KR101597183B1 - Organosilicone resin of core-shell structure - Google Patents

Abstract

The present invention relates to an organosilicon resin having a core-shell structure and, more particularly, to an organosilicon resin having a core-shell structure, which is manufactured by making a reaction between silicon particles having functional groups (Si-H or Si-alkenyl) capable of hydrosilylation curing reaction, wherein the silicon particles form a core and the organosilicon resin forms a shell. The organosilicon resin having the core-shell structure, according to the present invention, maintains high transparency and thermal resistance of the original silicon resin, and has low penetration capacity of oxygen gas, thereby having an efficacy of enhanced oxidization stability. Therefore, the organosilicon resin of the present invention can be applied to various fields such as LED lighting applications, display panels, protection of chips in mobile devices, etc.

Description

ORGANOSILICONE RESIN OF CORE-SHELL STRUCTURE < RTI ID = 0.0 >

The present invention relates to an organosilicone resin having a core-shell structure, and more particularly, to a silicone-based resin having a core-shell structure, and more particularly, to a process for hydrogen siloxane reaction of silicone particles having a functional group capable of hydrogen siloxane curing (Si-H or Si- The present invention relates to an organosilicon resin having a core-shell structure in which silicon particles form a core and an organosiloxane compound forms a shell.

In recent years, silicon-based encapsulants for LEDs have been spotlighted, and techniques for continuous development of materials and compositions have been developed. Japanese Unexamined Patent Application Publication No. 2003-002951 (Patent Document 1) discloses an aromatic epoxy resin as an LED optical semiconductor encapsulant, but has a disadvantage that yellowing occurs. Silicone resin is used as a material having improved heat resistance and light fastness, which has a disadvantage in that the oxygen permeability is relatively high. In particular, optical semiconductors use encapsulants for high luminous efficiency and protection of semiconductor chips and electrodes. Silicone resins generally satisfy the above-mentioned requirements of LED encapsulants, but they have a high gas permeability (especially oxygen permeability) There are disadvantages.

In the field of LED encapsulants, silicone resin is in the spotlight, and resin mainly used is a multi-liquid type silicone resin with addition curing type. The addition curing type silicone resin is produced by thermosetting a polysiloxane containing an alkenyl group and a polysiloxane containing a hydrogen atom in the presence of a platinum catalyst by a hydrogen silylation reaction. Japanese Patent Application Laid-Open No. 2004-186168 (Patent Document 2) discloses a silicone resin in which at least two alkenyl groups are bonded to a silicon atom in one molecule, an organosilane in which at least two hydrogen atoms are bonded to a silicon atom in one molecule, and / And a resin composition composed of a hydrogen polysiloxane. JP-A No. 2008-150437 (Patent Document 3) discloses an organopolysiloxane having an average of at least 0.2 alkenyl groups in a molecule, a siloxane having a hydrogen atom in the middle of the molecular chain, and a siloxane having hydrogen atoms bonded at both ends of the molecular chain A polyorganohydrogen siloxane resin composition is proposed. The curable compositions disclosed in the above Patent Documents 2 and 3 have a network structure in which an organic group is substituted for a siloxane skeleton obtained by a curing reaction of a silicone resin having a terminal functional group. As a result, the organic silicon resin is excellent in heat resistance, but has a disadvantage in that it has a high oxygen permeability and oxidizes an LED chip (particularly, a lead frame).

In Korean Patent Laid-open No. 10-2013-0067401 (Patent Document 4), a siloxane unit having a phenyl siloxane unit as a core and a siloxane unit having a terminal functional group such as Si-H and Si- - shell structure of phenylpolysiloxane resin.

In the present invention, the present inventors have completed the present invention by studying to develop a novel silicone resin having a low oxygen permeability and enhanced long-term oxidation stability while maintaining the inherent advantage of silicone resin material excellent in heat resistance and optical characteristics.

Japanese Laid-Open Patent Publication No. 2003-002951 Japanese Laid-Open Patent Publication No. 2004-186168 Japanese Patent Application Laid-Open No. 2008-150437 Korean Patent Publication No. 10-2013-0067401

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silicon material having a high refractive index and optical (light) transmittance and low oxygen gas permeability.

Accordingly, it is an object of the present invention to provide an organosilicone resin having a core-shell structure in which silicon particles constitute a core and a specific organosiloxane compound forms a shell.

It is another object of the present invention to provide a method for producing an organosilicon resin having a core-shell structure.

It is another object of the present invention to provide a cured coating film containing the above-mentioned organic-silicone resin having a core-shell structure.

In order to solve the above problems,

The end functional group selected from Si-H and Si- ( _C2-20 alkenyl groups) present on the surface of the silicon particle reacts with the siloxane monomer represented by the following formula (1) to form a shell ) Having a core-shell structure.

[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)

In the present invention,

(I) a process for producing silicon particles having a chlorine-end functional group (Si-Cl) by using a magnesium compound selected from the group consisting of Mg ₂ Si, KSi and NaSi and tetrachlorosilane;

Ⅱ) and the silicon particles having a terminal functional group-chloro, R-MgCl or R ₂ SiHCl (wherein, R is represented by C _1~20 alkyl, C _2~20 is an alkenyl group, or a functional group selected from a C _6-20 aryl group) Reacting the compound with a compound to prepare a silicone particle substituted with a functional group X represented by Formula 2 below; And

Iii) a step of reacting a silicon particle substituted with a functional group X represented by the following formula 2 and a siloxane monomer represented by the following formula 1 to prepare an organosilicon resin having a core-shell structure as defined above; And a core-shell structure of the organosilicon resin.

(2)

는 실리콘 입자를 나타내고, R은 C_{1 ∼20} 알킬기 및 C_6∼20 아릴기 중에서 선택된 불활성기를 나타내고, X는 수소원자 및 C_{2 ∼20} 알케닐기 중에서 선택된 수소화 반응성기를 나타내고, p와 q는 관능기 수를 나타내는 것으로 p는 0 내지 200의 정수이고, q/(p+q)는 0.01 ~ 0.95이다)(In the formula (2)

Denotes a silicon particle, R is a C ₁ alkyl group and a C _{~20 6~20} represents an inert group selected from an aryl group, X represents a group selected from hydride-reactive hydrogen atoms and C _{2 ~20} alkenyl group, p and q is a number of functional groups Wherein p is an integer from 0 to 200, and q / (p + q) is from 0.01 to 0.95.

[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)

In the present invention, a silicone particle core having a non-reactive substituent group R ¹ and a terminal functional group (X) on the surface of the core, and a silicone functional group (X) shell structure of the core-shell structure represented by the following formula (1).

In addition, the present invention provides a cured coating film which is prepared by curing an organic silicone resin having a core-shell structure and has a light transmittance of 97 to 99% and a reduced permeability of oxygen gas.

The organosilicone resin according to the present invention has an effect of enhancing the long-term oxidation stability because the oxygen gas permeability is low while maintaining the inherent heat resistance and high transparency of the silicone resin.

Accordingly, the organosilicon resin of the present invention can be used in addition to existing silicone encapsulants, and can be applied to various fields such as LED lighting, display panel, and device chip protector for mobile phones.

1 is a TEM photograph of silicon particles substituted with an allyl group / methyl group produced by Production Example 1. Fig.
2 is a TEM photograph of silicon particles substituted with an allyl group / phenyl group prepared in Preparation Example 2. Fig.
3 is a view showing a frame used for manufacturing a silicon thin film.
4 is a photograph of the silicon thin film produced in Experimental Example 2. Fig.

Hereinafter, the present invention will be described in more detail as an embodiment.

The organosilicone resin according to the present invention is a silicone resin in which silicon particles are surrounded by an organosiloxane compound. More specifically, it is preferable to use a silicone particle as a core, and a Si-H or Si-alkenyl group as a functional group capable of hydrogen sulfide curing reaction present on the surface of the silicon particle and a siloxane monomer represented by the following formula Is an organosilicon resin of a core-shell structure in which a short-term (R ¹ or R ⁸ ) reacts to form a shell of an organosiloxane.

[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)

In the core-shell structure organic silicon resin according to the present invention, the core portion is a silicon particle.

Silicon particles in the metal state are used as a polymer composite film material, and have excellent light transmission characteristics, but they have a disadvantage in that they are poor in dispersion performance in a polymer and occur in an oxidation reaction. Therefore, by introducing specific reactive functional groups capable of hydrogen sulfide curing reaction on the surface of silicon particles, hydrophobicity and reactivity can be imparted to the surface of the silicone particles, and the dispersibility in the organic polymer can be improved.

Various methods are known for preparing the silicon particles, for example, 1) pyrolysis of monosilane or disilane (Chem. Phys. Lett. 1987, 134, 477; J. Phys. Chem. 1993, (Heath, JR Science 1992, 258, 1131), 3) the reaction of zinc salt (Zintl salt, KSi, NaSi) with tetrachlorosilane in the reaction of tetrachlorosilane and alkyl trichlorosilane (J. Am. Chem. Soc. 1996, 118, 12461) are well known.

In the present invention, silicon particles were prepared by the above-mentioned method 3), specifically using magnesium silicide (Mg ₂ Si) or zintl salt (KSi, NaSi) and tetrachlorosilane (SiCl ₄ ) To synthesize nano-sized silicon particles.

In the present invention, the selection of a reactive group (for example, a hydrogen atom or an alkenyl group) and a non-reactive group (for example, alkyl or aryl) capable of hydrogen saccharification reaction on the surface of a silicon particle used as a core And the ratio can be controlled to control the physical properties of the organosilicon resin. That is, the silicon nanoparticles are present on the surface in the form of functional groups such as hydrogen atoms, C _1-20 alkyl groups, C _2-20 alkenyl groups and C _6-20 aryl groups, Can be easily controlled within a range of 0.001 to 0.95 to control the physical properties of the organosilicon resin.

The organosilicon resin of the present invention has a refractive index ranging from approximately 1.40 to 1.54.

The organosilicon resin of the core-shell structure according to the present invention is characterized in that the shell is composed of an organosiloxane compound and the reactive group (for example, hydrogen atom or alkenyl group) present on the surface of the core and the siloxane The monomer end groups are forming a chemical bond by the hydrogen silylation reaction.

In order to constitute a shell of the organosilicon resin of the present invention, the siloxane monomer represented by the above formula (1) is used. The siloxane monomer represented by the general formula (1) has a reactive group (for example, a hydrogen atom or an alkenyl group) having a terminal group bonded to a hydrogen atom or an alkenyl group as a terminal group and a hydrogen group By the reaction, the surface of the silicon particle is surrounded by the organosiloxane compound.

The siloxane monomer represented by the formula (1) may be represented by the following formula (1a) or (1b) depending on the kind of the terminal groups R ¹ and R ⁸ .

[Formula 1a]

[Chemical Formula 1b]

(In the above formula (1a) or (1b), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; n is an integer from 0 to 6; and a is an integer of 0 to 40)

The siloxane monomer represented by the above formula (1a) has a hydrogen atom (H) as a reactive hydrogen group at the terminal thereof, and the siloxane monomer represented by the above formula (1b) has an alkenyl group as a hydrogen- have. In the present invention, the siloxane monomer may be a compound represented by the above formula (1a) or (1b) or a mixture thereof.

The present invention is also characterized by a method for producing an organic silicone resin having a core-shell structure,

(I) a process for producing silicon particles having a chlorine-end functional group (Si-Cl) by using a magnesium compound selected from the group consisting of Mg ₂ Si, KSi and NaSi and tetrachlorosilane;

Ⅱ) and the silicon particles having a terminal functional group-chloro, R-MgCl or R ₂ SiHCl (wherein, R is represented by C _1~20 alkyl, C _2~20 is an alkenyl group, or a functional group selected from a C _6-20 aryl group) Reacting the compound with a compound to prepare a silicone particle substituted with a functional group X represented by Formula 2 below; And

Iii) a step of reacting a silicon particle substituted with a functional group X represented by the following formula 2 and a siloxane monomer represented by the following formula 1 to prepare an organosilicon resin having a core-shell structure as defined above; .

(2)

는 실리콘 입자를 나타내고, R은 C_{1 ∼20} 알킬기 및 C_6∼20 아릴기 중에서 선택된 불활성기를 나타내고, X는 수소원자 및 C_{2 ∼20} 알케닐기 중에서 선택된 수소화 반응성기를 나타내고, p와 q는 관능기 수를 나타내는 것으로 p는 0 내지 200의 정수이고, q/(p+q)는 0.01 ~ 0.95이다)(In the formula (2)

Denotes a silicon particle, R is a C ₁ alkyl group and a C _{~20 6~20} represents an inert group selected from an aryl group, X represents a group selected from hydride-reactive hydrogen atoms and C _{2 ~20} alkenyl group, p and q is a number of functional groups Wherein p is an integer from 0 to 200, and q / (p + q) is from 0.01 to 0.95.

[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)

The above process (i) is a process for producing silicon particles, wherein a magnesium compound and tetrachlorosilane are used to prepare silicon particles having a chlorine end functional group (Si-Cl) by a known method. The silicon particles thus produced have an average size of 1 nm to 70 nm and are uniform in size.

The process (ii) is a process of introducing a functional group onto the surface of the silicon particle, wherein a reactive group (for example, a hydrogen atom or an alkenyl group) capable of hydrogen saccharification reaction and a non-reactive group (for example, Aryl) is appropriately selected, and the distribution and the fraction of these functional groups are controlled.

The step iii) is a process for hydroisomerizing Si-H or Si- ( _C2-20 alkenyl group) as the reactive group present on the surface of the silicon particles and the siloxane monomer represented by the formula (1). The siloxane monomer is used in an amount of 1 to 3 equivalents relative to the number of reactive groups present on the surface of the silicon particles, preferably 1 to 1.5 equivalents.

The organosilicon resin having a core-shell structure prepared through the above-described method can be represented by the following structural formula.

(3)

는 실리콘 입자를 나타내고, R은 C_{1 ∼20} 알킬기 및 C_6∼20 아릴기 중에서 선택된 불활성기를 나타내고, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, 및 a는 각각 상기에서 정의한 바와 같고, m은 0 또는 1이고, p와 q는 관능기 수를 나타내는 것으로 p는 0 내지 200의 정수이고, q/(p+q)는 0.01 ~ 0.95이다)
(3)

Denotes a silicon particle, R is a C ₁ alkyl group and a C _{~20 6~20} represents an inert group selected from an aryl group, R ^1, R ^2, R ^3, R ^4, R ^5, R ^6, R ^7, and a have the same meanings as defined above, m is 0 or 1, p and q indicates the number of functional groups and p is an integer from 0 to 200, q / (p + q ) Is from 0.01 to 0.95)

On the other hand, the present invention is also characterized by a cured coating film prepared by curing an organosilicon resin having the core-shell structure.

The organosilicon resin of the core-shell structure according to the present invention can produce a cured film through a conventional curing method and, if necessary, another cured film can be prepared by incorporating another siloxane compound. In the present invention, there is no particular limitation on the production method of the cured coating film. In the following experimental example, only a practical example of producing a cured film by thermosetting at a temperature of 120 to 200 캜 using a platinum catalyst is exemplified.

The cured coating film containing the organosilicon resin of the core-shell structure prepared in the present invention had a light transmittance of 97 to 99% and a characteristic that oxygen permeability was significantly reduced as compared with the siloxane resin coating film. In the present invention, it was confirmed that the permeability of oxygen gas was reduced by up to 50% as compared with the coating film prepared by curing the siloxane monomer represented by the formula (1) used for producing the core-shell structure organosilicone resin.

The cured coating film containing the organosilicon resin of the core-shell structure of the present invention has a low oxygen permeability and thus has a delayed oxidation rate, so that a sufficient working time can be secured and a function as an oxygen capture (catcher or getter) There are advantages.

Hereinafter, the present invention will be described in more detail through Production Examples, Examples and Experimental Examples. However, these are for the purpose of illustrating the present invention, and the scope of the present invention is not limited thereto.

[Production Example] Production of silicon particles whose functional groups are substituted on the surface

Production Example 1: Preparation of silicon particles substituted with allyl group / methyl group

In a glove box filled with dry argon (Ar), 10 g (130.4 mmol) of magnesium suicide (Mg ₂ Si) was placed in a 500 mL two-necked flask (reaction tank), and the dried reflux condenser was connected. 18 mL (26.8 g, 157.8 mmol) of oxygen-free tetrachlorosilane and 400 mL of glyme were injected into the reaction tank using a double-tip needle, respectively. The reaction vessel was stirred under reflux for 10 days. After completion of the reaction, volatile solvent glyme and unreacted tetrachlorosilane were removed by bulb-to-bulb distillation. Thus, silicon particles having Si-Cl functional groups at their terminals were obtained.

To the reaction vessel containing the Si-Cl functional group-containing silicon particles obtained above, 250 mL of dried glyme was added and 2.0 mL of a 2M concentration allyl magnesium chloride-tetrahydrofuran solution was added dropwise for 5 minutes while stirring. After refluxing for a period of time, 10 mL of a 3 M methylmagnesium bromide-tetrahydrofuran solution was added dropwise and refluxed for 1 hour. The glyme was then removed with bulb-to-bulb distillation and worked up with distilled water and toluene to separate only the toluene layer. The toluene was removed by an evaporator and then separated by silica gel column chromatography (eluent: hexane) to obtain 0.5 g of a pale yellow gel-like allyl group / silicon group-substituted silicone particle.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of allyl group / methyl group present on the surface of the silicon particles was 1/5. Also, TEM analysis showed that the silicon particles substituted with allyl group / methyl group had a crystal domain of 3 to 15 nm in size. 1)

Production Example 2: Preparation of silicon particles substituted with allyl group / phenyl group

Silicone particles having Si-Cl functional groups were prepared in the same manner as in Preparation Example 1, and then 1.0 mL of a 2M-concentration allyl magnesium chloride-tetrahydrofuran solution was added dropwise for 1 minute, refluxed for 1 hour, 15 mL of a solution of phenylmagnesium bromide-tetrahydrofuran was added dropwise and refluxed for 1 hour. Then, purification was conducted in the same manner as in Preparation Example 1 to obtain 0.52 g of silicon particles substituted with pale yellow gel-like allyl group / phenyl group.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of allyl group / phenyl group present on the surface of the silicon particles was 1/10. Also, TEM analysis showed that the silicon particles substituted with allyl group / methyl group had a crystal domain of 3 to 15 nm in size. 2)

Preparation Example 3: Preparation of silicon particles substituted with allyl group / n-butyl group

Silicone particles having Si-Cl functional groups were prepared in the same manner as in Preparation Example 1, 1.0 mL of a 2M-concentration allylmagnesium chloride-tetrahydrofuran solution was added dropwise for 1 minute, refluxed for 1 hour, Butyllithium in hexane was added dropwise and refluxed for 1 hour. Then, purification was carried out in the same manner as in Preparation Example 1 to obtain 0.49 g of silicon particles substituted with a pale yellow gel-like butyl group / allyl group.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of allyl group / n-butyl group present on the surface of the silicon particles was 1/11. TEM analysis showed that the silicon particles substituted with the allyl group / n-butyl group had a crystal domain of 3 to 15 nm in size.

Preparation Example 4: Preparation of silicon particles substituted with vinyl group / phenyl group

Silicone particles having Si-Cl functional groups were prepared in the same manner as in Preparation Example 1, 2.0 mL of a 1 M solution of vinyl magnesium chloride-tetrahydrofuran solution was added dropwise for 1 minute, refluxed for 1 hour, Solution of phenylmagnesium chloride-tetrahydrofuran was added dropwise and refluxed for 1 hour. Then, purification was conducted in the same manner as in Preparation Example 1 to obtain 0.50 g of silicon particles substituted with a pale yellow gel-like vinyl group / phenyl group.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of vinyl groups / phenyl groups present on the surface of the silicon particles was 1/10. Also, it was confirmed by TEM analysis that the silicon particles substituted with the vinyl group / phenyl group produced had a crystal domain of 3 to 15 nm in size.

Production Example 5: Preparation of silicon particles substituted with vinyl group / methyl group

Silicone particles having Si-Cl functional groups were prepared in the same manner as in Preparation Example 1, 2.0 mL of a 1 M solution of vinyl magnesium chloride-tetrahydrofuran solution was added dropwise for 1 minute, refluxed for 1 hour, and 3 M Methylmagnesium chloride-diethyl ether solution (7 mL) was added dropwise and refluxed for 1 hour. And purified by the same manner as in Preparation Example 1 to obtain 0.47 g of silicon particles substituted with a pale yellow gel-like vinyl group / methyl group.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of vinyl group / methyl group present on the surface of the silicon particles was 1/9. Also, TEM analysis showed that the silicon particles substituted with allyl group / methyl group had a crystal domain of 3 to 15 nm in size.

Production Example 6: Preparation of silicon particles substituted with hydrogen atoms / phenyl groups

In a glove box filled with dry argon (Ar), 10 g (130.4 mmol) of magnesium suicide (Mg ₂ Si) was placed in a 500 mL two-necked flask (reaction tank), and the dried reflux condenser was connected. 12 mL (17.8 g, 104.8 mmol) of oxygen tetrachloride silane and 400 mL of glyme were injected into the reaction tank using a double-tip needle, respectively. The reaction vessel was stirred under reflux for 10 days. After completion of the reaction, volatile solvent glyme and unreacted tetrachlorosilane were removed by bulb-to-bulb distillation. Thus, silicon particles having Si-Cl functional groups at their terminals were obtained.

300 mL of dried glyme was added to the reaction vessel containing the Si-Cl functional group-containing silicon particles obtained above, and 7 mL (7.8 g, 35.8 mmol) of diphenylchlorosilane was added dropwise for 5 minutes while stirring, Lt; / RTI > The glyme and the unreacted diphenylchlorosilane were removed by bulb-to-bulb distillation and work-up with distilled water and toluene to remove only the toluene layer . After toluene was removed by an evaporator, the residue was separated by silica gel column chromatography (eluent: hexane) to obtain 0.52 g of a pale yellow gel-like silicon atom / phenyl group-substituted silicone particle.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of hydrogen atom / phenyl group present on the surface of the silicon particle was 1/2. In addition, TEM analysis confirmed that the hydrogen atoms / phenyl group-substituted silicon particles had a crystal domain of 3 to 15 nm in size.

Production Example 7: Preparation of silicon particles substituted with hydrogen atoms / methyl groups

Silicone particles having Si-Cl functional groups were prepared in the same manner as in Preparation Example 6, and 6 mL (5.1 g, 53.9 mmol) of dimethylchlorosilane was added dropwise for 5 minutes and stirred for 10 days. Then, purification was carried out in the same manner as in Preparation Example 6 to obtain 0.46 g of silicon particles substituted with a pale yellow gel-like methyl group / methyl group.

It was confirmed by hydrogen nuclear magnetic resonance spectroscopy ( ¹ H NMR) that the molar ratio of hydrogen atom / methyl group present on the surface of the silicon particle was 1/2. Also, it was confirmed from the TEM analysis that the silicon particles substituted with the hydrogen atom / methyl group had a crystal domain of 3 to 15 nm in size.

Organosilicon particles substituted with functional groups prepared in Preparation Examples 1 to 7 are briefly summarized in Table 1 below.

division Functional group-substituted organosilicon particles Reactive functional group Non-reactive functional group Molar ratio of reactive / non-reactive functional groups Particle size
(nm) Production Example 1 Allyl group Methyl group 1/5 3-15 Production Example 2 Allyl group Phenyl group 1/10 3-15 Production Example 3 Allyl group Butyl group 1/11 3-15 Production Example 4 Vinyl group Phenyl group 1/10 3-15 Production Example 5 Vinyl group Methyl group 1/9 3-15 Production Example 6 Hydrogen atom Phenyl group 1/2 3-15 Production Example 7 Hydrogen atom Methyl group 1/2 3-15

TEM images of the organosilicon particles substituted with functional groups prepared in Preparation Examples 1 and 2 were shown in FIGS. 1 and 2, respectively.

EXAMPLES Preparation of Organosilicon Resin of Core-Shell Structure

Example 1: Organic silicone resin of core-shell structure

0.5 g of the silicone particles prepared in Preparation Example 1 (allyl group / methyl group = 1/5 mole ratio) and 1,5-dihydrohexamethylsiloxane compound (formula 1a, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 1). Then 3.1 占 퐇 of 0.1 M (0.100 mol) of a 0.1 M Kastets catalyst in xylene was added thereto and the mixture was reacted at 100 占 폚 for 5 hours with stirring. ^The chemical shift and area of Si-allyl (hydrogen of double bond) of silicon particles were analyzed by ¹ H NMR to confirm the degree of reaction. The platinum catalyst was removed via silica gel column chromatography (eluent: hexane), and the solvent was evaporated under vacuum to obtain 0.58 g of an organosilicon resin.

Example 2: Organic-silicone resin having a core-shell structure

(Allyl group / phenyl group = 1/10 mole ratio) and 1,5-dihydro-3,3-diphenyltetramethylsiloxane (prepared by the same method as in Example 1) 0.69 g of an organosilicon resin was obtained using 0.2 g of the compound (Formula 1a, R ² = R ³ = phenyl, R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 1).

Example 3: Organic silicone resin having a core-shell structure

(1/10 molar ratio of allyl group / phenyl group) and 0.5 g of 1,5-dihydrohexamethylsiloxane compound (formula 1a, R ² ) in the same manner as in Example 1, 0.85 g of an organosilicon resin was obtained by using 0.35 g of a compound represented by the formula: R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 8).

Example 4: Core-shell structure of organosilicon resin

0.5 g of the silicone particles prepared in Preparation Example 3 (allyl group / butyl group = 1/11 mole ratio) and 1,5-dihydro-3,3-diphenyltetramethyl 0.7 g of an organosilicon resin was obtained using 0.2 g of a siloxane compound (formula 1a, R ² = R ³ = phenyl, R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 1).

Example 5: Core-shell structure of organosilicon resin

(Vinyl group / phenyl group = 1/10 mole ratio) and 1,5-dihydro-3-phenylpentamethylsiloxane compound (compound represented by Chemical Formula (1)) in the same manner as in Example 1, 0.59 g of an organosilicon resin was obtained by using 0.1 g of a compound represented by the general formula (1), R ² = phenyl, R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a =

Example 6: Core-shell structure of organosilicon resin

(Vinyl group / methyl group = 1/9 mole ratio) and 1,5-dihydro-3-phenylpentamethylsiloxane compound (compound represented by formula 0.63 g of an organosilicon resin was obtained by using 0.15 g of a compound represented by the general formula (1), R ² = phenyl, R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl,

Example 7: Core-shell structure of organosilicon resin

0.5 g of the silicon particles prepared in Preparation Example 6 (hydrogen atom / phenyl group = 1/2 mole ratio) and the alpha, omega-divinylpermethylsiloxane compound (Formula 1b, R ² 60 g of an organosilicon resin was obtained by using 60 g of a compound represented by the formula: R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 30).

Example 8: Organic silicone resin having a core-shell structure

Except that 0.5 g of the silicon particles prepared in Preparation Example 5 (hydrogen atom / methyl group = 1/2 mole ratio) and 1,5-divinylhexamethylsiloxane compound (formula 1b, R ² = 0.13 g of R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 1) to obtain 0.61 g of an organosilicon resin.

Example 9: Core-shell structure of organosilicon resin

0.5 g of the silicone particles prepared in Preparation Example 6 (hydrogen atom / phenyl group = 1/2 mole ratio) and 1,5-divinylhexamethylsiloxane compound (Formula 1b, R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 3) was used to obtain 0.59 g of an organosilicon resin.

Example 10: Organic silicone resin of core-shell structure

0.5 g of the silicon particles prepared in Preparation Example 7 (hydrogen atom / methyl group = 1/2 mole ratio) and 1,5-divinyl-3-phenylpentamethylsiloxane compound 0.60 g of an organosilicon resin was obtained using 0.12 g of 1b, R ² = phenyl, R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 2).

Example 11: Core-shell structure of organosilicon resin

0.5 g of the silicon particles prepared in Preparation Example 7 (hydrogen atom / methyl group = 1/2 mole ratio) and 1,5-divinyl-3,3-diphenyltetramethylsiloxane 0.58 g of an organosilicon resin was obtained using 0.10 g of a compound (Formula 1b, R ² = R ³ = phenyl, R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl, a = 1).

[Experimental Example]

Experimental Example 1. Measurement of refractive index of organosilicon resin

The specimens of the organosilicon resins prepared in Examples 1 to 11 were prepared and the refractive index was measured at 633 nm wavelength using Prism Coupler 2010 manufactured by USA Metricon. The results are summarized in Table 2 below.

Silicone resin Refractive index Silicone resin Refractive index Example 1 1.480 Example 7 1.425 Example 2 1.545 Example 8 1.499 Example 3 1.501 Example 9 1.510 Example 4 1.530 Example 10 1.521 Example 5 1.540 Example 11 1.518 Example 6 1.518

Experimental Example 2 Measurement of gas permeability

1) Manufacture of cured thin film using organic silicon resin

For the measurement of the physical properties of the core-shell structure organosilicon resin prepared in Example 1, a silicon-cured thin film was prepared as follows.

Namely, 0.1 g (silicon content: 4% by weight) of the core-shell structure of the organosilicon resin prepared in Example 1, 0.9 g of siloxane OE-6631A sold by Dow-Corning, 1.1 g of OE-6631B And 15 ppm of Pt catalyst were added and mixed well.

Further, a mixed solution having a silicon particle content of 1% by weight or 2% by weight was simultaneously made using the two-component siloxanes OE-6631A and OE-6631B at a ratio to the above-mentioned method.

An OHP film was attached to the bottom of the metal mold shown in Fig. 3, and each of the mixed solutions prepared above was transferred onto an OHP film, and then stored in a desiccator for 1 hour or longer under vacuum to remove a small amount of solvent remaining in the mixture. Then, curing was performed at a temperature of 150 ° C for 1 hour to prepare a thin film.

FIG. 4 is a photograph showing an example of a silicon thin film cured by using the organosilicon resin having the core-shell structure prepared in Example 1, wherein a mixed solution having a silicon content of 4 wt% is used.

2) Measurement of gas permeability of thin film

The silicon thin film prepared above was measured by Time-lag method at 30 ° C to measure the gas permeability. [R.M. Barrer, Permeation, diffusion and solution of gases in organic polymers, Trans. Faraday Soc., 35 (1939), pp. 628-643; R.M. Felder, G.S. Huvard, Permeation, diffusion, and sorption of gases and vapors, in: L. Marton, C. Marton (Eds.), Methods of Experimental Physics, Academic Press, New York, 1980, pp. 315-378.] The measurement principle of the time-lag can be determined by expressing the accumulated amount of permeate passing through the membrane into a chamber of a certain volume as a function of time. The pressure of the gas at the upper part of the membrane was fixed constantly and the volume of the lower part receiving the gas passing through the membrane was sufficiently large so that the pressure at the lower part was negligibly small as compared with the pressure at the upper part while measuring the permeability. The silicon thin film (80 mm x 4 mm rectangle) prepared above was fixed to the measurement window, and the gas permeability according to the following formula (1) was calculated while maintaining the equivalent pressure at 1,500 torr.

[Equation 1]

Gas permeability P (barrer) = (VT ₀ L / P ₀ T? PA) dp / dt

(Where V is the volume at the bottom (cm ³ ), L is the film thickness (cm), T ₀ and P ₀ are A is the gas permeable effective area of the membrane, and dp / dt is the pressure rising rate in the steady state.

Table 3 below shows the content of silicon particles in the organic silicone resin used in the manufacture of the thin film The results of gas permeability measurements of thin films A, B, C, and D prepared by different methods are summarized.

3) Light transmittance

The internal diffuse reflectance of Varian was measured using a UV / Vis spectrum analyzer Cary 100 Cornc. Equipped with a spectrophotometer at a wavelength of 450 nm at a radius of 1 cm and a thickness of 1 mm.

division Thin film A Thin film B Thin film C Thin film D PDMS ^b
pellicle Silicon particle content
(weight%) 0 One 2 4 Film thickness (占 퐉) 360 109 103 200 N ₂ transmittance
(barrer ^a ) 290.86 151.01 160.10 230.10 400 O ₂ transmission
(barrer ^a ) 558.76 280.10 320.10 406.41 800 O ₂ / N ₂
Selectivity 1.92 1.98 2.01 1.77 2 Light transmittance (%) 99 99 98 97 ^{a) Barrer = 10 -10 cm 3} (STD) · cm · cm -2 · s -1 · cmHg -1
^b) Journal of Polymer Science: Part B: Polymer Physics 38 (2000) 415-434.

In Table 3, the thin film A is a mixture of 1,5-dihydrohexamethylsiloxane compounds having R ² = R ³ = R ⁴ = R ⁵ = R ⁶ = R ⁷ = methyl group and a = The nitrogen permeability was 290.86 barrer and the oxygen permeability was 558.76 barrer. On the contrary, the thin films B and C are cured thin films including the core-shell structure organic silicon resin proposed in the present invention, and the nitrogen permeability and the oxygen permeability are remarkably reduced to about 50% as compared with the thin film A . It can be confirmed that the nitrogen permeability and the oxygen permeability are remarkably low as compared with the conventionally known PDMS thin film.

Further, a thin film having a silicon particle content of 1 wt% was prepared by the method 1) of Experimental Example 2 using the organosilicon resin having the core-shell structure prepared in Examples 2 to 11 above. The gas permeability and the light transmittance were measured by the methods of 2) and 3) of Experimental Example 2, respectively. The results are shown in Table 4 below.

Organic silicone resin Silicon particles
Content (% by weight) Film thickness
(탆) N ₂ transmittance
(barrer ^a ) O ₂ transmission
(barrer ^a ) Light transmittance
(%) Example 2 One 120 137.01 273.10 99 Example 3 One 110 150.00 290.00 99 Example 4 One 105 162.07 322.10 99 Example 5 One 130 120.10 249.41 99 Example 6 One 125 137.20 276.03 99 Example 7 One 138 280.02 572.07 98 Example 8 One 123 160.01 340.87 99 Example 9 One 117 161 310.02 99 Example 10 One 154 151.08 301.01 98 Example 11 One 140 145.02 289.07 99

As shown in Table 4, the characteristics of the cured thin film using the core-shell structure organic silicon resin including the silicon particles have an advantage of excellent light transmittance and reduced gas permeability.

INDUSTRIAL APPLICABILITY As described above, the organosilicone resin of the core-shell structure of the present invention has excellent thermal barrier properties against silicone gas, and also has excellent permeation inhibition rate against oxygen gas. Therefore, it can be used for LED encapsulant, display panel, Hard coating materials, water-repellent coating materials, heat-resistant film materials, and the like.

Claims (10)

By using the silicon particles as a core,
Wherein a shell is formed by reacting a terminal functional group selected from Si-H and Si- (C _{2 - 20} alkenyl group) present on the surface of the silicon particle with a siloxane monomer represented by the following formula (1) - Organosilicon resin of shell structure:
[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)
The method according to claim 1,
Wherein the siloxane monomer is a compound represented by the following formula (1a) or (1b) or a mixture thereof.
[Formula 1a]

[Chemical Formula 1b]

(In the above formula (1a) or (1b), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; n is an integer from 0 to 6; and a is an integer of 0 to 40)
The method according to claim 1,
Wherein the average size of the silicon particles is in the range of 1 nm to 70 nm.
The method according to claim 1,
The silicon particles have a hydrogen atom to the surface, C _1~20 alkyl, C _2~20 alkenyl groups and C _6~20 aryl group which is present as a functional group, a hydrogen atom to react with the siloxane monomers of the formula (1) and C _{2 And a} reactive functional group selected from an alkenyl group having 1 to ₂₀ carbon atoms is present in a proportion of 0.001 to 0.95 relative to the total functional group.
5. The method according to any one of claims 1 to 4,
Wherein the refractive index value of the core-shell structure is in the range of 1.48 to 1.54.
A process for producing silicon particles having a chlorinated end functional group by using a magnesium compound selected from the group consisting of Mg ₂ Si, KSi and NaSi and tetrachlorosilane;
And silicone particles having a terminal functional group-chloro, R-MgCl or R ₂ SiHCl compound represented by (wherein, R is C _1~20 alkyl, C _2~20 is an alkenyl group, or a functional group selected from a C _6-20 aryl group), and To produce a silicon particle substituted with a functional group X represented by the following formula (2); And
A process for producing an organosilicon resin having a core-shell structure as defined in claim 1 by reacting silicon particles substituted with a functional group X represented by the following formula (2) and a siloxane monomer represented by the following formula (1);
Of the core-shell structure.
(2)

(In the formula (2)

Denotes a silicon particle, R is a C ₁ alkyl group and a C _{~20 6~20} represents an inert group selected from an aryl group, X represents a group selected from hydride-reactive hydrogen atoms and C _{2 ~20} alkenyl group, p and q is a number of functional groups Wherein p is an integer from 0 to 200, and q / (p + q) is from 0.01 to 0.95.
[Chemical Formula 1]

Wherein R ¹ and R ⁸ are the same or different and are -H or CH ₂ ═CH- (CH ₂ ) _n -, wherein n is an integer of 0 to 6; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and each is a C _1-20 alkyl group or a C _6-20 aryl group; and a is an integer of 0 to 40)
The method according to claim 6,
Wherein the average size of the silicon particles is in the range of 1 nm to 70 nm.
The method according to claim 6,
Wherein the core-shell structure of the organosilicon resin is represented by the following formula (3).
(3)

(3)

Denotes a silicon particle, R is a C ₁ alkyl group and a C _{~20 6~20} represents an inert group selected from an aryl group, R ^1, R ^2, R ^3, R ^{4, R 5, R 6, R 7} , and a are respectively the same as defined in the claim 1, m is 0 or 1, p and q and p is an integer from 0 to 200 to represent the number of functional group, q / (p + q) is from 0.01 to 0.95)
A cured coating film comprising an organosilicon resin of one of the core-shell structures of any one of claims 1 to 4.
10. The method of claim 9,
Wherein the cured coating film has a light transmittance of 99 to 97% and an oxygen gas transmission rate of the cured coating film is reduced by up to 50% as compared to a coating film prepared by curing a siloxane monomer having no core-shell structure .

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