JP6805546B2 - Thermosetting resin composition, cured product, substrate for mounting optical semiconductor element and its manufacturing method, optical semiconductor device, and printed wiring board - Google Patents

Description

The present invention relates to a thermosetting resin composition, a substrate for mounting an optical semiconductor device using the thermosetting resin composition, a method for manufacturing the same, and an optical semiconductor device.

Thermosetting resins are used in a wide range of applications because they exhibit various excellent properties derived from their unique crosslinked structure. As one of the applications, in recent years, an optical semiconductor device combining an optical semiconductor element such as an LED (Light Emitting Diode) and a phosphor has been used for outdoor displays and portable devices because of its advantages such as high energy efficiency and long life. It is applied to various applications such as liquid crystal backlights and in-vehicle applications, and its demand is expanding.

As a kind of optical semiconductor device, a surface mount type optical semiconductor device can be mentioned. Some surface-mounted optical semiconductor devices have an optical semiconductor element and a reflector (reflecting unit) provided so as to surround the optical semiconductor element. Patent Document 1 discloses a resin composition for a mounting package for storing an optical semiconductor device, which uses a silicone resin having a structure in which either a vinyl group or an allyl group and a hydrogen atom are directly bonded to a silicon atom. Has been done.

Japanese Unexamined Patent Publication No. 2009-21394

Members for mounting optical semiconductor devices using a thermosetting resin composition for light reflection are becoming smaller and smaller. However, when the wall surface and the bottom portion are made thinner as the size is reduced, the light emitted from the optical semiconductor element may be partially transmitted and the reflectance may be reduced.

The present invention has been made in view of the above circumstances, and is a thermosetting resin composition capable of forming a cured product having sufficient reflectance even if it is thin, and a photosemiconductor using the thermosetting resin composition. It is an object of the present invention to provide a member for mounting an element and an optical semiconductor device using the member.

The present invention relates to a thermosetting resin composition containing a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and hollow particles.

The refractive index of the voids of the hollow particles may be 1.0 to 1.1. Further, the hollow particles may contain particles having a particle size of 0.1 to 100 μm. The content of the hollow particles may be 10 to 80 parts by mass with respect to 100 parts by mass of the total thermosetting resin. The outer shell of the hollow particles may be at least one material selected from the group consisting of soda glass silicate, glass aluminum silicate, sodium borosilicate glass, silas, crosslinked styrene resin, and crosslinked acrylic resin.

The thermosetting resin composition further contains at least one pigment selected from the group consisting of titanium oxide, zinc oxide, alumina, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide and magnesium hydroxide. You may.

The thermosetting resin composition may be in the form of tablets.

The present invention also relates to a cured product formed from the thermosetting resin composition. In another aspect, the present invention relates to a substrate for mounting an optical semiconductor device having a molded body formed from the above-mentioned thermosetting resin composition. The substrate for mounting an optical semiconductor element has a recess composed of a bottom surface and a wall surface, the bottom surface of the recess is a mounting portion for the optical semiconductor element, and at least a part of the wall surface of the recess has the above-mentioned thermosetting resin composition. It is a molded body formed from an object. Further, the substrate for mounting an optical semiconductor element of the present invention includes a substrate, a first connection terminal and a second connection terminal provided on the substrate, and includes a first connection terminal and a second connection terminal. May have a molded product formed from the above-mentioned thermosetting resin composition between the two.

The present invention also relates to a method for manufacturing a substrate for mounting an optical semiconductor device having a recess composed of a bottom surface and a wall surface. The manufacturing method according to the present invention includes a step of forming at least a part of the wall surface of the recess by transfer molding or compression molding using the above-mentioned thermosetting resin composition.

In yet another aspect, the present invention relates to an optical semiconductor device including the optical semiconductor element mounting substrate and the optical semiconductor element mounted on the optical semiconductor element mounting substrate.

In yet another aspect, the present invention relates to a printed wiring board for an optical member, which comprises a cured product of the thermosetting resin composition described above. The present invention also relates to an optical semiconductor device including a printed wiring board for an optical member, an optical semiconductor element, and a sealing resin for sealing the optical semiconductor element.

According to the present invention, a thermosetting resin composition capable of forming a cured product having sufficient reflectance even if it is thin, a substrate for mounting an optical semiconductor device using the thermosetting resin composition, and a method for producing the same. An optical semiconductor device and a printed wiring board can be provided.

It is a perspective view which shows one Embodiment of the substrate for mounting an optical semiconductor element. It is the schematic which shows one Embodiment of the process of manufacturing the substrate for mounting an optical semiconductor element. It is a perspective view which shows one Embodiment in the state which the optical semiconductor element is mounted on the substrate for mounting the optical semiconductor element. It is a schematic cross-sectional view which shows one Embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows the other embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows the other embodiment of an optical semiconductor device. It is a schematic cross-sectional view which shows one Embodiment of a copper-clad laminate. It is a schematic cross-sectional view which shows an example of the optical semiconductor device manufactured using the copper-clad laminate. It is a schematic cross-sectional view which shows the other embodiment of an optical semiconductor device.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In addition, in the use of the numerical range by the end point in this specification, an arbitrary number included in the range (for example, 0.5, 1.5, 2, 2.75, 3 for 0.5 to 5) 3.80, 4, 5, etc. are included) and any range within that range is included.

[Thermosetting resin composition]
The thermosetting resin composition of the present embodiment contains a hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin, and hollow particles. Hereinafter, each component contained in the thermosetting resin composition of the present embodiment will be described.

(Hydrosilyl group-containing silicone resin)
The hydrosilyl group-containing silicone resin is not particularly limited as long as it is a silicone resin having a hydrosilyl group, which is a group (Si—H) in which a hydrogen atom is directly bonded to a silicon atom.

The hydrosilyl group-containing silicone resin may have, for example, a unit represented by HSiO _3/2 , a unit represented by HSiO _2/2 , or a unit represented by HSiO _1/2 as a structural unit having a hydrosilyl group. it can.

Structural units having a hydrosilyl group include, for example, methylmethoxydisilane, dimethoxydisilane, methoxytrisilane, ethylmethoxydisilane, dimethylethoxysilane, propyldiethoxysilane, propylethoxydisilane, n-butyldimethoxysilane, phenyldimethoxysilane, and phenylmethoxy. Alkoxyhydroxysilanes such as disilane and triethoxysilane; methyldichlorosilane, n-propyldichlorosilane, isopropyldichlorosilane (1,1-dichloro-2-methyl-1-silapropane), n-butyldichlorosilane, n-pentyldi Alkyldichlorosilane such as chlorosilane, cyclopentyldichlorosilane, and cyclohexyldichlorosilane can be used for introduction into the silicone resin.

The hydrosilyl group-containing silicone resin may have a structure in which a group other than a hydrogen atom is bonded to a silicon atom, that is, a structural unit other than the hydrosilyl group. Examples of the structural unit other than the hydrosilyl group include a structural unit in which an organic group having 1 to 12 carbon atoms is bonded to a silicon atom. From the viewpoint of easiness of synthesis, the organic group having 1 to 8 carbon atoms is silicon. It may be a structural unit bonded to an atom. The organic group is preferably a hydrocarbon group from the viewpoint of easiness of synthesis, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group and a propyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a benzyl group. Examples of the aryl group include a phenyl group, a tolyl group and a xsilyl group. These groups may be halogenated hydrocarbon groups in which hydrogen atoms are partially substituted with chlorine atoms, fluorine atoms, or the like. As the organic group, an aryl group is preferable, and a phenyl group is more preferable, from the viewpoint of further improving the ease of synthesis and hardness of the silicone resin.

The hydrosilyl group-containing silicone resin may have a unit represented by R ¹ SiO _3/2 as a structural unit other than the hydrosilyl group, and a unit represented by R ¹ SiO _3/2 and R ² SiO. It may have at least one unit selected from a unit represented by _2/2 , a unit represented by R ³ SiO _1/2 , and a unit represented by SiO _4/2 .

R ¹ , R ² and R ³ each independently represent a monovalent organic group, and are preferably hydrocarbon groups having 1 to 12 carbon atoms from the viewpoint of availability. Examples of the hydrocarbon group include the same hydrocarbon groups as described above. From the viewpoint of easiness of synthesizing the hydrosilyl group-containing silicone resin, R ¹ , R ² and R ³ are preferably alkyl groups or aryl groups independently, and more preferably methyl groups or phenyl groups, respectively.

The weight average molecular weight of the hydrosilyl group-containing silicone resin is not particularly limited, but from the viewpoint of improving the moldability of the thermosetting resin composition, it is preferably 200 or more, more preferably 1000 or more, and more preferably 2000 or more. More preferred. On the other hand, the weight average molecular weight of the hydrosilyl group-containing silicone resin is preferably 15,000 or less, more preferably 10,000 or less, and further preferably 7,000 or less, from the viewpoint of further improving the hardness of the cured product. That is, the weight average molecular weight of the hydrosilyl group-containing silicone resin may be 200 to 15000, 1000 to 10000, or 2000 to 7000.

The weight average molecular weight Mw in the present specification is obtained by measuring under the following conditions using a calibration curve using standard polystyrene by gel permeation chromatography (GPC).
(GPC condition)
Pump: L-6200 type (manufactured by Hitachi, Ltd., product name)
Columns: TSKgel-G5000HXL and TSKgel-G2000HXL (manufactured by Tosoh Corporation, trade name)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: 30 ° C
Flow rate: 1.0 mL / min

The content of the hydrosilyl group-containing silicone resin in the thermosetting resin composition is not particularly limited, but from the viewpoint of improving the moldability of the thermosetting resin composition, 0.01 to 40 mass with respect to the entire resin composition. %, More preferably 0.1 to 35% by mass, and even more preferably 1.0 to 30% by mass.

(Silicone resin containing alkenyl group)
The thermosetting resin composition of the present embodiment contains an alkenyl group-containing silicone resin. The alkenyl group can form a cured product of a thermosetting resin composition by addition reaction with the hydrosilyl group contained in the above-mentioned hydrosilyl group-containing silicone resin, preferably in the presence of a curing catalyst.

The alkenyl group-containing silicone resin is not particularly limited, but the alkenyl group equivalent is preferably 50 to 1000 g / mol. The alkenyl group equivalent represents the weight of the alkenyl group-containing silicone resin required to obtain 1 mol of the alkenyl group.
When the alkenyl group equivalent is within the above range, the structure of the cured resin has a high crosslink density.

When the optical semiconductor device is continuously molded, the molded body may be cracked or cracked due to the low hardness of the molded body. That is, since it is difficult to control the transportation of the molded product by a machine, the molded product may not be able to withstand the impact generated during the transportation. In particular, when the molded body is a reflector of an optical semiconductor device, since it has a complicated shape, pressure tends to be concentrated on a part thereof, and the possibility of cracking or cracking increases. When the above-mentioned alkenyl group-containing silicone resin is used, the portion capable of hydrosilylation reaction increases, and the crosslink density of the formed cured product is high. Therefore, it is possible to obtain a molded product having high hardness. The molded product having high hardness can reduce the occurrence of cracks or cracks and improve the productivity of the optical semiconductor device.

In order to further improve the crosslink density and hardness of the cured product, the alkenyl group equivalent of the alkenyl group-containing silicone resin is more preferably 50 to 500 g / mol, and even more preferably 50 to 300 g / mol. The alkenyl group equivalent of the silicone resin can be calculated according to the following formula by measuring the iodine value.
Y = _MI2 x 100 / X

In the formula, X indicates the iodine value, Y indicates the alkenyl group equivalent, and _MI2 indicates the molecular weight of the iodine molecule. The iodine value can be calculated by adding iodine to an unsaturated bond and titrating excess iodine with a sodium thiosulfate solution according to the method described in JIS K 0070: 1992.

The alkenyl group present in the silicone resin does not necessarily have to be directly bonded to the silicon atom. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group and a 2-pentenyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance and light resistance.

The alkenyl group can be introduced into the silicone resin by using, for example, a silane compound having an alkenyl group. Examples of the silane compound having an alkenyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methylallyldimethoxysilane and the like. Alkenyl alkoxysilane and the like.

The alkenyl group-containing silicone resin preferably has a ladder-type structure as a siloxane skeleton. The ladder-type structure refers to a structure in which adjacent structural units are connected via two or more atoms. By using a silicone resin having a ladder-type structure, the crosslink density of the thermosetting resin composition after curing is further increased, and it becomes easier to form a tough cured product.

Examples of the silicone resin having a ladder-type structure include compounds having a structural unit as shown in the following formula (I). In the formula, each R ¹¹ independently represents an alkenyl group. The following formula (I) is understood to have the above-mentioned structural unit and two oxygen atoms connecting the structural units, and the silicone resin having a ladder-type structure is represented by (R ¹¹ SiO _3/2 ) _2. It may have a structure like this.

The silicone resin having a ladder-type structure preferably has a continuous structure represented by the formula (I), and in that case, the silicone resin can have, for example, a structure represented by the following formula (I'). In the following formula (I'), three sets of constituent units, two sets of two oxygen atoms connecting them, and two oxygen atoms connecting two adjacent structural units (not shown) on the right side are 1 set. It is understood that it has a set.

When the silicone resin has the structure represented by the formula (I) continuously, the number of repeating units of the structure represented by the formula (I) is not particularly limited, but from the viewpoint of further improving the crosslink density after curing, it is 3 to 5000. It is preferably 5 to 3000, more preferably 10 to 2000.

The alkenyl group-containing silicone resin may have a group other than the alkenyl group. Examples of the structural unit having a group other than the alkenyl group include a structural unit represented by R ⁴ SiO _3/2 or R ⁵ SiO _2/2 . That is, the alkenyl group-containing silicone resin has a structure represented by the formula (I) ((R ¹¹ SiO _3/2 ) ₂ ) and a structure represented by R ⁴ SiO _3/2 or R ⁵ SiO _2/2. You may be doing it. R ⁴ and R ⁵ each independently represent a monovalent organic group, and are preferably hydrocarbon groups having 1 to 12 carbon atoms from the viewpoint of availability. Examples of the hydrocarbon group include the same hydrocarbon groups as those of R ¹ , R ² and R ³ described above.

The alkenyl group-containing silicone resin preferably has 75 mol% or more of alkenyl groups, more preferably 85 mol% or more, and further preferably 95 mol% or more, based on the total amount of organic groups directly bonded to silicon. preferable. By containing such an alkenyl group-containing silicone resin, the crosslink density of the resin after curing is further increased, the cured product of the thermosetting resin composition becomes hard and hard to crack, and the automatic transportability during continuous molding further increases. It will be excellent. From the viewpoint of increasing the crosslink density, the upper limit of the amount of alkenyl groups present in the alkenyl group-containing silicone resin is preferably as large as 100 mol%. The amount of alkenyl groups can be calculated by measuring ¹ H-NMR of the silicone resin.

The alkenyl group-containing silicone resin preferably has 22 mol% or more of alkenyl groups, more preferably 23 mol% or more, and further preferably 24 mol% or more, based on the total amount of elements directly bonded to silicon. .. By including such an alkenyl group-containing silicone resin, the cured product of the thermosetting resin composition becomes hard and hard to crack, and the automatic transportability during continuous molding becomes more excellent. The upper limit of the amount of the alkenyl group present in the alkenyl group-containing silicone resin is not particularly limited, but may be 30 mol%. The amount of alkenyl groups can be calculated by measuring ¹ H-NMR of the silicone resin.

The weight average molecular weight of the alkenyl group-containing silicone resin is not particularly limited, but is preferably 200 or more, more preferably 800 or more, and more preferably 1200 or more, from the viewpoint of improving the moldability of the thermosetting resin composition. More preferred. The weight average molecular weight of the alkenyl group-containing silicone resin is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 7,000 or less, from the viewpoint of further improving the hardness of the cured product. That is, the weight average molecular weight of the alkenyl group-containing silicone resin may be 200 to 10000, 800 to 8000, or 1200 to 7000.

The content of the alkenyl group-containing silicone resin according to the present embodiment in the thermosetting resin composition is not particularly limited. The alkenyl group-containing silicone resin according to the present embodiment is, for example, preferably 0.001 to 70 parts by mass, more preferably 0.01 to 65 parts by mass, based on 100 parts by mass of the total amount of the silicone resin. , 0.1 to 60 parts by mass is more preferable. Further, the alkenyl group-containing silicone resin according to the present embodiment is preferably 0.0005 to 35% by mass, more preferably 0.008 to 30% by mass, based on the total amount of the resin composition. It is more preferably 01 to 20% by mass. Within this range, the thermosetting resin composition is more excellent in moldability.

The alkenyl group-containing silicone resin may be diluted with an organic solvent and used in order to further improve the handleability. The organic solvent is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran. Etc. Ether-based solvents; Examples thereof include aromatic solvents such as toluene, xylene, and mesityrene. From the viewpoint of the solubility of the alkenyl group-containing silicone resin, the organic solvent may be an alcohol solvent, a ketone solvent or a nitrogen atom-containing solvent.

The mixing ratio of the alkenyl group-containing silicone resin and the hydrosilyl group-containing silicone resin in the silicone resin is not particularly limited, but from the viewpoint of further enhancing the strength and heat resistance, the number of SiH groups (Y) in the hydrosilyl group-containing silicone resin is increased. , The ratio (Y / X, molar ratio) to the number (X) of alkenyl groups in the alkenyl group-containing silicone resin component is preferably 0.3 ≦ Y / X ≦ 3, and 0.5 ≦ Y / X. It is more preferably ≦ 2, and even more preferably 0.7 ≦ Y / X ≦ 1.5.

The silicone resin according to the present embodiment may contain other silicone resins in addition to the above-mentioned hydrosilyl group-containing silicone resin and alkenyl group-containing silicone resin, as long as the effects of the present invention are not impaired.

(Silicone resin (X))
The resin composition according to this embodiment preferably contains a silicone resin (X). The silicone resin (X) is a solid silicone resin at 25 ° C. In the present specification, the solid state at 25 ° C. means a softening point exceeding 25 ° C. For the softening point of the silicone resin, for example, TMA-120 type (manufactured by Seiko Instruments Co., Ltd., product name) is used as a measuring device, the measuring mode is Penetration (needle insertion mode), and the temperature rise rate is 10 ° C./min. , The load can be measured under the condition of 98.1 mN (10 gf). By containing the silicone resin (X), the resin composition has a high hardness when formed into a tablet shape, and is excellent in handleability.

The softening point of the silicone resin (X) is not particularly limited as long as it exceeds 25 ° C., but is preferably more than 25 ° C. and 180 ° C. or lower, and more preferably 26 ° C. or higher and 150 ° C. or lower.
Within this range, handling tends to be easier when used for transfer molding.

As the silicone resin (X), a silicone resin in which an organic group having 1 to 12 carbon atoms is bonded to a silicon atom is preferable, and a silicone resin in which an organic group having 1 to 8 carbon atoms is bonded to a silicon atom is more preferable. .. The organic group is preferably a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aralkyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group and a propyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a benzyl group. Examples of the aryl group include a phenyl group, a tolyl group and a xsilyl group. These groups may be halogenated hydrocarbon groups in which hydrogen atoms are partially substituted with chlorine atoms, fluorine atoms, or the like. As the organic group, an aryl group is preferable, and a phenyl group is more preferable, from the viewpoint of easy synthesis of the silicone resin and easy solidification at 25 ° C.

From the viewpoint of improving the transfer moldability, the silicone resin (X) may be a thermosetting silicone resin. Examples of the thermosetting silicone resin include silicon compounds having a group capable of an addition reaction.

Examples of the group capable of the addition reaction include an alkenyl group, an alkynyl group, a carbonyl group, a thiol group, an epoxy group, an amino group, a sulfide group and a hydrogen atom (Si—H) bonded to a silicon atom. Among these groups, a silicon compound having an alkenyl group and / or a hydrogen atom bonded to a silicon atom, that is, a silicon compound having a group capable of hydrosilylation is preferable.

Silicone resin (X) ^may as having a unit represented by R _{1 SiO ^3/2,} and unit represented by R _{1 SiO ^3/2,} units represented by R _{2 SiO 2/2} , R ^{3 It} may have at least one unit selected from the unit represented by SiO _1/2 and the unit represented by SiO _4/2 .

R ¹ , R ² and R ³ each independently represent a monovalent organic group, and are preferably hydrocarbon groups having 1 to 12 carbon atoms. Examples of the hydrocarbon group include the same groups as those described above.

From the viewpoint of easiness of synthesizing the silicone resin, R ¹ , R ² and R ³ are preferably an alkyl group or an aryl group, respectively, and more preferably a methyl group or a phenyl group.

From the viewpoint of increasing the softening point of the silicone resin, a silicone resin having an aryl group or a cycloalkyl group is preferable, and from the viewpoint of availability of industrial raw materials, a silicone resin having a phenyl group is preferable.

In the silicone resin (X) according to the present embodiment, the proportion of aryl groups or cycloalkyl groups bonded to the silicon atom is 20 mol% or more based on the total amount of the hydrocarbon groups bonded to the silicon atom. It may be a silicone resin.

The content ratio of the aryl group or the cycloalkyl group present in the silicone resin can be calculated by measuring the ¹ H-NMR spectrum of the silicone resin. Specifically, it is calculated from the ratio of the signal area derived from the aryl group or cycloalkyl group bonded to the silicon atom to the signal area derived from the linear alkyl group bonded to the silicon atom. Can be done.

The content ratio of the aryl group or the cycloalkyl group in the silicone resin (X) is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 50 mol% or more. By setting the content ratio of the aryl group or the cycloalkyl group to 20 mol% or more, it becomes easy to obtain a silicone resin tablet whose shape is hardly deformed.

The silicone resin (X) according to the present embodiment is Q when the silicon-containing bond units Q, T and D are defined as follows in the solid ²⁹ Si-NMR spectrum measured by the following DD / MAS method. A silicone resin having a ratio Q + T: D of the signal area derived from T and the signal area derived from D of 1: 0 to 1: 0.5 may be used.

That is, Q represents a silicon-containing bond unit in which four oxygen atoms are bonded to one silicon atom, and T represents three oxygen atoms bonded to one silicon atom and a hydrogen atom or a monovalent atom. It represents a silicon-containing bond unit having one organic group, and D represents a silicon-containing bond unit having two oxygen atoms bonded to one silicon atom and two hydrogen atoms or monovalent organic groups. .. In addition, R in the formula independently represents a monovalent organic group.

The "oxygen atom" in Q, T and D is mainly an oxygen atom that bonds between two silicon atoms, but for example, it may be an oxygen atom possessed by a hydroxyl group bonded to a silicon atom. The "organic group" is a monovalent organic group in which the atom bonded to the silicon atom is a carbon atom, and examples thereof include an organic group having 1 to 10 carbon atoms. Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group and an N-aryl substituted aminoalkyl group.

The signal area ratio may be Q + T: D from 1: 0 to 1: 0.5, but from the viewpoint of obtaining a silicone resin tablet having a higher hardness, Q + T: D is set to 1: 0 to 1: 0.3. It may be set to 1: 0 to 1: 0.2, or 1: 0 to 1: 0.1. By setting the signal area ratio to 1: 0.5 or less, it becomes easy to obtain a tablet having excellent automatic transportability.

The solid ²⁹ Si-NMR measurement method for confirming the signal area ratio is not particularly limited, and examples thereof include the CP / MAS method and the DD / MAS method. In the present embodiment, the DD / MAS method is used from the viewpoint of quantitativeness. The MAS method is adopted.

By the way, Roychen Joseph et al., Macromolecules, 1996, 29, p. In 1305-1321, a structural analysis of a composite of colloidal silica and polymethyl methacrylate is reported using solid ²⁹ Si-NMR. In addition, Aramata et al., BUNSEKI KAGAKU, 1998, 47, pp. 971-978 reports silica-siloxane interface analysis in silicone rubber using solid ²⁹ Si-NMR. These reports can be referred to as appropriate in the measurement of the solid ²⁹ Si-NMR spectrum.

The chemical shift of the silicon-containing bond units Q, T and D in the solid ²⁹ Si-NMR spectrum is in the range of Q unit: -90 to -120 ppm, T unit: 45 to -80 ppm, D unit: 0 to -40 ppm, respectively. Since it is observed, it is possible to separate the signals of the silicon-containing bond units Q, T and D and calculate the signal area derived from each unit. In the spectrum analysis, an exponential function can be adopted as the window function and the Line Browding coefficient can be set in the range of 0 to 50 Hz from the viewpoint of improving the analysis accuracy.

The signal area can be calculated using general spectrum analysis software (for example, NMR software "TopSpin" (registered trademark) manufactured by Bruker Co., Ltd.).

The number average molecular weight (Mn) of the silicone resin (X) is preferably less than 3000, more preferably less than 2000, and even more preferably less than 1500, from the viewpoint of fluidity during transfer molding. The Mn of the silicone resin (X) may be 700 or more.

The number average molecular weight (Mn) refers to a value measured using a calibration curve with standard polystyrene according to a gel permeation chromatography (GPC) method. Specifically, as a GPC measuring device, a pump (L-6200 type manufactured by Hitachi, Ltd.), a column (TSKgel-G5000HXL and TSKgel-G2000HXL, all manufactured by Tosoh Corporation, product name), a detector (Hitachi, Ltd.) Mn can be measured under the conditions of a temperature of 30 ° C. and a flow rate of 1.0 mL / min, using tetrahydrofuran (L-3300RI type) as an eluent.

(Curing catalyst)
From the viewpoint of reactivity, it is preferable that the resin composition of the present embodiment contains a curing catalyst that promotes the hydrosilylation reaction of the silicone resin. Examples of the curing catalyst include a calstead catalyst; a simple platinum substance; a carrier (alumina, silica, carbon black, etc.) on which solid platinum is supported; platinum chloride acid; a complex of platinum chloride acid and alcohol, aldehyde, ketone, etc. Platinum-olefin complex; platinum-vinylsiloxane complex; platinum-phosphine complex; platinum-phosphite complex and dicarbonyldichloroplatinum. These curing catalysts may be used alone or in combination of two or more.

Examples of the platinum-olefin complex include Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ and Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ . Examples of the platinum-vinylsiloxane complex include platinum-2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex and platinum-1,3-divinyltetramethyldisiloxane complex. Can be mentioned. Examples of the platinum-phosphine complex include platinum- (PPh ₃ ) ₄ and platinum- (PBu ₃ ) ₄ . Examples of the platinum-phosphite complex include platinum- [P (OPh) ₃ ] ₄ and platinum- [P (OBu) ₃ ] ₄ . In the formula, Bu represents a butyl group and Ph represents a phenyl group.

Among these curing catalysts, chloroplatinic acid, platinum-olefin complex or platinum-vinylsiloxane complex is preferable from the viewpoint of catalytic activity.

The amount of the curing catalyst contained in the thermosetting resin composition is not particularly limited, but from the viewpoint of further improving the curability of the thermosetting resin composition, 0.005 with respect to 100 parts by mass of the total amount of the silicone resin. ~ 0.5 parts by mass is preferable, 0.01 to 0.3 parts by mass is more preferable, and 0.01 to 0.2 parts by mass is further preferable. The amount of the curing catalyst with respect to the entire resin composition is preferably 0.01 to 3 ppm, more preferably 0.05 to 2.5 ppm, and 0, from the viewpoint of further improving the curability. It is more preferably .08 to 2.2 ppm.

(Pigment)
The thermosetting resin composition according to the present embodiment may contain a pigment in order to add a color to the cured product according to the intended use. The pigment according to the present embodiment can be selected according to the purpose of use of the cured product of the thermosetting resin composition to be produced. Examples of the pigment include white pigment, black pigment, red pigment, yellow pigment, orange pigment, purple (菫) color pigment, blue pigment and green pigment. The pigment may be an azo pigment, a lake pigment or a fluorescent pigment. In the present specification, the "pigment" may be any one used to add color to the cured product of the thermosetting resin composition, and the particle size, solubility in a solvent, etc. are particularly limited. Not done.

Examples of the black pigment include carbon black. Examples of the red pigment include lead tan, iron oxide red, quinacridone, diketopyrrolopyrrole, anthraquinone, perylene, perinone and indigoid. Examples of yellow pigments include chrome yellow and zinc chromate. Examples of the blue pigment include ultramarine blue, procyanide blue (ferrocyanide potassium), phthalocyanine blue, anthraquinone and indigoid. Examples of the orange pigment include diketopyrrolopyrrole, perylene, anthraquinone, perinone, quinacridone and indigoid. Examples of the purple (violet) pigment include dioxazine, quinacridone, perylene, indigoid, anthraquinone and xanthene. Examples of the green pigment include phthalocyanine, azomethine and perylene. These pigments may be used alone or in combination of two or more.

When the thermosetting resin composition is required to have light reflection characteristics, it is preferable to use a white pigment as the pigment. Since the thermosetting resin composition contains a white pigment, the cured product of the thermosetting resin composition has excellent reflectance, and when used as a light reflecting material provided on a substrate for mounting an optical semiconductor device. In addition, a high-brightness optical semiconductor device can be obtained.

Examples of the white pigment include titanium oxide, zinc oxide, alumina, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide and the like, and from the viewpoint of obtaining better light reflectivity. , Titanium oxide, alumina and zinc oxide are preferred. These may be used alone or in combination of two or more. It is also preferable to use it in combination with hollow particles described later.

The refractive index of the white pigment is not particularly limited, but is preferably 1.6 to 3.0, more preferably 1.8 to 3.0, and further preferably 2.0 to 3.0. preferable. White pigments having a refractive index in the range of 1.6 to 3.0 include titanium oxide having a refractive index of 2.5 to 2.7, zinc oxide having a refractive index of 1.9 to 2.0, and a refractive index of 1.6. Examples thereof include alumina having a refractive index of ~ 1.8, magnesium oxide having a refractive index of 1.7, zirconium oxide having a refractive index of 2.4, aluminum hydroxide having a refractive index of 1.6, and magnesium hydroxide having a refractive index of 1.6. Among these, it is preferable to contain titanium oxide having a higher refractive index. By using a white pigment having a refractive index larger than that of the thermosetting resin contained in the thermosetting resin composition for light reflection, the light reflectance of the cured product of the resin composition is increased. can do. The refractive index in the present specification is a value measured with light having a wavelength of 540 nm.

The titanium oxide may be surface-treated with a specific surface treatment agent based on fine particle-based titanium oxide whose content as titanium oxide (TiO ₂ ) is adjusted to 80 to 97% by weight. preferable. Examples of the surface treatment agent for titanium oxide include metal oxides such as silica, alumina and zirconia; and organic substances such as silane coupling agents, titanium coupling agents, organic acids, polyols and silicones. Titanium oxide surface-treated with at least one selected from silica, alumina and zirconia, or at least one selected from silica, alumina, zirconia and organic substances is preferable. From the viewpoint of improving the adhesion to the thermosetting resin, the surface may be further organically treated with a silane coupling agent such as epoxysilane. As the crystal type of titanium oxide, there are a rutile type having a refractive index of 2.7, an anatase type having a refractive index of 2.5, and a brookite type having a refractive index of 2.6. The crystal type of titanium oxide is not particularly limited, but the rutile type is preferable from the viewpoint of refractive index and light absorption characteristics.

Titanium oxide can be used by obtaining a commercially available product. As rutile type titanium oxide, for example, trade names manufactured by Sakai Chemical Industry Co., Ltd .: D-918, FTR-700, trade names manufactured by Ishihara Sangyo Co., Ltd .: Typake CR-50, CR-50-2, CR-60, CR- 60-2, CR-63, CR-80, CR-90, CR-90-2, CR-93, CR-95, CR-97, Trade names manufactured by Teika: JR-403, JR-805, JR -806, JR-701, JR-800, trade names manufactured by Fuji Titanium Industry Co., Ltd .: TR-600, TR-700, TR-750, TR-840, TR-900. Here, titanium oxide is obtained by producing a natural product as a raw material by a known sulfuric acid method or hydrochloric acid method. Titanium oxide obtained from each of the sulfuric acid method and the hydrochloric acid method has the same refractive index, but the color of titanium oxide, that is, the reflection spectrum characteristics, differs depending on the elements mixed in from the treatment liquid during production. can get. Generally, titanium oxide obtained by the hydrochloric acid method has a high light reflectance at a wavelength of 460 to 800 nm, and titanium oxide obtained by the sulfuric acid method has a light reflectance at a wavelength of 460 to 800 nm inferior to the former. In particular, when the thermosetting resin composition for light reflection is used in the optical semiconductor device of the present invention, the titanium oxide contained in the thermosetting resin composition for light reflection is a hydrochloric acid method having a wavelength of 460 to 800 nm and high light reflectance. It is preferable to use the one produced.

The central particle size of the white pigment is preferably 0.1 to 20 μm, more preferably 0.1 to 10 μm, from the viewpoint of dispersibility in the thermosetting resin composition for light reflection. It is more preferably 1 to 5 μm. By setting the central particle size of the white pigment within the above range, it is possible to obtain a thermosetting resin composition for light reflection that gives a molded product having high surface reflectance.

The blending amount of the white pigment is preferably 70 to 400 parts by mass, more preferably 90 parts by mass or more, and further preferably 130 parts by mass or more with respect to 100 parts by mass of the thermosetting resin. It is particularly preferably 130 to 380 parts by mass. When the thermosetting resin composition for light reflection is used for transfer molding, it is preferably 70 to 400 parts by mass with respect to 100 parts by mass of the thermosetting resin, and is used for substrate coating. In some cases, it is preferably 130 to 400 parts by mass. By adjusting the blending amount of the inorganic oxide, the light reflectance of the cured product of the resin composition can be adjusted. If the blending amount of the inorganic oxide is less than 70 parts by mass, it tends to be difficult to sufficiently obtain the light leakage characteristics of the cured product formed from the thermosetting resin composition for light reflection, and if it exceeds 400 parts by mass, the light reflection tends to be difficult. The moldability of the thermosetting resin composition for use tends to decrease.

(Hollow particles)
The thermosetting resin composition according to this embodiment contains hollow particles. The hollow particles are particles having voids inside, and the substance constituting the outer shell is not particularly limited. Hollow particles are useful as white pigments because they refract and reflect incident light on the surface and inner walls. Examples of the hollow particles include inorganic hollow particles and organic hollow particles. As the inorganic hollow particles, metal oxides such as inorganic glass and silica; metal salts such as calcium carbonate, barium carbonate, calcium silicate and nickel carbonate can be preferably used. Specifically, for example, soda glass silicate. , Aluminum silicate glass, borosilicate soda glass, silas particles and the like. As the organic hollow particles, polystyrene-based resin, poly (meth) acrylate-based resin, and crosslinked products thereof can be preferably used. The outer shell of the hollow particles is made of sodium silicate glass, aluminum silicate glass, sodium borosilicate glass, silas, and crosslinked from the viewpoint of having high heat resistance and pressure resistance and further suppressing the destruction of particles in the heat treatment and resin composition adjusting process. It is preferably composed of at least one material selected from the group consisting of styrene resin and crosslinked acrylic resin.

The particle size of the hollow particles is not limited, but preferably contains particles in the range of 0.1 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 0.1 to 30 μm. When the particle size of the hollow particles is 0.1 μm or more, the dispersibility is better, and when the particle size is 100 μm or less, the compact is easier to be thinned, and further dispersed in other fillers added as needed. The sex becomes better. The particle size of the hollow particles can be confirmed by measuring the particle size distribution.

The blending amount of the hollow particles is preferably 10 to 80 parts by mass, more preferably 10 to 70 parts by mass, and 10 to 60 parts by mass with respect to 100 parts by mass of the thermosetting resin. Is even more preferable. If it is 10 to 80 parts by mass, the light reflectance becomes better, and the bending strength and hardness of the cured product can be further increased.

The voids of the hollow particles preferably have a refractive index of 1.0 to 1.1. When the refractive index is in the above range, the light transmitted through the outer shell of the hollow particle is more refracted or reflected inside the hollow particle, so that the light reflectance can be further increased. As such a medium, air is usually preferable, but an inert gas such as nitrogen or argon may be used, or a mixed gas thereof may be used.

(Measurement method of refractive index)
The refractive index according to the present embodiment indicates a value of the d-line (587.562 nm, He) with respect to light at a temperature of 25 ° C. The refractive index can be measured using various refractometers according to principles such as the critical angle method, the prism coupling method, the Becke method, and the v-block method. Examples of the measuring device include a spectrometer, an Abbe refractometer, a Prurich refractometer, and an ellipsometer. The method for measuring the refractive index can be selected according to the properties (solid, liquid, etc.) of the object to be measured. When the object to be measured is a solid, the method for measuring the refractive index can be selected depending on the shape of the thin film, bulk or powder. For example, when the object to be measured is a solid, the object to be measured can be thinned by a known method and measured using an Abbe refractometer or an ellipsometer. For the refractive index of a white pigment such as an inorganic oxide, a measured value in the shape (bulk or thin film) of a component constituting the white pigment may be applied. When the white pigment is a powder, the Becke method is used. In the present specification, the refractive index of the thermosetting resin is measured by the V-block method (measuring device: KPR, manufactured by Carneux Optics), and the refractive index of the white pigment is measured by the Becke method (method of comparing with a standard solution). Is. Since the voids of the hollow particles are filled with air or an inert gas, the refractive index of the voids is "1.0 to 1.1", which corresponds to the refractive index of air or an inert gas. Numerical values can be applied.

(Other ingredients)
In addition to the above-mentioned components, the thermosetting resin composition includes an inorganic filler, a coupling agent, a curing retarder, a thermosetting resin other than a silicone resin, an antioxidant, a mold release agent, a dispersant, an ion trapping agent, and the like. Various additives can be further contained.

From the viewpoint of reducing the coefficient of linear expansion and the like, the thermosetting resin composition preferably contains an inorganic filler. Examples of the inorganic filler include silica, antimony oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate and the like.

In addition, in this specification, a substance exhibiting the effects of both a pigment and an inorganic filler shall be attributed to the pigment in principle. However, when the thermosetting resin composition contains two or more kinds of substances having the effects of both a pigment and an inorganic filler, one of the substances shall belong to the inorganic filler. As the substance belonging to the inorganic filler, substances other than titanium oxide, zinc oxide, alumina, aluminum oxide, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide, and magnesium hydroxide are prioritized.

The particle size of the inorganic filler preferably contains particles in the range of 0.1 to 100 μm, and more preferably particles in the range of 0.4 to 80 μm, from the viewpoint of improving the packing efficiency with the pigment. It is more preferable to contain particles of 0.5 to 75 μm. The content of the inorganic filler in the thermosetting resin composition is in the range of 4 to 85% by mass based on the total amount of the solid content after curing of the thermosetting resin composition from the viewpoint of further improving the moldability. It is preferably 10 to 80% by mass, more preferably 20 to 80% by mass.

From the viewpoint of further improving the strength and hardness of the cured product, the total amount of the hollow particles, the inorganic filler and the pigment contained in the thermosetting resin composition shall be 6 to 98% by mass based on the total amount of the resin composition. Is more preferable, and it is more preferably 15 to 95% by mass, and even more preferably 30 to 90% by mass.

A coupling agent may be added to the thermosetting resin composition, if necessary. By containing a coupling agent, the interfacial adhesiveness between the silicone resin and an inorganic component such as a pigment or an inorganic filler can be improved. Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, and the like. As the silane coupling agent, known compounds such as epoxysilane-based, aminosilane-based, cationicsilane-based, vinylsilane-based, acrylicsilane-based, and mercaptosilane-based can be generally used. The coupling agent may be a composite system of the above silane coupling agents. From the viewpoint of improving the curability, the amount of the coupling agent used is preferably 0.01 to 5% by mass based on the total amount of the thermosetting resin composition. The pigment or inorganic filler may be previously treated with the coupling agent.

A curing retarder may be added to the thermosetting resin composition from the viewpoint of improving storage stability, adjusting reactivity, and the like. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides.

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-in compounds, maleic acid esters and the like. Examples of the organic phosphorus compound include triorganophosphins, diorganophosphins, organophosphons, triorganophosphites and the like. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, 1st to 3rd grade alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halogenated dihydrate and stannous carboxylic acid. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these curing retardants, those having good retarding activity and being colorless or relatively uncolored such as pale yellow are preferable. The curing retarder may be used alone or in combination of two or more.

The amount of the curing retarder added is preferably in the range of 0.1 to 100 mol, more preferably in the range of 1 to 50 mol, with respect to 1 mol of the curing catalyst used.

For the purpose of modifying the properties, a thermosetting resin other than the silicone resin can be added to the thermosetting resin composition within a range that does not adversely affect the properties. Examples of the thermosetting resin include, but are not limited to, epoxy resin, acrylic resin, cyanate resin, phenol resin, polyimide resin, polyamide-imide resin, and urethane resin. Of these, epoxy resins are preferable because they are excellent in adhesiveness to metal parts. The thermosetting resin is preferably colorless or relatively uncolored such as pale yellow.

The epoxy resin is not particularly limited, but for example, hexafluorobisphenol A type diglycidyl ether, hydride bisphenol A type diglycidyl ether, bisphenol A diglycidyl ether, 2,2'-bis (4-glycidyloxycyclohexyl) propane. , 3,4-Epoxy Cyclohexylmethyl-3,4-Epoxy Cyclohexane Carboxylate, Vinyl Cyclohexendioxide, 2- (3,4-Epoxy Cyclohexyl) -5,5-Spiro- (3,4-Epoxy Cyclohexane)- Examples thereof include 1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate and diallyl monoglycidyl isocyanurate. From the viewpoint of heat resistance and ultraviolet resistance, an alicyclic epoxy resin is preferable, and from the same viewpoint, triglycidyl isocyanurate is more preferable.

When an epoxy resin is used, it is preferable to further contain an epoxy resin curing agent. From the viewpoint of heat-resistant discoloration, an acid anhydride-based curing agent is preferable as the curing agent, and examples of the acid anhydride-based curing agent include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methyl hydride. Examples thereof include naphthic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrides of aliphatic acids (cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, etc.). These epoxy resins or curing agents may be used alone or in combination of two or more.

(Characteristics of thermosetting resin composition)
When the thermosetting resin composition of the present embodiment is used as a light-reflecting material, the light reflectance after curing is preferably 80% or more at any of wavelengths of 440 to 700 nm. When the light reflectance is 80% or more, the brightness of the optical semiconductor device can be further improved. Further, from the viewpoint of being suitable for an optical semiconductor device using a blue light emitting diode, the light reflectance at a wavelength of 460 nm after curing is preferably 80% or more, and more preferably 90% or more.

When the thermosetting resin composition is used as a light-reflecting material, the light reflectance of the cured product is 440 to 700 nm after a heat resistance test in which it is exposed to an environment of 150 ° C. for 1000 hours from the viewpoint of improving heat-resistant coloring. It is preferable that it is 80% or more in any of the above. Further, from the viewpoint of being suitable for an optical semiconductor device using a blue light emitting diode, the light reflectance at a wavelength of 460 nm is more preferably 85% or more, and more preferably 90% or more at the time of measurement after the above-mentioned heat resistance test. Is even more preferable. The light reflection characteristics of such a thermosetting resin composition can be realized by appropriately adjusting the blending amounts of various components constituting the resin composition, and more specifically, for example, colorless heat. This can be achieved by highly filling the cured resin component and the white pigment having a high refractive index. In the present specification, unless otherwise specified, the light reflectance is a value measured by preparing a cured product having a thickness of 0.3 mm and using an integrating sphere spectrophotometer.

The thermosetting resin composition of the present embodiment preferably has a cured Type D durometer hardness of 40 or more, more preferably 50 or more, and even more preferably 55 or more. When the hardness is 40 or more, the toughness of the molded product becomes better. The upper limit of the hardness is not particularly limited, but can be about 100. The hardness of the type D durometer can be measured according to the method described in JIS K 6253-: 2012, and the thickness is 3 mm after transfer molding under the conditions of a temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds. It is a measurement of body hardness.

From the viewpoint of reducing cracks or cracks, the thermosetting resin composition of the present embodiment preferably has a breaking strength of 15 or more, more preferably 20 or more, and more preferably 25 or more. More preferred. The breaking strength is the same as when a three-point bending breaking test of a test piece with a thickness of 4 mm was performed at room temperature after transfer molding under the conditions of a temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds according to JIS K 7171: 2008. The value.

[Manufacturing method of thermosetting resin composition]
The method for producing the thermosetting resin composition according to the present embodiment is not particularly limited, but may include, for example, the following kneading step and pulverizing step.

(Kneading process)
The thermosetting resin composition can be prepared by uniformly dispersing and mixing various components exemplified above, and the mixing means, mixing conditions and the like are not particularly limited. Examples of the preparation method include a method of kneading various components using an apparatus such as a mixing roll, an extruder, a kneader, a roll, an extruder, a rake machine, and a stirring mixer that combines rotation and revolution. The kneading type is also not particularly limited, but melt kneading is preferable from the viewpoint of easy work, and kneading is preferably carried out at 15 to 30 ° C. from the viewpoint of simplifying the process. When heating is required, it may be in the temperature range of, for example, 30 to 100 ° C. When the temperature of melt-kneading is 30 ° C. or higher, various components can be melt-kneaded more sufficiently, and the dispersibility tends to be further improved. On the other hand, when melt-kneading is carried out at 100 ° C. or lower, it is possible to further suppress the increase in molecular weight of the resin composition and further suppress the curing of the resin composition before molding a molded product such as a substrate. The kneading time may be 5 to 40 minutes or 10 to 30 minutes. When the melt-kneading time is 5 minutes or more, it is possible to further suppress the resin from seeping out from the mold when molding the substrate or the like, and when it is 40 minutes or less, it is easy to control the polymerization of the resin composition and the molding is performed. It is possible to further suppress the curing of the resin composition before.

In the kneading step, first, the hydrosilyl group-containing silicone resin and the alkenyl group-containing silicone resin may be premixed in advance, and then other components may be added to carry out the above mixing. The thermosetting resin composition obtained by premixing has improved storage stability and is more excellent in moldability during molding. The hydrosilyl group-containing silicone resin and the alkenyl group-containing silicone resin used in the premixing may be a part or the whole amount used in the thermosetting resin composition.

The thermosetting resin composition that has undergone the kneading step is preferably in a state where it can be subjected to the dry pulverization described later. Therefore, a step of cooling the thermosetting resin composition may be performed if necessary.

(Crushing process)
In the pulverization step, for example, the thermosetting resin composition is dry pulverized. Dry pulverization can be performed using, for example, a pulverizer such as a high-speed stirring mill, a Henschel mixer, a power mill, a jet mill, or a roll granulator. These pulverizers can be used properly according to the target powder particle size.

The thermosetting resin composition according to this embodiment is preferably processed into a tablet shape. The tablet shape in the present specification means a solid state that retains a constant shape and has substantially no change in shape over time when left for about 30 minutes, for example. By being processed into a tablet shape, the handleability is further improved, and the efficiency of transfer molding, compression molding, etc. using the thermosetting resin composition can be improved. The shape of the tablet according to the present embodiment is not particularly limited and includes shapes such as columnar, prismatic, disk-shaped, and spherical, but columnar is preferable from the viewpoint of handleability.

The tablet molding conditions are not particularly limited, but for example, a tablet-like thermosetting resin composition can be obtained by pressure molding at room temperature at 0.5 to 60 MPa for about 1 to 15 seconds. The pressure molding for tablet molding is a process that is clearly different from the transfer molding or compression molding described later.

The tablet-like thermosetting resin composition according to the present embodiment preferably has a type A durometer hardness of 50 or more, more preferably 55 or more, and even more preferably 60 or more. If the hardness is 50 or more, the tablet is less likely to be deformed and the handleability is improved. Since the hardness of the tablet-like thermosetting resin composition is better, the upper limit of the type A durometer hardness is not particularly limited, but can be about 100. The type A durometer hardness is preferably a value measured after allowing the tablet-like thermosetting resin composition to stand at 25 ° C. for 3 minutes.

Type A durometer hardness can be measured according to the method described in JIS K 6253-: 2012. In the present specification, the value obtained by pressing the needle of the type A durometer against the tablet-like thermosetting resin composition and reading the value after 1 minute is defined as the type A durometer hardness.

From the viewpoint of reducing the surface tackiness, the surface of the tablet-like thermosetting resin composition may be coated with a filler. The inorganic filler used for the coating is not particularly limited, and examples thereof include the same inorganic fillers that can be contained in the thermosetting resin composition.

The method of coating the adherend with the filler is not particularly limited as long as it can come into contact with the tablet-like thermosetting resin composition. For example, a method of putting a filler in a container or a bag and coating the tablet-shaped thermosetting resin composition with the filler by vibration using a machine and a method of manually sprinkling the filler can be mentioned.

The thermosetting resin composition of the present embodiment is used in various applications such as an electrically insulating material, an optical semiconductor encapsulating material, an adhesive material, a coating material, and an epoxy resin molding material for transfer molding or compression molding, which require high heat resistance. It is useful. In particular, the thermosetting resin composition of the present embodiment is useful as a material for transfer molding. The thermosetting resin composition of the present embodiment is preferably white when used for light reflection applications.

[Cured product]
The cured product of the present embodiment can be formed by heat-curing the above-mentioned thermosetting resin composition. The conditions for thermosetting are not particularly limited, but for example, it can be cured by heating at a temperature of 170 to 200 ° C. for 60 to 300 seconds. Thermosetting may be performed as a part of the steps included in the molding method described later.

[Substrate for mounting optical semiconductor devices]
The substrate for mounting an optical semiconductor element according to this embodiment has a recess formed by a bottom surface and a wall surface. The bottom surface of the recess is the optical semiconductor device mounting portion (optical semiconductor device mounting region), and the wall surface of the recess, that is, at least a part of the inner peripheral side surface of the recess is a molded product formed from the thermosetting resin composition of the present embodiment. It consists of.

FIG. 1 is a perspective view showing an embodiment of a substrate for mounting an optical semiconductor element. The substrate 110 for mounting an optical semiconductor element has a metal wiring 105 (first connection terminal and second connection terminal) formed with Ni / Ag plating 104 and a metal wiring 105 (first connection terminal and second connection). The metal wiring 105 provided with the insulating resin molded body 103'provided between the terminals) and the reflector 103 on which the Ni / Ag plating 104 was formed, and the insulating resin molded body 103' and the reflector 103 were formed. It has an optical semiconductor element mounting region (recess) 200. The bottom surface of the recess 200 is composed of a metal wiring 105 on which Ni / Ag plating 104 is formed and an insulating resin molded body 103', and the wall surface of the recess 200 is composed of a reflector 103. The reflector 103 and the insulating resin molded body 103'are molded bodies formed by using the thermosetting resin composition of the present embodiment.

The method for manufacturing the substrate for mounting the optical semiconductor element is not particularly limited, and for example, it can be manufactured by transfer molding or compression molding using a thermosetting resin composition. FIG. 2 is a schematic view showing an embodiment of a process of manufacturing a substrate for mounting an optical semiconductor element. In the substrate for mounting an optical semiconductor element, for example, a step of forming a metal wiring 105 by a known method such as punching from a metal foil and etching, and applying Ni / Ag plating 104 by electroplating ((a) in FIG. 2), and then A step of arranging the metal wiring 105 in a mold 151 having a predetermined shape, injecting a thermosetting resin composition from a resin injection port 150 of the mold 151, and performing transfer molding or compression molding under predetermined conditions (FIG. 2). It can be manufactured through the steps (b)) and the step of removing the mold 151 ((c) of FIG. 2).

In this way, the optical semiconductor device mounting region (recess) 200 is formed on the optical semiconductor device mounting substrate so as to be surrounded by a reflector 103 made of a cured product of the thermosetting resin composition. Further, the bottom surface of the recess 200 has an insulating property composed of a metal wiring 105 as a first connection terminal, a metal wiring 105 as a second connection terminal, and a cured product of a thermosetting resin composition provided between them. It is composed of a resin molded body 103'. For example, when the reflector is formed by transfer molding, the molding conditions are a molding temperature of 120 to 200 ° C., a molding pressure of 0.5 to 25 MPa for 60 to 600 seconds, and an aftercure temperature of 120 ° C. to 180 ° C. for 1 to 3 It is preferably time. From the viewpoint of sufficient curing, the mold temperature is more preferably 150 to 190 ° C., and the molding pressure is more preferably 12 to 20 MPa. When the reflector is formed by compression molding, the molding temperature is 120 to 200 ° C. and the molding time is 30 to 600 seconds, particularly, the molding temperature is 130 to 160 ° C. and the molding time is 120 to 300 seconds from the viewpoint of sufficient curing. It is preferable to carry out with.

The color of the reflector 103 is not limited and can be appropriately determined depending on the type of pigment used, but it is preferably white from the viewpoint of further increasing the light reflectance.

[Optical semiconductor device]
The optical semiconductor device according to the present embodiment includes the optical semiconductor element mounting substrate and the optical semiconductor element mounted on the optical semiconductor element mounting substrate. As a more specific example, the substrate for mounting the optical semiconductor element, the optical semiconductor element provided in the recess of the substrate for mounting the optical semiconductor element, and the sealing resin portion that fills the recess and seals the optical semiconductor element. An optical semiconductor device including the above can be mentioned.

FIG. 3 is a perspective view showing an embodiment in which the optical semiconductor element 100 is mounted on the optical semiconductor element mounting substrate 110. As shown in FIG. 3, the optical semiconductor element 100 is mounted at a predetermined position in the optical semiconductor element mounting region (recess) 200 of the optical semiconductor element mounting substrate 110, and is electrically connected to the metal wiring 105 by the bonding wire 102. To. 4 and 5 are schematic cross-sectional views showing an embodiment of an optical semiconductor device. As shown in FIGS. 4 and 5, the optical semiconductor device includes an optical semiconductor element mounting substrate 110, an optical semiconductor element 100 provided at a predetermined position in the recess 200 of the optical semiconductor element mounting substrate 110, and the recess 200. The metal wiring 105 in which the optical semiconductor element 100 and the Ni / Ag plating 104 are formed is provided with a sealing resin portion made of a transparent sealing resin 101 containing a phosphor 106 that fills and seals the optical semiconductor element. Are electrically connected by a bonding wire 102 or a solder bump 107.

FIG. 6 is also a schematic cross-sectional view showing an embodiment of an optical semiconductor device. In the optical semiconductor device shown in FIG. 6, the LED element 300 is arranged at a predetermined position on the lead 304 on which the reflector 303 is formed via the die bonding material 306, and the LED element 300 and the lead 304 are electrically connected by the bonding wire 301. The LED element 300 is connected and the LED element 300 is sealed by the transparent sealing resin 302 containing the phosphor 305.

Although FIGS. 5 and 6 show an embodiment of an optical semiconductor device provided with one optical semiconductor element, two or more optical semiconductor elements may be provided in the recess.

Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto. For example, a molded product formed from the thermosetting resin composition according to the present embodiment can be used as a light-reflecting resin layer. As this embodiment, a copper-clad laminate, a substrate for mounting an optical semiconductor element, and an optical semiconductor element will be described.

The copper-clad laminate according to the present embodiment includes a resin layer formed by using the thermosetting resin composition described above, and a copper foil laminated on the resin layer.

FIG. 7 is a schematic cross-sectional view showing a preferred embodiment of the copper-clad laminate. As shown in FIG. 7, the copper-clad laminate 400 includes a base material 401, a resin layer 402 laminated on the base material 401, and a copper foil 403 laminated on the resin layer 402. There is. Here, the resin layer 402 is formed by using the thermosetting resin composition of the present embodiment described above. As the base material 401, the base material used for the copper-clad laminate can be used without particular limitation, and examples thereof include a resin laminate such as an epoxy resin laminate and a substrate for mounting an optical semiconductor element.

The copper-clad laminate 400 is produced, for example, by forming the thermosetting resin composition according to the present embodiment on the surface of the base material 401, stacking copper foils 403, and heat-pressurizing and curing to form the resin layer 402. can do. The method of forming on the surface of the base material 401 is not limited, and examples thereof include a method of directly applying, a method of laminating a copper foil with a resin containing the thermosetting resin composition according to the present embodiment by pressing or laminating. The conditions for heating and pressurizing are not particularly limited, but for example, conditions of 130 to 180 ° C., 0.5 to 4 MPa, and 30 to 600 minutes are preferable.

Using the copper-clad laminate, it is possible to manufacture a printed wiring board for an optical member such as for mounting an optical semiconductor element. The copper-clad laminate 400 shown in FIG. 7 has a resin layer 402 and a copper foil 403 laminated on one side of the base material 401, whereas the copper-clad laminate has resin layers 402 on both sides of the base material 401. And copper foil 403 may be laminated respectively.

FIG. 8 is a schematic cross-sectional view showing an example of an optical semiconductor device manufactured by using a copper-clad laminate. As shown in FIG. 8, the optical semiconductor device 500 is a surface-mounted optical semiconductor device including an optical semiconductor element 410 and a sealing resin 404 provided so as to seal the optical semiconductor element 410. In the optical semiconductor device 500, the optical semiconductor element 410 is adhered to the copper foil 403 via the adhesive layer 408, and is electrically connected to the copper foil 403 by the bonding wire 409.

Further, as another embodiment of the substrate for mounting an optical semiconductor element, an optical semiconductor including a resin layer formed between a plurality of conductor members (connection terminals) on a substrate by using the thermosetting resin composition described above. Examples include a substrate for mounting an element. Further, another embodiment of the optical semiconductor device is such that the optical semiconductor element is mounted on the above-mentioned substrate for mounting the optical semiconductor element.

FIG. 9 is a schematic cross-sectional view showing a preferred embodiment of the optical semiconductor device. As shown in FIG. 9, the optical semiconductor device 600 is formed between the base material 601 and a plurality of conductor members 602 formed on the surface of the base material 601 and a plurality of conductor members (connection terminals) 602. A surface-mounted optical device in which an optical semiconductor element 610 is mounted on a substrate for mounting an optical semiconductor element including a resin layer 603, and a transparent sealing resin 604 is provided so that the optical semiconductor element 610 is sealed. It is a semiconductor device. In the optical semiconductor device 600, the optical semiconductor element 610 is adhered to the conductor member 602 via the adhesive layer 608, and is electrically connected to the conductor member 602 by the bonding wire 609. The resin layer 603 is formed by using the thermosetting resin composition described above.

As the base material 601, the base material used for the substrate for mounting the optical semiconductor element can be used without particular limitation, and examples thereof include a resin laminated board such as an epoxy resin laminated board. The conductor member 602 functions as a connection terminal, and can be formed by a known method such as a method of photo-etching a copper foil. In the substrate for mounting an optical semiconductor element, a thermosetting resin composition is transfer-molded between a plurality of conductor members 602 on the base material 601 and heat-cured to form a resin layer 603 composed of the thermosetting resin composition. It can be produced by. The heating conditions for heat-curing the layer made of the transfer-molded thermosetting resin composition are not particularly limited, but for example, it is preferable to heat the layer at 130 to 200 ° C. for 30 to 600 minutes.

After that, the resin component excessively adhered to the surface of the conductor member 602 is removed by buffing or the like to expose the circuit composed of the conductor member 602 to form a substrate for mounting an optical semiconductor element. Further, in order to ensure the adhesion between the resin layer 603 and the conductor member 602, the conductor member 602 may be subjected to a roughening treatment such as a redox treatment and a CZ treatment (manufactured by MEC Co., Ltd.).

Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. The present invention can be implemented in various aspects different from the above embodiments without departing from the gist thereof.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The measurement method of each characteristic in the above synthesis example, example and comparative example is as follows.
(Measurement of weight average molecular weight (Mw))
The Mw of the silicone resin was measured by gel permeation chromatography (GPC) under the following conditions using a calibration curve using standard polystyrene.
(GPC condition)
Pump: L-6200 type (manufactured by Hitachi, Ltd., product name)
Columns: TSKgel-G5000HXL and TSKgel-G2000HXL (manufactured by Tosoh Corporation, trade name)
Detector: L-3300RI type (manufactured by Hitachi, Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: 30 ° C
Flow rate: 1.0 mL / min.

(Measurement of alkenyl group content)
Using "FT-NMR AV400M" (manufactured by Bruker Biospin Co., Ltd., trade name), ¹ H-NMR measurement of the silicone resin was performed, and the contents of alkenyl groups and alkyl groups in the silicone resin were measured. As the measurement conditions, a deuterated chloroform solution adjusted to contain 0.5% by mass of a silicone resin was used, and the number of integrations (NS) was 32.

(Measurement of alkenyl group equivalent)
Iodine value was measured according to JIS K 0070: 1992. The alkenyl group equivalent was calculated from the measured iodine value and the weight average molecular weight measured in (1).

<Synthesis of silicone resin>
An alkenyl group-containing silicone resin, a hydrosilyl group-containing silicone resin, and a methylphenyl silicone resin were obtained according to the following procedure.
(Synthesis Example 1)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of both-terminal dimethylchlorosilane-polydimethylsiloxane and 8.5 g of methylvinyldichlorosilane in 200 g of toluene was slowly added dropwise to 1000 g of water so as not to generate heat and hydrolyzed. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to obtain a colorless liquid alkenyl group-containing silicone resin. The Mw was 3685 and the alkenyl group equivalent was 1585 g / mol.

(Synthesis Example 2)
425 g of vinyltrimethoxysilane, 1.2 g of methyltriethoxysilane, 120 g of isopropyl alcohol, 240 g of toluene, 1.18 g of concentrated hydrochloric acid and 31.4 g of distilled water were added to a 1000 ml flask, and the mixture was stirred at 170 ° C. over time while refluxing. Next, toluene was distilled off under reduced pressure to obtain a colorless and transparent alkenyl group-containing silicone resin. The obtained resin was stored as a 50% acetone solution. The Mw was 4000 and the alkenyl group equivalent was 85.

(Synthesis Example 3)
A solution prepared by dissolving 100 g of phenyltrichlorosilane, 53 g of both-terminal dimethylchlorosilane-polydimethylsiloxane and 6.9 g of methyldichlorosilane in toluene was slowly added dropwise to 1000 g of water so as not to generate heat and hydrolyzed. Then, after stirring under reflux conditions for 60 minutes, the organic layer was neutralized with potassium hydroxide, azeotropically dehydrated, and then a solvent such as toluene was distilled off to obtain a colorless and transparent hydrosilyl group-containing silicone resin. Mw was 3865.

(Synthesis Example 4)
89.2 g of methyltriethoxysilane, 99 g of phenyltriethoxysilane, 23.6 g of isopropyl alcohol, 23.6 g of toluene, 0.28 g of concentrated hydrochloric acid and 36 g of distilled water were added to a 500 mL flask, and the mixture was refluxed at 110 ° C. for 3 hours. Stirred. Next, toluene was distilled off under reduced pressure to obtain a colorless solid methylphenyl silicone resin. Next, 23 g of triethoxyhydrosilane was added and heated at 170 ° C. for 3 hours to condense the alkoxysilane. The softening point of the silicone resin was 89 ° C., Mw was 2600, and it was bonded to the silicon atom. The proportion of aryl groups was 34%.
<Adjustment of thermosetting resin composition for light reflection>
Each component was blended according to the blending ratios shown in Tables 1 and 2, and the mixture was sufficiently kneaded and dispersed at room temperature with a raker to obtain a powdery thermosetting white resin composition.
<Molding of thermosetting material>
The thermosetting resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were transfer-molded under the conditions of a mold temperature of 180 ° C., a pressure of 14 MPa, and a curing time of 300 seconds, to have a thickness of 3 mm and a thickness of 0. , 6 mm, and 0.3 mm thick test pieces were prepared.

<Measurement of initial reflectance>
Using the test piece of the thermosetting product obtained above, the light reflectance at a wavelength of 460 nm was measured using an integrating sphere spectroscopic hardness tester CM600d (manufactured by Konita Minolta Co., Ltd.). Further, the difference ((R _2- R ₁ ) / R ₁ ) of the initial reflectance (R ₂ ) measured with the test piece having a thickness of 0.3 mm with respect to the initial reflectance (R ₁ ) measured with the test piece having a thickness of 3.0 mm. ) Was calculated.

The details of * 1 to 9 in Tables 1 and 2 are as follows.
* 1: Silicone resin containing an alkenyl group (Synthesis Example 1)
* 2: Silicone resin containing an alkenyl group (Synthesis Example 2)
* 3: Silicone resin containing hydrosilyl group (manufactured by Momentive Performance Materials Japan, trade name: TSF484)
* 4: Thermosetting silicone resin containing hydrosilyl group (Synthesis Example 3)
* 5: Methylphenyl silicone resin (Synthesis Example 4, Silicone Resin (X))
* 6: Trimethoxyvinylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-1003)
* 7: Platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane complex (manufactured by Wako Pure Chemical Industries, Ltd., platinum 1.7% by mass)
* 8: Fused silica (manufactured by Denka Co., Ltd., trade name: FB-950, center particle size 26 μm)
* 9: Fused silica (manufactured by Denka Co., Ltd., trade name: S440-4, center particle size 6 μm)
* 10: Fused silica (manufactured by Admatex Co., Ltd., trade name: SO-25R, center particle size 1 μm)
* 11: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: CR63, center particle size 0.2 μm)
* 12: Zinc oxide (manufactured by Admatex Co., Ltd., trade name AO-802)
* 13: Hollow particles (manufactured by Sumitomo 3M Ltd., trade name: S60-HS, center particle size 27 μm, refractive index of voids 1.0 to 1.1)
* 14: Hollow particles (manufactured by Sumitomo 3M Ltd., trade name: iM30K, center particle size 15 μm, refractive index of voids 1.0 to 1.1)

As shown in Tables 1 and 2, the reduction of reflectance when the molded product is thinned from a thickness of 3 mm to a thickness of 0.3 mm is compared with Examples 1 to 6 as compared with Comparative Examples 1 and 2 containing no hollow particles. It was confirmed that was more highly suppressed.

According to the present invention, a thermosetting resin composition capable of forming a cured product having sufficient reflectance even if it is thin, a substrate for mounting an optical semiconductor device using the thermosetting resin composition, and a method for producing the same. In addition, an optical semiconductor device can be provided.

100 ... Optical semiconductor device, 101 ... Transparent sealing resin, 102 ... Bonding wire, 103 ... Reflector, 103'... Insulating resin molded body, 104 ... Ni / Ag plating, 105 ... Metal wiring, 106 ... Fluorescent material, 107 ... Solder bump, 110 ... Optical semiconductor device mounting substrate, 150 ... Resin injection port, 151 ... Mold, 200 ... Optical semiconductor device mounting area, 300 ... LED element, 301 ... Bonding wire, 302 ... Transparent sealing resin, 303 ... Reflector, 304 ... lead, 305 ... phosphor, 306 ... die bonding material, 400 ... copper-clad laminate, 401 ... base material, 402 ... resin layer, 403 ... copper foil, 404 ... sealing resin, 408 ... adhesive layer, 409 ... Bonding wire, 410 ... Optical semiconductor device, 500, 600 ... Optical semiconductor device, 601 ... Base material, 602 ... Conductor member, 603 ... Resin layer, 604 ... Sealing resin, 608 ... Adhesive layer, 609 ... Bonding wire, 610 … Optical semiconductor device.

Claims (11)

Hydrosilyl group-containing silicone resin, an alkenyl group-containing silicone resin and void portions refractive index of seeing containing hollow particles is 1.0 to 1.1,
The outer shell of the hollow particles is soda glass silicate.
A thermosetting resin composition in which the content of the hollow particles is 10 to 80 parts by mass with respect to 100 parts by mass of the total thermosetting resin. The thermosetting resin composition according to claim 1, wherein the hollow particles contain particles having a particle size of 0.1 to 100 μm. Further titanium oxide, zinc oxide, oxidation aluminum, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide, and at least one pigment selected from the group consisting of magnesium hydroxide, heat according to claim 1 or 2 Curable resin composition. The thermosetting resin composition according to any one of claims 1 to 3 , which is in the form of a tablet. A cured product formed from the thermosetting resin composition according to any one of claims 1 to 4 . The method according to any one of claims 1 to 4 , which has a recess composed of a bottom surface and a wall surface, wherein the bottom surface of the recess is a mounting portion for an optical semiconductor element, and at least a part of the wall surface of the recess has a recess. A substrate for mounting an optical semiconductor device, which has a molded body formed from a thermosetting resin composition. A board and a first connection terminal and a second connection terminal provided on the board are provided.
Mounted on an optical semiconductor device having a molded body formed from the thermosetting resin composition according to any one of claims 1 to 4 between the first connection terminal and the second connection terminal. Board for. The thermosetting according to any one of claims 1 to 4 , which is a method for manufacturing a substrate for mounting an optical semiconductor device having a recess composed of a bottom surface and a wall surface, wherein at least a part of the wall surface of the recess is heat-curable. A method for manufacturing a substrate for mounting an optical semiconductor device, comprising a step of forming by transfer molding or compression molding using a resin composition. An optical semiconductor device including the optical semiconductor element mounting substrate according to claim 6 or 7, and the optical semiconductor element mounted on the optical semiconductor element mounting substrate. A printed wiring board for an optical member, comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 4 . An optical semiconductor device comprising the printed wiring board for an optical member according to claim 10 , an optical semiconductor element, and a sealing resin for sealing the optical semiconductor element.

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