JP6766334B2 - Organosilicon compounds, thermosetting compositions containing the organosilicon compounds, and encapsulants for opto-semiconductors. - Google Patents

Description

The present invention relates to an organosilicon compound, a thermosetting composition containing the compound, which is useful for applications such as an optical material and an electrically insulating material, a cured product obtained by thermosetting the compound, and an optical semiconductor using the same. Regarding sealing materials.

In recent years, light emitting devices such as light emitting diodes (LEDs) have been put into practical use in various display boards, light sources for reading images, traffic signals, large display units, backlights of mobile phones, and the like. These light emitting devices are generally sealed with a curable resin obtained by curing an aromatic epoxy resin and an alicyclic acid anhydride which is a curing agent. However, in this aromatic epoxy resin system, it is known that the alicyclic acid anhydride is easily discolored by an acid and that it takes a long time to cure. Further, when the light emitting device is left outdoors or exposed to a light source that generates ultraviolet rays, there is a problem that the sealed curable resin turns yellow.

In order to solve such a problem, a method of sealing an LED or the like with a curable resin using an alicyclic epoxy resin or an acrylic resin and a cationic polymerization initiator has been attempted (Patent Documents 1 and 2). See). However, the cationically polymerized curable resin is very brittle and has a drawback that crack fracture is likely to occur in a cold heat cycle test (also referred to as a heat cycle test). Further, this curable resin has a drawback that the sealed curable resin after curing is significantly colored as compared with the conventional curable resin using an aromatic epoxy resin and an acid anhydride. Therefore, this curable resin is not suitable for applications requiring colorless transparency, particularly for LED encapsulation applications requiring heat resistance and transparency.

Therefore, a resin composition for an LED encapsulant, which has improved the occurrence of crack fracture by the thermal cycle test and has excellent light resistance, has been studied (see Patent Document 3). Although the resin composition shown here contains a hydrogenated epoxy resin or an alicyclic epoxy resin as a matrix component, the coloration after curing is still large, and improvement against further discoloration is desired.

On the other hand, white LEDs are used for lighting and the like, and the heat generation of the LED package cannot be ignored as the output increases. When an epoxy resin is used as a sealing material, yellowing due to its heat generation is unavoidable. Therefore, a silicone resin has been used as a sealing material for white LEDs instead of the epoxy resin. Silicone resins used for LEDs can be broadly divided into two types: methyl silicone resins and phenyl silicone resins. Although the methyl silicone resin is extremely excellent in heat resistance and weather resistance, it has a drawback that the light extraction efficiency of the LED is poor because of its low refractive index. Further, the cured methyl silicone resin has a drawback that it is very brittle, easily cracks are easily broken by a thermal cycle test, and has high gas permeability. On the other hand, the phenylsilicone resin has a satisfactory refractive index. It is superior to methyl silicone resin in gas permeability. The same applies to the thermal cycle test, but it is not sufficient to cope with the increase in LED output. In particular, it was difficult to improve because the gas permeability and the characteristics of the thermal cycle test have a contradictory relationship.

Therefore, a sealing material that has both gas permeability and cold cycle test characteristics while maintaining high refractive index, heat resistance, etc., which can cope with high output of white LEDs, and thermosetting used for it. The composition was sought after.

Japanese Unexamined Patent Publication No. 61-1234, Japanese Patent Application Laid-Open No. 02-289611 Japanese Unexamined Patent Publication No. 2003-277473 Japanese Unexamined Patent Publication No. 2006-070049 International Publication No. 2004/081084 Japanese Unexamined Patent Publication No. 2004-331647 International Publication No. 2003/24870 International Publication No. 2004/24741

One of the problems of the present invention is to provide a thermosetting composition capable of obtaining a good cured product for a cold cycle test while maintaining the performance of gas permeability, and this thermosetting composition One of the problems is to provide a sealing material for an organosilicon compound to be contained in a product, a cured product made of a thermosetting composition, a molded product, and a light emitting diode.

The present inventor has made diligent studies to solve the above problems. As a result, it was found that the cured product of the thermosetting composition containing the structure of the double-decker type silicon compound and containing the compound and the curing agent is excellent in the thermal cycle test while maintaining the gas permeability performance. , The present invention has been completed.
That is, the present invention has the following configuration.

式（１）中、Ｒ_１は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルであり、Ｒ_２は独立して、水素または式（２）で表される基であり、４つのＲ_２のうちの少なくとも１つは、式（２）で表される基である。

式（２）中、Ｒ_３は炭素数１〜２０の炭化水素基であり、Ｒ_４は独立して、炭素数１〜２０のアルキル、フェニル、シクロペンチル、またはシクロヘキシルであり、Ｒ_５は、炭素数１〜２０のアルキルまたはフェニルであり、ｎは０〜１,０００の整数である。 [1] An organosilicon compound represented by the formula (1).

In formula (1), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms, and R ₂ is independently a hydrogen or a group represented by the formula (2). at least one of the four R ₂ is a group represented by the formula (2).

In formula (2), R ₃ is a hydrocarbon group having 1 to 20 carbon atoms, R ₄ is independently an alkyl, phenyl, cyclopentyl, or cyclohexyl having 1 to 20 carbon atoms, and R ₅ is carbon. The number 1 to 20 is alkyl or phenyl, where n is an integer from 0 to 1,000.

式（３）中、Ｒ_１は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。

式（４）中、
Ｒ_４は独立して、炭素数１〜２０のアルキル、フェニル、シクロペンチル、またはシクロヘキシルであり、Ｒ_５は炭素数１〜２０のアルキルまたはフェニルであり、Ｒ_６は炭素数２〜２０の不飽和炭化水素基であり、ｎは０〜１,０００の整数である。
[2] A method for producing an organosilicon compound obtained by hydrosilylating a compound represented by the formula (3) and a compound represented by the formula (4).

In formula (3), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms.

In equation (4),
R ₄ is independently an alkyl, phenyl, cyclopentyl, or cyclohexyl with 1 to 20 carbon atoms, R ₅ is an alkyl or phenyl with 1 to 20 carbon atoms, and R ₆ is unsaturated with 2 to 20 carbon atoms. It is a hydrocarbon group, and n is an integer of 0 to 1,000.

[3] The organosilicon compound according to [1] or the organosilicon compound (A) produced by the production method according to [2], and the silicon compound (B) having at least two vinyl groups are contained. Thermosetting composition.

[4] The thermosetting composition according to [3], which further contains a platinum catalyst (C).

[5] The thermosetting composition according to [3] or [4], which further contains a silicon compound (D) having at least two SiH groups at the terminal.

[6] The thermosetting composition according to any one of [3] to [5], wherein a metal oxide or a phosphor is further dispersed.

[7] A cured product obtained by thermosetting the thermosetting composition according to any one of [3] to [6].

[8] A molded product obtained by molding the cured product according to [7].

[9] A coating film formed by applying the thermosetting composition according to any one of [3] to [6].

[10] A sealing material for an optical semiconductor, which comprises the thermosetting composition according to any one of [3] to [6].

The cured product obtained by using the thermosetting composition of the present invention has the characteristics of high transparency and high refractive index, and is excellent in heat resistance as compared with the conventional phenyl silicone-based sealing material. It also has excellent adhesive strength. In addition, since this cured product has a double-decker type silsesquioxane skeleton, it is also excellent in insulating properties.

FIG. 1 is a ¹ H-NMR spectrum of Si4V synthesized in Synthesis Example 2. FIG. 2 is a ²⁹ Si-NMR spectrum of Si4V synthesized in Synthesis Example 2. FIG. 3 is a ²⁹ Si-NMR spectrum of the compound (1-1) synthesized in Example 1. FIG. 4 is a ²⁹ Si-NMR spectrum of the compound (1-2) synthesized in Example 2. FIG. 5 is a ²⁹ Si-NMR spectrum of the compound (1-3) synthesized in Example 3.

<Organosilicon compound of the present invention>
The organosilicon compound of the present invention is represented by the formula (1).

Ｒ_３は炭素数２〜２０までの炭化水素基であり、Ｒ_４は独立して、炭素数１〜２０のアルキル、フェニル、シクロペンチル、またはシクロヘキシルであり、Ｒ_５は炭素数１〜２０のアルキルまたはフェニルであり、ｎは０〜１,０００の整数である。
In formula (1), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms, and R ₂ is independently a hydrogen or a group represented by the formula (2). at least one of the four R ₂ is a group represented by the formula (2).

R ₃ is a hydrocarbon group having 2 to 20 carbon atoms, R ₄ is independently an alkyl having 1 to 20 carbon atoms, phenyl, cyclopentyl, or cyclohexyl, and R ₅ is an alkyl having 1 to 20 carbon atoms. Alternatively, it is phenyl, where n is an integer from 0 to 1,000.

式（３）中、Ｒ_１は独立して、炭素数１〜４のアルキル、シクロペンチル、シクロヘキシル、またはフェニルである。

式（４）中、Ｒ_４は独立して、炭素数１〜２０のアルキル、フェニル、シクロペンチル、またはシクロヘキシルであり、Ｒ_５は炭素数１〜２０のアルキルまたはフェニルら選択される基であり、Ｒ_６は炭素数２〜２０の不飽和炭化水素基であり、ｎは０〜１,０００の整数である。
The organosilicon compound of the present invention can be obtained by hydrosilylating a compound represented by the formula (3) (silsesquioxane derivative) and an organopolysiloxane represented by the formula (4).

In formula (3), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms.

In formula (4), R ₄ is independently an alkyl, phenyl, cyclopentyl, or cyclohexyl having 1 to 20 carbon atoms, and R ₅ is a group selected from alkyl or phenyl having 1 to 20 carbon atoms. R ₆ is an unsaturated hydrocarbon group having 2 to 20 carbon atoms, and n is an integer of 0 to 1,000.

A known method can be used for the hydrosilylation reaction between the compound represented by the formula (3) and the compound represented by the formula (4), and a solvent is not always required. When used, it is not particularly limited as long as it does not inhibit the progress of the reaction. Preferred solvents are hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, methylene chloride and tetrachloride. These include halogenated hydrocarbon solvents such as carbon and ester solvents such as ethyl acetate. These solvents may be used alone or in combination of two or more. Among these solvents, aromatic hydrocarbon-based solvents, among which toluene is most preferable.

The hydrosilylation reaction can be carried out at room temperature and normal pressure and may be heated to accelerate the reaction. Cooling may be performed to control heat generation due to the reaction or an unfavorable reaction. A catalyst can be used in the hydrosilylation reaction if necessary. The reaction can proceed more easily by adding a hydrosilylation catalyst. Examples of preferred hydrosilylation catalysts are Karsted't catalysts, Spier catalysts, hexachloroplatinic acids and the like, which are generally well known catalysts. Since these hydrosilylation catalysts are highly reactive, the reaction can be sufficiently proceeded by adding a small amount. The amount used is ^10-9 to 1 mol% as a ratio of the transition metal contained in the catalyst to the hydrosilyl group. The preferred addition ratio is ^10-7 to ^10-3 mol%.

The molecular weight of the organosilicon compound of the present invention is preferably 1,000 to 100,000 in terms of weight average molecular weight (Mw).

Further, in the organic silicon compound of the present invention, a cured product obtained by preparing and curing a thermosetting composition containing the compound has a refractive index, transparency, heat resistance (heat-resistant yellowing, transparency resistance), and cold heat. It is an excellent raw material for a cured product that has excellent cycle characteristics and has improved the drawbacks of a cured product made of a conventionally used phenyl silicone resin or methyl silicone resin.
When used for LEDs and the like, the refractive index of the cured product can be used without any problem as long as it is 1.4 or more, preferably 1.49 or more, and the upper limit is not particularly limited.

The silsesquioxane derivative, which is a compound represented by the formula (3), can be synthesized, for example, by the method disclosed in International Publication No. 2004/024741. An example of the compound represented by the formula (3) (hereinafter referred to as DD-4H) is shown. Me in the structural formula is methyl.

The organopolysiloxane having an unsaturated hydrocarbon group represented by the formula (4) can be synthesized by a known method, or a commercially available compound may be used.
Examples of the compound represented by the formula (4) include trimethylvinylsilane represented by the formula (5). Further, 1-butyl-1,1,3,3,5,5,7,7-7-vinyltetrasiloxane represented by the formula (6) can be exemplified. Bu in the structural formula is butyl. Further, as a commercially available compound, Gelest Inc. Examples of "MonoVinyl Terminated PolyDimethicyloxynes" available from, with molecular weights of 5,500 to 6,500 and 55,000 to 65,000. Preferably, compounds like having an unsaturated group in ends of the hydrocarbon group, more _preferably, CH 2 = CH- group and _{CH 2} = _CH-CH 2 - is a radical. N in the formula (4) is an integer of 0 to 1,000, and is preferably 0 to 10.

The thermocurable composition of the present invention hydrosilylates an organosilicon compound represented by the formula (1) or a compound represented by the formula (3) with a compound represented by the formula (4). It contains the obtained organosilicon compound (A) and the silicon compound (B) having at least two vinyl groups in one molecule.
A curing catalyst (C) is further added to the thermosetting composition and heated to obtain a cured product. It is also a preferred embodiment that the thermosetting composition further contains a silicon compound (D) having at least two SiH groups at the terminal.

The silicon compound (B) having at least two vinyl groups is not particularly limited as long as it is a silicon compound having at least two vinyl groups for cross-linking, for example, a linear polysiloxane having vinyl groups at both ends or a terminal. A branched polysiloxane having at least two vinyl groups can be used. Specifically, it has 1,1,3,3-divinyltetramethyldisiloxane, 1,1,5,5-divinylhexamethyltrisiloxane, a linear polysiloxane having vinyl groups at both ends, and a T structure. Examples thereof include branched polysiloxane having a terminal vinyl group, and it is preferable to use a compound having a molecular weight of 150 to 10,000, preferably 200 to 5,000.

The silicon compound (B) having at least two vinyl groups may be used alone or in a blend of two or more different compounds.

The silicon compound (D) having at least two SiH groups at the ends is not particularly limited as long as it is a silicon compound having at least two SiH groups for cross-linking. For example, a linear poly having SiH groups at both ends. A siloxane, a linear polysiloxane having a SiH group in the side chain, a branched polysiloxane having at least two SiH groups at the end, or a compound represented by the formula (3) can be used. Specifically, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, linear polysiloxane having SiH groups at both ends, T. Examples thereof include branched polysiloxane having a structure and a terminal SiH group, and it is preferable to use a compound having a molecular weight of 150 to 10,000, preferably 200 to 5,000. The silicon compound having at least two SiH groups at the terminal may be used alone or in a blend of two or more different compounds.

These molecular weights are weight average molecular weights in the range that can be measured by GPC, and are molecular weights calculated from the structure of the compound in the case of low molecular weights that cannot be measured by GPC.

The content of compound (A) in the thermosetting composition of the present invention is 0.1% by weight based on the total amount of compound (A), compound (B), and compound (D) from the viewpoint of heat resistance. The above is preferable, 1% by weight or more is more preferable, and 5% by weight or more is further preferable. The content of the compound (B) is preferably 1 to 50% by weight, preferably 3 to 30% by weight, based on the total amount of the compound (A), the compound (B), and the compound (D). Is more preferable, and 5 to 15% by weight is even more preferable. In the thermosetting composition of the present invention, the content ratio of the total SiH group and the total vinyl group is preferably 1: 2 to 2: 1 in terms of the molar ratio of functional groups of SiH group and vinyl group.

The curing catalyst (C) is not particularly limited as long as it is a transition metal catalyst usually used as a reaction catalyst, but it is preferable to use a platinum catalyst. As an example of the platinum catalyst, a conventional hydrosilylation catalyst can be selected. Examples of preferred hydrosilylation catalysts are Karsted't catalysts, Spier catalysts, hexachloroplatinic acids and the like.

The amount of the transition metal contained in the catalyst is 0.1 ppm to 10 ppm in terms of weight ratio with respect to the thermosetting composition. When the addition ratio is 0.1 ppm or more, the curing is good. Further, when the addition ratio is 10 ppm or less, the pot life after preparing the thermosetting composition is not too short, the pot life can be preferably used, and the obtained cured product is less likely to be colored. The preferred addition ratio is 0.5 ppm to 4 ppm.

The thermosetting composition of the present invention does not require a solvent. Since the thermosetting composition of the present invention can be used in applications where mixing of solvents is not preferred, the applications are greatly expanded.

The following components may be further added to the thermosetting composition of the present invention.
(I) Powdered reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, molten silica and crystalline silica, transparent fillers such as glass beads, aluminum hydroxide and the like. Metal hydroxides, other kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc. These are preferably blended within a range that does not impair the transparency of the thermosetting composition of the present invention. The preferable ratio when these are blended is in the range of 0.1 to 0.6 as a weight ratio to the total amount of the thermosetting composition of the present invention.

(Ii) Colorants or pigments such as titanium dioxide, molybdenum red, dark blue, ultramarine, cadmium yellow, cadmium red and organic pigments.
(Iii) Flame retardants such as antimony trioxide, brom compounds and phosphorus compounds.
(Iv) Ion adsorbent.
The preferable ratio when the components (ii) to (iv) are blended is 0.0001 to 0.30 by weight with respect to the total amount of the thermosetting composition.

(V) Silane coupling agent.
(Vi) Nanoparticle dispersion of metal oxides such as zirconia, titania, alumina and silica.
The preferable ratio when the components (v) to (vi) are blended is 0.01 to 0.50 in terms of weight ratio to the total amount of the thermosetting composition.

(Vii) Phenolic, sulfur, phosphorus and other antioxidants.
The preferable ratio when the curing accelerator is used is in the range of 0.0001 to 0.1 as a weight ratio to the total amount of the thermosetting composition of the present invention.
(Viii) An ultraviolet absorber for improving light resistance.
The preferable ratio when the ultraviolet absorber is used is in the range of 0.0001 to 0.1 as a weight ratio to the total amount of the thermosetting composition of the present invention.

The thermosetting composition of the present invention can be produced, for example, by the following method.
(A) The organosilicon compound of the present invention,
(B) A silicon compound having at least vinyl groups at both ends,
(C) Curing catalyst,
Further, if necessary, the above optional components are stirred and mixed, and then the pressure is reduced to defoam. Then, this mixture is poured into a mold, heated at 100 ° C. for 1 hour, and finally heated at 150 ° C. for 1 to 2 hours to cure.

The heat resistance of the cured product is evaluated for heat resistance transparency and heat resistance yellowing. The heat-resistant transparency was evaluated by measuring the transmittance of the cured product before and after the heat-resistant test with an ultraviolet-visible spectrophotometer and measuring the light transmittance retention rate. The heat-resistant yellowing was evaluated by the retention rate of the yellowness (YI value) of the cured product before and after the heat-resistant test. The retention rates of yellowness (YI value) and light transmittance at 180 ° C. are preferably 5 or less and 90% or more, respectively. When each value falls within these ranges, it indicates that the cured product is colorless and has high transparency, and is particularly preferably used in fields such as optical semiconductor encapsulants where transparency is required. it can.

The extremely good properties of the cured product obtained by thermosetting the thermosetting composition of the present invention in terms of heat resistance and transparency are due to the structure of the silsesquioxane derivative which is a compound represented by the formula (3). ing. That is, the double-decker type silsesquioxane skeleton has a property of being superior in heat resistance and transparency as compared with silsesquioxane, which is a normal random structure, due to its three-dimensional structure, and the cured product is colored by heating. Gives a suppressive effect.

By molding a cured product obtained by thermosetting the thermosetting composition of the present invention into a molded product, it can be used for various purposes. By dispersing a metal oxide or a phosphor in the above composition, it has a light emitting function and can be used as an LED composition. In addition, examples of applications include optical semiconductor encapsulants, semiconductor encapsulants, insulating films, sealing materials, adhesives, optical lenses, and the like.

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

[Synthesis Example 1]
<Synthesis of silsesquioxane derivative (DD-4H)>
Phenyltrimethoxysilane (6,540 g), sodium hydroxide (880 g), ion-exchanged water (660 g), and 2-propanol (26.3 L) in a reaction vessel equipped with a reflux condenser, thermometer, and dropping funnel. Was prepared. Heating (80 ° C.) was started with stirring under a nitrogen stream. The mixture was stirred for 6 hours from the start of reflux and allowed to stand overnight at room temperature (25 ° C.). Then, the reaction mixture was transferred to a filter, pressurized with nitrogen gas, and filtered. The obtained solid was washed once with 2-propyl alcohol, filtered, and then dried under reduced pressure at 80 ° C. to obtain a colorless solid (DD-ONa) (3,300 g) represented by the following formula.

Next, cyclopentyl methyl ether (2,005 g), 2-propanol (243 g), ion-exchanged water (1,400 g), and hydrochloric acid (461 g) were placed in a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. The mixture was charged and stirred at room temperature (25 ° C.) under a nitrogen atmosphere. Subsequently, the above-mentioned compound (DD-ONa) (800 g) and cyclopentyl methyl ether (2,003 g) were charged into the dropping funnel to form a slurry, which was added dropwise to the reactor over 30 minutes, and 30 minutes after the completion of the dropping. Stirred. Then, it was allowed to stand and separated into an organic layer and an aqueous layer. The obtained organic layer was made neutral by washing with water, dust was removed with a membrane filter, and concentrated under reduced pressure at 60 ° C. using a rotary evaporator to obtain 678 g of a colorless solid. This colorless solid was washed with methyl acetate (980 g) and dried under reduced pressure to obtain a colorless powder solid (DD-4OH) (496 g) represented by the following formula.

Next, the compound (DD-4OH) (7,160 g), toluene (72,600 g), dimethylchlorosilane (2,850 g) obtained above were placed in a reactor equipped with a dropping funnel, a thermometer, and a reflux condenser. Was charged and sealed with dry nitrogen. Triethylamine (3,230 g) was then added dropwise from the dropping funnel over about 20 minutes. At this time, the solution temperature is 35 ° C to 40 ° C. After completion of the dropping, the mixture was stirred for 1 hour, then ion-exchanged water (16,700 g) was added, and an excess amount of dimethylchlorosilane was hydrolyzed to separate an organic layer and an aqueous layer. After the organic layer was washed with water to neutralize it, it was concentrated under reduced pressure at 85 ° C. using a rotary evaporator, and the obtained residue was washed with methanol (19,950 g) to obtain 8,588 g of a colorless solid. This colorless solid was washed with methyl acetate (9,310 g) and dried under reduced pressure to obtain a colorless powder solid (7,339 g). The obtained colorless powder solid is judged to have the following structure (DD-4H) from the following analysis results. ^{1 1} H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.16 (d, 24H), 4.84-4.89 (m, 4H), 7.05-7.50 (m, 40H) .. ²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); 3.85 (s, 4Si), -71.90 (s, 4Si), -75.05 (s, 4Si).

[Synthesis Example 2]
<Synthesis of Si4V>
A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached to a 1 L four-necked flask, and 89 g of hexamethylcyclotetrasiloxane and 200 g of tetrahydrofuran were charged. The temperature was cooled to 0 ° C., and 174 g of n-butyllithium was charged into the dropping funnel and dropped. After reacting for 1 hour, 52 g of vinyldimethylchlorosilane was charged into the dropping funnel and added dropwise. Then, it reacted at room temperature for 15 hours. 201 g of toluene was added into the flask, and 101 g of water was charged into the dropping funnel and dropped. The content was transferred to a separatory funnel and the organic layer was washed 5 times with water. The recovered organic layer was purified by distillation to obtain 96 g of a colorless and transparent liquid. From the results of ¹ H-NMR in FIG. 1 and ²⁹ Si-NMR analysis in FIG. 2, it was identified as having a structure (Si4V).

[Example 1]
The silsesquioxane derivative (DD-4H) synthesized in Synthesis Example 1, which is a compound represented by the formula (3), and the one-ended terminal synthesized in Synthesis Example 2, which is a compound represented by the formula (4). The compound (1-1) was synthesized by hydrosilylation reaction as described below by adjusting the charging ratio of Si4V having a vinyl group to 1: 4 in terms of the number of moles.

A reaction vessel having an internal volume of 100 mL equipped with a thermometer, a reflux condenser, and a magnetic stir bar was charged with 5.2 g of DD-4H and 5.9 g of Si4V (4 times the mole of DD-4H).
Heating and stirring were started in a nitrogen atmosphere. After the temperature of the contents reached 100 ° C., 1 μL of the calstead catalyst was added, and the mixture was heated and stirred as it was for 5 hours. Then, IR measurement was carried out, and heating and stirring were further carried out for 1 hour. Peak derived from the structure of the Si-H (2130cm ^-1), the reaction was terminated sure that was Tsu kuna such changes. The unreacted component was distilled off under a reduced pressure condition of 180 ° C. and 0.1 kPa with an evaporator to obtain a transparent liquid.
The results of ²⁹ Si-NMR analysis of FIG. 3, it was possible to obtain compounds _{wherein R 2} in the formula (1) is replaced by compounds represented by 4 together formula (2) (1-1) ..

[Examples 2 to 3]
In Example 1, the molar ratios of DD-4H, which is a compound represented by the formula (4), and organopolysiloxane (Si4V) having a vinyl group at one end produced in Synthesis Example 2 were changed. The same procedure as in Example 1 was carried out to obtain compounds (1-2) and (1-3). Table 1 shows the charging amount and charging ratio of DD-4H and Si4V. Figure 4 below, the results of ²⁹ Si-NMR analysis of FIG. 5, the formula (1) compound substituted by the number as described in the table 1 with _{R 2} has the formula (2) in (1-2 1-3) could be obtained.

Table 1

[Examples 4 to 6]
In Examples 1 and 2, Si4V was changed to an organopolysiloxane having a vinyl group at one end and a molecular weight of 6,000 (product name: MCR-V21, manufacturer: Gelest Inc.), and toluene was used as the solvent. It was carried out in the same manner as in Examples 1 and 2 except that it was used. Table 2 shows the amount of DD-4H, MCR-V21 and toluene charged, and the ratio of DD-4H and MCR-V21 charged. As a result, the same as the compounds shown in Examples 1 and 2, R ₂ in the formula (1) was replaced with the number shown in Table 2 in the formula (2) (2-1, 2). -2, 2-3) could be obtained.

Table 2

[Example 7]
Examples 1 and 2 were carried out in the same manner as in Examples 1 and 2 except that vinylpentamethyldisiloxane (MV) (manufacturer: Gelest Inc.) was used instead of Si4V. Table 3 shows the amount of DD-4H, MV, and toluene charged and the ratio of DD-4H and MV charged. As a result, a compound (3) in which R ₂ in the formula (1) is replaced with a number as shown in Table 3 in the formula (2) is obtained in the same manner as the compounds shown in Examples 1 and 2. Was made.

Table 3

[Example 8]
Examples 1 and 2 were carried out in the same manner as in Examples 1 and 2 except that vinyl phenyldimethylsilane (VPDMS) (manufacturer: Gelest Inc.) was used instead of Si4V. Table 4 shows the amount of (DD-4H), VPDMS, and toluene charged, and the ratio of DD-4H and VPDMS charged. As a result, a compound (4) in which R ₂ in the formula (1) is replaced with a number as shown in Table 4 in the formula (2) is obtained in the same manner as the compounds shown in Examples 1 and 2. I was able to do it.

Table 4

Hereinafter, preparation of a thermosetting composition, a cured product obtained from this composition, and a physical property evaluation test method will be described.

The main materials used are as follows.
Organosilicon compounds: Compounds (1-1) to (1-3) synthesized in Examples
PSQ Polymer: PSQ Derivative DVTS: 1,5-Divinyl-1, 1, 3, 3, 5, 5-Hexamethyltrisiloxane (Gelest) synthesized by the method described in Example 1 of WO2011 / 145638. Obtained from)
Vinylsiloxane: A linear dimethylpolysiloxane having a molecular weight of 750 and having vinyl groups at both ends of the molecular chain. (ViMe ₂ SiO _1/2 ) _1.5 (Me ₂ SiO _2/2 ) _1.5 . It can be synthesized by a known method.
Adhesive imparting agent: 3-glycidoxypropyltrimethoxysilane (JNC Corporation S510)

<Preparation of thermosetting composition>
The compounds as shown in Table 5 were placed in the screw tube. The screw tube was set in a rotation / revolution mixer (Awatori Rentaro ARE-250 manufactured by Shinky Co., Ltd.), and mixed and defoamed to obtain a varnish. A platinum catalyst was added so that the amount of platinum was 1 ppm, and the mixture was mixed and defoamed again with a rotation / revolution mixer to obtain thermosetting compositions 1 to 3 and comparative composition 1.
Table 5 shows the compounding ratio of each composition.

<Creation of cured product>
Two pieces of glass are sandwiched between Nichias Corporation's Naflon SP packing (4 mm diameter) as a spacer, and the thermosetting composition is poured therein. After defoaming under reduced pressure, 80 ° C. for 1 hour and 120 ° C. for 1 hour. The glass was cured by heating at 150 ° C. for 2 hours in that order, and the glass was peeled off to obtain a cured product having a thickness of 4 mm and a smooth surface.
OE-6630 (manufactured by Toray Dow Corning Silicone) was mixed at a ratio of solution A: solution B = 1: 4 to obtain a comparative composition 2, and the same cured product was used as the comparative cured product 2.

<Creation of curing package>
Enomoto Co., Ltd. lead frame 5050 D / G PKG with a blue LED chip and gold wire mounted on it with the above thermosetting composition and OE-6630 with Musashi Engineering Co., Ltd. dispenser MEASURING MASTER MPP-1. It was injected using and cured in the same manner to obtain a cured package.

<Measurement of light transmittance>
The transmittance was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation. Moreover, the total light transmittance was calculated from the transmittance of 400 nm-800 nm.
The transparency of the cured product was visually judged by the presence or absence of coloring, and when there was no coloring, it was judged that the transparency was good.

<Refractive index>
As the test piece, a cured product having a thickness of 4 mm was cut with a band saw to prepare a test piece according to JIS K7142. Using this test piece, the refractive index was measured using the D line (586 nm) of a sodium lamp with an Abbe refractometer (NAR-2T manufactured by Atago Co., Ltd.). Methylene iodide was used as the intermediate solution.

<Hardness>
It was measured by a durometer WR-105D manufactured by Nishi Tokyo Precision Co., Ltd. according to JIS K6253.

<Glass transition temperature (Tg)>
A cured product film having a thickness of 0.9 mm was similarly heat-cured to prepare a film, which was measured by a thermomechanical analyzer TMA / SS6100 manufactured by SII Nanotechnology Co., Ltd.

<Heat resistance test>
The heat resistance test was carried out and evaluated by the following method.
Two cured products having a thickness of 4 mm were prepared, and the obtained cured products were placed in an oven at 180 ° C. (constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.) and heat-treated for 160 hours. After 160 hours, those with almost no coloring were marked with ◯, and those with almost no coloring were marked with x.

<Cold heat cycle test>
In the cold cycle test, the cured package prepared by the above method is placed in the test area of the cold shock device TSA-101S-W manufactured by ESPEC CORPORATION, exposed at -40 ° C for 30 minutes, and exposed at 105 ° C for 30 minutes for one cycle. As a result, it was carried out by repeating 100 cycles. The moving time between the two exposure temperatures was 5 minutes. After 100 cycles, a lighting test was conducted, and those that were all lit were marked with ⊚, those that were lit more than half were marked with ◯, those that were lit less than half were marked with Δ, and those that were all turned off were marked with x.

<Sulfur resistance test>
The sulfur resistance test was carried out by placing the cured package prepared by the above method in a 450 ml airtight container containing 5 g of sulfur powder, leaving it at 80 ° C. for 16 hours, and then observing the degree of blackening due to sulfur. Those that did not show discoloration were marked with ◎, those that turned light gray were marked with ○, those that turned dark gray were marked with △, and those that turned black were marked with ◎.

Table 6 shows the results of various physical property evaluation tests of the cured products 1 to 3 and the comparative cured products 1 and 2 obtained by curing the compositions 1 to 3 and the comparative compositions 1 and OE-6630 of Table 5. Shown.
It has been clarified that the cured products 1 to 3 are cured products having high hardness, excellent heat resistance, excellent gas permeability resistance, and cold heat cycle resistance.
By blending the compound having the double-decker type silsesquioxane structure of the present invention, it is possible to exert the effect of improving the cold heat cycle resistance while maintaining the gas permeability of the comparative cured product 1. Shown.

Table 5

Table 6

From this, the cured product obtained by using the thermosetting composition of the present invention has good transparency, high refractive index of 1.49 or more, and other good properties. It was clarified that the characteristics of the thermal cycle test can be improved while maintaining the gas permeability resistance as compared with the phenylsilicone-based sealing material.

The molded product made of the cured product of the present invention can be suitably used for applications such as semiconductor encapsulants, opto-semiconductor encapsulants, insulating films, sealing materials, and optical lenses. In addition, adhesives, electronic materials, insulating materials, interlayer insulating films, paints, inks, coating materials, molding materials, potting materials, liquid crystal sealing materials, sealing materials for display devices, solar cell sealing materials, resist materials, color filters, etc. It can be used as a material for electronic paper, a material for holograms, a material for solar cells, a material for fuel cells, a recording material, a waterproof material, a moisture-proof material, a solid electrolyte for batteries, and a gas separation membrane. Further, it can be used as an additive to other resins.

Claims (10)

An organosilicon compound represented by the formula (1).

In formula (1), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms, and R ₂ is independently a hydrogen or a group represented by the formula (2). at least one of the four R ₂ is a group represented by the formula (2).

In formula (2), R ₃ is a hydrocarbon group having 2 to 20 carbon atoms, R ₄ is independently an alkyl, phenyl, cyclopentyl, or cyclohexyl having 1 to 20 carbon atoms, and R ₅ is carbon. The number 1 to 20 is alkyl or phenyl, where n is an integer from 0 to 1,000 .
A method for producing an organosilicon compound obtained by hydrosilylating a compound represented by the formula (3) and a compound represented by the formula (4).

In formula (3), R ₁ is independently an alkyl, cyclopentyl, cyclohexyl, or phenyl having 1 to 4 carbon atoms.

In formula (4), R ₄ is independently an alkyl, phenyl, cyclopentyl, or cyclohexyl having 1 to 20 carbon atoms, R ₅ is an alkyl or phenyl having 1 to 20 carbon atoms, and R ₆ is an alkyl or phenyl group having 1 to 20 carbon atoms. It is an unsaturated hydrocarbon group of 2 to 20, and n is an integer of 0 to 1,000 . Thermosetting containing the organosilicon compound according to claim 1 or the organosilicon compound (A) produced by the production method according to claim 2, and the silicon compound (B) having at least two vinyl groups. Composition. The thermosetting composition according to claim 3, further comprising a curing catalyst (C). The thermosetting composition according to claim 3 or 4, further comprising a silicon compound (D) having at least two SiH groups at the ends. The thermosetting composition according to any one of claims 3 to 5, further comprising a metal oxide or a phosphor dispersed therein. A cured product obtained by thermosetting the thermosetting composition according to any one of claims 3 to 6. A molded product obtained by molding the cured product according to claim 7. A coating film formed by applying the thermosetting composition according to any one of claims 3 to 6. An encapsulant for an optical semiconductor comprising the thermosetting composition according to any one of claims 3 to 6.

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