicone that general formula (1) indicates Hydride compounds, above-mentioned two functionalities alkoxysilane compound containing trialkylsilyl group in molecular structure are preferably the two functionality alkoxyl silicone alkanisations that general formula (2) indicate Close object.

For hydrolysis, preferably in the presence of above-mentioned metallic compound particle, in a solvent, through 1~180 point Then acid catalyst and water are added in the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure of clockwise makes it in the thermotonus of room temperature~110 DEG C 1~180 minute.By the way that reaction is hydrolyzed under the above conditions, it is able to suppress reaction sharply.Reaction temperature is more preferably 40 ~105 DEG C.

Moreover it is preferred that after obtaining silanol compound by hydrolysis, directly with 50 DEG C or more and be solvent Boiling point temperature below heats reaction solution 1~100 hour, carries out condensation reaction.In addition, in order to improve the polymerization of polysiloxanes Degree, can also be reheated or be added base catalyst.

For the various conditions of hydrolysis, reaction scale, the size of reaction vessel, shape etc. are considered, such as to acid concentration, anti- It answers temperature, reaction time etc. to be set, thus can get the physical property for being suitable for intended applications.

As acid catalyst used in hydrolysis, hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphorus can be enumerated The acid catalysts such as acid, polyphosphoric acid, polybasic carboxylic acid or its acid anhydrides, ion exchange resin.Particularly preferably used formic acid, acetic acid or The acidic aqueous solution of phosphoric acid.

As the preferred content of these acid catalysts, whole alkoxysilane compound containing trialkylsilyl group in molecular structure for being used when relative to hydrolysis 100 parts by weight, more than preferably 0.05 parts by weight, more than more preferably 0.1 parts by weight, below preferably 10 parts by weight, more excellent It is selected as 5 parts by weight or less.Herein, so-called whole alkoxysilane compound containing trialkylsilyl group in molecular structure amounts, refer to comprising alkoxysilane compound containing trialkylsilyl group in molecular structure, Qi Shui The amount including all compounds in object and its condensation product is solved, hereinafter also so.By 0.05 weight of amount for making acid catalyst Measure part more than, can successfully be hydrolyzed, in addition, by for 10 parts by weight hereinafter, becoming easy control hydrolysis.

For solvent, it is contemplated that dispersion stabilization of metallic compound particle etc. and be suitable for selection.Solvent can be used only 1 Kind, it can also be used in the form of mixture of more than two kinds.About solvent, diacetone alcohol, propylene glycol monomethyl ether second can be enumerated Acid esters, ethyl lactate, gamma-butyrolacton.It, can be special from the viewpoint of the easiness that transmitance and hydrolysis, condensation reaction control Propylene glycol monomethyl ether, gamma-butyrolacton, diacetone alcohol is preferably used.In addition, laggard by terminating in hydrolysis One step adds solvent, so that it is also preferred that resin combination, which is adjusted to concentration appropriate,.It, can also be in addition, according to purpose After hydrolyzing, alcohol of generation etc. appropriately distillated under heating and/or decompression, removed, then add suitable solvent.

The amount of the solvent used when about hydrolysis, relative to whole 100 parts by weight of alkoxysilane compound containing trialkylsilyl group in molecular structure, preferably More than 50 parts by weight, more than more preferably 80 parts by weight.Furthermore it is preferred that being 500 parts by weight hereinafter, more preferably 200 weight Part or less.More than 50 parts by weight of amount by making solvent, it is able to suppress the generation of gel.In addition, by for 500 parts by weight with Under, hydrolysis carries out rapidly.

In addition, as water used in hydrolysis, preferably ion exchange water.The amount of water can be selected arbitrarily, but opposite In 1 mole of alkoxysilane compound containing trialkylsilyl group in molecular structure, preferably used in the range of 1.0~4.0 moles.

Fluorophor absorbs the light issued from LED chip, carries out wavelength convert, and it is different from the light of LED chip to issue wavelength Light.A part of the light issued as a result, from LED chip is mixed with a part of the light issued from fluorophor, can be made including white The LED package of the multi-color system of color.Specifically, by making fluorophor, (it issues yellow using light from LED chip Luminescent color) and the optical combination of blue LED die progress, its can be made to issue white light.In above-mentioned such fluorophor, including The various fluorescence such as the fluorophor of glow green, the fluorophor for the coloured light that turns blue, the fluorophor of coloured light that turns to be yellow, the fluorophor of burn red Body.

It as fluorophor, as long as can finally reappear the color of defined, is not particularly limited, can be used known glimmering Body of light.As an example, as fluorophor corresponding with blue LED die, can enumerate YAG system fluorophor, TAG system fluorophor, Esters of silicon acis fluorophor, nitride fluorophor, nitrogen oxides system fluorophor etc..

Matrix resin is the substance to form continuous phase, as long as molding processibility, the transparency, heat resistance, cementability etc. are excellent Epoxy resin, organic siliconresin (including organopolysiloxanes such as organic silicon rubber, silicon gel may be used in different material Solidfied material (cross-linking agent)), carbamide resin, fluororesin, material known to polycarbonate resin etc..It is suitable by being carried out to these resins Design, can obtain the resin useful to fluorescencer composition of the invention.

In addition, can also add dispersing agent as additive for keeping coated film stable or levelling agent, as sheet material table Bonding additives such as the silane coupling agent of the modifying agent in face etc..In addition, it is inorganic also to add silicon dioxide granule, organic silicone microparticle etc. Particle is as fluorophor sedimentation inhibitors.The substance of particularly preferred thermosetting property or light solidity.From viewpoints such as the transparency, heat resistances Consider, can suitably use epoxy resin, organic siliconresin or their mixture.

From the viewpoint of heat resistance, matrix resin is most preferably organic siliconresin.In organic siliconresin, preferably addition Reaction-curable silicon composition.For addition reaction curing type silicone composition, in room temperature or 50~200 DEG C Temperature is heated, is solidified, the transparency, heat resistance, excellent in adhesion.It, can about addition reaction curing type silicone composition Using containing the organosilicon with the alkenyl for being bonded to silicon atom, the organosilicon with the hydrogen atom for being bonded to silicon atom and The composition of the platinum group catalyst of catalytic amount.

In the present invention, preferably using has siloxanes key and containing the organic of the silicon atom for being directly connected to aryl Silicone resin.When particularly, for siloxanes key and containing the organic siliconresin of the silicon atom that is directly connected to naphthalene, energy Enough make high refractive index and heat-resisting light resistance while realizing, so it is preferred that.

As the organic siliconresin with siloxanes key and containing the silicon atom for being directly connected to aryl, tool can be enumerated There are siloxanes key and the organic siliconresin containing the silicon atom for being directly connected to phenyl, there is siloxanes key and contain and divide It is not directly connected to the organic siliconresin etc. of the silicon atom of methyl and phenyl.

As the organic siliconresin with siloxanes key and containing the silicon atom for being directly connected to naphthalene, tool can be enumerated Have siloxanes key and containing be directly connected to respectively methyl and naphthalene silicon atom organic siliconresin, have siloxanes key, And the organic siliconresin etc. containing the silicon atom for being directly connected to methyl, phenyl and naphthalene respectively.

It should be noted that including in the organic siliconresin containing the silicon atom for being directly connected to methyl and phenyl respectively Following two situation: the case where being directly connected to methyl and phenyl on 1 silicon atom；Contain respectively and has been directly connected to methyl Silicon atom and be directly connected to phenyl silicon atom the case where.It has been directly connected to methyl, phenyl and naphthalene respectively for containing Silicon atom organic siliconresin for it is also the same.

Organic siliconresin is described in detail.Contain organosilicon, the tool with the alkenyl for being bonded to silicon atom There is the addition of the organosilicon and the platinum group catalyst as hydrosilylation reaction catalyst of the hydrogen atom for being bonded to silicon atom anti- It is preferred for answering curing type silicone composition.For example, Dow Corning Toray (strain) sealing material processed can be used " OE6630 ", " OE6636 " etc., " SCR-1012 " of Shin-Etsu Chemial Co., Ltd, " SCR1016 " etc..Particularly, make For the matrix resin of fluorescencer composition of the invention, particularly preferably make the bridging property organosilicon of the composition comprising (A)~(D) Composition carries out hydrosilylation reactions and the cross-linking agent that is formed.Cross-linking agent store elastic modulus at 60 DEG C~250 DEG C subtracts It is few, high bonding force can be obtained by heating, thus, it may be preferable to be used as the matrix tree for fluorophor sheet material without bonding agent Rouge.Hereinafter, the cross-linking agent is known as thermal welding resin.

(A) organopolysiloxane that following averaged unit formulas indicate,

(R¹ ₂SiO_2/2)_a(R¹SiO_3/2)_b(R²O_1/2)_C

(in formula, R¹For phenyl, carbon atom number be 1~6 alkyl or cycloalkyl or carbon atom number be 2~6 alkenyl, Wherein, R¹In 65~75 moles of % be phenyl, R¹In 10~20 moles of % be alkenyl, R²For hydrogen atom or carbon atom number For 1~6 alkyl, a, b and c are the number for meeting 0.5≤a≤0.6,0.4≤b≤0.5,0≤c≤0.1 and a+b=1 Value.)；

(B) organopolysiloxane { being 5~15 parts by weight relative to 100 parts by weight of (A) ingredient } that the following general formula indicates,

R³ ₃SiO(R³ ₂SiO)_mSiR³ ₃

(in formula, R³For phenyl, carbon atom number be 1~6 alkyl or cycloalkyl or carbon atom number be 2~6 alkenyl, Wherein, R³In 40~70 moles of % be phenyl, at least one in R3 is alkenyl, the integer that m is 5~50.)；

(C) { hydrogen atom for being bonded to silicon atom in the ingredient is relative to (A) for organic trisiloxanes that the following general formula indicates The molar ratio of the total amount of alkenyl in ingredient and (B) ingredient becomes 0.5~2 amount },

(HR⁴ ₂SiO)₂SiR⁴ ₂

(in formula, R⁴The alkyl or cycloalkyl for being 1~6 for phenyl or carbon atom number, wherein R⁴In 30~70 moles of % For phenyl.)；And

(D) hydrosilylation reactions catalyst { is enough to promote the alkenyl and (C) ingredient in (A) ingredient and (B) ingredient In the hydrogen atom for being bonded to silicon atom hydrosilylation reactions amount.

In the general formula of (A) ingredient, the value of a, b and c can get obtained cross-linking agent in the sufficient hardness of room temperature, and And it can realize softening in high temperature.In the general formula of (B) ingredient, if the content of phenyl is less than the lower limit of above range, obtain Cross-linking agent it is insufficient in the softening of high temperature, on the other hand, if be more than above range the upper limit, obtained cross-linking agent it is transparent Property lose, mechanical strength also reduces.In addition, in formula, R³In at least one be alkenyl.This is because if not having alkene Base, then the ingredient cannot participate in cross-linking reaction, which is possible to ooze out from obtained cross-linking agent.In addition, in formula, m is 5~ Integer in the range of 50, this is the range that operation workability is kept while maintaining the mechanical strength of obtained cross-linking agent.

(B) content of ingredient is the amount relative to 100 parts by weight of (A) ingredient in the range of 5~15 parts by weight, is to be used for Realize obtained cross-linking agent in the range of high temperature adequately softened.

R in the general formula of (C) ingredient, in formula⁴The alkyl or cycloalkyl for being 1~6 for phenyl or carbon atom number.As R⁴ Alkyl, methyl, ethyl, propyl, butyl, amyl, heptyl can be enumerated.As R⁴Naphthenic base, cyclopenta, cycloheptyl can be enumerated Base.It should be noted that R⁴In, the content of phenyl is in the range of 30~70 moles of %.This is the cross-linking agent that can be achieved In the sufficient range softened and ensure the transparency and mechanical strength of high temperature.

(C) content of ingredient is the hydrogen atom for being bonded to silicon atom in the ingredient relative in (A) ingredient and (B) ingredient Alkenyl total amount amount of molar ratio in the range of 0.5~2, this is to can get obtained cross-linking agent filling in room temperature The range for the hardness divided.

(D) ingredient is for promoting to be bonded to silicon atom in the alkenyl and (C) ingredient in (A) ingredient and (B) ingredient Hydrogen atom hydrosilylation reactions hydrosilylation reactions catalyst.As (D) ingredient, platinum group catalysis can be enumerated Agent, rhodium series catalysts, palladium series catalyst, from can remarkably promote silicon composition it is cured from the aspect of, preferably platinum Series catalysts.As the platinum group catalyst, platinum micropowder, chloroplatinic acid, the alcoholic solution of chloroplatinic acid, platinum-alkenyl silicon oxygen can be enumerated Alkane complex, platinum-olefin complex, platinum-carbonyl-complexes, particularly preferably platinum-alkenylsiloxane complex.As the chain Alkenyl siloxane, can enumerate 1,3- divinyl -1,1,3,3- tetramethyl disiloxanes, 1,3,5,7- tetramethyls -1,3, and 5,7- Tetravinyl cyclotetrasiloxane, will a part ethyl of the methyl in these alkenylsiloxanes, phenyl etc. replace obtained by Alkenylsiloxane, vinyl allyl, hexenyl in these alkenylsiloxanes etc. is replaced obtained by alkenyl silicon Oxygen alkane.From the aspect of from the having good stability of the one alkenylsiloxane complex of platinum, particularly preferably 1,3- divinyl- 1,1,3,3- tetramethyl disiloxane.In addition, being examined in terms of the platinum-alkenylsiloxane complex stability can be improved Consider, preferably adds 1,3- divinyl -1,1 in the complex, 3,3- tetramethyl disiloxanes, 1,3- diallyl -1,1, 3,3- tetramethyl disiloxanes, 1,3- divinyl -1,3- dimethyl -1,3- diphenyl disiloxane, divinyl -1 1,3-, 1,3,3- tetraphenyl disiloxane, 1,3,5,7- tetramethyls -1,3, the alkenylsiloxanes such as 5,7- tetravinyl cyclotetrasiloxanes, The organosiloxane oligomers such as dimethylsiloxane oligomer, particularly preferably addition alkenylsiloxane.

For the content of (D) ingredient, as long as be enough to promote alkenyl in (A) ingredient and (B) ingredient and (C) at The amount of the hydrosilylation reactions of the hydrogen atom for being bonded to silicon atom in point, is not particularly limited, relative to organosilicon group For closing object, amount of the metallic atom in terms of mass unit in the range of 0.01~500ppm preferably in the ingredient, into one Amount of the step preferably in the range of 0.01~100ppm, particularly preferably amount in the range of 0.01~50ppm.This is To silicon composition it is full cross-linked and do not generate the range of the problems such as coloring.

Silicon composition includes at least above-mentioned (A) ingredient~(D) ingredient, but as other optional members, can also be with Contain acetenyl hexanol (ethynylhexanol), 2- methyl -3- butyne-2-alcohol, 3,5- dimethyl -1- hexin -3- alcohol, 2- benzene The alkynols such as base -3- butyne-2-alcohol；The yne compounds such as 3- methyl-pirylene, 3,5- dimethyl -3- hexene -1- alkynes；1, 3,5,7- tetramethyls -1,3,5,7- tetravinyl cyclotetrasiloxanes, 1,3,5,7- tetramethyls -1,3,5,7- tetra- hexene basic ring, four silicon The reaction suppressors such as oxygen alkane, benzotriazole.The content of the reaction suppressor does not limit, but preferably with respect to silicon composition Weight in the range of 1~5,000ppm.By adjusting the content of reaction suppressor, thus also adjustable obtained cross-linking agent Store elastic modulus.

Fluorescencer composition of the invention can contain organic silicone microparticle.By containing organic silicone microparticle, not only glued Connecing property, processability are good, and film thickness uniformity also good fluorophor sheet material.Especially by use average grain diameter be 0.1 μ M or more and 2.0 μm of organic silicone microparticle below, discharge when can obtain using slotting die coaters (slit die coater) The fluorophor sheet material excellent, film thickness uniformity is excellent.

In addition, the metallic compound particle for being grafted is micro- to organosilicon if there is organic silicone microparticle in the composition Grain is coated.Thus the compatibility of matrix resin Yu metallic compound particle is further increased, therefore, becomes more difficult production Their interface of life.The adaptation with the light-emitting surface of LED chip further increases as a result, therefore can get further bright Spend improvement effect.In addition, can make the store elastic modulus (G ') at 100 DEG C is low energy storage bullet when fluorophor sheet material is made Property modulus, to improve and the adaptation of LED chip.

It should be noted that so-called herein " the metallic compound particle for being grafted is coated organic silicone microparticle ", Refer to the state on the surface of the metallic compound uniform particle covering organic silicone microparticle of above-mentioned being grafted.The state can be by making With SEM, the solidfied material of tem observation fluorescencer composition, fluorophor sheet material section and know.

The example that the metallic compound particle for being grafted is coated the state of organic silicone microparticle is shown in Fig. 5 and Fig. 6, is not coated The example of state be shown in Fig. 7 and Fig. 8.It is used in combination in the section that Fig. 5 and Fig. 6 is to cut out the fluorophor sheet material of aftermentioned embodiment 19 Photo obtained by scanning electron microscope (SEM) observation, Fig. 7 and Fig. 8 are aftermentioned comparative example 12 and 13 is respectively cut out glimmering The section of body of light sheet material and photo obtained by being observed with SEM.

It is as shown in Figures 5 and 6, considerable in the state that the metallic compound particle for being grafted is coated organic silicone microparticle It observes organic silicone microparticle 103 to be dispersed in matrix resin 101, the metallic compound particle 104 for being grafted covers organic Silicon particle surface.In the case where the metallic compound particle for being grafted not coating organic silicone microparticle, as shown in Figures 7 and 8, Fluorophor 105 can be observed to be present in matrix resin 101, organic silicone microparticle 103 each other, metallic compound particle 102 each other It agglomerates respectively and forms aggregation.

It is believed that become Fig. 5 and as shown in Figure 6, that the metallic compound particle of being grafted is coated organosilicon is micro- The reason of state of grain is that the metallic compound particle and organic silicone microparticle for being grafted are weak by hydrogen bond, Van der Waals force etc. It is bonded and forms pseudo- bonding.

Organic silicone microparticle is preferably the particle formed by organic siliconresin and/or organic silicon rubber.Particularly preferably pass through The organic silicone microparticle that following methods obtain: by organotrialkoxysilane, organic dialkoxy silicane, organic triacetoxyl group silicon The hydrolysis of the organosilans such as alkane, organic diacetoxy silane, organic trioxime silane, organic dioxime silane, is then condensed.

As organotrialkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl three can enumerated just Npropoxysilane, three isopropoxy silane of methyl, three n-butoxy silane of methyl, three isobutoxy silane of methyl, methyl three are secondary Butoxy silane, three tert-butoxy silane of methyl, ethyl trimethoxy silane, n-propyl trimethoxy silane, isopropyl front three Oxysilane, three butoxy silane of normal-butyl, three butoxy silane of isobutyl group, sec-butyl trimethoxy silane, three fourth of tert-butyl Oxysilane, N- (beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyl group trimethoxy silicon Alkane, vinyltrimethoxysilane, phenyltrimethoxysila,e etc..

As organic dialkoxy silicane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, methyl can be enumerated Ethyldimethoxysilane, Methylethyl diethoxy silane, diethyldiethoxysilane, diethyldimethoxysilane, 3-amino propyl methyl diethoxy silane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, N- (2- ammonia Base ethyl) -3- aminoisobutyric ylmethyl dimethoxysilane, N- ethylamino isobutyl methyl diethoxy silane, (phenylamino Ylmethyl) methyl dimethoxysilane, vinyl methyl diethoxy silane etc..

As organic triacetoxysilane, methyl triacetoxysilane, ethyltriacetoxysilane, second can be enumerated Alkenyl triacetoxysilane etc..

As organic diacetoxy silane, dimethyl 2 acetoxyl group silane, Methylethyl diacetoxy can be enumerated Silane, vinyl methyl diacetoxy silane, vinyl ethyl diacetoxy silane etc..

As organic trioxime silane, methyl trimethoxy base ethyl ketoxime silane, vinyl trimethyl ethyl ketoxime silicon can be enumerated Alkane can enumerate double methyl ethyl ketone oxime silane of Methylethyl etc. as organic dioxime silane.

Above-mentioned organic silicone microparticle can specifically obtain by the following method: report in Japanese Unexamined Patent Application 63-77940 bulletin It is reported in the method reported in the method in road, Japanese Unexamined Patent Publication 6-248081 bulletin, Japanese Unexamined Patent Publication 2003-342370 bulletin Method, the method reported in Japanese Unexamined Patent Publication 4-88022 bulletin etc..In addition, it is also known that following methods: by organic three alcoxyl Base silane, organic triacetoxysilane, organic diacetoxy silane, organic trioxime silane, has organic dialkoxy silicane The organosilans such as machine dioxime silane and/or its partial hydrolystate are added in alkaline aqueous solution, are made its hydrolytic condensation and are obtained The method of organic silicone microparticle；Organosilan and/or its partial hydrolystate are added in water or acid solution, obtain the organosilan And/or after the hydrolyzable moiety condensation product of its partial hydrolystate, the method that alkali carries out condensation reaction and obtains organic silicone microparticle is added； Make organosilan and/or its hydrolysate upper layer, make the mixed liquor lower layer of alkali or alkali and organic solvent, makes at their interface The organosilan and/or its hydrolysate hydrolytie polycondensation and the method etc. for obtaining particle, it is available in any of the above-described kind of method Organic silicone microparticle used in the present invention.

Wherein, the poly- silsesquioxane of spherical organic is manufactured making organosilan and/or its partial hydrolystate hydrolytic condensation , it is preferable to use being added by being reported in Japanese Unexamined Patent Publication 2003-342370 bulletin in such reaction solution when alkane particle Organic silicone microparticle obtained from the method for macromolecule dispersing agent.

In addition, when manufacturing organic silicone microparticle, it is possible to use the organic silicone microparticle being manufactured in the following manner: make organosilicon Alkane and/or the hydrolysis of its partial hydrolystate, condensation are made using existing to play in solvent as protecting colloid in acidic aqueous solution The state of macromolecule dispersing agent and salt adds organosilan and/or its partial hydrolystate after obtaining hydrolysate, adds alkali Carry out condensation reaction.

Macromolecule dispersing agent is water soluble polymer and the substance that plays a role in a solvent as protecting colloid, Any one of synthesis macromolecule, natural polymer can be used, specifically, polyvinyl alcohol, polyvinylpyrrolidone can be enumerated Deng.As the adding method of macromolecule dispersing agent, the method made an addition to reacted in advance in initial liquid can be enumerated, simultaneously added with machine The method of trialkoxy silane and/or its partial hydrolystate makes organotrialkoxysilane and/or its partial hydrolystate carry out water The method added after solution partial condensates, also may be selected any method in these methods.Herein, about macromolecule dispersing agent Additive amount, relative to 1 parts by weight of reaction solution capacity, preferably 5 × 10^-7~10^-2The range of parts by weight then has if the range Machine silicon particle is less likely to occur to agglomerate each other.

As the organic substituent contained in organic silicone microparticle, preferably methyl and phenyl, these substituent groups can be passed through Content adjusts the refractive index of organic silicone microparticle.For example, in the case where matrix resin is organic siliconresin, in order not to make LED The brightness of packaging body reduces, and preferably makes the refractive index d1 of organic silicone microparticle and based in addition to the organic silicone microparticle and fluorophor Ingredient refractive index d2 refringence it is smaller.The refractive index d1 of organic silicone microparticle, with based on remove organic silicone microparticle and fluorescence The specific refractivity of the refractive index d2 of ingredient other than body is preferably smaller than 0.10, further preferably 0.03 or less.By that will roll over It penetrates rate control within the above range, the specular scattering of the interface of organic silicone microparticle and organic siliconresin can be reduced, obtain High transparency, high transparency will not be such that the brightness of LED package reduces.

Abbe (Abbe) refractometer, Poole not Ritchie can be used as total reflection method about the measurement of refractive index (Pulfrich) refractometer, immersion liquid type refractometer, immersion method, the method for minimum deviation angle etc., but the detecting refractive index of organic siliconresin Middle Abbe refractometer is useful, and immersion method is useful in the detecting refractive index of organic silicone microparticle.

In addition, the raw material of organic silicone microparticle can be made up of change as the method for controlling above-mentioned refringence Ratio is measured to be adjusted.That is, for example, by adjusting the methyl trialkoxysilane and phenyl trialkoxysilane as raw material Mixing ratio keeps the composition ratio of methyl more, thus can realize the low-refraction close to 1.4；Conversely, the composition ratio by making phenyl It is more, it thus can realize higher high index of refraction.

In the present invention, the average grain diameter of organic silicone microparticle is indicated by median particle diameter (D50).As under the average grain diameter Limit, preferably 0.1 μm or more, further preferably 0.5 μm or more.In addition, preferably 2.0 μm hereinafter, further as the upper limit Preferably 1.0 μm or less.Furthermore it is preferred that using monodispersed, spherical shape particle.In the present invention, organic silicone microparticle is averaged Partial size, that is, median particle diameter (D50) and size distribution can be measured by SEM observation.The measurement image obtained using SEM is carried out Image procossing is so as to find out particle diameter distribution, by the accumulative percent of pass in thus obtained size distribution, from small particle side 50% partial size is found out as median particle diameter D50.If this method, then it also can use and calculate organic silicone microparticle itself The same method of the method for average grain diameter is made after fluorophor sheet material and observes its section by SEM so as to find out organic silicone microparticle Particle diameter distribution, be 50% by accumulative percent of pass in thus obtained volume reference size distribution, from small particle side Partial size is found out as median particle diameter D50.In this case, compared with true average grain diameter, from the section of fluorophor sheet material The organic silicone microparticle average grain diameter that SEM image is found out theoretically is 78.5% value, is actually about 70%~85% Value.

As the content of organic silicone microparticle, for 100 parts by weight of resin, as lower limit, preferably 1 parts by weight with On, it is more than further preferably 10 parts by weight.In addition, preferably 100 parts by weight are hereinafter, further preferably 80 as the upper limit Below parts by weight.By can get particularly good fluorophor dispersion stability effect containing organic silicone microparticles more than 1 parts by weight On the other hand fruit by containing 80 parts by weight organic silicone microparticle below, will not make on the excess stickiness of fluorescencer composition It rises.

Fluorescencer composition of the invention can contain solvent.As long as solvent can adjust the viscous of the resin of flow regime Degree, is not particularly limited.For example, toluene, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), hexane, acetone, terpineol, 2 can be enumerated, 2,4- trimethyl -1,3- pentanediol mono isobutyrates (TEXANOL), methyl cellosolve, butyl carbitol, butyl carbitol acetate Ester, propylene glycol monomethyl ether etc..

Fluorescencer composition of the invention is also containing dispersing agent, levelling agent for keeping coated film stable, as being made Bonding additives such as the silane coupling agent of the modifying agent of sheet surface when fluorophor sheet material etc..

In addition, in order to reduce the store elastic modulus (G ') at 100 DEG C, also containing the silane-containing as heat adhesive The methylbenzene base system organic siliconresin of alcohol radical.The structure of the methylbenzene base system organic siliconresin of above-mentioned siliceous silane alcohol base is particularly preferred For the following general formula (E).

(E) general formula:

(R⁵SiO₃)d(PhSiO₃)e(R⁵OHSiO₂)f(PhOHSiO₂)g(R⁶SiO₂)h

In formula, R⁵And R⁶Respectively carbon atom number is 1~6 alkyl or cycloalkyl, and Ph is phenyl, and d, e, f, g and h are full The numerical value of 20≤d≤40,20≤e≤40,5≤f≤15,5≤g≤15,20≤h≤40 and d+e+f+g+h=100 enough.

In the present invention, so-called fluorophor sheet material lamilate refers to containing substrate and is coated on fluorescencer composition above-mentioned The lamilate of the fluorophor sheet material formed on substrate.

(substrate)

It as substrate, is not particularly limited, known metal, film, glass, ceramics, paper etc. can be used.Specifically, can Enumerate metal plates or foil, cellulose ethanoate, the polyethylene terephthalates such as aluminium (also including aluminium alloy), zinc, copper, iron (PET), polyethylene, polyester, polyamide, polyimides, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl alcohol Acetal, aromatic polyamides, organosilicon, polyolefin, for the tetrafluoroethene of thermoplastic fluorocarbon resin and the copolymer (ETFE) of ethylene The film of equal plastics, by α-polyolefin resin, polycaprolactone resin, acrylic resin, organic siliconresin and their being total to ethylene Poly resin formed plastics film, be laminated with the paper of above-mentioned plastics or by the paper of above-mentioned plastic coat, be laminated or be vapor-deposited with above-mentioned The paper of metal, the plastic foil for being laminated or being vapor-deposited with above-mentioned metal etc..In addition, substrate be metal plate when, can to surface carry out chromium system, The electroplating processes of nickel system etc., ceramics processing.

Wherein, consider from the easy degree of the production of fluorophor sheet material, the easy degree of the singualtion of fluorophor sheet material, it is excellent Choosing uses glass, resin film.Especially consider from adaptation when fluorophor sheet material to be attached to LED chip, substrate is preferably Soft is membranaceous.Furthermore it is preferred that the film that intensity is high, so that there is no the worry of fracture etc. when handling film-like substrate. From the aspect of these requirements characteristic, economy, preferably resin film, wherein from the aspect of economy, operability, preferably For the plastic foil in the group being made of PET, polyphenylene sulfide, polypropylene.In addition, the case where making fluorophor sheet drying, It is excellent from the aspect of heat resistance in the case where needing 200 DEG C or more of high temperature when fluorophor sheet material is attached at LED chip It is selected as polyimide film.The easy degree removed from sheet material considers, can implement demoulding processing in the surface to substrate in advance.

The thickness of substrate is not particularly limited, as lower limit, preferably 25 μm or more, more preferably 38 μm or more.In addition, As the upper limit, preferably 5000 μm hereinafter, more preferably 3000 μm or less.

(fluorophor sheet material)

In the present invention, so-called fluorophor sheet material refers to the sheet material in inside containing fluorophor.As a spy of the invention The fluorophor sheet material of sign is the fluorophor sheet material containing fluorophor, matrix resin and metallic compound particle, which is characterized in that institute The refractive index for stating metallic compound particle is 1.7 or more, and average grain diameter is 1~50nm, and the metallic compound particle is connect The mean refractive index N1 of cladodification, the metallic compound particle and described matrix resin and the refractive index N2 of the fluorophor meet Following relationship (i), the viscoelastic sexual behaviour of sheet material meet following relationship (ii), (iii) and (iv).

(i)0.20≥|N1-N2|

About fluorophor, matrix resin, metallic compound particle and its grafting contained in above-mentioned fluorophor sheet material and It is common in the detailed content of other preferred components, with fluorescencer composition above-mentioned.In addition, about mean refractive index N1, N2 and Indicate the explanation of the relational expression (i) of their relationship, also with it is common in fluorescencer composition above-mentioned.

Next, being illustrated to the viscoelastic sexual behaviour of fluorophor sheet material of the invention.From keeping quality, haulage and processing Property from the viewpoint of, fluorophor sheet material of the invention is preferably high near room temperature elasticity.On the other hand, from following LED chip Shape and deform and with the light extraction face of LED chip it is closely sealed from the viewpoint of, preferably in a certain temperature conditions elasticity become It is low, and show flexibility, adaptation, mobility.For fluorophor sheet material of the invention, particularly preferably by 60 DEG C with On heating and show mobility.Fluorophor sheet material of the invention is important to the adaptation height in the light extraction face of LED chip , the light extraction that light is extracted from LED chip thus can be improved tremendously.Therefore, as the viscoplasticity row of fluorophor sheet material For, it is necessary to meet (ii) above-mentioned~(iv).

The store elastic modulus (G ') of so-called fluorophor sheet material herein is that moving for fluorophor sheet material is carried out using rheometer Store elastic modulus (G ') when state determination of viscoelasticity (temperature dependency).So-called dynamic viscoelastic is with certain sine When frequency applies shear strain to material, the shear stress occurred when being up to steady state is decomposed into consistent with the phase of strain Ingredient (elastic component) and ingredient (viscosity component) with 90 ° of phase delay of strain, to the dynamic characteristics of material into The method of row analysis.

For Measurement of Dynamic Viscoelasticity (temperature dependency), common viscosity determination of viscoelasticity device can be used to be moved State determination of viscoelasticity.In the present invention, for value when being measured under the following conditions.

Measurement device: viscosity determination of viscoelasticity device HAAKE MARSIII

(Thermo Fisher SCIENTIFIC system)

Determination condition: OSC temperature-independent measurement

Geometry: parallel circle template (20mm)

Minute: 1980 seconds

Angular frequency: 1Hz

Angular speed: 6.2832rad/ seconds

Temperature range: 25~200 DEG C (there is cryogenic temperature control function)

Heating rate: 0.08333 DEG C/sec

Sample shape: round (diameter 18mm).

It herein, divided by value obtained by shear strain is store elastic modulus with the consistent stress component of shear strain phase (G').Store elastic modulus (G ') indicates the elasticity of the material for dynamic strain at each temperature, therefore, with fluorescence The hardness of body sheet material, i.e. processability are closely related.

It on the other hand, is damage divided by value obtained by shear strain with 90 ° of phase delay of the stress component with shear strain It loses elasticity modulus (G ").Loss elastic modulus indicates the viscosity of material, therefore, with the mobility of fluorophor sheet material, i.e. adaptation It is closely related.

In addition, with loss elastic modulus (G ") divided by obtained by store elastic modulus (G ') value be loss tangent (tan δ), For the index for the state that expression material is configured.If tan δ, less than 1, it is the state of solid that elasticity, which is overriding,.Another party Face, if tan δ is 1 or more, then it represents that viscosity is overriding, is the state of liquid.

For the fluorophor sheet material in the present invention, pass through at 25 DEG C 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and And make tan δ < 1, to have adequately elasticity at room temperature (25 DEG C).Therefore, even for the cutting processing using cutter For rapid shear stress, can also by sheet material by around without deformation in a manner of cut, can get high dimensional accuracy Processability.From when preventing operation rupture, from the viewpoint of processability, store elastic modulus of the fluorophor sheet material at 25 DEG C is more Preferably 9.0 × 10⁵Pa or less.

From the viewpoint of the low temperature for attaching temperature, tan δ when room temperature is more preferably 0.7 or less.In addition, as under Limit, is not particularly limited, preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.25 or more.

In addition, for fluorophor sheet material, pass through at 100 DEG C 1.0 × 10²Pa≤G ' < 1.0 × 10⁴Pa, and make δ >=1 tan, so that sheet material has adequately viscosity at 100 DEG C, mobility is high.Therefore, on one side with 100 DEG C or more of temperature pair Fluorophor sheet material with the physical property, which is heated, to carry out on one side to when the attaching of LED chip, and fluorophor sheet material is according to LED chip Light-emitting surface shape and quickly flow, deform, can get high adhesion.It is mentioned as a result, from the light extraction that LED chip extracts light Height, brightness improve.From the viewpoint of the low temperature for attaching temperature, store elastic modulus of the fluorophor sheet material at 100 DEG C is more Preferably 9.0 × 10³Pa or less.

From the viewpoint of adaptation, tan δ at 100 DEG C is more preferably 1.6 or more.In addition, as the upper limit, without spy It does not limit, but preferably 4.0 hereinafter, more preferably 3.6 hereinafter, further preferably 3.3 or less.

In addition, for fluorophor sheet material, pass through at 200 DEG C 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and make Tan δ < 1, to can finally LED chip be made steadily to work.This is because if with 200 DEG C or more of temperature to fluorophor Sheet material is heated, then sheet material is fully cured completion, therefore the whole integration of resin, not will receive when LED chip is lighted The influence of the hot factor such as heat.From the viewpoint of preventing crackle, store elastic modulus (G ') of the fluorophor sheet material at 200 DEG C is more Preferably 9.0 × 10⁵Pa or less.

For tan δ when 200 DEG C, from the viewpoint of thermal stability, more preferable δ≤0.08 tan.In addition, conduct Lower limit is not particularly limited, but preferably 0.01 or more, and more preferably 0.02 or more, further preferably 0.03 or more.

As long as can get above-mentioned store elastic modulus (G ') as fluorophor sheet material, wherein the resin contained can be for not Solid state.In addition, preferably contained resin is not whole one if considering the operational keeping quality etc. of sheet material Body be fully cured but cured state to a certain extent.As an example, under conditions of preferred consolidation is to be stored at room temperature It is carried out in the not changed degree of store elastic modulus (G ') in 1 month or more long-time.

Fluorophor sheet material of the invention can be obtained by fluorescencer composition above-mentioned.The detailed content of its manufacturing method will be Hereinafter illustrate.

The thickness of fluorophor sheet material of the invention is not particularly limited, but preferably 10~1000 μm.If less than 10 μm, Due to concave-convex because of caused by fluorophor particle, it is difficult to carry out uniform sheet forming.If becoming more than 1000 μm It is easy to produce crackle, it is difficult to carry out sheet forming.More preferably 30~100 μm.

On the other hand, from the viewpoint of the heat resistance for improving sheet material, the film thickness of sheet material is preferably 200 μm hereinafter, more excellent 100 μm are selected as hereinafter, further preferably 50 μm or less.

The film thickness of sheet material in the present invention refers to: being based on JIS K7130 (1999) plastics-film and sheet material-thickness measurement side The thickness measuring method A method using mechanical scanning in method and the film thickness (average film thickness) measured.

So-called heat resistance indicates the patience to the heat generated in LED package.Heat resistance can be commented by following manner Valence: comparing the brightness for making LED package when room temperature luminous and when high temperature shines, and measures the brightness under high temperature with which kind of degree It reduces.

LED chip is in the environment for generating a large amount of heat in small space, especially in the case where great power LED, Fever is significant.Above-mentioned fever causes the temperature of fluorophor to rise, and reduces so as to cause the brightness of LED package.Therefore, how high Effect ground releases generated heat and is important.In the present invention, by making sheet material film thickness within the above range, it is excellent that heat resistance can be obtained Different sheet material.In addition, the amount of phosphor of each LED package generates difference if sheet material film thickness is there are deviation, as a result, Luminescent spectrum generates deviation.Therefore, the deviation of sheet material film thickness is preferably within ± 5%, further preferably within ± 3%.It needs It is noted that so-called film thickness deviation herein, is based on JIS K7130 (1999) plastics-film and sheet material-thickness measuring method In the thickness measuring method A method using mechanical scanning and measure film thickness, utilize formula as follows to calculate.

More specifically, using the determination condition of the thickness measuring method A method using mechanical scanning, commercially available contact is used The micrometers such as formula thickness gauge measure film thickness, the maximum value or minimum value of the film thickness being calculated and the difference of average film thickness, with the value It divided by average film thickness and is expressed as a percentage, obtained value is film thickness deviation B (%).

Film thickness deviation B (%)=/ average film thickness × 100 (maximum film thickness deviation value *-average film thickness)

* maximum film thickness deviation value selection film thickness maximum value or minimum value in and average film thickness the biggish side of difference.

Hereinafter, illustrating an example of the manufacturing method of fluorescencer composition of the invention.By metallic compound particle above-mentioned, Matrix resin, fluorophor, organic silicone microparticle, solvent etc. are mixed with specified amount.By mentioned component to become forming for defined After mode mixes, stirred using homogenizer, rotation-revolution type blender, triple-roller mill, ball mill, planetary ball mill, ball mill etc. It mixes kneading machine mixing and is dispersed to homogeneous, this makes it possible to obtain fluorescencer compositions.Mix the process that after dispersing or mixing disperses In, deaeration is further preferably carried out under vacuum or reduced pressure.In addition it is also possible to by certain specific ingredients mix in advance or into The processing such as row curing.Also it can use evaporator to remove solvent and desired solid component concentration is made.

Hereinafter, illustrating an example of the manufacturing method of fluorescencer composition of the invention.It is glimmering by being made by the above method Body of light composition is coated on substrate, is dried, and fluorophor sheet material lamilate is made.Coating can using reverse roll coater, Knife type coater, slotting die coaters, direct gravure coater, compensation slot roller coating machine, kiss coater, natural roller coating machine (natural roll coater), Kohler coater, roller blade coating machine (roll blade coater), baribar roller Formula knife type coater, double-flow coating machine (two stream coater), rod coater, bar coater (wire bar Coater), applicator (applicator), dip coater, curtain coater, spin coater, scraper coating machine etc. carry out. In order to obtain the film thickness uniformity of fluorophor sheet material, it is preferable to use slotting die coaters are coated.

The common heating device such as air drier, infrared drier can be used to carry out for the drying of fluorophor sheet material.It is glimmering In the heating of body of light sheet material, the common heating devices such as air drier, infrared drier can be used.In this case, heating Condition usually heats 1 minute~5 hours in 40~250 DEG C, is preferably to heat 2 minutes~4 hours in 60 DEG C~200 DEG C.This Outside, it can also be periodically heating and curing with step curing (step-curing) etc..

The concentration of metallic compound particle in fluorophor sheet material of the invention, can according to the viscosity of fluorescencer composition, Drying condition (speed) after coating changes.If the viscosity of fluorescencer composition is high, metallic compound particle is not easy to flow It is dynamic, it is not easy to obtain region and the concentration region of variation of constant concentration.It is therefore preferable that solvent-laden fluorophor combination is wrapped in production Object.The viscosity of thickener is preferably 3000~100,000mPas.In addition, even if increasing drying temperature, accelerating rate of drying, gold Belong to compound particles to be also not easy to flow, thus it is not easy to obtain region and the concentration region of variation of constant concentration.It is preferred dry Dry condition is as described above.

After making fluorophor sheet material lamilate, change substrate also can according to need.Especially by high refractive index nano When the face paste of the big side of the concentration of particle invests the light-emitting surface of LED chip, substrate is changed preferably to adjust attaching face.The situation Under, as easy method, it can enumerate and be replaced the method for stickup, using vacuum laminator, dry film lamination using heating plate The method etc. of machine, but not limited to this.In the face of the big side of the concentration for making high refractive index nanoparticles and the hair of LED chip When smooth surface is opposite, same method can also be used.

For fluorophor sheet material lamilate of the invention, it is preferable that be attached at transverse direction (lateral), longitudinal direction (vertical), the light-emitting surface of the usually LED chip of structure such as flip-chip, the surface that thus may be formed at LED chip are laminated There is the LED chip with fluorophor sheet material of fluorophor sheet material, can especially be suitably used for the big longitudinal direction of light-emitting area, upside-down mounting core The LED chip of piece type.It should be noted that so-called light-emitting surface, refers to the face that the light from LED chip is extracted.

Herein, the case where there is the case where light-emitting surface from LED chip is single plane and not being single plane.Make The case where for single plane, can mainly enumerate LED chip only with top light-emitting surface.Specifically, longitudinal type can be enumerated LED chip, LED chip that side covering is only extracted from upper surface to light with reflecting layer etc..On the other hand, about not being single The case where plane, can enumerate the LED chip with top light-emitting surface and side light-emitting surface, the LED chip with curved surface light-emitting surface.

Since using the light issued from side, so as to keep it bright, therefore preferably light-emitting surface is not single plane Situation.Especially from can increase from the viewpoint of light-emitting area and chip manufacturing process be easy, it is however preferred to have top light-emitting surface With the flip chip type LED chip of side light-emitting surface.In addition, in order to improve luminous efficiency, can also based on optical design and incite somebody to action Light-emitting area is processed into textured (Japanese: テ Network スチヤ mono-) etc..

Fluorophor sheet material lamilate of the invention can not also be attached directly to LED chip, but use transparent resin etc. Bonding agent is attached.On the other hand, it by being directly coated LED chip with fluorophor sheet material, will not be lost due to reflection etc. Light from LED chip can directly make it be incident to the fluorophor sheet material as wavelength conversion layer, so it is preferred that.Face as a result, Colo(u)r bias is few, can obtain uniform white light with high efficiency.So-called wavelength conversion layer refers to herein: absorbing from LED chip The light and Wavelength-converting of sending, issue the layer of the wavelength light different from the light of LED chip.

For by the LED chip obtained by the above method with fluorophor sheet material, carry out metal line, seal and by its It after packaging body is made, is assembled in component, thus can be suitably used for various illuminations, liquid crystal backlight, headlamp are representative Various LED light emission devices.

Fig. 9 shows the preference of the LED chip with fluorophor sheet material.It (a) is to attach setting in the upper surface of LED chip The LED chip of fluorophor sheet material is had obtained from fluorophor sheet material.It (b) is not only in the upper surface of LED chip 1 but also in side Face also attaches the LED chip that fluorophor sheet material is had obtained from setting fluorophor sheet material 2.Even for the light issued from side Wavelength convert can also be carried out, so it is preferred that.(c) be the LED for using flip chip type, will be as the upper surface of light-emitting surface and side The LED chip of fluorophor sheet material is had obtained from coating with fluorophor sheet material 2.It (d) is by the dense of high refractive index nanoparticles The face paste for spending big side invests the LED chip that fluorophor sheet material is had obtained from the light-emitting surface of LED chip.

Figure 10 A~Figure 10 B shows the preference of LED package.(a) be to be provided with LED chip 1 with reflecting mirror (reflector) fluorescencer composition 4 is injected in 5 installation base plate 7, is then sealed and is obtained using transparent sealant 6 The LED package arrived.It (b) is to attach fluorophor sheet material on the LED chip 1 being set on the installation base plate 7 with reflecting mirror 5 2, the then LED package obtained from transparent sealant 6 is sealed.It (c) is not only in the upper surface of LED chip 1 And it is also pasted with the LED package of fluorophor sheet material 2 in side, wavelength, which can also be carried out, even for the light issued from side turns It changes, so it is preferred that.Further it is also equipped with the lens formed by transparent sealant 6.

(d) do not use reflecting mirror 5, be sealed using the lens formed body of transparent sealant 6, in addition to this with (b) Equally.(e) reflecting mirror 5 is not used, it is in addition to this same as (c).

(f) LED of flip chip type is used, and will be coated as the upper surface of light-emitting surface and side fluorophor sheet material 2, In addition to this same as (c).It, can also be as it should be noted that when being coated the side of LED chip 1 with fluorophor sheet material 2 (f) fluorophor sheet material 2 is made to extend to the upper surface of installation base plate 7 as shown in.(g) reflecting mirror 5 is not used, using transparent close The lens formed body of closure material 6 is sealed, in addition to this same as (e).It (h) is to utilize transparent adhesive 9 by LED chip 1 It is in addition to this same as (b) obtained from being attached with fluorophor sheet material 2.(i) the pre-prepd fluorescence with substrate 10 is used Body sheet material 2 does not carry out substrate 10 from fluorophor sheet material 2 using in addition to this same as (h) with removing.As substrate 10 Material, preferably glass.

It's not limited to that for applicable LED package of the invention.For example, it can be the transparent sealants 6 in (b) The encapsulation of fluorophor sheet material 2 is also pasted with for shape shown in (c) and not only in the upper surface of LED chip 1 but also in side Body.As set forth above, it is possible to combine the architecture of each component illustrated by (a)~(i).In addition it is also possible to replace with except this Known component in addition, or the known component of combination in addition to this.

Herein, as long as the excellent material such as transparent sealant molding processibility, the transparency, heat resistance, cementability, then Can be used epoxy resin, organic siliconresin (including the organopolysiloxanes such as organic silicon rubber, silicon gel solidfied material (crosslinking Object)), carbamide resin, fluororesin, material known to polycarbonate resin etc..In addition, transparent adhesive can be used it is above-mentioned transparent close Closure material.

Illustrate the manufacturing method for having used the LED package of fluorescencer composition of the invention.Figure 12 show used it is glimmering Preferred manufacturer's rule of the LED chip of body of light composition, but it is not limited to this method.It is of the invention glimmering as having used The manufacturing method of body of light composition, the particularly preferably manufacturing method including at least the LED package of following processes: process (A) Fluorescencer composition is injected into packaging body frame；And process (B) will be sealed after above-mentioned operation (A) using sealing material Fill body sealing.

Firstly, (a) is used as packaging body frame 18, prepare the installation base plate 7 for having reflecting mirror 5.Then, (b) in the installation Installation settings LED chip 1 on substrate 7.

Next, fluorescencer composition of the invention (c) to be injected into the envelope for being provided with LED chip 1 with desired amount It fills in body frame 18.About method for implanting at this time, injection moulding, compression forming, cast molding, transfer molding, painting can be enumerated It covers, encapsulating (distribution (dispense)), printing, the methods of transfer, but not limited to this.Encapsulating can be particularly preferably used (to divide With).

After injection, fluorescencer composition is made to be heating and curing, it is possible thereby to meet the shape of the shape of packaging body for fluorescence Body composition is set on LED chip.Be heating and curing the common heating device such as usable air drier, infrared drier It carries out.The condition of being heating and curing is usually 40~250 DEG C and 1 minute~5 hours, preferably 60 DEG C~200 DEG C and 2 minutes~4 is small When.In this case, can also be periodically heating and curing with step curing etc..

Then, it (d) injects transparent sealant 6 and is heating and curing, LED chip 1 is sealed.Method for implanting at this time And heating condition is on the basis of the condition of above-mentioned fluorescencer composition.By the above process, LED package 19 can be manufactured.Root According to needs, protective layer, the lens etc. formed by transparent resin also can be set.

Then, illustrate the manufacturing method for having used the LED package of fluorophor sheet material lamilate of the invention.Institute as follows It states, the representative manufacture method of the LED package of fluorophor sheet material lamilate of the invention has been used to have following methods: (1) will After fluorophor sheet material is cut into monolithic, the method that is attached at each LED chip；(2) LED before being fixed with cutting (dicing) The method for disposably carrying out the cutting of chip and the cutting of fluorophor sheet material via disposable attach on the chip of chip, but simultaneously It is not limited to this.Particularly preferably including at least the manufacturing method of the LED package of following processes: (A) aligns process, makes above-mentioned One block of fluorophor sheet material is opposed with the light-emitting surface of a LED chip；And (B) bonding process, using heating crimping tool, It pressurizes while heating, keeps the said one block of above sheet Nian Jie with the light-emitting surface of said one LED chip.Into One step preferably above-mentioned (A) process is the manufacturing method of the LED package of following contraposition processes: making one of above-mentioned fluorophor sheet material The light-emitting surface pair in the face of the big side of the concentration of inorganic particulate and said one LED chip in the upper surface and the lower surface of block It sets.

Fluorophor sheet material lamilate of the invention can not also be attached directly to LED chip, but use transparent resin etc. Bonding agent is attached, and when having used the fluorophor sheet material of thermal welding resin used as matrix resin, can not had easily It is attached at LED chip in the case where having bonding agent, so it is preferred that.

When fluorophor sheet material is attached at LED chip, by pressurizeing while being heated with desired temperature, from And it is crimped and is attached.Heating temperature be preferably 60 DEG C or more and 250 DEG C hereinafter, more preferably 60 DEG C or more and 160 DEG C with Under.By being 60 DEG C or more, become easy for increasing room temperature and the resin design for the elastic modulus difference for attaching temperature.This Outside, by for 250 DEG C hereinafter, can reduce the thermal expansion of substrate and fluorophor sheet material, be heat-shrinked, therefore, can be improved attaching Precision.Especially aperture processing is being implemented to fluorophor sheet material in advance, is carrying out the feelings such as aligning with the prescribed portion on LED chip Under condition, the position precision of attaching is important.In order to improve the precision of attaching, more preferably attached at 160 DEG C or less.

As the method that fluorophor sheet material is attached at LED chip surface, as long as can be carried out with desired temperature The device of crimping heats then using existing any device using chip mounter (mounter), flip-chip bond device etc. Crimping tool.In addition, vacuum laminator can be used, have 100 when disposably being attached on the LED chip of wafer-level The heating crimping tool of heating part etc. of~200mm square or so is attached.In any case, with desired temperature Fluorophor sheet material is crimped on LED chip and carries out thermal welding by degree, then lets cool to room temperature, substrate is removed.By having this The relationship for inventing such temperature and elasticity modulus, it is not only close securely to let cool the fluorophor sheet material to room temperature after thermal welding Together in LED chip, and can easily be removed from substrate.

The method for illustrating to carry out cutting processing to fluorophor sheet material.There are following methods: for fluorophor sheet material, to LED chip is previously cut to monolithic before attaching, and is then attached at the method for each LED chip；It is attached with by fluorophor sheet material After the LED chip of wafer-level, method that the cutting with chip simultaneously disposably cuts fluorophor sheet material.? It is glimmering by what is be formed uniformly by the processing using laser or the cutting using cutter in the case where being cut in advance before attaching The processing of body of light sheet material is divided into defined shape.Due to being endowed high-energy using the processing of laser, so being not easy very much to keep away Exempt from the burning of resin, the deterioration of fluorophor, therefore is preferred using the cutting of cutter.As using cutter cutting process, Have simple cutter indentation and the method cut and the method cut using rotating knife, can suitably use either one Method.As the device cut using rotating knife, can suitably utilize be referred to as cutting machine (dicer) for by semiconductor Substrate (chip) cuts (dicing) into the device of one single chip.When using cutting machine, it can be set by the thickness of rotating knife, condition Therefore the fixed width critically to control cut-off rule compared with carrying out cutting by simple cutter indentation, can obtain higher Machining accuracy.

When the fluorophor sheet material to the state laminated with substrate is cut, singualtion can be carried out by substrate, or Can also by fluorophor sheet material singualtion, without being cut to substrate.Or it is also possible to introduce on substrate and does not penetrate through Cut line, so-called semi-shear (half cut).The fluorophor sheet material for having carried out singualtion as described above is heat fused in On the light-emitting surface of each LED chip.When fluorophor sheet material is carried out singualtion by substrate, singualtion LED chip attaches The one of the process of cutting is illustrated in Figure 13.It include: the process that fluorophor sheet material is cut into monolithic in the process of Figure 13；And in institute Desired temperature crimps the fluorophor sheet material for being already cut into monolithic, thus the process for being attached at LED chip.Figure 13's It (a) is that the fluorophor sheet material 2 of the state laminated with substrate 20 is fixed on the case where being fixed temporarily sheet material 21.Shown in Figure 13 In process, singualtion is carried out for fluorophor sheet material 2 and substrate 20, therefore be fixed on be fixed temporarily sheet material 21 in advance, so that It must operate and be easy.Next, carrying out cutting to fluorophor sheet material 2 and substrate 20 as shown in (b) to carry out singualtion.It connects , as shown in (c), on the LED chip 1 being installed on installation base plate 7, the fluorophor sheet material 2 and base that will be singulated Material 20 is aligned, and as shown in (d), using heating crimping tool 22, is crimped with desired temperature.At this point, in order to The engaging-in air not between fluorophor sheet material 2 and LED chip 1 preferably carries out crimping process under vacuum or under decompression.After crimping It lets cool to room temperature, such as removes substrate 20 shown in (e).Herein, whens substrate 20 is glass etc., substrate can not also be removed and As directly carry out shown in (f) using.

In addition, in the continuous situation of substrate by fluorophor sheet material singualtion when, directly can disposably make its hot melt The LED chip of wafer-level before being connected to cutting.When in the continuous situation of substrate by fluorophor sheet material singualtion, monolithic Change the process of LED chip attaching cutting one is illustrated in Figure 14.It also include: to cut fluorophor sheet material in the process of Figure 14 It is heated at the process of monolithic and to the fluorophor sheet material for being already cut into monolithic, thus the process for being attached at LED chip. In the example of the process shown in Figure 14, firstly, when by process shown in (b) by fluorophor 2 singualtion of sheet material, substrate 20 It is not singulated.In (b) of Figure 14, substrate 20 is absolutely not cut, but as long as substrate 20 be it is continuous, then can also be by It cuts part.Then, as shown in (c), the surface before making the fluorophor sheet material 2 being singulated and cutting is formed with LED chip Chip 23 it is opposed, aligned.It, will be glimmering with desired temperature using heating crimping tool 22 in the process shown in (d) Body of light sheet material 2 is crimped with the chip 23 that the surface before cutting is formed with LED chip.At this point, in order not in fluorophor sheet material 2 It is formed with engaging-in air between the chip 23 of LED chip 1 with the surface before cutting, is preferably crimped under vacuum or under decompression Process.It is let cool after crimping to room temperature, after removing substrate 20 as shown in (e), chip is carried out cutting to carry out singualtion, Obtain the LED chip 24 with fluorophor sheet material being singulated as shown in (f).

In the LED chip for the wafer-level being disposably heat fused in fluorophor sheet material before cutting, can also paste Fluorophor sheet material is cut together with the attached cutting with LED chip wafer.Fluorophor sheet material and chip is latter in attaching One of process when being cut to secondary property is illustrated in Figure 15.It include: with desired temperature in the process of Figure 15 by fluorophor Sheet material is crimped on the process on a plurality of LED chips to disposably be attached；And to fluorophor sheet material and LED chip into The process that row is disposably cut.In the process of Figure 15, in the case where not carrying out cutting processing to fluorophor sheet material 2 in advance, Being formed with 2 side of fluorophor sheet material with the surface before cutting, the chip 23 of LED chip is opposed to go forward side by side Row contraposition.It then,, will be before fluorophor sheet material 2 and cutting with desired temperature using heating crimping tool 22 as shown in (b) Surface be formed with the chip 23 of LED chip and crimped.In this case, in order not to the table before fluorophor sheet material 2 and cutting Face is formed with engaging-in air between the chip 23 of LED chip, preferably carries out crimping process under vacuum or under decompression.It is put after crimping It is cooled to room temperature, after removing substrate 20 as shown in (c), while being cut to chip, fluorophor sheet material 2 is cut It cuts, to carry out singualtion, obtains the LED chip 24 with fluorophor sheet material being singulated as shown in (d).In addition, The surface before fluorophor sheet material 2 and cutting is formed with by LED with desired temperature using heating crimping tool as shown in (b) After the chip 23 of chip is crimped, such as shown in (e) in the case where not peeling base 20 by substrate also with fluorophor sheet material It is cut together and carries out singualtion, (it has base to the fluorophor sheet material that has for obtaining being singulated as shown in (f) Material) LED chip 24.In this case, can not remove and directly carry out using for other than glass whens substrate 20 is glass etc. Plastic foil when, substrate can be installed on the LED chip with fluorophor sheet material (it has substrate) will be singulated Afterwards, substrate is removed.

Using arbitrary process in above-mentioned Figure 13~15, have fluorophor sheet material is attached at upper surface When the LED chip of electrode, in order to remove the fluorophor sheet material of electrode section, it is expected that in advance to the portion before attaching fluorophor sheet material Divide and carries out aperture processing.Aperture processing can suitably use method known to laser processing, mold perforation etc., but since laser adds Labour union causes the burning of resin, the deterioration of fluorophor, so more preferably being processed using the perforation of mold.When implementing perforation processing, Since perforation processing can not be carried out after fluorophor sheet material to be attached to LED chip, so must be before attaching to phosphor plates Material implements perforation processing.For using the perforation of mold processing, it can be opened according to electrode shape of the LED chip of attaching etc. The hole of arbitrary shape, arbitrary size.For the size in hole, shape, as long as can be designed mold, it can be formed arbitrary big Small, arbitrary shape, but the electrode engagement part in order not to reduce the area of light-emitting surface, on the LED chip of 1mm square or so Preferably 500 μm hereinafter, with the size correspondingly with 500 μm of holes formed below.In addition, carrying out wire bonding (wire ) etc. bonding electrode needs to have a degree of size, at least 50 μm or so of size, therefore hole and the size phase It is 50 μm or so with answering.When the size in hole is excessive compared with for electrode, light-emitting surface exposes that light leakage occurs, LED package Color characteristics decline.In addition, being engaged bad in wire bonding with wire contacts when too small compared with for electrode.Cause This, for aperture processing, it is necessary to 50 μm or more and 500 μm of apertures below are processed with the high-precision within ± 10%, In order to improve the precision of perforation processing, store elastic modulus G ' of the fluorophor sheet material at 25 DEG C meets 1.0 × 10⁴Pa≤G’≤ 1.0×10⁶Pa and tan δ < 1 also becomes extremely important.

It is aligned simultaneously by the prescribed portion of the fluorophor sheet material and LED chip that implement cutting processing aperture processing It is necessary to have the adhering devices of optical registration (alignment) mechanism when attaching.At this point, make fluorophor sheet material and LED chip it is close and It is aligned and is difficult in operation, practical upper often implementation in the following manner: make fluorophor sheet material and LED chip gently It is aligned in the state of contact.At this point, if fluorophor sheet material has adhesiveness, make that it is contacted with LED chip and movement is It is very difficult.For fluorophor sheet material lamilate of the invention, without adhesiveness, therefore hold if if room temperature is aligned Easily carry out the contraposition for contacting fluorophor sheet material gently with LED chip.

Illustrate to have used LED chip with fluorophor sheet material and the LED encapsulation of fluorophor sheet material lamilate of the invention The manufacturing method of the batch production of body.Firstly, the manufacturing method of LED chip of the explanation with fluorophor sheet material.As fluorophor Attaching method of the sheet material on LED chip can be enumerated as shown in Figure 16 using having carried out list by each LED chip The method that the fluorophor sheet material lamilate 26 of piece is attached one by one；And as shown in Figure 17 a plurality of After being disposably coated fluorophor sheet material 2 on LED chip, method of the shearing to carry out individuation is carried out, either method can be used.

About the attaching of fluorophor sheet material, squeeze in the state that substrate softens and flows carrying out.Especially exist In the case where the fluorophor sheet material for having used heat sealability, from the viewpoint of enhancing cementability, attaching temperature is preferably 60 DEG C More than, more preferably 80 DEG C or more.In addition, the heat sealability resin for fluorophor sheet material has the following properties: by heating, Viscosity temporarily reduces, and when further continuous heating, the property of heat cure occurs.Therefore, from the viewpoint of keeping cementability, patch The temperature of attached process is preferably 150 DEG C hereinafter, from further remaining the viscosity of fluorophor sheet material more than certain to keep From the viewpoint of shape, more preferably 120 DEG C or less.In addition, air remaining in order to prevent, preferably subtracts 0.01MPa is below Pressure is attached.

As the manufacturing device for carrying out above-mentioned attaching, vacuum diaphragm laminating machine (vacuum diaphragm can be enumerated Laminator), vacuum furnace laminating machine, vacuum oil pressure pressuring machine, servo vacuum pressuring machine, vacuum electric pressuring machine, TOM molding Vacuum adherings machine such as machine etc..Wherein, more from primary accessible quantity and can pressurize from surface without departing from ground From the aspect of, preferably vacuum diaphragm laminating machine.

Then, for the manufacturing method for the LED package for having used fluorophor sheet material, two methods are enumerated.It needs to illustrate , the manufacturing method of LED package is not limited to these examples.

First manufacture is illustrated in Figure 18.(a) LED chip 1 is temporarily fixed on pedestal 30 via double-sided adhesive tape 29 On.(b) fluorophor sheet material lamilate 26 is carried out in such a way that fluorophor sheet material 2 is contacted with LED chip 1 laminated.(c) by (b) Laminates be fitted into the lower chamber 32 of vacuum diaphragm laminating machine 35 after, upper chamber 31 and lower chamber are directed at while heating It is depressurized room 32.Heating under reduced pressure is carried out until sucking by air-breathing/exhaust outlet 34 into upper chamber 31 after the flowing of substrate 25 Air to make diaphragm 33 expand, by substrate 25 squeeze fluorophor sheet material 2, in a manner of following the light-emitting surface of LED chip 1 into Row attaches.(d) after upper and lower chambers being reverted to atmospheric pressure, laminates are taken out from vacuum diaphragm laminating machine 35, it will after letting cool Substrate 25 is removed.Then, it is cut using cutter etc. between LED chip 36, production has fluorophor through singualtion The LED chip 37 of sheet material.(e) LED chip 37 with fluorophor sheet material is engaged on installation base plate 27 via au bump 8 Packaging body electrode 28.(f) LED package 38 can be manufactured by the above process.As needed, setting is formed by transparent resin Protective layer, lens etc..

Second manufacture is illustrated in Figure 19.(a) LED chip 1 is engaged in the envelope on installation base plate 27 via au bump 8 Fill body electrode 28.(b) fluorophor sheet material lamilate 26 is laminated in such a way that fluorophor sheet material 2 is contacted with LED chip 1.(c) will (b) after laminates are fitted into the lower chamber 32 of vacuum diaphragm laminating machine 35, method same as the Production Example of Figure 10 is utilized Fluorophor sheet material 2 is attached to the light-emitting surface of LED chip 1.(d) after upper and lower chambers being reverted to atmospheric pressure, by laminates from true It takes out in empty web lamination machine 35, removes substrate 25 after letting cool.Then, between LED package 36 carry out cutting into Row singualtion.(e) LED package 39 can be manufactured by the above process.As needed, the protection formed by transparent resin is set Layer, lens etc..

Embodiment

Hereinafter, illustrating the present invention by embodiment.But the present invention is not limited to this.

Nanoparticle 1: titanium oxide " opt-Lake TR-527 " (catalyst chemical conversion industry (strain) system composition: average grain diameter 15nm, refractive index 2.50,20 weight % of Titanium particles)

Nanoparticle 2: titanium oxide " opt-Lake TR-520 " (catalyst chemical conversion industry (strain) system composition: average grain diameter 15nm, refractive index 2.50,30 weight % of Titanium particles)

Nanoparticle 3: titanium oxide " opt-Lake TR-521 " (catalyst chemical conversion industry (strain) system composition: average grain diameter 15nm, refractive index 2.50,30 weight % of Titanium particles)

Nanoparticle 4: tin oxide particles " SN1 " (average grain diameter 19nm, refractive index 2.38)

Nanoparticle 5: aluminium oxide particles " SA1 " (average grain diameter 34nm, refractive index 1.76)

Nanoparticle 6: cerium oxide particles " CS1 " (average grain diameter 34nm, refractive index 2.20)

Nanoparticle 7: zirconium oxide " ZS1 " (average grain diameter 15nm, refractive index 2.40,20 weight % of Zirconia particles)

Nanoparticle 8: magnesia particle " MS1 " (average grain diameter 44nm, refractive index 1.76)

Nanoparticle 9: zinc oxide particles " AS1 " (average grain diameter 94nm, refractive index 1.95)

Nanoparticle 10: Titanium particles " TS1 " (average grain diameter 30nm, refractive index 2.50,20 weight of Titanium particles Measure %)

Nanoparticle 11: Titanium particles " TS2 " (average grain diameter 50nm, refractive index 2.50,20 weight of Titanium particles Measure %)

Nanoparticle 12: Titanium particles " TS3 " (average grain diameter 70nm, refractive index 2.50,20 weight of Titanium particles Measure %)

Nanoparticle 13: Titanium particles " TS4 " (average grain diameter 80nm, refractive index 2.50,20 weight of Titanium particles Measure %)

Nanoparticle 14: zirconium oxide " ZS2 " (average grain diameter 20nm, refractive index 2.40,20 weight % of Zirconia particles)

Nanoparticle 15: Zirconia particles " ZS3 " (average grain diameter 30nm, refractive index 2.40,20 weight of Zirconia particles Measure %)

Nanoparticle 16: Zirconia particles " ZS4 " (average grain diameter 50nm, refractive index 2.40,20 weight of Zirconia particles Measure %)

Nanoparticle 17: Zirconia particles " ZS5 " (average grain diameter 70nm, refractive index 2.40,20 weight of Zirconia particles Measure %)

Nanoparticle 18: Zirconia particles " ZS6 " (average grain diameter 80nm, refractive index 2.40,20 weight of Zirconia particles Measure %)

Nanoparticle 19: niobium oxide particle " NS1 " (average grain diameter 15nm, refractive index 2.30,20 weight of niobium oxide particle Measure %).

(grafting of metallic compound particle)

By methyltrimethoxysilane 16.6g, phenyltrimethoxysila,e the 56.2g, " opt- that number average bead diameter is 15nm Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight % of methanol) 194g, propylene glycol monomethyl ether 126.9g are fitted into reaction vessel, and water is added dropwise into the solution while stirring 21.9g and phosphoric acid 0.36g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, in bath temperature To obtained solution heating stirring 2.5 hours under conditions of being 105 DEG C, the same of the methanol generated by hydrolysis is being distilled off Shi Jinhang reaction.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room temperature, It obtains by the Titanium particles of polysiloxane-graftedization.

By methyltrimethoxysilane 20.4g, phenyltrimethoxysila,e the 69.4g, " opt- that number average bead diameter is 15nm Lake TR-520 " (trade name, catalyst chemical conversion industry (strain) system composition: 30 weight % of Titanium particles, 70 weight of gamma-butyrolacton Amount %) 70.6g, gamma-butyrolacton 44.1g be fitted into reaction vessel, while stirring into the solution dropwise addition water 30.6g and phosphorus Sour 0.48g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, is 105 DEG C in bath temperature Under the conditions of to obtained solution heating stirring 2.5 hours, carried out while the methanol generated by hydrolysis is distilled off anti- It answers.Then, bath temperature be 130 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room temperature, obtain being gathered The Titanium particles of polysiloxane graftedization.

By methyltrimethoxysilane 8.2g, phenyltrimethoxysila,e 55.5g, dimethyldimethoxysil,ne 7.2g, " opt-Lake TR-521 " (trade name, catalyst chemical conversion industry (strain) system composition: Titanium particles 30 that number average bead diameter is 15nm Weight %, 70 weight % of diacetone alcohol) 71.1g, gamma-butyrolacton 23.9g be fitted into reaction vessel, and it is molten to this while stirring Water 34.5g and phosphatase 11 .0g is added dropwise in liquid, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, the installation distillation dress on flask It sets, to obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, is generated being distilled off by hydrolysis Methanol while reacted.Then, bath temperature be 130 DEG C under conditions of further to solution heating stirring 2 hours after, it is cold But to room temperature, obtain by the titanium oxide grain of polysiloxane-graftedization in.

It is by 3- glycidoxypropyltrime,hoxysilane 28.78g, phenyltrimethoxysila,e 56.4g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, methanol of 15nm 80 weight %) 194g, propylene glycol monomethyl ether 253.3g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.36g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

By vinyltrimethoxysilane 18.1g, 3- glycidoxypropyltrime,hoxysilane 67.2g, number average bead diameter For " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, first of 15nm 80 weight % of alcohol) 194g, propylene glycol monomethyl ether 253.6g be fitted into reaction vessel, to the solution while stirring Middle dropwise addition water 21.9g and phosphoric acid 0.36g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, the installation distillation dress on flask It sets, to obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, is generated being distilled off by hydrolysis Methanol while reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, it is cold But it to room temperature, obtains by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by vinyltrimethoxysilane 18.05g, phenyltrimethoxysila,e 56.36g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 205.7g, propylene glycol monomethyl ether 131.3g be fitted into reaction vessel, drip while stirring into the solution Add water 21.9g and phosphoric acid 0.36g, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, Bath temperature be 105 DEG C under conditions of to obtained solution heating stirring 2.5 hours, the methanol generated by hydrolysis is being distilled off While reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room Temperature is obtained by the Titanium particles of polysiloxane-graftedization.

By methyltrimethoxysilane 16.6g, phenyltrimethoxysila,e the 56.2g, " opt- that number average bead diameter is 15nm Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight % of methanol) 194g, propylene glycol monomethyl ether 126.9g are fitted into reaction vessel, and water is added dropwise into the solution while stirring 21.9g and phosphoric acid 0.36g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, in bath temperature To obtained solution heating stirring 1 hour under conditions of being 105 DEG C, while the methanol generated by hydrolysis is distilled off It is reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 1 hour after, be cooled to room temperature, obtain To by the Titanium particles of polysiloxane-graftedization.

By methyltrimethoxysilane 16.6g, phenyltrimethoxysila,e the 56.2g, " opt- that number average bead diameter is 15nm Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight % of methanol) 194g, propylene glycol monomethyl ether 126.9g are fitted into reaction vessel, and water is added dropwise into the solution while stirring 21.9g and phosphoric acid 0.36g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, in bath temperature To obtained solution heating stirring 1 hour under conditions of being 105 DEG C, while the methanol generated by hydrolysis is distilled off It is reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 15 minutes after, be cooled to room temperature, obtain To by the Titanium particles of polysiloxane-graftedization.

In the glove box for eliminating oxygen and moisture, by Powder Oxidation titanium particle " TKP-102 " (trade name, TAYCA (strain) System) it thinly spreads on glass system plate, by plate setting in plasma etcher (MEIWAFOSIS, SEDE), carry out 15 minutes plasma treatments.By the particle transfer Jing Guo plasma treatment into test tube with cover, by preprepared 9.6mM 2,2,6,6- tetramethyl piperidine -1- oxide (2,2,6,6-tetramethylpiperidine 1-oxyl, TEMPO) benzene second Alkene solution is fitted into test tube, and after being sealed with lid, insertion has been heated to 125 DEG C of aluminium alloy cylinder heater (aluminum Block heater) in, carry out free radical polymerization.After 12 hours, test tube is taken out from heater and glove box, is added The chloroform being bubbled through oxygen stops polymerization completely.After separating Titanium particles with solvent by centrifuge separation, titanium oxide is taken out Particle.Titanium particles are cleaned with acetone, are obtained through being grafted the Titanium particles of processing.

By methyltrimethoxysilane 5.59g, phenyltrimethoxysila,e the 19.0g, " opt- that number average bead diameter is 15nm Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight % of methanol) 264.6g, propylene glycol monomethyl ether 103.3g are fitted into reaction vessel, and water is added dropwise into the solution while stirring 7.39g and phosphoric acid 0.12g pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, in bath temperature To obtained solution heating stirring 2.5 hours under conditions of being 105 DEG C, the same of the methanol generated by hydrolysis is being distilled off Shi Jinhang reaction.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room temperature, It obtains by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 4.88g, phenyltrimethoxysila,e 72.46g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 213.4g, propylene glycol monomethyl ether 139.6g be fitted into reaction vessel, drip while stirring into the solution Add water 21.9g and phosphoric acid 0.37g, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, Bath temperature be 105 DEG C under conditions of to obtained solution heating stirring 2.5 hours, the methanol generated by hydrolysis is being distilled off While reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room Temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 9.76g, phenyltrimethoxysila,e 64.41g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 199.65g, propylene glycol monomethyl ether 130.6g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.37g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 14.64g, phenyltrimethoxysila,e 56.36g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 185.94g, propylene glycol monomethyl ether 121.7g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.36g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 19.52g, phenyltrimethoxysila,e 48.31g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 172.22g, propylene glycol monomethyl ether 112.7g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.35g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 24.40g, phenyltrimethoxysila,e 40.25g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 158.50g, propylene glycol monomethyl ether 103.7g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.33g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 29.28g, phenyltrimethoxysila,e 32.20g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 144.79g, propylene glycol monomethyl ether 94.73g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.31g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 34.16g, phenyltrimethoxysila,e 24.15g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 131.07g, propylene glycol monomethyl ether 85.75g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.30g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 39.04g, phenyltrimethoxysila,e 16.10g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 117.35g, propylene glycol monomethyl ether 76.78g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.28g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 43.92g, phenyltrimethoxysila,e 8.05g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 103.64g, propylene glycol monomethyl ether 67.81g be fitted into reaction vessel, while stirring into the solution Water 21.9g and phosphoric acid 0.27g is added dropwise, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, To obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, the first generated by hydrolysis is being distilled off It is reacted while alcohol.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to Room temperature is obtained by the Titanium particles of polysiloxane-graftedization.

It is 15nm's by dimethyldimethoxysil,ne 14.64g, dimethoxydiphenylsilane 35.24g, number average bead diameter " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight of methanol Amount %) 94.59g, propylene glycol monomethyl ether 61.89g be fitted into reaction vessel, drip while stirring into the solution Add water 21.9g and phosphoric acid 0.25g, pays attention to that reaction temperature is not made to be more than 40 DEG C.After dropwise addition, distilling apparatus is installed on flask, Bath temperature be 105 DEG C under conditions of to obtained solution heating stirring 2.5 hours, the methanol generated by hydrolysis is being distilled off While reacted.Then, bath temperature be 115 DEG C under conditions of further to solution heating stirring 2 hours after, be cooled to room Temperature is obtained by the Titanium particles of polysiloxane-graftedization.

(surface treatment of metallic compound particle)

Methyltrimethoxysilane 24.5g, phenyltrimethoxysila,e 83.3g, gamma-butyrolacton 124.0g are packed into reaction In container, water 38g and phosphoric acid 0.57g is added dropwise while stirring, pays attention to that reaction temperature is not made to be more than 30 DEG C.After dropwise addition, burning Distilling apparatus is installed on bottle, to obtained solution heating stirring 2.5 hours under conditions of bath temperature is 105 DEG C, is being distilled off It is reacted while the methanol generated by hydrolysis.Then, further solution is heated under conditions of bath temperature is 130 DEG C After stirring 2 hours, it is cooled to room temperature, obtains polymer solution.The polymer solution that 10.0g is obtained is taken, adds " opt- thereto Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system composition: 20 weight % of Titanium particles, 80 weight % of methanol) 13.3g and propylene glycol monomethyl ether are simultaneously stirred, and obtain silicone composition.

It is packed into " opt-Lake TR-527 " (trade name, processed group of catalyst chemical conversion industry (strain) of 400mL in the reaction vessel At: 20 weight % of Titanium particles, 80 weight % of methanol), it adds phenyltrimethoxysila,e 5.2g (Gelest corporation), in 60 DEG C are heated 2 hours, and white depositions are as a result generated.Then, supernatant is removed, adds 100mL into the white depositions As a result acetone makes to improve with the compatibility of solvent due to the importing of phenyl, sediment dissolves substantially.It will be a small amount of by filtering Insoluble matter remove after, solvent is distilled off from the acetone soln, 10 hours be dried under reduced pressure in 80 DEG C, thus obtain The TiO 2 particles of surface modification have been carried out with phenyltrimethoxysila,e.

PGMEA: propylene glycol monomethyl ether

γ BL: gamma-butyrolacton

DAA: diacetone alcohol

PGME: propylene glycol monomethyl ether

Second second: ethyl acetate

BX9: processed polyethylene terephthalate (polyethylene terephthalate film) is demoulded " Cerapeel " BX9 (beautiful film processing (strain) system in east, average film thickness is 50 μm)

Glass: glass (float glass plate plate thickness: 0.3mm)

HP2: processed polyethylene terephthalate (polyethylene terephthalate film) " Cerapeel is demoulded HP2 " (beautiful film processing (strain) system in east, average film thickness is 50 μm)

PPS: polyphenylene sulfide (polyphenylene sulfide film)

" Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm)

PP: polypropylene (polypropylene screen)

" Torayfan " (eastern beautiful (strain) system, average film thickness are 50 μm)

PI: polyimides (polyimide film)

" Kapton 200H/V " (Dong Li-Du Pont (strain) system, average film thickness are 50 μm)

PO: polyolefin (polyolefin film)

" Opulent X-44B " (Mitsui Chemicals Tohcello.Inc. system, average film thickness are 50 μm)

AL: aluminium (aluminum substrate plate thickness: 0.24mm).

Blender, thermometer, return pipe, dropping funel are installed in the four round flask of 2L, 2L is added into flask 2.5% ammonium hydroxide of the polyether modified siloxane " BYK333 " as surfactant containing 1ppm, carries out with 300rpm It is heated up while stirring using oil bath.When temperature reaches 50 DEG C inside, methyl trimethoxy oxygen was added dropwise from dropping funel through 30 minutes Mixture (23/77mo1%) 200g of base silane and phenyltrimethoxysila,e.Stirring 60 minutes is continued in the temperature Afterwards, acetic acid (reagent is superfine) about 5g is added, after being stirred, is filtered.Water 600mL is added to the generation particle on filter 2 times, addition methanol 200mL 1 time, are filtered, clean.Filter cake on filter is taken out, after size degradation, was carried out through 10 hours Freeze-drying, thus obtains white powder 60g.Obtained particle is observed with SEM, result is monodisperse spheroidal particle. The refractive index of the particle, result 1.54 are measured using immersion method.By the section of the tem observation particle, as a result confirm It is the particle of single structure in particle.

Fluorophor: Nemoto Lumi-Materials Company Limited system " YAG81003 " (YAG system fluorophor, Median particle diameter (D₅₀): 8.6 μm, refractive index: 1.8).

For cooperating the ingredient of organic siliconresin

Resin principal component (MeViSiO_2/2)_0.25(Ph₂SiO_2/2)_0.3(PhSiO_3/2)_0.45(HO_1/2)_0.03(average composition, phase When in (A) ingredient.)

Hardness regulator ViMe₂SiO(MePhSiO)_17.5SiMe₂(average composition is equivalent to (B) ingredient to Vi.)

Crosslinking agent (HMe₂SiO)₂SiPh₂(it is equivalent to (C) ingredient.)

※ wherein, Me: methyl, Vi: vinyl, Ph: phenyl

Reaction suppressor 1- acetenyl hexanol

Platinum catalyst platinum complex (1,3- divinyl -1,1,3,3- tetramethyl disiloxane solution) platinum content is 5 weights Measure %.

For the organic siliconresin 1,7~19 for making fluorescencer composition, cooperate above-mentioned silicone ingredients, makes base Body resin.In addition, using commercially available product (two liquid melanges), according to circumstances changing A liquid and B liquid for organic siliconresin 2~6 Blending ratio (A/B ratio) makes matrix resin.

Organic siliconresin 1:

16.7 parts by weight of resin principal component, 16.7 parts by weight of hardness regulator, 66.7 parts by weight of crosslinking agent,

0.025 parts by weight of reaction suppressor, 0.03 parts by weight of platinum catalyst

Organic siliconresin 2: " OE6630 (A liquid, B liquid) " (Dow Corning Toray corporation)

A/B ratio 1/4

Organic siliconresin 3: " OE6336 (A liquid, B liquid) " (Dow Corning Toray corporation)

A/B ratio 1/1

Organic siliconresin 4: " KER6075 (A liquid, B liquid) " (SHIN-ETSU HANTOTAI's chemical industry system)

A/B ratio 1/1

Organic siliconresin 5: " KER6075 (A liquid, B liquid) " (SHIN-ETSU HANTOTAI's chemical industry system)

A/B ratio 1/1.14

Organic siliconresin 6: " KER6075 (A liquid, B liquid) " (SHIN-ETSU HANTOTAI's chemical industry system)

A/B ratio 0.5/1

Organic siliconresin 7:

16.7 parts by weight of resin principal component, 20.0 parts by weight of hardness regulator, 66.7 parts by weight of crosslinking agent,

Organic siliconresin 8:

18.2 parts by weight of resin principal component, 18.2 parts by weight of hardness regulator, 63.6 parts by weight of crosslinking agent,

Organic siliconresin 9:

15.4 parts by weight of resin principal component, 15.4 parts by weight of hardness regulator, 69.2 parts by weight of crosslinking agent,

Organic siliconresin 10:

25.0 parts by weight of resin principal component, 20.0 parts by weight of hardness regulator, 50.0 parts by weight of crosslinking agent,

Organic siliconresin 11:

25.0 parts by weight of resin principal component, 25.0 parts by weight of hardness regulator, 50.0 parts by weight of crosslinking agent,

Organic siliconresin 12:

41.7 parts by weight of resin principal component, 9.1 parts by weight of hardness regulator, 41.7 parts by weight of crosslinking agent,

Organic siliconresin 13:

33.3 parts by weight of resin principal component, 43.3 parts by weight of hardness regulator, 23.3 parts by weight of crosslinking agent,

Organic siliconresin 14:

33.3 parts by weight of resin principal component, 33.3 parts by weight of hardness regulator, 33.3 parts by weight of crosslinking agent,

Organic siliconresin 15:

41.7 parts by weight of resin principal component, 18.2 parts by weight of hardness regulator, 41.7 parts by weight of crosslinking agent,

Organic siliconresin 16:

16.7 parts by weight of resin principal component, 4.3 parts by weight of hardness regulator, 70.7 parts by weight of crosslinking agent,

Organic siliconresin 17:

23.3 parts by weight of resin principal component, 53.3 parts by weight of hardness regulator, 23.3 parts by weight of crosslinking agent,

Organic siliconresin 18:

33.3 parts by weight of resin principal component, 5.0 parts by weight of hardness regulator, 33.3 parts by weight of crosslinking agent,

Organic siliconresin 19:

18.9 parts by weight of resin principal component, 5.6 parts by weight of hardness regulator, 75.5 parts by weight of crosslinking agent,

0.025 parts by weight of reaction suppressor, 0.03 parts by weight of platinum catalyst.

Using refractive index film thickness measuring device " Prism Coupler MODEL2010/M " (Metricon corporation), The refractive index of refractive index measurement sample is measured, and thus determines the mean refraction of metallic compound particle and matrix resin Rate N1.The refractive index N2 of fluorophor is substituted into following formula, by | N1-N2 | in a manner of calculate refringence.

The mixed-metal compounds particle in matrix resin uses the planetary churning deaerator of KURABO corporation " MAZERSTAR KK-400 " was carried out deaeration and is made dispersion liquid with 1,000rpm stirring 10 minutes.It is added dropwise in ilm substrate It after 5cc dispersion liquid, is heated 1 hour in 150 DEG C in an oven, production mean refractive index N1 measures sample.It should be noted that must When wanting, solvent can be removed using evaporator after making liquid.

The dispersed metallic compounds particle in matrix resin is made transparent sample for evaluation, is seen using optical microscopy Examine sample, the evaluation transparency.

A: absolutely not by defect caused by nanoparticle agglomeration, transparent film is formd.

B: although in the presence of by defect caused by nanoparticle agglomeration, more transparent film is formd.

C: lead to gonorrhoea (opaque) due to nanoparticle agglomeration.

The mixed-metal compounds particle in matrix resin uses the planetary churning deaerator of KURABO corporation " MAZERSTAR KK-400 " was carried out deaeration and is made dispersion liquid with 1,000rpm stirring 10 minutes.Using applicator in glass It after making film on substrate, is heated 1 hour in 150 DEG C in an oven, makes transparent sample for evaluation (75 μm).It needs to illustrate , when necessary, solvent can be removed using evaporator after making liquid.

When being coated with the fluorescencer composition made in each Examples and Comparative Examples using slotting die coaters, by discharge pressure setting For 0.1Pa, the easiness that resin at this time is discharged from nozzle is evaluated.

It is very good: after discharge starts, resin being discharged within 3 seconds.

It is good: after discharge starts, to be greater than 3 seconds and be that resin is discharged in the time within 10 seconds.

Difference: after discharge starts, resin is discharged more than 10 seconds.

Using the surface for the fluorophor sheet material that optical microphotograph sem observation is made based on embodiment, confirms the defects of being recessed, comment The easiness of valence formation sheet material film.

A: the defects of being absolutely not recessed forms uniform film.Extraordinary film thickness uniformity.

B: quantity the defects of recess is to form relatively uniform film within 10.Essentially without the film thickness of problem Uniformity.

C: the quantity of recess is 11 or more, does not form uniform film.Film thickness uniformity is poor.

Illumination photometry for the fluorophor sheet material in embodiment 19~96, comparative example 11~36, according to following main points system Make sample and is measured.

As shown in figure 11, in LED light source 17 (Prizmatix corporation " MS-LED-460 ", wavelength: 460nm, output work Rate: > 50mW) on, configure in order the 13 (OPTICAL of diffusion sheet material sheared in a manner of covering LED light source 17 SOLUTIONS CORPORATION system " LSD-60x1PC10-F12 "), be provided with diameter be 1mm hole ferrous metal screening The high face of the refractive index of fluorophor sheet material is attached at the (survey of sample obtained by GaN substrate by tabula rasa 16 in a manner of not introducing bubble Random sample product) 12, the shading cylinder 15 of ferrous metal, (the KONICA MINOLTA corporation chroma meter " CL- of illumination photometer 11 200A ") acceptance part, to measurement sample 12 illumination (1x) be measured.In general, at a certain distance, certain angle surveyed Periodically, illumination is proportional to brightness.Using the illumination of comparative example 11 as 100, show opposite relative to the illumination of comparative example 11 Value.

(the 1st after decimal point is rounded up)

GaN substrate (plate thickness 0.5mm) is set on hot plate, after the temperature of heating plate is set as 130 DEG C, with fluorescence The mode of body piece face and GaN substrate face contact overlaps fluorophor sheet material lamilate in GaN substrate.Then, using rubber Roller smoothes out with the fingers substrate (Ranvier's membrane) side 60 seconds of fluorophor sheet material lamilate, and fluorophor sheet material is attached at GaN substrate.

Make GaN base plate sample mobile from heating plate, restores to room temperature, substrate is peelled off, to make sample substrate.

11 parallel scars, production 100 are cut out with the interval of 1mm in length and breadth on the surface of sample substrate using NT cutter A grid.After polyester film adhesive adhesive tape (temple ridge makes made " Circuit tape No.647 ") is crimped thereon securely, The end of adhesive tape is removed quickly with 45 ° of angle, confirms the unstripped and remaining number of squares of fluorophor sheet material by visual observation, Evaluate adaptation.

S: remaining number of squares is 100

A: remaining number of squares is 95~99

B: remaining number of squares is 90~94

C: remaining number of squares is 85~89

D: remaining number of squares is 84 or less.

Measurement device: viscosity determination of viscoelasticity device HAAKE MARS III

(Thermo Fisher SCIENTIFIC system)

Determination condition: OSC temperature-independent measurement

Geometry: parallel circle template (20mm)

Minute: 1980 seconds

Angular frequency: 1Hz

Angular speed: 6.2832rad/ seconds

Heating rate: 0.08333 DEG C/sec

Sample shape: round (diameter 18mm).

After the fluorophor sheet material lamilate made based on Examples and Comparative Examples to be cut into the circle that diameter is 18mm, stripping From film only using fluorophor sheet material as measurement sample.The viscoelastic sexual behaviour of each fluorophor sheet material is shown in table 34,36,38,40.

<heat-resistance test>

The circulating current in the LED package for having used fluorophor sheet material is so that the surface temperature of packaging body becomes room temperature (25 DEG C)~170 DEG C, LED chip is lighted, is surveyed using moment Multichannel photometric system (MCPD-3000, great Zhong electronics corporation system) Determine brightness.Brightness when room temperature (25 DEG C) and 170 DEG C is measured, brightness conservation rate is calculated using following formula, thus evaluates heat resistance.It is bright It is higher to spend conservation rate, indicates that heat resistance is more excellent.When being evaluated as B or more, there is no problem in practical, when being evaluated as A or more, It is excellent on practical.

Brightness conservation rate I (%)=(brightness when brightness/room temperature (25 DEG C) at 170 DEG C) × 100

(the 1st after decimal point is rounded up)

S: conservation rate is that 90% or more heat resistance is very good

A: conservation rate is that 81~89% heat resistances are good

B: conservation rate is that there is no problem in practical for 51~80% heat resistances

C: conservation rate is 50% or less poor heat resistance.

As the index of the operability (rupture when operation, deformed due to softness) used when fluorophor sheet material, implement Determination of Hardness.For the sheet material made based on embodiment, the Durometer hardness based on JIS K6253 (2012) plastics is tried Method is tested, the soft hardometer of rubber plastic " Durometer Type D " (product number: GSD-720J TECLOCK company is used System) it is used as measurement device, measure the sheet material hardness of room temperature (25 DEG C).According to experience before this, the hardness of fluorophor sheet material and behaviour Make easiness correlation, therefore, operability is had rated together with hardness.When being evaluated as B or more, there is no problem in practical, evaluation It is excellent in practical when for A or more.

LED package in embodiment 1~18, comparative example 1~10 is made according to following main points.Use distributor (Musashino Engineering, Co., Ltd.'s system " MPP-1 "), obtained fluorescencer composition is poured into and is equipped with LED core Packaging body frame (the Enomoto Co., Ltd. system of piece (Showa electrician (strain) makes " GM2QT450G ", mean wavelength: 453.4nm) Frame " TOP LED BASE ") in, solidify 1 hour in 80 DEG C, solidifies 2 hours in 150 DEG C, thus make LED package.For LED package obtained, the electric current for the 20mA that circulates is to be lighted, and using moment Multichannel photometric system, (big tomb electronics is public Department's system " MCPD-7700 ") brightness after test just starts is measured, using 10 average value as brightness.By the photograph of comparative example 1 Degree is used as 100, shows the relative value of the illumination relative to comparative example 1.

(the 1st after decimal point is rounded up)

Embodiment 1 (there are organic silicone microparticle, the effects of grafting)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), passing through grafting example 1 The obtained Titanium particles 3.0g of method in add 6.0g organic siliconresin 1 and mixed, with 1000rpm progress 10 minutes Stir deaeration.After placing the desired time, solvent, the sample that production solid component concentration is 80wt% are removed using evaporator Then product make detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.60.In addition, the transparency is very good.

Then, using planetary churning deaerator, in the Titanium particles that the method by grafting example 1 obtains 15.0g organic siliconresin 1 is added in 30.0g and is mixed, and stirring deaeration in 3 minutes is carried out with 1000rpm.Desired by placement Time after, using evaporator remove solvent, production solid component concentration be 80wt% sample.Then, addition 6.67g is organic Silicon particle, 26.67g fluorophor, 2.35g butyl carbitol are simultaneously mixed.Then, using planetary churning deaerator, After carrying out stirring deaeration in 5 minutes with 1000rpm, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 1 is made.Refractive index Difference | N1-N2 | it is 0.20.The test of discharge property is carried out using the fluorescencer composition 1, as a result, is started with discharge simultaneously from nozzle Resin is discharged, has confirmed good discharge.LED package is made, brightness measuring is carried out, as a result, relative to comparative example 1, Relative illumination becomes 110, obtains brightness improvement effect.

Comparative example 1 (there are organic silicone microparticle, the effects of grafting)

Metallic compound particle is not added, in addition to this, fluorophor combination is made by operation similarly to Example 1 Object.Then, LED package is made by operation similarly to Example 1, and is evaluated.As a result it is shown in table 3 and 4.

Comparative example 2 (there are organic silicone microparticle, the effects of grafting)

As metallic compound particle, it is changed to Powder Oxidation titanium particle " TKP-102 " (trade name, TAYCA (strain) system), In addition to this, fluorescencer composition is made by operation similarly to Example 1.Then, pass through operation similarly to Example 1 LED package is made, and is evaluated.As a result it is shown in table 3 and 4.Bad dispersibility in matrix resin, is agglomerated, because This, fails to make fluorescencer composition.

Comparative example 3 (there are organic silicone microparticle, the effects of grafting)

As metallic compound particle, it is changed to " opt-Lake TR-527 " (trade name, catalyst chemical conversion industry (strain) system Composition: 20 weight % of Titanium particles, 80 weight % of methanol), in addition to this, made by operation similarly to Example 1 glimmering Body of light composition.Then, LED package is made by operation similarly to Example 1, and is evaluated.As a result be shown in table 3 and 4.Compared with comparative example 1, brightness is further decreased.

Embodiment 2~9, comparative example 4,5 (there are organic silicone microparticle, the effects of grafting)

It is changed to the composition recorded in table 1,3, in addition to this, fluorophor group is made by operation similarly to Example 1 Close object.Then, LED package is made by operation similarly to Example 1, and is evaluated.As a result shown in table 1~4.From this It is found that when being fluorescencer composition of the invention, brightness significantly improves a little embodiments.In comparative example 4,5, brightness is not mentioned It is high.

Embodiment 10~18, comparative example 6~10 (no organic silicone microparticle, the effect of grafting)

Organic silicone microparticle is not added, the composition recorded in table 5,7 is changed to, in addition to this, by similarly to Example 1 Operation production fluorescencer composition.Then, LED package is made by operation similarly to Example 1, and is evaluated.Knot Fruit is shown in table 5~8.From these embodiments it is found that when being fluorescencer composition of the invention, brightness is improved.In comparative example 6~10 In, brightness does not improve.

Embodiment 19 (there are organic silicone microparticle, the effect of grafting, fluorophor sheet materials)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), passing through grafting example 1 The obtained Titanium particles 3.0g of method in add 6.0g organic siliconresin 1 and mixed, with 1000rpm progress 3 minutes Stir deaeration.After placing the desired time, solvent, the sample that production solid component concentration is 80wt% are removed using evaporator Then product make detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.60.In addition, the transparency is very good.

Then, using planetary churning deaerator, in the Titanium particles that the method by grafting example 1 obtains 15.0g organic siliconresin 1 is added in 30.0g and is mixed, and stirring deaeration in 3 minutes is carried out with 1000rpm.Desired by placement Time after, using evaporator remove solvent, production solid component concentration be 80wt% sample.Then, addition 6.67g is organic Silicon particle, 26.67g fluorophor, 2.35g butyl carbitol are simultaneously mixed.Then, using planetary churning deaerator, After carrying out stirring deaeration in 5 minutes with 1000rpm, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 1 is made.Refractive index Difference | N1-N2 | it is 0.20.The test of discharge property is carried out using the fluorescencer composition 1, as a result, is started with discharge simultaneously from nozzle Resin is discharged, has confirmed good discharge.

Using slotting die coaters, fluorescencer composition 1 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 110, obtains brightness improvement effect.

Embodiment 20~27, comparative example 11~15 (there are organic silicone microparticle, the effect of grafting, fluorophor sheet materials)

It is changed to the composition recorded in table 9,11, in addition to this, fluorophor is made by operation similarly to Example 19 Composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result it is shown in Table 9~12.From these embodiments it is found that for fluorescencer composition of the invention is formed as fluorophor sheet material made of sheet When, film thickness uniformity is good, and brightness also significantly improves.In comparative example 10~14, film thickness uniformity is bad, and brightness does not also mention It is high.

Embodiment 28~36, comparative example 16~20 (no organic silicone microparticle, the effect of grafting, fluorophor sheet material)

Organic silicone microparticle is not added, the composition recorded in table 13,15 is changed to, in addition to this, by same with embodiment 19 The operation of sample makes fluorescencer composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and It is evaluated.As a result shown in table 1 3~16.From these embodiments it is found that for fluorescencer composition of the invention is formed as sheet Made of fluorophor sheet material when, film thickness uniformity is usage range, and brightness also improves.In comparative example 16~20, uniform film thickness Property is bad, and brightness does not also improve.

Embodiment 37 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 9.52g 1.58g organic siliconresin 1 is added in the Titanium particles that the method for change example 1 obtains and is mixed, and carries out 3 points with 1000rpm Clock stirs deaeration.After placing the desired time, solvent is removed using evaporator, production solid component concentration is 80wt%'s Then sample makes detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refraction Rate N1 is 1.63.In addition, the transparency is very good.

Then, logical in 47.57g using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system) Add and 7.93g organic siliconresin 1 and mixed in the Titanium particles that the method for crossing grafting example 1 obtains, with 1000rpm into Row stirring deaeration in 3 minutes.After placing the desired time, solvent is removed using evaporator, production solid component concentration is The sample of 80wt%.Then, 6.67g organic silicone microparticle, 26.67g fluorophor, 2.66g butyl carbitol are added and is mixed. Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), with 1000rpm progress 5 minutes After stirring deaeration, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 29 is made.Refringence | N1-N2 | it is 0.17. The test of discharge property is carried out using the fluorescencer composition 29, as a result, is started that resin simultaneously is discharged from nozzle with discharge, is confirmed Good discharge.

Using slotting die coaters, fluorescencer composition 29 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 111, obtains biggish brightness improvement effect.

Embodiment 38 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 12.0g 0.6g organic siliconresin 1 was added in the Titanium particles that the method for change example 1 obtains and is mixed, with 1000rpm progress 3 minutes Stir deaeration.After placing the desired time, solvent, the sample that production solid component concentration is 80wt% are removed using evaporator Then product make detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.70.In addition, the transparency is very good.

Then, using planetary churning deaerator, in the titanium oxide that 60.0g is obtained by the method for grafting example 1 3.0g organic siliconresin 1 is added in particle and is mixed, and stirring deaeration in 3 minutes is carried out with 1000rpm.It places desired After time, solvent, the sample that production solid component concentration is 80wt% are removed using evaporator.Then, 6.67g organosilicon is added Particle, 26.67g fluorophor, 2.89g butyl carbitol are simultaneously mixed.Then, using planetary churning deaerator, with After 1000rpm carries out stirring deaeration in 5 minutes, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 30 is made.Refractive index Difference | N1-N2 | it is 0.10.The test of discharge property is carried out using the fluorescencer composition 30, as a result, is started with discharge simultaneously from spray Resin is discharged in mouth, has confirmed good discharge.

Using slotting die coaters, fluorescencer composition 30 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 115, obtains big brightness improvement effect.

Embodiment 39 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 7.94g 2.26g organic siliconresin 1 is added in the Titanium particles that the method for change example 10 obtains and is mixed, and carries out 3 points with 1000rpm Clock stirs deaeration.After placing the desired time, solvent is removed using evaporator, production solid component concentration is 80wt%'s Then sample makes detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refraction Rate N1 is 1.73.In addition, the transparency is very good.

Then, logical in 39.67g using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system) 11.33g organic siliconresin 1 is added in the Titanium particles that the method for crossing grafting example 5 obtains and is mixed, with 1000rpm Carry out stirring deaeration in 3 minutes.After placing the desired time, solvent is removed using evaporator, production solid component concentration is The sample of 80wt%.Then, 6.67g organic silicone microparticle, 26.67g fluorophor, 2.53g butyl carbitol are added and is mixed. Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), with 1000rpm progress 5 minutes After stirring deaeration, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 31 is made.Refringence | N1-N2 | it is 0.07. The test of discharge property is carried out using the fluorescencer composition 31, as a result, is started that resin simultaneously is discharged from nozzle with discharge, is confirmed Good discharge.

Using slotting die coaters, fluorescencer composition 31 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 117, obtains very big brightness improvement effect.

Embodiment 40 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 8.32g 2.08g organic siliconresin 1 is added in the Titanium particles that the method for change example 10 obtains and is mixed, and carries out 3 points with 1000rpm Clock stirs deaeration.After placing the desired time, solvent is removed using evaporator, production solid component concentration is 80wt%'s Then sample makes detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refraction Rate N1 is 1.75.In addition, the transparency is very good.

Then, logical in 41.60g using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system) 10.40g organic siliconresin 1 is added in the Titanium particles that the method for crossing grafting example 5 obtains and is mixed, with 1000rpm Carry out stirring deaeration in 3 minutes.After placing the desired time, solvent is removed using evaporator, production solid component concentration is The sample of 80wt%.Then, 6.67g organic silicone microparticle, 26.67g fluorophor, 2.56g butyl carbitol are added and is mixed. Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), with 1000rpm progress 5 minutes After stirring deaeration, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 32 is made.Refringence | N1-N2 | it is 0.05. The test of discharge property is carried out using the fluorescencer composition 32, as a result, is started that resin simultaneously is discharged from nozzle with discharge, is confirmed Good discharge.

Using slotting die coaters, fluorescencer composition 32 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 119, obtains very big brightness improvement effect.

Embodiment 41 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 9.52g 1.58g organic siliconresin 1 is added in the Titanium particles that the method for change example 10 obtains and is mixed, and carries out 3 points with 1000rpm Clock stirs deaeration.After placing the desired time, solvent is removed using evaporator, production solid component concentration is 80wt%'s Then sample makes detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refraction Rate N1 is 1.78.In addition, the transparency is very good.

Then, logical in 47.57g using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system) Add and 7.93g organic siliconresin 1 and mixed in the Titanium particles that the method for crossing grafting example 1 obtains, with 1000rpm into Row stirring deaeration in 3 minutes.After placing the desired time, solvent is removed using evaporator, production solid component concentration is The sample of 80wt%.Then, 6.67g organic silicone microparticle, 26.67g fluorophor, 2.66g butyl carbitol are added and is mixed. Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), with 1000rpm progress 5 minutes After stirring deaeration, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 33 is made.Refringence | N1-N2 | it is 0.02. The test of discharge property is carried out using the fluorescencer composition 33, as a result, is started that resin simultaneously is discharged from nozzle with discharge, is confirmed Good discharge.

Using slotting die coaters, fluorescencer composition 33 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 122, obtains very big brightness improvement effect.

Comparative example 21 (effect of refractive index, fluorophor sheet material)

Using organic siliconresin 2, without the use of metallic compound particle, make detecting refractive index and commented with sample and the transparency Valence sample.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.54.In addition, the transparency is very good.

Next, taking out 26.67g organic siliconresin 2,6.67g organic silicone microparticle, 26.67g fluorophor, 1.8g fourth are added Base carbitol is simultaneously mixed.Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), After carrying out stirring deaeration in 5 minutes with 1000rpm, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 34 is made.Refraction Rate is poor | N1-N2 | it is 0.26.Using the fluorescencer composition 34 carry out discharge property test, as a result, with discharge start simultaneously from Resin is discharged in nozzle, has confirmed good discharge.

Using slotting die coaters, fluorescencer composition 34 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.In addition, carrying out illumination photometry, as a result, relative to comparative example 11, relative illumination becomes It is 90, there is no brightness improvement effect.

Comparative example 22 (effect of refractive index, fluorophor sheet material)

Using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through grafting in 3.88g 3.8g organic siliconresin 1 was added in the Titanium particles that the method for change example 1 obtains and is mixed, with 1000rpm progress 3 minutes Stir deaeration.After placing the desired time, solvent, the sample that production solid component concentration is 80wt% are removed using evaporator Then product make detecting refractive index sample and transparent sample for evaluation.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.58.In addition, the transparency is very good.

Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), pass through in 19.0g 19.0g organic siliconresin 1 is added in the Titanium particles that the method for grafting example 1 obtains and is mixed, and is carried out with 1000rpm Stirring deaeration in 3 minutes.After placing the desired time, solvent is removed using evaporator, production solid component concentration is The sample of 80wt%.Then, 6.67g organic silicone microparticle, 26.67g fluorophor, 2.14g butyl carbitol are added and is mixed. Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), with 1000rpm progress 5 minutes After stirring deaeration, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 35 is made.Refringence | N1-N2 | it is 0.22. The test of discharge property is carried out using the fluorescencer composition 35, as a result, is started that resin simultaneously is discharged from nozzle with discharge, is confirmed Good discharge.

Using slotting die coaters, fluorescencer composition 35 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.Then, it is pasted using the replacement that photopolymer layer press implements fluorescence sheet material, by substrate Film is changed to polyphenylene sulfide film " Torelina 3000 " (eastern beautiful (strain) system, average film thickness are 50 μm).Carry out illumination photometry, knot Fruit, relative to comparative example 11, relative illumination becomes 100, there is no brightness improvement effect.

Comparative example 23 (effect of refractive index, fluorophor sheet material)

Using organic siliconresin 3, without the use of metallic compound particle, make detecting refractive index and commented with sample and the transparency Valence sample.Carry out refractive index evaluation, as a result, mean refractive index N1 is 1.40.In addition, the transparency is very good.

Next, taking out 26.67g organic siliconresin 3,6.67g organic silicone microparticle, 26.67g fluorophor, 1.8g fourth are added Base carbitol is simultaneously mixed.Then, using planetary churning deaerator " MAZERSTAR KK-400 " (KURABO system), After carrying out stirring deaeration in 5 minutes with 1000rpm, using triple-roller mill mixing dispersion 6 times, fluorescencer composition 36 is made.Refraction Rate is poor | N1-N2 | it is 0.40.Using the fluorescencer composition 36 carry out discharge property test, as a result, with discharge start simultaneously from Resin is discharged in nozzle, has confirmed good discharge.

Using slotting die coaters, fluorescencer composition 36 is coated on " Cerapeel " BX9 as substrate, and (the beautiful film in east adds Work (strain) system, average film thickness be 50 μm) demoulding process face on, in 120 DEG C heat 30 minutes, be dried, obtain 80 μm, The fluorophor sheet material lamilate of 100mm square.In addition, carrying out illumination photometry, as a result, relative to comparative example 11, relative illumination becomes It is 80, there is no brightness improvement effect.

Embodiment 42~47 (effect of solvent, fluorophor sheet material)

It is changed to the solvent recorded in table 19, in addition to this, is operated in the same way with grafting example 1, obtains being grafted Titanium particles.Other than using the Titanium particles, fluorescencer composition is made by operation similarly to Example 19. Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result shown in table 19,20. From these embodiments it is found that when for fluorescencer composition of the invention being formed fluorophor sheet material made of sheet, thickener it is saturating Bright property is also good, and brightness also improves.

Embodiment 48~52, comparative example 24 (effect of high refractive index nanoparticles, fluorophor sheet material)

It is changed to the metallic compound particle recorded in table 22, in addition to this, operates in the same way, obtains with grafting example 1 The nanoparticle for being grafted.Other than using the nanoparticle, fluorophor is made by operation similarly to Example 19 Composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result it is shown in Table 21,22.From these embodiments it is found that for fluorescencer composition of the invention is formed as fluorophor sheet material made of sheet When, brightness improves.In comparative example 24, brightness is not improved.

Embodiment 19,53~57, comparative example 25~28 (effect of the partial size of high refractive index nanoparticles, fluorophor sheet material)

It is changed to the metallic compound particle recorded in table 23, in addition to this, operates in the same way, obtains with grafting example 1 The nanoparticle for being grafted.Other than using the nanoparticle, fluorophor is made by operation similarly to Example 19 Composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result it is shown in Table 23,24.From these embodiments it is found that for fluorescencer composition of the invention is formed as fluorophor sheet material made of sheet When, brightness improves.In comparative example 25~28, brightness is not improved.

Embodiment 58~64 (effect of substrate, fluorophor sheet material)

Fluorescencer composition is made by operation similarly to Example 19.Then, it is changed to the substrate recorded in table 25, In addition to this, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result it is shown in table 25.Relative to comparative example 11, the film thickness uniformity of embodiment 58~64 is good.In addition, carrying out illumination photometry, as a result, relative to Comparative example 11, embodiment 58~64 obtain brightness improvement effect.As can be known from these results, even if change substrate, for brightness Effect also do not change.

Embodiment 65~71 (effect of fluorophor sheet material film thickness, fluorophor sheet material)

Fluorescencer composition is made by operation similarly to Example 19.Then, it is changed to the sheet material recorded in table 26 In addition to this film thickness makes fluorophor sheet material lamilate by operation similarly to Example 19, and evaluated.As a result show In table 26.Carry out heat-resistance test, as a result, confirm with the tendency that film thickness thickens, heat resistance is deteriorated.In addition, being shone Degree measurement, as a result it is found that relative to comparative example 11, the brightness of embodiment 65~71 is improved.

Embodiment 72 (effect of high refractive index nanoparticles, fluorophor sheet material)

It is changed to the metallic compound particle recorded in table 19, in addition to this, operates in the same way, obtains with grafting example 1 The nanoparticle for being grafted.Other than using the nanoparticle, fluorophor is made by operation similarly to Example 19 Composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result it is shown in Table 28.From embodiment 72 it is found that for when fluorescencer composition of the invention is formed as fluorophor sheet material made of sheet, brightness It improves.

[table 27]

The effect of [table 27]<high refractive index nanoparticles, fluorophor sheet material>

[table 28]

Embodiment 19,73~82, comparative example 14 (effect of the molar ratio of alkoxysilane compound containing trialkylsilyl group in molecular structure, fluorophor sheet material)

It is changed to the grafting method recorded in table 29,31, in addition to this, is made by operation similarly to Example 19 glimmering Body of light composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and is evaluated.As a result It is shown in table 29~32.Operability is evaluated, as a result, relative to comparative example 11, embodiment 19,73~82 is obtained in reality With there is no problem as a result, especially embodiment 19,73~75 is good operability.In addition, illumination photometry is carried out, knot Fruit, relative to comparative example 11, embodiment 19,73~82 obtains big brightness improvement effect.

Embodiment 19,83~91, (there are organic silicone microparticle, viscoelastic sexual behaviour, fluorescence for comparative example 11,13,14,29~35 Body sheet material)

In addition to this matrix resin for being changed to record in table 33,35,37 passes through operation system similarly to Example 19 Make fluorescencer composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and carries out viscoplasticity Behavior and various evaluations.As a result it is shown in table 33~38.Carry out fitness test, as a result, in the model of viscoelastic sexual behaviour of the invention Embodiment 19,83~91 in enclosing obtains good adaptation, and in contrast, comparative example 11,13,14,29~35 is close Close undesirable result.In addition, carrying out illumination photometry, as a result, relative to comparative example 11, embodiment 19,83~91 obtains brightness Improvement effect.Comparative example 11,13,14,29~35 there is no brightness improvement effect.It as can be known from these results, is of the invention When fluorophor sheet material, brightness improvement effect can get.

Embodiment 28,92~96, comparative example 16,18,19,36 (no organic silicone microparticle, viscoelastic sexual behaviour, fluorophor sheet material)

Organic silicone microparticle is not added, the matrix resin recorded in table 39 is changed to, in addition to this, by same with embodiment 19 The operation of sample makes fluorescencer composition.Then, fluorophor sheet material lamilate is made by operation similarly to Example 19, and Carry out viscoelastic sexual behaviour and various evaluations.As a result it is shown in table 39,40.Carry out fitness test, as a result, in viscoplasticity of the invention Embodiment 28,92~96 in the range of behavior obtains good adaptation, and in contrast, comparative example 16,18,19,36 For closely sealed undesirable result.In addition, carrying out illumination photometry, as a result, relative to comparative example 11, embodiment 28,92~96 is obtained Brightness improvement effect.Comparative example 16,18,19,36 there is no brightness improvement effect.It as can be known from these results, is of the invention When fluorophor sheet material, brightness improvement effect can get.

Description of symbols

1 LED chip

2 fluorophor sheet materials

3 electrodes

4 fluorescencer compositions

5 reflecting mirrors

6 transparent sealants

7 installation base plates

8 au bumps

9 transparent adhesives

10 substrates

11 illumination photometers

12 measurement samples

13 diffusion sheet materials

14 brackets

15 shading cylinders

16 barn doors

17 LED light sources

18 packaging body frames

19 LED packages

20 substrates

21 are fixed temporarily sheet material

22 heating crimping tools

23 surfaces are formed with the chip of LED chip

24 have the LED chip of fluorophor sheet material

25 substrates

26 fluorophor sheet material lamilates

27 installation base plates

28 electrodes

29 double-sided adhesive tapes

30 pedestals

31 upper chambers

32 lower chambers

33 diaphragms

35 vacuum diaphragm laminating machinees

34 air-breathings/exhaust outlet

36 cut portions

37 have the LED chip of fluorophor sheet material

38,39 LED packages

101 matrix resins

102 metallic compound particles

103 organic silicone microparticles

The metallic compound particle of 104 being grafted

105 fluorophor

Claims

1. a kind of fluorescencer composition contains fluorophor, matrix resin and metallic compound particle, which is characterized in that described The refractive index of metallic compound particle is 1.7 or more, and average grain diameter is 1~50nm, the metallic compound particle and described The mean refractive index N1 of matrix resin and the refractive index N2 of the fluorophor meet following relationship, the metallic compound particle quilt Grafting,

0.20 >=| N1-N2 |,

The fluorescencer composition also contains organic silicone microparticle, and the surface of the organic silicone microparticle is by the metal compound through grafting Object particle is coating.

2. fluorescencer composition as described in claim 1, wherein the metallic compound particle uses the contracting of alkoxy silane It closes object and has carried out grafting.

3. fluorescencer composition as described in claim 1, wherein the metallic compound particle uses the contracting of alkoxy silane It closes object and has carried out grafting, the alkoxy silane includes alkoxy silane and methylic alkoxy silane containing phenyl.

4. fluorescencer composition as claimed in claim 1 or 2, wherein the metallic compound particle passes through following manner quilt Grafting, the mode are as follows: in the presence of metallic compound particle, utilize acid catalyst by alkoxyl silicone alkanisation in a solvent After hydrate hydrolysis, the hydrolysate is made to carry out condensation reaction.

5. fluorescencer composition as claimed in claim 4, which is characterized in that the alkoxysilane compound containing trialkylsilyl group in molecular structure contains 70~ Two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure of trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure of 100 moles of %, 0~30 mole of %.

6. fluorescencer composition as claimed in claim 1 or 2, wherein the metallic compound particle is selected from being closed by calorize At least 1 in object particle, tin compound particle, titanium compound particle, zirconium compounds particle and molecular group of niobium compound grain The metallic compound particle of kind.

7. fluorescencer composition as claimed in claim 1 or 2, wherein described matrix resin is organic siliconresin.

8. fluorescencer composition as claimed in claim 7, wherein described matrix resin is with siloxanes key and to contain It is directly connected to the organic siliconresin of the silicon atom of aryl.

9. fluorescencer composition as claimed in claim 8, wherein described matrix resin has siloxanes key, and containing straight It is connected to the silicon atom of naphthalene in succession.

10. a kind of fluorophor sheet material is that fluorescencer composition according to any one of claims 1 to 9 is formed as sheet Made of.

11. a kind of fluorophor sheet material contains fluorophor, matrix resin and metallic compound particle, which is characterized in that the gold Belong to compound particles refractive index be 1.7 or more, and average grain diameter be 1~50nm, being grafted of metallic compound particle, The refractive index N2 of the mean refractive index N1 of the metallic compound particle and described matrix resin and the fluorophor meets following Relationship (i), the viscoelastic sexual behaviour of sheet material meet following relationship (ii), (iii) and (iv),

The relationship of refractive index

(i) 0.20 >=| N1-N2 |

Viscoelastic sexual behaviour

(ii) when temperature is 25 DEG C, store elastic modulus G ' meets 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and δ < 1 tan；

(iii) when temperature is 100 DEG C, store elastic modulus G ' meets 1.0 × 10²Pa≤G’<1.0×10⁴Pa, and tan δ >= 1；

(iv) when temperature is 200 DEG C, store elastic modulus G ' meets 1.0 × 10⁴Pa≤G’≤1.0×10⁶Pa, and δ < 1 tan,

The fluorophor sheet material also contains organic silicone microparticle, and the surface of the organic silicone microparticle is by the metallic compound through grafting Particle is coating.

12. fluorophor sheet material as claimed in claim 11, wherein the metallic compound particle uses the contracting of alkoxy silane It closes object and has carried out grafting.

13. fluorophor sheet material as claimed in claim 11, wherein the metallic compound particle uses the contracting of alkoxy silane It closes object and has carried out grafting, the alkoxy silane includes alkoxy silane and methylic alkoxy silane containing phenyl.

14. the fluorophor sheet material as described in claim 11 or 12, wherein the metallic compound particle passes through following manner quilt Grafting, the mode are as follows: in the presence of metallic compound particle, utilize acid catalyst by alkoxyl silicone alkanisation in a solvent After hydrate hydrolysis, the hydrolysate is made to carry out condensation reaction.

15. fluorophor sheet material as claimed in claim 14, which is characterized in that the alkoxysilane compound containing trialkylsilyl group in molecular structure contains 70~ Two functionality alkoxysilane compound containing trialkylsilyl group in molecular structure of trifunctional's alkoxysilane compound containing trialkylsilyl group in molecular structure of 100 moles of %, 0~30 mole of %.

16. the fluorophor sheet material as described in claim 11 or 12, wherein the metallic compound particle is selected from being closed by calorize At least 1 in object particle, tin compound particle, titanium compound particle, zirconium compounds particle and molecular group of niobium compound grain The metallic compound particle of kind.

17. the fluorophor sheet material as described in claim 11 or 12, wherein described matrix resin is organic siliconresin.

18. fluorophor sheet material as claimed in claim 17, wherein described matrix resin has siloxanes key, and containing straight It is connected to the silicon atom of aryl in succession.

19. fluorophor sheet material as claimed in claim 18, wherein described matrix resin has siloxanes key, and containing straight It is connected to the silicon atom of naphthalene in succession.

20. the fluorophor sheet material as described in claim 11 or 12, wherein the film thickness of sheet material is 10~1000 μm.

21. a kind of fluorophor sheet material lamilate, contains phosphor plates described in any one of substrate and claim 10~20 Material.

22. fluorophor sheet material lamilate as claimed in claim 21, wherein the substrate is glass.

23. fluorophor sheet material lamilate as claimed in claim 21, wherein the substrate is selected from by poly terephthalic acid second The plastic foil in group that diol ester (PET), polyphenylene sulfide (PPS), polypropylene (PP) form.

24. a kind of LED chip with fluorophor sheet material, wherein LED chip Luminescent mask in claim 10~20 Described in any item fluorophor sheet materials.

25. a kind of LED package has used fluorescencer composition according to any one of claims 1 to 9.

26. a kind of LED package has used fluorophor sheet material described in any one of claim 10~20.

27. a kind of manufacturing method of LED package, to have used fluorophor according to any one of claims 1 to 9 to combine The manufacturing method of the LED package of object, the manufacturing method include at least following processes:

Process (A), the fluorescencer composition is injected into packaging body frame；And

Process (B) is sealed LED package using sealing material after the process (A).

28. a kind of manufacturing method of LED package is to have used phosphor plates described in any one of claim 10~20 The manufacturing method of the LED package of material, the manufacturing method include at least following processes:

(A) process is aligned, keeps a block of the fluorophor sheet material opposed with the light-emitting surface of a LED chip；And

(B) bonding process pressurizes while heating using heating crimping tool, makes one area of the sheet material Block is Nian Jie with the light-emitting surface of one LED chip.

29. the manufacturing method of LED package as claimed in claim 28, wherein (A) process is following contraposition processes: Make side in the upper surface and the lower surface of a block of the fluorophor sheet material, high refractive index nanoparticles concentration is big Face is opposed with the light-emitting surface of one LED chip.

30. a kind of manufacturing method of LED package is to have used phosphor plates described in any one of claim 10~20 The manufacturing method of the LED package of material, the manufacturing method include carrying out the light-emitting surface of LED chip with the fluorophor sheet material Coating process.

31. the manufacturing method of the LED package as described in any one of claim 28~30, which is characterized in that LED chip Light-emitting surface is not single plane.