JP2013080819A - Resin molding for light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve energy efficiency and heighten light emission intensity per unit area.SOLUTION: A light-emitting device 1 comprises: a base part 3a; a support substrate 3, formed on the base part 3a, and having a light reflection part 3b provided with a plurality of opening parts 3c; a light emitting element 5, disposed in the plurality of the opening parts 3c, and having an anode electrode 13 and a cathode electrode 15; and a plurality of electrode wirings 7, extending in a belt-shape between the base part 3a and the light reflection part 3b, for supplying a current to the light emitting element 5.

Description

  The present invention relates to a resin molded body for a light emitting device.

  Conventionally, various light-emitting devices including a plurality of light-emitting elements arranged two-dimensionally have been proposed. For example, Patent Document 1 discloses a light-emitting device configured by forming a plurality of recesses on a main surface of a substrate and arranging a light-emitting element in each recess. In this light emitting device, the light is reflected by the inner surface of the concave portion in which the light emitting element is disposed, thereby improving the directivity of the light emitted from the light emitting element and increasing the light emission intensity of the light emitting device. In addition, a plurality of electrode wirings for supplying current to the light emitting elements extend in a strip shape between adjacent concave portions on the main surface of the substrate, and the plurality of light emitting elements are connected in parallel.

Japanese Patent Laid-Open No. 11-266036 JP 2010-62272 A JP 2009-302241 A

In the light emitting device of Patent Document 1, the concave portions in which the light emitting elements are arranged are densely arranged in order to increase the light emission intensity. For this reason, the space between adjacent recesses on the main surface of the substrate is reduced, and the width of the electrode wiring extending in a band shape between the recesses is reduced. As a result, the resistance of the electrode wiring is increased, and the voltage drop in the electrode wiring is increased, resulting in a problem that the energy efficiency is deteriorated.
On the other hand, when the width of the electrode wiring is increased, the interval between the concave portions in which the light emitting elements are arranged is widened, and the light emitting elements cannot be arranged densely. Therefore, there has been a problem that the light emission intensity per unit area of the light emitting device is lowered.
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 2 and 3).
The present invention has been made to solve the above-described problem, and provides a resin molded body for a light-emitting device having high durability, capable of improving energy efficiency and increasing emission intensity per unit area. With the goal.

That is, the present invention has the following configuration.
1. A base substrate, a support substrate formed on the base and having a light reflecting portion made of a resin cured body having a plurality of openings, and a light emitting element disposed in the plurality of openings and having an anode electrode and a cathode electrode An element, and a plurality of electrode wirings extending in a strip shape between the base portion and the light reflecting portion and supplying a current to the light emitting element, wherein the plurality of openings are formed on each of the electrode wirings. The opening portion arranged along one of the peripheral edge portions on the one side and the peripheral edge portion on the other side, and the peripheral edge portion on one side of each of the electrode wirings is arranged along the peripheral edge portion on one side of each of the electrode wirings And the other peripheral edge of each electrode wiring is exposed from the opening arranged along the other peripheral edge of each electrode wiring, and the one peripheral edge of each electrode wiring The light emitting elements in the openings arranged along the portion. The anode electrode or the cathode electrode is connected to a peripheral portion on one side of the electrode wiring exposed from the opening, and the opening in the opening arranged along the peripheral portion on the other side of each electrode wiring. The anode electrode or the cathode electrode in the light emitting element is connected to a peripheral portion on the other side of the electrode wiring exposed from the opening, and is a cured resin used in a light emitting device, The ten-point average roughness (Rz) of the opening surface of the opening 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. Because
The light reflectance at 460 nm of the opening surface of the resin cured body and 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 article 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 the 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 light-emitting devices according to any one of 1 to 2, which is a cured resin body of the conductive resin composition (I).

  According to the light emitting device of the present invention, it is possible to improve energy efficiency and increase the light emission intensity per unit area.

It is a top view of the light-emitting device concerning one embodiment of the present invention. It is II-II sectional drawing of the light-emitting device of FIG. It is a top view which shows the modification of the light-emitting device of FIG. It is a top view which shows the modification of the light-emitting device of FIG. It is a top view which shows the modification of the light-emitting device of FIG.

Hereinafter, an embodiment of a light emitting device according to the present invention will be described with reference to the drawings.
As shown in FIGS. 1 and 2, the light emitting device 1 according to the present embodiment includes a support substrate 3 having a rectangular shape in plan view, a plurality of light emitting elements 5 arranged on the support substrate 3, and each light emitting element 5. A plurality of connected electrode wires 7 (7a to 7f) are provided.

The support substrate 3 includes a flat base portion 3a and a plate-like light reflecting portion 3b formed on the base portion 3a and having a plurality of openings 3c. The base part 3a and the light reflecting part 3b have electrical insulation and are formed of a curable resin composition.
As shown in FIG. 2, a plurality (six in the illustrated example) of electrode wirings 7 are formed between the base portion 3a and the light reflecting portion 3b. As shown in FIG. 1, each electrode wiring 7 has a planar waveform having a plurality of (five places in the illustrated example) bent portions, and extends in a strip shape in the vertical direction of FIG. 1. And the electrode wirings 7a-7f are arrange | positioned adjacently in the state mutually spaced apart in the left-right direction of FIG. The electrode wirings 7a to 7f are connected to an external drive circuit (not shown) so that a forward voltage is applied between the anode electrode 13 and the cathode electrode 15 of the light emitting element 5 as will be described later. It has become. In this embodiment, as will be described later, the anode electrode 13 in each light-emitting element 5 is connected to the electrode wirings 7b, 7d, and 7f of the electrode wirings 7a to 7f, and the electrode wiring 7a of the electrode wirings 7a to 7f. , 7c, 7e are connected to the cathode electrode 15 of each light emitting element 5.

  For example, the electrode wirings 7a to 7f are printed on a ceramic green sheet serving as the base portion 3a by a conductive paste such as silver or copper serving as the electrode wirings 7a to 7f by screen printing or the like, and further the light reflecting portion 3b. The curable resin molded body to be formed on the ceramic green sheet can be formed integrally with the support substrate 3.

  As shown in FIG. 1, the plurality of openings 3c of the light reflecting portion 3b are arranged at positions corresponding to the bent portions of the respective electrode wirings 7a to 7f having a waveform shape, and the peripheral edges of the respective electrode wirings 7a to 7f. By being arranged along the part, it is arranged in a staggered manner.

  More specifically, the left side (one side) peripheral part and the right side (other side) peripheral part of the four electrode wirings 7b to 7e excluding the electrode wirings 7a and 7f located at both ends in the left-right direction in FIG. A plurality of openings 3c are arranged along each of the above. The left peripheral portion of each of the four electrode wirings 7b to 7e is exposed from the opening 3c arranged along the left peripheral portion of each of the electrode wirings 7b to 7e. On the other hand, the right peripheral portion of each of the four electrode wirings 7b to 7e is exposed from the opening 3c arranged along the right peripheral portion of each of the electrode wirings 7b to 7e. In FIG. 1, for convenience of explanation, a sealing body 17 to be described later is not shown, and the peripheral portions of the electrode wirings 7 a to 7 f exposed from the respective openings 3 c are shown by cross hatching.

  Further, in the electrode wiring 7a located at the left end in the left-right direction in FIG. 1, the opening 3c is disposed only along the right peripheral edge, and the right peripheral edge is exposed from the opening 3c. On the other hand, the electrode wiring 7f located at the right end in FIG. 1 has an opening 3c disposed along only the left peripheral edge, and the left peripheral edge is exposed from the opening 3c.

  Each opening 3c of the light reflecting portion 3b has a circular shape in plan view as shown in FIG. 1, and as shown in FIG. 2, its inner peripheral surface 3d faces inward from the upper surface to the lower surface of the light reflecting portion 3b. It is formed to be inclined. By so doing, the light emitted radially from each light emitting element 5 is reflected by the inner peripheral surface 3d as described later, and the directivity of the light emitted from the light emitting device 1 is enhanced.

  A light emitting element 5 is disposed in each opening 3c of the light reflecting portion 3b. As shown in FIG. 2, each light-emitting element 5 includes a light-transmitting crystal growth substrate 9 made of sapphire and the like, and an n-type semiconductor layer 11 n and a p-type semiconductor layer 11 p are sequentially stacked on the crystal growth substrate 9. And the anode electrode 13 connected to the p-type semiconductor layer 11p, and the cathode electrode 15 connected to the n-type semiconductor layer 11n.

  The semiconductor stacked portion 11 has a pn junction region formed by a p-type semiconductor layer 11p and an n-type semiconductor layer 11n, and the pn junction region emits light when a forward current is supplied as will be described later. It is supposed to be. The n-type semiconductor layer 11n and the p-type semiconductor layer 11p are formed, for example, by epitaxially growing a semiconductor such as GaN. The semiconductor stacked portion 11 may be appropriately configured according to a desired emission wavelength, and may be formed of a III-V group compound semiconductor such as GaAs or AlGaInP, for example. As the light emitting element 5, a light emitting element such as an organic EL element having an anode electrode and a cathode electrode may be used.

  Each light emitting element 5 is connected to the electrode wiring 7 by so-called flip chip connection. More specifically, the anode electrode 13 in each light-emitting element 5 is connected to the left and right peripheral edges of the electrode wirings 7b and 7d exposed from the opening 3c and the left peripheral edge of the electrode wiring 7f. On the other hand, the cathode electrode 15 in each light emitting element 5 is connected to the right peripheral portion of the electrode wiring 7a exposed from the opening 3c and the right and left peripheral portions of the electrode wirings 7c and 7e. Therefore, the anode electrode 13 in each light emitting element 5 is connected to one of the two adjacent electrode wirings of the electrode wirings 7a to 7f, and each light emitting element is connected to the other of the two adjacent electrode wirings. 5 is connected. Therefore, a forward current can be supplied to each light emitting element 5 connected between the two electrode wirings by applying a forward voltage between two adjacent electrode wirings.

  Inside each opening part 3c of the light reflection part 3b, the sealing body 17 which has translucency and seals each opening part 3c is formed. The sealing body 17 is formed, for example, by filling each opening 3c with silicon resin or the like. For example, when the sealing body 17 is formed of silicon resin, the refractive index is about 1.4. When the crystal growth substrate 9 is formed of sapphire, the refractive index of the crystal growth substrate 9 is about 1.7. Therefore, when the external atmosphere of the light emitting device 1 is air (refractive index = about 1.0), the refractive index of the sealing body 17 is closer to the refractive index of the crystal growth substrate 9 than the refractive index of air. The total reflection of light emitted from the inside of the crystal growth substrate 9 to the outside can be reduced, and the light extraction efficiency to the outside of the light emitting device 1 can be improved.

  In the light emitting device 1 configured as described above, each of the electrode wirings 7a to 7f is connected to an external drive circuit (not shown), and a forward voltage is applied between the electrode wirings adjacent to the electrode wirings 7a to 7f. A forward current is supplied to the pn junction region in the semiconductor stacked portion 11 of each light emitting element 5, and the pn junction region emits light. The light emitted from the pn junction region enters the sealing body 17 via the crystal growth substrate 9 or directly enters the sealing body 17 and is emitted from the sealing body 17 to the outside. At this time, the light incident on the inner peripheral surface 3d of the light reflecting portion 3b is reflected by the inner peripheral surface 3d and emitted to the outside.

  According to the light emitting device 1 according to the present embodiment, the electrode wiring 7b extends in a band shape, and the anode electrodes 13 in the five light emitting elements 5 arranged along the left peripheral portion of the electrode wiring 7b, and the electrode wiring The anode electrodes 13 of the five light emitting elements 5 arranged along the right peripheral edge of 7b are collectively connected by one electrode wiring 7b. Similarly, the electrode wiring 7d connects together the anode electrodes 13 in the light emitting elements 5 (5 on the left side and 5 on the right side) arranged along the peripheral portions on both the left and right sides. On the other hand, the electrode wirings 7c and 7e collectively connect the cathode electrodes 15 in the light emitting elements 5 (5 on the left side and 5 on the right side) arranged along the peripheral portions on both the left and right sides.

  Therefore, the width of the electrode wirings 7b to 7e can be increased, and the electrical resistance of the electrode wirings 7b to 7e can be reduced. Therefore, the voltage drop in the electrode wirings 7b to 7e is reduced, and the energy efficiency can be improved.

  Further, according to the present embodiment, since the electrode wirings 7b to 7e are formed between the base portion 3a and the light reflecting portion 3b in the support substrate 3, the distance between the openings 3c as in the conventional example. Without increasing the width, the width of the electrode wiring 7 can be increased by connecting the anode electrode 13 or the cathode electrode 15 adjacent to each other at the left and right as described above. Therefore, according to the present embodiment, it is possible to increase the width of the electrode wiring 7 while arranging the light emitting elements 5 at a high density with a close arrangement interval of the openings 3c. Therefore, the light emission intensity per unit area of the light emitting device 1 can be increased and the energy efficiency can be improved.

  Further, according to the light emitting device 1 of the present embodiment, the plurality of openings 3c of the light reflecting portion 3b are arranged at positions corresponding to the bent portions of the electrode wirings 7, so that the light emitting elements 5 are staggered. Has been placed. In particular, in the present embodiment, since the plurality of openings 3c are two-dimensionally closely packed and arranged, the light emitting elements 5 can be arranged with high density, and the light emission intensity per unit area of the light emitting device 1 can be increased. Can be increased.

  As mentioned above, although one Embodiment of this invention was described, this invention is not limited to the said embodiment, A various change is possible unless it deviates from the meaning. For example, in the above-described embodiment, five openings 3c of the light reflecting portion 3b are arranged in the left-right direction in FIG. 1 and five are arranged along the peripheral edge of the electrode wiring 7, but this is not limitative. Any number of openings 3c may be arranged instead. Further, the shape of the opening 3c is not limited to the circular shape in plan view shown in FIG. 1, and may be formed in an arbitrary shape such as a polygonal shape such as a rectangular shape or a hexagonal shape.

Moreover, in the said embodiment, although the several light emitting element 5 is connected in parallel by electrode wiring 7a-7f, you may connect in series, for example. In this case, as shown in FIG. 3, the five light emitting elements 5 arranged along the right edge of the electrode wiring 7b are rotated 180 degrees, and the cathode of the light emitting element 5 is placed on the right edge of the electrode wiring 7b. The electrode 15 is connected, and the anode electrode 13 of the light emitting element 5 is connected to the left peripheral portion of the electrode wiring 7c. Similarly, the five light emitting elements 5 arranged along the right peripheral portion of the electrode wiring 7d are also rotated by 180 degrees, and the cathode electrode 15 of the light emitting element 5 is connected to the right peripheral portion of the electrode wiring 7d. The anode electrode 13 of the light emitting element 5 is connected to the left peripheral portion of the electrode wiring 7e. In this way, the light emitting elements 5 in the five light emitting element rows 51 to 55 each including five light emitting elements 5 arranged in a line in the horizontal direction in FIG. 3 are connected in series by the six electrode wirings 7a to 7f. Connected to. Then, the electrode wirings 7a and 7f located at both ends in the left-right direction are connected to an external drive circuit (not shown), and a forward voltage is applied. Thereby, a forward current is supplied to each light emitting element 5, and the pn junction region of the semiconductor stacked portion 11 emits light.

  Further, in the light emitting device 1 shown in FIG. 1, the electrode wirings 7a to 7d are independently formed. For example, the electrode wirings 7a, 7c, and 7e are provided on one side (upper side in FIG. 1) on the base portion 3. The electrode wirings 7b, 7d, and 7f may be connected to each other at the other end (lower side in FIG. 1) on the base 3 while being connected to each other at the end. In this case, a voltage can be applied collectively between the electrode wirings 7a, 7c, 7e and the electrode wirings 7b, 7d, 7f.

  Further, in the above embodiment, each electrode wiring 7 extending in a strip shape is formed in a corrugated shape having a plurality of (five in the illustrated example) bent portions, but the number and shape of the bent portions of each electrode wiring 7 are the same. It is not limited to. For example, as shown in FIG. 4, the number of bent portions of each electrode wiring 7 may be one. Further, for example, as shown in FIG. 5, each electrode wiring 7 may be formed linearly without forming a bent portion in each electrode wiring 7.

  The concave surface of the opening of the light emitting device 1 having the light reflecting portion 3b having a plurality of openings made of a cured resin body has an Rz of 1 μm or more and 10 μm or less. Thereby, when the resin cured body which comprises the light reflection part b used for the support substrate 3 is mass-produced, the resin cured body which comprises the reflection part 3b in which the shape was uniform can be manufactured efficiently. If Rz is less than 1 μm, for example, when the support substrate 3 made of the resin cured body is manufactured using a transfer mold molding die, the releasability of the support substrate 3 from the die decreases, Deformation and cohesive failure 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 the releasability of the support substrate 3 having a plurality of openings made of a cured resin resin and high reflectance of the resin molded body. .

  The resin cured body used for the light reflecting portion 3b used for the support substrate 3 uses a thermomechanical analyzer (TMA), a temperature range of −50 to 250 ° C., a temperature increase rate of 5 ° C./min, and a sample size length of 1 to 5 mm. It is preferable that the glass transition temperature of the said resin cured body measured on condition of 10 is 10 degreeC or more. Thereby, the heat resistance of the resin cured body used for the light reflecting portion 3b 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.

  In addition, the opening surface 3c of the light emitting device 1 and the inner wall surface 3d of the recess having the light reflecting portion b including a plurality of openings made of the resin cured body have a light reflectance at 460 nm of 80% or more, and It is preferable that the light reflectivity retention on the opening surface 3c and the inner wall surface 3d after the resin molded body 1 is heated at 180 ° C. for 72 hours is 90% or more. By using such a resin cured body, the reliability of the light emitting device 1 having the light reflecting portion b having a plurality of openings is significantly improved.

Further, it is more preferable that at least one peak top in the solid ¹³ C-nuclear magnetic resonance spectrum (hereinafter referred to as “solid ¹³ C NMR spectrum”) of the cured resin is present in the range of −1 ppm to 2 ppm and 13 ppm to 18 ppm. . Such a cured resin body further improves the reliability of the light emitting device.

  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 below is mentioned, for example.

  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.

(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 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, three at least one of R ^1, 1 to 50 carbon atoms containing a group represented by the following 1 or more A monovalent organic group is preferred.

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. Moreover, the group shown below is especially preferable from the ease of acquisition of a raw material.

(In the formula, R ¹ represents a hydrogen atom or a methyl group.)

  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.

  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. Such carboxylic acids and acid anhydrides are not particularly limited, but each carboxylic acid shown below,

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. .

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. 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.

1 Light-emitting device
3 Support substrate
3a Base part
3b Light reflection part
3c opening
3d inner surface
5 Light emitting elements
7 Electrode wiring
13 Anode electrode 15 Cathode electrode 17 Sealed body

Claims (3)

A support substrate 3 having a base portion and a light reflecting portion made of a resin cured body having a plurality of openings formed on the base portion, and an anode electrode and a cathode electrode disposed in the plurality of openings. And a plurality of electrode wirings extending in a band shape between the base portion and the light reflecting portion and supplying a current to the light emitting elements, wherein the plurality of openings include the electrode wirings. The one edge of each electrode wiring is arranged along the one edge of the electrode wiring, and the one edge of each electrode wiring is arranged along the one edge of the electrode wiring. The peripheral edge of the other side of each electrode wiring is exposed from the opening arranged along the peripheral edge of the other side of each electrode wiring, and the one side of each electrode wiring is exposed The light emitting elements in the openings arranged along the peripheral edge The anode electrode or the cathode electrode is connected to a peripheral edge on one side of the electrode wiring exposed from the opening, and the opening in the opening arranged along the peripheral edge on the other side of each electrode wiring. The anode electrode or the cathode electrode in the light emitting element is connected to a peripheral portion on the other side of the electrode wiring exposed from the opening, and is a resin molded body used for a light emitting device, The ten-point average roughness (Rz) of the opening surface of the opening 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. Because
The light reflectance at 460 nm of the opening surface of the resin cured body and 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).