JP2013080820A - Resin molding and light emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light emitting device which decreases the dark luminance thereby forming a high definition display device having a high contrast ratio.SOLUTION: A light emitting device has: multiple light emitting elements having different emission wavelengths; a substrate having multiple recessed parts where the light emitting elements are placed; and sealing members provided at the respective recessed parts. The recessed parts are spaced away from each other and are provided with the sealing members, each of which contains a coloring member of a similar color to the emission wavelength of the light emitting element.

Description

  The present invention relates to a light-emitting device capable of multicolor light emission used for light sources such as various pilot lamps, display devices, backlights, and displays, and more particularly to a light-emitting device having a high contrast ratio and durability.

In a large display device using light emitting diodes (hereinafter also referred to as LEDs) of three primary colors of red (R), green (G), and blue (B), these colors are arranged in a matrix, for example, and the respective light emission Full color display can be achieved by combining colors.

For example, when a surface-mounted LED is used in such a display device, it is known that a light absorption layer is provided on the light emission observation surface of the package excluding the light emitting portion in order to increase the contrast ratio (for example, Patent Documents). 1).
It is also known to improve the contrast by using a coloring member that is substantially the same as each emission color on the surface of the substrate that reflects the light from the light emitting element (for example, Patent Document 2), and to contain a coloring member in the mold member. (For example, Patent Document 3).

JP 2000-183405 A JP 2000-22221 A JP-A-9-283806 JP 2010-62272 A JP 2009-302241 A

However, when using a colored member as in Patent Document 2, if the LED itself is small, it is difficult to provide the colored member. In particular, in the case of a multicolor light emitting LED on which RGB semiconductor light emitting elements (hereinafter also referred to as light emitting elements) are mounted, it is difficult to provide different colored members for each light emitting element. The same applies to the case where a colored member is contained in the mold member as described in Patent Document 3. Such a colored member is effective for a single color light emitting LED, but if a single color light emitting LED is used, the display device becomes large and it is difficult to obtain a high-definition image.
Furthermore, heat generated from semiconductors (and light when the semiconductor is a light-emitting diode) has been increasing, and the heat resistance (light resistance) of semiconductor packaging resins has been increasingly required. Responding to these requirements, a resin that has high heat resistance and is cured by a hydrosilylation reaction has been applied as a semiconductor package resin (Patent Documents 4 and 5).
In view of the above, an object of the present invention is to provide a light-emitting device that has a high contrast ratio and a high-definition display device by reducing dark luminance, and has high moldability and durability.

That is, the present invention has the following configuration.
1. A resin molded body for a light-emitting device, comprising: a plurality of light-emitting elements having different emission wavelengths; a cured resin body having a plurality of recesses on which the light-emitting elements are placed; and a sealing member provided in each recess. The recess is composed of three recesses that are spaced apart from each other and have openings having substantially the same shape, and each of the recesses is provided with a green light emitting element, a red light emitting element, and a blue light emitting element. A resin molded body for a light emitting device,
The ten-point average roughness (Rz) of the opening surface and the frame side surface of the recess is 1 μm or more and 10 μm or less,
Using a thermomechanical analyzer (TMA), the glass transition temperature of the cured resin measured at a temperature range of −50 to 250 ° C., a heating rate of 5 ° C./min, and a sample size length of 1 to 5 mm is 10 ° C. or higher. And
The light reflectance at 460 nm of the opening surface of the resin cured body or the inner wall surface of the recess is 80% or more, and the light on the opening surface and the inner wall surface after heating the resin cured body at 180 ° C. for 72 hours. A resin molded body for a light-emitting device having a reflectance retention of 90% or more.
2. 2. The resin molded body for a light-emitting device according to 1, wherein at least one peak top in a solid ¹³ C-nuclear magnetic resonance spectrum of the cured resin is present in a range of −1 ppm to 2 ppm and 13 ppm to 18 ppm,
3. The cured resin is (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) containing at least two SiH groups in one molecule. A compound containing (C) a hydrosilylation catalyst, (D) a silicone compound containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and (E) a curing containing an inorganic filler. The resin molded body for a light-emitting device according to any one of 1 to 2, which is a cured resin body of the conductive resin composition (I).

  According to the present invention, a light-emitting device capable of realizing a display device that is durable, has a high contrast ratio, and is capable of high-definition display can be provided.

FIG. 1A is a front view showing an example of a light emitting device according to the present invention. 1B is a cross-sectional view taken along the line X-X ′ of FIG. 1A. FIG. 2A is a front view showing an example of a light emitting device according to the present invention. FIG. 2B is a cross-sectional view taken along the line Y-Y ′ of FIG. 2A.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, the form shown below illustrates the light-emitting device for embodying the technical idea of the present invention, and the present invention does not limit the light-emitting device to the following.

  Further, the present specification by no means specifies the member shown in the claims as the member of the embodiment. In particular, the dimensions, materials, shapes, relative arrangements, and the like of the components described in the embodiments are not intended to limit the scope of the present invention only to the extent that there is no specific description. It is just an example. It should be noted that the size and positional relationship of the members shown in each drawing may be exaggerated for clarity of explanation. Furthermore, in the following description, the same name and symbol indicate the same or the same members, and detailed description thereof will be omitted as appropriate. Furthermore, each element constituting the present invention may be configured such that a plurality of elements are constituted by the same member and the plurality of elements are shared by one member, and conversely, the function of one member is constituted by a plurality of members. It can also be realized by sharing.

  1A shows a front view (top view) of a light-emitting device 100 according to the embodiment, and FIG. 1B shows a cross-sectional view taken along line X-X ′ of FIG. 1A. In the present embodiment, the base 101 of the light emitting device is made of a cured resin, and has three concave portions 101A, 101B, and 101C that are separated from each other on the upper surface thereof. In each recess, the conductive member 102 is exposed on the bottom surface, and the conductive member is partially included in the base 101 and provided so as to protrude from the side surface of the base. The protruding conductive member is bent along the bottom surface of the base 101, and functions as a conductor wiring of the light emitting elements 103A, 103B, and 103C disposed on the base. Each light emitting element is fixed on the conductive member 102 by a joining member such as resin or metal paste. The conductive electrode 104 electrically connects the p electrode and the n electrode of each light emitting element to the conductive member. In addition, sealing members 105A, 105B, and 105C such as resin are filled in the respective concave portions of the base 101 so as to seal them.

  In this embodiment, the light emitting elements placed in the recesses 101A (first recess), 101B (second recess), and 101C (third recess) are the green light emitting element 103A, the red light emitting element 103B, The blue light emitting element 103C includes a sealing member 105A containing a green coloring member, a sealing member 105B containing a red coloring member, and a blue coloring member. The sealing member 105 </ b> C is characterized. As described above, the contrast ratio can be further improved by including in the sealing member a colored member having the same color as the emission wavelength of the light emitting element to be mounted.

(Concave)
The recess has an opening on the upper surface (light emission observation surface) side of the substrate, and a light emitting element can be placed on the bottom surface of the recess, and a bonding region such as a wire for conducting with the conductive member is provided. It has a size that can be secured. The depth of the recess needs to be higher than at least the height of the light emitting element, and can be appropriately selected in consideration of optical characteristics such as light distribution characteristics.

  In the present embodiment, there are a plurality of recesses, and the recesses are provided so as to be separated from each other. For example, as shown in FIG. 1A and FIG. 1B, the first concave portion 101A, the second concave portion 101B, and the third concave portion 101C having the same opening shape are arranged so as to be spaced apart at equal intervals. The shape of each recess may be a track shape as shown in FIG. 1A, a circle, an ellipse, a square, a rectangle, other polygons, or a combination of these. In addition, the size of the opening of the recess, the area of the bottom surface, the inclination of the side surface of the recess, and the like can be appropriately selected according to desired light distribution characteristics.

  Moreover, as another form, it can also be set as the shape which has the level | step-difference part 206 on the upper surface of the base | substrate 201 as shown to FIG. 2A and FIG. 2B. The recesses 201A, 201B, and 201C are separated from each other at the bottom of the stepped portion 206, and sealing members 205A, 205B, and 205C containing a colorant having the same color as the emission wavelength of the light emitting elements 203A, 203B, and 203C are provided. . A covering member 207 may be provided on the step portion 206 above each of the recesses. By including a diffusing member or the like in the covering member 207, the color mixing property can be improved. As the covering member, a member similar to a resin used for a sealing member described later can be used.

  Rz of the opening surface of the cured resin body is 1 μm or more and 10 μm or less. Thereby, when the resin molded body 101 for light emitting devices is mass-produced, the resin molded body having a uniform shape can be efficiently manufactured. When the Rz is less than 1 μm, when the resin molded body is manufactured using a transfer mold molding die, the releasability of the resin molded body from the mold is reduced, and deformation or cohesive failure of the resin molded body is caused. Tend to occur. When Rz exceeds 10 μm, the light reflectance tends to decrease. Therefore, when Rz is 1 μm or more and 10 μm or less, it is possible to achieve both improvement in releasability during production of the resin molded body 101 for the light emitting device and high reflectance of the resin molded body.

  The resin cured body constituting the resin molded body 101 for a light emitting device is a thermomechanical analyzer (TMA), and is in a temperature range of −50 to 250 ° C., a temperature rising rate of 5 ° C./min, and a sample size length of 1 to 5 mm. It is preferable that the measured glass transition temperature of the cured resin is 10 ° C. or higher. Thereby, the heat resistance of the resin cured body constituting the resin molded body 101 for the light emitting device is improved, and thermal deterioration accompanied with discoloration is suppressed even when exposed to a high temperature caused by the light emitting element. As a result, the reflectance in the initial stage of use can be maintained at a high level. The glass transition temperature (Tg) is more preferably 20 ° C. or higher, and further preferably 50 ° C. or higher.

  Further, the opening surface of the resin cured body constituting the resin molded body 101 for the light emitting device and the inner wall surface of the recess have a light reflectance at 460 nm of 80% or more, and the resin cured body is heated at 180 ° C. for 72 hours. It is preferable that the retention ratio of the light reflectivity on the opening surface and the inner wall surface of the resin molded body 101 for a light emitting device after being 90% or more. By using such a resin cured body, the reliability when used in the side-emitting type resin molded body 1 for a semiconductor light emitting device is remarkably improved.

In addition, at least one peak top in the solid 13C-nuclear magnetic resonance spectrum (hereinafter referred to as “solid 13C NMR spectrum”) of the resin molded body 101 for a light-emitting device exists in the ranges of −1 ppm to 2 ppm and 13 ppm to 18 ppm. Further preferred. Such a cured resin body further improves the reliability of the resin molded body 101 for a light emitting device.
In addition, the resin material which gives the resin cured body which has the above characteristics is mentioned later.

(Sealing member)
The sealing member is a member that protects a semiconductor light emitting element or a conductive wire mounted on the upper surface of the plate-like base or a base having a concave portion from dust, moisture, external force, etc., and protects light from the light emitting element. What has translucency which can permeate | transmit is preferable. In the present embodiment, the sealing member contains a coloring member having the same color as the emission wavelength of the light emitting element placed in the recess. For example, a sealing member containing a blue coloring member is provided in the recess where the blue light emitting element is placed. Specifically, as shown in FIGS. 1A and 1B, a green light emitting element 103A is placed in the recess 101A, and a sealing member 105A containing a green coloring member is provided. Similarly, a red light emitting element 103B is placed in the recess 101B, a sealing member 105B containing a red colored member is provided, a blue light emitting element 103C is placed in the recess 101C, and a sealing member 105C containing a blue colored member is placed. Is provided. Thus, by providing a sealing member containing a different colored member for each recess, a light-emitting device with a high contrast ratio can be obtained.

  Specific examples of the sealing member include silicone resin, epoxy resin, and urea resin. The filling amount of the sealing member may be an amount that covers a protective element such as a body light emitting element or a Zener diode, and a conductive wire. For example, as shown in FIG. 1B, the sealing members 105A, 105B, and 105C The filling can be performed so as to reach the upper surface of the substrate 101. Moreover, as a sealing member, you may make it laminate | stack the sealing member which does not contain a coloring member with the sealing member containing a coloring member. That is, different sealing members may be laminated instead of filling the entire recess with a single sealing member.

  The sealing member is cured by heating. In this case, the sealing member may be heated at the same time after all the recesses are filled with the sealing member, whereby the curing can be efficiently performed with fewer steps. Or you may pass through several heating processes, such as heating after filling a sealing member in one recessed part, and filling a sealing member in another recessed part, and heating after that. Accordingly, it is possible to reduce a problem that a sealing member containing a colored member of a different color is mixed in an adjacent recess.

(Coloring member)
The coloring member contained in the sealing member has a color tone similar to the emission wavelength of the light emitting element, and examples thereof include pigments and dyes. It is preferable that the sealing member is uniformly dispersed, and a material that hardly inhibits the curing of the sealing member is preferable. Moreover, a thing with the high light transmittance is preferable. In the case of a pigment, it is preferable to use a pigment having a particle size of 3.0 μm or less, preferably 2.5 μm or less and uniformly dispersed in a solvent or the like before being mixed with the sealing member. These are variously selected in consideration of the composition, specific gravity, viscosity and the like of the sealing member to be used, and the addition amount can be appropriately selected according to the purpose and application.

  As long as the pigment satisfies the above conditions, the composition is not particularly limited, and organic pigments, inorganic pigments, and the like can be used. For example, specific examples of organic pigments include phthalocyanine-based and anthraquinone-based pigments as blue pigments. Examples of the green pigment include phthalocyanine-based pigments. Examples of red pigments include perylene, azo lake, quinacridone, pyrrolo-peel, and azo. These can be used singly or in combination depending on the color.

(Substrate and conductive member)
In the present embodiment, the substrate is provided with a conductive member for protecting electronic parts such as a light emitting element and a protective element and supplying an electric current from the outside to the electronic parts. Since the substrate is used as a display device, the substrate is preferably mounted at a high density with an adjacent light emitting device, and preferably has a square shape or a shape close to this. However, it is not particularly limited to this, and may be a triangle, a quadrangle, a polygon, or a shape close to these in a plan view (top view).

As the base material, an insulating member is preferable, and a member that hardly transmits light from the light emitting element, external light, or the like is preferable. Moreover, what has a certain amount of intensity | strength is preferable.
As a material for the conductive member (lead terminal), a material using a material having a relatively large thermal conductivity is preferable. By forming with such a material, heat generated in the light-emitting element can be efficiently released. For example, it is preferable to have a thermal conductivity of about 200 W / (m · K) or more. Furthermore, a material having a relatively large mechanical strength or a material that can be easily punched or etched or etched is preferable. Specific examples include metals such as copper, aluminum, gold, silver, tungsten, iron, nickel, iron-nickel alloys, phosphor bronze, iron-containing copper, and the like.

  Further, the base may be provided with a black member for improving contrast. In that case, the contrast can be improved by making the upper surface (the surface provided with the recesses) at least black. The black member can be easily provided by a method such as applying a black colored member, or the substrate itself may be black. In that case, a white material having a high reflectance can be used for the sidewall of the recess. As the black member, when the substrate itself is black, a black additive, for example, a thermosetting resin added with carbon can be used, and when it is provided to be applied to the surface of the substrate, Black phenol ink, black epoxy resin, or the like can be used.

(Light emitting element)
A light emitting element having an arbitrary wavelength can be selected. For example, in order to obtain a display device used as a full-color display, light emitting devices of three colors of blue, green, and red are used for the light emitting device. As the blue and green light emitting elements, those using ZnSe or a nitride semiconductor (InXAlYGa1-X-YN, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) can be used. As the red light emitting element, GaAs, InP, or the like can be used. Furthermore, a semiconductor light emitting element made of a material other than this can also be used. The composition, emission color, size, number, and the like of the light emitting element to be used can be appropriately selected according to the purpose.
Further, a light-emitting element that outputs not only light in the visible light region but also ultraviolet rays and infrared rays can be obtained. In addition to the semiconductor light emitting element, a light receiving element, a protective element (for example, a Zener diode or a capacitor) that protects the semiconductor element from destruction due to overvoltage, or a combination thereof can be mounted.

(Die bond member)
The die bond member is a bonding member for mounting a light emitting element, a protection element, or the like on a base body or a conductive member. Either a conductive die bond member or an edge die bond member can be selected depending on the substrate of the mounted element. it can. For example, in the case of a semiconductor light emitting device in which a nitride semiconductor layer is laminated on sapphire, which is an insulating substrate, it can be used either insulating or conductive. When a conductive substrate such as a SiC substrate is used, a conductive die bond Conduction can be achieved by using a member. As the insulating die bond member, an epoxy resin, a silicone resin, or the like can be used. In the case of using these resins, a metal layer having a high reflectance such as an Al film can be provided on the back surface of the semiconductor light emitting element in consideration of deterioration due to light or heat from the semiconductor light emitting element. In this case, a method such as vapor deposition, sputtering, or bonding a thin film can be used. In addition, as the conductive die bond member, a conductive paste such as silver, gold, or palladium, solder such as Au—Sn eutectic, or a brazing material such as a low melting point metal can be used.

(Conductive wire)
The conductive wire that connects the electrode of the semiconductor light emitting element and the conductive member provided on the support is required to have good ohmic properties, mechanical connectivity, electrical conductivity, and thermal conductivity with the conductive member. The thermal conductivity is preferably 0.01 cal / (s) (cm 2) (° C./cm) or more, more preferably 0.5 cal / (s) (cm 2) (° C./cm) or more. In consideration of workability and the like, the diameter of the conductive wire is preferably Φ10 μm or more and Φ45 μm or less. Specific examples of such conductive wires include conductive wires using metals such as gold, copper, platinum, and aluminum, and alloys thereof. Such a conductive wire can easily connect the wire bonding region formed in the conductor wiring and the electrode of the semiconductor element by a wire bonding apparatus.

  In each of the above-described embodiments, the resin material that gives the resin cured body for reflecting the light emitted from the light emitting element is not particularly limited, but from the viewpoint of carrying out transfer molding, a thermosetting resin is used. Is preferred. As the thermosetting resin, those used in the field of surface-mounted light-emitting devices can be used without particular limitation, and examples thereof include epoxy resins, modified epoxy resins, silicone resins, modified silicone resins, acrylate resins, and polyurethanes. It is done. These thermosetting resins can be used alone or in combination of two or more.

  Among these thermosetting resins, epoxy resins, modified epoxy resins, silicone resins and modified silicone resins are preferable. For example, 100 parts by weight of a mixture of an epoxy resin and an equivalent acid anhydride, 0.1 to 2 parts by weight of a curing accelerator, 0.5 to 3 parts by weight of a promoter, 5 to 30 parts by weight of a white pigment, and 30 inorganic fillers An epoxy resin composition obtained by adding ~ 70 parts by weight can be used. Furthermore, an epoxy resin composition that has been partially cured by heating to a B-stage can be used.

  In the epoxy resin composition described above, examples of the epoxy resin include an epoxy resin obtained from triglycidyl isocyanurate, hydrogenated bisphenol A diglycidyl ether, and the like. Examples of the acid anhydride include hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like. Examples of the curing accelerator include DBU (1,8-diazabicyclo [5,4,0] undecene-7). Examples of the cocatalyst include ethylene glycol. Examples of the white pigment include titanium oxide. Examples of the inorganic filler include silica particles and glass fibers.

  In addition, from the viewpoint of further suppressing the occurrence of warpage of the cured resin body due to heat generation of the light emitting element and the thermal deterioration accompanying discoloration, (A) one molecule of a carbon-carbon double bond having reactivity with the SiH group. Preferred is an organic compound containing at least two in it, (B) a thermosetting resin composition containing at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst. A component, (B) component and (C) component, (D) a silicone compound containing at least one carbon-carbon double bond reactive with SiH group in one molecule, and (E) an inorganic filler. The thermosetting resin composition (X) contained is more preferable.

  Since the thermosetting resin composition (X) has a relatively low linear expansion coefficient, the difference from the linear expansion coefficient of the metal material used for the lead is small. Moreover, since the thermosetting resin composition (X) has high heat resistance and is unlikely to undergo thermal deterioration with discoloration, the light reflectance is maintained at a high level in the initial stage of use even when exposed to high temperatures.

  Below, each component of (A)-(E) is demonstrated in detail.

  The component (A) is not particularly limited as long as it is an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups in one molecule.

  The skeleton of the component (A) does not contain a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer as an organic compound. More preferred are compounds containing no elements other than N, O, S and halogen. In the case of those containing siloxane units, there is a problem that the adhesiveness between the semiconductor package and the lead frame or the sealing resin tends to be low.

  The component (A) can be classified into an organic polymer compound and an organic monomer compound.

  As the component (A) of the organic polymer system, for example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based, polyacrylate ester-based, polyamide-based, phenol-formaldehyde Examples thereof include those having a skeleton of a system (phenolic resin system) or a polyimide system.

  Among these, examples of the polyether-based polymer include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the like. More specific examples include the polymers shown below.

(Wherein R ¹ and R ² are C 1 -C 6 divalent organic groups containing no elements other than C, H, N, O, S and halogen as constituent elements, n, m, and l are 1 to 1; Represents a number of 300.)
Examples of other polymers include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, and neopentyl glycol. Polyester polymers obtained by condensation of lactones or ring-opening polymerization of lactones; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, Copolymers such as styrene, polybutadiene, copolymers of butadiene and styrene, acrylonitrile, polyisoprene, polybutadiene, isoprene or butadiene and acrylonitrile, styrene Polyolefin-based (saturated hydrocarbon-based) polymer obtained by hydrogenation of copolymer with dope; polyacrylate, ethyl acrylate, butyl acrylate, etc. obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate Acrylate ester copolymer of acrylate ester of vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc .; graft polymer obtained by polymerizing vinyl monomer in the organic polymer; polysulfide polymer; Nylon 6 by ring-opening polymerization of aminocaprolactam, nylon 66 by polycondensation of hexamethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of ε-aminoundecanoic acid, ε- Nylon 12 by ring-opening polymerization of minolaurolactam, a polyamide-based polymer such as copolymer nylon having two or more components among the above nylons; for example, polycarbohydrate produced by polycondensation from bisphenol A and carbonyl chloride Nate polymer; diallyl phthalate polymer; phenol-formaldehyde resin (phenolic resin) such as novolak type phenolic resin, resol type phenolic resin, ammonia resol type phenolic resin, benzylic ether type phenolic resin; .

  An alkenyl group having a carbon-carbon double bond can be introduced into these polymer skeletons to obtain the component (A). In this case, the alkenyl group having a carbon-carbon double bond may be present anywhere in the molecule, but is preferably present in the side chain or the terminal in terms of reactivity.

  Various methods for introducing an alkenyl group into the polymer skeleton can be used. However, the method can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. Can do.

  As a method for introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group or an epoxy group at the terminal, main chain or side chain is reactive with the functional group. By reacting an organic compound having both an active group having an alkenyl group and an alkenyl group, an alkenyl group can be introduced into the terminal, main chain or side chain.

Examples of organic compounds having both an active group and an alkenyl group that are reactive with the functional group include 3 to 20 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. of unsaturated fatty acids, acid halides, acid anhydrides such as and allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , allyl bromo formate _{(CH 2} = CHCH ₂ OCOBr) unsaturated aliphatic C3~C20 such as alcohol-substituted Carbonic acid halide, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) Ether, 1-hexenyl (chloro Methoxy) benzene, allyloxy (chloromethyl) benzene, allyl isocyanate.

  There is also a method of introducing an alkenyl group using a transesterification method. This method is a method of transesterifying an alcohol residue of an ester portion of a polyester resin or an acrylic resin with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst. The alkenyl group-containing alcohol and alkenyl group-containing phenol derivative used for transesterification with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have one. A catalyst may or may not be used, but titanium and tin catalysts are preferred.

  Examples of the alkenyl group-containing alcohol include vinyl alcohol, allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, and 7-octene. -1-ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether, trimethylolethanetri Examples include allyl ether, pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether, and the like. Moreover, as an alkenyl group containing phenol derivative, what is shown to following [, for example] is mentioned.

  Among these, in view of availability, allyl alcohol, vinyl alcohol, 3-buten-1-ol, 2- (allyloxy) ethanol, and those shown below are preferable.

  Further, the ester residue of the above-mentioned alcohol or phenol derivative such as acetate ester and the ester portion of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the residual alcohol remaining in the ester portion of the polyester resin or acrylic resin to be produced. There is also a method of introducing an alkenyl group by a method in which a low molecular weight esterified product such as an acetate of a group is distilled out of the system by vacuum devolatilization.

  Moreover, after polymerizing methyl (meth) acrylate etc. by living polymerization, an alkenyl group can also be introduce | transduced into the terminal by the method of stopping a polymerization reaction by combining the compound which has an alkenyl group at the living terminal.

  Examples of a method for introducing an alkenyl group during polymerization include a radical chain transfer agent having an alkenyl group having low radical reactivity when the organic polymer skeleton of the component (A) used in the present invention is produced by radical polymerization. Can be used to introduce an alkenyl group into the side chain or terminal of the organic polymer skeleton. Examples of such radical chain transfer agents include vinyl monomers having alkenyl groups with low radical reactivity in the molecule, such as allyl methacrylate and allyl acrylate, and allyl mercaptans.

  Although the molecular weight of (A) component is not specifically limited, Any thing of 100-100,000 can be used conveniently, If it is an alkenyl-group containing organic polymer, the thing of 500-20,000 is especially preferable. When the molecular weight is less than 300, characteristics due to the use of an organic polymer such as imparting flexibility are hardly exhibited, and when the molecular weight exceeds 100,000, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group is hardly exhibited. .

  Examples of the organic monomer-based component (A) include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic Examples thereof include compounds and mixtures thereof.

  In the component (A), the bonding position of the carbon-carbon double bond having reactivity to the SiH group is not particularly limited, and may be present anywhere in the molecule. Although it does not specifically limit as a carbon-carbon double bond which has reactivity with respect to SiH group, The group shown with the following general formula (I) is suitable from a reactive point.

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Moreover, the group shown below is especially preferable from the ease of acquisition of a raw material.

  As the carbon-carbon double bond having reactivity with the SiH group of the component (A), an alicyclic group represented by the following general formula (II) is preferable because the heat resistance of the cured resin is high. is there. Moreover, the alicyclic group shown below is especially preferable from the ease of acquisition of a raw material.

(In the formula, R ² represents a hydrogen atom or a methyl group.)

  The carbon-carbon double bond having reactivity with the SiH group may be directly bonded to the skeleton portion of the component (A) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms, but preferably does not contain elements other than C, H, N, O, S and halogen as constituent elements. Examples of these substituents include those shown below. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent.

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Examples include oxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group, and groups shown below.

  Specific examples of the component (A) of the organic polymer system include 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol allyl ether. , Allylated polyphenylene oxide, polymers shown below, and the like.

(Wherein R ¹ is H or CH ₃ , R ² , R ³ is a C 1 -C 6 divalent organic group containing no elements other than C, H, N, O, S and halogen as constituent elements, X and Y are divalent substituents having 0 to 10 carbon atoms, and n, m, and l are numbers 1 to 300.)

(In the formula, R ¹ is H or CH ₃ , R ⁴ , R ⁵ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

Wherein R ¹ is H or CH ₃ , R ⁶ , R ⁷ is a divalent organic group having 1 to 20 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

Wherein R ¹ is H or CH ₃ , R ⁸ , R ⁹ is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n, m, l represents a number from 1 to 300.)

(Wherein R ¹ is H or CH ₃ , R ¹⁰ , R ¹¹ , R ¹² is a divalent organic group having 1 to 6 carbon atoms, X and Y are divalent substituents having 0 to 10 carbon atoms, n , M, l, and p represent numbers of 1 to 300).

  Specific examples of the organic monomer component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2 -Tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, a part of glycidyl groups of conventionally known epoxy resins as shown below Or put it all on the allyl group Such example was compound, and the like.

  As the component (A), low molecular weight compounds that are difficult to express separately as described above for the skeleton portion and the alkenyl group can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene, decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene, norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  (A) As a component, from a viewpoint that heat resistance can be improved more, what contains 0.001 mol or more of carbon-carbon double bond which has reactivity with respect to SiH group per 1 g of (A) component. Preferably, what contains 0.005 mol or more per 1 g of component (A), more preferably 0.008 mol or more per 1 g of component (A).

  In the component (A), the average number of carbon-carbon double bonds having reactivity with the SiH group may be at least two per molecule, but 2 should be used to further improve the mechanical strength. It is preferable that the number exceeds 3, and more preferably 3 or more. When the number of carbon-carbon double bonds having reactivity to the SiH group of the component (A) is 1 or less per molecule, even if the component (A) and the component (B) react, Only the graft structure is generated, and the crosslinked structure is not generated.

  As the component (A), from the viewpoint of good reactivity, it is preferable that one or more vinyl groups are contained in one molecule, and two or more vinyl groups are contained in one molecule. It is more preferable. Further, from the viewpoint that the storage stability tends to be good, it is preferable that 6 or less vinyl groups are contained in one molecule, and it is more preferable that 4 or less vinyl groups are contained in one molecule.

  The molecular weight of the component (A) is such that the mechanical heat resistance is high, the stringiness of the raw material liquid is small, the moldability and the handleability are good, and the powders such as the components (E) and (F) Is preferably less than 900, more preferably less than 700, and even more preferably less than 500, from the viewpoint of easy uniform mixing with and a moldability of the curable resin composition tablet. .

  The viscosity of component (A) is preferably less than 1000 poise, more preferably less than 300 poise, and even more preferably 30 poise at 23 ° C. in order to obtain uniform mixing with other components and good workability. Is less than. The viscosity can be measured with an E-type viscometer.

  The component (A) preferably has a low content of a compound having a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group from the viewpoint of higher light resistance, and is a phenolic hydroxyl group and / or a derivative of a phenolic hydroxyl group. What does not contain the compound which has is preferable. The phenolic hydroxyl group in the present invention is a hydroxyl group directly bonded to an aromatic hydrocarbon nucleus exemplified by a benzene ring, naphthalene ring, anthracene ring and the like, and the derivative of the phenolic hydroxyl group is a hydrogen atom of the above-mentioned phenolic hydroxyl group. Represents a group substituted by an alkyl group such as a methyl group or an ethyl group, an alkenyl group such as a vinyl group or an allyl group, or an acyl group such as an acetoxy group.

  From the viewpoint of particularly good light resistance, the weight ratio of the aromatic ring component (A) is preferably 50% by weight or less, more preferably 40% by weight or less, and more preferably 30% by weight or less. Are more preferred. Most preferred are those that do not contain an aromatic hydrocarbon ring.

  From the viewpoint that the cured resin obtained is less colored and has high light resistance, the component (A) includes vinylcyclohexene, dicyclopentadiene, vinylnorbornene, triallyl isocyanurate, 2,2-bis (4-hydroxycyclohexyl). ) Diallyl ether of propane and 1,2,4-trivinylcyclohexane are preferred, triallyl isocyanurate, diallyl ether of 2,2-bis (4-hydroxycyclohexyl) propane, and 1,2,4-trivinylcyclohexane in particular. preferable.

  As the component (A), a compound represented by the following general formula (III) is preferable from the viewpoint of particularly high heat resistance and light resistance.

(In the formula, three R ^{1 s} are the same or different and represent a monovalent organic group having 1 to 50 carbon atoms.)
R ^{1 in the} general formula (III) is preferably a monovalent organic group having 1 to 20 carbon atoms, more preferably a carbon number, from the viewpoint that the heat resistance of the obtained cured resin can be higher. It is a monovalent organic group having 1 to 10 carbon atoms, and more preferably a monovalent organic group having 1 to 4 carbon atoms. Examples of these preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group, and each monovalent group exemplified below. Is mentioned.

As R ¹ of the general formula (III), the viewpoint that the adhesiveness between the resin molded body and the lead or the resin molded body and the sealing agent can be improved, or the mechanical strength of the obtained resin molded body can be increased. From the above, it is preferable that at least one of the three R ¹ is a monovalent organic group having 1 to 50 carbon atoms containing one or more epoxy groups, and the number of carbons containing one or more epoxy groups represented by the following. More preferably, it is a monovalent organic group of 1-50.

Examples of these preferable R ¹ groups include a glycidyl group and groups shown below.

R ^{1 in the} general formula (III) is preferably C, H, or O as a constituent element preferably containing 2 or less oxygen atoms from the viewpoint that the heat resistance of the obtained cured resin can be improved. A monovalent organic group having 1 to 50 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. Examples of these preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group, and each group shown below. .

The R ¹ in the general formula (III), from the viewpoint of reactivity becomes good, but at least one of the three R ^1, carbon atoms containing one or more groups represented by the following Chemical Formula 23] A monovalent organic group of 1 to 50 is preferable.

Moreover, it is more preferable that at least one of the three R ¹ is a monovalent organic group having 1 to 50 carbon atoms including one or more groups represented by the following general formula (IV). Moreover, it is more preferable that at least two of the three R ¹ are organic compounds represented by the following general formula (V).

(In the formula, R ² represents a hydrogen atom or a methyl group.)

(Wherein R ³ represents a direct bond or a divalent organic group having 1 to 48 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)
R ^{3 in the} general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms, but preferably a direct bond from the viewpoint of further improving the heat resistance of the obtained resin molded body. Or a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and still more preferably a direct bond or a divalent organic group having 1 to 4 carbon atoms. Organic group. Examples of these preferable R ³ include the groups shown below.

As R ^{3 in the} general formula (V), from the viewpoint of further improving the heat resistance of the obtained cured resin, it is preferably directly bonded or contains two or less oxygen atoms and is a constituent element. It is a C1-H48 bivalent organic group containing only C, H, and O, More preferably, it is a direct bond or a C1-C48 bivalent hydrocarbon group. Examples of these preferable R ³ include the groups shown below.

R ^{4 in the} general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.

  However, even in a preferable example of the organic compound represented by the general formula (III) as described above, it is possible to contain at least two carbon-carbon double bonds having reactivity to the SiH group in one molecule. is necessary. From the viewpoint of further improving the heat resistance, it is more preferable to use an organic compound containing three or more carbon-carbon double bonds having reactivity to the SiH group in one molecule.

  Preferable specific examples of the organic compound represented by the general formula (III) as described above include triallyl isocyanurate, each compound shown below, and the like.

  As a preferable specific example of the component (A) in another form, as described above as an example of the component (A), an organic material containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule. Examples include a reaction product of one or more compounds selected from compounds and a compound (β) having a SiH group (hereinafter referred to as “(β) component”). Such a reactant has good compatibility with the component (B) and has a low volatility, and therefore has an advantage that the problem of outgas from the obtained resin molded body hardly occurs.

  The component (β) is a compound having a SiH group, and a chain and / or cyclic polyorganosiloxane having a SiH group is an example. Specific examples include the compounds shown below.

  Here, from the viewpoint that compatibility with an organic compound containing at least two carbon-carbon double bonds having reactivity with the SiH group in one molecule is easily improved, the compound is represented by the following general formula (VI). A cyclic polyorganosiloxane having at least 3 SiH groups per molecule is preferred.

(In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
The substituent R ¹ in the compound represented by the general formula (VI) is preferably a group not containing a constituent element other than C, H, and O, more preferably a hydrocarbon group, and still more preferably a methyl group. It is. In view of availability, the compound represented by the general formula (VI) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane.

  Other examples of the (β) component include compounds having a SiH group such as bisdimethylsilylbenzene.

  Various (β) components as described above can be used singly or in combination of two or more.

  In the present invention, as described above, it is obtained by subjecting an organic compound containing at least two carbon-carbon double bonds having reactivity to SiH group in one molecule to a hydrosilylation reaction with the (β) component. The compound obtained can be used as the component (A). In addition, when an organic compound containing at least two carbon-carbon double bonds having reactivity to SiH group in one molecule is subjected to a hydrosilylation reaction, the (A) component of the present invention is obtained. A mixture containing the obtained compound and a plurality of other compounds may be obtained. The curable resin composition of the present invention can also be produced by using as it is without separating the compound that can be the component (A) from such a mixture.

  Here, this hydrosilylation reaction will be described in detail.

  In this hydrosilylation reaction, the mixing ratio of the organic compound containing at least two carbon-carbon double bonds reactive to SiH groups in one molecule and the (β) component is not particularly limited. In general, the ratio between the total number of carbon-carbon double bonds (X) having reactivity with SiH groups in the former and the total number of SiH groups (Y) in the latter is limited in that gelation can be suppressed. X / Y ≧ 2, more preferably X / Y ≧ 3. Further, from the viewpoint that the compatibility of the component (A) with the component (B) is easily improved, preferably 10 ≧ X / Y, more preferably 5 ≧ X / Y.

In this hydrosilylation reaction, an appropriate catalyst may be used. Examples of the catalyst include platinum alone, alumina, silica, carbon black and the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin complex _{(e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, Pt (CH 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt _{[P (OBu) 3] 4} ) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, , M represents an integer), dicarbonyldichloroplatinum, Karstedt catalyst, platinum-hydrocarbon complexes described in U.S. Pat. Nos. 3,159,601 and 3,159,662 of Ashby, A platinum alcoholate catalyst described in US Pat. No. 3,220,972 of Lamoreaux, and a platinum chloride-olefin complex described in US Pat. No. 3,516,946 of Modic.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. Etc.

  Among these catalysts, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts can be used individually by 1 type or in combination of 2 or more types.

The addition amount of the catalyst is not particularly limited, but in order to obtain a curable resin composition having sufficient curability and having a relatively low cost, 1 mol of Siβ group of (β) component, The amount is preferably 10 ⁻⁸ to 10 ⁻¹ mol, more preferably 10 ⁻⁶ to 10 ⁻² mol.

Moreover, a co-catalyst can be used with the said catalyst. Specific examples of the cocatalyst include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, Examples thereof include sulfur compounds such as sulfur and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but is preferably 10 ⁻² to 10 ² mol, more preferably 10 ⁻¹ mol to 10 mol, with respect to 1 mol of the hydrosilylation catalyst.

  In the hydrosilylation reaction, various methods can be used as a method of mixing an organic compound containing at least two carbon-carbon double bonds reactive to SiH groups in one molecule, the component (β) and the catalyst. The catalyst can be mixed with an organic compound containing at least two carbon-carbon double bonds that are reactive to SiH groups in one molecule, and the resulting mixture is mixed with the (β) component. Is preferred. In the method of mixing an organic compound containing at least two carbon-carbon double bonds having a reactivity to SiH group in one molecule and the (β) component, and mixing the resulting mixture with a catalyst, the reaction It may be difficult to control. Also, a method of mixing the (β) component and a catalyst, and mixing the resulting mixture with an organic compound containing at least two carbon-carbon double bonds having reactivity with SiH groups. In the case of taking this, since it has reactivity with the water in which the component (β) is mixed in the presence of the catalyst, there is a possibility that the finally obtained compound may be altered.

  The reaction temperature can be variously set, but is preferably 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. If the reaction temperature is low, the reaction time for sufficient reaction will be long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required.

  A solvent may be used for the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. Among these solvents, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting an organic compound containing at least two carbon-carbon double bonds having a reactivity with respect to the SiH group in one molecule and the (β) component, the solvent and / or the unreacted SiH group It is also possible to remove the organic compound and / or the (β) component containing at least two carbon-carbon double bonds having a reactivity with respect to each molecule. These are volatile components, and by removing them, the component (A) obtained does not contain volatile components. As a result, in the case of curing the component (A) and the component (B), problems of voids and cracks due to volatilization of volatile components are less likely to occur. Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to devolatilization under reduced pressure. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the temperature in this case is preferably 100 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to cause alterations such as thickening.

  As described above, the component (A) which is a hydrosilylation reaction product of the organic compound (β) component containing at least two carbon-carbon double bonds having reactivity to the SiH group in one molecule. Examples include a reaction product of bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane, a reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, divinylbenzene and 1 , 3,5,7-tetramethylcyclotetrasiloxane reactant, dicyclopentadiene and 1,3,5,7-tetramethylcyclotetrasiloxane reactant, triallyl isocyanurate and 1,3,5,7- The reaction product of tetramethylcyclotetrasiloxane, diallyl monoglycidyl isocyanurate and 1,3,5,7-tetramethylsilane The reaction product of b cyclotetrasiloxane, and the like reaction product of a vinyl norbornene and bis dimethylsilyl benzene.

  The component (A) may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the obtained curable resin composition tends to be high, and the strength of the obtained resin cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, from the viewpoint that the heat resistance of the obtained cured resin is likely to be high, it is preferable to have one or more reactive groups in one molecule on average.

  (A) A component can be used individually by 1 type or in combination of 2 or more types.

  Next, the component (B) will be described in detail. The component (B) is a compound containing at least two SiH groups in one molecule.

  The component (B) is not particularly limited as long as it is a compound containing at least two SiH groups in one molecule. For example, the compound described in International Publication WO96 / 15194 is at least two in one molecule. Those having SiH groups can be used.

  Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and from the viewpoint of good compatibility with the component (A), Further, a cyclic organopolysiloxane having at least two SiH groups in one molecule represented by the following general formula (VI) is preferable.

(In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
The substituent R ¹ in the compound represented by the general formula (VI) is preferably composed of C, H, and O, more preferably a hydrocarbon group, and still more preferably a methyl group. The compound represented by the general formula (VI) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability.

  The molecular weight of the component (B) is not particularly limited, but is preferably low molecular weight from the viewpoint of easier expression of fluidity and easy mixing with powders such as the components (E) and (F). Used. In this case, the molecular weight is preferably 50 to 100,000, more preferably 50 to 1,000, and still more preferably 50 to 700.

  As the component (B), in order to facilitate uniform mixing with other components, particularly powders such as the component (E) and the component (F), more specifically, heating above the melting point for uniform mixing. Therefore, the liquid is preferably liquid at 23 ° C., and the viscosity at 23 ° C. is preferably 50 Pa seconds or less, more preferably 20 Pa seconds or less, and even more preferably 5 Pa seconds or less. The viscosity can be measured with an E-type viscometer.

  (B) A component can be used individually by 1 type or in combination of 2 or more types.

  As a preferred specific example of the component (B), an organic compound (α) containing at least one carbon-carbon double bond having reactivity to the SiH group in one molecule (hereinafter referred to as “α component”). And a compound obtained by hydrosilylation reaction of a compound (β) having at least two SiH groups in one molecule. Such a compound has good compatibility with the component (A) and has a low volatility, and therefore has an advantage that the problem of outgas from the resulting curable resin composition hardly occurs.

  Here, the (α) component is the same as the above-described organic compound (A), which is the same as the organic compound containing at least two carbon-carbon double bonds reactive to the SiH group in one molecule (hereinafter “ (Α1) component ”) can also be used. When the component (α1) is used, the resulting resin cured body has a high crosslink density and is likely to be a resin cured body having high mechanical strength.

  In addition, an organic compound (α2) (hereinafter referred to as “α2 component”) containing one carbon-carbon double bond having reactivity to the SiH group in one molecule can be used. When the (α2) component is used, the obtained cured resin is likely to have low elasticity.

  The component (α2) is not particularly limited as long as it is an organic compound containing one carbon-carbon double bond having reactivity with respect to the SiH group in one molecule, but the component (A) of the component (B) In terms of improving the compatibility with respect to the above, it is not a compound containing a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, but C, H, N, A compound containing only O, S, and halogen is preferable. In the (α2) component, the bonding position of the carbon-carbon double bond having reactivity to the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The compound as the component (α2) can be classified into a polymer compound and a monomer compound.

  Examples of the polymer compound include polysiloxane, polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, unsaturated hydrocarbon, polyacrylate ester, polyamide, phenol-formaldehyde (Phenol resin type), polyimide type compound, etc. are mentioned.

  Examples of monomeric compounds include, for example, aromatic hydrocarbons such as phenols, bisphenols, benzene, and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds; silicon-based compounds Compounds; mixtures thereof; and the like.

  The carbon-carbon double bond having reactivity with the SiH group in the component (α2) is not particularly limited. For example, a group represented by the following general formula (I) is preferable from the viewpoint of reactivity.

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)
Moreover, the group shown below is especially preferable from the ease of acquisition of a raw material.

  In addition, as the carbon-carbon double bond having reactivity with the SiH group in the component (α2), the alicyclic group represented by the following general formula (II) is high in heat resistance of the cured resin. To preferred.

(In the formula, R ² represents a hydrogen atom or a methyl group.)
Moreover, the alicyclic group shown below is especially preferable from the ease of acquisition of a raw material.

  The carbon-carbon double bond having reactivity to the SiH group may be directly bonded to the skeleton portion of the (α2) component, or may be covalently bonded through a divalent or higher substituent. The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. However, in terms of easy compatibility with the component (A) of the component (B), C is used as a constituent element. , H, N, O, S, and those containing only halogen are preferred. Examples of these substituents include divalent or higher groups shown below. Moreover, two or more of these divalent or higher valent substituents may be connected by a covalent bond to constitute one divalent or higher valent substituent. (→ Please leave as 0)

  Examples of the group covalently bonded to the skeleton as described above include vinyl group, allyl group, methallyl group, acrylic group, methacryl group, 2-hydroxy-3- (allyloxy) propyl group, 2-allylphenyl group, 3 -Allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 2,2-bis (allyl) Examples thereof include oxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and groups shown below.

  Specific examples of the component (α2) include propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-undecene, and Idemitsu Petroleum. Chains such as Chemical Corporation linearene, 4,4-dimethyl-1-pentene, 2-methyl-1-hexene, 2,3,3-trimethyl-1-butene, 2,4,4-trimethyl-1-pentene Aliphatic hydrocarbon compounds, cyclohexene, methylcyclohexene, methylenecyclohexane, norbornylene, ethylidenecyclohexane, vinylcyclohexane, camphene, carene, α-pinene, β-pinene and other cyclic aliphatic hydrocarbon compounds, styrene, α-methylstyrene, Indene, phenylacetylene, 4-ethynyltoluene, allylbenzene, 4-phenyl-1 Aromatic hydrocarbon compounds such as butene, allyl ethers such as alkyl allyl ether and allyl phenyl ether, fats such as glycerin monoallyl ether, ethylene glycol monoallyl ether, 4-vinyl-1,3-dioxolan-2-one Aromatic compounds such as aromatic compounds, 1,2-dimethoxy-4-allylbenzene, o-allylphenol, substituted isocyanurates such as monoallyl dibenzyl isocyanurate, monoallyl diglycidyl isocyanurate, vinyltrimethyl Examples thereof include silicon compounds such as silane, vinyltrimethoxysilane, and vinyltriphenylsilane.

  Further, specific examples of the component (α2) include polyether resins such as one-end allylated polyethylene oxide and one-end allylated polypropylene oxide, hydrocarbon resins such as one-end allylated polyisobutylene, and one-end allylated polybutyl. Examples thereof include polymers or oligomers having a vinyl group at one end, such as acrylic resins such as acrylate and one-end allylated polymethyl methacrylate.

  The structure of the (α2) component may be linear or branched, and the molecular weight is not particularly limited, and various types can be used. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and still more preferably in that the viscosity of the curable resin composition is low and the moldability is likely to be good. Is 1.5 or less. In this specification, molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform.

  When the (α2) component has Tg, there are no particular limitations on Tg, and various types are used, but Tg is preferably 100 ° C. or less in that the obtained resin cured body tends to be tough. More preferably, it is 50 degrees C or less, More preferably, it is 0 degrees C or less. Examples of preferred resins include polybutyl acrylate resins. On the contrary, Tg is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and most preferably, in terms of increasing the heat resistance of the obtained cured resin. It is 170 ° C or higher. Tg can be obtained as a temperature at which tan δ is maximum in the dynamic viscoelasticity measurement.

  The component (α2) is preferably a hydrocarbon compound from the viewpoint of increasing the heat resistance of the resulting cured resin body. In this case, a preferable carbon number is 7-10.

  The (α2) component may have other reactive groups. Examples of the reactive group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. When it has these functional groups, the adhesiveness of the obtained curable resin composition tends to be high, and the strength of the obtained resin cured product tends to be high. Of these functional groups, an epoxy group is preferable from the viewpoint that the adhesiveness can be further increased. Moreover, in the point that the heat resistance of the resin cured body obtained becomes high easily, it is preferable to have one or more reactive groups in one molecule on average. Specific examples include monoallyl diglycidyl isocyanurate, allyl glycidyl ether, allyloxyethyl methacrylate, allyloxyethyl acrylate, and vinyltrimethoxysilane.

  The (α1) component as described above can be used alone or in combination of two or more. In addition, the component (α2) can also be used alone or in combination of two or more.

  Next, the (β) component will be described in detail. The component (β) is a compound having at least two SiH groups in one molecule, and chain and / or cyclic polyorganosiloxanes are also examples. Specific examples include the compounds shown below.

Here, from the viewpoint of easy compatibility with the component (α), a cyclic polyorganosiloxane having at least three SiH groups in one molecule represented by the following general formula (VI) is preferable. The substituent R ¹ in the compound represented by the following general formula (VI) is preferably a group composed of C, H, and O, more preferably a hydrocarbon group, and still more preferably a methyl group. . Further, from the viewpoint of availability, 1,3,5,7-tetramethylcyclotetrasiloxane is preferable.

(In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10).
Other examples of the component (β) include compounds having a SiH group such as bisdimethylsilylbenzene.

  The various (β) components described above can be used alone or in combination of two or more. .

  As described above, in the present invention, a compound obtained by subjecting the (α) component and the (β) component to a hydrosilylation reaction can be used as the (B) component. In addition, when the (α) component and the (β) component are subjected to a hydrosilylation reaction, a mixture containing one or more other compounds may be obtained together with the compound that can be used as the (B) component of the present invention. Such a mixture can be used as the component (B) as it is without separating the compound that can be used as the component (B) from the mixture to produce the curable resin composition of the present invention.

  Specifically, the hydrosilylation reaction between the (α) component and the (β) component is as follows. The mixing ratio of the (α) component and the (β) component is not particularly limited, but when considering the strength of the cured resin obtained by hydrosilylation of the obtained (B) component and (A) component, Since it is preferable that there are more SiH groups, the total number of carbon-carbon double bonds (X) having reactivity to SiH groups in the generally mixed (α) component and the total number of SiH groups in the mixed (β) component. The ratio (Y / X) to (Y) is preferably Y / X ≧ 2, more preferably Y / X ≧ 3. Further, from the viewpoint that the compatibility of the component (B) with the component (A) is likely to be improved, preferably 10 ≧ Y / X, and more preferably 5 ≧ Y / X.

In the hydrosilylation reaction of the (α) component and the (β) component, an appropriate catalyst may be used. Examples of the catalyst include platinum alone, alumina, silica, carbon black and the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum-olefin complex _{(e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, Pt (CH 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex _{(e.g., Pt (ViMe 2 SiOSiMe 2 Vi} ) n, Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt _{[P (OBu) 3] 4} ) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, , M represents an integer)), dicarbonyldichloroplatinum, Karstedt catalyst, Ashby US Pat. Nos. 3,159,601 and 3,159,662, platinum-hydrocarbon composites, Ramolo And platinum platinum catalyst described in US Pat. No. 3,220,972 (Lamoreaux), platinum chloride-olefin complex described in US Pat. No. 3,516,946 (Modic).

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity.

  The various catalysts described above can be used singly or in combination of two or more.

The addition amount of the catalyst is not particularly limited, but preferably 10 ⁻⁸ mol to 10 ⁻¹ mol in order to obtain a curable resin composition having sufficient curability and having a relatively low cost. More preferably, it is 10 ^{< -6>} mol-10 ^{<-2 >} mol.

Moreover, a co-catalyst can be used with the said catalyst. Specific examples of the cocatalyst include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, Examples thereof include sulfur compounds such as sulfur and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but is preferably 10 ⁻² mol to 10 ² mol, more preferably 10 ⁻¹ mol to 10 mol, per 1 mol of the hydrosilylation catalyst.

  As the method of mixing the (α) component, the (β) component and the catalyst in the reaction, various methods can be used. The (α) component is mixed with the catalyst, and the resulting mixture is used as the (β) component. It is preferable to mix them. When the method of mixing the catalyst with the mixture of the (α) component and the (β) component is employed, it may be difficult to control the reaction. When the method of mixing the (α) component with the mixture of the (β) component and the catalyst is used, the final obtained is because it is reactive to moisture mixed with the (β) component in the presence of the catalyst. The product may be altered.

  The reaction temperature can be variously set, but is preferably 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required.

  A solvent may be used for the hydrosilylation reaction between the component (α) and the component (β). Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. A solvent can be used individually by 1 type or in combination of 2 or more types. Among these solvents, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent used can also be set as appropriate.

  In addition, various additives may be used for the purpose of controlling reactivity.

  After reacting the (α) component and the (β) component, the solvent and / or the unreacted (α) component and / or the (β) component can also be removed. These are volatile components. By removing these components, component (B) having no volatile components can be obtained. As a result, when the component (A) and the component (B) are cured, the problem of voids and cracks due to volatilization of volatile components is unlikely to occur. Examples of the removal method include treatment with activated carbon, aluminum silicate, silica gel and the like in addition to devolatilization under reduced pressure. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the temperature in this case is preferably 100 ° C, more preferably 60 ° C. When treated at high temperatures, it tends to cause alterations such as thickening.

  Specific examples of the component (B) that is a hydrosilylation reaction product of the components (α) and (β) as described above include bisphenol A diallyl ether and 1,3,5,7-tetramethylcyclotetrasiloxane. Reaction product, reaction product of vinylcyclohexene and 1,3,5,7-tetramethylcyclotetrasiloxane, reaction product of divinylbenzene and 1,3,5,7-tetramethylcyclotetrasiloxane, dicyclopentadiene and 1,3 , 5,7-tetramethylcyclotetrasiloxane reactant, triallyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane reactant, diallyl monoglycidyl isocyanurate and 1,3,5,7- Reactant of tetramethylcyclotetrasiloxane, allyl glycidyl ether and 1,3,5,7-tetramethyl Reaction product of rucyclotetrasiloxane, reaction product of α-methylstyrene and 1,3,5,7-tetramethylcyclotetrasiloxane, monoallyl diglycidyl isocyanurate and 1,3,5,7-tetramethylcyclotetrasiloxane Examples thereof include a reaction product, a reaction product of vinyl norbornene and bisdimethylsilylbenzene.

  When mixing the component (A) and the component (B), the combination of the component (A) and the component (B) is exemplified by at least one selected from the components (A) exemplified above and the above ( B) Various combinations of at least one selected from the components can be mentioned.

  The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the required strength is not lost, but the number of SiH groups (Y) in the component (B) is the carbon in the component (A). -The ratio (Y / X, molar ratio) to the number (X) of carbon double bonds is preferably 0.3≤Y / X≤3, more preferably 0.5≤Y / X≤2, more preferably It is 0.7 <= Y / X <= 1.5. When it deviates from the preferred range, sufficient strength may not be obtained, or thermal degradation may easily occur.

The component (C) of the present invention is a hydrosilylation catalyst. The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, platinum having a solid platinum supported on a carrier such as simple substance of alumina, alumina, silica, carbon black, chloroplatinic acid, platinum chloride, etc. Complexes of acids and alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt (CH ₂ ═CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), platinum-vinyl Siloxane complexes (eg, Pt (ViMe ₂ SiOSiMe ₂ Vi) n, Pt [(MeViSiO) ₄ ] m), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phos Phyto complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ ) where Me is Methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karlstedt catalyst, and Ashby, USA Platinum-hydrocarbon composites described in US Pat. Nos. 3,159,601 and 3,159,622, platinum alcoholate catalysts described in Lamoreaux, US Pat. No. 3,220,972, Modic, US Pat. Examples thereof include platinum chloride-olefin composites described in US Pat. No. 3,516,946.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl ₄ , etc. Is mentioned.

  Among these catalysts, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts can be used individually by 1 type or in combination of 2 or more types.

The amount of the catalyst added is not particularly limited, but in order to have sufficient curability and keep the cost of the curable resin composition relatively low, 10 ⁻⁸ mol to 10 ⁻¹ mol, more preferably 10 ⁻⁶ mol to 10 ⁻² mol.

Moreover, a co-catalyst can be used with the said catalyst. Specific examples of the cocatalyst include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, Examples thereof include sulfur compounds such as sulfur and amine compounds such as triethylamine. The addition amount of the cocatalyst is not particularly limited, but is preferably 10 ⁻² mol to 10 ² mol, more preferably 10 ⁻¹ mol to 10 mol, per 1 mol of the hydrosilylation catalyst.

  The component (D) of the present invention is a silicone compound containing at least one carbon-carbon double bond having reactivity to the SiH group in one molecule. By using the component (D), when mixed with the inorganic filler of the component (E), a thermosetting resin composition (X) that gives a cured resin body having a smaller linear expansion coefficient can be obtained.

  The silicone compound of component (D) is a compound whose skeleton is substantially formed of Si—O—Si bonds, and various compounds such as linear, cyclic, branched, and partial networks are available. Used. Various substituents may be bonded to such a skeleton.

  Examples of the substituent bonded to the skeleton include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an octyl group, an aryl group such as a phenyl group, a 2-phenylethyl group, and a 2-phenylpropyl group, a methoxy group, an ethoxy group, Examples include an alkoxy group such as an isopropoxy group and a group such as a hydroxyl group. Among these, a methyl group, a phenyl group, a hydroxyl group, and a methoxy group are preferable, and a methyl group and a phenyl group are more preferable in that heat resistance tends to be high. In addition, examples of the substituent having a carbon-carbon double bond that has reactivity with the SiH group include a vinyl group, an allyl group, an acryloxy group, a methacryloxy group, an acryloxypropyl group, and a methacryloxypropyl group. Among these, a vinyl group is preferable in terms of good reactivity.

  The component (D) may be a compound represented by the following formula.

_{R n (CH 2 = CH)} m SiO (4-n-m) / 2
(In the formula, R is a group selected from a hydroxyl group, a methyl group or a phenyl group, and n and m are numbers satisfying 0 ≦ n <4, 0 <m ≦ 4, and 0 <n + m ≦ 4)
Specific examples of the component (D) include polydimethylsiloxane having a vinyl group as a terminal group or side chain group, polydiphenylsiloxane, polymethylphenylsiloxane, and two or three random or block copolymers selected from these siloxanes. Examples thereof include polymers, 1,3-divinyltetramethyldisiloxane, 1,3,5,7-tetravinylcyclotetrasiloxane. (D) A component can be used individually by 1 type or in combination of 2 or more types.

  Of these, linear polysiloxanes having vinyl groups at the ends are preferable, linear polysiloxanes having vinyl groups at both ends are more preferable, and both ends are more preferable in that the effects of the present invention are more easily obtained. A linear polymethylphenylsiloxane having a vinyl group is more preferable, and a linear polymethylphenylsiloxane having a vinyl group at both ends, wherein the amount of phenyl groups with respect to all substituents is 20 mol% or more. It is particularly preferred that

  The molecular weight of the component (D) is preferably 1,000 or more and 1,000,000 or less, more preferably 5,000 or more and 100,000 or less, and still more preferably, as the weight average molecular weight (Mw). 10,000 or more and 100,000 or less. When the molecular weight is high, the obtained resin cured body tends to have low stress. When the molecular weight is large, it becomes difficult to obtain compatibility with the component (A).

  The amount of component (D) used is preferably 30% by weight or more, more preferably 50% by weight or more, and still more preferably 80% by weight or more based on the total amount of component (A) and component (B). .

  Further, the mixing ratio of the component (A), the component (B), and the component (D) is not particularly limited as long as the required strength is not lost, but the number of SiH groups (Y) in the component (B) ( The ratio of the number of carbon-carbon double bonds (X) having reactivity to SiH groups in component A) and component (D) is preferably 0.3 ≦ Y / X ≦ 3, more preferably 0. 0.5 ≦ Y / X ≦ 2, more preferably 0.7 ≦ Y / X ≦ 1.5. When it deviates from the preferred range, sufficient strength may not be obtained or thermal deterioration may easily occur.

  The component (E) of the present invention is an inorganic filler. The component (E) has an effect of increasing the strength and hardness of the obtained cured resin or reducing the linear expansion coefficient.

  As the inorganic filler of the component (E), various inorganic fillers that are generally used and / or proposed as fillers for conventional epoxy-based sealing materials are used. For example, quartz, fumed silica, Silica-based inorganic fillers such as precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous silica, alumina, zircon, silicon nitride, aluminum nitride, silicon carbide, glass fiber, alumina fiber, carbon fiber, Examples include mica, graphite, carbon black, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, potassium titanate, calcium silicate, inorganic balloon, silver powder, and the like. The inorganic filler is preferably low radiation from the viewpoint of hardly damaging the semiconductor element.

  The inorganic filler may be appropriately surface treated. Examples of the surface treatment include treatment with a coupling agent, alkylation treatment, trimethylsilylation treatment, and silicone treatment.

  Examples of the coupling agent in this case include a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic group or acrylic such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Such as alkoxysilanes having the like.

  In addition, the method of adding an inorganic compound is mentioned. For example, an inorganic compound is added to the curable resin composition of the present invention and reacted in the curable resin composition or in a partial reaction product of the curable resin composition, and an inorganic filler is added in the curable resin composition. The method of generating is mentioned. Examples of such inorganic compounds include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenated silanes, metal alkoxides such as titanium and aluminum, acyloxides, and halides.

  Among the inorganic fillers as described above, silica-based inorganic fillers are used from the viewpoint that the curing reaction is difficult to inhibit, the effect of reducing the linear expansion coefficient is large, and the adhesion to the lead or the lead frame is likely to be high. preferable. Furthermore, from the viewpoint of good balance of physical properties such as moldability and electrical characteristics, fused silica is preferable, from the viewpoint that the thermal conductivity of the cured resin body is likely to be high, and a resin molded body design with high heat dissipation becomes possible. Is preferably crystalline silica. Alumina is preferable from the viewpoint that heat dissipation is likely to be higher. Titanium oxide is preferable from the viewpoint that the light reflectance of the resin used for the resin molding is high and the light extraction efficiency in the resulting light emitting device is likely to be high. In addition, glass fiber, potassium titanate, and calcium silicate are preferable from the viewpoint that the reinforcing effect is high and the strength of the resin molding is likely to be high.

  As the average particle size and particle size distribution of the inorganic filler, various types are used without particular limitation, including those used and / or proposed as fillers for conventional sealing materials such as epoxy type, The average particle size usually used is 0.1 μm to 120 μm, and preferably 0.5 μm to 60 μm, more preferably 0.5 μm to 15 μm, from the viewpoint of easy flowability.

  The specific surface area of the inorganic filler can also be variously set, including those used and / or proposed as fillers for conventional sealing materials such as epoxy.

  As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape are used. Various aspect ratios are used. From the viewpoint that the strength of the obtained cured resin is likely to be high, those having an aspect ratio of 10 or more are preferable. From the viewpoint of isotropic shrinkage of the resin, a powder form is preferable to a fiber form. From the viewpoint that the flowability at the time of molding tends to improve even during high filling, a spherical shape is preferred.

  The various inorganic fillers described above can be used singly or in combination of two or more.

  Although the usage-amount of (E) component is not specifically limited, It is preferable that the total amount of (E) component which occupies for the whole thermosetting resin composition (X) is 70 weight% or more, and is 80 weight% or more. More preferably, it is more preferably 90% by weight or more. When the amount of the component (E) is small, it is difficult to obtain the effect of improving the strength and hardness, the effect of reducing the coefficient of linear expansion, and the like.

  As the order of mixing the inorganic filler of the component (E), various methods can be used, but from the viewpoint that the storage stability of the intermediate raw material of the thermosetting resin composition (X) tends to be good, A method of mixing the component (A) with the component (C) and the inorganic filler and the component (B) is preferable. When the method of mixing the component (A) with the component (B) mixed with the component (C) and / or the inorganic filler, the component (B) is present in the presence and / or absence of the component (C). Since the components have reactivity with moisture and / or inorganic fillers in the environment, they may be altered during storage. Further, from the viewpoint that the reaction components (A), (B) and (C) are well mixed and a stable molded product is easily obtained, the components (A), (B) and (C ) It is preferable to mix the component and the inorganic filler.

  As means for mixing the inorganic filler of component (E), various means conventionally used and / or proposed for epoxy resins and the like can be used. For example, a two-roll, three-roll, planetary stirring and defoaming device, a homogenizer, a dissolver, a planetary mixer and other stirrers, a plast mill and other melt kneaders, and the like can be mentioned. Among these, from the viewpoint that sufficient dispersibility of the inorganic filler is easily obtained even with high filling, a three-roll, melt-kneader is preferable. The mixing of the inorganic filler may be performed at normal temperature or may be performed by heating. Moreover, you may carry out under a normal pressure and may carry out in a pressure-reduced state. From the viewpoint that sufficient dispersibility of the inorganic filler is easily obtained even at high filling, it is preferable to mix in a heated state, improving the wettability of the surface of the inorganic filler and obtaining sufficient dispersibility. From the viewpoint of ease, it is preferable to mix in a reduced pressure state.

  The thermosetting resin composition (X) desirably contains the component (F). The component (F) is a white pigment and has an effect of increasing the light reflectance of the obtained cured resin.

  Various components can be used as the component (F), for example, titanium oxide, zinc oxide, magnesium oxide, antimony oxide, zirconium oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate. , Magnesium carbonate, and inorganic hollow particles. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu. Among these, titanium oxide or zinc oxide is preferable from the viewpoint of ease of handling, availability, and cost.

  Various components can be used as the component (F) titanium oxide, which may be anatase type or rutile type, but has no photocatalytic action and the thermosetting resin composition (X) becomes stable. The rutile type is preferable in that it is easy.

  The average particle size of the component (F) is not particularly limited, and various types can be used, but the light reflectance of the obtained cured resin is likely to be high, and the tablet of the thermosetting resin composition (X) is From the viewpoint of becoming harder, it is preferably 1 μm or less, more preferably 0.3 μm or less, and still more preferably 0.25 μm or less. The tablet of the thermosetting resin composition (X) will be described later. On the other hand, from the viewpoint that the fluidity of the thermosetting resin composition (X) is high, it is preferably 0.05 μm or more, more preferably 0.1 μm or more.

  The average particle diameter can be measured using a laser diffraction / scattering particle size distribution analyzer.

As the method for producing the component (F) titanium oxide, those produced by any method such as sulfuric acid method and chlorine method can be used.
The component (F) may be subjected to surface treatment. In the surface treatment of the component (F), the surface of the component (F) is coated with at least one selected from an inorganic compound and an organic compound. Examples of inorganic compounds include aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, and antimony compounds. Examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, and organic siloxanes. Examples thereof include organosilicon compounds, higher fatty acids and metal salts thereof, and organometallic compounds.

  (F) The surface of the component is coated with an inorganic compound or an organic compound using a known method such as a wet method or a dry method, for example, when dry pulverizing, wet pulverizing or slurrying titanium oxide. Can do. In addition, there are various methods such as a liquid phase method and a gas phase method.

  Among these, it is preferable that the cured resin obtained is treated with an organosiloxane from the viewpoint of high light reflectivity and good heat resistance and light resistance. In addition, by including an organic siloxane-treated titanium oxide, it is possible to obtain an excellent light-emitting device that has high light extraction efficiency and does not decrease light extraction efficiency even when used for a long period of time.

  Here, various organic siloxane treating agents can be used, and examples thereof include silane coupling agents, hexamethyldisiloxane, hexamethyldisilazane and the like. Various silanes can be used as the silane coupling agent. For example, polysiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, and copolymers of two or more thereof, hexamethylcyclotrisiloxane , Cyclosiloxanes such as heptamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, chlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane Epoxy such as 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Silanes having functional groups, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, Silanes having a methacrylic group or an acrylic group such as methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β- Silanes having vinyl groups such as methoxyethoxy) silane and vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Mercaptosilanes such as silane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ -(Β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Silanes having an amino group such as trimethoxysilane, silanes having an isocyanate group such as isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, hexyl Silanes having alkyl groups such as trimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, and other silanes such as γ-chloropropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane Is mentioned. Among these organosiloxane treating agents, those not containing a carbon-carbon double bond are preferred. When the carbon-carbon double bond is included, the heat resistance tends to be lowered. Moreover, it is also possible to use together surface treating agents other than organosiloxane. Examples of such a surface treatment agent include Al, Zr, and Zn.

  Further, the component (F) may be surface-treated with an inorganic compound. The surface treatment method using an inorganic compound is not particularly limited, and various surface treatment methods using an aluminum compound, a silicon compound, a zirconium compound, and the like can be given. Various methods can be applied as the surface treatment method, and various methods such as a wet method, a dry method, a liquid phase method, and a gas phase method can be exemplified. Titanium oxide may be surface-treated with an inorganic compound or an organic compound for the purpose of improving durability, improving affinity with a medium, and preventing the collapse of particle shape. By subjecting the component (F) to a surface treatment with an inorganic compound, the affinity with each component contained in the thermosetting resin composition (X) is improved, and the thermosetting resin composition (X) as the component (F). It is considered that the dispersibility of the resin is improved and the strength of the cured resin body is improved.

  Although the usage-amount of (F) component is not specifically limited, It is preferable that the quantity of (F) component which occupies for the whole thermosetting resin composition (X) is 10 weight% or more, and is 15 weight% or more. Is more preferable, and it is further more preferable that it is 20 weight% or more. If it is less than 10% by weight, the light reflectance of the obtained cured resin may be lowered.

  The total amount of the component (E) and the component (F) is not particularly limited, but the total amount of the component (E) and the component (F) in the entire thermosetting resin composition (X) is 85% by weight or more. Is preferable, and more preferably 90% by weight or more.

  When the total amount of the component (E) and the component (F) is small, it is difficult to obtain the effect of increasing the strength and hardness and the effect of reducing the linear expansion coefficient.

  As the mixing order of the component (F), various methods can be used, but the preferred embodiment is the same as (E) described above. Moreover, you may add (F) component and (E) component simultaneously.

  As means for mixing the component (F), the same means as the means for mixing the component (E) can be used.

  The thermosetting resin composition (X) desirably contains a component (G).

  The component (G) is a metal soap and is added to improve moldability including mold release properties of the thermosetting resin composition (X).

  Examples of the component (G) include various conventionally used metal soaps. The metal soap here is generally a combination of long-chain fatty acids and metal ions. A nonpolar or low-polar part based on fatty acids and a polar part based on a metal-bonded part are combined in one molecule. Can be used in the present invention. Examples of the long chain fatty acid include a saturated fatty acid having 1 to 18 carbon atoms, an unsaturated fatty acid having 3 to 18 carbon atoms, and an aliphatic dicarboxylic acid. Among these, from the viewpoint of easy availability and high industrial feasibility, saturated fatty acids having 1 to 18 carbon atoms are preferable, and from the viewpoint of high effect of releasability, 6-18 saturated fatty acids are more preferred. Examples of metal ions include ions of alkali metals, alkaline earth metals, zinc, cobalt, aluminum, strontium, and the like.

  Specific examples of metal soaps include lithium stearate, lithium 12-hydroxystearate, lithium laurate, lithium oleate, lithium 2-ethylhexanoate, sodium stearate, sodium 12-hydroxystearate, lauric acid Sodium, sodium oleate, sodium 2-ethylhexanoate, potassium stearate, potassium 12-hydroxystearate, potassium laurate, potassium oleate, potassium 2-ethylhexanoate, magnesium stearate, magnesium 12-hydroxystearate, Magnesium laurate, magnesium oleate, magnesium 2-ethylhexanoate, calcium stearate, calcium 12-hydroxystearate, calcium laurate , Calcium oleate, calcium 2-ethylhexanoate, barium stearate, barium 12-hydroxystearate, barium laurate, zinc stearate, zinc 12-hydroxystearate, zinc laurate, zinc oleate, 2-ethylhexane Examples thereof include zinc acid, lead stearate, lead 12-hydroxystearate, cobalt stearate, aluminum stearate, manganese oleate, and barium ricinoleate. Among these metal soaps, metal stearates are preferable from the viewpoints of easy availability, high safety, and high industrial feasibility. Particularly, from the viewpoint of economy, calcium stearate and stearic acid are preferred. Most preferred is one or more selected from the group consisting of magnesium and zinc stearate.

  Although there is no restriction | limiting in particular in the addition amount of metal soap, Preferably it is 0.01 weight part-5 weight part with respect to 100 weight part of the whole thermosetting resin composition (X), More preferably, it is 0.025 weight part- 4 parts by weight, more preferably 0.05 parts by weight to 4 parts by weight. When the addition amount is too large, the physical properties of the obtained cured resin are lowered, and when the addition amount is too small, mold releasability may not be obtained.

  Various additives can be added to the thermosetting resin composition (X). As the additive, any of various additives used in a resin cured body for a surface-mounted light-emitting device can be used, for example, a curing retarder, an adhesion improver, an anti-aging agent, a radical inhibitor, an ultraviolet absorber. , Solvents, additives for light emitting elements, release agents and the like.

  The curing retarder can be used, for example, for the purpose of improving the storage stability of the thermosetting resin composition (X) or adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide.

  Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols such as 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne and 1-ethynyl-1-cyclohexanol. , Maleic esters such as ene-yne compounds and dimethyl malate. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

  Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred. Moreover, these hardening retarders can be used individually by 1 type or in combination of 2 or more types.

Amount of the curing retarder can be selected at various levels, towards hydrosilylation catalyst 1mol used, preferably ^{10 -1} mol to 10 ³ mol, more preferably 1 mol to 50 mol.

  Examples of the adhesion improver include commonly used adhesives, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene-vinyltoluene. Examples include copolymers, polyethylmethylstyrene, and aromatic polyisocyanates.

  Examples of the coupling agent include silane coupling agents and titanate coupling agents. Examples and preferred examples of the coupling agent are the same as those described above. These coupling agents can be used alone or in combination of two or more.

  The addition amount of the coupling agent can be variously set, but is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 100 parts by weight of the total amount of the component (A) and the component (B). Parts by weight to 25 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the obtained cured resin may be adversely affected.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl cyclohexylene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl ester Cyanurate, such as diallyl monoglycidyl isocyanurate and the like. These epoxy compounds can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the epoxy compound is preferably 1 part by weight to 50 parts by weight, more preferably 3 parts by weight to 25 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). If the addition amount is small, the effect of improving adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured resin may be adversely affected.

  Moreover, in this invention, in order to improve the effect of an above-described coupling agent and an epoxy compound, a silanol condensation catalyst can be used further. Thereby, the adhesiveness can be improved and / or stabilized. Such a silanol condensation catalyst is not particularly limited, but is preferably at least one selected from the group consisting of boron compounds, aluminum compounds and titanium compounds.

  Examples of the aluminum compound used as a silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisoflopoxide, aluminum trisec-butoxide: ethyl acetoacetate aluminum diisopropoxide, aluminum tris ( Aluminum chelates such as ethyl acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkylacetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. Can be mentioned. From the viewpoint of handleability, aluminum chelates are more preferable. Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium: titanium chelates such as titanium tetraacetylacetonate: general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.

  Examples of the boron compound that serves as a silanol condensation catalyst include boric acid esters. As the borate ester, those represented by the following general formulas (VII) and (VIII) can be preferably used.

B (OR ¹ ) ₃ (VII)
B (OCOR ¹ ) ₃ (VIII)
(In the formula, R ¹ represents an organic group having 1 to 48 carbon atoms.)

  Specific examples of boric acid esters include tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, Examples thereof include tri-tert-butyl borate, triisopropyl borate, trinormalpropyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide. These boric acid esters may be used alone or in a combination of two or more. Mixing may be performed in advance, or may be performed at the time of producing the cured resin.

  Of these borate esters, trimethyl borate, triethyl borate, and trinormal butyl borate are preferable, and trimethyl borate is more preferable among them from the viewpoint of easy availability and high industrial practicality.

  From the viewpoint of suppressing the volatility at the time of curing, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, trinormal butyl borate, tri-sec-butyl borate, boric acid Tri-tert-butyl, triisopropyl borate, tripropylpropyl borate, triallyl borate, and boron methoxyethoxide are preferred. Among these, normal trioctadecyl borate, tri-tert-butyl borate, triphenyl borate, and tributyl normal borate are more preferred. preferable.

  From the viewpoint of suppression of volatility and good workability, trinormal butyl borate, triisopropyl borate and trinormal propyl borate are preferable, and trinormal butyl borate is more preferable. From the viewpoint of low colorability at high temperatures, trimethyl borate and triethyl borate are preferred, and trimethyl borate is more preferred.

  The amount of the silanol condensation catalyst used can be variously set, but is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the coupling agent and / or epoxy compound. is there. If the addition amount is small, the effect of improving adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured resin may be adversely affected.

  These silanol condensation catalysts can be used alone or in combination of two or more.

  In the present invention, a silanol source compound can be further used in order to further enhance the effect of improving adhesiveness. Thereby, the adhesiveness can be improved and / or stabilized. Examples of such silanol source compounds include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane. These silanol source compounds can be used singly or in combination of two or more.

  The amount of the silanol source compound used can be variously set, but is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the coupling agent and / or epoxy compound. is there. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the obtained cured resin may be adversely affected.

  In the present invention, at least one selected from carboxylic acids and acid anhydrides can be used in order to enhance the effect of the coupling agent or epoxy compound. Thereby, the adhesiveness can be improved and / or stabilized. Although it does not specifically limit as such carboxylic acids and acid anhydrides, Each carboxylic acid shown by the following [Chemical Formula 43],

2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylheimic acid, norbornene dicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid, Examples include lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene carboxylic acid, naphthalene dicarboxylic acid, and single or complex acid anhydrides thereof It is done. These carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

  Among these carboxylic acids and acid anhydrides, from the viewpoint of having hydrosilylation reactivity, less possibility of bleeding from the cured resin, and hardly impairing the physical properties of the obtained cured resin, And those containing a carbon-carbon double bond having reactivity with the compound. Preferred carboxylic acids and / or acid anhydrides include, for example, carboxylic acids, tetrahydrophthalic acid, methyltetrahydrophthalic acid, single acid anhydrides, complex acid anhydrides and the like shown below.

  The amount of carboxylic acids and / or acid anhydrides can be variously set, but is preferably 0.1 to 50 parts by weight, more preferably 1 part by weight with respect to 100 parts by weight of the coupling agent and / or epoxy compound. Parts to 10 parts by weight. If the addition amount is small, the effect of improving adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured resin may be adversely affected.

  The silane compound described above can be used in the curable resin composition of the present invention. The silane compound contributes to improving the adhesion with the lead and is effective in preventing moisture from entering from the interface between the cured resin and the lead. Specific examples of such silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. preferable.

  Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent, etc., in addition to the anti-aging agents generally used such as hindered phenol type.

  As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.

  These anti-aging agents can be used alone or in combination of two or more.

  Examples of the radical inhibitor include 2,6-di-tert-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α-naphthylamine, N, N′-secondary butyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine. These radical inhibitors can be used singly or in combination of two or more.

  Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Is mentioned. An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.

  The thermosetting resin composition (X) can be used by dissolving in a solvent. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. An ether solvent, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and a halogen solvent such as chloroform, methylene chloride, and 1,2-dichloroethane can be preferably used. Among these, toluene, tetrahydrofuran, 1,3-dioxolane, and chloroform are preferable. These solvents can be used alone or in combination of two or more.

  Although the usage-amount of a solvent can be set suitably, Preferably it is 0.1 mL-10 mL with respect to 1 g of thermosetting resin compositions (X) to be used. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent will remain in the material and easily cause problems such as thermal cracks. It is disadvantageous and the industrial utility value decreases.

  Additives for light emitting elements are used, for example, to improve various properties of the light emitting elements. Examples of additives include phosphors such as yttrium, aluminum, and garnet phosphors activated by cerium that absorb light from the light emitting element to emit longer wavelength fluorescence, and blue that absorbs a specific wavelength. Coloring agents such as ing agents, diffusion materials such as titanium oxide, aluminum oxide, melamine resin, CTU guanamine resin, benzoguanamine resin for diffusing light, metal oxides such as aluminosilicate, aluminum nitride, boron nitride, etc. Examples thereof include thermally conductive fillers such as metal nitrides. These additives can be used alone or in combination of two or more. Moreover, these additives may be contained uniformly or may be contained with a gradient in content.

  A mold release agent is used in order to improve the mold release property at the time of shaping | molding of thermosetting resin composition (X). Examples of the release agent include the component (G) already described and waxes. Examples of waxes include natural wax, synthetic wax, oxidized or non-oxidized polyolefin, and polyethylene wax. In addition, it is better not to use a release agent when sufficient release properties can be obtained without adding a release agent.

  The thermosetting resin composition (X) includes other color traps, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, and ion trapping agents such as antimony-bismuth. , Thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity enhancer , Antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, etc. Can be added in a range.

  Furthermore, various thermoplastic resins can be added to the thermosetting resin composition (X) for the purpose of modifying the characteristics. Various thermoplastic resins can be used. For example, polymethylmethacrylate resins such as homopolymers of methyl methacrylate, random, block or graft polymers of methyl methacrylate and other monomers (for example, Hitachi Chemical Co., Ltd.) Optretz, etc.), homopolymers of butyl acrylate, random butyl acrylate and other monomers, acrylic resins typified by polybutyl acrylate resins such as block or graft polymers; bisphenol A, 3, 3, Polycarbonate resins such as polycarbonate resin containing 5-trimethylcyclohexylidenebisphenol as a monomer structure (for example, APEC manufactured by Teijin Limited); homoborn or copolymerization of norbornene derivatives, vinyl monomers, etc. Cycloolefin resins such as resins obtained by ring-opening metathesis polymerization of norbornene derivatives, and hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.); ethylene and Olefin-maleimide resins such as maleimide copolymers (eg, TI-PAS manufactured by Tosoh Corporation); bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene; and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids such as terephthalic acid and isophthalic acid and aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.); polyethersulfone resin; polyarylate resin; polyvinyl acetal resin Polyethylene resin; polypropylene resin; polystyrene resin; polyamide resin; silicone resins; other such as fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  The thermoplastic resin may have a carbon-carbon double bond and / or a SiH group having reactivity to the SiH group in the molecule. From the viewpoint that the obtained cured resin is likely to be tougher, the molecule has one or more carbon-carbon double bonds and / or SiH groups having reactivity to SiH groups in the molecule on average. Preferably it is.

  The thermoplastic resin may have other crosslinkable groups. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured resin is likely to be high, it is preferable to have one or more crosslinkable groups on average in one molecule.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less, more preferably 5000 or less, from the viewpoint that compatibility with the component (A) or the component (B) tends to be good. It is. On the contrary, the number average molecular weight is preferably 10,000 or more, more preferably 100,000 or more from the viewpoint that the obtained cured resin is easily tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and still more preferably from the viewpoint that the thermosetting resin composition (X) tends to have low viscosity and good moldability. Is 1.5 or less. Although the usage-amount of a thermoplastic resin does not have limitation in particular, Preferably it is 5 to 50 weight% of the whole thermosetting resin composition (X), More preferably, it is 10 to 30 weight%. When the addition amount is small, the resulting cured resin body tends to be brittle, and when the addition amount is large, the heat resistance (elastic modulus at high temperature) tends to be low.

  A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  The thermoplastic resin may be dissolved in the component (A) and / or the component (B) and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed. Then, it may be in a dispersed state. From the viewpoint that the obtained cured resin is more likely to be transparent, it is preferable to dissolve in the component (A) and / or the component (B) and mix in a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A) and / or the component (B), or may be mixed uniformly using a solvent or the like, and then the solvent is removed and uniform dispersion is performed. It is good also as a state and / or a mixed state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but is preferably 10 nm to 10 μm. There may be a particle size distribution, which may have a single dispersion or a plurality of peak particle sizes, but from the viewpoint that the thermosetting resin composition (X) has a low viscosity and tends to have good moldability, It is preferable that the variation coefficient of the particle diameter is 10% or less.

  Further, the thermosetting resin composition (X) may be mixed with other thermosetting resin particles. The thermosetting resin particles can be obtained by curing and pulverizing the thermosetting resin. When the thermosetting resin particles are used dispersed in the thermosetting resin composition (X), the average particle diameter can be variously set, but is preferably 10 nm to 10 μm. There may be a particle size distribution, which may be monodispersed or have a plurality of peak particle sizes, but the viewpoint that the thermosetting resin composition (X) has a low viscosity and tends to have good moldability. Therefore, it is preferable that the coefficient of variation of the particle diameter is 10% or less.

  The thermosetting resin composition (X) is prepared by, for example, mixing the above-described essential components (A) to (E) and (F) to (G) and other optional components according to the above-described method. Can be prepared. The thermosetting resin composition (X) thus obtained can be used as it is as a liquid or paste. Further, the thermosetting resin composition (X) may be used after mixing each component, additive, etc., and then partially reacting (B-stage) by heating or the like. Viscosity can be adjusted by using B-stage, and transfer moldability can also be adjusted. In addition, there is an effect of further suppressing curing shrinkage.

  The thermosetting resin composition (X) preferably has fluidity at a temperature of 150 ° C. or less from the viewpoint of good moldability by transfer molding or the like.

  Further, the curability of the thermosetting resin composition (X) can be arbitrarily set, but from the viewpoint that the molding cycle can be shortened, the gelation time at 120 ° C. is preferably within 120 seconds, and within 60 seconds. It is more preferable that Further, the gelation time at 150 ° C. is preferably within 60 seconds, and more preferably within 30 seconds. Further, the gelation time at 100 ° C. is preferably within 180 seconds, and more preferably within 120 seconds.

  The gelation time in this case is examined as follows. An aluminum foil having a thickness of 50 μm is placed on a hot plate adjusted to a preset temperature, and 100 mg of the thermosetting resin composition (X) is placed on the aluminum foil, and the time until gelation is measured to obtain the gelation time.

  In the process of producing a resin molded body using the thermosetting resin composition (X), voids are generated in the thermosetting resin composition (X) and outgassing from the thermosetting resin composition (X). From the standpoint that process problems are unlikely to occur, the weight loss during curing is preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 1% by weight or less. In addition, the weight reduction during curing was performed by increasing the temperature of a sample (thermosetting resin composition (X)) 10 mg from room temperature to 150 ° C. at a rate of 10 ° C./min using a thermogravimetric analyzer, It can be determined as a ratio of the reduced weight to the initial weight.

Further, when used as an electronic material or the like, the content of Si atoms in the volatile component is preferably 1% or less from the viewpoint of hardly causing the problem of silicone contamination.
The thermosetting resin composition (X) desirably contains an N element for the following reason. Electrical and electronic parts are generally required to have flame retardancy. Conventionally, halogen-based flame retardants have been mainly used, but they have been shifted to non-halogen-based flame retardants in order to reduce environmental impact. Further, in view of regulations in the electrical industry such as RoHS compliance, an environment-friendly flame retardant is desired, and Japanese Patent Application Laid-Open No. 2010-77333 and Special Table 2007-514828 or Japanese Patent Application No. 2002-128969 and Japanese Patent Application Laid-Open No. 2002-60385. The nitrogen-containing compounds described therein are one of the promising non-halogen flame retardants. Therefore, also in the package of this invention, it is preferable to contain a nitrogen atom especially in a resin component. In particular, a skeleton incorporating an isocyanurate skeleton which is a main skeleton as a nitrogen-based flame retardant is particularly preferable.

Further, the nitrogen compounds described in JP-A-5-148423 and JP-A-2004-67948 or JP-A-2009-117809 and JP-A-2010-77333 also act as a reaction retarding agent in the hydrosilylation curing reaction, and are sufficient. It is possible to ensure complete storage stability and at the same time completely accelerate curing (Patent Documents 5 to 7). Also from such a point, it is preferable to contain a nitrogen atom in the resin component. In addition to the resin skeleton, nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole, which are conventionally known reaction control agents for hydrosilylation reactions, may coexist.
Although there is no restriction | limiting in particular about the method of calculating | requiring N content in a product, N atom incorporated into the resin frame | skeleton or N atom of a nitrogen-containing organic compound is detectable by the measurement by 14N or 14N-solid state NMR.

  The N content in the product is not particularly limited, but is preferably 1000 ppm or more. Including nitrogen-containing inorganic fillers such as boron nitride and aluminum nitride as filler components is not a problem at all, and it is possible to draw out both the flame retardant effect by including N in the organic component itself and the flame retardant effect by nitrogen-containing inorganic filler. .

  The Tg of the cured resin obtained by curing the thermosetting resin composition (X) is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoint of good heat resistance. is there. Tg uses a dynamic viscoelasticity measuring device (trade name: DVA-200, manufactured by IT Measurement Control Co., Ltd.) and a prismatic test piece of 3 mm × 5 mm × 30 mm, and predetermined measurement conditions (tensile mode, measurement frequency 10 Hz). Dynamic viscoelasticity measurement is performed at a strain of 0.1%, a static / power ratio of 1.5, and a temperature rising side degree of 5 ° C./min), and is obtained as a peak temperature of tan δ in the measurement result.

  Further, from the viewpoint that problems such as ion migration are unlikely to occur in the lead frame and the like, and the reliability becomes high, the extracted ion content from the cured resin is preferably less than 10 ppm, more preferably less than 5 ppm, and still more preferably. It is less than 1 ppm.

  In this case, the extracted ion content is examined as follows. 1 g of the cut resin cured body is put in a Teflon (registered trademark) container together with 50 ml of ultrapure water and sealed, and treated under conditions of 121 ° C., 2 atm and 20 hours. The obtained extract was analyzed with an ICP mass spectrometer (trade name: HP-4500, manufactured by Yokogawa Analytical Systems Co., Ltd.), and the obtained Na and K content values were measured in the resin cured body as a sample. Obtained by converting to the concentration of. On the other hand, the same extract was analyzed by ion chromatography (using DX-500 manufactured by Dionex Co., Ltd., column: AS12-SC), and the obtained Cl and Br content values were determined as the concentration in the cured resin body as a sample. Calculate by converting to The contents of Na, K, Cl and Br obtained as described above in the cured resin body are summed to obtain the extracted ion content.

  The linear expansion coefficient of the cured resin is not particularly limited, but an average linear expansion coefficient from 23 ° C. to 150 ° C. is preferable from the viewpoint of easy adhesion to metals such as lead frames and ceramics. Is 30 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less.

  In addition, the thermosetting resin composition (X) has a spectral reflectance of 80 R% or more at 420 nm, 440 nm, and 460 nm after curing, and the retention ratio of the spectral reflectance after a heat test at 180 ° C. for 72 hours (heat test). It is desirable that the later spectral reflectance / initial spectral reflectance × 100) is 90% or more. The spectral reflectance is preferably 75% or more and more preferably 80% or more in the wavelength band of 420 to 700 nm from the viewpoint that the light extraction efficiency of the light emitting element tends to be high.

  The spectral reflectance of the cured resin is measured as a spectral reflectance at a wavelength of 400 nm to 700 nm (20 nm interval) using a micro-surface spectral color difference meter (Nippon Denshoku Industries Co., Ltd. VSS400). Here, the average value of the measurement values at any four locations (measurement area 0.1 mmφ) on the concave opening surface of the resin molding was adopted as the measurement value at each wavelength.

  The retention ratio of the spectral reflectance after the heat resistance test (for example, a test in which heating is performed in an oven at 180 ° C. for 72 hours) with respect to the initial spectral reflectance was obtained by the following calculation formula.

Retention rate (%) = [(spectral reflectance after heat test) / (initial spectral reflectance)] × 100
From the viewpoint of high reliability when used as an electronic material, the retention is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

  The light reflectance at a wavelength of 470 nm of the surface of the molded product obtained by curing the thermosetting resin composition (X) is preferably 90% or more, more preferably 95% or more, still more preferably 97% or more, particularly preferably. 99% or more.

  The light reflectance of the surface can be measured as follows.

  Using a PET film as a release film, a 0.5 mm-thick molded body without voids is prepared by press molding under a predetermined temperature condition. The obtained molded body is subjected to predetermined post-curing as necessary. The light reflectance can be obtained by measuring the total reflection at 470 nm using a spectrophotometer provided with an integrating sphere for the obtained molded body.

  In the thermosetting resin composition (X), it is desirable that the warp of the cured resin body is ± 1.0 mm or less when the thermosetting resin composition (X) is molded on one side of a lead frame for a light emitting element to form a package.

  The warpage in this case is measured based on the maximum warpage measuring method described in JIS C 6481. The light-emitting device is suspended vertically at the center of one side, and a straight ruler is applied parallel to that side. The straight ruler is applied to the concave surface of the light emitting device, and the maximum distance between the straight ruler and the base material surface of the light emitting device is measured to a unit of 1.0 mm with a metal straight scale. When the resin is molded on the concave surface of the light emitting device, measure the maximum distance between the straight ruler and the resin surface molded on the light emitting device to a unit of 1.0 mm with a metal straight scale. The value obtained by subtracting the thickness is rounded to the nearest 1.0 mm.

  The other sides are also measured sequentially, and the greatest gap is warped. In addition, the light-emitting device shown for the (molding method) of an Example was used for the light-emitting device used for the measurement of curvature.

  The thermosetting resin composition (X) can be made into a tablet when it contains at least the component (F) in addition to the components (A) to (E). As used herein, a tablet means a solid that retains a constant shape at room temperature, has substantially no change in shape over time, and does not stick together or become integrated when brought into contact with each other. . The shape of the tablet is not particularly limited, and includes a cylindrical shape, a prismatic shape, a disk shape, a spherical shape, and the like, and a general cylindrical shape for transfer molding is preferable.

  Specifically, at least one of the tablets is a liquid having a viscosity at 23 ° C. of 50 Pa seconds or less (A) and (B), (A) and (B) for curing the component (C). It is characterized by containing the components (E) and (F), which are both powders, and (D). In such a tablet, the entire thermosetting resin composition (X) can flow when the viscosity of the component (A) and the component (B) is lowered at high temperature, and further, when the heating is continued, the curing reaction proceeds and is desired. It is possible to mold to the shape of

  The molding method is not particularly limited, and a molding method such as transfer molding or compression molding that is generally used for molding a thermosetting resin composition can be used. When using these molding methods, if the curable resin composition as a raw material is in the form of a paste or clay, it cannot maintain a constant shape and is attached, integrated, or deformed. Supply to the molding machine becomes very difficult. On the other hand, the tablet shape makes it easy to measure, transport, and supply to a molding machine, and can be automated, greatly improving productivity.

  The total ratio of the component (E) and the component (F) in the tablet (hereinafter sometimes referred to as “filling rate”) is preferably 70 to 95% by weight. The distribution of the (E) component and the (F) component in the filling rate is not particularly limited and can be set freely. When the filling rate is less than 70% by weight, the coefficient of thermal expansion of the resulting cured resin body is increased, which causes a problem of dimensional change of the molded resin body, and the resulting thermosetting resin composition (X) is hard. There is a problem that it becomes paste or clay and cannot be tableted. When the filling rate exceeds 95% by weight, the viscosity of the thermosetting resin composition (X) at a high temperature becomes too high and the moldability is lowered, and the resulting tablet becomes too brittle.

  In the thermosetting resin composition (X), when at least one of the component (A) and the component (B) is liquid at room temperature, it tends to be a paste or clay when the filling rate is low. In this case, the tablet does not become a tablet, but the moldability at high temperature tends to be good. On the other hand, when the filling rate is high, since there are few components to be flowed, it tends to be flaky or powdery. These can be compressed into a tablet shape by being compressed, but they tend to have poor fluidity at high temperatures and easily deteriorate moldability. Until now, it has been difficult to achieve both tableting and moldability by simply increasing the filling rate.

  However, in the thermosetting resin composition (X), the proportion of the particles of 12 μm or less in the total powder of the component (E) and the component (F) is 40% by volume or more. It was found that moldability can be achieved.

  The reason for this is speculated as follows. In the mixed system of liquid and particles, it is considered that the liquid component covers the surface of the particle, and the extra liquid component covering all the particles seems to contribute to the deformation. For this reason, even if the filling rate is the same, the larger the proportion of small particles, the larger the total surface area and the more liquid components that are consumed for coating. Since the viscosity of the liquid decreases significantly at high temperatures, the change in fluidity with respect to the proportion of small particles is small at high temperatures, but the viscosity is high at low temperatures, so when there are many small particles, it flows like paste or clay. It can be considered that the flakes or powders cannot be obtained.

  In other words, by increasing the proportion of small particles in the particles, the state at room temperature can be hardened while maintaining the fluidity of the curable resin composition at high temperatures. This means that the average particle size without reference to the literature (Japanese Patent Laid-Open No. 2008-112977 or Japanese Patent Laid-Open No. 2009-155415) using an epoxy resin or a silicone resin that is solid at room temperature It cannot be conceived from Patent Document 3 which describes only the above.

  In this embodiment, transfer molding is used as a molding method for producing a resin molded body, but is not limited to this, and thermoplastic resins such as injection molding, RIM molding, casting molding, press molding, compression molding, etc. Various molding methods generally used for thermosetting resins such as epoxy resins and silicone resins are used. Of these, transfer molding is preferred in that the molding cycle is short and the moldability is good. The molding conditions can be arbitrarily set, for example, the molding temperature is also arbitrary. However, in terms of fast curing and a short molding cycle, the moldability tends to be good, more preferably 100 ° C. or higher, more preferably 120 ° C. or higher. A temperature of 150 ° C. or higher is preferable. After molding by the various methods as described above, post-curing (after-curing) is optional as required. Post-curing tends to improve heat resistance.

  Molding may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. It is preferable that the reaction is carried out while raising the temperature in a multistage or continuous manner, rather than at a constant temperature, in that a uniform cured resin body without distortion can be easily obtained. Moreover, it is preferable to perform at a constant temperature in that the molding cycle can be shortened.

  Although various curing times can be set, it is preferable to react at a relatively low temperature for a long time rather than reacting at a high temperature for a short time because a uniform cured resin body having no distortion can be easily obtained. Conversely, the reaction at a high temperature in a short time is preferable in that the molding cycle can be shortened.

  The pressure at the time of molding can be variously set as required, and the molding can be performed at normal pressure, high pressure, or reduced pressure. It is preferable to cure under reduced pressure in terms of suppressing the generation of voids, improving the filling property, and easily removing volatile components generated in some cases. In terms of preventing cracks in the molded body, it is preferable to cure under pressure.

  As the resin molded body, the above-described various resin molded bodies can be used. As the light emitting element, any conventionally used light emitting element can be used, and examples thereof include a light emitting diode (LED) and a laser diode (LD). Examples of the light emitting diode include a blue LED chip, an ultraviolet LED chip, a red LED chip, a green LED chip, and a yellow-green LED chip. A chip having a PN junction structure or an NPN junction structure, and two electrodes are horizontal or Includes chips arranged vertically. The light receiving element is connected to a plurality of leads so as to be energized by a known connection method such as wire bonding or flip chip bonding. For example, when the light emitting element has two electrodes and the plurality of leads have a first lead and a second lead, one electrode of the light emitting element is connected to the inner side of the first lead. Connecting to the lead portion and connecting the other electrode of the light emitting element to the inner lead portion of the second lead.

  As the transparent resin for sealing the light emitting element, any of the transparent resins for sealing conventionally used in surface mounted light emitting devices can be used. For example, epoxy resin, silicone resin, acrylic resin, urea resin And imide resin. Further, from the viewpoints of adhesiveness, transparency and light resistance with the cured resin contained in the resin molded body, SiH as proposed in JP-A-2002-80733 and JP-A-2002-88244 Thermosetting comprising an aliphatic organic compound having at least two carbon-carbon double bonds reactive with a group, a compound having at least two SiH groups in one molecule, and a hydrosilylation catalyst It is preferable to use a conductive resin composition as a sealant.

  Further, instead of the transparent resin, a lens may be mounted in the concave portion after mounting the light emitting element of the resin molding. The lens is not particularly limited, and any lens generally used in the field of surface-mounted light-emitting elements can be used, or a transparent resin may be molded into a lens shape. On the other hand, it is possible to perform hermetic sealing by covering with glass or the like without sealing with a transparent resin and mounting of a lens.

  The shape of the light-emitting device is not limited, and various shapes used in the field of surface-mounted light-emitting devices can be adopted. However, a MAP type in which a cured resin body is attached to one side of a metal lead frame is preferable. By using the MAP type, the curing of the present invention is particularly easily obtained.

  The light emitting device of the present invention can be used for various known applications. Specifically, for example, backlights such as liquid crystal display devices, illumination, sensor light sources, vehicle instrument light sources, signal lights, indicator lights, display devices, light sources of planar light emitters, displays, decorations, various lights, etc. .

Furthermore, an Example and a comparative example are given and this invention is demonstrated more concretely. In this example, ten-point average roughness (Rz), glass transition temperature (Tg), spectral reflectance, and solid ¹³ CNMR spectrum were measured as follows.

[Ten point average roughness (Rz)]
Ten-point average roughness (Rz) of the surface of the resin molded body where the recesses are opened is measured with a contour measuring instrument (Surfcom 500DX, manufactured by Tokyo Seimitsu Co., Ltd.) according to JIS B0633: 01 / ISO04288: 96. R: Measurement was performed under the condition of 2 μm.

[Glass transition temperature (Tg)]
Using a surgical knife made by ELP, a resin sample having dimensions of 2 to 5 mm in the longitudinal direction, 0.5 to 1 mm in the width direction, and 0.5 to 1 mm in thickness was cut out from the resin molding. This sample is a thermomechanical analyzer (TMA, manufactured by SII Nano Technology, Inc., model: TMA / SS6100). Then, under a nitrogen gas flow, the change in the expansion coefficient was measured in the range from room temperature to 250 ° C. at a temperature increase / decrease rate of 5 ° C./min and a compression load of 29.4 mN, and the glass transition temperature was calculated.

[Spectral reflectance]
The spectral reflectance at wavelengths of 400 nm to 700 nm (20 nm intervals) was measured using a micro-surface spectral color difference meter (trade name: VSS400, manufactured by Nippon Denshoku Industries Co., Ltd.). Here, at each wavelength, measurement was performed at any four locations (measurement area 0.1 mmφ) on the concave opening surface of the resin molded body, and the average value of the obtained measurement values was taken as the spectral reflectance at that wavelength.

  Further, the retention rate (%) of the spectral reflectance (B) after the heat resistance test (test for heating in an oven at 180 ° C. for 72 hours) with respect to the initial spectral reflectance (A) was calculated by the following formula.

      Retention rate (%) = (B / A) × 100

[Solid ¹³ C NMR spectrum]
A resin sample of 0.5 g was cut out from the resin molding, ground in a mortar, and packed into a 3.2 mmφ solid NMR sample tube. This sample tube was loaded into a VARIAN NMR apparatus (600 MHz), ¹³ C CP / MAS NMR measurement was performed at a magic angle spinning speed of 20 kHz, and a solid ¹³ C NMR spectrum of the sample was obtained.

(Synthesis Example 1)
A stirrer, a dropping funnel and a condenser were set in a 5 L four-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and heated and stirred in an oil bath at 120 ° C. To this, a mixed solution of 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. The obtained compound has a structure shown below in which a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with triallyl isocyanurate by ¹ H-NMR measurement. I understood it.

(Synthesis Example 2)
720 g of toluene and 240 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 2 L autoclave, the gas phase was replaced with nitrogen, and then heated and stirred at a jacket temperature of 50 ° C. To this, a mixed solution of 171 g of allyl glycidyl ether, 171 g of toluene and 0.049 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 90 minutes. After completion of the dropping, the jacket temperature was raised to 60 ° C., and the reaction was further continued for 40 minutes. It was confirmed by ¹ H-NMR that the allyl group reaction rate was 95% or more.

To the resulting reaction mixture, a mixture of 17 g of triallyl isocyanurate and 17 g of toluene was added dropwise, the jacket temperature was raised to 105 ° C., and 66 g of triallyl isocyanurate, 66 g of toluene and a xylene solution of platinum vinylsiloxane complex ( 0.033 g of a mixed solution was added dropwise over 30 minutes. Four hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling.

The unreacted rate of 1,3,5,7-tetramethylcyclotetrasiloxane was 0.8%. The total amount of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane, toluene, and allyl glycidyl ether by-products (inner transition products of allylic glycidyl ether vinyl group (cis isomer and trans isomer)) is 5,000 ppm or less in total. The solution was distilled off under reduced pressure until a colorless and transparent liquid was obtained. ^{According to} the measurement of ¹ H-NMR, this was obtained by reacting a part of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane with allyl glycidyl ether and triallyl isocyanurate. It was found to have a structure shown in Chemical formula 46]. In the following, a + b = 3, c + d = 3, e + f = 3, a + c + e = 3.5, and b + d + f = 5.5.

(Formulation example 1)
Each component was mix | blended according to the content of Table 1, and thermosetting resin composition AD was prepared.

Example 1
50 parts by weight of the composition C shown in Table 1 obtained in the above blending example, 27 parts by weight of the following (D) component, 557 parts by weight of the following (E) component, and 239 parts by weight of the following (F) component were mixed uniformly. A thermosetting resin composition was prepared. In addition, it weighed so that it might become a total of 100g with the ratio of each said component, and mixed uniformly. The same applies to the following examples and comparative examples. This thermosetting resin composition is a thermosetting resin composition (Xa).

Component (D): Linear methylphenyl silicone containing vinyl groups at both ends (trade name: PDV2331, manufactured by Gelest, the amount of phenyl groups based on all substituents is 22 to 25 mol%)
(E) component: spherical silica (trade name: MSR-2212-TN, manufactured by Tatsumori, specific gravity 2.2, average particle size 24.8 μm, ratio of particles having a particle size of 12 μm or less: 28%)
Component (F): Titanium oxide (trade name: Taipei PC-3, manufactured by Ishihara Sangyo Co., Ltd., rutile type, specific gravity 4.2, chlorine method, surface organic: Al, Si, polymethylhydrogensiloxane, average particle size 0 .21 μm, ratio of particles of 12 μm or less: 100%)
Transfer molding was performed using a G-Line manual press manufactured by Apic Yamada Co., Ltd. The mold clamping force was 30 ton, the injection pressure was 7.7 MPa, and the injection speed was 3 mm / s. A white compound of 5.0 g is weighed, shaped into a cylindrical shape, loaded into a cylinder, and sprayed with a fluorine type mold release agent (Daikin Kogyo Co., Ltd .: Die Free GA-7500). did. The molding conditions are 170 ° C./3 minutes and 7.8 to 13.7 MPa. After molding, it was post-cured at 180 ° C./1 h. In the mold used for transfer molding, the Rz of the bottom surface of the upper recess was adjusted to 6.0 μm on the upper mating surface of the upper mold.

  Further, after the molding, curing was performed at 180 ° C. for 1 hour. When the resin molded body was removed from the upper mold, the resin molded body was not damaged due to deformation or interface peeling.

About the obtained resin molding, ten-point average roughness (Rz), glass transition temperature (Tg), spectral reflectance, and solid ¹³ CNMR spectrum were examined. The results are shown in Table 2.

(Example 2)
Composition D 5.25 parts by weight obtained in the above formulation example, 2.81 parts by weight of the following (D) component, 58.23 parts by weight of the following (E) component, 33.51 of the following (F) component A thermosetting resin composition was prepared by mixing 0.2 parts by weight of the following (G) component with parts by weight. This thermosetting resin composition is a thermosetting resin composition (Xb).

Component (D): Linear methylphenyl silicone containing both terminal vinyl groups (PDV-2331)
Component (E): Silica (MSR-2212-TN)
Component (F): Zinc oxide [manufactured by Sakai Chemical Industry Co., Ltd., 1 type of zinc oxide, specific gravity 5.6, average particle size 0.6 μm]
(G) Component: Calcium stearate A resin molded body was produced in the same manner as in Example 1 except that the thermosetting resin composition obtained above was used. When the resin molded body was removed from the upper mold, the resin molded body was not damaged due to deformation or interface peeling. About the obtained resin molding, ten-point average roughness (Rz), glass transition temperature (Tg), spectral reflectance, and solid ¹³ CNMR spectrum were examined. The results are shown in Table 2.

(Comparative Example 1)
100 parts by weight of methyltrichlorosilane and 200 parts by weight of toluene are placed in a 1 L flask, and a mixed liquid of 8 parts by weight of water and 60 parts by weight of isopropyl alcohol is cooled to 5 to 20 ° C. The solution was added dropwise over time. The reaction mixture was then heated and stirred at reflux temperature for 20 minutes. Then, the mixture was cooled to room temperature, and 12 parts by weight of water was added dropwise at 30 ° C. or lower for 30 minutes, followed by stirring for 20 minutes. Further, 25 parts by weight of water was added dropwise, followed by stirring at 40 to 45 ° C. for 60 minutes. Thereafter, 200 parts by weight of water was added to separate the organic layer. The organic layer was washed until neutral, then azeotropically dehydrated, filtered, and stripped under reduced pressure to give 36.0 parts by weight of a thermosetting organopolyamide (melting point: 76 ° C.) represented by the following formula: Polysiloxane was obtained.
(CH ₃ ) _1.0 Si (OC ₃ H ₇ ) _0.06 (OH) _0.11 O _1.4
100 parts by weight of the thermosetting organopolysiloxane obtained above, titanium dioxide (white pigment, rutile type, average particle size 0.3 μm, trade name: PFC-104, manufactured by Ishihara Sangyo Co., Ltd.), inorganic filling 560 parts by weight of material (spherical fused silica, average particle size 20 μm, trade name: MSR-200, manufactured by Tatsumori Co., Ltd.), inorganic filler (spherical fused silica, average particle size 0.5 μm, trade name: Admafine S0- 25R, Admatech Co., Ltd.) 40 parts by weight and 3 parts by weight of a curing catalyst (zinc benzoate, manufactured by Wako Pure Chemical Industries, Ltd.) are uniformly melt-mixed in a continuous kneader, cooled and pulverized, and silicone-based thermosetting A resin composition was prepared.

A resin molded body was produced in the same manner as in Example 1 except that the silicone-based thermosetting resin composition obtained above was used and Rz of the upper concave bottom surface formed in the upper mold was not adjusted. . When the resin molded body was removed from the upper mold, the resin molded body was deformed or broken. About the obtained resin molding, ten-point average roughness (Rz), glass transition temperature (Tg), spectral reflectance, and solid ¹³ CNMR spectrum were examined. The results are shown in Table 2.

(Comparative Example 2)
The light emitting device is taken out from a commercially available white LED bulb (trade name: Everreds, manufactured by Panasonic Corporation), and the ten-point average roughness (Rz), glass transition temperature (Tg), spectral reflectance, and solid state ¹³ CNMR of the resin molded body are taken out. The spectrum was examined. The results are shown in Table 2.

  From the comparison between Example 2 and Comparative Examples 3 and 4, when the resin molded body is removed from the upper mold by adjusting the Rz of the concave opening surface of the resin molded body to be 1 μm to 10 μm. It is clear that the deformation of the resin molded body and the occurrence of breakage due to interfacial peeling are remarkably suppressed, and the defective product rate is greatly reduced.

  Further, from comparison between Examples 1 and 2 and Comparative Examples 1 and 2 in Table 2, the use of the thermosetting resin composition (X) significantly improves the spectral reflectance, heat resistance and reflection retention. I understand that Moreover, although the comparative example 1 shows favorable spectral reflectance, since glass transition temperature is as low as -2 degreeC, intensity | strength is not enough at the time of mold release from a metal mold | die, and the cutting process accompanying the isolation | separation of an LED package When it is used, the mechanical strength becomes insufficient, and the quality sufficient as a product such as chipping of the resin molded part is not satisfied.

(Examples 3 to 10, Comparative Examples 3 to 4)
Using thermosetting resin composition (X), a precision hot press (CYPF-10, manufactured by Shinto Kogyo Co., Ltd.), mold inserts with different surface roughness [(10-point average roughness (Rz) = 0 .9, 2.5, 5.8, 10.6, 15.6 (μm)] is mounted on the upper mold, and a mold having a ten-point average roughness (Rz) of 0.9 is mounted on the lower mold. The upper and lower press plates were press-molded such that 170 ° C. × curing time 2 minutes, mold release rate 0.2 mm / s, sample shape: φ30 × thickness 1 mm, and then peeled off when the mold was opened The mode was evaluated.

  At this time, when the resin molded body has no defects such as cracks and breakage, it is peeled off from the mold interface. AF: Interfacial peeling (Adhesive Failure), when the resin molded body is stuck to the mold, etc. CF: Cohesive failure.

When a flat plate sample could be obtained, the molded body surface roughness Rz (μm) and the spectral reflectance (%) of the molded body surface (@ 460 nm, N = 5 average) were measured, and the surface appearance was observed. The surface condition (unevenness) was observed and evaluated with the naked eye. A smooth surface and glossy surface was evaluated as ◯, a slightly surface glossy and smooth surface material as Δ, and a surface gloss as low as possible with the naked eye being observed with the naked eye.
A solid ¹³ C NMR spectrum was also examined.

From Tables 4 and 5, the thermosetting resin molded bodies (Xa, Xb) used in Examples 3 to 6 and Examples 7 to 10 have different ten-point average roughness (Rz = 0.9 to 15. 6) When it was molded using a mold, it showed excellent releasability and mechanical strength.
Moreover, when the molded body surface roughness (Rz) is 10 or more (Comparative Example 3 and Comparative Example 4), the spectral reflectance of the molded body surface is compared with the molded bodies obtained in Examples 3 to 6 and 7 to 10. Decreased by about 2%. Furthermore, the glossiness decreased by visual observation, and surface irregularities were observed with the naked eye.
Thus, the conditions under which a resin molded body having excellent surface reflectivity can be obtained by defining the surface roughness of the molded body have been clarified.

(Reference Examples 1 to 10)
Under the same conditions as in Examples 3 to 10 and Comparative Examples 3 to 4, that is, using the thermosetting resin composition (Xc, Xd) using a precision hot press (CYPF-10, manufactured by Shinto Kogyo Co., Ltd.), Insert mold inserts [(10-point average roughness (Rz) = 0.9, 2.5, 5.8, 10.6, 15.6 (μm)] with different surface roughness into the upper mold, An upper and lower press plate with a point average roughness (Rz) = 0.9 attached to the lower die, 170 ° C. × curing time 2 minutes, mold release speed 0.2 mm / s, sample shape: φ30 × thickness 1 mm Thereafter, the release mode of the molded product when the mold was opened was evaluated, and the solid ¹³ CNMR spectrum was evaluated.

  As shown in Tables 6 and 7, regardless of the mold roughness, any molded product of the thermosetting resin composition (Xc, Xd) becomes cohesive failure (CF), inferior in releasability and resin strength. Low and satisfactory molded bodies could not be obtained.

100, 200... Light emitting device
101, 201 ... Base
101A, 201A ... concave portion (first concave portion)
101B, 201B ... concave portion (second concave portion)
101C, 201C... Recess (third recess)
102, 202 ... conductive member
103A, 203A ... Light emitting element (green light emitting element)
103B, 203B... Light emitting element (red light emitting element)
103C, 203C ... Light emitting element (blue light emitting element)
104, 204 ... conductive wire
105A, 205A ... Sealing member (first sealing member)
105B, 205B ... sealing member (second sealing member)
105C, 205C ... sealing member (third sealing member)
206 ... Step portion
206 ... Coating member

Claims (3)

A light emitting device comprising: a plurality of light emitting elements having different emission wavelengths; a resin cured body having a plurality of recesses on which the light emitting elements are placed; and a sealing member provided in each of the recesses. Is composed of three recesses that are spaced apart from each other and have openings of substantially the same shape, and each recess has a green light emitting element, a red light emitting element, and a blue light emitting element mounted thereon, respectively. Resin molded body for
The ten-point average roughness (Rz) of the opening surface and the frame side surface of the recess is 1 μm or more and 10 μm or less,
Using a thermomechanical analyzer (TMA), the glass transition temperature of the cured resin measured at a temperature range of −50 to 250 ° C., a heating rate of 5 ° C./min, and a sample size length of 1 to 5 mm is 10 ° C. or higher. And
The light reflectance at 460 nm of the opening surface of the resin cured body or the inner wall surface of the recess is 80% or more, and the light on the opening surface and the inner wall surface after heating the resin cured body at 180 ° C. for 72 hours. A resin molded body for a light-emitting device having a reflectance retention of 90% or more. 2. The resin molded body for a light emitting device according to claim 1, wherein at least one peak top in a solid ¹³ C-nuclear magnetic resonance spectrum of the cured resin is present in a range of −1 ppm to 2 ppm and 13 ppm to 18 ppm. The cured resin is (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) containing at least two SiH groups in one molecule. A compound containing (C) a hydrosilylation catalyst, (D) a silicone compound containing at least one carbon-carbon double bond reactive with a SiH group in one molecule, and (E) a curing containing an inorganic filler. The resin molded body for a light-emitting device according to claim 1, which is a cured resin body of the conductive resin composition (I).

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