TW201934619A - Liquid organosilicon compound and thermosetting resin composition to which same is added - Google Patents

Abstract

The purpose of the present invention is to provide a thermosetting resin composition from which a cured product having a high refractive index and good transparency and heat resistance can be obtained. The present invention relates to a liquid organosilicon compound, a method for preparing the same, and a thermosetting resin composition containing said liquid organosilicon compound.

Description

Liquid organic silicon compound and thermosetting resin composition containing the compound

The present invention relates to a liquid organosilicon compound, a thermosetting composition useful for optical materials, electrical insulation materials, and the like containing the compound, a cured product obtained by thermally curing the composition, and the use of the composition. Resin sealing material for semiconductors.

White light-emitting diodes (Light Emitting Diodes, LEDs) are used in applications such as lighting. However, with the increase in output, heat generation of LED packages becomes a problem. In addition, when an epoxy resin is used as a sealing material, since yellowing due to heat generation is unavoidable, a silicone resin is used as a sealing material for white LEDs instead of the epoxy resin. Silicone resins for LEDs are broadly divided into phenyl silicone resins and methyl silicone resins.

The phenyl silicone resin generally used has a high refractive index and good light extraction efficiency. Furthermore, the gas barrier properties are also high, and the adhesion to the package is also good. Therefore, they have excellent reliability such as resistance to moisture absorption and reflow and resistance to thermal cycling. However, although heat yellowing resistance is superior to epoxy resin, it is not sufficient to cope with the increase in output of LEDs.

The methyl silicone resin has excellent heat yellowing resistance, but because of its low refractive index, the light extraction efficiency of the LED is not good. In addition, the methyl silicone resin is mainly composed of dimethyl silicone, and therefore has low gas barrier properties and poor adhesion to the package, and has a problem of easy peeling during moisture absorption and reflow. When peeling occurs, the brightness of the light generated from the LED decreases, which is unfavorable.

Furthermore, in recent years, high-power LEDs have appeared. In particular, when the package size is small, the resin portion is locally heated, causing a problem of cracking. In the high-temperature energization test using high-power LEDs, the temperature of the resin portion can also be said to be a high-temperature region of 200 ° C or higher, and long-term reliability in a higher-temperature region is required.

In the high-temperature region, not only the brightness deterioration caused by yellowing is severe, but also cracks are caused by the deterioration of the resin among the commonly used phenyl silicone resins. Regarding dimethyl silicone resin, although the brightness degradation caused by yellowing is small, in the high temperature region, the deterioration of the resin shrinks, cracks are generated, and the brightness is deteriorated. Happening.

As described above, in recent years, the required characteristics of LED sealing materials have become increasingly strict. Therefore, a sealing material and a thermosetting resin composition having both a high refractive index and heat resistance, which can cope with the increase in output of a white LED, are desired.

In recent years, a silsesquioxane material having excellent heat resistance and UV resistance has attracted attention, and an LED sealing material using the material has been reported.

Patent Document 1 discloses a sealing material for LEDs, which is a thermosetting resin composition using a thermosetting resin in which SiH group is introduced into a cage-type octasesquioxane and an organic polysiloxane having an alkenyl group. .

Patent Document 2 discloses a thermosetting resin composition using an incomplete cage-type silsesquioxane commonly referred to as a double-layer type. The silsesquioxane is a structure-controlled compound obtained by the hydrolysis and condensation of phenyltrimethoxysilane. Since the position of the Si-Ph group is controlled by the structure rather than randomly, it has a high refractive index and heat resistance. And excellent light resistance.

Patent Document 2 discloses a thermosetting resin containing a SiH group and a vinyl group, which is a compound obtained by modifying a SiH group of a silanol group of a silsesquioxane having an incomplete cage structure, and a compound having an alkenyl group. It is obtained by the reaction of an organic polysiloxane, and it is hardened to have a high refractive index and high heat resistance. Furthermore, it is shown to be similar to a polyphthalamide resin substrate or a silver substrate as a packaging material for LEDs. Good adhesion.
[Prior Art Literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-102167 Patent Document 2: International Publication No. 2011/145638

[Problems to be Solved by the Invention]
However, in Patent Document 1, only a heat resistance test at 200 ° C for 168 hours is performed, and in Patent Document 2 only a heat resistance test at 180 ° C for 1000 hours is performed. As described above, neither of Patent Document 1 and Patent Document 2 describes long-term reliability in a high-temperature region of 200 ° C. to 250 ° C. or higher emitted by a high-power LED.

One of the problems of the present invention is to provide a thermosetting composition capable of obtaining a hardened material having a high refractive index, transparency, and good heat resistance, and another of the problems is to provide a liquid contained in the thermosetting composition. Organic silicon compounds, hardened materials obtained from thermosetting compositions, molded bodies, and sealing materials for light-emitting diodes.
[Means for solving problems]

The present inventors have made intensive studies in order to solve the problems. As a result, a liquid organic silicon compound was successfully synthesized, which contains a double-layer silicon compound structure and is not a solid. Therefore, a solvent is not required, and it was found that the hardened material of the thermosetting composition containing the compound and the hardener is transparent, The present invention has been excellent in terms of heat resistance and the like.

That is, the present invention has the following configuration.
[1] A liquid organic silicon compound represented by the following general formula (1).

[Chemical 1]

In the general formula (1), R ¹ is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
In the general formula (1), R ² is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
n is an integer of 1-50 each independently.
In the general formula (1), R ^{3 is} each independently an unsaturated hydrocarbon group having 2 to 5 carbon atoms and having one double bond.
[2] A production method for producing the liquid organosilicon compound according to the above [1], the production method comprising combining a compound represented by the following general formula (2-1) with the following general formula (2 -2) A step of equilibrating the compound represented by the formula.

[Chemical 2]

[Chemical 3]

In the general formula (2-1), R ^{21 is} each independently an unsaturated hydrocarbon group having one to two carbon atoms having 2 to 5 carbon atoms.
In the general formula (2-2), R ²² is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
n is an integer from 0 to 50.
[3] A thermosetting resin composition containing the liquid organic silicon compound according to the above [1].
[4] The thermosetting resin composition according to the above [3], which contains a liquid organic silicon compound represented by the following structural formula (4).

[Chemical 4]

[5] The thermosetting resin composition according to the above [3] or [4], which contains a platinum catalyst.
[6] The thermosetting resin composition according to any one of the above [3] to [5], which contains at least one of a metal oxide and a phosphor.
[7] A cured product obtained by thermally curing the thermosetting resin composition according to any one of [3] to [6].
[8] A coating film obtained by applying the thermosetting resin composition according to any one of [3] to [6].
[9] A resin sealing material for a semiconductor, comprising the thermosetting resin composition according to any one of [3] to [6].
[Effect of the invention]

The cured product of the thermosetting resin composition of the present invention is excellent in, for example, high refractive index, transparency, heat resistance, heat yellowing resistance, and the like. Therefore, the molded body containing the cured product can be suitably used for applications such as sealing materials for semiconductors, sealing materials for optical semiconductors, die bonding materials for optical semiconductors, insulating films, sealants, and optical lenses. In addition, it can be used for transparent materials, optical materials, optical films, optical sheets, adhesives, electronic materials, insulating materials, interlayer insulating films, coatings, inks, coating materials, molding materials, potting materials, liquid crystal sealants, and display devices. Sealants, solar cell sealing materials, resist materials, color filters, electronic paper materials, hologram materials, solar cell materials, fuel cell materials, display materials, recording materials, waterproof materials, Moisture-proof materials, solid electrolytes for batteries, and gas separation membranes. In addition, it can be used as an additive in other resins.

<1. The liquid organic silicon compound of the present invention>
The liquid organic silicon compound of the present invention is represented by the following general formula (1).

[Chemical 5]

In the general formula (1), R ¹ is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
In the general formula (1), R ² is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
n is an integer of 1-50 each independently.
In the general formula (1), R ^{3 is} each independently an unsaturated hydrocarbon group having 2 to 5 carbon atoms and having one double bond.

The preferred hydrocarbon group as R ^{1 is} a group independently selected from alkyl groups having 1 to 4 carbon atoms, the alicyclic group is a group independently selected from cyclopentyl and cyclohexyl, and the aromatic hydrocarbon groups are independently independent A group selected from phenyl and naphthyl. When R ¹ is a phenyl group, it is excellent in heat resistance, and when it is a methyl group, it is excellent in fluidity.

The preferred hydrocarbon group as R ^{2 is} a group independently selected from an alkyl group having 1 to 4 carbon atoms, an alicyclic group is a group independently selected from a cyclopentyl group and a cyclohexyl group, and the aromatic hydrocarbon group is a phenyl group . When R ² is a methyl group, it is excellent in heat resistance, and when it is a phenyl group, it is excellent in gas barrier properties.
n is an integer of 1-50 each independently. The preferred n is 1 to 30, and the more preferred n is 3 to 23. If it is in the said range, compatibility with other polymerizable silicon compounds will be sufficient, and hardened | cured material will not become cloudy.
Specific examples of the preferable unsaturated hydrocarbon group for R ³ include a vinyl group.

<2. Method for producing liquid organic silicon compound represented by general formula (1)>
The liquid organosilicon compound represented by the general formula (1) of the present invention is obtained by balancing a compound represented by the following general formula (2-1) and a compound represented by the following general formula (2-2) Steps.

[Chemical 6]

In the general formula (2-1), R ^{21 is} each independently an unsaturated hydrocarbon group having one to two carbon atoms having 2 to 5 carbon atoms.
Specific examples of the preferable unsaturated hydrocarbon group for R ²¹ include a vinyl group.

[Chemical 7]

In the general formula (2-2), R ²² is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group.
The preferred hydrocarbon group as R ^{22 is} a group independently selected from an alkyl group having 1 to 4 carbon atoms, an alicyclic group is a group independently selected from a cyclopentyl group and a cyclohexyl group, and the aromatic hydrocarbon group is a phenyl group. .
n is an integer from 0 to 50. The preferred n is 1 to 35, and the more preferred n is 5 to 25. If it is in the said range, reactivity will be sufficient and a reaction liquid will not become gelatinous.

The compound represented by the general formula (1) can be obtained by an equilibrium reaction between a compound represented by the general formula (2-1) and a compound represented by the general formula (2-2).
The reaction solvent may be any solvent as long as it is a solvent that does not condense with the compound. Examples of the solvent include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, diethyl ether, tetrahydrofuranyl (THF), dioxane, and cyclopentyl methyl ether. Ether solvents, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ester solvents such as ethyl acetate, and lactamamine solvents such as N-methyl-2-pyrrolidone (NMP). The solvent may be a single solvent or two or more solvents. Among these, toluene is more preferable.
The reaction temperature is usually 40 ° C to 150 ° C, and preferably 110 ° C to 120 ° C.
As the catalyst, a strong acid or a strong base is usually used. In the method for producing a liquid organosilicon compound of the present invention, in consideration of the stability of the reaction of silsesquioxane, a strong acid is preferred as a catalyst. Examples of the catalyst include hydrochloric acid, sulfuric acid, fluorosulfuric acid, trifluoromethanesulfonic acid, activated clay, and a sulfonic acid-based ion exchange resin. Among them, a sulfonic acid-based ion exchange resin is more preferred.

<3. Thermosetting resin composition of the present invention>
3-1. First component The thermosetting resin composition of the present invention contains a liquid organic silicon compound represented by the general formula (1) as a first component. The liquid organosilicon compound represented by the general formula (1) has heat resistance and improves the heat resistance of the thermosetting resin composition.

The content of the liquid organic silicon compound represented by the general formula (1) is preferably 1% to 99% by mass, and more preferably 20% to 80% by mass based on the total amount of the thermosetting resin composition. If it is in the said range, compatibility with other components will be sufficient and the whiteness of hardened | cured material can be suppressed.

3-2. Second component The thermosetting resin composition of the present invention contains a liquid organic silicon compound represented by the following structural formula (4) as a second component.

[Chemical 8]

The content of the liquid organic silicon compound represented by the structural formula (4) is preferably 1% to 99% by mass, and more preferably 20% to 80% by mass with respect to the total amount of the thermosetting resin composition. Within the above range, the reactivity with the thermosetting resin composition is sufficient, and the cured product can be suppressed from becoming gelatinous.

3-3. Other ingredients
3-3-1. Hardening catalyst The thermosetting resin composition of the present invention contains a hardening catalyst as other components as necessary.

The hardening catalyst is not particularly limited as long as it is a transition metal catalyst generally used as a reaction catalyst, and a platinum catalyst is preferably used. As an example of a platinum catalyst, a general hydrosilylation catalyst can be selected. Examples of preferred hydrosilylation catalysts are Karstedt catalyst, Speier catalyst, hexachloroplatinic acid, etc., which are commonly known platinum catalysts.

The use amount of the hardening catalyst is preferably 0.1 to 10 mass ppm based on the mass ratio of the transition metal contained in the catalyst to the thermosetting resin composition. If the addition ratio is within the above range, it is difficult to cause hardening failure, and there is no possibility that the pot life after preparation of the thermosetting resin composition becomes too short to be usable, and hardening does not occur. The color of things. A more preferable addition ratio is 0.5 mass ppm to 4 mass ppm.

3-3-2. Metal oxide The thermosetting resin composition of the present invention contains a metal oxide as another component as necessary. When a metal oxide is contained, light-scattering property improves. Preferable metal oxides include silicon oxide, titanium oxide, and zinc oxide. The content of the metal oxide is preferably 1% to 90% by mass, and more preferably 5% to 85% by mass based on the total amount of the thermosetting resin composition. When it is in the said range, when using a thermosetting resin composition as a light-diffusion material or a light-reflective material, it has sufficient light-diffusion property and light-reflective property, and does not lose a moldability.
One kind of metal oxide may be used, or two or more kinds may be used in combination.

3-3-3. Phosphor The thermosetting resin composition of the present invention contains a phosphor as other components as necessary. When a phosphor is included, a part of the blue light of the LED can be converted into yellow, green, and red and into white light. Preferred phosphors include yttrium aluminum garnet, calcium aluminum oxynitride, silicon aluminum oxynitride, and ruthenium aluminum garnet.

The content of the phosphor is preferably 1% to 90% by mass, and more preferably 5% to 85% by mass based on the total amount of the thermosetting resin composition. If it is in the said range, the wavelength conversion property of a thermosetting resin composition will be sufficient, and moldability will not be lost.
Only one phosphor may be used, or two or more phosphors may be used in combination.
[Example]

The present invention will be described in more detail based on examples. The scope of the present invention is not limited by the following examples.

The thermosetting resin composition and the like of the present invention were identified by the following analysis method.
<Measurement of number average molecular weight and weight average molecular weight>
The number average molecular weight and weight average molecular weight of the polymer synthesized in the present invention are measured in the following manner.
A high performance liquid chromatography system CO-2065plus manufactured by JASCO Corporation was used, and 20 μL of a THF solution with a sample concentration of 1 wt% was used as the analysis sample. The column was: Shodex KF804L (Showa Denko (Manufactured by Co., Ltd.) (two connected in series), column temperature: 40 ° C, detector: RI, eluent: THF, and flow rate of the eluent: 1.0 mL per minute by Gel Permeation Chromatography , GPC) method, and calculated by polystyrene conversion.

<Nuclear magnetic resonance (NMR) (nuclear magnetic resonance spectrum)>
The measurement sample was dissolved in heavy acetone (manufactured by Wako Pure Chemical Industries, Ltd.) using 400 MHZ NMR manufactured by Japan Electronics Co., Ltd. for measurement. In addition, the average silicone chain length introduced was determined based on the integration ratio of ¹ H-NMR.
＜ viscosity ＞
The TV-22 viscometer cone and plate type manufactured by Toki Sangyo Co., Ltd. was used for measurement at a constant temperature bath temperature of 25 ° C.

The reagents used in the examples are as follows.
Divinyl polysiloxane 1 [equivalent to formula (2-2), polydimethylsiloxane having a number average molecular weight of 700 at both ends of the vinyl]: manufactured by JNC Corporation

[Chemical 9]

Divinyl polysiloxane 2 [equivalent to formula (2-2), polydimethyl siloxane having a number average molecular weight of 2100 at both ends of the polydimethyl siloxane]: manufactured by JNC Corporation

[Chemical 10]

MVS-H (hardening retarder, substance name, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane): Platinum catalyst manufactured by JNC Corporation: Pt-VTSC-3.0X (1,3-divinyl-1,1,3,3 tetramethyldisilanium platinum (0) complex xylene solution, platinum content: 3.0 wt%) (Japan umicore) Co., Ltd.

The solvent used in the reaction is not particularly limited as long as it is a solvent that does not inhibit the progress of the reaction. Aromatic hydrocarbon solvents such as benzene, toluene, xylene, ether solvents such as tetrahydrofuran (THF), cyclomethylpentyl ether, dioxane, hydrocarbon solvents such as hexane, heptane, methanol, ethanol, isopropanol And other alcohol-based solvents. These solvents may be used singly or in combination.

[Synthesis example 1]
<Synthesis of silsesquioxane derivative (DD-4OH)>
The following DD-4OH was synthesized by the method described in Japanese Patent No. 5704168.

[Chemical 11]

[Synthesis example 2]
<Synthesis of silsesquioxane derivative (DD (Me) -OH)>
The following DD (Me) -OH was synthesized by the method described in Japanese Patent No. 4379120.

[Chemical 12]

[Synthesis example 3]
＜ Synthesis of Organic Polysiloxanes ＞
The compound represented by the following structural formula (4) was synthesized by a method described in Japanese Patent No. 5704168.

[Chemical 13]

[Synthesis example 4]
<Synthesis of silsesquioxane derivative [DD (Ph) -OH]>
A reaction vessel equipped with a thermometer and a dropping funnel was charged with 100.0 g of DD-4OH, 49.4 g of phenyltrichlorosilane, and 660 ml of tetrahydrofuran. After cooling to 5 ° C, 42.6 g of triethylamine was added, and the mixture was stirred at room temperature for 4 hours. After cooling to 5 ° C, 100 ml of pure water was added, and the mixture was stirred at room temperature for 1 hour. After adding 500 ml of cyclopentyl methyl ether, washing with water was performed until the organic layer showed neutrality. The solid obtained by distilling off the solvent under reduced pressure was dispersed in 140 ml of methanol, and then filtered under reduced pressure. After drying under reduced pressure at 45 ° C, 110.0 g of a white solid [DD (Ph) -OH] represented by the following formula was obtained.

[Chemical 14]

The obtained white solid was determined to have the structure (DD-4H) of the [DD (Ph) -OH] based on the following analysis results. ¹ H-NMR (solvent: heavy acetone): δ (mass ppm): 6.7-6.8 (m, 1.2H), 7.2-7.8 (m, 50H)

[Example 1]
<Synthesis of silsesquioxane derivative [Compound 1: DD (Ph) -Si6V]>
A reaction vessel equipped with a reflux cooler and a thermometer was charged with 5.0 g of DD (Ph) -OH, 1.0 g of ion exchange resin RCP160M manufactured by Mitsubishi Chemical Corporation, 20 ml of toluene, and 5.8 g of two manufactured by JNC Corporation. Vinyl polysiloxane After heating under reflux for 1 hour, the ion exchange resin was separated by filtration. After the reaction solution was washed with 20 ml of water, the solvent was distilled off under reduced pressure. After the reaction solution was washed with 20 ml of methanol, the solvent was distilled off under reduced pressure. It was dried under reduced pressure at 45 ° C to obtain 6.8 g of a colorless and transparent liquid [DD (Ph) -Si6V].

The obtained colorless and transparent liquid was judged to have the following structure based on the following analysis results. ¹ H-NMR (solvent: heavy acetone): δ (mass ppm): -0.1-0.2 (m, 72H), 5.7-6.2 (m, 5.3H), 7.2-7.9 (m, 50H) viscosity = 4200 mPas Average molecular weight: Mn = 2000 weight average molecular weight: Mw = 2900

[Chemical 15]

[Example 2]
<Synthesis of Silsesquioxane Derivative [Compound 2: DD (Ph) -Si23V]>
A reaction vessel equipped with a reflux cooler and a thermometer was charged with 5.0 g of DD (Ph) -OH, 1.0 g of ion exchange resin RCP160M manufactured by Mitsubishi Chemical Corporation, 20 ml of toluene, and 15.3 g of two manufactured by JNC Corporation. Vinyl polysiloxane After heating under reflux for 1 hour, the ion exchange resin was separated by filtration. After the reaction solution was washed with 20 ml of water, the solvent was distilled off under reduced pressure. After the reaction solution was washed with 20 ml of methanol, the solvent was distilled off under reduced pressure. It was dried under reduced pressure at 45 ° C to obtain 12.0 g of a colorless and transparent liquid [DD (Ph) -Si23V].

The obtained colorless and transparent liquid was judged to have the following structure based on the following analysis results. ¹ H-NMR (solvent: heavy acetone): δ (mass ppm): -0.1-0.2 (m, 277H), 5.7-6.2 (m, 7.1H), 7.2-7.9 (m, 50H) viscosity = 275 mPas quantity Average molecular weight: Mn = 4300 Weight average molecular weight: Mw = 6600

[Chemical 16]

[Example 3]
<Synthesis of Silsesquioxane Derivative [Compound 3: DD (Me) -Si8V]>
A reaction vessel equipped with a reflux cooler and a thermometer was charged with 5.0 g of DD (Me) -OH, 1.0 g of ion exchange resin RCP160M manufactured by Mitsubishi Chemical Corporation, 20 ml of toluene, and 7.8 g of two manufactured by JNC Corporation. Vinyl polysiloxane After heating under reflux for 1 hour, the ion exchange resin was separated by filtration. After the reaction solution was washed with 20 ml of water, the solvent was distilled off under reduced pressure. After the reaction solution was washed with 20 ml of methanol, the solvent was distilled off under reduced pressure. It was dried under reduced pressure at 45 ° C to obtain 7.6 g of a colorless and transparent liquid [DD (Me) -Si8V].

The obtained colorless and transparent liquid was judged to have the following structure based on the following analysis results. ¹ H-NMR (solvent: heavy acetone): δ (mass ppm): 0.0-0.2 (m, 100H), 0.3-0.4 (m, 4.3H), 5.7-6.2 (m, 2.7H) 7.1-7.7 (m , 40H) viscosity = 1300 mPas number average molecular weight: Mn = 4300 weight average molecular weight: Mw = 7000

[Chemical 17]

[Example 4]
<Synthesis of silsesquioxane derivative [Compound 4: DD (Me) -Si25V]>
A reaction vessel equipped with a reflux cooler and a thermometer was charged with 5.0 g of DD (Me) -OH and 1.0 g of ion exchange resin RCP160M manufactured by Mitsubishi Chemical Corporation, 20 ml of toluene, and 18.6 g of JNC Corporation Vinyl polysiloxane After heating under reflux for 1 hour, the ion exchange resin was separated by filtration. After the reaction solution was washed with 20 ml of water, the solvent was distilled off under reduced pressure. After the reaction solution was washed with 20 ml of methanol, the solvent was distilled off under reduced pressure. It was dried under reduced pressure at 45 ° C to obtain 10.7 g of a colorless and transparent liquid [DD (Me) -Si25V].

The obtained colorless and transparent liquid was judged to have the following structure based on the following analysis results. ¹ H-NMR (solvent: heavy acetone): δ (mass ppm): 0.0-0.2 (m, 297H), 0.3-0.4 (m, 4.0H), 5.7-6.2 (m, 4.8H) 7.2-7.9 (m , 40H) viscosity = 262 mPas number average molecular weight: Mn = 5900 weight average molecular weight: Mw = 9800

[Chemical 18]

[Example 5]
<Preparation of thermosetting resin composition>
The compound synthesized in the example or the divinyl polysiloxane 1 and the organopolysiloxane represented by the following structural formula (4) were added to a spiral bottle. The spiral vial was set in a rotation and revolution mixer ["defoaming and stirring Taro (registered trademark)" ARE-250] manufactured by Thinky Co., Ltd., and mixed and defoamed.

[Chemical 19]

Next, it is added so that the concentration of the hardening retarder becomes 10 mass ppm and the concentration of the platinum catalyst becomes 1 mass ppm, and mixing and defoaming are performed again using a rotation and revolution mixer to obtain a cured product as a thermosetting resin composition. a to hardened material d and comparative hardened material a to comparative hardened material b. Table 1 shows the blending amount (parts by mass) of each thermosetting resin composition.

＜ Production of hardened products ＞
Regarding the thermosetting resin composition, a Naflon SP gasket (4 mm diameter) manufactured by Nichias Co., Ltd. was held as a spacer between two pieces of glass, and flowed into the glass. The thermosetting resin composition was sequentially heated at 80 ° C. for 1 hour, and then at 150 ° C. for 4 hours to harden it. The glass was peeled off to obtain a smooth surface with a thickness of 30 mm × 35 mm × 4 mm. Hardened material a to hardened material d and comparative hardened material a to comparative hardened material b. Divided into two, and 30 mm × 20 mm × 4 mm was used as a sample for measuring transmittance. 30 mm × 10 mm × 4 mm was used as a sample for refractive index measurement.

About the obtained hardened | cured material a-hardened | cured material c and comparative hardened | cured material a, the physical property was evaluated by the following method. The results are shown in Table 2.

＜ Transmittance measurement ＞
A UV-visible spectrophotometer V-650 manufactured by JASCO Corporation was used to measure the transmittance of light at a wavelength of 450 nm at one place in the center of the cured product.

<Refractive index>
The Japanese Industrial Standards (JIS) K7142 (2014) was used to make test pieces (30 mm × 10 mm × 4 mm). Using the test piece, the refractive index of one place of the test piece was measured using an Abbe refractometer (NAR-2T manufactured by Atago Co., Ltd.) using a D line (586 nm) of a sodium lamp. As the intermediate liquid, 1-bromonaphthalene (Wako Pure Chemical Industries, Ltd.) was used.

＜ Test of heat resistance ＞
The heat resistance test is performed and evaluated by the following method, which is stricter than the conventional method (for example, heating at 200 ° C. for 168 hours in Existing Document 1).
The hardened product having a thickness of 4 mm was placed in an oven (cleaning oven: DE410 manufactured by Yamato Scientific Co., Ltd.) at 250 ° C., and heat-treated for 1,000 hours.

· Heat-resistant transparency The light transmittance of the hardened material after the test was measured with an ultraviolet-visible spectrophotometer, and the retention rate at the wavelength (%) was calculated based on the transmittance at a wavelength of 450 nm (after heat treatment at 250 ° C for 1000 hours After the transmittance / initial transmittance × 100), heat-resistant transparency (retention ratio of each cured product / retention ratio of the comparative cured product a) was calculated and evaluated. Here, the "initial transmittance" is a transmittance before heat treatment.

· Heat-resistant dimensional stability The thickness of the center of the hardened material after the test was measured with a digital thickness meter, and the dimensional retention (%) (thickness after heat treatment at 250 ° C for 1000 hours / initial thickness × 100) was calculated and then calculated The heat-resistant dimensional stability (the dimensional retention of each cured product / the dimensional retention of the comparative cured product a) was evaluated. Here, the "initial thickness" is the thickness before the heat treatment.

Heat-resistant weight stability The weight of the hardened product after the test was measured with a digital balance, and the heat-resistant weight stability was calculated after calculating the weight retention rate (%) (weight after 1000 hours heat treatment at 250 ° C / initial weight × 100). (Weight retention of each cured product / weight retention of the comparative cured product a) and evaluation was performed. Here, "initial weight" is the weight before heat processing.

[Table 1]

Table 1 Blending ratio of hardened products

[Table 2]


Table 2 Physical properties of hardened products

As shown in Table 2, it was found that the cured product a to the cured product c to which the compound 1 to compound 3 of the present invention were added was excellent in heat resistance dimensional stability. Moreover, it turns out that hardened | cured material a and hardened | cured material b which added the compound 1 and compound 2 of this invention are excellent in heat resistance transparency, and hardened | cured material a which added the compound 1 of this invention is excellent in heat resistance weight stability.

The present invention will be described in detail using specific aspects, but it will be clear to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present invention will be described in detail with reference to specific aspects, but it will be clear to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. Furthermore, this application is based on a Japanese patent filed on February 20, 2018 (Japanese Patent Application No. 2018-27674), which is incorporated by reference in its entirety. In addition, all references cited herein are incorporated as a whole.
[Industrial availability]

The organosilicon compound of the present invention and a thermosetting resin composition containing the compound can be used in sealing materials for optical semiconductors such as LEDs, insulating films, sealants, adhesives, optical lenses, and the like.

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Claims (9)

A liquid organic silicon compound, which is represented by the following general formula (1): In the general formula (1), R ¹ is a group independently selected from a hydrocarbon group having 1 to 8 carbon atoms, an alicyclic group, or an aromatic hydrocarbon group; in the general formula (1), R ² is from 1 to 8 carbon atoms. Is independently selected from a hydrocarbon group, an alicyclic group, or an aromatic hydrocarbon group; n is each independently an integer of 1 to 50; in the general formula (1), R ^{3 is} each independently a carbon number of 2 to 5 and has one Unsaturated hydrocarbon group with a double bond. A method for producing a liquid organic silicon compound, comprising producing the liquid organic silicon compound according to item 1 of the scope of patent application, the production method comprising combining a compound represented by the following general formula (2-1) with the following A step of performing an equilibrium reaction on the compound represented by the general formula (2-2); In the general formula (2-1), R ^{21 is} independently an unsaturated hydrocarbon group having a double bond having 2 to 5 carbon atoms; in the general formula (2-2), R ²² is a hydrocarbon group having 1 to 8 carbon atoms , An alicyclic group or an aromatic hydrocarbon group, each independently selected; n is an integer of 0-50. A thermosetting resin composition containing the liquid organosilicon compound according to item 1 of the patent application scope. The thermosetting resin composition according to item 3 of the scope of patent application, which contains a liquid organic silicon compound represented by the following structural formula (4): . The thermosetting resin composition according to item 3 or 4 of the patent application scope, which contains a platinum catalyst. The thermosetting resin composition according to any one of claims 3 to 5 of the patent application scope, which comprises at least one of a metal oxide or a phosphor. The hardened | cured material is heat-hardened by the thermosetting resin composition as described in any one of Claims 3-6 of a patent application range. A coating film obtained by applying the thermosetting resin composition according to any one of claims 3 to 6 of the scope of patent application. A resin sealing material for a semiconductor, comprising the thermosetting resin composition according to any one of claims 3 to 6 of a patent application scope.