JP2007242246A - Lighting apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lighting apparatus 400 having an optical member 401 such as an outer lens and a light guide plate capable of transmitting or guiding the light emitted from a light source 102 which has a high efficiency of incident light from the light source 102 to the optical member 401 and superior luminance with excellent durability. <P>SOLUTION: The light source 102 is constructed of a package 201 having a recessed part, a semiconductor light-emitting element 202 arranged in the recessed part of the package 201, and a sealing member 203 to seal the semiconductor light-emitting element 202. The sealing member 203 is formed by an elastic body, and the optical member 401 and the sealing member 203 are jointed without including an air layer in substance, and the difference of refractive index of the optical member 401 and the sealing member is made 0.17 or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an illumination device including an external optical member such as an outer lens or a light guide plate that can transmit or guide light emitted from a light source.

  2. Description of the Related Art In recent years, surface light emitting devices that emit light from LED chips, which are point light sources, in a planar shape are used as light sources such as liquid crystal backlights. The surface light-emitting device is configured to allow light from one or more LED light sources to enter from one end surface of a light guide plate having opposing main surfaces, and to emit light from the entire one main surface of the light guide plate. Is done.

  6A and 6B are diagrams schematically showing the configuration of a conventional surface light emitting device, FIG. 6A is a side view of the surface light emitting device, and FIG. 6B is a surface light emitting device. It is a top view of an apparatus. A surface light emitting device 600 shown in FIGS. 6A and 6B includes a light guide plate 601 having a first main surface and a second main surface in an outer frame 603 and made of a transmissive resin, and the light guide plate. LED light source 602 provided to face the end surface of 601; substrate 605 fixing LED light source 602; diffusion sheet 607 provided on the first main surface side of the light guide plate; 2 and a reflection sheet 606 provided on the main surface side of the light guide plate 601 so that the light from the LED light source 602 is emitted from the entire one main surface of the light guide plate 601.

  FIG. 7 is a cross-sectional view schematically showing a configuration of a conventional LED light source used as the LED light source 602 of FIGS. 6 (a) and 6 (b). In FIG. 7, the same components as those in FIG. 6 are denoted by the same reference numerals. In an LED light source 700 (602) shown in FIG. 7, an LED element 702 is placed in a recess of a package 701 provided with a lead electrode 704 and covered with a sealing resin 703.

  In the surface light emitting device 600 configured as described above, the light output from the LED light source 602 decreases as it propagates through the light guide plate 601, and the amount of light decreases as it moves away from the LED light source 602. A light diffusing dot pattern is formed on a certain second main surface to obtain uniform surface light emission. This light diffusing dot pattern increases the area of the light diffusing dots sequentially by increasing the density of the dots or the area of each dot as the distance from the LED light source increases, so that the luminance in the light emitting surface is made uniform. Yes.

  However, the conventional LED light source 700 (602) shown in FIG. 7 has a gap between the light guide plate 601 and the LED light source 602 when used in the surface light emitting device 600 of FIGS. There is a problem that light is absorbed by the air layer in the gap.

  In contrast, in Patent Document 1, a transparent elastic body such as silicone resin is used to fill a gap between the light guide plate and the LED light source, and the light guide plate and the LED light source are brought into close contact with each other. There has been disclosed a surface light-emitting device that improves the light introduction efficiency into the light plate and can obtain uniform surface light emission with high output.

  Moreover, a light emitting device having a configuration using an outer lens is also known as another type of illumination device including a light source and an external optical member.

  For example, in Patent Document 2, an LED is disposed in a frame-shaped lamp house (base portion) excellent in stress relaxation, sealed with a soft resin having high reflow resistance, and heat that is difficult to be thermally deformed thereon. An optical semiconductor device is disclosed that has a high light output by suppressing the occurrence of peeling and cracks due to thermal expansion and contraction due to reflow by providing an outer lens made of a curable resin.

JP 2003-234008 A JP 2005-039030 A

  However, the illumination devices described in Patent Documents 1 and 2 are not sufficient in luminance and durability, and further improvements in luminance and durability have been demanded.

  The present invention has been made in view of the above problems. That is, the present invention is an illumination device including an external optical member such as an outer lens or a light guide plate that can transmit or guide light emitted from a light source, and has high light incident efficiency from the light source to the external optical member, It aims at providing the illuminating device which was excellent also in durability while being excellent in the brightness | luminance.

  The present inventors have fixed a semiconductor light emitting element in a package using a sealing member made of an elastic body, joined the optical member and the sealing member substantially without an air layer, and optical By keeping the difference in refractive index between the member and the sealing member within a predetermined range, the light incident efficiency from the light source to the optical member can be improved, and the lighting device has excellent luminance and durability. The inventors have found that the present invention can be obtained and have completed the present invention.

  That is, the gist of the present invention is an illumination device having at least a light source and an optical member capable of transmitting or guiding light emitted from the light source, wherein the light source is provided in a package having a recess, and in the recess of the package. A semiconductor light emitting element to be disposed; and a sealing member for sealing the semiconductor light emitting element. The sealing member is made of an elastic body, and the optical member and the sealing member are substantially air. The present invention resides in a lighting device characterized in that the optical member and the sealing member are bonded to each other without a layer, and the difference in refractive index between the optical member and the sealing member is within 0.17.

  Here, it is preferable that the sealing member is provided so as to protrude from the opening surface of the recess of the package.

  Further, in the solid Si-nuclear magnetic resonance spectrum, the sealing member is (i) the position of the peak top is in the region where the chemical shift is −40 ppm or more and 0 ppm or less, and the half width of the peak is 0.3 ppm or more and 3.0 ppm. The peak is selected from the group consisting of the following peaks, and (ii) the peak top position is in the region where the chemical shift is −80 ppm or more and less than −40 ppm, and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less. It has at least one peak, the silicon content of the sealing member is 20% by weight or more, and the silanol content of the sealing member is 0.1% by weight or more and 10% by weight or less. (Claim 3).

  The total content of Si, Al, Zr, Ti, Y, Nb and B in the sealing member is preferably 20% by weight or more (Claim 4).

  Moreover, it is preferable to further include a wavelength conversion unit containing at least one wavelength conversion material that absorbs light from the semiconductor light emitting element and converts it into light of different wavelengths.

  Moreover, it is preferable that this sealing member contains the at least 1 type of wavelength conversion material which absorbs the light from this semiconductor light-emitting device, and converts it into the light of a different wavelength (Claim 6).

Further, it is preferable that the wavelength conversion material is a phosphor.
Further, when thermogravimetric / differential heat measurement is performed on the sealing member, it is preferable that the weight loss when the temperature is raised from 35 ° C. to 380 ° C. under air flow is 10% by weight or less. ).

  In addition, the optical member is formed as a light guide plate having an emission surface and a reflection surface facing each other, and the light source is bonded to one end surface or two opposite end surfaces of the light guide plate, and the light from the light source is Preferably, the light guide plate is configured to enter from the end face and to exit from the exit surface.

  The optical member is formed as an outer lens having an entrance surface and an exit surface, the light source is bonded to the entrance surface of the outer lens, and light from the light source is incident from the entrance surface of the outer lens. It is also preferable that the light is emitted from the emission surface.

  The illumination device of the present invention has high light incident efficiency from the light source to the external optical member, is excellent in luminance, and is excellent in durability. Moreover, it is excellent also in reflow tolerance depending on the aspect.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.

The illuminating device of the present invention includes at least a light source and an optical member capable of transmitting or guiding light emitted from the light source (sometimes referred to as an “external optical member” as appropriate), and the light source includes a recess. And a semiconductor light emitting device disposed in the recess of the package, and a sealing member that seals the semiconductor light emitting device, and includes the following features (i) to (iii): It will be.
(I) The sealing member is made of an elastic body.
(Ii) The optical member and the sealing member are joined substantially without an air layer.
(Iii) The refractive index difference between the optical member and the sealing member is within 0.17.

That is, the lighting device of the present invention allows the sealing member used for the light source to function not only to protect the semiconductor light emitting element but also to serve as a bonding member, and to bond the light source and the external optical member with high adhesion. In addition, the refractive index of the external optical member (hereinafter may be represented by the symbol “n _e ”) and the refractive index of the sealing member (hereinafter may be represented by the symbol “n _o ”). )) (Expressed in absolute value. This is hereinafter referred to as “refractive index step” as appropriate, and sometimes represented by the symbol “| n _e −n _o |”) within a specific range. Thus, the light incident efficiency from the light source to the external optical member is improved, and high luminance is realized.

As an aspect of the illumination device of the present invention, there are mainly the following two aspects.
(1) The optical member is formed as a light guide plate having an emission surface and a reflection surface facing each other, the light source is bonded to one end surface of the light guide plate or two opposite end surfaces, and light from the light source is transmitted from the end surface of the light guide plate. The aspect (surface light-emitting device) comprised so that it may enter and may make it radiate | emit from an output surface.
(2) The optical member is formed as an outer lens having an entrance surface and an exit surface, the light source is bonded to the entrance surface of the outer lens, and light from the light source is incident from the entrance surface of the outer lens and emitted from the exit surface. The aspect (semiconductor lighting device) comprised as follows.

  In the following description, first, the (1) surface light-emitting device will be described in detail as an embodiment of the illumination device of the present invention, and then, the above (2) as another embodiment of the illumination device of the present invention. The semiconductor lighting device will be briefly described mainly focusing on the difference from the case of the surface light emitting device.

  Note that examples of the semiconductor light emitting element included in the light source include a light emitting diode (hereinafter referred to as “LED”) element, a laser diode (hereinafter referred to as “LD”) element, and the like. In the following description, a case where an LED element is mainly used as a semiconductor light emitting element will be described as an example. A light source using an LED element as a semiconductor light emitting element may be referred to as an “LED light source”. However, the semiconductor light emitting element is not limited to the LED element, and any semiconductor light emitting element such as an LD element can be used.

[I. Surface emitting device]
In the surface light-emitting device that is the illumination device according to the first embodiment of the present invention, the optical member is formed as a light guide plate having an emission surface and a reflection surface facing each other, and the light source is one end surface of the light guide plate or two opposite surfaces. Joined to the end face, the light from the light source is made incident from the end face of the light guide plate and emitted from the exit face. And while a light source is comprised including the package which has a recessed part, the semiconductor light-emitting device arrange | positioned in the recessed part of a package, and the sealing member which seals a semiconductor light-emitting device, said (i)-( It has the characteristics of iii).

  FIGS. 1A and 1B are diagrams schematically showing a configuration of an illumination device (surface light-emitting device) according to the first embodiment of the present invention. FIG. 1A is a side view, FIG. 1 (b) is a top view. A surface light emitting device 100 shown in FIGS. 1A and 1B includes an emission surface (light emission surface) that is one main surface and a reflection surface that is the other main surface opposite to the emission surface in an outer frame 103. , An LED light source 102 disposed on the end face of the light guide plate 101, a substrate 105 fixing the LED light source 102, and a diffusion provided on the first main surface side of the light guide plate 101. A sheet 107 and a reflection sheet 106 provided on the second main surface side of the light guide plate 101 are provided, and light from the LED light source 102 is emitted from the entire one main surface of the light guide plate 101. It is configured.

  FIG. 2 is a cross-sectional view schematically showing an example of the configuration of the light source 102 provided in the illumination device (surface emitting device) according to the first embodiment of the present invention. 2, the same components as those in FIG. 1 are denoted by the same reference numerals. An LED light source 200 (102) shown in FIG. 2 includes a package 201 having a recess, an LED element 202 mounted in the recess, and a sealing member 203 that seals the LED element 202. A lead electrode 204 is provided in the recess of the package 201, and the LED light source 102 is connected to the lead electrode 204 so that a voltage can be applied to the LED light source 102 from the outside of the package 201.

  The LED light source 200 (102) shown in FIG. 2 is provided so that the sealing member 203 protrudes from the upper surface of the package 201, at least the protruding portion is made of an elastic body, and the sealing member, the light guide plate, The refractive index step of the film satisfies a predetermined range. Thus, when the LED light source 102 is mounted on the end face of the light guide plate 101, the shape of the elastic body is changed by an external force applied to the joint portion 104, and the end face of the light guide plate 101 and the LED light source 102 are joined with good adhesion. And light can be efficiently introduced into the light guide plate 101.

  In the present embodiment, when the LED light source 102 of the surface light emitting device 100 is used while being joined to the end surface of the light guide plate 101, the directivity is processed not on the LED light source 102 but on the end surface, reflecting surface, or exit surface of the light guide plate 101. Can be controlled. In other words, the LED light source 102 can have any shape without worrying about directivity. The present embodiment is characterized in that an elastic body is used as the sealing member 203 and that the portion is used not as a mere sealing member but as a bonding portion 104 with the end face of the light guide plate 101. Thereby, it can be set as a junction part with high adhesiveness, without using an adhesive agent. In addition, since a sealing member that is a part of the LED light source 102 is used as a joint portion, there is a possibility that the adhesive may adhere to a portion where the light guide plate 101 and the LED light source 102 are not joined when an adhesive is used separately. The adhesive is exposed. As a result, problems such as adhesion of dust occur, but in this embodiment, since the light guide plate 101 and the LED light source 102 are efficiently joined only at the part where they are joined, such a problem does not occur. The light from the LED light source 102 is efficiently incident on the light guide plate 101.

〔light source〕
(package)
In the present embodiment, the package 201 has a recess, and an LED element (semiconductor light emitting element) 202 described later is disposed therein. The shape and size of the package 201 and the shape and size of the recess are not particularly limited, and may be appropriately selected depending on the application and the shape of the LED element (semiconductor light emitting element) 202 to be used together. Shape is preferred. The material of the package 201 is not particularly limited, but usually, ceramics such as aluminum oxide and aluminum nitride; metals such as iron, copper, aluminum, nickel, gold, silver, and platinum or alloys thereof; polycarbonate resin, polyphenylene sulfide resin, epoxy Materials such as resin, acrylic resin, silicone resin, ABS (acrylonitrile-butadiene-styrene) resin, nylon resin, polyphthalamide and the like are used. A lead electrode 204 is provided in the recess of the package 201, and the LED light source 102 is connected to the lead electrode 204 so that a voltage can be applied to the LED light source 102 from the outside of the package 201. Yes.

(LED element)
In the present embodiment, the type of the LED element 202 is not particularly limited as long as it has a pair of positive and negative electrodes on the same surface side and can emit a part of light emission from the side end surface. In the case of using a fluorescent material, it is preferable to use a semiconductor light emitting element having a light emitting layer capable of emitting a wavelength capable of exciting the fluorescent material to be used. Examples of such semiconductor light emitting devices include various semiconductors such as ZnSe and GaN. Nitride semiconductors (In _X Al _Y Ga ₁ -XY) capable of emitting short wavelengths capable of efficiently exciting fluorescent materials. N, 0 ≦ X, 0 ≦ Y, and X + Y ≦ 1) are preferable. Examples of the semiconductor structure include a homostructure having a MIS junction, a PIN junction, and a pn junction, a heterostructure, and a double heterostructure. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the crystallinity thereof. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.

  When a nitride semiconductor is used, a material such as sapphire, spinel, SiC, Si, ZnO or the like is preferably used for the semiconductor substrate. In order to form a nitride semiconductor with good crystallinity with high productivity, it is preferable to use a sapphire substrate. A nitride semiconductor can be formed on the sapphire substrate by MOCVD or the like. A buffer layer of GaN, AlN, GaAIN or the like is formed on the sapphire substrate, and a nitride semiconductor having a pn junction is formed thereon.

  As an example of a light emitting device having a pn junction using a nitride semiconductor, a first contact layer formed of n-type gallium nitride, a first clad layer formed of n-type aluminum nitride / gallium on a buffer layer, Examples include a double hetero structure in which an active layer formed of indium / gallium nitride, a second cladding layer formed of p-type aluminum nitride / gallium, and a second contact layer formed of p-type gallium nitride are sequentially stacked. . Nitride semiconductors exhibit n-type conductivity without being doped with impurities. When forming a desired n-type nitride semiconductor, for example, to improve luminous efficiency, it is preferable to appropriately introduce Si, Ge, Se, Te, C, etc. as an n-type dopant. On the other hand, when forming a p-type nitride semiconductor, the p-type dopants such as Zn, Mg, Be, Ca, Sr, and Ba are doped. Since a nitride semiconductor is difficult to be converted to a p-type simply by doping with a p-type dopant, it is preferable to reduce the resistance by heating in a furnace or plasma irradiation after the introduction of the p-type dopant. After the electrodes are formed, a light emitting element made of a nitride semiconductor can be formed by cutting the semiconductor wafer into chips.

  In the present invention, when emitting mixed color light, particularly white light, as the LED light source, the emission wavelength of the LED element is usually 350 nm in consideration of the complementary color relationship with the emission wavelength from the fluorescent material and the deterioration of the translucent resin. Above all, it is preferable to be in the range of 360 nm or more, more preferably 370 nm or more, and usually 530 nm or less, especially 490 nm or less, more preferably 475 nm or less. By setting the emission wavelength within the above range, both the excitation efficiency and the light emission efficiency between the LED element and the fluorescent material can be improved. In addition, when a resin or inorganic glass that is not easily deteriorated by ultraviolet rays is used as a sealing member below the upper surface of the package, an LED having a main emission wavelength in an ultraviolet region shorter than 350 nm or a short wavelength region of visible light An element can also be used. When an LED element having a wavelength in the ultraviolet region is used, the chromaticity is determined only by the emission color converted by the fluorescent material, so that the semiconductor light emission is compared with the case where a semiconductor light emitting element that emits visible light is used. Variations such as the wavelength of the element can be absorbed, and mass productivity can be improved.

  As the LED element, an LED element capable of emitting ultraviolet light having a main light emission peak in a short wavelength region near 400 nm may be used. In this case, the sealing member adjacent to the LED element is preferably composed of a resin or glass that is relatively resistant to ultraviolet rays and a fluorescent material that can absorb visible rays and emit visible light.

(Sealing member)
In the present invention, the sealing member 203 covering the LED element 202 is provided so as to protrude from the upper surface of the package 201, and the protruding portion is made of an elastic body. All of the sealing members do not have to be elastic, and at least a portion protruding from the upper surface of the package may be elastic.

  For example, FIG. 2 shows a sealing member having a two-layer structure, which is composed of an upper layer 203 (a) and a lower layer 203 (b). The upper layer 203 (a) including the elastic member and the lower layer 203 (b) is made of an inelastic member having no elasticity or an elastic member having a low elastic modulus so that it protrudes from the upper surface of the package at the time of bonding. When the elastic body of the portion to be deformed is deformed not only in the protruding portion but also in the inside thereof, the wire joining the element electrode and the lead electrode is damaged by the strain stress, or the element and the substrate It is possible to make it difficult to cause problems such as damage to the mount resin portion joining the two and damage to the position. Thus, by setting it as a two-layer structure or a multilayer structure of two or more layers, it can have a function which changes with the site | parts of a sealing member. In the case of a two-layer structure, the position of the boundary is not particularly limited, but at least a portion protruding from the upper surface of the package uses an elastic body as an upper layer, and preferably an elastic body slightly below the upper surface of the package. Thus, only the elastic body as the upper layer can be prevented from peeling off.

  The sealing member can also contain a fluorescent material that absorbs the light emission wavelength from the LED element and converts it to a different wavelength. When such a fluorescent material is not contained in the sealing member, it is possible to emit monochromatic light from the LED element, but by using the fluorescent material, mixed light of light from the LED element and light from the fluorescent material can be emitted. It can be set as the LED light source which has. By using mixed color light, an LED light source having an arbitrary emission wavelength can be obtained, and in particular, white light emission used for a backlight or the like is easily obtained. Further, by using a filler, a diffusing agent, or the like in addition to the fluorescent substance, it is possible to obtain mixed color light with excellent uniformity.

  Further, when the sealing member has a multilayer structure of two layers or two or more layers, the fluorescent material and the diffusing agent can be contained in both of them, or can be contained in only one of them. When one of them contains a fluorescent substance, it is preferable to contain it in the lower layer made of an elastic body or an inelastic body rather than the upper layer made of an elastic body. By doing in this way, since an LED element and a fluorescent substance can be arrange | positioned in the vicinity, the light from an LED element can be absorbed and converted more efficiently. When the fluorescent material is also contained in the upper layer made of an elastic material, the fluorescent material may be the same as the fluorescent material contained in the lower layer, a fluorescent material having a different emission wavelength, or a fluorescent material having a different composition. Moreover, when using a different fluorescent substance, you may use the fluorescent substance which absorbs the light emission wavelength from the other fluorescent substance instead of the light from an LED element, and converts it into a different wavelength. Accordingly, even a fluorescent material that is not excited by light from the LED element can be used, so that mixed color light having a wider emission wavelength can be obtained.

  The height of the portion where the sealing member protrudes from the upper surface of the package is preferably 2 mm or less, more preferably 1 mm or less. If it protrudes more than 2 mm, it is not preferable because there is a problem such as loss during operation.

  Further, when the sealing member has a multilayer structure of two layers or two or more layers, the portion protruding from the upper surface of the package is at least an elastic body, but in the lower sealing member, an epoxy resin, an acrylic resin, A transparent resin or glass having excellent weather resistance such as silicone is preferably used.

  The sealing member is usually formed using a liquid mainly composed of the material of the sealing member (hereinafter referred to as “sealing member forming liquid” as appropriate). Specifically, for example, when a resin or the like that is cured by heat or light (such as ultraviolet rays) is used as a material for the sealing member, a phosphor in a liquid state before curing, a diffusing agent, which will be described later, What mixed components, such as a filler, is used as a sealing member formation liquid, and it fills the recessed part of a package and makes it harden | cure by forming a sealing member. In addition, when a resin or the like that can be dissolved or dispersed in a solvent is used as a material for the sealing member, a phosphor or diffusion material described later may be added to a solution or dispersion in which this resin is dissolved or dispersed in a solvent. What mixed components, such as an agent and a filler, is used as a sealing member formation liquid, and it fills the recessed part of a package, and forms a sealing member by removing a solvent.

(Elastic body)
The elastic body used for the sealing member protruding from the upper surface of the package has fluidity before being provided at a desired position, and is cured by heat or light (such as ultraviolet rays) before being applied to the end face of the light guide plate at room temperature. What becomes the hardness (elastic modulus) which can deform | transform at the time of joining is preferable.

  When there is little volume change at the time of hardening of an elastic body, it can cover an LED element by one layer. Thereby, there are few work processes and it can prevent mixing of a foreign material accordingly. In addition, a material that easily changes in volume during curing can be used as an upper layer of a two-layer structure or a multilayer structure of two or more layers, thereby preventing damage to each component due to the volume change.

  Specific examples of the elastic body include a resin having a siloxane skeleton as a main skeleton (for example, a silicone resin). A resin containing silica as a main component is stable and hardly deteriorated with respect to light in a wide wavelength range over a long wavelength range of ultraviolet to visible light. Moreover, since it is difficult to absorb such light, the loss of light from the LED light source can be reduced as much as possible, and the light can be efficiently incident on the light guide plate. In particular, from the viewpoint of achieving a refractive index step in a range described later, it is preferable to use a specific sealing member described later (the sealing member of the present invention) as the elastic material. This sealing member will be described later again.

(Refractive index step)
The present invention includes an external optical element refractive index n _e and the difference in a refractive index difference between the refractive index n _o of the sealing member (the light guide plate in this embodiment) | n _e -n _o | is 0.17 within It is characterized by being. Among them, the refractive index difference | n _e -n _o | preferably is 0.16 or less, more preferably 0.15 or less, more preferably 0.14 or less. Refractive index difference | n _e -n _o | and values is greater than the above range, even if an external optical element (light guide plate) and even adhesion between the sealing member were good, through the sealing member from the light source Therefore, the light incident efficiency of the light entering the external optical member (light guide plate) is lowered, and the luminance of the resulting illumination device (surface emitting device in the present embodiment) is lowered, which is not preferable. In addition, the lower limit value of the refractive index step | n _e −n _o | is not particularly limited, and is preferably as low as possible. Theoretically, the lower limit value of the refractive index step | n _e −n _o | is zero.

  Further, although the refractive index of the sealing member is not particularly defined, it is preferably adjusted as appropriate according to the refractive index of the light guide plate used in combination from the viewpoint of achieving a refractive index step in the above defined range.

  Specifically, when the sealing member has a multilayer structure, the refractive index value of the sealing member is the outermost elastic sealing member in direct contact with the external optical member (for example, the sealing member 203 in FIG. 2). In (a)), it is usually 1.40 or more, preferably 1.45 or more, and usually 1.80 or less, preferably 1.75 or less. If the refractive index of the elastic sealing member is lower than this range, the refractive index step with the external optical member becomes large, and there is a tendency that light cannot be efficiently incident on the external optical member. On the contrary, if the refractive index of the elastic sealing member is higher than this range, the content of the high refractive index component in the sealing member becomes high, and it tends to be difficult to maintain elasticity or the transparency is lowered. This is not preferable. In the case of a multilayer structure, the refractive index of the outermost elastic sealing member that is in direct contact with the external optical member is the refractive index of the lower sealing member (for example, in the case of FIG. 2, the sealing member 203 (b)). When the value is intermediate between the refractive index of the external optical member, the light from the LED element can be extracted more efficiently, and a lighting device with high luminance can be obtained.

  Also, when the sealing member has a single layer without a multilayer structure, the above refractive index range is preferable. Among them, the sealing member has a refractive index of the LED element surface (generally 2.2 or more). When positioned between the high refractive index) and the refractive index of the external optical member, both the light extraction efficiency from the LED element to the sealing member and the light extraction efficiency from the sealing member to the external optical member are improved. This is particularly preferable because the brightness of the light emitted from the external optical member increases due to the effect.

  The refractive index of the sealing member is not particularly limited, and is measured by an optical method such as a spectroscopic ellipsometer, reflectance measurement, or prism coupler.

  Here, the prism coupler performs measurement based on the following principle. That is, when a film made of a sealing member is prepared as a measurement sample and brought into contact with the prism bottom, a small air gap is formed between the measurement sample film and the prism bottom. After the laser beam hits the bottom of the prism, it is generally totally reflected from the bottom of the prism to the detector. However, when the incident angle of the laser beam is gradually reduced from the vertical, the laser beam can pass through the air gap at a discrete incident angle θ called a mode angle. At this mode angle, the laser light enters the measurement sample film and becomes an optical waveguide propagation mode. In a rough approximation, the refractive index of the film is obtained from the first mode angle, and the film thickness is obtained from the difference between the first mode angle and the second mode angle.

(Fluorescent substance)
There are no particular restrictions on the composition of the phosphor that can be used in the present invention, but the crystal matrix, such as Y ₂ O ₃ and Zn ₂ SiO ₄ , represented by metal oxides such as Ca ₅ (PO ₄ ) ₃ Cl, etc. Ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, etc., represented by representative phosphates and sulfides represented by ZnS, SrS, CaS, etc. In addition, a combination of metal ions such as Ag, Cu, Au, Al, Mn, and Sb as an activator or a coactivator is preferable.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , aluminate such as Y ₃ Al ₅ O ₁₂ , Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , boric acid circles such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) halophosphate such as ₆ Cl _2, Sr ₂ P _{2 7,} it may be mentioned (La, Ce) phosphate PO _4, etc. and the like.

  However, the above-mentioned crystal matrix and activator or coactivator are not particularly limited in elemental composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.

Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, phosphors that differ only in part of the structure are omitted as appropriate. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb”. ³⁺ ”,“ La ₂ O ₂ S: Eu ”,“ Y ₂ O ₂ S: Eu ”and“ (La, Y) ₂ O ₂ S: Eu ”are changed to“ (La, Y) ₂ O ₂ S: “Eu” collectively. Omitted parts are separated by commas (,).

・ Red phosphor:
Illustrating the specific wavelength range of the fluorescence emitted by the phosphor emitting red fluorescence (hereinafter referred to as “red phosphor” as appropriate), the peak wavelength is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less. Preferably, it is 680 nm or less.

Examples of such a red phosphor include europium activation represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of broken particles having a red fracture surface and emits light in the red region. An alkaline earth silicon nitride-based phosphor, composed of growing particles having a substantially spherical shape as a regular crystal growth shape, emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu Examples thereof include europium-activated rare earth oxychalcogenide-based phosphors.

  Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu, Mn, Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ ( SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu-activated silicate phosphor such as Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce _{, (Tb, Gd) 3 Al} 5 O 12: Ce -activated aluminate phosphor such as Ce, (Ca, Sr, Ba ) 2 Si 5 N 8: Eu, ( g, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride phosphor such as Eu, (Mg, Ca, Sr , Ba) AlSiN 3: Ce , etc. Ce-activated nitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, (Ba ₃ Mg) Si _{2 O 8: Eu, Mn, (} Ba, Sr, Ca, Mg) 3 (Zn, Mg) Si 2 O 8: Eu, Eu such as Mn, Mn-activated silicate phosphor, 3.5MgO · 0.5MgF ₂ GeO ₂ : Mn-activated germanate phosphor such as Mn, Eu-activated oxynitride phosphor such as Eu-activated α sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi, etc. eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Eu Bi, etc., with Bi Oxysulfide phosphor, (Gd, Y, Lu, La) VO 4: Eu, Eu Bi, etc., Bi-activated vanadate phosphor, SrY ₂ S _4: Eu, such as Ce Eu, Ce-activated sulfide Phosphor, Ca-activated sulfide phosphor such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) ) _X Si _{y Nz} : Eu, Ce activated nitride phosphor such as Eu, Ce (where x, y, z are integers of 1 or more), (Ca, Sr, Ba, Mg) ₁₀ (PO _{4 ) 6 (F, Cl, Br} , OH): Eu, Eu such as Mn, Mn-activated halophosphate phosphor, ((Y, Lu, Gd , Tb) 1-x S _{x Ce y) 2 (Ca,} Mg) 1-r (Mg, Zn) can be used for _{2 + r Si zq Ge q O} 12+ δ Ce -activated silicate phosphor such like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn ²⁺ , SrCaAlSiN ₃ : Eu, and the like.

・ Green phosphor:
When a specific wavelength range of fluorescence emitted by a phosphor emitting green fluorescence (hereinafter referred to as “green phosphor” as appropriate) is exemplified, the peak wavelength is usually 490 nm or more, preferably 500 nm or more, and usually 570 nm or less. Preferably, it is 550 nm or less.

As such a green phosphor, for example, a europium activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

In addition, as the green phosphor, Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al _{2 Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Tb-activated silicate phosphor such as Ce and Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu such as Eu Activated borate phosphor, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu activated halosilicate phosphor such as Eu, Zn ₂ SiO ₄ : Mn activated silicate phosphor such as Mn, CeMgAl ₁₁ O _{19: Tb, Y 3 Al 5} O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2 _{Tb, La 3 Ga 5 SiO 14} : Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca ) Ga 2 S 4: Eu, Tb, and Sm, such as Eu, Tb, Sm-activated thiogallate phosphor, Ce-activated aluminate phosphor such as Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce, Ca-activated silicate phosphor such as Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce, Ce-activated such as CaSc ₂ O ₄ : Ce Eu-activated oxynitride fluorescence such as oxide phosphor, SrSi ₂ O ₂ N ₂ : Eu, (Sr, Ba, Ca) Si ₂ O ₂ N ₂ : Eu, Eu-activated β sialon, Eu-activated α-sialon _{body, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu Eu-activated aluminate phosphor, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, and Tb, etc. Ce, Tb-activated phosphate Phosphor, ZnS: Cu, Al, ZnS: Sulfide phosphor such as Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb-activated borate phosphor such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn-activated halosilicate phosphors such as Eu and Mn, (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphors and thiogallate phosphors such as Eu, _{(Ca, Sr) 8 (Mg} , Zn) (SiO 4) 4 Cl 2: Eu, Eu such as Mn, Mn-activated halo silicate phosphor It is also possible to use such.

  Examples of green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes, terbium complexes having hexyl salicylate as a ligand, etc. It is also possible to use organic phosphors.

・ Blue phosphor:
When a specific wavelength range of fluorescence emitted by a phosphor emitting blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate) is exemplified, the peak wavelength is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less. Preferably, it is 470 nm or less.

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting light in a blue region. phosphor, which is constituted by growing particles having a nearly spherical shape typical of regular crystal growth and emits light in the blue region, _{(Ca, Sr, Ba) 5} (PO 4) 3 Cl: europium-activated halo represented by Eu A calcium phosphate-based phosphor, composed of growing particles having a substantially cubic shape as a regular crystal growth shape, emits light in a blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu It is composed of alkaline earth chloroborate phosphors and fractured particles having fractured surfaces, and emits light in the blue-green region (S _{, Ca, Ba) Al 2 O} 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: activated alkaline earth with europium aluminate-based phosphor such as represented by Eu and the like.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu activation such as Eu, Mn, Sb Halophosphate phosphor, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ Eu-activated silicate phosphor such as MgSi ₂ O ₈ : Eu, Eu-activated phosphate phosphor such as Sr ₂ P ₂ O ₇ : Eu, sulfide fluorescence such as ZnS: Ag, ZnS: Ag, Al Body, Ce activated silicate phosphor such as Y ₂ SiO ₅ : Ce, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn-activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu-activated halosilicate phosphor such as Eu can be used.

In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrarizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .
In addition, fluorescent substance may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The median particle diameter of these phosphor particles is not particularly limited, but is usually 100 nm or more, preferably 2 μm or more, particularly preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, particularly preferably 20 μm or less. Further, as long as the shape of the phosphor particles does not affect the formation of the sealing member, for example, the fluidity of the phosphor part forming liquid (liquid obtained by adding the phosphor to the above-described sealing member forming liquid), etc. As long as it does not affect the above, there is no particular limitation.

In the present invention, the method for adding phosphor particles is not particularly limited. If the dispersed state of the phosphor particles is good, it only needs to be post-mixed in the sealing member forming liquid.
In particular, when forming a specific sealing member (sealing member of the present invention), which will be described later, as a sealing member, in the case where aggregation of phosphor particles is likely to occur, a reaction solution containing a raw material compound before hydrolysis When the phosphor particles are mixed in advance (hereinafter referred to as “pre-hydrolysis solution” as appropriate) and subjected to hydrolysis and polycondensation in the presence of the phosphor particles, the surfaces of the particles are partially subjected to silane coupling treatment, and fluorescent The dispersed state of body particles is improved.

  Although some phosphors are hydrolyzable, the sealing member of the present invention is potentially present as a silanol body in the liquid state (sealing member forming liquid) before coating, Since there is almost no free water, even such a phosphor can be used without being hydrolyzed. Further, if the sealing member forming liquid after hydrolysis / polycondensation is used after being subjected to dehydration and dealcoholization treatment, there is also an advantage that the combined use with such a phosphor becomes easy.

  Furthermore, the sealing member of the present invention may be a fluorescent glass in which an ionic fluorescent material or an organic / inorganic fluorescent component is uniformly dissolved and dispersed.

(Diffusion agent)
The kind of diffusing agent that can be used in the present invention is not particularly limited, and metal oxides and metal oxide salts such as barium titanate, barium sulfate, titanium oxide, aluminum oxide, silicon oxide, light calcium carbonate, and heavy calcium carbonate. Various known diffusing agents represented by the above can be used. One of these diffusing agents may be used alone, or two or more thereof may be used in combination with any composition and combination. The particle size value of the diffusing agent is preferably in the range where the central particle size is usually 1.0 μm or more, especially 1.5 μm or more, and usually 5 μm or less, especially 3 μm or less. Use of a diffusing agent having a particle size value in the above range is preferable because light from the LED element and the fluorescent material can be diffusely reflected and color unevenness can be suppressed. When the diffusing agent is in a crushed form, the long side length measured by transmission electron microscopy is usually preferably in the range of 1.0 μm or more and 3.0 μm or less. The content of the diffusing agent is preferably in the range of usually 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the sealing member. Thereby, the luminous intensity and reliability of the LED light source can be improved without reducing the light extraction efficiency from the LED element and the fluorescent material. In addition, the half width of the emission spectrum can be narrowed, and a light emitting device with high color purity can be obtained.

  Among these, in the present invention, from the viewpoint of adjusting the refractive index of the sealing member and obtaining the prescribed refractive index step, it is preferable that a metal element that gives a metal oxide having a high refractive index is present in the sealing member. . Examples of metal elements that give metal oxides having a high refractive index include Si (silicon), Al (aluminum), Zr (zirconium), Ti (titanium), Y (yttrium), Nb (niobium), and B (boron). ) And the like. These metal elements may be used alone or in combination of two or more in any combination and ratio.

  From the above viewpoint, in the present invention, the sealing member is made of Si (silicon), Al (aluminum), Zr (zirconium), Ti (titanium), Y (yttrium), Nb (niobium), and B (boron). It is preferable that the main component is a metalloxane bond that contains one or more elements selected from the group consisting of: Specifically, the total content of these Si, Al, Zr, Ti, Y, Nb, and B (hereinafter sometimes referred to as “specific metal elements”) is usually 20% by weight or more, especially 25% by weight. % Or more, more preferably 30% by weight or more. On the other hand, the upper limit is usually 70% by weight or less from the viewpoint of securing the flexibility of the sealing member and suppressing cracks and poor adhesion.

  Moreover, when using the specific sealing member (sealing member of this invention) mentioned later especially, it is clear also from having the characteristic of (1) mentioned later regarding a solid Si-NMR spectrum, the above-mentioned. Among the specific metal elements, it is necessary to contain at least Si. Other Al, Zr, Ti, Y, Nb and B are not essential, but Al or B from the viewpoint of improving heat resistance, and Zr, Ti, Y or Nb from the viewpoint of increasing the refractive index. Among these, in order to use as a sealing member having a light emission wavelength in the blue to ultraviolet region, it is particularly preferable to contain Al, Zr, Y, or B with little ultraviolet absorption. .

  If the presence form of the specific metal element (Si, Al, Zr, Ti, Y, Nb, B) is transparent to the emission wavelength of the semiconductor light emitting device in the sealing member, a uniform glass layer as a metalloxane bond is formed. Even if it forms, it may exist in the particulate form in the sealing member. When the specific metal element is present in the form of particles, the structure inside the particle may be either amorphous or crystalline, but is preferably a crystalline structure in order to give a high refractive index. In order not to impair the transparency of the sealing member, the particle size is usually not more than the emission wavelength of the semiconductor light emitting device, preferably not more than 100 nm, more preferably not more than 50 nm, particularly preferably not more than 30 nm. An example of the most preferable configuration is a flexible material in which Si bonded to an organic group is a main component, and Al, Zr, Ti, Y, Nb, and B are connected by a metalloxane bond as a refractive index improver or a crosslinking degree adjuster. In an amorphous binder having a property, oxide particles of Al, Zr, Ti, Y, and Nb having a high degree of crystallinity as a refractive index improver are dispersed as nanoparticles.

  The total content of the specific metal elements in the sealing member is analyzed by, for example, inductively coupled plasma spectrometry (hereinafter abbreviated as “ICP” as appropriate) using a method described later in the description of the examples. And can be calculated based on the result.

  Moreover, in order to adjust the total content of the specific metal elements in the sealing member so as to be within the specified range, a high refractive index containing at least one or more elements among the specific metal elements described above. Particles (hereinafter referred to as “high refractive index specific metal particles” as appropriate) may be dispersed in the sealing member. Although the kind of high refractive index specific metal particle is not particularly limited, it is usually preferably a particle made of a metal oxide containing one or more of the above-mentioned specific metal elements. In particular, when using a specific sealing member to be described later (sealing member of the present invention), the compound represented by the following general formula (1) or general formula (2) is hydrolyzed and polycondensed to produce a polymer. By drying the condensate and before or after hydrolysis / polycondensation, the above-mentioned high refractive index specific metal particles are added to the reaction system, so that the total content of the specific metal elements in the sealing member is within the above specified range. As a result, a sealing member having a high refractive index is obtained. The details of the procedure will be described again.

(Filler)
Furthermore, in this embodiment, a filler may be included in the sealing member in addition to the fluorescent material. The specific material is the same as that of the diffusing agent, but the central particle diameter is different from that of the diffusing agent. Specifically, in the present specification, the “filler” refers to one having a center particle diameter of 5 μm or more and 100 μm or less. When the filler having such a particle size is contained in the translucent resin, the chromaticity variation of the light emitting device is improved by the light scattering action, and the thermal shock resistance of the translucent resin can be enhanced. The filler preferably has a particle size and / or shape similar to that of the fluorescent material. In the present specification, the term “similar particle size” refers to a case where the difference in the center particle size of each particle is less than 20%, and the term “similar shape” refers to a perfect circle of each particle size. This is the case where the difference in circularity value representing the degree of approximation is less than 20%. By using such a filler, the fluorescent material and the filler interact with each other, and the fluorescent material can be favorably dispersed in the resin, thereby suppressing color unevenness. In the present specification, “circularity” refers to a value obtained by the following formula.

  Furthermore, it is preferable that the fluorescent substance and the filler each have a center particle size of usually 15 μm or more, particularly 20 μm or more, and usually 50 μm or less, especially 40 μm or less. By adjusting the particle size in this way, it is possible to arrange the particles with a preferable interval. As a result, a light extraction path is ensured, and the directivity can be improved while suppressing a decrease in luminous intensity due to filler mixing. In addition, when the fluorescent material and filler having such a particle size range are included in the translucent resin and the sealing member is formed by the stencil printing method, clogging of the dicing blade is recovered in the dicing process after the sealing member is cured. As a result, a dresser effect can be provided, and mass productivity is improved.

〔Light guide plate〕
The light guide plate of the surface light-emitting device of this embodiment has an output surface (light-emitting surface) and a reflective surface that face each other, and an LED light source is disposed on one end surface or two opposite end surfaces. Light from the LED light source enters from the end face of the light guide plate and exits from the exit surface.

  In the present invention, since the refractive index of the sealing member can be adjusted as appropriate, the material of the light guide plate is not particularly limited, but it is usually preferable to use a material excellent in light transmittance and moldability. Specific examples thereof include acrylic resins, polycarbonate resins, cycloolefin polymers, norbornene resins, and polystyrene resins. Among these, acrylic resins, cycloolefin polymers, and polycarbonate resins are preferable because they are excellent in light transmittance, moldability, and dimensional stability. As a material for the light guide plate, any one of these materials may be used alone, or two or more may be used in any combination and ratio. These materials are formed into a desired shape by a method such as injection molding.

  Further, although the refractive index of the light guide plate is not particularly defined, it is preferable to adjust appropriately according to the refractive index of the sealing member used in combination from the viewpoint of achieving a refractive index step in the range described later. Specifically, the value of the refractive index of the light guide plate is usually 1.4 or more, preferably 1.5 or more, and usually 1.9 or less, preferably 1.7 or less. If the refractive index of the light guide plate is too low, total reflection in the light guide plate is insufficient, and it tends to be difficult to obtain uniform light emission. Conversely, if the refractive index of the light guide plate is too high, Since it is difficult to extract light to the light emitting surface side and the luminance tends to decrease, neither is preferable.

  The size, shape, thickness, and the like of the light guide plate are arbitrary and may be appropriately selected according to the application. Further, the end surface on which the LED light source is disposed may be a single plane or may have irregularities. When using an elastic body as a sealing member of an LED light source and using it as a joint as in this embodiment, the elastic body is used on the premise that the shape is changed. It is not what you are doing. Therefore, in order to emit light incident on the light guide plate uniformly in a planar shape, it is necessary to provide the light guide plate itself with a function for uniformly emitting light to the light emitting surface. Therefore, surface light emission characteristics can be improved by applying reflection processing or graining to the reflective surface or light emitting surface. The embossing process can select the size and shape according to the light intensity, and can be used in an array such as a uniform array or a random array or a combination thereof.

  Further, in order to diffuse light, the portion facing the LED light source on the end surface of the light guide plate, that is, the incident end surface of the portion where the LED light source is joined may be provided with unevenness instead of a single plane. In this way, the incident direction can be set in advance, so that light can be refracted and incident in an arbitrary direction. Moreover, even when the unevenness is provided on the end face, if the sealing member of the LED light source is an elastic body as in this embodiment, the shape can be changed corresponding to the unevenness. The air layer between the LED light source and the end face of the light guide plate can be reduced, and the light incident efficiency is hardly lowered. The unevenness of the end face of the light guide plate may be only a convex part or a concave part, and the shape thereof can be arbitrarily selected such as a triangular pyramid, a cone, a triangular prism, a cylinder, or a rough surface.

[Others]
When the lighting device of the present invention is implemented as a surface light emitting device including a light guide plate as an external optical member, the embodiment is not limited to the first embodiment described above, and does not depart from the spirit of the present invention. It is possible to carry out by arbitrarily changing the range.

  For example, like the LED light source 300 (102) shown in FIG. 3, the sealing member can be configured as a single sealing member 203 (c). In this case, the sealing member 203 (c) is formed of an elastic body, and the above-described fluorescent material is contained in the sealing member 203 (c). Moreover, components, such as the above-mentioned diffusing agent and filler, are contained as necessary. FIG. 3 is a cross-sectional view schematically showing another example of the configuration of the light source 102 provided in the illumination device (surface emitting device) according to the first embodiment of the present invention. In FIG. 3, the same components as those in FIGS. 1 and 2 are represented by the same reference numerals.

[II. Semiconductor lighting device]
In the semiconductor lighting device that is the lighting device according to the second embodiment of the present invention, the optical member is formed as an outer lens having an incident surface and an output surface, the light source is joined to the incident surface of the outer lens, and light from the light source Is made to enter from the entrance surface of the outer lens and exit from the exit surface. And while a light source is comprised including the package which has a recessed part, the semiconductor light-emitting device arrange | positioned in the recessed part of a package, and the sealing member which seals a semiconductor light-emitting device, said (i)-( It has the characteristics of iii).

  FIG. 4 is a cross-sectional view schematically showing the configuration of the semiconductor lighting device according to the second embodiment of the present invention. 4, the same components as those in FIGS. 1 to 3 are represented by the same reference numerals. A semiconductor lighting device 400 shown in FIG. 4 is an LED light source including a package 201, an LED element 202, and a sealing member 203, like the LED light source 102 used in the surface light emitting device according to the first embodiment of the present invention. 102 and an outer lens 401 as an external optical member is provided above the package 201 of the LED light source 102. On the lower surface of the outer lens 401, there is provided a recess that has a shape corresponding to the protruding shape of the sealing member 203 of the LED light source 102 and is designed to have a size that is the same as or slightly smaller than the protruding shape. The protruding portion of the sealing member 203 is fitted. Accordingly, when the outer lens 401 is mounted on the upper surface of the LED light source 102, the shape of the sealing member 203, which is an elastic body, is changed by an external force applied to the joint portion, and the inner surface of the concave portion of the outer lens 401 and the LED light source 102 are changed. The upper surface (particularly, the upper surface of the sealing member 203) can be bonded with good adhesion, and light can be efficiently incident on the outer lens 401.

  In the semiconductor lighting device 400 of this embodiment, the details of the package 201, the LED element 202, and the sealing member 203 constituting the LED light source 102 are the same as those of the LED light source 102 in the first embodiment described above. Description is omitted. 4 shows the case where the LED light source 200 of FIG. 2 is used as the LED light source 102, of course, the LED light source 300 of FIG. 3 may be used as long as the provisions of the present invention are satisfied. It is also possible to use LED light sources having other configurations.

  The outer lens 401 can be appropriately selected in size, shape, thickness, etc. depending on the application, etc., but it is preferable to use a lens having excellent light transmittance, moldability, directivity, impact resistance, etc. preferable. Specific examples include acrylic resins, polycarbonate resins, cycloolefin polymers, norbornene resins, polystyrene resins, and the like. These are formed into a desired shape by a known method such as injection molding.

Also in this embodiment, the refractive index difference is a difference between the refractive index n _o of the refractive index n _e and the sealing member of the outer lens 401 which is an external optical member | n _e -n _o | is usually 0. It is configured to be within 17, preferably within 0.14, and more preferably within 0.10.

[III. Sealing member]
The light source of the lighting device of the present invention preferably uses a specific sealing member (hereinafter referred to as “the sealing member of the present invention”) described below as a sealing member made of an elastic body. By using the sealing member of the present invention, it becomes possible to join the optical member and the sealing member without substantially interposing an air layer, and a difference in refractive index between the optical member and the sealing member. The (refractive index step) can be adjusted within the predetermined range, and as a result, an illumination device having high light entrance efficiency from the light source to the external optical member and excellent in luminance is realized. Further, it has excellent transparency, light resistance, heat resistance and the like, and has an advantage that it does not cause cracking or peeling even after long-term use.

[III-1. Configuration of sealing member of the present invention]
The sealing member of the present invention has the following features (1) to (3).
(1) In a solid Si-NMR spectrum,
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. .
(2) The silicon content is 20% by weight or more.
(3) The silanol content is 0.1% by weight or more and 10% by weight or less.
Hereinafter, these features (1) to (3) will be described first.

[III-1-1. Solid Si-NMR spectrum]
A compound containing silicon as a main component is represented by the SiO ₂ · nH ₂ O formula, but structurally, oxygen atoms O are bonded to each vertex of a tetrahedron of silicon atoms Si, and these oxygens It has a structure in which silicon atom Si is further bonded to atom O and spreads in a net shape. The schematic diagram shown below represents the Si—O net structure while ignoring the tetrahedral structure, and in the repeating unit of Si—O—Si—O—, Some parts are substituted with other members (for example, —H, —CH _3, etc.). When attention is paid to one silicon atom Si, as shown in (A) of the schematic diagram, four —OSi are silicon atoms having Si (Q ^4), a silicon atom Si (Q ³⁾ having three -OSi as shown in the schematic diagram (B) or the like is present. Then, in the solid-state Si-NMR measurement, peaks based on each silicon atom Si above is sequentially referred to Q ⁴ peak, Q ³ peak, and ....

These silicon atoms having four bonded oxygen atoms are generally referred to as Q sites. In the present invention, Q ^{0 to} Q ⁴ peaks derived from the Q site are referred to as a Q ⁿ peak group. The Q ⁿ peak group of the silica film containing no organic substituent is usually observed as a multimodal peak continuous in the region of chemical shift of −80 to −130 ppm.

In contrast, silicon atoms to which three oxygen atoms are bonded and other atoms (usually carbon) are bonded are generally referred to as T sites. The peak derived from the T site is observed as each peak of T ^{0 to} T ³ as in the case of the Q site. In the present invention, each peak derived from the T site is referred to as a T ⁿ peak group. The T ⁿ peak group is generally observed as a multimodal peak continuous in the region on the higher magnetic field side (usually −80 to −40 ppm) than the Q ⁿ peak group.

Furthermore, a silicon atom to which two oxygen atoms are bonded and two other atoms (usually carbon) are bonded is generally referred to as a D site. Similarly to the peak group derived from the Q site and the T site, the peak derived from the D site is also observed as each peak of D ^{0 to} D ⁿ (D ⁿ peak group), which is further than the peak group of Q ⁿ and T ^n. It is observed as a multimodal peak in the region on the high magnetic field side (usually the region with a chemical shift of 0 to −40 ppm). The ratio of the area of each peak group of D ⁿ , T ⁿ , and Q ⁿ is equal to the molar ratio of silicon atoms placed in the environment corresponding to each peak group. In terms of molar amount, the total area of the D ⁿ peak group and the T ⁿ peak group usually corresponds to the molar amount of all silicon directly bonded to carbon atoms.

When measuring the solid Si-NMR spectrum of the sealing member of the present invention, the D ⁿ peak group and T ⁿ peak group originating from silicon atoms in which carbon atoms directly bonded organic groups, bonded to a carbon atom of an organic group Q ⁿ peaks derived from non-silicon atoms appear in different regions. Among these peaks, the peak of less than −80 ppm corresponds to the Q ⁿ peak as described above, and the peaks of −80 ppm or more correspond to the D ⁿ and T ⁿ peaks. In the sealing member of the present invention, the Q ⁿ peak is not essential, but at least one, preferably a plurality of peaks are observed in the D ⁿ and T ⁿ peak regions.

  In addition, the value of the chemical shift of a sealing member can be calculated based on the result of performing solid Si-NMR measurement using the following method, for example. In addition, analysis of measurement data (half-width or silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.

[Solid Si-NMR spectrum measurement and silanol content calculation]
When performing a solid Si-NMR spectrum about a sealing member, a solid Si-NMR spectrum measurement and waveform separation analysis are performed on condition of the following. Moreover, the half width of each peak is calculated | required about the sealing member from the obtained waveform data. Also, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Ask.

<Device conditions>
Equipment: Chemagnetics Infinity CMX-400 Nuclear Magnetic Resonance Spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: Room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 times Observation width: 30 kHz
Broadening factor: 20Hz

<Data processing method>
For the sealing member, 512 points are taken in as measurement data, zero-filled to 8192 points, and Fourier transformed.

<Waveform separation analysis method>
For each peak of the spectrum after Fourier transform, optimization calculation is performed by a non-linear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.

  For peak identification, refer to AIChE Journal, 44 (5), p.1141, 1998, etc.

[III-1-2. Silicon content)
The sealing member of the present invention must have a silicon content of 20% by weight or more (feature (2)). The basic skeleton of a conventional sealing member is an organic resin such as an epoxy resin having carbon-carbon and carbon-oxygen bonds as basic skeletons. On the other hand, the basic skeleton of the sealing member of the present invention is the same inorganic siloxane bond as glass (silicate glass). As is apparent from the chemical bond comparison table in Table 1 below, this siloxane bond has the following characteristics excellent as a sealing member.

(I) Light resistance is good because the bond energy is large and thermal decomposition and photolysis are difficult.
(II) It is slightly polarized electrically.
(III) The degree of freedom of the chain structure is large, a structure with high flexibility is possible, and the chain structure can freely rotate around the center of the siloxane chain.
(IV) The degree of oxidation is large and no further oxidation occurs.
(V) Rich in electrical insulation.

  From these characteristics, silicone-based sealing members formed with a skeleton in which siloxane bonds are bonded three-dimensionally and with a high degree of crosslinking are different from conventional resin-based sealing members such as epoxy resins such as glass or rock. It can be understood that the protective film is close to inorganic material and rich in heat resistance and light resistance. In particular, a silicone-based sealing member having a methyl group as a substituent has no absorption in the ultraviolet region, so that it does not easily undergo photolysis and has excellent light resistance.

As described above, the silicon content of the sealing member of the present invention is 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO ₂ is 47% by weight.

  The silicon content of the sealing member is calculated based on the result of performing inductively coupled plasma spectrometry (hereinafter abbreviated as “ICP” where appropriate) using the following method, for example. be able to.

[Measurement of silicon content]
A single cured product of the sealing member is pulverized to about 100 μm, fired in a platinum crucible in the air at 450 ° C. for 1 hour, then 750 ° C. for 1 hour, and 950 ° C. for 1.5 hours. After removing the residue, add 10 times or more amount of sodium carbonate to a small amount of the resulting residue, heat with a burner to melt, cool this, add demineralized water, and further adjust the pH to neutral with hydrochloric acid. The volume is adjusted to about several ppm as silicon, and ICP analysis is performed.

[III-1-3. Silanol content)
The sealing member of the present invention has a silanol content of usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 10% by weight or less, preferably 8% by weight or less, more preferably 5% by weight. % Or less (feature (3)).

  Usually, a glass body obtained by a sol-gel method using alkoxysilane as a raw material does not completely polymerize and become an oxide under mild curing conditions at 150 ° C. for about 3 hours, and a certain amount of silanol remains. A glass body obtained only from tetraalkoxysilane has high hardness and high light resistance, but has a high degree of cross-linking so that the degree of freedom of molecular chains is small, and complete condensation does not occur, so the amount of residual silanol is large. Further, when the hydrolysis / condensation liquid is dry-cured, the viscosity increases quickly due to the large number of cross-linking points, and the drying and curing proceed simultaneously, resulting in a bulk body having a large distortion. When such a member is used as a sealing member, new internal stress is generated due to condensation of residual silanol during long-term use, and problems such as cracks, peeling, and disconnection are likely to occur. In addition, the fracture surface of the member has more silanol and less moisture permeability, but it has high surface hygroscopicity and tends to invade moisture. Although it is possible to reduce the silanol content by high-temperature baking at 400 ° C. or higher, the heat resistance of semiconductor light-emitting devices is almost 260 ° C. or lower, which is not realistic.

  On the other hand, the sealing member of the present invention has excellent performance with low silanol content, little change with time, excellent long-term performance stability, and low moisture absorption and moisture permeability. However, since a member that does not contain silanol is inferior in adhesion to the semiconductor light emitting device, there is an optimum range for the silanol content in the sealing member of the present invention as described above.

  The silanol content of the sealing member is, for example, [III-1-1. The solid Si-NMR spectrum was measured using the method described in [Solid Si-NMR Spectrum Measurement and Calculation of Silanol Content], and from the ratio of the peak area derived from silanol to the total peak area, It can be calculated by obtaining the ratio (%) of silicon atoms that are silanols in all silicon atoms and comparing it with the separately analyzed silicon content.

[III-1-4. Reason why the effect of the present invention can be obtained by the above features (1) to (3)]
The sealing member of the present invention has the above-mentioned features (1) to (3), so that the thick film portion is hardened without cracking and is excellent in adhesion to the case and chip sealing characteristics. A cured product having excellent durability against light and heat after curing can be obtained. The reason for this is not clear, but is presumed as follows.

As a method for obtaining a sealing member made of inorganic glass, a melting method in which low melting point glass is melted and sealed, and a solution obtained by hydrolyzing and polycondensing alkoxysilane or the like at a relatively low temperature are applied and dried and cured. There is a sol-gel method. Of these, only the ^Qn peak is mainly observed for the member obtained from the melting method, but it requires a high temperature of at least 350 ° C. or more for melting, and is not a practical method because the semiconductor light emitting device is thermally deteriorated.

On the other hand, the hydrolysis / polycondensation product obtained from the tetrafunctional silane compound in the sol-gel method becomes a completely inorganic glass and is extremely excellent in heat resistance and weather resistance, but the curing reaction is silanol condensation (dehydration / dehydration). Since the crosslinking proceeds due to the (alcohol) reaction, the dehydration occurs, resulting in weight reduction and volume shrinkage. Therefore, ^{if the} raw material is composed only of tetrafunctional silane having a Q ⁿ peak, the degree of curing shrinkage becomes too large, cracks are likely to occur in the coating, and it becomes impossible to increase the thickness. In such a system, attempts are made to increase the film thickness by adding inorganic particles as an aggregate or by overcoating, but generally the limit film thickness is about 10 μm. When sol-gel glass is used as the sealing member, there is a problem that a film thickness of 500 to 1000 μm must be secured because it is necessary to mold on a wiring portion having a complicated shape. Further, as described above, in order to sufficiently reduce the residual silanol and obtain a completely inorganic glass, heating at a high temperature of 400 ° C. or more is required, which is not realistic because the semiconductor device is thermally deteriorated.

In contrast, in the sealing member of the present invention, by adjusting the crosslink density, in order to give flexibility to the film, introducing a bifunctional silane having a trifunctional silane and / or D ⁿ peak with T ⁿ peak At the same time, by performing hydrolysis and polycondensation, the volume reduction by dehydration condensation and the crosslinking density are appropriately reduced within a range that does not hinder the function, and the hydrolysis / condensation process and the drying process are controlled. A transparent glass film-like or transparent elastomer-like member having a thickness of 1000 μm can be obtained. Therefore, in the sealing member of the present invention, the presence of a T ⁿ peak and / or a D ⁿ peak observed at −80 ppm or more is essential.

As a method for increasing the film thickness by using a bifunctional or trifunctional raw material as a main component as described above, for example, a technique of a hard coat film such as glasses is known, and the film thickness is several μm or less. Since these hard coat films are thin, solvent volatilization is easy and uniform curing is possible, and differences in adhesion to the base material and linear expansion coefficient have been the main cause of cracks. On the other hand, in the sealing member of the present invention, since the film thickness is as large as the paint, the film itself has a certain strength and can absorb some differences in linear expansion coefficient. Therefore, the generation of internal stress different from the case of the thin film becomes a new problem. In other words, when molding into a deep container with a small opening area such as an LED cup, if heat curing is performed in a state where drying at the deep part of the film is insufficient, solvent volatilization occurs after cross-linking and the volume is reduced, resulting in large cracks. And foaming occurs. A large internal stress is applied to such a film, and when the solid Si-NMR of this film is measured, the detected D ⁿ , T ⁿ , and Q ⁿ peak groups have a siloxane bond angle as compared with the case where the internal stress is small. A distribution occurs, each with a broader peak. This fact means that the bond angle represented by two -OSi with respect to Si has a large strain. That is, even with a film made of the same raw material, the narrower the half-value width of these peaks, the less likely cracking occurs and the higher the quality film.

It should be noted that the phenomenon in which the half-value width increases in accordance with the strain is observed more sensitively as the degree of restraint of the molecular motion of the Si atoms increases, and the ease of appearing becomes D ⁿ <T ⁿ <Q ⁿ .

  In the sealing member of the present invention, the half width of the peak observed in the region of −80 ppm or more is smaller (narrow) than the half width range of the sealing member known so far by the sol-gel method. To do.

When organized according to chemical shift, in the sealing member of the present invention, the half width of the T ⁿ peak group observed at a peak top position of −80 ppm or more and less than −40 ppm is usually 5.0 ppm or less, preferably 4.0 ppm. In the following, it is usually 0.3 ppm or more, preferably 0.4 ppm or more.

Similarly, the full width at half maximum of the D ⁿ peak group observed at the peak top position of −40 ppm or more and 0 ppm or less is generally smaller than that of the T ⁿ peak group due to the small restraint of molecular motion, and usually 3.0 ppm or less. , Preferably 2.0 ppm or less, and usually in the range of 0.3 ppm or more.

  If the half width of the peak observed in the above chemical shift region is larger than the above range, the molecular motion is constrained and the strain becomes large, and cracks are likely to occur, which may result in a member having poor heat resistance and weather resistance. There is. For example, in the case where a large amount of tetrafunctional silane is used, or in the state where rapid drying is performed in the drying process and a large internal stress is stored, the full width at half maximum is larger than the above range.

  In addition, when the half width of the peak is smaller than the above range, Si atoms in the environment are not involved in the siloxane crosslinking, and the trifunctional silane remains in an uncrosslinked state and is formed mainly of siloxane bonds. There is a risk of becoming a member that is inferior in heat resistance and weather resistance to a substance.

Furthermore, as described above, in the solid Si-nuclear magnetic resonance spectrum of the sealing member of the present invention, at least one, preferably a plurality of peaks are observed in the D ⁿ and T ⁿ peak regions. Therefore, the solid Si-nuclear magnetic resonance spectrum of the sealing member of the present invention has at least one peak selected from the group consisting of the D ⁿ peak group and the T ⁿ peak group having a half width in the above-mentioned range, preferably It is desirable to have two or more.

In addition, the composition of the sealing member of the present invention is limited to the case where the crosslinking in the system is mainly formed of inorganic components such as silica. That is, even when a peak of the above-described half-value width range is observed at -80 ppm or more in a sealing member containing a small amount of Si component in a large amount of organic component, good heat resistance as defined in the description of the sealing member of the present invention・ Light resistance and coating performance cannot be obtained. The sealing member having a silicon content of 20% by weight or more according to the definition of the description of the sealing member of the present invention contains 43% by weight or more of SiO ₂ in terms of silica (SiO ₂ ).

In addition, since the sealing member of the present invention contains an appropriate amount of silanol, silanol is hydrogen-bonded to the polar portion present on the device surface, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.
Moreover, the sealing member of the present invention can form a covalent bond by dehydration condensation with a hydroxyl group on the device surface by heating in the presence of an appropriate catalyst, and can exhibit stronger adhesion. .
On the other hand, if there is too much silanol, the inside of the system will thicken and it will be difficult to apply, or it will become highly active and solidify before the light boiling component volatilizes by heating, resulting in increased foaming and internal stress. This may cause cracks and the like.

[III-1-5. Hardness measurement value)
The sealing member of the present invention is preferably a member that exhibits an elastomeric shape. Specifically, the hardness measurement value (Shore A) by durometer type A is usually 5 or more, preferably 7 or more, more preferably 10 or more, and usually 90 or less, preferably 80 or less, more preferably 70 or less. Yes (feature (4)). By having a hardness measurement value in the above range, the sealing member of the present invention is less prone to cracking and can provide the advantages of excellent reflow resistance and temperature cycle resistance.

  The hardness measured value (Shore A) can be measured by the method described in JIS K6253. Specifically, the measurement can be performed using an A-type rubber hardness meter manufactured by Furusato Seiki Seisakusho.

  As described above, the sealing member of the present invention preferably has a predetermined hardness measurement value (Shore A). That is, the sealing member of the present invention preferably has an elastomeric shape in which the crosslinking density is adjusted. A plurality of members having different coefficients of thermal expansion will be used for the semiconductor light emitting device. By presenting an elastomeric shape as described above, the sealing member of the present invention relieves stress due to expansion and contraction of each of the above-mentioned parts. Can do. That is, the sealing member of the present invention has a low internal stress. Therefore, it is possible to provide a semiconductor light emitting device that is less likely to cause peeling, cracking, disconnection, and the like during use and that is excellent in reflow resistance and temperature cycle resistance.

  Here, the reflow refers to a soldering method in which a solder paste is printed on a substrate, a component is mounted thereon, and heated and joined. The reflow resistance refers to a property that can withstand a thermal shock of a maximum temperature of 260 ° C. for 10 seconds.

  Conventional inorganic encapsulants are extremely hard and brittle, so they cannot follow the thermal expansion and contraction of components with different thermal expansion coefficients used in semiconductor light-emitting devices, and frequently cause peeling, cracking, and disconnection during use In addition, a product excellent in reflow resistance and temperature cycle resistance has not been obtained. However, according to the sealing member of the present invention, it is possible to provide a semiconductor light emitting device having excellent reflow resistance and temperature cycle resistance as described above.

[III-1-6. (Peak area ratio)
The sealing member of the present invention preferably satisfies the following condition (4 ′). That is, the sealing member of the present invention has (4 ') (chemical shift-total peak area of 40 ppm or more and 0 ppm or less) / (chemical shift-total peak area of less than 40 ppm) in the solid Si-nuclear magnetic resonance spectrum. The ratio (hereinafter referred to as “peak area ratio according to the present invention” in the description of the sealing member of the present invention as appropriate) is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably Is preferably 100 or less, more preferably 50 or less.

  The fact that the peak area ratio according to the present invention is in the above range indicates that the sealing member of the present invention is difunctional silane (D site) such as trifunctional silane (T site) or tetrafunctional silane (Q site). It represents having more than bifunctional or higher silane. Thus, by having many bifunctional silanes, it becomes possible for the sealing member of this invention to satisfy | fill conditions (4) (it exhibits an elastomer form), and it becomes possible to relieve stress.

  However, the sealing member of the present invention may exhibit an elastomeric shape even if the condition (4 ′) is not satisfied. For example, the case where the sealing member of the present invention is manufactured using a coupling agent such as an alkoxide of a metal other than silicon as a crosslinking agent corresponds to this case. The method for satisfying the condition (4) in the sealing member of the present invention is arbitrary, and is not limited to this condition (4 ').

[III-1-7. UV transmittance)
The sealing member of the present invention preferably has a light transmittance of 80% or more, particularly 85% or more, and more preferably 90% or more at the emission wavelength of a semiconductor light emitting device having a film thickness of 0.5 mm. The light-emitting efficiency of semiconductor light-emitting devices has been enhanced by various technologies. However, if the transparency of a translucent member for sealing a chip or holding a phosphor is low, a semiconductor light-emitting device using the same Since the luminance is reduced, it is difficult to obtain a semiconductor light emitting device product with high luminance.

  Here, the “emission wavelength of the semiconductor light-emitting device” is a value that varies depending on the type of the semiconductor light-emitting device, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm. It refers to the following range of wavelengths. When the light transmittance at a wavelength in this range is low, the sealing member absorbs light, the light extraction efficiency is lowered, and a high-luminance device cannot be obtained. Furthermore, the energy corresponding to the decrease in the light extraction efficiency is changed to heat, which causes thermal deterioration of the device, which is not preferable.

  In the ultraviolet to blue region (300 nm to 500 nm), the sealing member easily deteriorates. Therefore, if the sealing member of the present invention having excellent durability is used for a semiconductor light emitting device having an emission wavelength in this region. This is preferable because the effect is increased.

  The light transmittance of the sealing member can be measured with an ultraviolet spectrophotometer using, for example, a sample of a single cured product film having a smooth surface formed to a thickness of 0.5 mm by the following method.

(Measurement of transmittance)
An ultraviolet spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) is used, using a single-cured material having a smooth surface with a thickness of about 0.5 mm that is not scattered by scratches or unevenness of the sealing member. The transmittance is measured at 800 nm.

  However, the shape of the semiconductor device is various, and the majority is used in a thick film state exceeding 0.1 mm. However, a thin phosphor layer (for example, nanofluorescence) is located at a position away from the LED chip (light emitting element). There are also applications using thin films, such as when providing a layer having a thickness of several μm containing body particles or fluorescent ions), or when providing a high refractive light extraction film on a thin film directly above the LED chip. In such a case, it is preferable to show a transmittance of 80% or more at this film thickness. Even in such a thin-film application form, the sealing member of the present invention exhibits excellent light resistance and heat resistance, is excellent in sealing performance, and can be stably formed without cracks.

[III-1-8. Weight source by TG-DTA measurement]
The sealing member of the present invention has excellent durability, but the durability can be evaluated by thermogravimetry-differential thermal analysis (hereinafter abbreviated as “TG-DTA” as appropriate). Specifically, when TG-DTA measurement is performed on the sealing member of the present invention, the weight loss when heated from 35 ° C. to 380 ° C. under air flow is usually 10% by weight or less, preferably 9%. It is in the range of not more than wt%, more preferably not more than 8 wt%.

[III-1-9. Others]
The sealing member of the present invention can be applied in the form of a thick film, has excellent transparency, and is excellent in sealing properties, heat resistance, ultraviolet resistance, etc., and therefore can be applied as various shapes of sealing members. it can. In particular, in a semiconductor light emitting device having an emission wavelength in a blue to ultraviolet region, it can be used as a useful member with little deterioration.

[III-2. Manufacturing method of sealing member]
The method for producing the sealing member of the present invention is not particularly limited. For example, a compound represented by the following general formula (1) or general formula (2) and / or an oligomer thereof is hydrolyzed and polycondensed to obtain a polymer. It can be obtained by drying the condensate (hydrolysis / polycondensate). However, in the sealing member of the present invention, when it is intended to obtain a highly durable elastomeric sealing member, it is preferable that the siloxane bond is a main component and the crosslinking density is reduced. Accordingly, it is desirable that the compound or oligomer represented by the general formula (1) is mainly used as a raw material, and a composition mainly containing a bifunctional unit is used as a main material. In addition, when the bifunctional unit is mainly used as a raw material in this way, the system becomes stable and gelation hardly occurs. Therefore, in this case, when the hydrolysis / polycondensation product contains a solvent, the solvent may be distilled off in advance before drying.
Hereinafter, this manufacturing method (this is appropriately referred to as “the manufacturing method of the sealing member of the present invention”) will be described in detail.

[III-2-1. material〕
As the raw material, a compound represented by the following general formula (1) (hereinafter, appropriately referred to as “compound (1)” in the description of the sealing member of the present invention) and / or an oligomer thereof is used.

  In general formula (1), M is at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, silicon is preferable.

In general formula (1), m represents the valence of M, and is an integer of 1 or more and 4 or less. “M +” represents that it is a positive valence.
n represents the number of X groups and is an integer of 1 or more and 4 or less. However, m ≧ n.

  In the general formula (1), X is a hydrolyzable group that is hydrolyzed with water in solution or moisture in the air to produce a hydroxyl group rich in reactivity, and any conventionally known one is arbitrarily used. can do. For example, C1-C5 lower alkoxy group, acetoxy group, butanoxime group, chloro group and the like can be mentioned. Here, Ci (i is a natural number) represents that the number of carbon atoms is i. Moreover, these hydrolysable groups may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Especially, since the component liberated after reaction is neutral, a C1-C5 lower alkoxy group is preferable. In particular, a methoxy group or an ethoxy group is preferable because it is highly reactive and the solvent to be liberated is light boiling.

  Furthermore, when X is an acetoxy group or a chloro group in the general formula (1), acetic acid and hydrochloric acid are liberated after the hydrolysis reaction, so when used as a sealing member that requires insulation. It is preferable to add a step of removing the acid component.

In the general formula (1), Y ¹ can be arbitrarily selected from any known monovalent organic groups of so-called silane coupling agents. Among them, the organic group particularly useful as Y ¹ in the general formula (1) in the method for producing a sealing member of the present invention is selected from the following group represented by Y ⁰ (useful organic group group). . Furthermore, other organic groups may be appropriately selected for improving affinity with other materials constituting the semiconductor light emitting device, improving adhesion, adjusting the refractive index of the sealing member, and the like.

<Useful organic group Y ⁰ >
Y ⁰ is a monovalent or higher-valent organic group derived from an aliphatic compound, alicyclic compound, aromatic compound, or aliphatic aromatic compound.
The carbon number of the organic group belonging to the group Y ⁰ is usually 1 or more, and usually 1000 or less, preferably 500 or less, more preferably 100 or less, and still more preferably 50 or less.

Furthermore, at least a part of the hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with a substituent such as an atom and / or an organic functional group exemplified below. At this time, a plurality of hydrogen atoms of the organic group belonging to the group Y ⁰ may be substituted with the following substituents. In this case, one or more selected from the following substituents may be substituted. It may be replaced by a combination.

Examples of substituents that can be substituted with hydrogen atoms of organic groups belonging to group Y ⁰ include atoms such as F, Cl, Br, and I; vinyl groups, methacryloxy groups, acryloxy groups, styryl groups, mercapto groups, epoxy groups, Examples thereof include organic functional groups such as an epoxycyclohexyl group, a glycidoxy group, an amino group, a cyano group, a nitro group, a sulfonic acid group, a carboxy group, a hydroxy group, an acyl group, an alkoxy group, an imino group, and a phenyl group.

In all of the above cases, among the substituents that can be substituted with the hydrogen atoms of the organic group belonging to the group Y ⁰ , at least a part of the hydrogen atoms of the organic functional group is F, It may be substituted with a halogen atom such as Cl, Br, or I.

However, among those exemplified as substituents capable of substituting for hydrogen of the organic group belonging to group Y ⁰ , the organic functional group is an example that can be easily introduced, and various other physicochemical functions depending on the purpose of use. Organic functional groups having properties may be introduced.
In addition, the organic group belonging to the group Y ⁰ may have various atoms or atomic groups such as O, N, or S as a linking group therein.

In general formula (1), Y ¹ can be selected from various groups depending on the purpose from the organic groups belonging to the useful organic group Y ⁰ described above, but from the viewpoint of excellent ultraviolet resistance and heat resistance, it is a methyl group. It is preferable to use as a main component.

  Specific examples of the compound (1) described above include, for example, compounds in which M is silicon, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxy. Silane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetra Ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, methyltrichlorosilane, γ-acinopropyltriethoxysilane, 4-amino Butyltriethoxysilane, p-aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimeth Xysilane, aminoethylaminomethylphenethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 4-aminobutyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, styrylethyltrimethoxy Silane, 3-mercaptopropyl trimethoxysilane, vinyl trichlorosilane, vinyltris (2-methoxyethoxy) silane, etc. trifluoropropyl trimethoxysilane.

  Examples of the compound (1) in which M is aluminum include aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triethoxide, and the like.

  Examples of the compound (1) in which M is zirconium include, for example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n-butoxide, Zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide and the like can be mentioned.

  Moreover, as a compound whose M is titanium among compounds (1), for example, titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, titanium tetramethoxypropoxide , Titanium tetra n-propoxide, titanium tetraethoxide and the like.

  However, the compounds specifically exemplified in these are some of commercially available coupling agents that are readily available. For more details, see, for example, “Optimum Utilization Technology for Coupling Agents” in Chapter 9 published by the Science and Technology Research Institute. It can be shown by a list of coupling agents and related products. Of course, the coupling agent that can be used in the method for producing a sealing member of the present invention is not limited by these examples.

In addition, the compound represented by the following general formula (2) (hereinafter referred to as “compound (2)” as appropriate in the description of the sealing member of the present invention) and / or its oligomer is also the above compound (1) and / or It can be used in the same manner as the oligomer.

In the general formula (2), M, X and Y ¹ each independently represent the same as in the general formula (1). In particular, as Y ¹ , various groups can be selected according to the purpose from the organic groups belonging to the useful organic group group Y ⁰ as in the case of the general formula (1), but they are excellent in ultraviolet resistance and heat resistance. From the point of view, it is preferable to mainly use a methyl group.
Moreover, in General formula (2), s represents the valence of M and is an integer of 2-4. “S +” indicates that it is a positive integer.
Further, in the general formula (2), Y ² represents a u-valent organic group. Here, u represents an integer of 2 or more. Therefore, in the general formula (2), Y ² may be arbitrarily selected from divalent or higher ones among known organic groups of so-called silane coupling agents.
In the general formula (2), t represents an integer of 1 or more and s−1 or less. However, t ≦ s.

  Examples of the compound (2) include those in which a plurality of hydrolyzable silyl groups are bonded as side chains to various organic polymers and oligomers, and those in which a hydrolyzable silyl group is bonded to a plurality of terminals of the molecule. Etc.

Specific examples of the compound (2) and product names thereof are listed below.
・ Bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical, KBE-846)
2-diethoxymethylethylsilyldimethyl-2-furanylsilane (manufactured by Shin-Etsu Chemical, LS-7740)
N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine (manufactured by Chisso, Silaace XS1003)
N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8227)
N-glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8228)
N, N-bis [(methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8206)
N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine (Toshiba Silicone, TSL8212)
N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide (Toshiba Silicone, TSL8213)
N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8208)
N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (Toshiba Silicone, TSL8214)
N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide (Toshiba Silicone, TSL8215)
N, N ′, N ″ -tris [3- (trimethoxysilyl) propyl] isocyanurate (manufactured by Hydras Chemical, 12267-1)
・ 1,4-Bishydroxydimethylsilylbenzene (manufactured by Shin-Etsu Chemical Co., Ltd., LS-7325)

  As the raw material, compound (1), compound (2), and / or oligomers thereof can be used. That is, in the method for producing a sealing member of the present invention, as a raw material, compound (1), oligomer of compound (1), compound (2), oligomer of compound (2), and compound (1) and compound (2) Any of these oligomers may be used. In addition, when using the oligomer of a compound (1) or the oligomer of a compound (2) as a raw material, although the molecular weight of the oligomer is arbitrary as long as the sealing member of this invention can be obtained, it is 400 or more normally.

  Here, when the compound (2) and / or the oligomer thereof is used as a main raw material, the main chain structure in the system becomes an organic bond main body and may be inferior in durability. For this reason, it is desirable to use the minimum amount of the compound (2) for providing functions such as adhesion, refractive index adjustment, reactivity control, and inorganic particle dispersibility. When compound (1) and / or its oligomer (compound (1) -derived component) and compound (2) and / or its oligomer (compound (2) -derived component) are used at the same time, the compound ( 2) It is desirable that the amount of the derived component used is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.

  Moreover, in the manufacturing method of the sealing member of this invention, when using the oligomer of a compound (1) or a compound (2) as a raw material, you may make it prepare an oligomer beforehand, but it is an oligomer in a manufacturing process. May be prepared. That is, a monomer such as compound (1) or compound (2) may be used as a raw material, and this may be used once as an oligomer in the production process, and the subsequent reaction may proceed from this oligomer.

  Furthermore, as a raw material, you may use only 1 type among these compounds (1), a compound (2), and its oligomer, However, You may mix 2 or more types by arbitrary combinations and compositions. Further, the compound (1), the compound (2), and the oligomer thereof hydrolyzed in advance (that is, -X is an OH group in the general formulas (1) and (2)) may be used.

However, in the method for producing a sealing member of the present invention, as a raw material, the compound (1), the compound (2) and the compound (1) containing silicon as M and having at least one organic group Y ¹ or organic group Y ² It is necessary to use at least one of the oligomers (including those hydrolyzed). In addition, since it is preferable that the crosslinking in the system is mainly formed by inorganic components including a siloxane bond, when the compound (1) and the compound (2) are used together, the compound (1) is mainly used. It is preferable to become.

  In order to obtain a sealing member mainly composed of a siloxane bond, it is preferable to use the compound (1) and / or an oligomer thereof as a main material. Furthermore, it is more preferable that the oligomer of the compound (1) and / or the oligomer of the compound (2) is composed of a bifunctional composition. In particular, the bifunctional unit of the oligomer of the compound (1) and / or the oligomer of the compound (2) is preferably used as a bifunctional oligomer.

  Further, in the case of using mainly the oligomer of compound (1) and / or the oligomer of compound (2) as a main component (hereinafter appropriately referred to as “bifunctional component oligomer” in the description of the sealing member of the present invention). The amount of these bifunctional component oligomers used is usually 50% by weight or more, preferably 60% by weight, based on the total weight of the raw materials (that is, the sum of the weights of the compound (1), the compound (2), and the oligomer). % Or more, more preferably 70% by weight or more. In addition, the upper limit of the said ratio is 97 weight% or less normally. Because the use of the bifunctional component oligomer as the main ingredient is one of the factors that can easily manufacture the sealing member of the present invention by the method of manufacturing the sealing member of the present invention. is there.

Hereinafter, advantages of using the bifunctional component oligomer as the main ingredient will be described in detail.
For example, in a sealing member manufactured by a conventional sol-gel method, a hydrolysis / polycondensation product obtained by hydrolysis and polycondensation of the raw material (including one contained in a coating solution (hydrolysis solution)) It had a high reaction activity. Therefore, if the hydrolysis / polycondensate is not diluted with a solvent such as alcohol, the polymerization in the system proceeds and cures quickly, making it difficult to mold and handle. For example, conventionally, when it is not diluted with a solvent, it may be cured even if the temperature is about 40 ° C to 50 ° C. Therefore, in order to ensure the handleability of the hydrolyzed / polycondensate obtained after hydrolysis, it was essential to allow a solvent to coexist with the hydrolyzed / polycondensed product.

  In addition, if the hydrolysis / polycondensate is dried / cured in the presence of a solvent in the hydrolysis / polycondensate, in addition to shrinkage due to dehydration condensation at the time of curing, shrinkage due to solvent removal (desolvent shrinkage) is taken into account. Is done. Thereby, in the conventional semiconductor light emitting device, the internal stress of the cured product tends to be large, and cracks, peeling, disconnection, and the like due to the internal stress tend to occur.

  Furthermore, if a bifunctional component monomer is frequently used as a raw material for the purpose of softening the sealing member in order to relieve the internal stress, there is a concern that the number of low-boiling annular bodies in the polycondensate increases. Since the low boiling ring is volatilized at the time of curing, when the number of low boiling rings increases, the weight yield decreases. In addition, the low-boiling annular body volatilizes from the cured product and may cause stress. Furthermore, the sealing member containing a large amount of low-boiling annular bodies may have low heat resistance. For these reasons, conventionally, it has been difficult to obtain a sealing member as a high-performance elastomeric cured body.

  On the other hand, in the method for producing a sealing member of the present invention, as a raw material, a bifunctional component is oligomerized in advance in a separate system (that is, a system that does not participate in the hydrolysis / polycondensation step) and has a reactive end. A material obtained by distilling off low boiling impurities is used as a raw material. Therefore, even if a large amount of bifunctional components (that is, the above-mentioned bifunctional component oligomers) is used, those low boiling impurities do not volatilize, and it is possible to improve the weight yield of the cured product and to have good performance. An elastomeric cured product can be obtained.

  Furthermore, the reaction activity of a hydrolysis and polycondensate can be suppressed by using a bifunctional component oligomer as a main raw material. This is presumably due to the steric hindrance and electronic effect of the hydrolyzed / polycondensed product and the decrease in the amount of silanol terminals due to the use of the bifunctional component oligomer. By suppressing the reaction activity, the hydrolysis / polycondensation product will not be cured without the presence of a solvent. Therefore, it is possible to make the hydrolysis / polycondensation product one-component and solvent-free. it can.

  In addition, since the reaction activity of the hydrolyzate / polycondensate has decreased, it has become possible to increase the curing start temperature higher than before. Therefore, when a solvent below the curing start temperature of the hydrolysis / polycondensate coexists in the hydrolysis / polycondensation product, the curing of the hydrolysis / polycondensation product starts when the hydrolysis / polycondensation product is dried. The solvent will volatilize before it is done. Thereby, even if it is a case where a solvent is used, it becomes possible to suppress generation | occurrence | production of the internal stress resulting from solvent removal shrinkage | contraction.

[III-2-2. (Hydrolysis / polycondensation process)
In the method for producing a sealing member of the present invention, first, the compound (1), the compound (2), and / or their oligomers are subjected to hydrolysis / polycondensation reaction (hydrolysis / polycondensation step). This hydrolysis / polycondensation reaction can be carried out by a known method. In the following description of the sealing member of the present invention, when referring to the compound (1), the compound (2), and the oligomer thereof without distinction, they are referred to as “raw material compounds”.

  The theoretical amount of water used for conducting the hydrolysis / polycondensation reaction of the raw material compound is a 1/2 molar ratio of the total amount of hydrolyzable groups in the system based on the reaction formula shown in the following formula (3). .

なお、上記式（３）は、一般式（１），（２）のＭがケイ素である場合を例として表わしている。また、「≡Ｓｉ」及び「Ｓｉ≡」は、ケイ素原子の有する４つの結合手のうち３つを省略して表わしたものである。

In addition, the said Formula (3) represents as an example the case where M of General formula (1), (2) is a silicon | silicone. “≡Si” and “Si≡” are represented by omitting three of the four bonds of the silicon atom.

  In the description of the method for producing a sealing member of the present invention, the theoretical amount of water necessary for the hydrolysis, that is, the amount of water corresponding to a ½ molar ratio of the total amount of hydrolyzable groups (hydrolysis rate) 100%), and the amount of water used at the time of hydrolysis is expressed as a percentage of the reference amount, that is, "hydrolysis rate".

  In the method for producing a sealing member of the present invention, the amount of water used for carrying out the hydrolysis / polycondensation reaction is usually in the range of 80% or more, especially in the range of 100% or more, when expressed by the above hydrolysis rate. Is preferred. When the hydrolysis rate is less than this range, the hydrolysis and polymerization are insufficient, so that the raw material may volatilize during curing or the strength of the cured product may be insufficient. On the other hand, if the hydrolysis rate exceeds 200%, free water always remains in the curing system, causing deterioration of the chip and phosphor due to moisture, or the cup part absorbs water, and foaming during curing. It may cause cracks and peeling. However, what is important in the hydrolysis reaction is that hydrolysis and polycondensation are performed with water of around 100% or more (for example, 80% or more). If a step of removing free water is added before coating, 200% is obtained. It is possible to apply a hydrolysis rate exceeding. In this case, if too much water is used, the amount of water to be removed and the amount of solvent used as a compatibilizer increase, the concentration process becomes complicated, and polycondensation proceeds so much that the coating performance of the member decreases. Therefore, the upper limit of the hydrolysis rate is usually 500% or less, particularly 300% or less, preferably 200% or less.

  When the raw material compound is hydrolyzed / condensed, a known catalyst or the like may be allowed to coexist to promote hydrolysis / condensation polymerization. In this case, as a catalyst to be used, an organic acid such as acetic acid, propionic acid or butyric acid, an inorganic acid such as nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, or an organometallic compound catalyst can be used. Of these, in the case of a member used in a portion in direct contact with the semiconductor light emitting device, an organometallic compound catalyst that has little influence on the insulating properties is preferable.

  The hydrolysis / polycondensation product (polycondensation product) of the above raw material compound is preferably liquid. However, even a solid hydrolysis / polycondensate can be used as long as it becomes liquid by using a solvent.

  When the inside of the system is separated and becomes non-uniform during the hydrolysis / polycondensation reaction, a solvent may be used. As the solvent, for example, C1-C3 lower alcohols, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, and other solvents that can be uniformly mixed with water can be arbitrarily used. Of these, those which do not exhibit strong acidity or basicity are preferred because they do not adversely affect hydrolysis and polycondensation. The solvent may be used alone or in combination of two or more. The amount of solvent used can be freely selected. However, since the solvent is often removed when applied to a semiconductor light emitting device, it is preferably set to the minimum necessary amount. In order to facilitate the removal of the solvent, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. In addition, even if it does not add a solvent from the exterior, since solvents, such as alcohol, are produced | generated by a hydrolysis reaction, even if it is heterogeneous at the beginning of reaction, it may become uniform during reaction.

  When the hydrolysis / polycondensation reaction of the raw material compound is carried out at normal pressure, it is usually 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 135 ° C or lower. More preferably, it is performed in a range of 130 ° C. or lower. Although it is possible to carry out at a higher temperature by maintaining the liquid phase under pressure, it is preferable not to exceed 150 ° C.

  Although the hydrolysis / polycondensation reaction time varies depending on the reaction temperature, it is usually 0.1 hour or longer, preferably 1 hour or longer, more preferably 3 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, more preferably It is carried out in the range of 15 hours or less.

  Under the above hydrolysis / polycondensation conditions, if the time is shortened or the temperature is too low, the hydrolysis / polymerization is insufficient, and the raw material may volatilize during curing or the strength of the cured product may be insufficient. is there. In addition, if the time is too long or the temperature is too high, the molecular weight of the polymer increases and the amount of silanol in the system decreases, resulting in poor adhesion at the time of application or curing too early, resulting in a poor cured structure. It becomes uniform and tends to cause cracks. Based on the above tendency, it is desirable to appropriately select conditions according to desired physical property values.

  After the hydrolysis / polycondensation reaction is completed, the obtained hydrolysis / polycondensation product is stored at room temperature or lower until the time of use. When used as a shaped member, it should be used within 60 days, preferably within 30 days, more preferably within 15 days at room temperature storage after the completion of the hydrolysis and polycondensation reaction by heating. Is preferred. This period can be extended by low-temperature storage in a range that does not freeze as required.

[III-2-3. (Solvent distillation)
When a solvent is used in the hydrolysis / polycondensation step, it is usually preferable to distill off the solvent from the hydrolysis / polycondensate before drying (solvent distillation step). Thereby, the liquid hydrolysis and polycondensation product which does not contain a solvent can be obtained. As described above, conventionally, when the solvent is distilled off, the hydrolysis / polycondensation product is cured, making it difficult to handle the hydrolysis / polycondensation product. However, in the method for producing a sealing member according to the present invention, when bifunctional component oligomers are used, the reactivity of the hydrolysis / polycondensate is suppressed. The condensate does not cure and the solvent can be distilled off. By distilling off the solvent before drying, cracking, peeling, disconnection, and the like due to solvent removal shrinkage can be prevented.

  Usually, when the solvent is distilled off, the water used for the hydrolysis is also distilled off. Moreover, the solvent represented by XH etc. which are produced | generated by the hydrolysis and polycondensation reaction of the raw material compound represented by said general formula (1) (2) are also contained in the solvent distilled off.

The method for distilling off the solvent is arbitrary as long as the effects of the present invention are not significantly impaired. However, it should be avoided that the solvent is distilled off at a temperature higher than the curing start temperature of the hydrolysis / polycondensate.
When a specific range of the temperature conditions when the solvent is distilled off is given, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 150 ° C. or lower, preferably 130 ° C. or lower. More preferably, it is 120 degrees C or less. If the lower limit of this range is not reached, the solvent may be distilled off insufficiently, and if it exceeds the upper limit, the hydrolyzate / polycondensate may be gelled.

  Further, the pressure condition when the solvent is distilled off is usually atmospheric pressure. Further, if necessary, the pressure is reduced so that the boiling point of the reaction solution when the solvent is distilled off does not reach the curing start temperature (usually 120 ° C. or higher). The lower limit of the pressure is such that the main component of the hydrolysis / polycondensate does not distill.

  However, distilling off the solvent is not an essential operation. In particular, when a solvent having a boiling point equal to or lower than the curing temperature of the hydrolysis / polycondensate is used, the solvent before the hydrolysis of the hydrolysis / polycondensation is started at the time of drying the hydrolysis / polycondensation product. Since volatilization occurs, the generation of cracks and the like due to desolvation shrinkage can be prevented without particularly performing the solvent distillation step. However, since the volume of the hydrolyzate / polycondensate may change due to volatilization of the solvent, it is preferable to distill off the solvent from the viewpoint of precisely controlling the size and shape of the sealing member.

[III-2-4. Dry)
The sealing member of the present invention can be obtained by drying the hydrolysis / polycondensate obtained by the hydrolysis / polycondensation reaction described above (drying process or curing process). As described above, the hydrolyzed / polycondensed product is normally in a liquid state, but is dried in a state where the hydrolyzed / polycondensed product is placed in a mold having a desired shape, whereby the sealing member of the present invention having the desired shape is obtained. Can be formed. Moreover, it becomes possible to form the sealing member of this invention directly in the target site | part by drying in the state which apply | coated this hydrolysis and polycondensate to the target site | part. The liquid hydrolysis / polycondensate is referred to as “hydrolysis / polycondensation liquid” or “sealing member forming liquid” as appropriate in the description of the method for producing a sealing member of the present invention. In addition, the solvent is not necessarily vaporized in the drying step, but here, the hydrolyzate / polycondensate having fluidity loses the fluidity and is cured to be called a drying step. Therefore, when there is no vaporization of the solvent, the above “drying” may be recognized as “curing”.

In the drying step, the hydrolysis / polycondensate is further polymerized to form a metalloxane bond, and the polymer is dried and cured to obtain the sealing member of the present invention.
At the time of drying, the hydrolysis / polycondensate is heated to a predetermined curing temperature to be cured. The specific temperature range is arbitrary as long as the hydrolysis / polycondensate can be dried. However, since the metalloxane bond is usually formed efficiently at 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. This is done. However, when it is heated together with the semiconductor light emitting device, it is usually preferable to carry out the drying at a temperature not higher than the heat resistance temperature of the device component, preferably 200 ° C. or lower.

  In addition, the time for maintaining the curing temperature (curing time) for drying the hydrolyzed / polycondensate is not generally determined depending on the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or longer, preferably 0.8. 5 hours or more, more preferably 1 hour or more, and usually 10 hours or less, preferably 5 hours or less, more preferably 3 hours or less.

  In addition, the temperature raising conditions in the drying step are not particularly limited. That is, it may be maintained at a constant temperature during the drying process, or the temperature may be changed continuously or intermittently. Further, the drying process may be further divided into a plurality of times. Further, in the drying process, the temperature may be changed stepwise. By changing the temperature stepwise, it is possible to obtain an advantage that foaming due to residual solvent or dissolved water vapor can be prevented.

  However, when the hydrolysis / polycondensation reaction described above is performed in the presence of a solvent, the solvent is not contained in the hydrolysis / polycondensate even if the solvent distillation step is not performed or the solvent distillation step is performed. Is left in the drying step, the first drying step for substantially removing the solvent at a temperature below the boiling point of the solvent and the second drying step at a temperature above the boiling point of the solvent. It is preferable to carry out the process separately from the drying step. The “solvent” mentioned here includes a solvent represented by XH or the like produced by hydrolysis / polycondensation reaction of the above-mentioned raw material compounds. In addition, “drying” in the description of the method for producing a sealing member of the present invention refers to a step in which the hydrolysis / polycondensation product of the raw material compound loses the solvent and is further polymerized / cured to form a metalloxane bond. .

  In the first drying step, the contained solvent is substantially removed at a temperature not higher than the boiling point of the solvent without actively proceeding with further polymerization of the hydrolysis / polycondensate of the raw material compound. . That is, the product obtained in this step is a product of hydrolysis / polycondensate before drying, which is concentrated into a viscous liquid or soft film by hydrogen bonding, or is hydrolyzed after removal of the solvent. The polycondensate is present in liquid form.

  However, it is usually preferable to perform the first drying step at a temperature lower than the boiling point of the solvent. When the first drying is performed at a temperature equal to or higher than the boiling point of the solvent, the resulting film is foamed by the vapor of the solvent, making it difficult to obtain a uniform film having no defects. This first drying step may be performed in a single step when the evaporation efficiency of the solvent is good, such as when it is a thin-film member, but a plurality of cases when the evaporation efficiency is poor such as when molded on a cup. The temperature may be increased in steps of In the case of a shape with extremely poor evaporation efficiency, it may be dried and concentrated in advance in another efficient container, and then applied in a state where the fluidity remains, and further dried. When the evaporation efficiency is poor, it is preferable to devise a method in which the entire member is uniformly dried without taking a means of concentrating only the surface of the member, such as ventilation drying with a large air volume.

  In the second drying step, the hydrolysis / polycondensate is heated at a temperature equal to or higher than the boiling point of the solvent in a state where the solvent of the hydrolysis / polycondensation product is substantially eliminated by the first drying step, By forming a metalloxane bond, a stable cured product is obtained. If a large amount of solvent remains in this step, the volume is reduced due to evaporation of the solvent while the crosslinking reaction proceeds, so that a large internal stress is generated, causing peeling and cracking due to shrinkage. Since the metalloxane bond is usually formed efficiently at 100 ° C. or higher, the second drying step is preferably performed at 100 ° C. or higher, more preferably 120 ° C. or higher. However, when it is heated together with the semiconductor light emitting device, it is usually preferable to carry out the drying at a temperature not higher than the heat resistance temperature of the device component, preferably 200 ° C. or lower. The curing time in the second drying step is not generally determined by the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, and usually 10 It is carried out for a period of time or less, preferably 5 hours or less, more preferably 3 hours or less.

Thus, by clearly separating the solvent removal step (first drying step) and the curing step (second drying step), the sealing of the present invention can be performed even when the solvent distillation step is not performed. It becomes possible to obtain a sealing member having excellent light resistance and heat resistance having physical properties of the stopper member without cracking or peeling.
However, curing may proceed even during the first drying step, and solvent removal may also proceed during the second drying step. However, the curing during the first drying step and the solvent removal during the second drying step are usually small enough not to affect the effects of the present invention.

  In addition, as long as the above-mentioned 1st drying process and 2nd drying process are implement | achieved substantially, the temperature rising conditions in each process are not restrict | limited in particular. That is, it may be held at a constant temperature during each drying step, or the temperature may be changed continuously or intermittently. In addition, each drying step may be further divided into a plurality of times. Furthermore, even when the temperature temporarily becomes higher than the boiling point of the solvent during the first drying step, or when there is a period during which the temperature becomes lower than the boiling point of the solvent during the second drying step, In particular, so long as the solvent removal step (first drying step) and the curing step (second drying step) as described above are achieved independently, they are included in the scope of the present invention.

  Further, when a solvent having a boiling point lower than the curing temperature of the hydrolysis / polycondensate, preferably less than the curing temperature is used as the solvent, the solvent coexisting with the hydrolysis / polycondensation product has a particularly high temperature. Even if the hydrolysis / polycondensation product is heated to the curing temperature without adjustment, it will be distilled off from the hydrolysis / polycondensation product when the temperature reaches the boiling point during the drying process. . That is, in this case, in the process of raising the hydrolysis / polycondensate to the curing temperature in the drying step, the solvent is substantially removed at a temperature below the boiling point of the solvent before the hydrolysis / polycondensation product is cured. The process (1st drying process) to perform is implemented. Thereby, the hydrolysis / polycondensation product becomes a liquid hydrolysis / polycondensation product containing no solvent. After that, drying is performed at a temperature equal to or higher than the boiling point of the solvent (that is, the curing temperature), and a step of curing the hydrolysis / polycondensate (second drying step) proceeds. Therefore, when a solvent having a boiling point equal to or lower than the curing temperature is used as the solvent, the first drying step and the second drying step are performed even if the implementation is not intended. For this reason, use of a solvent having a boiling point not higher than the curing temperature of the hydrolysis / polycondensate, preferably less than the above-mentioned curing temperature, is that the hydrolysis / polycondensation product contains a solvent when performing the drying step. Even if it does, it does not have a big influence on the quality of a sealing member, and it can be said that it is preferable.

[III-2-5. When manufacturing a hard sealing member]
By the way, in the lighting device of the present invention, when the sealing member has a multilayer structure (for example, in the case of the LED light source 200 shown in FIG. 2, the sealing members 203 (a) and 203 (b)), the external optical member is contacted. As the sealing member on the side not to be used (for example, in the case of the LED light source 200 shown in FIG. 2, the sealing member 203 (b)), a sealing member having a low elastic modulus or a sealing member having no elasticity is used. Is possible. When the sealing member of the present invention is not made into an elastomer for the purpose of use in this application, that is, when producing a so-called hard sealing member, the compound represented by the general formula (1) or the general formula (2) And / or is the same as the method described above in that the oligomers thereof are hydrolyzed / polycondensed and the polycondensate (hydrolyzed / polycondensed product) is dried. There are different parts. Hereinafter, a case where such a so-called hard sealing member is manufactured will be described.

[III-2-5-1. material〕
Even in the case of manufacturing a hard sealing member, the same raw materials as in the case of manufacturing an elastomeric sealing member can be used. However, when using the compound (1) as a raw material, if the hardness of the produced sealing member is to be increased, the trifunctional or higher functional compound (1) (ie, the bifunctional compound (1) as the raw material) It is preferable to increase the ratio of the trifunctional or tetrafunctional compound (1)). This is because a trifunctional or higher functional compound can serve as a crosslinking component, so that the crosslinking of the sealing member can be promoted by increasing the ratio of the trifunctional or higher functional compound.

  Here, when a tetrafunctional or higher functional compound is used as the crosslinking agent, it is preferable to adjust the cross-linking degree of the entire system by increasing the use ratio of the bifunctional as compared with the case of using the trifunctional compound. When the oligomer of the compound (1) is used, there are a bifunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, an oligomer having a plurality of these units, and the like. At this time, when the ratio of the trifunctional or higher monomer unit to the bifunctional monomer unit is increased in the entire final sealing member, a hard sealing member can be obtained in the same manner as described above.

In addition, when using the compound (2), the basic concept is the same as when using the above compound (1). However, when the molecular weight of the organic group portion of the compound (2) is large, the distance between cross-linking points is substantially increased as compared with the case where the molecular weight is small, so that the flexibility tends to increase.
As described above, the sealing member whose solid Si-NMR peak half-width is within the range of the present invention has the degree of crosslinking adjusted by controlling the ratio of the bifunctional monomer unit and the trifunctional or higher monomer unit, There is little stress distortion, and moderate flexibility useful as a sealing member can be obtained.

[III-2-5-2. operation〕
Also when manufacturing a hard sealing member, a hydrolysis and polycondensation process is performed similarly to the case of manufacturing an elastomeric sealing member. However, when producing a hard sealing member, the hydrolysis / polycondensation reaction is preferably performed in the presence of a solvent.

Moreover, a drying process is performed also when manufacturing a hard sealing member. However, in the case of manufacturing a hard sealing member, the drying step includes a first drying step for substantially removing the solvent at a temperature not higher than the boiling point of the solvent, and a second step for drying at a temperature not lower than the boiling point of the solvent. The drying process is preferably performed separately. The details of the first drying step are such that the product obtained in the first drying step is usually a viscous liquid or a soft film formed by hydrogen bonding, and the solvent is removed to hydrolyze / Except that the polycondensate does not exist in a liquid state, it is the same as in the case of producing an elastomeric sealing member. The details of the second drying step are the same as in the case of manufacturing an elastomeric sealing member.
In addition, when manufacturing a hard sealing member, the solvent distillation process performed when manufacturing an elastomeric sealing member is not normally performed.

  Thus, even when a hard sealing member is manufactured by clearly separating the solvent removal step (first drying step) and the curing step (second drying step), the sealing of the present invention. It becomes possible to obtain a sealing member having excellent light resistance and heat resistance having physical properties of the stopper member without cracking or peeling.

[III-2-6. Addition of high refractive index specific metal particles)
When the above-mentioned high refractive index specific metal particles are added, the type thereof is not particularly limited as long as it is a particle containing at least one or more of the above-mentioned specific metal elements, but usually from an oxide of the specific metal element The following particles (metal oxide particles) are used.

  As a method of adding high refractive index specific metal particles, a method of adding the powder to the hydrolysis / polycondensation reaction solution alone, or a method of adding to the hydrolysis / polycondensation solution together with a solvent as an aqueous or solvent-based sol Etc. Any of these may be adopted, but in order to obtain a transparent sealing member, a method of adding it as a solvent-based sol having a small particle size and high dispersion is simple.

  The high-refractive-index specific metal particles are desirable because, when the dispersed state of the crystals is stable, they can be introduced into the sealing member as they are, and the effect of increasing the refractive index is remarkably obtained. On the other hand, when the dispersion state is unstable, it may be accompanied by a ligand for stable dispersion. In addition, the surface of the high refractive index specific metal particles has catalytic activity, and there is a risk of impairing the heat resistance and light resistance of the organic group portion of the sealing member, or the affinity with the matrix portion is low and aggregation is likely to occur. In this case, a known coating layer can be appropriately provided on the surface of the high refractive index specific metal particles. In these cases, it is preferable that the ligand and the coating layer itself are excellent in heat resistance and light resistance. In general, such a ligand or a coating layer often has a low refractive index, so that the amount of the coating layer used is preferably kept to the minimum necessary.

  The timing of adding the high refractive index specific metal particles is not particularly limited, and may be before hydrolytic polycondensation of the above-mentioned raw material compound (pre-addition method) or after (post-addition method). In the post-addition method, if the affinity between the reaction liquid after hydrolysis and polycondensation and the high refractive index specific metal particles is poor and aggregation of the high refractive index specific metal particles occurs during curing, the pre-addition method is adopted. It is preferable to do. When the raw material compound is hydrolyzed and polycondensed in the presence of high refractive index specific metal particles, a coating layer of the sealing member itself is formed on the surface of the particles, and can be stably applied and cured.

  From the viewpoint of improving the refractive index of the sealing member with a small amount, the refractive index of the high refractive index specific metal particles is usually 1.6 or more, preferably 1.8 or more, and more preferably 1.9 or more.

[III-2-7. Others]
In addition, you may give various post-processing as needed with respect to the obtained sealing member after the above-mentioned drying process. Examples of the post-treatment include surface treatment for improving adhesion to the mold part, production of an antireflection film, production of a fine uneven surface for improving light extraction efficiency, and the like.

[IV. Others]
As described above, the present invention has been described in detail using the embodiment. However, the illumination device of the present invention is not limited to the above-described embodiment, and appropriate modifications may be made without departing from the spirit of the present invention. It is possible to implement.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof.

[I. Synthesis of sealing member and measurement of physical properties]
[Synthesis Example 1]
50 g of both-end silanol dimethyl silicone oil (XC96-723 manufactured by Toshiba Silicone Co., Ltd.), 5.0 g of phenyltrimethoxysilane, and zirconium tetra n-propoxide solution (75 wt% n-propanol of zirconium tetra n-propoxide as catalyst) 11 g of a solution obtained by diluting 5 parts by weight of toluene with 95 parts by weight of toluene) was stirred for 15 minutes at room temperature and atmospheric pressure, and after initial hydrolysis, stirring was continued for another 8 hours while heating to 50 ° C. Then, after cooling a reaction liquid to room temperature, the sealing member formation liquid was obtained by hold | maintaining under reduced-pressure heating conditions (50 degreeC, 1 mPa) for 30 minutes (this is suitably referred to as "sealing member formation liquid 1 below. Moreover, what hardened this sealing member formation liquid 1 is suitably called "sealing member 1". In addition, the hydrolysis rate of the sealing member forming liquid 1 is 148%.

[Synthesis Example 2]
In Synthesis Example 1, the same reaction as in Synthesis Example 1 except that 82.5 g of a 20 wt% zirconia sol solution (hydrophobized surface-treated product, average particle size 3 nm, toluene dispersion product) was added to the reaction solution as a refractive index adjusting agent. In accordance with the procedure, a sealing member forming liquid was obtained (hereinafter referred to as “sealing member forming liquid 2” as appropriate. Also, a material obtained by curing the sealing member forming liquid 1 is referred to as “sealing member 2” as appropriate). . In addition, the hydrolysis rate of the sealing member forming liquid 2 is 148%.

[Synthesis Example 3]
In Synthesis Example 1, the same procedure as in Synthesis Example 1 except that 82.5 g of a 40 wt% zirconia sol solution (hydrophobized surface-treated product, average particle size 3 nm, toluene dispersion product) was added as a refractive index adjusting agent to the reaction solution. According to the procedure, a sealing member forming liquid was obtained (hereinafter, this is appropriately referred to as “sealing member forming liquid 3”. Also, a material obtained by curing this sealing member forming liquid 1 is appropriately referred to as “sealing member 3”). In addition, the hydrolysis rate of the sealing member forming liquid 3 is 148%.

(Measurement of refractive index)
The sealing member forming liquids 1 to 3 obtained by the synthesis examples 1 to 3 are applied onto a glass substrate having a thickness of 1 mm by a spin coating method, and held at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours. By curing, thin films of sealing members 1 to 3 having a thickness of about 1 μm were obtained. The refractive index of the thin film of the obtained sealing members 1 to 3 was measured by the prism coupler method. Further, the refractive index of the dimethyl silicone resin and the epoxy resin used in Comparative Examples 2 and 3 to be described later was also measured by the same procedure.

Specifically, a low-refractive index GGG prism is brought into contact with the above-described sealing member sample formed on a glass substrate and a wavelength of 408 nm is used, and [I. The refractive index and the film thickness were measured by measuring two or more optical waveguide propagation mode angles by the method described in the section “Surface emitting device”.
Equipment: Metricon model 2010 prism coupler Laser: 632.8 nm He-Ne laser
408 nm semiconductor laser prism: GGG prism for low refractive index (possible refractive index range: 1.0 to 1.80)
Rutile prism for high refractive index (possible refractive index range: 1.80 to 2.45)

[Measurement of TG-DTA]
Samples of sealing members of Examples 1 to 3 described later and dimethyl silicone resins and epoxy resins used in Comparative Examples 2 and 3 described later are used as samples, respectively, and thermogravimetry-differential thermal analysis is performed according to the following procedure. : Hereinafter abbreviated as “TG-DTA” as appropriate.) Measurement was performed.
Using a TG-DTA measuring device (TG / DTA6200 manufactured by Seiko Instruments Inc.) with a fragment of about 10 mg of a sample of the sealing material, 35 ° C. to 500 ° C. at a temperature rising rate of 20 ° C./min under a flow of 20 ml / min of air. The sample was heated to 0 ° C. and the weight loss by heating was measured. From this data, the weight loss from 35 ° C. until reaching 380 ° C. was determined. It can be seen that the sealing member of the example mainly composed of inorganic crosslinks has high heat resistance and is hardly deteriorated because the weight loss is small as compared with the conventional resin mainly composed of organic crosslinks.

[II. Production of lighting device and measurement of characteristics]
[Production of Lighting Device (Examples 1-3, Comparative Examples 1-3)]
As Examples 1 to 3 and Comparative Examples 1 to 3, lighting devices were manufactured according to the following procedure.
In any of the examples and comparative examples, a glass filler-containing polyphthalamide resin cup was used as the package. The size of the cup is 3.2 mm x 2.8 mm x 1.9 mm, and a silver plated copper electrode is provided on the inner surface of the concave portion of the cup, and a voltage is applied to the electrode from the outside of the cup. Is configured to be possible.
As the semiconductor light emitting device, an LED chip (MB290 manufactured by Cree) having a face-up GaN-based semiconductor having an emission peak of 405 nm as a light emitting layer was used. A gold electrode is formed on the upper surface of the LED chip, and the lower surface is formed of a conductive SiC substrate.

An outline of a procedure for manufacturing the lighting device is shown in FIGS. 5A to 5C, the same components as those in FIGS. 1 to 4 are denoted by the same reference numerals. Further, a polycarbonate film described later is represented by reference numeral 501.
First, an epoxy resin was used as a die-bonding agent, and the LED chip was die-bonded to the electrode surface in the recess of the package by a die-bonding device. Furthermore, the electrode formed on the upper surface of the LED chip and the electrode in the package recess were wire-bonded to establish electrical continuity (see FIG. 5A).

Next, the LED light source was produced by sealing the LED chip in a package recessed part using the material mentioned below as a sealing member.
Example 1: The sealing member forming liquid 1 obtained in Synthesis Example 1 was used (sealing member 1).
Example 2: The sealing member forming liquid 2 obtained in Synthesis Example 2 was used (sealing member 2).
Example 3: The sealing member forming liquid 3 obtained in Synthesis Example 3 was used (sealing member 3).
-Comparative example 1: The sealing member was not used.
Comparative Example 2: A dimethyl silicone resin (JCR6101UP manufactured by Toray Dow Corning Silicone) was used.
Comparative Example 3: An epoxy resin was used.

In Examples 1 to 3 and Comparative Examples 2 and 3, the sealing member was cured by the following procedure.
First, using a micropipette, the sealing member forming liquid was dropped into the cup recess provided with the LED chip so as to rise about 1 mm from the upper edge of the package. Subsequently, the sealing member was cured by holding at 120 ° C. for 1 hour and subsequently at 150 ° C. for 3 hours to obtain an LED light source having an elastic transparent sealing member.
In each of the obtained LED light sources of Examples 1 to 3 and Comparative Examples 2 and 3, the sealing member was shaped to rise about 0.8 mm from the upper edge of the package (see FIG. 5B).

On the LED light source of each Example and Comparative Example obtained by the above procedure, a 210 μm thick transparent polycarbonate film (refractive index 1.59) cut into a 5 mm × 5 mm square as an external optical member By placing and pressing from above with a pressure of 7.8 kPa, the lighting devices of Examples 1 to 3 and Comparative Examples 1 to 3 are obtained.
In Examples 1 to 3 and Comparative Examples 2 and 3, the upper end of the sealing member is deformed by an external force applied at the time of placement, and the LED light source and the polycarbonate film are bonded with good adhesion (see FIG. 5C). . In any of Examples 1 to 3 and Comparative Examples 2 and 3, the rising height of the sealing member protruding from the upper edge of the package is about 0.5 mm.
On the other hand, in Comparative Example 1, the upper opening of the package recess is covered with the polycarbonate film.

[Measurement of luminance change rate of lighting equipment]
The brightness | luminance change rate of the illuminating device of Examples 1-3 and Comparative Examples 1-3 can be calculated | required with the following procedures.

  First, the LED chip of each lighting device is turned on by energizing 20 mA, and the brightness of light emitted through a polycarbonate film (external optical member) is measured by a spectroscope such as USB2000 manufactured by Ocean Optics, for example. A.

  Subsequently, in the state where a white spacer made of Teflon (registered trademark) having a thickness of 1 mm is interposed between the LED light source of each lighting device and the polycarbonate film (external optical member), the LED chip is similarly energized with 20 mA. The brightness of the light emitted through the white spacer and the polycarbonate film (external optical member) is measured, and the brightness is defined as B.

Using the values of the luminances A and B, the luminance change rate C (%) is obtained according to the following formula (1).

[III. Evaluation)
For the lighting devices of Examples 1 to 3 and Comparative Examples 1 to 3, the types and physical properties of the sealing member and the external optical member and the value of the luminance change rate obtained by the above procedure are shown in Table 2 below.

As shown in Table 2, in the illuminating devices of Examples 1 to 3 in which the refractive index difference | n _e −n _o | between the sealing member and the external optical member is 0.17 or less, the sealing member and the external optical member The rate of change in luminance when touching is large, and the luminance is greatly improved as compared with the case of non-contact.
When a hard epoxy resin is used as the sealing member as in the lighting device of Comparative Example 3, the refractive index step is relatively small, but it does not adhere to the external optical member through the air layer. Since light is transmitted, luminance is not improved.

  The use of the lighting device of the present invention is not particularly limited, and can be used for various lighting devices including an external optical member. Among them, light emitted from a light source such as an LED is planar by a light guide plate. It is particularly preferably used in applications such as a surface light-emitting device that emits light and a semiconductor lighting device that emits light from a light source through an outer lens.

(A), (b) is a figure which shows typically the structure of the illuminating device (surface light-emitting device) which concerns on 1st Embodiment of this invention, (a) is a side view, (b) is a top view. It is. It is sectional drawing which shows typically an example of a structure of the light source with which the illuminating device (surface light-emitting device) which concerns on 1st Embodiment of this invention is provided. It is sectional drawing which shows typically another example of a structure of the light source with which the illuminating device (surface light-emitting device) which concerns on 1st Embodiment of this invention is provided. It is sectional drawing which shows typically the structure of the illuminating device (semiconductor illuminating device) which concerns on 2nd Embodiment of this invention. (A)-(c) is for demonstrating the preparation procedure of the illuminating device in an Example. (A), (b) is a figure which shows typically the structure of the conventional surface emitting device, (a) is a side view, (b) is a top view. It is sectional drawing which shows typically the example of a structure of the light source with which the conventional surface emitting apparatus is provided.

Explanation of symbols

100,600 surface light emitting device (lighting device)
101,601 Light guide plate (optical member, external optical member)
102, 200, 300, 602 LED light source (light source)
103,603 Outer frame 104 Joining part 105,605 Substrate 106,606 Reflection sheet 107,607 Diffusion sheet 201,701 Package 202,702 LED element (semiconductor light emitting element)
203, 203 (a), 203 (b), 203 (c), 703 Sealing member 204, 704 Lead electrode 400 Semiconductor light emitting element (illumination device)
401 Outer lens (optical member, external optical member)
501 Polycarbonate film (optical member, external optical member)

Claims (10)

In an illumination device having at least a light source and an optical member capable of transmitting or guiding light emitted from the light source,
The light source includes a package having a recess, a semiconductor light emitting element disposed in the recess of the package, and a sealing member for sealing the semiconductor light emitting element.
The sealing member is made of an elastic body, the optical member and the sealing member are joined substantially without an air layer, and a difference in refractive index between the optical member and the sealing member. Is within 0.17, The illuminating device characterized by the above-mentioned. The lighting device lighting device according to claim 1, wherein the sealing member is provided so as to protrude from an opening surface of the concave portion of the package. In the solid Si-nuclear magnetic resonance spectrum, the sealing member is
(I) The peak top position is in the region of chemical shift −40 ppm or more and 0 ppm or less, and the peak half-width is 0.3 ppm or more and 3.0 ppm or less, and
(Ii) The position of the peak top is in a region where the chemical shift is −80 ppm or more and less than −40 ppm, and the peak half-value width is at least one peak selected from the group consisting of peaks of 0.3 ppm or more and 5.0 ppm or less. With
The silicon content of the sealing member is 20% by weight or more, and
The lighting device according to claim 1 or 2, wherein a silanol content of the sealing member is 0.1 wt% or more and 10 wt% or less. The lighting device according to any one of claims 1 to 3, wherein the total content of Si, Al, Zr, Ti, Y, Nb, and B in the sealing member is 20% by weight or more. . The light emitting device according to any one of claims 1 to 4, further comprising a wavelength conversion unit that includes at least one wavelength conversion material that absorbs light from the semiconductor light emitting element and converts it into light of different wavelengths. The lighting device described. The sealing member contains at least one type of wavelength conversion material that absorbs light from the semiconductor light emitting element and converts it into light of a different wavelength, according to any one of claims 1 to 5, The lighting device described. The illumination device according to claim 5 or 6, wherein the wavelength conversion material is a phosphor. 2. The weight loss when the temperature is raised from 35 ° C. to 380 ° C. under air flow when thermogravimetric / differential heat measurement is performed on the sealing member is 10% by weight or less. The illuminating device as described in any one of -7. The optical member is formed as a light guide plate having an emission surface and a reflection surface facing each other, and the light source is bonded to one end surface of the light guide plate or two opposite end surfaces to guide light from the light source. The illumination device according to claim 1, wherein the illumination device is configured to be incident from an end surface of the light plate and to be emitted from the emission surface. The optical member is formed as an outer lens having an entrance surface and an exit surface, the light source is bonded to the entrance surface of the outer lens, and the light from the light source is incident from the entrance surface of the outer lens. The illumination device according to any one of claims 1 to 8, wherein the illumination device is configured to emit light from an emission surface.

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