JP2017078103A - Organic silicon compound, thermosetting composition comprising the organic silicon compound, and optical semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting composition excellent in gas permeability and characteristics of a cold-hot cycle test.SOLUTION: The present invention provides a thermosetting composition comprising an organic silicon compound and a vinyl group-containing silicon compound (Rs independently represent a C1-4 alkyl group, alicyclic group or phenyl group; Rs independently represent H or a linear siloxane chain group).SELECTED DRAWING: None

Description

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

  In recent years, light emitting devices such as light emitting diodes (LEDs) have been put to practical use in various display boards, image reading light sources, traffic signals, large display units, mobile phone backlights, 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 as 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 is yellowed.

  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 cation-polymerized curable resin is very fragile and has a defect that it is liable to cause crack fracture in a cold cycle test (also referred to as a heat cycle test). Further, this curable resin has a defect that the sealed curable resin is markedly colored after curing, as compared with a curable resin using a conventional aromatic epoxy resin and acid anhydride. Therefore, this curable resin is not suitable for applications requiring colorless transparency, particularly for LED sealing applications requiring heat resistance and transparency.

  Then, the generation | occurrence | production of the crack fracture | rupture by a thermal cycle test is improved, and the resin composition for LED sealing materials excellent in light resistance is examined (refer patent document 3). Although the resin composition shown here uses a hydrogenated epoxy resin or an alicyclic epoxy resin as a matrix component, the coloration after curing is still large, and an improvement for further discoloration is desired.

  On the other hand, white LEDs are used for applications such as lighting, and 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 the heat generation is unavoidable. Therefore, a silicone resin has been used as a sealing material for white LEDs in place of the epoxy resin. Silicone resins used for LEDs are roughly divided into two types: methylsilicone resins and phenylsilicone resins. Although methylsilicone resin is very 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. Furthermore, the cured methylsilicone resin is very brittle, has a disadvantage that it is prone to crack fracture by a thermal cycle test and has high gas permeability. On the other hand, the phenyl silicone resin has a satisfactory refractive index. Gas permeability is superior to methyl silicone resin. The same applies to the thermal cycle test, but it is not sufficient to cope with the increased output of the LED. In particular, since the gas permeability and the characteristics of the thermal cycle test have a contradictory relationship, it was difficult to improve.

  Therefore, a sealing material that has both gas permeability and characteristics of a thermal cycle test while maintaining performance such as high refractive index and heat resistance, which can cope with a large output of a white LED, and thermosetting used for it. A composition was sought.

JP-A-61-112334, Japanese Patent Laid-Open No. 02-289611 JP 2003-277473 A JP 2006-070049 A International Publication No. 2004/081084 JP 2004-331647 A International Publication No. 2003/24870 International Publication No. 2004/24741

  An object of the present invention is to provide a thermosetting composition capable of obtaining a good cured product for a cold cycle test while maintaining gas permeability performance. An object is to provide an organic silicon compound to be contained in a product, a cured product formed of a thermosetting composition, a molded body, and a sealing material for a light-emitting diode.

The present inventor has intensively studied to solve the above problems. As a result, it has been found that a cured product of a thermosetting composition containing a structure of a double-decker silicon compound and containing the compound and a curing agent is excellent in a thermal cycle test while maintaining gas permeability. 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 alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl, and R ₂ is independently hydrogen or a group represented by 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 alkyl having 1 to 20 carbon atoms, phenyl, cyclopentyl, or cyclohexyl, and R ₅ is carbon. N is an integer of 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１〜２０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 alkyl having 1 to 4 carbons, cyclopentyl, cyclohexyl, or phenyl.

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

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

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

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

[6] The thermosetting composition according to any one of [3] to [5], in which 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] An encapsulant for optical semiconductors comprising 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 high transparency and high refractive index characteristics, and is superior in heat resistance as compared with conventional phenyl silicone-based sealing materials. Furthermore, it has excellent adhesion strength. Further, since this cured product has a double-decker silsesquioxane skeleton, it is excellent in insulation.

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

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

Ｒ_３は炭素数１〜２０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 alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl, and R ₂ is independently hydrogen or a group represented by 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 1 to 20 carbon atoms, R ₄ is independently alkyl having 1 to 20 carbon atoms, phenyl, cyclopentyl, or cyclohexyl, and R ₅ is an alkyl having 1 to 20 carbon atoms. Or it is phenyl and n is an integer of 0-1,000.

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１〜２０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 hydrosilylation reaction of a compound represented by formula (3) (silsesquioxane derivative) and an organopolysiloxane represented by formula (4).

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

In formula (4), R ₄ is independently alkyl having 1 to 20 carbons, phenyl, cyclopentyl, or cyclohexyl, R ₅ is a group selected from alkyl having 1 to 20 carbons or phenyl, R ₆ is an unsaturated hydrocarbon group having 1 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 formula (3) and the compound represented by formula (4), and a solvent is not necessarily 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. Halogenated hydrocarbon solvents such as carbon and ester solvents such as ethyl acetate. These solvents may be used alone or in combination. Among these solvents, aromatic hydrocarbon solvents, and 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. It may be cooled to control exothermic reaction or undesirable reaction. In the hydrosilylation reaction, a catalyst can be used as necessary. By adding a hydrosilylation catalyst, the reaction can proceed more easily. Examples of preferred hydrosilylation catalysts are Karsted't catalyst, Spier catalyst, hexachloroplatinic acid and the like, which are generally well known catalysts. Since these hydrosilylation catalysts are highly reactive, the reaction can proceed sufficiently if added in a small amount. The amount used is 10 ⁻⁹ to 1 mol% in terms of the ratio of the transition metal contained in the catalyst to the hydrosilyl group. A preferable 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).

In addition, the organosilicon compound of the present invention has a refractive index, transparency, heat resistance (heat-resistant yellowing resistance, transparency resistance), and cooling heat, which is obtained by preparing and curing a thermosetting composition containing the compound. It is excellent in cycle characteristics and is a raw material of an excellent cured product in which defects of a cured product made of a phenyl silicone resin and a methyl silicone resin that have been conventionally used are improved.
When used for an LED or the like, if the refractive index of the cured product is 1.4 or more, it can be used without any problem, 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 by, for example, a method disclosed in International Publication No. 2004/024741. Examples of the compound represented by the formula (3) (hereinafter referred to as DD-4H) are 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.
An example of the compound represented by the formula (4) is 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, commercially available compounds include Gelest Inc. Examples of the molecular weights are 5,500-6,500 and 55,000-65,000 in “MonoVinyl Terminated Polydimethylsiloxanes” available from A compound having an unsaturated group at the terminal of the hydrocarbon group is preferable, and a CH ₂ ═CH— group or a CH ₂ ═CH—CH ₂ — group is more preferable. N in Formula (4) is an integer of 0 to 1,000, and preferably 0 to 10.

The thermosetting composition of the present invention undergoes a hydrosilylation reaction between an organosilicon compound represented by formula (1) or a compound represented by formula (3) and a compound represented by formula (4). The resulting organosilicon compound (A) and a silicon compound (B) having at least two vinyl groups in one molecule are contained.
A cured product is obtained by further adding a curing catalyst (C) to the thermosetting composition and heating. Moreover, it is also a preferable aspect that this thermosetting composition further contains a silicon compound (D) having at least two SiH groups at the terminals.

  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 crosslinking. For example, a linear polysiloxane having vinyl groups at both ends or a terminal polysiloxane. Branched polysiloxanes having at least two vinyl groups can be used. Specifically, 1,1,3,3-divinyltetramethyldisiloxane, 1,1,5,5-divinylhexamethyltrisiloxane, linear polysiloxane having vinyl groups at both ends, and having 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.

  Further, the silicon compound (D) having at least two SiH groups at the terminals is not particularly limited as long as it is a silicon compound having at least two SiH groups for crosslinking. A siloxane, a linear polysiloxane having a SiH group in the side chain, a branched polysiloxane having at least two SiH groups at the terminal, or a compound represented by the formula (3) can be used. Specifically, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, a 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 a molecular weight of 200 to 5,000. The silicon compound having at least two SiH groups at the end 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 molecular weights calculated from the structure of the compound in the case of a low molecular weight that cannot be measured by GPC.

  In the thermosetting composition of the present invention, the content of the compound (A) is 0.1% by weight based on the total amount of the compound (A), the compound (B), and the compound (D) from the viewpoint of heat resistance. Preferably, it is preferably 1% by weight or more, more preferably 5% by weight or more. Moreover, it is preferable that content of a compound (B) is 1 to 50 weight% with respect to the whole quantity of a compound (A), a compound (B), and a compound (D), and it is 3 to 30 weight%. Is more preferable, and it is still more preferable that it is 5 to 15 weight%. In the thermosetting composition of the present invention, the content ratio of the total SiH groups and the total vinyl groups is preferably 1: 2 to 2: 1 in terms of the functional group molar ratio of SiH groups to vinyl groups.

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

  The amount used is 0.1 ppm to 10 ppm in terms of the weight ratio of the transition metal contained in the catalyst to the thermosetting composition. If the addition ratio is 0.1 ppm or more, curing is good. Moreover, if the addition ratio is 10 ppm or less, the pot life after preparing the thermosetting composition will not be too short, it can be used suitably, and coloring of the resulting cured product will not easily occur. A preferable 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 for applications where mixing of solvents is not preferred, the applications are greatly expanded.

The thermosetting composition of the present invention may further contain the following components.
(I) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, aluminum hydroxide, etc. Metal hydroxide, 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. A desirable ratio when blending these is a weight ratio with respect to the total amount of the thermosetting composition of the present invention, and is in a range of 0.1 to 0.6.

(Ii) Coloring agents or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
(Iii) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
(Iv) Ion adsorbent.
A preferable ratio when the components (ii) to (iv) are blended is 0.0001 to 0.30 in a weight ratio with respect to the total amount of the thermosetting composition.

(V) Silane coupling agent.
(Vi) A nanoparticle dispersion of a metal oxide such as zirconia, titania, alumina, or silica.
A preferable ratio when the components (v) to (vi) are blended is 0.01 to 0.50 in a weight ratio with respect to the total amount of the thermosetting composition.

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

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 vinyl groups at least at both ends,
(C) curing catalyst,
Furthermore, after stirring and mixing the said arbitrary component as needed, it depressurizes and defoams. The mixture can be poured into a mold, heated at 100 ° C. for 1 hour, and finally heated at 150 ° C. for 1 to 2 hours to be cured.

  The heat resistance of the cured product is evaluated for heat-resistant transparency and heat-resistant yellowing. The heat transparency was evaluated by measuring the transmittance of the cured product before and after the heat resistance test with an ultraviolet-visible spectrophotometer and maintaining the light transmittance. Moreover, heat yellowing was evaluated by the retention of the yellowness (YI value) of the cured product before and after the heat test. The yellowness (YI value) and light transmittance retention 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 highly transparent, and is particularly preferably used in fields such as optical semiconductor encapsulants that require transparency. it can.

  The very good property of heat-resistant transparency of the cured product obtained by thermosetting the thermosetting composition of the present invention is attributed to the structure of the silsesquioxane derivative, which is a compound represented by the formula (3). ing. In other words, the double-decker silsesquioxane skeleton has excellent heat resistance and transparency compared to the usual random structure silsesquioxane due to its three-dimensional structure, and the cured product can be colored by heating. Gives an inhibitory effect.

  By molding a cured product obtained by thermosetting the thermosetting composition of the present invention to form a molded product, it can be used for various applications. By dispersing a metal oxide or phosphor in the composition, the composition has a light emitting function and can be used as an LED composition. Moreover, as an application, an optical semiconductor sealing material, a semiconductor sealing material, an insulating film, a sealing material, an adhesive agent, an optical lens, etc. are mentioned.

  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)>
To a reaction vessel equipped with a reflux condenser, thermometer, and dropping funnel, phenyltrimethoxysilane (6,540 g), sodium hydroxide (880 g), ion-exchanged water (660 g), and 2-propanol (26.3 L) Was charged. 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.). The reaction mixture was then transferred to a filter, filtered with nitrogen gas and pressurized. 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, a cyclopentyl methyl ether (2,005 g), 2-propanol (243 g), ion-exchanged water (1,400 g), and hydrochloric acid (461 g) were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. The mixture was stirred and stirred at room temperature (25 ° C.) under a nitrogen atmosphere. Subsequently, the above-obtained compound (DD-ONa) (800 g) and cyclopentyl methyl ether (2,003 g) were charged into a dropping funnel, and the resulting mixture was added dropwise to the reactor over 30 minutes. Stir. Then, it left still and divided into the organic layer and the water layer. The obtained organic layer was neutralized by washing with water, then 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. The colorless solid was washed with methyl acetate (980 g) and dried under reduced pressure to obtain a colorless powdery solid (DD-4OH) (496 g) represented by the following formula.

Next, a reactor equipped with a dropping funnel, a thermometer, and a reflux condenser was added to the compound (DD-4OH) (7,160 g), toluene (72,600 g), dimethylchlorosilane (2,850 g) obtained above. Was sealed with dry nitrogen. Triethylamine (3,230 g) was then added dropwise from the addition funnel over about 20 minutes. The solution temperature at this time is 35 to 40 degreeC. After completion of the dropwise addition, the mixture was stirred for 1 hour, and then ion-exchanged water (16,700 g) was added to hydrolyze an excessive amount of dimethylchlorosilane to separate into an organic layer and an aqueous layer. The organic layer was neutralized by washing with water, and concentrated under reduced pressure at 85 ° C. using a rotary evaporator. The resulting 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 powdery solid (7,339 g). The obtained colorless powdery solid is judged to have the following structure (DD-4H) from the following analysis results. 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, 4 Si), −71.90 (s, 4 Si), −75.05 (s, 4 Si).

[Synthesis Example 2]
<Synthesis of Si4V>
A 1 L 4-neck flask was equipped with a magnetic stirrer, condenser, thermometer, and dropping funnel, 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 dropped. Then, it was made to react at room temperature for 15 hours. Toluene 201 g was added to the flask, and 101 g of water was charged into the dropping funnel and dropped. The content liquid was transferred to a separating funnel, and the organic layer was washed 5 times with water. The collected 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 (Si 4 V).

[Example 1]
Silsesquioxane derivative (DD-4H) synthesized in Synthesis Example 1, which is a compound represented by Formula (3), and one end synthesized in Synthesis Example 2, which is a compound represented by Formula (4) The charge ratio was adjusted so that Si4V having a vinyl group was 1: 4 in terms of the number of moles, and the compound (1-1) was synthesized by hydrosilylation reaction as described below.

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 mol of DD-4H).
Heating and stirring were started under a nitrogen atmosphere. After the temperature of the contents reached 100 ° C., 1 μL of karsted catalyst was added, and the mixture was heated and stirred as it was for 5 hours. Thereafter, IR measurement was performed, and the mixture was further heated and stirred for 1 hour. After confirming that the peak (2130 cm ⁻¹ ) derived from the Si—H structure was not changed, the reaction was terminated. Unreacted components were distilled off under reduced pressure at 180 ° C. and 0.1 kPa with an evaporator to obtain a transparent liquid.
From the result of ²⁹ Si-NMR analysis in FIG. 3, the compound (1-1) in which all four R _{2 s} in the formula (1) were substituted with the compound represented by the formula (2) could be obtained. .

[Examples 2-3]
In Example 1, it implemented except having changed the preparation molar ratio of DD-4H which is a compound represented by Formula (4), and the organopolysiloxane (Si4V) which has the vinyl group at the one end manufactured in the synthesis example 2. In the same manner as in Example 1, compounds (1-2) and (1-3) were obtained. Table 1 shows the charged amounts and charged ratios of DD-4H and Si4V. From the results of ²⁹ Si-NMR analysis shown in FIGS. 4 and 5 below, the compound (1-2) in which R ₂ in formula (1) is substituted with the number described in Table 1 in formula (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 a solvent. The procedure was the same as in Examples 1 and 2 except that they were used. Table 2 shows the charged amounts of DD-4H, MCR-V21, and toluene, and the charged ratios of DD-4H and MCR-V21. As a result, in the same manner as the compounds described in Examples 1 and 2, R ₂ in formula (1) was substituted with a number as described in Table 2 in formula (2) (2-1, 2 -2, 2-3) could be obtained.

Table 2

[Example 7]
In Example 1 and 2, it carried out like Example 1 and 2 except having used vinyl pentamethyldisiloxane (MV) (manufacturer: Gelest Inc.) instead of Si4V. Table 3 shows the charged amounts of DD-4H, MV, and toluene and the charged ratios of DD-4H and MV. As a result, similar to the compounds described in Examples 1 and 2, the compound (3) in which R ₂ in the formula (1) is substituted with a number as described in Table 3 in the formula (2) is obtained. I was able to.

Table 3

[Example 8]
In Example 1 and 2, it carried out like Example 1 and 2 except having used vinyl phenyl dimethylsilane (VPDMS) (manufacturer: Gelest Inc.) instead of Si4V. Table 4 shows the charged amounts of (DD-4H), VPDMS, and toluene, and the charged ratios of DD-4H and VPDMS. As a result, a compound (4) is obtained which is similar to the compounds described in Examples 1 and 2 and in which R ₂ in formula (1) is substituted with a number as described in Table 4 in formula (2). I was able to.

Table 4

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

The main materials used are as follows.
Organosilicon compound: Compounds (1-1) to (1-3) synthesized in Examples
PSQ polymer: PSQ derivative synthesized by the method described in Example 1 of Japanese Patent Publication No. WO 2011/145638 DVTS: 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane (Gelest) 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.
Adhesion imparting agent: 3-glycidoxypropyltrimethoxysilane (JNC Corporation S510)

<Preparation of thermosetting composition>
The compound as shown in Table 5 was put into the screw tube. The screw tube was set in a rotation / revolution mixer (Shinky Co., Ltd. Awatori Nerita ARE-250), mixed and degassed to obtain a varnish. A platinum catalyst was added so that the platinum content would be 1 ppm, and mixing and defoaming were again carried out using a rotation / revolution mixer, whereby thermosetting compositions 1 to 3 and comparative composition 1 were obtained.
Table 5 shows the mixing ratio of each composition.

<Creation of cured product>
Two pieces of glass are sandwiched by Niflon SP packing (4 mm diameter) manufactured by Nichias Co., Ltd. as a spacer, and the thermosetting composition is poured into this, and after degassing under reduced pressure, 80 ° C. for 1 hour, 120 ° C. for 1 hour It was cured by heating at 150 ° C. for 2 hours in order, and the glass was peeled off to obtain a cured product having a smooth surface with a thickness of 4 mm.
OE-6630 (manufactured by Toray Dow Corning Silicone) was mixed at a ratio of A liquid: B liquid = 1: 4 to obtain a comparative composition 2, which was cured in the same manner as a comparative cured product 2.

<Creation of curing package>
Enomoto Co., Ltd. lead frame 5050 D / G PKG mounted with blue LED chip and gold wire, the above thermosetting composition and OE-6630 are dispensed by Musashi Engineering Co., Ltd. dispenser MEASURING MASTER MPP-1. And then cured to form a cured package.

<Light transmittance measurement>
The transmittance was measured with an ultraviolet-visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation. Further, the total light transmittance was calculated from the transmittance of 400 nm to 800 nm.
The transparency of the cured product was judged by visual observation based on the presence or absence of coloring. When there was no coloring, it was judged that the transparency was good.

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

<Hardness>
In accordance with JIS K6253, measurement was performed with a durometer WR-105D manufactured by Nishitokyo Seimitsu Co., Ltd.

<Glass transition temperature (Tg)>
A cured product film having a thickness of 0.9 mm was prepared by heating and curing in the same manner, and measured with a thermomechanical analyzer TMA / SS6100 manufactured by SII Nanotechnology.

<Heat resistance test>
The heat resistance test was performed and evaluated by the following method.
Two cured products having a thickness of 4 mm were prepared, and the obtained cured products were put into a 180 ° C. oven (constant temperature dryer: DX302 manufactured by Yamato Scientific Co., Ltd.) and subjected to heat treatment for 160 hours. After 160 hours, the case where coloring was hardly seen was marked with ◯, and the case where coloring was seen was marked with x.

<Cooling cycle test>
In the thermal cycle test, the cured package prepared by the above method is put in the test area of the thermal shock apparatus TSA-101S-W manufactured by Espec Co., Ltd., exposed at -40 ° C for 30 minutes, and exposed at 105 ° C for 30 minutes for one cycle. As shown in FIG. In addition, the movement time between both exposure temperatures was implemented in 5 minutes. After 100 cycles, a lighting test was performed, where 数 indicates that all were turned on, ○ indicates that more than half were lit, △ indicates that less than half were lit, and × indicates that all were not lit.

<Sulfur resistance test>
The sulfur resistance test was carried out by placing the cured package prepared by the above method in a 450 ml sealed container containing 5 g of sulfur powder and placing the cured package at 80 ° C. for 16 hours, and then observing the degree of blackening due to sulfur. Those in which no discoloration was observed were marked with ◎, those with a light gray color were marked with ◯, those with a dark gray color were marked with △, and those with a black color were marked with ◎.

Table 6 shows the results of various physical property evaluation tests of cured products 1 to 3 and comparative cured products 1 to 2 obtained by curing each of the compositions 1 to 3, the comparative composition 1 and OE-6630 of Table 5. Show.
It was revealed that the cured products 1 to 3 were cured products having high hardness, excellent heat resistance, excellent gas permeation resistance and cold cycle resistance.
This indicates that by blending the compound having a double-decker silsesquioxane structure of the present invention, the effect of improving the heat cycle resistance while maintaining the gas permeation resistance of the comparative cured product 1 is demonstrated. Show.

Table 5

Table 6

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

  The molded body made of the cured product of the present invention can be suitably used for applications such as semiconductor sealing materials, optical semiconductor sealing materials, insulating films, sealing materials, and optical lenses. Also, adhesives, electronic materials, insulating materials, interlayer insulating films, paints, inks, coating materials, molding materials, potting materials, liquid crystal sealing materials, display device sealing materials, solar cell sealing materials, resist materials, color filters, It can be used for electronic paper materials, hologram materials, solar cell materials, fuel cell materials, recording materials, waterproof materials, moisture-proof materials, battery solid electrolytes, and gas separation membranes. Moreover, it can use for the additive etc. to other resin.

Claims (10)

An organosilicon compound represented by the formula (1).

In formula (1), R ₁ is independently alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, or phenyl, and R ₂ is independently hydrogen or a group represented by 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 alkyl having 1 to 20 carbon atoms, phenyl, cyclopentyl, or cyclohexyl, and R ₅ is carbon. N is an integer of 0 to 1,000. The manufacturing method of the organosilicon compound obtained by hydrosilylating the compound represented by Formula (3), and the compound represented by Formula (4).

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

In formula (4), R ₄ is independently alkyl having 1 to 20 carbons, phenyl, cyclopentyl, or cyclohexyl, R ₅ is alkyl or phenyl having 1 to 20 carbons, and R ₆ is carbon number. 1 to 20 unsaturated hydrocarbon groups, and n is an integer of 0 to 1,000.   A thermosetting comprising the organosilicon compound according to claim 1 or the organosilicon compound (A) produced by the production method according to claim 2, and a silicon compound (B) having at least two vinyl groups. Composition.   Furthermore, the thermosetting composition of Claim 3 containing a curing catalyst (C).   Furthermore, the thermosetting composition of Claim 3 or 4 containing the silicon compound (D) which has an at least 2 SiH group at the terminal.   Furthermore, the thermosetting composition of any one of Claims 3-5 which disperse | distributed the metal oxide or fluorescent substance.   Hardened | cured material formed by thermosetting the thermosetting composition of any one of Claims 3-6.   The molded object obtained by shape | molding the hardened | cured material of Claim 7.   The coating film formed by apply | coating the thermosetting composition of any one of Claims 3-6.   The sealing material for optical semiconductors which consists of a thermosetting composition of any one of Claims 3-6.

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