KR20210000276A - Radical curable silicone composition and cured product - Google Patents

Abstract

The present invention relates to a radical-curable silicone composition and cured product, which have excellent quantum dot dispersibility, and are able to be cured at a low temperature. According to the present invention, the radical-curable silicone composition includes: (A) a straight-chain organopolysiloxane represented by Formula (1); and (B) a polymerization initiator, wherein Formula (1) is (R^1R(^2_2)SiO_(1/2))_a(R^3R(^2_2)SiO_(1/2))_b(R(^2_2)SiO_(2/2))_c(R^3R^2SiO_(2/2))_d(R^1R^2SiO_(2/2))_e.

Description

Radical curable silicone composition and cured product {RADICAL CURABLE SILICONE COMPOSITION AND CURED PRODUCT}

The present invention relates to a radical curable silicone composition and a cured product thereof.

In recent years, with the spread of personal computers, televisions, and smartphones, the demand for image display devices is increasing. In the backlight of such an image display device, an LED (light emitting diode) is widely used. Since the emission spectrum of the LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain a backlight of a liquid crystal display or white light for general lighting by using an LED, it is necessary to arrange a phosphor suitable for each chip on the LED chip to convert the emission wavelength. Specifically, a method of installing a yellow phosphor on a blue-emitting LED chip and a method of installing red and green phosphors on a blue-emitting LED chip are currently most widely used.

When an LED is used for the backlight of a display, as the half width of the emission spectrum of the phosphor becomes narrower, the color reproduction area of the display becomes wider. However, the half-width of the emission spectrum of the phosphor is relatively wide. For this reason, when an LED using a yellow phosphor is used as a backlight for a display, the color reproduction area is not sufficient.

In recent years, quantum dots are attracting attention as a wavelength conversion material. Quantum dots are suitable for backlight applications because it is possible to adjust the band gap according to the particle diameter, narrowing the half-value width of the emission spectrum by uniform particle diameter, and generating light having excellent distribution color purity.

These quantum dots are dispersed in a matrix material and used as a sealing material or a filter. Acrylic resins, epoxy resins, and the like are used as the matrix, but such resins have problems in durability and crack resistance (Patent Documents 1 and 2).

Further, since the heat resistance of the quantum dot itself is low, a matrix material that can be cured at a low temperature is required. It is also necessary that the quantum dots do not aggregate in the matrix and are uniformly dispersed.

Japanese Patent Publication No. 2018-13724 Japanese Patent Publication No. 2016-536641

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a radical curable silicone composition in which quantum dots are dispersed and curable at low temperatures.

In order to solve the above problem, in the present invention,

(A) a linear organopolysiloxane represented by the following formula (1)

(R^OneR² ₂SiO_1/2)_a(R³R² ₂SiO_1/2)_b(R² ₂SiO_2/2)_c(R³R²SiO_2/2)_d(R^OneR²SiO_2/2)_e (One)

(In the formula, R ¹ is an alkenyl group having 2 to 8 carbon atoms, R ² is each independently a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted C 6 to 12 Is an aryl group, provided that at least 10 mol% of all R ² is the aryl group, and R ³ is a group represented by the following formula (2): a, b, c, d, e are each, a≥0, b ≥0, c≥0, d≥0, e≥0, and is a number that satisfies a+b>0, b+d>0, and a+b+c+d+e=1.)

(In the formula, R ⁴ is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or Any of unsubstituted aryl groups having 6 to 12 carbon atoms, * represents a bond with an adjacent silicon atom),

And,

(B) polymerization initiator

It provides a radical curable silicone composition characterized in that it contains.

In the case of the radical curable silicone composition of the present invention, quantum dots can be satisfactorily dispersed, and curing at low temperatures is possible by radical curing.

It is preferable that the radical curable silicone composition of the present invention further contains (C) quantum dots.

With such a radical curable silicone composition, since quantum dots do not aggregate in the matrix and are uniformly dispersed, an excellent wavelength conversion material can be obtained.

In addition, in the radical curable silicone composition of the present invention, it is more preferable that each of R ² is independently a methyl group or a phenyl group.

The straight-chain organopolysiloxane (component (A)) having such R ² is easily industrially available.

In the radical curable silicone composition of the present invention, it is preferable that the polymerization initiator is an organic peroxide or a photopolymerization initiator.

Such a polymerization initiator can more effectively cure the composition of the present invention.

In this case, it is more preferable that the organic peroxide has a 10-hour half-life temperature of 50 to 150°C.

In the case of such an organic peroxide, the storage stability of the composition and the controllability of curability are excellent, and in the case of containing (C) quantum dots, curing at low temperature is possible, so that the thermal effect on the quantum dots can be suppressed. have.

In addition, the present invention provides a cured silicone product, characterized in that the cured product of the radical curable silicone composition.

Since the silicone cured product of the present invention has excellent transparency and good hardness, it is useful for applications such as backlights and lighting of displays. In addition, when the cured product further contains (C) quantum dots, since the quantum dots do not aggregate in the matrix and are uniformly dispersed, it is excellent as a wavelength conversion material, and is useful for applications such as sealing materials and filters. Do.

The radical curable silicone composition of the present invention has good dispersibility of quantum dots and can be cured at a low temperature by radical curing, and is therefore useful for applications such as backlights and lighting of displays.

The present inventors, as a result of earnestly examining in order to achieve the above object, found that the above problems could be solved, and the present invention was completed if it is a silicone resin composition containing components (A) and (B) described later.

That is, the present invention is a radical curable silicone composition,

(A) a linear organopolysiloxane represented by the following formula (1)

(R^OneR² ₂SiO_1/2)_a(R³R² ₂SiO_1/2)_b(R² ₂SiO_2/2)_c(R³R²SiO_2/2)_d(R^OneR²SiO_2/2)_e (One)

(In the formula, R ¹ is an alkenyl group having 2 to 8 carbon atoms, R ² is each independently a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted C 6 to 12 Is an aryl group, provided that at least 10 mol% of all R ² is the aryl group, and R ³ is a group represented by the following formula (2): a, b, c, d, e are each, a≥0, b ≥0, c≥0, d≥0, e≥0, and is a number that satisfies a+b>0, b+d>0, and a+b+c+d+e=1.)

(In the formula, R ⁴ is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or Any of unsubstituted aryl groups having 6 to 12 carbon atoms, * represents a bond with an adjacent silicon atom),

And,

(B) polymerization initiator

It is a radical curable silicone composition characterized in that it contains.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[Radical curing silicone composition]

The radical curable silicone composition of the present invention contains components (A) and (B) described later as essential components. In addition to the essential components, this composition may further contain optional components as necessary.

Hereinafter, each component will be described in detail.

[(A) component]

The component (A) is a linear organopolysiloxane represented by the following formula (1).

(R^OneR² ₂SiO_1/2)_a(R³R² ₂SiO_1/2)_b(R² ₂SiO_2/2)_c(R³R²SiO_2/2)_d(R^OneR²SiO_2/2)_e (One)

(In the formula, R ¹ is an alkenyl group having 2 to 8 carbon atoms, R ² is each independently a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted C 6 to 12 Is an aryl group, provided that at least 10 mol% of all R ² is the aryl group, and R ³ is a group represented by the following formula (2): a, b, c, d, e are each, a≥0, b ≥0, c≥0, d≥0, e≥0, and is a number that satisfies a+b>0, b+d>0, and a+b+c+d+e=1.)

(In the formula, R ⁴ is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or Any of unsubstituted aryl groups having 6 to 12 carbon atoms, * represents a bond with an adjacent silicon atom),

In the above formula (1), examples of the alkenyl group having 2 to 8 carbon atoms represented by R ¹ include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, and the like. Group is preferred. Among these groups, the hydrogen atom may be further substituted with an arbitrary substituent (halogen atom, etc.).

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and the like, particularly preferably a methyl group. Do. Further, examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. Among these groups, the hydrogen atom may be further substituted with an arbitrary substituent (halogen atom, etc.).

In addition, at least 10 mol% or more of all R ² is a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and preferably 15 mol% or more. If the aryl group is less than 10 mol% of the total R ^2, the dispersibility of the quantum dots is deteriorated, and the transparency of the composition and the cured product thereof may be impaired.

It is particularly preferable that R ² is each independently a methyl group or a phenyl group. The straight-chain organopolysiloxane (component (A)) having such R ² is easily industrially available.

Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms represented by R ⁴ include methylene group, ethylene group, propylene group, trimethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene A linear, branched or cyclic alkylene group having 1 to 8 carbon atoms such as a group, preferably one having 1 to 4 carbon atoms, and particularly preferably a methylene group, ethylene group, propylene group, and trimethylene group. Among these groups, the hydrogen atom may be further substituted with an arbitrary substituent (halogen atom, etc.).

R ⁵ is either a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and is preferably a hydrogen atom or a methyl group.

The linear organopolysiloxane represented by the above formula (1) is a (R ¹ R ² ₂ SiO _1/2 ) unit (also referred to as “a unit.” hereinafter), (R ³ R ² ₂ SiO _{1/) 2} ) Unit (b unit), (R ² ₂ SiO _2/2 ) unit (c unit), (R ³ R ² SiO _2/2 ) unit (d unit), (R ¹ R ² SiO _2/2 ) unit (e unit), and the composition ratios a, b, c, d, and e of each unit are, respectively, a≥0, b≥0, c≥0, d≥0, e≥0, and a+b >0, b+d>0, and a+b+c+d+e=1. The linear organopolysiloxane contains either a b unit or a d unit as an essential unit, and has an R ³ group in either or both of the molecular chain terminal and the molecular chain non-terminal portion. In the component (A), the presence of a radically crosslinkable R ³ group enables radical curing at a low temperature, and the hardness of the cured product is improved by radical crosslinking. In addition, the radical curable silicone composition of the present invention is particularly useful as a wavelength converting material because the aryl group is 10 mol% or more of the total R ² , and quantum dots do not aggregate in the matrix and are uniformly dispersed.

Although a suitable example of the component (A) is shown below, it is not limited to these. In addition, in the formula, Me represents a methyl group, and Ph represents a phenyl group (the same applies hereinafter).

(In the formula, the arrangement of the siloxane units in parentheses is arbitrary, and * represents a bond with an adjacent silicon atom.)

(In the formula, the arrangement of the siloxane units in parentheses is arbitrary.)

(In the formula, the arrangement of the siloxane units in parentheses is arbitrary.)

(A) component may be used individually by 1 type, or may use 2 or more types together.

The viscosity of the component (A) is preferably 10 to 100,000,000 mPa·s, and particularly preferably in an oily form in the range of 200 to 10,000 mPs·s. In addition, the viscosity is a measured value with a rotational viscometer at 25 degreeC, unless specifically mentioned below.

[(B) component]

Component (B) is a polymerization initiator that polymerizes the polymerizable functional group of component (A), and as component (B), an organic peroxide that generates radicals by heat or a photopolymerization initiator that generates radicals by light such as ultraviolet rays is used. I can.

As the organic peroxide, an organic peroxide having a 10-hour half-life temperature of 50 to 150°C is preferable, more preferably 60 to 110°C, from the point of control of the storage stability and curability of the composition, and the heat resistance temperature of the quantum dot. It is an organic peroxide.

Specific examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 1,1-bis(t -Butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di-tetrabutylperoxy-cyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine, 1,6-bis(p-toluoylperoxycarbonyloxy)hexane, di(4-methylbenzoylperoxy)hexamethylenebis Carbonate, 2,5-dimethoxy-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, etc. Can be lifted.

In addition, organic peroxides can also be obtained commercially, for example, from Nichiyu Corporation. Specifically, perbutyl NHP (50.6), perhexyl PV (53.2), perbutyl PV (54.6), peroyl 355 (59.4), peroyl L (61.6), perocta O (65.3), peroyl SA ( 65.9), Perhexa 25O(66.2), Perhexyl O(69.9), Naper PMB(70.6), Perbutyl O(72.1), Naper BMT(73.1), Naper BW(73.6), Perhexa MC(83.2), Fur Hexa TMH (86.7), Perhexa HC (87.1), Perhexa C (90.7), Pertetra A (94.7), Perhexyl I (95.0), Perbutyl MA (96.1), Perbutyl 355 (97.1), Perbutyl 355 (97.1), Perbutyl L (98.3), perbutyl I (98.7), perbutyl E (99.0), perhexyl Z (99.4), perhexa 25Z (99.7), perbutyl A (101.9), perhexa 22 (103.1), perbutyl Z (104.3), perhexa V (104.5), perbutyl P (119.2), percumyl D (116.4), perhexyl D (116.4), perhexa 25B (117.9), perbutyl C (119.5), perbutyl D ( 123.7), Permenter H (128.0), Perhexine 25B (128.4), Percumyl P (145.1), and the like. In addition, the numbers in parentheses following the compound name are each 10-hour half-life temperature (unit: °C).

Among the organic peroxides, from the viewpoint of compatibility with the component (A) and a 10-hour half-life temperature, preferably 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Nizi oil ( Note), Perhexa (registered trademark) 25O, 10 hours half-life temperature 66.2 ℃).

These organic peroxides can be used alone or in combination of two or more.

The amount of the organic peroxide added may be an effective amount, but is usually 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass per 100 parts by mass of the organopolysiloxane of the component (A).

As specific examples of the photopolymerization initiator, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one (Irgacure 651 manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl- Ketone (Irgacure 184 manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173 manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy) Roxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one (Irgacure 127 manufactured by BASF), phenylglyoxylic acid methyl ester (Irgacure MBF manufactured by BASF), 2-methyl-1-[ 4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907 manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure 369 made by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819 made by BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO made by BASF) ), etc.

Among the photoinitiators, from the viewpoint of compatibility with the component (A), preferably, 2,2-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure manufactured by BASF 1173), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819 manufactured by BASF), and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO manufactured by BASF).

These photoinitiators can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of curability, the amount of the photoinitiator added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the component (A).

[Component (C)]

The radical curable silicone composition of the present invention may further contain quantum dots as component (C). Component (C) (quantum dot) acts as a wavelength converting material. Quantum dots are usually particles having an average particle diameter of 20 nm or less, and can absorb and convert light energy. Quantum dots can adjust the color of light by changing their particle diameter. Since the band gap is determined according to the size of the particle diameter, light with high color purity can be obtained by making the particle diameter even. Further, the radical curable silicone composition containing quantum dots as the component (C) becomes an excellent wavelength converting material because the quantum dots do not aggregate in a matrix and are uniformly dispersed.

Examples of quantum dots that radiate in the visible light region include CdS, ZnSe, and CdSe-based particles having a shell such as ZnS. In addition, cadmium-free quantum dots such as InP, CuInS ₂ , AgInS ₂ , Te, PbS, InAs, etc. can also be used. In the present invention, any conventional quantum dot can be used.

The component (C) can be used alone or in combination of two or more. Moreover, you may use what was previously dispersed in an organic solvent or the like.

The addition amount of the component (C) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the component (A).

[Other ingredients]

In the radical curable silicone composition of the present invention, a known antioxidant such as 2,6-di-t-butyl-4-methylphenol may be blended in order to suppress the occurrence of coloration, cloudiness, and oxidation deterioration of the cured product. Further, in order to impart resistance to photodeterioration, a light stabilizer such as a hindered amine stabilizer may be blended. Further, if necessary, inorganic fillers such as fumed silica may be blended in order to improve the strength, or dyes, pigments, flame retardants, and the like may be blended. In order to improve the adhesion, an adhesion aid (such as a silane coupling agent) may be blended.

[Curing method and curing conditions]

In the radical curable silicone composition of the present invention, known methods and conditions can be employed in the thermal radical curing type curing method and curing conditions containing an organic peroxide. For example, it can be cured under a nitrogen atmosphere at 70 to 150°C for 10 minutes to 5 hours. When the polymerization initiator is an organic peroxide having a 10-hour half-life temperature of 50 to 150°C, low-temperature curing is possible.

Further, the photocurable type radical curable silicone composition containing a photoinitiator can be cured by irradiating light such as ultraviolet rays. Examples of the ultraviolet light source include UVLED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps. The irradiation amount of ultraviolet rays (accumulated amount of light) is, for example, preferably 1 to 10,000 mJ/cm 2, and more preferably 10 to 9,000 mJ/cm 2 for a sheet formed by forming the composition of the present invention to a thickness of about 2.0 mm. to be. That is, when ultraviolet rays having an illuminance of 100 mW/cm 2 are used, curing can be performed by irradiating ultraviolet rays for about 0.01 to 100 seconds.

Example

Hereinafter, the present invention will be specifically described using examples, but these examples do not limit the present invention at all.

[Synthesis Example 1]

In a 2 L four-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 1,000 g of organopolysiloxane represented by the following formula (3) was dissolved in 500 g of toluene, and heated to 85°C using an oil bath. . 1 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5% by mass in terms of platinum) was added thereto, and 44.3 g of organohydrogendisiloxane represented by the following formula (4) was added dropwise while stirring. did. After completion of the dropwise addition, the mixture was stirred at 95°C for 2 hours, and then cooled to 25°C. Thereafter, 5 g of activated carbon was added, and after stirring at room temperature for 1 hour, it was removed by filtration. Toluene was distilled off under reduced pressure to obtain 842.3 g of a colorless, transparent oily reaction product (A-1) (viscosity at 25°C: 6180 mPa·s).

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

[Synthesis Example 2]

In a 2L 4-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 1,000 g of organopolysiloxane represented by the following formula (5) was dissolved in 500 g of toluene, and heated to 85°C using an oil bath. . To this, 1 g of a toluene solution (0.5% by mass in platinum equivalent) of platinum hexachloride 1,3-divinyltetramethyldisiloxane was added, and 46.9 g of organohydrogendisiloxane represented by the above formula (4) was added dropwise while stirring. did. After completion of the dropwise addition, the mixture was stirred at 95°C for 2 hours, and then cooled to 25°C. Thereafter, 5 g of activated carbon was added, and after stirring at room temperature for 1 hour, it was removed by filtration. Toluene was distilled off under reduced pressure to obtain 987.23 g of a colorless and transparent oily reaction product (A-2) (viscosity at 25°C: 4,000 mPa·s).

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

[Synthesis Example 3]

In a 2 L four-neck flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 200 g of organopolysiloxane represented by the following formula (6) was dissolved in 100 g of toluene, and heated to 85°C using an oil bath. To this, 0.2 g of a toluene solution of platinum hexachloride 1,3-divinyltetramethyldisiloxane (0.5% by mass in terms of platinum) was added, and 30.7 g of organohydrogendisiloxane represented by the above formula (4) while stirring was added. It was loaded. After completion of the dropwise addition, the mixture was stirred at 95°C for 2 hours, and then cooled to 25°C. Thereafter, 5 g of activated carbon was added, and after stirring at room temperature for 1 hour, it was removed by filtration. Toluene was distilled off under reduced pressure to obtain 216.6 g of a colorless and transparent oily reaction product (A-3) (viscosity at 25°C: 2,400 mPa·s).

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

[Comparative Synthesis Example 1]

In a 2 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 500 g of organopolysiloxane represented by the following formula (7) was dissolved in 250 g of toluene, and heated to 85°C using an oil bath. To this, 0.1 g of a toluene solution (0.5% by mass in platinum equivalent) of platinum hexachloride 1,3-divinyltetramethyldisiloxane was added, and 7.8 g of organohydrogendisiloxane represented by the above formula (4) while stirring was added. It was loaded. After completion of the dropwise addition, the mixture was stirred at 95°C for 2 hours, and then cooled to 25°C. Thereafter, 2.5 g of activated carbon was added and stirred at room temperature for 1 hour, and then removed by filtration. Toluene was distilled off under reduced pressure to obtain 485 g of a colorless and transparent oily reaction product (A-4) (viscosity at 25°C: 6,000 mPa·s).

[Comparative Synthesis Example 2]

In a 2 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer, 500 g of organopolysiloxane represented by the following formula (8) was dissolved in 250 g of toluene, and heated to 85°C using an oil bath. To this, 0.1 g of a toluene solution (0.5% by mass in platinum equivalent) of platinum hexachloride 1,3-divinyltetramethyldisiloxane was added, and 7.8 g of organohydrogendisiloxane represented by the above formula (4) while stirring was added. It was loaded. After completion of the dropwise addition, the mixture was stirred at 95°C for 2 hours, and then cooled to 25°C. Thereafter, 2.5 g of activated carbon was added and stirred at room temperature for 1 hour, and then removed by filtration. Toluene was distilled off under reduced pressure to obtain 480 g of a colorless, transparent oily reaction product (A-5) (viscosity at 25°C: 5,000 mPa·s).

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

[Examples 1 to 6 and Comparative Examples 1 to 6]

Components (A-1) to (A-6) shown below and component (C) were each mixed in the composition of Tables 1 and 2 (numbers in the table represent parts by mass), and toluene at 80°C under reduced pressure Was distilled off. Then, the component (B) was added and mixed uniformly to prepare a radical curable silicone composition.

(A) Ingredient:

(A-1) Organopolysiloxane represented by the following formula obtained in Synthesis Example 1

(In the formula, the arrangement of the siloxane units in parentheses is not constant, so an asterisk (*) represents a bond with an adjacent silicon atom.)

(A-2) Organopolysiloxane represented by the following formula obtained in Synthesis Example 2

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

(A-3) Organopolysiloxane represented by the following formula obtained in Synthesis Example 3

(In the formula, the arrangement of the siloxane units in parentheses is not constant.)

Comparative ingredients:

(A-4) Organopolysiloxane represented by the following formula obtained in Comparative Synthesis Example 1

(A-5) Organopolysiloxane represented by the following formula obtained in Comparative Synthesis Example 2

(A-6) Organopolysiloxane represented by the above formula (3)

(B) component:

(B-1) Perhexa (registered trademark) 25O (manufactured by Nichiyu Corporation, 10 hour half-life temperature 66.2℃)

(B-2) Irgacure 1173 (manufactured by BASF)

(C) component:

(C-1) InP/ZnS core-shell quantum dot (manufactured by SIGMA-ALDRICH, 5 mg/mL toluene solution (quantum dot content: 0.6% by mass), emission peak 530 nm)

The compositions obtained in Examples and Comparative Examples were evaluated by the following method, and the results are shown in Tables 3 and 4.

[Exterior]

For the cured product obtained by curing each composition and composition under the following curing conditions, the external appearance was visually observed, and when transparency was maintained, it was evaluated as?

[Hardness]

·Heat curing type

The hardness of the cured product having a thickness of 2 mm produced by heating the composition in a hot air circulation oven at 80°C for 2 hours in a nitrogen atmosphere was measured for the type A hardness at 23°C.

·Ultraviolet curing type

Organopolysiloxane composition using an eye UV electronic control device (model UBX0601-01) manufactured by Eye Graphics Co., Ltd., under a nitrogen atmosphere, at 25°C, so that the irradiation amount in ultraviolet light having a wavelength of 365 nm is 8,000 mJ/cm 2 About the hardness of a 2 mm-thick cured product which was irradiated with ultraviolet rays and hardened, the type A hardness in 23 degreeC was measured.

As shown in Table 3, in Examples 1 to 6 using the radical curable silicone composition of the present invention, the dispersibility of quantum dots was excellent, and transparency was maintained even after curing. On the other hand, as shown in Table 4, in Comparative Examples 1 to 4 in which an organopolysiloxane having no phenyl group (aryl group) or a small content was used instead of the component (A) of the present invention, the cloudiness due to aggregation of quantum dots happened. In Comparative Examples 5 and 6 using an organopolysiloxane having no group (R ³ ) represented by the formula (2), curing did not occur under the curing conditions.

In addition, this invention is not limited to the said embodiment. The above-described embodiment is an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operation and effect is included in the technical scope of the present invention.

Claims (6)

(A) a linear organopolysiloxane represented by the following formula (1)
(R^OneR² ₂SiO_1/2)_a(R³R² ₂SiO_1/2)_b(R² ₂SiO_2/2)_c(R³R²SiO_2/2)_d(R^OneR²SiO_2/2)_e (One)
(Wherein, R^OneIs an alkenyl group having 2 to 8 carbon atoms, R²Is each independently a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, provided that all R²At least 10 mol% of the aryl group, R³Is a group represented by the following formula (2). a, b, c, d, e are each a≥0, b≥0, c≥0, d≥0, e≥0, and a+b>0, b+d>0, a+b+ It is a number that satisfies c+d+e=1.)

(Wherein, R⁴Is each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R⁵Is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and * represents a bond with an adjacent silicon atom.),
And,
(B) polymerization initiator
Radical curable silicone composition, characterized in that it contains. The radical curable silicone composition according to claim 1, further comprising (C) quantum dots. The radical curable silicone composition of claim 1 or 2, wherein each of R ² is independently a methyl group or a phenyl group. The radical curable silicone composition according to claim 1 or 2, wherein the polymerization initiator is an organic peroxide or a photopolymerization initiator. The radical curable silicone composition according to claim 4, wherein the organic peroxide has a 10-hour half-life temperature of 50 to 150°C. A cured silicone product which is a cured product of the radical curable silicone composition according to claim 1 or 2.