Curable siloxane resin composition
View Patent ↗Provided is a curable siloxane composition with low dielectric constant and low dielectric loss, in which organic alkoxy silane having a silicon-based asymmetric structure and organic alkoxy silane having a silicon-based symmetric structure are included. The curable siloxane composition has low dielectric constant and dielectric loss in a high frequency range, low water absorption, excellent workability, and high copper foil peel strength, and thus physical properties suitable for application to printed circuit boards for high-frequency communication electronic devices may be provided.
1. A siloxane resin composition, comprising
first organic alkoxy silane having a silicon-based structure represented by the following Chemical Formula 1,
R 1 a R 2 b Si(OR 3 ) 2 [Chemical Formula 1]
wherein, in the above Chemical Formula 1,
R 1 comprises a linear or branched C 2-20 alkenyl group,
R 2 comprises H, a linear or branched C 1-20 alkyl group, a C 6-20 aryl group, or a C 2-20 alkenyl group,
R 3 comprises a linear or branched C 1-7 alkyl group, and
1≤a≤2, 0≤b≤1, and a+b=2,
second organic alkoxy silane having a silicon-based symmetric structure represented by the following Chemical Formula 2,
R 4 2 Si(OR 5 ) 2 [Chemical Formula 2]
wherein, in the above Chemical Formula 2,
R 4 comprises a C 6-20 aryl group, and
R 5 comprises a linear or branched C 1-7 alkyl group,
a siloxane resin prepared with the first organic alkoxy silane and the second organic alkoxy silane represented by the following Chemical Formula 3,
(R 1 a R 2 b SiO) x (R 4 2 SiO) y [Chemical Formula 3]
wherein, in the above Chemical Formula 3,
1≤x, 1≤y, and x≤y, and
a radical polymerization initiator.
2. The siloxane resin composition of claim 1 , wherein:
the first organic alkoxy silane comprises one or more of vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, allyldimethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, or dimethoxymethyl (4-vinylphenyl)silane.
3. The siloxane resin composition of claim 1 , wherein:
the second organic alkoxy silane comprises one or more of diphenyldimethoxysilane, diphenyldiethoxysilane, bis(4-methylphenyl)dimethoxysilane, bis(4-methylphenyl)diethoxysilane, bis(o-tolyl)dimethoxysilane, bis(o-tolyl)diethoxysilane, bis(m-tolyl)diethoxysilane, bis(m-tolyl)dimethoxysilane di(naphthalen-1-yl)dimethoxysilane, or di(naphthalen-1-yl)diethoxysilane.
4. The siloxane resin composition of claim 1 , further comprising:
third organic alkoxy silane having a silicon-based symmetric structure represented by the following Chemical Formula 4,
R 6 2 Si(OR 7 ) 2 [Chemical Formula 4]
wherein, in the above Chemical Formula 4,
R 6 comprises a linear, branched, or cyclic C 1-20 alkyl group, and
R 7 comprises a linear or branched C 1-7 alkyl group, and
a siloxane resin prepared with the first organic alkoxy silane, the second organic alkoxy silane, and the third organic alkoxy silane represented by the following Chemical Formula 5,
(R 1 a R 2 b SiO) x (R 4 2 SiO) y (R 6 2 SiO) z [Chemical Formula 5]
wherein, in the above Chemical Formula 5,
1≤x, 1≤y, 1≤z, and x≤y+z.
5. The siloxane resin composition of claim 4 , wherein:
the third organic alkoxy silane comprises one or more of dimethyldimethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane di-n-butyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, dicyclopentyldimethoxysilane, or dicyclopentyldiethoxysilane.
6. The siloxane resin composition of claim 4 , wherein:
the sum of the molar content of the second organic alkoxy silane and the molar content of the third organic alkoxy silane is greater than the molar content of the first organic alkoxy silane, and the molar content of the second organic alkoxy silane is greater than the molar content of the third organic alkoxy silane.
7. The siloxane resin composition of claim 1 , further comprising:
a cross-linking agent.
8. The siloxane resin composition of claim 7 , wherein:
the cross-linking agent comprises at least one selected from the group consisting of vinyltetramethyldisiloxane, vinylpentamethyldisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,3-divinyltetraethoxydisiloxane, 1,3-divinyltetrakis(trimethylsiloxy)disiloxane 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetrakis(dimethylsiloxy)disiloxane, hexamethyldisiloxane 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane, 1,5-divinyl-3-phenylpentamethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane, octavinyl-T8-silsesquioxane, phenyltris(trimethylsiloxy)silane, phenyltris(dimethylsiloxy)silane, tris(trimethylsiloxy)silane, tris(vinyldimethylsiloxy)methylsilane, tris(vinyldimethylsiloxy)phenylsilane, tris(dimethylsiloxy)silane, divinylbenzene, p-divinylbenzene, vinyldimethylsilane, vinyltrimethylsilane, vinyltriethylsilane, vinyltriphenylsilane, vinyl-t-butyldimethylsilane, vinyl-di-n-octylmethylsilane, vinylphenylmethylsilane, vinylphenyldimethylsilane, divinyldimethylsilane, trivinylsilane, trivinylmethylsilane, tetravinylsilane, vinyldimethylmethoxysilane, vinylphenylmethylmethoxysilane, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl triisopropoxysilane, vinyltri-t-butoxysilane, vinyltriisoprophenoxysilane, vinyltriphenoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltris(methoxypropoxy)silane, trivinylmethoxysilane, trivinylethoxysilane, vinylmethylbis(trimethylsiloxy)silane, vinyltris(dimethylsiloxy)silane, vinyltris(trimethylsiloxy)silane, tetrakis(vinyldimethylsiloxy)silane, vinylmethyldiacetoxysilane, vinyltriacetoxysilane, 2-prophenyltrimethylsilane, (1-methoxyvinyl)trimethylsilane, 1,2-divinyltetramethyldisilane, 1,4-divinyltetramethyldisilylethane, 1,4-bis(vinyldimethylsilyl)benzene, 1-allyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyltetramethyldisiloxane and 1,3-diallyltetrakis(trimethylsiloxy)disiloxane, allyldimethylsilane, allyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane, diallyldimethylsilane, diallyldiphenylsilane, triallylmethylsilane, tetraallylsilane, allyldimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltriphenoxysilane, allyltris(trimethylsiloxy)silane, 2,4,6,8-tetramethylcyclotetrasiloxane, octamethyl-T8-silsesquioxane, 1,1-bis(trimethylsilylmethyl)ethylene, 1,1-bis(trimethoxysilylmethyl)ethylene, methallyltrimethylsilane, diethoxymethylsilane, dimethoxymethylsilane, n-octadecylmethyldiethoxysilane, n-octadecyldimethylethoxysilane, n-octadecyldimethylmethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecyldimethylsilane, n-octylmethyldiethoxysilane, n-octylmethyldimethoxysilane, n-octyldimethylmethoxysilane, n-octyldimethylethoxysilane, isobutylmethyldimethoxysilane, bis(trimethylsiloxy)methylmethoxysilane, tris(trimethylsilyl)silane, 1,2-diethoxytetramethyldisilane, phenyldimethylethoxysilane, n-propylmethyldimethoxysilane, n-propyldimethylmethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethynetrimethylsilane, diphenylmethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylsilane, phenyldimethylsilane, 1,3-dimethyltetramethoxydisiloxane, tetrakis(dimethylsiloxy)silane, methyltris(methoxyethoxy)silane, ethyldimethylsilane, dimethylethoxysilane, tris(trimethylsiloxy)silane, tert-butyldimethylsilane, di-tert-butylmethylsilane, 1,1,2,2-tetramethyldisilane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,5-diethoxyhexamethyltrisiloxane, phenyltrimethylsilane, 1,4-bis(4-vinylphenoxy) butane, di-4-vinylbenzyl ether, divinyldiphenyl, divinylnaphthalene, 1-heptene, 1-octene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, and combinations thereof.
9. The siloxane resin composition of claim 1 , wherein:
the radical polymerization initiator comprises a peroxide radical polymerization initiator.
10. The siloxane resin composition of claim 9 , wherein:
the peroxide radical polymerization initiator comprises at least one selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane, tert-butyl-hydroperoxide, tert-amylhydroperoxide, cumylhydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, isopropylcumylhydroperoxide, isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexyne-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(tert-butyl)-peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane, di(tert-butylperoxy-isopropyl)benzene, tert-butylcumylperoxide, di-(tert-amyl)-peroxide, dicumylperoxide, butyl4,4-di(tert-butylperoxy) valerate, tert-butylperoxybenzoate, 2,2-di(tert-butylperoxy) butane, tert-amylperoxy-benzoate, tert-butylperoxy-acetate, tert-butylperoxy-(2-ethylhexyl) carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy-3,5,5-trimethyl-hexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxyacetate, tert-amylperoxy-(2-ethylhexyl) carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylpooxy)cyclohexane, tert-butyl-monoperoxy-malate, 1,1′-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butyl peroxydiethylacetate, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, tert-amylperoxy-2-ethylhexanoate, di(3-methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, ammonium peroxodisulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy) hexane, 2,2′-azodi(2-methylbutyronitrile), 2,2′-azodi (isobutyronitrile), didecanoylperoxide, dilauroylperoxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amylperoxypivalrate, tert-butylperoxyneoheptanoate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butylperoxypivalate, dicetylperoxydicarbonate, dimyristyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxycarbonate, diisopropylperoxydicarbonate, tert-butylperoxyneodecanoate, di-sec-butylperoxydicarbonate, tert-amylperoxyneodecanoate, cumyl peroxyneoheptanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumylperoxyneodecanoate, diisobutyrylperoxide, and combinations thereof.
11. The siloxane resin composition of claim 1 , wherein:
a cured material of the siloxane resin composition has dielectric constant of 3.3 or less at a frequency of 10 GHz and dielectric loss of 0.005 or less at a frequency of 10 GHz.
12. The siloxane resin composition of claim 1 , wherein:
a cured material of the siloxane resin composition has hygroscopicity of 0.1% or less as measured based on ASTM D570 standard.
13. A siloxane resin manufacturing method, comprising:
preparing a mixture by mixing first organic alkoxy silane having a silicon-based asymmetric structure, second organic alkoxy silane having a silicon-based symmetric structure, third organic alkoxy silane having a silicon-based symmetric structure, and an acid or base catalyst;
carrying out a condensation reaction at 40° C. to 300° C. by agitating the mixture;
removing the acid or base catalyst; and
adding a peroxide radical polymerization initiator.
14. The siloxane resin manufacturing method of claim 13 , wherein:
the acid catalyst comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, toluenesulfonic acid, acetic acid, butyric acid, palmitic acid, oxalic acid, or tartaric acid.
15. The siloxane resin manufacturing method of claim 13 , wherein:
the base catalyst comprises one or more of an alkali metal compound, an alkaline-earth metal compound, a quaternary ammonium compound, ammonia, or an amine compound.
16. The siloxane resin manufacturing method of claim 13 , wherein:
the removing of the base catalyst comprises adding an organic solvent to dissolve siloxane and then separating the organic solvent, in which a siloxane resin is dissolved, from the base catalyst by a solvent extraction method.
17. A sheet, comprising a cured material for the siloxane resin composition according to claim 1 .