JP6010210B2 - Resin molded body for surface mount type light emitting device and light emitting device using the same - Google Patents

Description

  The present invention relates to a white thermosetting composition excellent in continuous moldability, a resin molded body for a surface-mounted light-emitting device using the same, and a surface-mounted light-emitting device.

  In recent years, electronic components have been mounted on a substrate with high density as electronic devices have been reduced in size, weight, performance, and functionality. As an electronic component for mounting at high density, for example, SMD (Surface Mounted Device) that can be connected to a wiring pattern on a substrate by reflow soldering or the like is widely used (for example, see Patent Document 1). ).

  An LED (Light Emitting Diode), which is an example of such an electronic component, is an optical semiconductor device in which an optical semiconductor element and a phosphor are combined, and has attracted attention as a light-emitting device with low power consumption and long life.

  A resin-molded body for a surface-mounted light-emitting device using a white thermosetting composition is used for a wall portion provided so as to surround the outer periphery of an optical semiconductor element and a filling portion between electrodes at the bottom of the substrate. It acts as a reflector that reflects the emitted light and guides it upward. Thus, sufficient light reflectivity is calculated | required by the resin hardening body which consists of a white thermosetting composition.

  Patent Document 2 discloses a resin molded body for a surface-mounted light-emitting device using a white thermosetting composition having a high reflectance in the visible light to near-ultraviolet light region. Patent Document 3 discloses a molding resin composition that can be filled with titanium oxide and maintain whiteness for a long time.

JP 2003-218398 A JP 2006-140207 A JP 2008-255338 A

  In order to produce a large amount of surface-mounted light-emitting devices in a short time, a method is generally used in which the white thermosetting composition is integrally formed with a lead by heat-pressure molding, for example, transfer molding. However, mold wear derived from the hardness of the inorganic filler component contained in the light white thermosetting composition occurred, and there was a problem in continuous moldability.

  The present invention has been made in view of the above circumstances, and a resin-molded body for a surface-mounted light-emitting device comprising a white thermosetting composition excellent in continuous moldability, and a surface-mounted light-emitting device using the same The purpose is to provide.

  The present invention is characterized by the following items (1) to (5).

(1) In a resin-molded body for a surface-mounted light-emitting device that has a recess for mounting an optical semiconductor element, and at least a part of the recess is a molded body of a white thermosetting composition.
The light reflectance of 460 nm of the resin cured product obtained by heat-pressing and curing the white thermosetting composition is 80% or more,
In the heat and pressure molding using a mold subjected to surface coating or surface plating treatment, the white thermosetting composition is used, and the white thermosetting composition is used so that the number of continuous molding that does not require mold recoating is 10,000 or more. The thermosetting composition is (A) a siloxane compound having two or more alkenyl groups bonded to a silicon atom in one molecule, and (B) organosilicon having two or more hydrogen atoms bonded to a silicon atom in one molecule. A resin molded article for a surface-mount light-emitting device, comprising as an essential component a composition, (C) a white pigment, (D) an inorganic filler, (E) a curing catalyst, and (F) a reaction control agent.

  (2) The resin molded body for a surface-mounted light-emitting device according to (1), wherein the white pigment (C) is zinc oxide.

  (3) The surface according to (1) or (2), wherein the component (A) is represented by an average composition formula (I) and has a weight average molecular weight (Mw) of 30,000 or more. Resin molded body for mounting type light emitting devices.

(R ¹ SiO _3/2 ) _d (R ¹ ₂ SiO) _e (R ¹ ₃ SiO _1/2 ) _f (I)
(R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group, provided that 0.05 to 45 mol% of the group represented by R ¹ is an alkenyl group, and d, e and f are d / (D + e + f) = 0.65 to 1, e / (d + e + f) = 0 to 0.35, f / (d + e + f) = 0 to 0.05
(4) The component (B) has at least two silicon-bonded hydrogen atoms in one molecule, and 0.5 to 3.0 silicon-bonded hydrogen atoms per alkenyl group in the component (A). The resin molded product for a surface-mounted light-emitting device according to any one of (1) to (3).

  (5) An optical semiconductor device having the resin molded body for a surface-mounted light-emitting device according to (1) to (4) and an optical semiconductor element mounted on the resin molded body for the surface-mounted light-emitting device.

  ADVANTAGE OF THE INVENTION According to this invention, the surface mount type light-emitting device using the resin molded object for surface mount type light-emitting devices using this can be provided using the white thermosetting composition excellent in continuous moldability and light reflectivity. .

It is sectional drawing which shows typically the structure of one Embodiment of the resin molding which concerns on this invention. It is sectional drawing which shows typically the structure of other embodiment of the resin molding which concerns on this invention. It is sectional drawing which shows typically the structure of other embodiment of the resin molding which concerns on this invention. It is a perspective view which shows typically the structure of other embodiment of the resin molding which concerns on this invention. FIG. 5 (a) is a top view, FIG. 5 (b) is a partially enlarged top view, and FIG. 5 (c) is a drawing schematically showing the structure of the resin molded body obtained by the method for producing a resin molded body according to the present invention. ) Is a partially enlarged sectional view.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Resin molding for surface mount type light emitting device]
A resin molded body for a surface-mounted light-emitting device according to the present invention (hereinafter simply referred to as “resin molded body” unless otherwise specified) is formed by integrally molding a cured resin body and a plurality of leads, and the plurality of leads are exposed at the bottom. It has a recessed part.

  FIG. 1 is a cross-sectional view schematically showing a configuration of a resin molded body 1 according to an embodiment of the present invention. The resin molded body 1 includes a first lead 10 and a second lead 11 as a plurality of leads, and a resin cured body 12, and has a recess 13. Furthermore, the first lead 10 and the second lead 11 are exposed on at least a part of the side surface in the thickness direction of the resin molded body 1. The resin molded body 1 of the present embodiment has a thin plate shape with a planar shape that is substantially square and has a thickness, and has a recess 13 that has a substantially circular opening at the center. The concave portion is for mounting an optical semiconductor element, and at least a part of the concave portion forms a resin molded body for a surface-mounted light-emitting device made of a molded body of a white thermosetting composition.

  The first lead 10 and the second lead 11 are a pair of positive and negative, are arranged in parallel so as to be separated from each other, and are integrated to form a frame unit (not shown). A lead frame is configured by arranging a plurality of frame units in parallel in the vertical and horizontal directions and integrating them. The lead frame can be manufactured by punching or etching a thin metal plate. The lead frame is formed using a metal material that is a good electrical conductor. Although it does not specifically limit as such a metal material, For example, iron, phosphor bronze, a copper alloy etc. are mentioned.

  The surface of the lead may form a plating layer. Thereby, the reflectance of the light emitted from the light emitting element can be further increased.

  Examples of the plating material include gold, silver, copper, and aluminum. For example, when the plating layer is made of silver, the film thickness is not particularly limited, but is preferably 0.5 μm to 20 μm, and more preferably 1 μm to 15 μm.

  Further, the concave opening 12c of the resin cured body 12 and the inner wall surface 13b of the concave 13 obtained by pressure-molding and post-curing the white thermosetting composition have a spectral reflectance at 460 nm of 80% or more. By using such a cured resin body 12, the reliability when the resin molded body 1 is used in a surface-mounted light emitting device is significantly improved.

  It should be noted that the surface treatment method of the mold used in the pressure molding as described above, particularly the transfer molding method, specifically the coating and surface plating treatment, and the state requiring the mold recoating will be described in detail later. To do.

[White thermosetting composition]
A white thermosetting composition that gives a resin cured body for reflecting light emitted from a light emitting element includes (A) a siloxane compound having two or more alkenyl groups bonded to a silicon atom in one molecule, and (B) a silicon atom. An organic silicon composition having two or more hydrogen atoms bonded to 1 in a molecule, (C) a white pigment, (D) an inorganic filler, (E) a curing catalyst, and (F) a reaction control agent are contained as essential components. Hereinafter, each component will be described in detail.

<(A) Siloxane compound having two or more alkenyl groups bonded to silicon atoms in one molecule>
(A) component raise | generates addition reaction by the following (B) component and hydrosilylation reaction, and gives hardened | cured material. The molecular structure of the component (A) is not particularly limited, and may be any of linear, branched, three-dimensional network, cyclic, and the like. When the component (A) has a molecular chain terminal, the alkenyl group bonded to the silicon atom is bonded to both of the molecular chain terminal and the molecular chain non-terminal silicon atom. May be. The component (A) can be used alone or in combination of two or more.

  Examples of the component (A) include alkenyl group-containing organopolysiloxanes represented by the following average composition formula (I) and having a weight average molecular weight (Mw) of 30,000 or more.

(R ¹ SiO _3/2 ) _d (R ¹ ₂ SiO) _e (R ¹ ₃ SiO _1/2 ) _f (I)
(R ¹ is independently of each other an unsubstituted or substituted monovalent hydrocarbon group, provided that 0.05 to 45 mol% of the group represented by R ¹ is an alkenyl group, and d, e and f are d /(D+e+f)=0.65 to 1, e / (d + e + f) = 0 to 0.35, f / (d + e + f) = 0 to 0.05.
In the above formula (I), R ^{1 s} are each independently an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group, cycloalkyl groups such as cyclohexyl group, phenyl group, tolyl group, xylyl group, and naphthyl group. Aryl groups such as benzyl groups, aralkyl groups such as benzyl groups, phenylethyl groups and phenylpropyl groups, alkenyl groups such as vinyl groups, aryl groups, propenyl groups and isopropenyl groups, and some or all of the hydrogen atoms of these groups Substituted with a halogen atom such as fluorine, bromine or chlorine, a cyano group, or the like, for example, a halogen-substituted alkyl group such as a chloromethyl group, a chloropropyl group, a bromoethyl group or a trifluoropropyl group, a cyanoethyl group, or the like.

It is preferable that at least one of R ¹ is an alkenyl group, and 0.05 to 45 mol%, particularly 2 to 40 mol%, particularly 5 to 30 mol% of the group represented by R ¹ is an alkenyl group. . If the alkenyl group is less than 0.05 mol%, there are few crosslinking points, and molding defects such as insufficient strength and releasability are likely to occur. If it exceeds 45 mol%, the cured product becomes brittle and scorch occurs during molding, resulting in poor filling. The moldability will be reduced. As the group other than the alkenyl group, 20 to 99.5 mol%, preferably 30 to 80 mol%, more preferably 40 to 60 mol% of the group represented by R ¹ is a methyl group. It is preferable because it is excellent in ease, UV resistance, and yellowing characteristics. Further, a phenyl group may be used in combination for the purpose of imparting flexibility and strength. Other R ¹ is preferably an alkyl group such as an ethyl group or a propyl group, or a cycloalkyl group such as a cyclohexyl group.

  In the above formula (I), d, e and f represent the molar ratio of each siloxane unit, d / (d + e + f) = 0.65-1, e / (d + e + f) = 0-0.35, f / (d + e + f ) = 0 to 0.05, preferably d / (d + e + f) = 0.75 to 0.95, e / (d + e + f) = 0.05 to 0.25, f / (d + e + f) = 0 The component (A) is an organopolysiloxane having a resin structure that requires a T unit structure.

  The weight average molecular weight (Mw) of the organopolysiloxane is 30,000 or more, preferably 50,000 to 1,000,000, more preferably 60,000 to 90,000. When the weight average molecular weight is 30,000 or less, the strength of the cured product is weak, the molded product becomes brittle, and the mass production moldability is poor.

Component (A) is generally a combination of T units (R ¹ SiO _3/2 ), and optionally D units (R ¹ ₂ SiO _2/2 ) and / or M units (R ¹ ₃ SiO _1/2 ). Can be expressed as When the component (A) is represented by this notation, the ratio of the number of moles of T units to the total number of moles of all siloxane units is 65 mol% or more, preferably 75 mol% or more. If the T unit is less than 65 mol%, the overall balance of hardness, adhesion, appearance, etc. may be lost. The balance may be D units or M units, and the total number of moles of D units and M units is preferably 35 mol% or less.

  The component (A) can be obtained as a hydrolytic condensate of organosilane represented by the following general formula (II).

R ¹ _n SiX _4-n (II)
In the formula, X is a halogen atom such as chlorine or an alkoxy group having 1 to 4 carbon atoms. From the viewpoint of obtaining a solid organopolysiloxane, X is preferably a halogen atom, particularly a chlorine atom. n is 1, 2 or 3. R ¹ is as described above.

  Examples of the organosilane represented by the above formula (II) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrichlorosilane, and vinyltrichlorosilane. Methoxysilane, vinyltriethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldi Ethoxysilane, trimethylmonochlorosilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, dimethylphenylmonochlorosilane Dimethylphenyl monomethoxy silane, dimethyl phenyl mono silane, dimethyl vinyl monochlorosilane, dimethyl vinyl monomethoxy silane, dimethyl vinyl mono-ethoxysilane and the like.

  The organosilane may be hydrolyzed and condensed by a known method. For example, an acid catalyst such as acetic acid, hydrochloric acid or sulfuric acid, or an alkali catalyst such as sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide is present. It is preferable to carry out below.

  Further, as the component (A), a cyclic siloxane compound having the following structure can also be used.

(In the formula, r is an integer of 3 to 20, preferably 3 to 8. R ¹ is as described above.)
Specific examples of the organopolysiloxane represented by the average composition formula (I) include those represented by the following formula (III).

(PhSiO _3/2 ) _0.33 (MeSiO _3/2 ) _0.42 (Ph ₂ SiO) _0.55 (MeViSiO) _0.20 (Me ₃ SiO _1/2 ) _0.01 (III)
(In the formula, Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group.)
<(B) Organosilicon composition having two or more hydrogen atoms bonded to silicon atoms in one molecule>
The component (B) acts as a crosslinking agent, and a cured product is formed by the addition reaction of the SiH group in the component with the alkenyl group in the component (A).

  The component (B) may be any component as long as it has two or more SiH groups in one molecule, and is particularly represented by the following average composition formula (IV), preferably at least two SiH groups, preferably What has 3 or more is good, for example, what has 2-500 pieces, Preferably 3-300 pieces is mentioned.

H _a (R ² ) _b SiO _{(4-ab) / 2} (IV)
(In the formula, R ² is each independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ (b ≦ 2 and 0.8 ≦ a + b ≦ 3)

Here, R ² is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, which does not contain an aliphatic unsaturated bond. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group, cycloalkyl groups such as cyclohexyl group, phenyl group, tolyl group, xylyl group, and naphthyl group. Aryl groups such as aralkyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups, etc., and some or all of the hydrogen atoms of these groups substituted with halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc. Examples thereof include halogen-substituted alkyl groups such as chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, and cyanoethyl group. Preferably, it is preferable to use a methyl group or a methyl group and a phenyl group as R ² because of excellent reactivity with the alkenyl group in the component (A).

  In the above formula (IV), a and b are numbers satisfying 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.8 ≦ b ≦ 2, and 1 ≦ a + b ≦ 2.7. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

As the component (B), tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclo Tetrasiloxane, Trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, Trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, Dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends, Dimethylhydrogensiloxy at both ends Capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group capped methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group Chain methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane _{copolymer, (CH} 3) consists of 2 _{HSiO 1/2} units and _{SiO 4/2} units, copolymers _{composed, (CH} 3) 2 _{HSiO 1/2} units and SiO _Examples thereof include a copolymer composed of _4/2 units and (C ₆ H ₅ ) SiO _3/2 units.

  Moreover, a compound as shown by the following structure can also be used.

  Moreover, a polycyclic hydrocarbon group containing organosilicon compound as shown by the following structure can also be used.

(In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 6, more preferably 1 to 3, and n is 1 to 50, preferably 1 to 30. , More preferably an integer of 1 to 20.)

  The molecular structure of the component (B) may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule is 3 to 1,000, preferably 3 300 is good.

  The amount of the component (B) is sufficient to give 0.5 to 3.0, preferably 0.75 to 2.0, SiH groups per alkenyl group in the component (A). And it is sufficient. If the SiH group is less than 0.5, the crosslink density is low, and the resulting cured product has low heat resistance and mechanical strength. Further, there is a problem that moldability is deteriorated due to the slow crosslinking of the silicone resin and foaming. If the number of SiH groups exceeds 3.0, dehydrogenation reaction is liable to occur and this may cause fine foaming.

<(C) White pigment>
A white thermosetting composition contains (C) component. The component (C) 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 (C), for example, zinc oxide, magnesium oxide, antimony oxide, zirconium oxide, strontium oxide, niobium oxide, boron nitride, barium titanate, zinc sulfide, barium sulfate, inorganic hollow And particles. Examples of the inorganic hollow particles include sodium silicate glass, aluminum silicate glass, borosilicate soda glass, and shirasu.

  The Mohs hardness of typical white pigments is zinc oxide (4-5), titanium oxide (7-7.5), magnesium oxide (6.5), antimony oxide (3), zirconium oxide (6), strontium oxide. (6.5-7), niobium oxide (5-6), boron nitride (9), barium titanate (7), zinc sulfide (3.5-4), barium sulfate (3.5), magnesium carbonate ( 3.5-4), and in order to suppress mold deterioration during continuous molding, it is better that the Mohs hardness is low. The preferred Mohs hardness is 6.5 or less, the more preferred Mohs hardness is 6 or less, more preferably 5 or less.

  As the component (C), oxidation is easy because it is easy and easy to handle, high in cost, high light reflectance, preferable Mohs hardness, low degree of mold deterioration, and high continuity molding. Zinc is preferred. On the other hand, as described in non-patent literature (Materials, Vol. 22, 1973, No. 23, pp 706-708), it is known that when mechanochemical stress is applied to zinc oxide, the color changes to yellow. . Therefore, when blending with the resin composition, it is necessary to mix under appropriate conditions.

  As zinc oxide, zinc white, activated zinc white, zinc oxide one kind powder, zinc oxide two kinds powder, zinc oxide three kinds powder, zinc oxide whisker and the like can be preferably used. Among these, zinc oxide single powder can be preferably used because it is low in impurities and inexpensive and can be obtained in large quantities.

  The average particle size of the component (C) is not particularly limited, and various types are used, but the obtained resin cured product tends to have high spectral reflectance, and the white thermosetting composition tablet becomes harder. From the viewpoint, 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 white thermosetting composition will be described later. On the other hand, from the viewpoint of high fluidity of the white thermosetting composition, 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.

  The component (C) may be subjected to a surface treatment. In the surface treatment of the component (C), the surface of the component (C) 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.

  (C) 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 zinc oxide. Can do. In addition, there are various methods such as a liquid phase method and a gas phase method.

  In these, it is preferable to process with organosiloxane from a viewpoint that the spectral reflectance of the resin cured body obtained is high, and heat resistance and light resistance become favorable. In addition, by including an organosiloxane-treated zinc 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 after long-term use.

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.

  Moreover, (C) component may be surface-treated with the 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. Zinc 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 further preventing collapse of particle shape. By subjecting the component (C) to a surface treatment with an inorganic compound, the affinity with each component contained in the white thermosetting composition is improved, and the dispersibility of the component (C) with respect to the white thermosetting composition is improved. It is considered that the strength of the cured body is improved.

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

<(D) Inorganic filler>
The component (D) of the present invention is an inorganic filler. (D) component has the effect of making the intensity | strength and hardness of the resin cured body obtained high, or reducing a linear expansion coefficient.

  As the inorganic filler of component (D), 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 adhesiveness 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-methacryloxypropyltriethoxysila, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups 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 white thermosetting composition used in the present invention, and reacted in the white thermosetting composition or a partial reaction product of the white thermosetting composition. And a method of generating an inorganic filler. 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 that the balance of physical properties such as moldability and electrical characteristics is good, fused silica is preferable, from the viewpoint that the thermal conductivity of the cured resin body tends 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. 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 molded body tends 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 (D) component is not specifically limited, It is preferable that the quantity of (D) component which occupies for the whole white thermosetting composition is 50 weight% or more. When the amount of the component (D) is small, it is difficult to obtain the effect of improving the strength and hardness, the effect of reducing the linear expansion coefficient, and the like. The total amount of component (C) and component (D) is not particularly limited, but the total amount of component (C) and component (D) in the entire white thermosetting composition is preferably 70% by weight or more. 80% by weight or more is more preferable.

<(E) Curing catalyst>
The (E) component curing catalyst is used to accelerate the addition reaction between the (A) component and the (B) component. Although a well-known thing can be used as a curing catalyst, it is preferable to use platinum or a platinum compound. Typical platinum compounds include platinum black, secondary platinum chloride, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, aldehydes, vinyl siloxanes, or acetylene alcohols.

  The amount of the platinum metal-based catalyst may be an amount effective as a catalyst, and is usually from 0.1 to 1,000 ppm, preferably from 1 to 1,000 ppm relative to the total amount of the component (A) and the component (B) as a platinum metal equivalent amount. Used in the range of 500 ppm.

<(F) Reaction control agent>
(F) A component should just be used as a reaction control agent which controls the cure rate of a white thermosetting composition, and a well-known thing may be used. For example, alkyne alcohols represented by acetylene alcohol, vinyl siloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, nitrogen atom-containing compounds such as benzotriazole, and the like. Illustrated.

  The compounding amount of the reaction control agent may be an amount (catalyst amount) that is suitable for the molding process in combination with the curing catalyst of the component (E). In particular, when using a white thermosetting composition in the form of a one-component tablet excellent in mass productivity to form a resin molded body for a surface mount light emitting device, the component (E) and the component (F) are white thermosetting compositions. The pot life (room temperature) of the product is 8 hours or more, preferably 12 hours or more, more preferably 24 hours or more, and the spiral flow retention when left standing at room temperature for the above time or more is preferably 70% or more, preferably 80 It is preferable to use it in a combination and usage amount so as to be at least%.

  The white thermosetting composition can contain a component (G). Component (G) is a metal soap, and is added to improve moldability including mold releasability of the white thermosetting composition.

  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 viewpoint of easy availability, high safety, and high industrial feasibility, and particularly from the viewpoint of economy, calcium stearate and stearic acid. Most preferred is one or more selected from the group consisting of magnesium and zinc stearate.

  The addition amount of the metal soap is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.025 to 4 parts by weight with respect to 100 parts by weight of the whole white thermosetting composition. More preferably, it is 0.05 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 white thermosetting composition. 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.

  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 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Parts 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 used as the adhesion improver include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis ( 4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene 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, Roh allyl diglycidyl isocyanurate, 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.

  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 (ethyl) Acetoacetate), aluminum chelate M (manufactured by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate) and other aluminum chelates It is done. 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 (V) and (VI) can be preferably used.

B (OR ³ ) ₃ (V)
B (OCOR ³ ) ₃ (VI)
(Wherein R ³ 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.

  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.

  In the white thermosetting composition of the present invention, the above silane compound can be used. 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 carboxylic acid esters, 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 white thermosetting composition can also 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 white thermosetting compositions 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.

  The mold release agent is used for improving the mold release property at the time of molding the white thermosetting composition. 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.

  Other white thermosetting compositions include coloring agents, flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, and thixotropic properties. Imparting agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic Agents, radiation shielding agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, thermal conductivity-imparting agents, physical property modifiers, etc. are added within a range not to impair the purpose and effect of the present invention. can do.

  Furthermore, various thermoplastic resins can be added to the white thermosetting composition 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 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 from the viewpoint that the compatibility with the component (A) and / or the component (B) tends to be good, the number average molecular weight is preferably 10,000 or less, more preferably 5000 or less. 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. Although the molecular weight distribution is not particularly limited, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and still more preferably 1 from the viewpoint that the white thermosetting composition tends to have low viscosity and good moldability. 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 white thermosetting composition, 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 white thermosetting composition has a low viscosity and tends to have good moldability, The coefficient of variation is preferably 10% or less.

  Furthermore, you may mix the particle | grains of other thermosetting resin in a white thermosetting composition. The thermosetting resin particles can be obtained by curing and pulverizing the thermosetting resin. When the thermosetting resin particles are used dispersed in the white thermosetting composition, 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 from the viewpoint that the white thermosetting composition 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.

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

  The white thermosetting composition 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 white thermosetting composition 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. Is more preferable. 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 set temperature, and about 100 mg of the white thermosetting composition is placed on the aluminum foil, and the time until gelation is measured to obtain the gelation time.

  Viewpoint that in the process of producing a resin molded body using a white thermosetting composition, generation of voids in the white thermosetting composition and out-of-process problems due to outgas from the white thermosetting composition are unlikely to occur. Therefore, the weight loss during curing is preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably 1% by weight or less. The weight reduction during curing was performed by increasing the temperature of a sample (white thermosetting composition) 10 mg from room temperature to 150 ° C. at a rate of 10 ° C./min using a thermogravimetric analyzer. As a percentage of the initial weight.

  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.

The light reflectance at a wavelength of 460 nm on the surface of the molded product obtained by curing the white thermosetting composition is 80% or more, preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more.
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 arbitrary four locations (measurement area 0.1 mmφ) on the concave opening surface of the resin molded body was adopted as the measurement value at each wavelength.

  The light reflectance of the surface can also 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 460 nm using a spectrophotometer provided with an integrating sphere for the obtained molded body.

  The white thermosetting composition desirably has a warped resin cured body of ± 1.0 mm or less when formed into a package by molding on one side of a lead frame for a light emitting element.

  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.

  The white thermosetting composition can be a tablet. 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), and (E) for curing the (A) and (B) components. Component (F) and component (F) are both powder (C) and component (D). In such a tablet, the viscosity of the component (A) and the component (B) decreases at a high temperature, so that the whole white thermosetting composition can flow. Further, when the heating is continued, the curing reaction proceeds to a desired shape. It is possible to mold.

  The molding method is not particularly limited, and a molding method such as transfer molding or compression molding, which is generally used for molding a white thermosetting composition, can be used. When using these molding methods, if the thermosetting resin composition that is the raw material is in the form of a paste or clay, it will not be possible to maintain a constant shape, and it will be attached, integrated, or deformed. The 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 proportion of the component (B) and the component (C) in the tablet (hereinafter sometimes referred to as “filling rate”) is preferably 70 to 95% by weight. The distribution of the component (B) and the component (C) in the filling rate is not particularly limited and can be freely set. When the filling rate is less than 70% by weight, the thermal expansion coefficient of the obtained resin cured body is increased, which causes a problem of dimensional change of the resin molded body, and the obtained white thermosetting composition is a hard paste or There is a problem that it becomes clayy and cannot be tableted. When the filling rate exceeds 95% by weight, the viscosity of the white thermosetting composition at a high temperature becomes too high and the moldability is lowered, and the resulting tablet becomes too brittle.

[Molding method]
Various methods are used as the molding method of the resin-molded body for a surface-mounted light-emitting device in the present invention. For example, various molding methods generally used for thermosetting resins such as thermoplastic resins, epoxy resins, and silicone resins, such as injection molding, transfer molding, RIM molding, casting molding, press molding, compression molding, and the like 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 increase the 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 to carry out the reaction while raising the temperature in a multistage manner or continuously, as compared with the case where the temperature is constant, in that a uniform cured product 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 product without 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.

[Surface treatment of molding dies]
The surface shape of the molding die for the resin molded body according to the present invention is plated or coated with a component different from the die material for the purpose of improving wear resistance, preventing corrosion, and improving mold release properties. Can do. A hard chrome plating having a thickness of 5 μm or less is formed on the surface of the mold, and a fluororesin having a thickness of 2 μm or less is coated on the plating. By providing the hard chrome plating layer under the fluororesin, the mold release effect can be maintained for a long time. The fluororesin is preferably PTFE or PEF. In addition, forming a hard chromium plating layer and a fluororesin film by a vacuum vapor deposition method is also effective in improving mold release. The mold surface treatment is not limited to the above method, and the same effect can be expected with DLC (diamond-like carbon). This DLC decomposes hydrocarbon gas by arc discharge plasma in a high vacuum, and forms a film by causing ions and excited molecules in the plasma to be electrically accelerated and collided with energy. The film has a dense amorphous structure, the surface is very smooth, and no crystal grain boundary is generated. Therefore, the film exhibits excellent characteristics such as a low coefficient of friction, wear resistance, and releasability.

[Mold cleaning method]
As a mold cleaning method at the time of molding, a commercially available mold cleaning sheet such as a melamine resin or a tablet can be suitably used.

[Continuous formability]
There is no physical deterioration of the mold surface, such as scratches on the mold surface, plating, or peeling of the coating, and defects in the molded product (surface cracks or voids) occur, the degree of sticking of the molded product to the mold, the mold surface The number of times of continuous molding without removing the mold from the molding machine is preferably 10,000 times or more, more preferably 50,000 or more. More preferably, it is 100,000 times or more.

[Mold recoat]
When physical deterioration such as peeling or scratching of the mold surface coating layer or plating layer is observed, mold recoating, that is, resurface treatment is required. Although there is no limitation on the method for resurface treatment of the mold, the already adhered film is removed using a chemical solution (film removal), the base metal is exposed, and coating or plating is again performed thereon. In this way, the mold can be used repeatedly.

[Surface mount type light emitting device]
The surface mount light emitting device of the present invention (hereinafter simply referred to as “light emitting device”) has a resin-cured body and a plurality of leads integrally formed, and has a recess in which the plurality of leads are exposed at the bottom. A light emitting element mounted on the bottom of the recess and connected to a plurality of leads so as to be energized, and a transparent resin layer for sealing the light emitting element are provided. A plurality of light emitting elements may be mounted on the bottom of the recess of the resin molded body.

  That is, the light-emitting device of the present invention is the same as a conventional surface-mounted light-emitting device, except that a cured resin body and a plurality of leads are integrally formed as a resin molded body, and a recess is exposed at the bottom. Can have a configuration.

  Here, 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 emitting 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.

  Moreover, as an adhesive for adhering the light emitting element to the bottom of the concave portion of the resin molded body, for example, silver paste, eutectic solder (AuSn, AuGe, AuSi, etc.), gold bump, or the like is used. The melting point of the eutectic solder is preferably in the range of 200 ° C to 350 ° C. When a high-power LED is used, the pn junction temperature rises, so it is preferable to use eutectic solder, gold bumps, or the like that can obtain stable joint strength at high temperatures. For example, the light emitting element forms an adhesive layer on the surface of the lead having the plating layer at the bottom of the concave portion of the resin molded body (at this time, the lead and the adhesive layer are electrically connected) and emits light thereon. The element is mounted and fixed on the lead surface by heating and melting. The adhesive layer can be formed by a general technique such as printing of paste material, dispensing, preform, foil molding, metallization, ball molding, and the like. By providing the adhesive layer made of metal, the heat dissipation of the light emitting device can be improved.

  Moreover, the flatness of the region bonded to the light emitting element on the lead surface is preferably 0.001 to 50 μm. Flatness is expressed as the height of the center of the measurement region with respect to the reference surface when a surface including any three corners of the region to be measured is used as the reference surface. If the flatness is less than 0.001 μm, the surface of the plating layer formed on the lead surface becomes too smooth, the adhesion strength between the plating layer and the adhesive layer is lowered, and the adhesive layer tends to be easily peeled off. is there. Moreover, when flatness exceeds 50 micrometers, the junction area of a plating layer and an adhesive bond layer will become small. As a result, the heat dissipation of the light emitting device tends to decrease, and the bonding strength between the light emitting element and the lead frame tends to decrease. 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.

  For example, the transparent resin layer is prepared by injecting a liquid transparent resin into a cup, cavity, package (resin molded body) recess, or the like in which a light emitting element is arranged at the bottom by a dispenser or other method and curing it by heating or the like. Alternatively, the solid or high-viscosity liquid composition may be flowed by heating or the like, and injected into the package recess as described above, and further cured by heating or the like. Alternatively, the transparent resin can be formed by transfer molding, injection molding, or insert molding.

  Further, instead of the transparent resin, a lens may be mounted in the concave portion after the light emitting element of the resin molded body is mounted. 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. .

[Method for producing white thermosetting composition]
The white thermosetting composition of the present embodiment can be obtained by uniformly dispersing and mixing the various components described above, and means and conditions thereof are not particularly limited. As a general method for producing a white thermosetting composition, various components of a predetermined blending amount are sufficiently uniformly stirred and mixed with a mixer, etc., and then mixed with a mixing roll, an extruder, a kneader, a roll, an extruder, etc. And kneading using a planetary mixer that combines rotation and revolution, and cooling and pulverizing the obtained kneaded product.

  The kneading conditions may be appropriately determined depending on the type and blending amount of each component. For example, kneading is preferably performed at 15 to 100 ° C. for 5 to 40 minutes, and kneading at 20 to 100 ° C. for 10 to 30 minutes is more preferable. preferable. When the kneading temperature is less than 15 ° C., it becomes difficult to knead each component and the dispersibility tends to decrease. When the kneading temperature exceeds 100 ° C., the high molecular weight of the thermosetting resin proceeds, and thermosetting during kneading. The resin may be cured. Further, if the kneading time is less than 5 minutes, a sufficient dispersion effect may not be obtained. If the kneading time exceeds 40 minutes, the thermosetting resin may increase in molecular weight, and the thermosetting resin may be cured.

[Preparation of white thermosetting composition tablet]
The manufacturing method of the tablet used in the molding method of the present invention is not limited as long as the finished shape is cylindrical. For example, in a method of extrusion molding a thermosetting resin composition comprising a thermosetting resin and a filler, a cylindrical strand is discharged and cut at equal intervals to obtain a cylindrical tablet. Examples include a method of adding a predetermined amount of a thermosetting resin composition to a cylindrical concave jig and pushing the cylindrical convex jig to obtain a cylindrical tablet. These may be manual or may be automated.

[Molding method using thermosetting resin composition tablet]
The molding method of the present invention is performed using a generally known transfer molding machine. Specifically, a tablet made of a thermosetting resin composition is inserted into a recess called a pot of a resin molding die provided in a transfer molding machine, and then the mold is closed to advance the injection plunger. By pressing and extruding the resin, the resin composition is injected into the mold cavity from the resin flow path, and molding is performed. Here, the process until the tablet is loaded in the pot for the resin mold is mainly automated, and for example, the tablet made for molding is a dedicated tablet. There are various methods such as loading directly into the mold pot via the transport device, and arranging the tablet array in the dedicated supply device after passing through the transport device and then loading into the mold pot. There is no limit to the method of loading into the mold pot. When the tablet side is directly gripped by the robot arm and loaded into the pot, or the tablet is pre-loaded in a cylindrical punched supply device, There are various methods such as a method of dropping the tablet from the supply device into the mold pot and loading it by carrying the whole to the upper portion of the mold pot and sliding the slit at the lower portion of the supply device. However, when this process is used, if the tablet is soft, it may be deformed during transport, and may not be regularly loaded into the supply device or the mold pot. In some cases, a predetermined amount of the tablet may not be loaded due to contamination of the transport device or the supply device or a part of the tablet adhering. For this reason, the tablet used in the present invention has a surface temperature adjusted between −40 ° C. and 10 ° C., so that the surface of the material becomes hard and the tackiness is improved, so that the tablet at the time of molding Stable production is possible without causing any troubles in transporting tablets and supplying tablets to the mold pots in the molding machine. When the surface temperature of the tablet is higher than 10 ° C., the resin composition on the surface of the tablet adheres to the tablet supply device or the transport device, and there is a tendency to cause dirt. Further, the case where the surface temperature is below the patent range is not preferable because it is over-spec and the utility cost for cooling the tablet becomes very high. Furthermore, the cylindrical tablet whose surface temperature is adjusted from −40 ° C. to 10 ° C. takes less than 2 minutes from when it is put into the tablet supply device or transport device until it is put into the mold pot inside the transfer molding machine. Preferably there is. When this time is exceeded, the tackiness of the tablet surface is lowered, and the resin composition on the tablet surface tends to adhere to the tablet supply device or the transport device, which may cause dirt. Therefore, it is important that the tablet used in the molding method of the present invention hardens its surface by cooling, that is, the strength falls within a specific range. Specifically, when the shape of the cylindrical tablet made of the white thermosetting resin composition is 13 mm in diameter and 20 mm in height, a load is applied from the upper surface of the tablet using a flat probe having a diameter of 13 mm, The maximum load when the tablet height is displaced by 5 mm is preferably 3.5 kgf or more from the viewpoint of tablet shape retention. When the maximum load is less than 3.5 kgf, there is a tendency to cause deformation at the time of tablet supply or conveyance.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Synthesis Example 1)
1,057.7 parts by weight of phenyltrichlorosilane, 854.3 parts by weight of methyltrichlorosilane, 180.7 parts by weight of diphenyldichlorosilane, 402.9 parts by weight of methylvinyldichlorosilane, 216 parts by weight of isopropyl alcohol, toluene 1 The mixture consisting of 567 parts by mass was vigorously stirred in 6,535 parts by mass of water and added dropwise over 60 minutes. The mixture was further stirred for 60 minutes and then washed with water until neutrality. After washing with water, a toluene solution having a siloxane concentration of 25% by mass was added, 0.42 parts by mass of potassium hydroxide was added, and the mixture was heated to reflux for 5 hours for polymerization. Next, 13.8 parts by mass of trimethylchlorosilane was added and neutralized by stirring at room temperature for 60 minutes. After neutralization, filtration was performed to distill off toluene, thereby obtaining 1110 parts by mass of colorless and transparent organopolysiloxane represented by the following average composition formula (A-1) (weight average molecular weight is 60,000). The molar ratio of each siloxane unit contained in the obtained organopolysiloxane is T unit (d) 74 mol%, D unit (e) 25 mol%, M unit (f) 1 mol%, The proportion of vinyl groups in the groups was 10 mol%.

(PhSiO _3/2 ) _0.33 (MeSiO _3/2 ) _0.42 (Ph ₂ SiO) _0.05 (MeViSiO) _0.20 (Me ₃ SiO _1/2 ) _0.01 (A-1)
(In the formula, Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group).

(Examples 1-2, Comparative Examples 1-2)
According to the blending ratio (parts by mass) shown in Table 1, each component is blended, and after the resulting white curable composition mixture is stretched with a round bar-shaped jig, it is folded and stretched again. Repeatedly homogenized. In the case of flakes or powders, they were crushed with a mortar and made uniform. Or it knead | mixed using the electric cutter roller (feed rate 1.3min / mm, Oshima Kogyo Co., Ltd. make, ER-440).

<Tablet preparation method>
The prepared white curable resin composition was compressed by 0.39 MPa using a tablet manufacturing jig made of a metal pestle and mortar having a diameter of 13 mm, and the amount charged was adjusted to a height of 20 mm.
The obtained tablets were stored frozen (−20 ° C.), refrigerated (5 ° C.), and kept constant (23 ° C.) according to the evaluation.

<Molding method of cured resin>
The flat plate used as the resin hardening body of 50 (mm) x 50 (mm) x 1 (mm) was produced using the transfer molding 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 a spray type fluorine-based mold release agent (Daikin Kogyo Co., Ltd .: Die Free GA-7500) is applied to the mold surface. Molded. 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.

<Evaluation of continuous formability>
Continuous molding was performed by the transfer molding method described above. At that time, the occurrence of defective molded products (surface cracks and voids), the degree of sticking of the molded product to the mold, and the degree of dirt on the mold surface (particularly clouding / whitening) were evaluated according to the number of moldings. When these defects were not recovered by normal mold cleaning, the entire mold surface was observed with a real microscope or a scanning microscope. At this time, scratches on the mold surface of 1 μm or more, occurrence of plating or peeling of the coating were observed, and the number of molding shots at the time when physical deterioration of the mold surface was observed was taken as the end point of continuous molding. Observation of the mold surface defect was carried out using a stereo microscope (trinocular zoom stereo microscope, Mage Techno EMZ-8TR) and a scanning electron microscope (JSM-6060LA (manufactured by JEOL Ltd.)).

<Evaluation of white thermosetting composition>
The spectral reflectance of the resin cured body of the flat plate obtained by the above molding was measured as a spectral reflectance at a wavelength of 400 nm to 700 nm (20 nm interval) using a minute surface spectral color difference meter (VSS400 manufactured by Nippon Denshoku Industries Co., Ltd.), 460 nm. The value of was acquired as data.

* 1 to 8 in Table 1 are as follows.
* 1: Organopolysiloxane synthesized in Synthesis Example 1 (A-1)
* 2: Organosilicon compound (B-1) represented by the following formula

* 3: Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., specific gravity 5.6, average particle size 0.6 μm, trade name: 1 type of zinc oxide)
* 4: Titanium oxide (produced by Ishihara Sangyo Co., Ltd., rutile type, specific gravity 4.2, chlorine method, surface organic: AI, Si, polymethylhydrogensiloxane, average particle size 0.21 μm, ratio of particles of 12 μm or less 100, Product name: Thai Bake PC-3)
* 5: Magnesium carbonate (Wako Pure Chemical Industries, Ltd., specific gravity 2.95)
* 6: Fused spherical silica (manufactured by Tatsumori Co., Ltd., specific gravity 2.2, average particle size 24.8 μm, ratio of particles of 12 μm or less: 28%, trade name: MSR-2212-TN)
* 7: Chloroplatinic alcohol solution with a platinum content of 2% by mass * 8: 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane

  As shown in Table 1, the white thermosetting compositions obtained in Examples 1 and 2 were white and showed high reflectivity, and were excellent in continuous moldability. On the other hand, the white thermosetting compositions obtained in Comparative Examples 1 and 2 had problems in reflectance and continuous moldability. According to the present invention, by selecting an appropriate white pigment, a white thermosetting composition excellent in continuous moldability is provided, and a resin molded body for a surface-mounted light-emitting device and an optical semiconductor device with high productivity and high reflectance are obtained. Can be provided.

1, 2, 3, 4 Resin molding 10 First lead 10a First inner lead part 10b First outer lead part 11 Second lead 11a Second inner lead part 11b Second outer lead part 12, 14, 16, 17 Resin Hardened body 12a Reflecting portion 12b Insulating portion 12c Recess opening surface 13, 15 Recess 13a Bottom portion 13b Inner wall surface

Claims (6)

It has a recess for mounting an optical semiconductor element, and at least a part of the recess is a method for producing a resin-molded body for a surface-mounted light-emitting device comprising a molded body of a white thermosetting composition,
Including a step of transferring a white thermosetting composition and then curing to obtain a resin cured body,
The resin cured body has a light reflectance of 460 nm of 80% or more,
The white thermosetting composition has a number of continuous moldings of 10,000 or more which does not require mold recoating in transfer molding using a mold subjected to surface coating or surface plating.
The white thermosetting composition is (A) a siloxane compound having two or more alkenyl groups bonded to silicon atoms in one molecule, and (B) an organic compound having two or more hydrogen atoms bonded to silicon atoms in one molecule. A silicon composition, (C) a white pigment, (D) an inorganic filler, (E) a curing catalyst, and (F) a reaction control agent, as essential components,
(A) component is average composition formula (I)
(R ¹ SiO _3/2 ) _d (R ¹ ₂ SiO) _e (R ¹ ₃ SiO _1/2 ) _f (I)
(R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group, provided that 0.05 to 45 mol% of the group represented by R ¹ is an alkenyl group, and d, e and f are d / (D + e + f) = 0.65 to 1, e / (d + e + f) = 0 to 0.35, f / (d + e + f) = 0 to 0.05
The weight average molecular weight (Mw) is 30,000 or more,
Surface mount type light emitting device resin characterized in that the Mohs hardness of component (C) is 6.5 or less and the amount of component (C) in the entire white thermosetting composition is 10% by weight or more. Manufacturing method of a molded object. The manufacturing method according to claim 1, wherein the component (C) is zinc oxide. (B) component is the following average composition formula (IV)
H _a (R ² ) _b SiO _{(4-ab) / 2} (IV)
(In the formula, R ² is each independently an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ (b ≦ 2 and 0.8 ≦ a + b ≦ 3)
The manufacturing method according to claim 1 or 2, wherein Component (B) is tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetra Siloxane, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, both ends dimethylhydrogensiloxy group Blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group blocked Le hydrogen diphenylsiloxane-dimethylsiloxane _{copolymer, (CH} 3) 2 _HSiO consisting _1/2 units and _{SiO 4/2} units, and copolymers _{thereof, (CH} 3) 2 _{HSiO 1/2} units and SiO _{4 / 2} unit and a copolymer comprising (C ₆ H ₅ ) SiO _3/2 unit,

as well as

(In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12, preferably 1 to 6, more preferably 1 to 3, and n is 1 to 50, preferably 1 to 30. , More preferably an integer of 1-20)
The production method according to claim 1, wherein the production method is selected from the group consisting of: The component (B) has at least two silicon-bonded hydrogen atoms in one molecule, and has 0.5 to 3.0 silicon-bonded hydrogen atoms per alkenyl group in the component (A). The manufacturing method according to any one of claims 1 to 4. The manufacturing method of an optical semiconductor device including the process of mounting an optical semiconductor element in the resin molding for surface mount type light-emitting devices obtained by the manufacturing method in any one of Claims 1-5.

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