KIM JONG-SUNG (KR)
LEE BYEONG-DU (KR)
YOON JIN-HWAN (KR)
JIN KYEONG-SIK (KR)
HOE KYU-YOUNG (KR)
REE MOON-HOR (KR)
KIM JONG-SUNG (KR)
LEE BYEONG-DU (KR)
YOON JIN-HWAN (KR)
JIN KYEONG-SIK (KR)
HOE KYU-YOUNG (KR)
EP0449263A2 | 1991-10-02 | |||
US4859740A | 1989-08-22 |
1. | A nanoparticle of coreshell type comprising: an organic polymer core particle with a network structure; and a shelllayer comprising a silsesquioxane prepolymer and surrounding the core particle. |
2. | The nanoparticle of coreshell type of claim 1, wherein a diameter of the nanoparticle is in a range from 2 nm to 120 nm. 3. The nanoparticle of coreshell type of claim 1 , wherein a diameter of the organic polymer core particle is in a range from 1 nm to 100 nm. 4. The nanoparticle of coreshell type of claim 1 , wherein the organic polymer core particle is prepared by polymerizing i) a multifunctional unsaturated monomer with more than two vinyl groups (a first unsaturated monomer), or ii) a mixture of a multifunctional unsaturated monomer with more than two vinyl groups and an unsaturated monomer with one vinyl group (a second unsaturated monomer). 5. The nanoparticle of coreshell type of claim 4, wherein the first unsaturated monomer is at least one selected from the group consisting of divinyl benzene, trivinyl benzene, divinyl pyridine, divinyl naphthalene, divinyl xylene, methyl silsesquioxane glycol diacrylate, trimethylol propane triacrylate, diethylene glycol divinyl ether, trivinyl cyclohexane, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, trimethylol propane trimethacrylate, glycidyl methacrylate, 2,2dimethyl propane 1 ,3diacrylate, 1 ,3butylene glycol diacrylate, 1 ,3butylene glycol dimethacrylate, 1 ,4butandiol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1 ,6hexanediol dimethacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol 200 diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, bisphenolA diacrylate ethyl ester, bisphenolA dimethacrylate ethyl ester, polyethylene glycol 600 dimethacrylate, polybutandiol diacrylate, pentaerythritol triacrylate, trimethylol propane triethoxy triacrylate, glycerylpropyloxytriacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol monohydroxy pentaacrylate, divinyl silane, trivinyl silane, dimethyl vinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl disiloxane, polymethyl vinyl siloxane, polyvinyl hydroxide siloxane, and polyphenyl vinyl siloxane. 6. The nanoparticle of coreshell type of claim 4, wherein the second unsaturated monomer is at least one selected from the group consisting of metharcylic acid, methacryl amide, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, styrene, αmethyl styrene, vinyl toluene, pmethyl styrene, ethyl vinyl benzene, vinyl benzene, vinyl naphthalene, vinyl xylene, 2vinyl pyridine, 4vinyl pyridine, 2methyl5vinyl pyridine, 2ethyl5vinyl pyridine, 3 methyl5vinyl pyridine, 2,3dimethyl5vinyl pyridine, 2methyl3ethyl5vinyl pyridine, methyl quinolin, isoquinolin, Nvinyl caprolactam, Nvinyl pyrrolidone, vinyl imidazole, Nvinyl carbazole, maleimide, Nvinyl oxazolidone, Nvinyl phthalimide, vinyl pyrrole, vinyl aniline, and vinyl piperidine. 7. The nanoparticle of coreshell type of claim 1 , wherein the silsesquioxane prepolymer is prepared by using at least one silsesquioxane monomer selected from the group consisting of trichlorosilane, methyl triethoxy silane, methyl trimethoxy silane, methyl diethoxy silane, methyl dimethoxy silane, ethyl triethoxy silane, ethyl trimethoxy silane, ethyl diethoxy silane, ethyl dimethoxy silane, bis(trimethoxy silyl)ethane, bis(triethoxy silyl)ethane, bis(triethoxy silyl)methane, bis(triethoxy silyl)octane, bis(trimethoxy silyl)hexane, bis(triethoxy silyl)ethyl benzene, and bis(trimethoxy silyl)ethyl benzene. 8. A method of preparing a nanoparticle of coreshell type comprising: a) preparing a microemulsion by providing: i) a multifunctional unsaturated monomer with more than two vinyl groups (a first unsaturated monomer) or ii) a multifunctional unsaturated monomer with more than two vinyl groups and a unsaturated monomer with one vinyl group (a second unsaturated monomer), into a surfactant solution including a surfactant and a cosurfactant; b) preparing an organic polymer core particle with a network structure by adding an initiator into the microemulsion and reacting them with the monomer; and c) preparing a silsesquioxane prepolymer shelllayer on the surface of the organic polymer core particle with a network structure by adding a silsesquioxane monomer and catalyst into the microemulsion and reacting them. 9. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the surfactant of a) is at least one cationic surfactant selected from the group consisting of: sodium dodecyl sulfate (SDS), sodium bis(2ethylhexyl)sulfosuccinate (AOT), dodecyl benzene sulfonic acid, sodium dioctyl sulfosuccinate, sodium alkyl phenol ether sulfonate, and sodium alkyl sulfonate. 10. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the surfactant solution of the step a) comprises a surfactant in a range from 0.1 M to 10 M. 11. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the first unsaturated monomer is at least one selected from the group consisting of divinylbenzene, trivinylbenzene, divinyl pyridine, divinylnaphthalene, divinylxylene, methyl silsesquioxane glycol diacrylate, trimethylol propane triacrylate, diethylene glycol divinyl ether, trivinyl cyclohexane, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, trimethylol propane trimethacrylate, glycidyl methacrylate, 2,2dimethyl propane 1 ,3 diacrylate, 1 ,3butylene glycol diacrylate, 1 ,3butylene glycol dimethacrylate, 1 ,4butandiol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1 ,6hexanediol dimethacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol 200 diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, bisphenolA diacrylate ethylester, bisphenolA dimethacrylate ethylester, polyethylene glycol 600 dimethacrylate, polybutandiol diacrylate, pentaerythritol triacrylate, trimethylolpropane triethoxy triacrylate, glycerylpropyloxytriacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol monohydroxy pentaacrylate, divinyl silane, trivinyl silane, dimethyl vinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl disiloxane, polymethyl vinyl siloxane, polyvinyl hydroxide siloxane, and polyphenyl vinyl siloxane. 1. |
3. | The method of preparing a nanoparticle of coreshell type of claim 8, wherein the second unsaturated monomer is at least one selected from the group consisting of metharcylic acid, methacryl amide, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, styrene, αmethyl styrene, vinyl toluene, pmethyl styrene, ethyl vinyl benzene, vinyl benzene, vinyl naphthalene, vinyl xylene, 2vinyl pyridine, 4vinyl pyridine, 2methyl5vinyl pyridine, 2 ethyl5vinyl pyridine, 3methyl5vinyl pyridine, 2,3dimethyl5vinyl pyridine, 2methyl3 ethyl5vinyl pyridine, methyl quinolin, isoquinolin, Nvinyl caprolactam, Nvinyl pyrrolidone, vinyl imidazole, Nvinyl carbazole, maleimide, Nvinyl oxazolidone, Nvinyl phthalimide, vinyl pyrrole, vinyl aniline, and vinyl piperidine. 13. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the weight ratio of the mixture between the surfactant and i) the first unsaturated monomer or ii) the mixture of the first unsaturated monomer and the second unsaturated monomer in the step a) is in a range from 1 :100 to 100:1. 14. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the weight ratio of the silsesquioxane monomer and i) the first unsaturated monomer or ii) the mixture of the first unsaturated monomer and the second unsaturated monomer is in a range from 1 :100 to 100:1. 15. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the catalyst used in c) is more than one base catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. 16. The method of preparing a nanoparticle of coreshell type of claim 8, wherein the catalyst used in c) is at least one acid catalyst selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, citric acid, and lactic acid. 17. A method of preparing a low dielectric insulation film comprising: a) mixing a nanoparticle of coreshell type and a silicate polymer to form a mixture; b) reacting the mixture of the nanoparticle of coreshell type and the silicate polymer by solgel reaction; and c) heattreating the reacted mixture such that minute pores are formed. 18. The method of preparing a low dielectric insulation film of claim 17, wherein the nanoparticle of coreshell type and silicate polymer mixture is mixed such that the weight ratio of the mixture is in a range from 1 :99 to 50:50. 19. The method of preparing a low dielectric insulation film of claim 17, wherein the heat treatment is performed at a temperature in a range between 200 0C to 500 0C, in a nitrogen atmosphere or a vacuum. 20. The method of preparing a low dielectric insulation film of claim 17, wherein the silicate polymer is at least one selected from the group consisting of methyl silsesquioxane, ethyl silsesquioxane, and hydrogen silsesquioxane. 21. The method of preparing a low dielectric insulation film of claim 20, wherein the silicate polymer comprises a repeating unit induced from at least one monomer selected from the group consisting of trichlorosilane, methyl triethoxy silane, methyl trimethoxy silane, methyl diethoxy silane, methyl dimethoxy silane, ethyl triethoxy silane, ethyl trimethoxy silane, ethyl diethoxy silane, ethyl dimethoxy silane, bis(trimethoxy silyl)ethane, bis(triethoxy silyl)ethane, bis(triethoxy silyl)methane, bis(triethoxy silyl)octane, bis(trimethoxy silyl)hexane, bis(triethoxy silyl)ethylbenzene, and bis(trimethoxy silyl)ethylbenzene. 2. |
4. | A low dielectric insulation film prepared by the method of claim 17, comprising the complex of the silsesquioxane prepolymer and the silicate polymer, with minute pores formed therein. 23. The low dielectric insulation film of claim 22, wherein a size of at least some of the pores is less than or equal to 100 nm. AMENDED CLAIMS [received by the International Bureau on 02 September 2005 (02.09.2005); original claims 118 amended; remaining claims unchanged (4 pages)] WHAT IS CLAIMED IS: 1. (Amended) A pore forming material comprising: an organic polymer core particle with a network structure; and a shelllayer comprising a silsesquioxane prepolymer and surrounding the core particle. |
5. | (Amended) The pore forming material of claim 1 , wherein a diameter of the nanoparticle is in a range from 2 nm to 120 πm. |
6. | (Amended) The pore forming material of claim 1 , wherein a diameter of the organic polymer core particle is in a range from 1 πm to 100 nm. |
7. | (Amended) The pore forming material of claim 1, wherein the organic polymer core particle is prepared by polymerizing ι) a multifunctional unsaturated monomer with more than two vinyl groups (a first unsaturated monomer), or ti) a mixture of a multifunctional unsaturated monomer with more than two vinyl groups and an unsaturated monomer with one vinyl group (a second unsaturated monomer). |
8. | (Amended) The pore forming material of claim 4, wherein the first unsaturated monomer is at least one selected from the group consisting of divinyl benzene, trivinyl benzene, divinyl pyridine, divinyl naphthalene, divinyl xylene, methyl silsesquioxane glycol diacrylate, tπmethylol propane triacrylate, diethylene glycol divinyl ether, trivinyl cyclohexaπe, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, tπmethylol propane trimethacrylate, glycidyl methacrylate, 2,2dimethyl propane 1 ,3diacryIate. 1 ,3butylene glycol diacrylate, 1 ,3butylene glycol dimethacrylate, 1 ,4butandiol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1 ,6hexanediol dimethacrylale, tπpropylene glycol diacrylate, triethyleπe glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol 200 diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, bisphenolA diacrylate ethyl ester, bispheπσ!A dimethacrylate ethyl ester, polyethylene glycol 600 dimethacrylate, polybutandiol diacrylate, pentaerythritol triacrylate, trimethylo! propane triethoxy triacrylate, glycerylpropyloxytriacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol monohydroxy pentaacrylate, divinyl silane, trivinyl silane, dimethyl vinyl silane, divinyl methyl silane, methyl trivinyl silane, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyl silane, dimethyl vinyl diεiloxane, polymethyl vinyl siloxane, polyvinyl hydroxide siloxane, and polyphenyl vinyl siloxane. 6 (Amended) The pore forming material of claim 4, wherein the second unsaturated monomer is at least one selected from the group consisting of metharcylic acid, methacryl amide, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, styrene, αmethyl styrene, vinyl toluene, pmethyl styreπe, ethyl vinyl benzene, vinyl benzene, vinyl naphthalene, vinyl xylene, 2vinyl pyridine, 4vinyl pyridine, 2methyl5vinyl pyridine, 2ethyl 5vinyl pyridine, 3methyl5vinyl pyridine, 2,3dimethyl5vinyl pyridine, 2methyl3ethyl5 vinyl pyridine, methyl quinolin, isoquinolin, Nvϊnyl caprolactam, Nvinyl pyrrolϊdone, vinyl imidazole, Nvinyl carbazole, maleimide, Nvinyl oxazolidone, Nviny! phthalimide, vinyl pyrrole, vinyl aniline, and vinyl piperidine. 7. (Amended) The pore forming material of claim 1 , wherein the silsesquioxane prepoiymer is prepared by using at least one silsesquioxane monomer selected from the group consisting of trichlorosilane, methyl triethoxy silane, methyl trimethoxy silane, methyl diethoxy siiane, methyl dimethσxy silane, ethyl triethoxy silane, ethyl trimethoxy silane, ethyl diethoxy silane, ethyl dimethoxy silane, bis(trimethoxy silyl)ethane, bis(triethoxy silyl)ethane, bis(triethoxy si!yl)methane, bis(tπ'ethoxy sityl)octaπe, bis(trimethoxy silyl)hexane, biε(trfethoxy silyl)ethyl benzene, and biε(trimethoxy silyl)ethyl benzene. 8, (Amended) A method of preparing a pore forming material comprising : a) preparing a microemulsion by providing: i) a multifunctional unsaturated monomer with more than two vinyl groups (a first unsaturated monomer) or ii) a multifunctional unsaturated monomer with more than two, vinyl groups and a unsaturated monomer with one vinyl group (a second unsaturated monomer), into a surfactant solution including a surfactant and a cosurfactant; b) preparing an organic polymer core particle with a network structure by adding an initiator into the microemulsion and reacting them with the monomer; and c) preparing a silsesquioxane prepoiymer shelllayer on the surface of the organic polymer core particle with a network structure by adding a silsesquϊoxane monomer and catalyst into the microemulsion and reacting them. 9. (Amended) The method of claim 8, wherein the surfactant of a) is at least one anionic surfactant selected from the group consisting of: sodium dodecyl sulfate (SDS), sodium bis(2ethylhexyl)sulfosuccinate (AOT), dodecyl benzene sulfonic acid, sodium dioctyl sulfosuccinate, sodium alkyl phenol ether sulfonate, and sodium alkyl sulfonate. 10. (Amended) The method of claim 8, wherein the surfactant solution of the step a) comprises a surfactant in a range from 0,1 IvI to 10 M. 11. (Amended) The method of claim 8, wherein the first unsaturated monomer is at least one selected from the group consisting of divinylbenzene, trivϊnylbenzene, divinyl pyridine, diviπylnaphthalene, divinylxyleπe, methyl silsesquioxane glycol diacrylate, trimethylol propane triacrylate, dϊethylene glycol divinyl ether, trivinyl cyclohexane, allyl methacrylate, ethylene glycol dimethacrylate, dϊethylene glycol dimethacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, trimethylol propane trimethacrylate, glycidyl methacrylate, 2,2dimethyJ propane 1 ,3diacryIate, 1 ,3butylene glycol diacrylate, 21 1,3butylene glycol dϊmethacrylate, 1,4butandiol diacrylate, diethylene glycol diacrylate, diethyleπe glycol dimethacrylate, 1,6hexanediol dimethacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, polyethylene glycol 200 diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, bispheπolA diacrylate ethylester, bisphenolA dimethacrylate ethylester, polyethylene glycol 600 dimethacrylate, polybutandiol diacrylate, peπtaerythritol triacrylate, trimethylolpropane triethoxy triacrylate, glycerylpropyloxytriacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dϊpentaerythritol monohydroxy pentaacrylate, divinyl silane, trivinyl εilaπe, dimethyl vinyl silane, diviπyl methyl silane, methyl trivinyl siiaπe, diphenyl divinyl silane, divinyl phenyl silane, trivinyl phenyl silane, divinyl methyl phenyl silane, tetravinyi silane, dimethyl vinyl disiloxane, polymethyl vinyl siloxaπe, polyvinyl hydroxide siloxane, and polyphenyl vinyl siloxane. 12. (Amended) The method of claim 8, wherein the second unsaturated monomer is at least one selected from the group consisting of metharcylic acid, methacryl amide, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hexyl methacrylate, cyclohexyl methacrylate, styrene, αmethyl styrene, vinyl toluene, pmethyl styrene, ethyl vinyl benzene, vinyl benzene, vinyl naphthalene, vinyl xylene, 2vinyl pyridine, 4vϊnyl pyridine, 2methyl5vinyl pyridine, 2ethyl5viπyl pyridine, 3methyl 5vinyI pyridine, 2,3dimethyl5viπyl pyridine, 2methyl3ethyl5vinyl pyridine, methyl quinolin, isoquinolin, Nvinyl caprolactam, Nviπyl pyrrolidone, vinyl imidazole, Nvinyl carbazole, maleimide, Nvinyl oxazolidone, Nvinyl phthalimide, vinyl pyrrole, vinyl aniline, and vinyl piperidine. 13. (Amended) The method of claim 8, wherein the weight ratio of the mixture between the surfactant and i) the first unsaturated monomer or Ii) the mixture of the first unsaturated monomer and the second unsaturated monomer in the step a) is in a range from 1:100 to 100:1. 14. (Amended) The method of claim 8, wherein the weight ratio of the silsesquioxane monomer and i) the first unsaturated monomer or ii) the mixture of the first unsaturated monomer and the second unsaturated monomer is in a range from 1:100 to 100:1, 15. (Amended) The method of claim 8, wherein the catalyst used in c) is more than one base catalyst selected from the group consisting of sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. 16. (Amended) The method of claim 8, wherein the catalyst used in c) is at least one acid catalyst selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, citric acid, and lactic acid. 17. (Amended) A method of preparing a low dielectric insulation film comprising: 22 a) mixing a pore forming material of claim 1 and a silicate polymer to form a mixture; b) reacting the mixture of the pore forming material and the silicate polymer by sol gel reaction; and c) heattreating the reacted mixture such that minute pores are formed, 18. (Amended) The method of preparing a low dielectric insulation film of claim 17, wherein the pore forming material and silicate polymer mixture is mixed such that the weight ratio of the mixture is in a range from 1 :99 to 50:50, 19. The method of preparing a low dielectric insulation film of claim 17, wherein the heat treatment is performed at a temperature in a range between 200 0C to 500 0C, in a nitrogen atmosphere or a vacuum, 20. The method of preparing a low dielectric insulation film of claim 17, wherein the silicate polymer is at least one selected from the group consisting of methyl silsesquioxane, ethyl silsesquioxane, and hydrogen silsesquioxane. 21. The method of preparing a low dielectric insulation film of claim 20, wherein the silicate polymer comprises a repeating unit induced from at least one monomer selected from the group consisting of trichlorosilane, methyl triethoxy silane, methyl trimethoxy silane, methyl diethoxy silane, methyl dimethoxy silane, ethyl triethoxy silane, ethyl trimethoxy silane, ethyl diethoxy silane, ethyl dirπethoxy silane, biε(trimethoxy silyl)ethaπe, bis(triethoxy silyl)ethane, bis(triethoxy silyl)methane, bis(triethoxy silyl)octane, bis(trimethoxy silyl)hexaπe, bis(triethoxy silyl)ethylbenzene, and bis(trimethoxy silyl)ethyl benzene. 22. A low dielectric insulation film prepared by the method of claim 17, comprising the complex of the silsesquioxane prepolymer and the silicate polymer, with minute pores formed therein. 23. The low dielectric insulation film of claim 22, wherein a size of at least some of the pores is less than or equal to 100 πm. 23. |
As shown in the above Table 1 , low dielectric insulation films prepared according to Examples 1 to 4 of the present invention had uniformly and minutely formed pores and low dielectric constants. However, those prepared according to Comparative Examples 1 to 4 showed phase separation and high dielectric constants. In conclusion, according to embodiments of the present invention, a nanoparticle of core-shell type comprises an organic polymer core particle, with a silsesquioxane prepolymer with hydroxyl, methoxy, and ethoxy end groups surrounding it. The nanoparticle can advantageously work as a pore formation material for evenly forming a pore having a size (diameter) of less than 10 nm inside the silsesquioxane polymer material due to its high compatibility with a silicate polymer. This may result in a silsesquioxane insulation film with an ultra-low dielectric constant. Therefore, according to embodiments of the present invention, a silsesquioxane polymer insulation film with minute pores inside can be variously applied as an insulation material for semi-conductors and electronic parts due to its high dielectric rate and much improved insulation.