CN101473447A - Copper indium selenide-based photovoltaic device and method of making same - Google Patents

Copper indium selenide-based photovoltaic device and method of making same Download PDF

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CN101473447A
CN101473447A CNA2007800223277A CN200780022327A CN101473447A CN 101473447 A CN101473447 A CN 101473447A CN A2007800223277 A CNA2007800223277 A CN A2007800223277A CN 200780022327 A CN200780022327 A CN 200780022327A CN 101473447 A CN101473447 A CN 101473447A
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organic siliconresin
photovoltaic device
based photovoltaic
silicon
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CN101473447B (en
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T·D·巴纳德
Y·哈尔莫图
H·哈坦纳卡
M·伊藤
D·E·卡佐里斯
M·苏托
B·朱
L·M·伍兹
J·H·阿姆斯特龙戈
R·M·里贝林
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DuPont Toray Specialty Materials KK
ITN Energy Systems Inc
Dow Silicones Corp
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Dow Corning Toray Co Ltd
Dow Corning Corp
ITN Energy Systems Inc
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Abstract

The invention relates to a copper indium diselenide-based photovoltaic device and a manufacturing method thereof. A Copper Indium Selenide (CIS) based photovoltaic device includes a CIS based solar absorber layer including copper, indium, and selenium. The CIS-based photovoltaic device further includes a substrate including a silicone layer formed of the silicone composition, and a metal foil layer. Due to the presence of the silicone layer and the metal foil layer, the substrate is both flexible and sufficiently resistant to annealing temperatures in excess of 500 ℃ to achieve maximum efficiency of the device.

Description

Copper indium diselenide-based photovoltaic device and manufacture method thereof
[0001] present patent application requires all in the U.S. Provisional Patent Application 60/792,770 of submission on April 18th, 2006 and 60/792,852 priority and ownership equity.
Technical field
[0002] method of relate generally to copper indium diselenide-based photovoltaic device of the present invention and the described photovoltaic device of manufacturing.More specifically, the present invention relates to photovoltaic device, it comprises substrate, and described substrate comprises polymeric layer.
Background of invention
[0003] (copper indium diselenide, CIS) based photovoltaic device is used for being known by us from solar energy and the generating of other light source copper indium diselenide.Be exposed to any application of light source for device wherein, the CIS based photovoltaic device can be used for power supply.As a result, the potential application of CIS based photovoltaic device has far reaching significance.
[0004] up to the present, the CIS based photovoltaic device is restricted in the application facet that it can be used, and this is because the inversely related between multifunctionality and the efficient.More specifically, effective in order to make cost, photovoltaic device must be with such efficient generating, and it makes the per unit cost be equal to or less than conventional power source, as battery.In order to make CIS based photovoltaic device, surpassing under 500 ℃ the temperature experience processing or annealing under about 575 ℃ temperature usually at the device that comprises CIS or copper indium callium diselenide (CIGS) (CIGS) layer on the substrate with suitable efficient.
[0005] up to the present, owing to surpassing under 500 ℃ the annealing temperature, can't fully resist and break and mechanical failure, material seldom is proved to be the substrate that can be used for the CIS based photovoltaic device.Various types of glass mainly are used as substrate; Yet glass has increased the weight of device, and rigidity normally.The rigidity of glass substrate causes device not to be suitable for needing flexible application, or is not suitable for the application of the blunt power (blunt force) that device therein may stand to cause that glass substrate is broken or otherwise damage.Except the potential application of limiting device, glass substrate also requires device to be made separately.More specifically, if the flexible substrate that is fit to is found, the takeup type of device (roll-to-roll) creates possibility, the manufacturing cost that it will increase production efficiency greatly and reduce device.Owing to conspicuous reason, the decline of substrate weight also will be favourable.
[0006] some flexible substrate that is formed by polyimides has been developed recently and has been used for the CIS based photovoltaic device.Polyimide substrate has been eliminated the shortcoming of the overweight and inflexibility of glass substrate; Yet polyimide substrate causes device to break and mechanical failure surpassing the tendency that severely degrade is arranged under 425 ℃ the temperature.So, the device that comprises polyimide substrate can not suitably be formed with the maximizing efficiency with device.
[0007] because the existing shortcoming that comprises the CIS based photovoltaic device of glass or polyimide substrate, still having an opportunity provides CIS based photovoltaic device, this CIS based photovoltaic device comprises such substrate, described substrate is flexible and is enough to resist and surpasses 500 ℃ annealing temperature, to obtain the maximal efficiency of device.
Summary of the invention
[0008] the invention provides copper indium diselenide (CIS) based photovoltaic device.The CIS base device comprises CIS base solar absorbed layer, and CIS base solar absorbed layer comprises copper, indium and selenium.The CIS based photovoltaic device further comprises substrate, and described substrate comprises siloxane layer and the metal foil layer that is formed by silicone composition.Because the existence of siloxane layer and metal foil layer, described substrate is flexible, is enough to resist the annealing temperature under surpassing 500 ℃ again, to obtain the maximal efficiency of device.
Description of drawings
[0009] other advantage of the present invention will be realized easily, because, consider that together with accompanying drawing other advantage of the present invention will be better understood, wherein by with reference to following detailed:
[0010] Fig. 1 is the photo of copper indium diselenide of the present invention (CIS) based photovoltaic device.
[0011] Fig. 2 is the vertical view of copper indium diselenide of the present invention (CIS) based photovoltaic device.
[0012] Fig. 3 is the schematic side cross-sectional view of the substrate of copper indium diselenide of the present invention (CIS) based photovoltaic device, and this substrate has siloxane layer and metal foil layer.
[0013] Fig. 4 is the schematic cross section of copper indium diselenide of the present invention (CIS) based photovoltaic device; With
[0014] Fig. 5 is the single chip integrated schematic illustrations of copper indium diselenide (CIS) based photovoltaic device, and this copper indium diselenide (CIS) based photovoltaic device comprises having the substrate that fiber increases.
Detailed Description Of The Invention
[0015] referring to Fig. 1,2 and 4, the invention provides copper indium diselenide (CIS) based photovoltaic device 104, it comprises lining The end 106. This substrate comprises siloxane layer 306 and metal foil layer 312, and described siloxane layer 306 is by the siloxanes group Compound forms. CIS base device 104 operationally is converted into electric current with incident electromagnetic energy 108 such as light. Array 102 Can be provided, it comprises a plurality of CIS based photovoltaic devices 104. In one embodiment, in array 102, CIS based photovoltaic device 104 monolithics are integrated on the substrate 106. Array 102 can be used to from dropping on array 102 On electromagnetic energy 108 generation currents. The electric current that array 102 produces---it is connected via terminals 110---Can be used to various purposes; For example, array 102 can be used to provide electricity to spacecraft or high height above sea level airship Power.
[0016] siloxane layer 306 offers the substrate 106 flexible abilities that do not demonstrate substantive crackle with being enough to resist the annealing temperature above 500 ℃.And in case solidify, silicone composition has high resistivity usually.As a result, CIS based photovoltaic device 104 can be manufactured with maximized efficient, describe as following further details, and because substrate 106 flexible, CIS based photovoltaic device 104 can further be used to on-plane surface and use.
[0017] in an embodiment of the invention, silicone composition is further defined to: the hydrosilylation curable silicone compositions, it comprise organic siliconresin (silicone resin) (A), organo-silicon compound (organosilicone compound) (B) and hydrosilylation catalysts (C).Organic siliconresin (A) has the alkenyl group or the silicon bonded hydrogen atom of silicon bonding.Organic siliconresin (A) normally comprises R 2SiO 3/2The unit is T unit and/or SiO 4/2The unit is the Q unit, together with R 1R 2 2SiO 1/2The unit is M unit and/or R 2 2SiO 2/2The unit is the copolymer of D unit, wherein, and R 1Be C 1To C 10Hydrocarbyl group or C 1To C 10The halo hydrocarbyl group, the two not fatty family is unsaturated, and R 2Be R 1, thiazolinyl or hydrogen.For example, organic siliconresin can be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.As used herein, term " not fatty family is unsaturated " refers to that alkyl or halo alkyl do not contain aliphat carbon-carbon double bond or carbon carbon triple bond.
[0018] by R 1The C of expression 1To C 10Alkyl and C 1To C 10The halo alkyl more generally speaking, has 1 to 6 carbon atom.The acyclic hydrocarbon group and the halo alkyl that comprise at least 3 carbon atoms can have branched structure or non-branching structure.By R 1The example of the alkyl of expression comprises, but be not limited to, alkyl, as methyl, ethyl, propyl group, 1-Methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, amyl group, 1-methyl butyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl, octyl group, nonyl and decyl; Cycloalkyl is as cyclopenta, cyclohexyl and methylcyclohexyl; Aryl is as phenyl and naphthyl; Alkaryl is as tolyl and xylyl; And aralkyl, as benzyl and phenethyl.The example of the halo alkyl of being represented by R1 includes, but not limited to 3,3,3-trifluoro propyl, 3-chloropropyl, chlorphenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoro propyl group and 2,2,3,3,4,4,5,5-octafluoro amyl group.
[0019] by R 2The thiazolinyl---it can be identical or different in organic siliconresin---of expression has 2 to 10 carbon atoms usually, and alternatively, 2 to 6 carbon atoms are exemplified as, but are not limited to, vinyl, pi-allyl, cyclobutenyl, hexenyl and octenyl.In one embodiment, R 2It mainly is thiazolinyl.In this embodiment, in organic siliconresin, usually at least 50 moles of %, alternatively at least 65 moles of %, the group of being represented by R2 of at least 80 moles of % is a thiazolinyl alternatively.As used herein, the mole % (molar percentage) of thiazolinyl is defined in R in the molal quantity of silicon bonding thiazolinyl in the organic siliconresin and this resin in R2 2The ratio of the total mole number of group multiply by 100.In another embodiment, R 2Mainly be hydrogen.In this embodiment, in organic siliconresin, usually at least 50 moles of %, at least 65 moles of %, at least 80 moles of %'s by R alternatively alternatively 2The group of expression is a hydrogen.The mole % of hydrogen is defined in R in the molal quantity of the hydrogen of silicon bonding in the organic siliconresin and this resin in R2 2The ratio of the total mole number of group multiply by 100.
[0020] according to first execution mode, organic siliconresin (A) has formula:
(R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z (I)
R wherein 1And R 2As above describe and example, w, x, y and z are molar fractions.Usually, the organic siliconresin per molecule of formula (I) expression on average has at least two silicon bonding thiazolinyls.More specifically, subscript w has from 0 to 0.9 value usually, and alternatively from 0.02 to 0.75, alternatively from 0.05 to 0.3.Subscript x has from 0 to 0.9 value usually, and alternatively from 0 to 0.45, alternatively from 0 to 0.25.Subscript y has from 0 to 0.99 value usually, and alternatively from 0.25 to 0.8, alternatively from 0.5 to 0.8.Subscript z has from 0 to 0.85 value usually, and alternatively from 0 to 0.25, alternatively from 0 to 0.15.Equally, ratio y+z/ (w+x+y+z) normally from 0.1 to 0.99, and alternatively from 0.5 to 0.95, alternatively from 0.65 to 0.9.Further, ratio w+x/ (w+x+y+z) normally from 0.01 to 0.90, and alternatively from 0.05 to 0.5, alternatively from 0.1 to 0.35.
[0021] works as R 2When mainly being thiazolinyl, the instantiation of the organic siliconresin of above-mentioned formula (I) representative includes, but not limited to have the resin of following formula:
(Vi 2MeSiO 1/2) 0.25(PhSiO 3/2) 0.75，(ViMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75，
(ViMe 2SiO 1/2) 0.25(MeSiO 3/2) 0.25(PhSiO 3/2) 0.50，
(ViMe 2SiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.1And
(Vi 2Me 2SiO 1/2) 0.15(ViMe 2SiO 1/2) 0.1(PhSiO 3/2) 0.75，
Wherein Me is a methyl, and Vi is a vinyl, and Ph is a phenyl, and the numeric suffix outside round parentheses is represented with above-mentioned for the described arbitrary w of formula (I), x, y or the corresponding molar fraction of z.The order of unit is considered limitation of the scope of the invention never in any form in the aforementioned formula.
[0022] works as R 2When mainly being hydrogen, the instantiation of the organic siliconresin of above-mentioned formula (I) expression includes, but not limited to have the resin of following formula:
(HMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75, (HMeSiO 2/2) 0.3(PhSiO 3/2) 0.6(MeSiO 3/2) 0.1With
(Me 3SiO 1/2) 0.1(H 2SiO 2/2) 0.1(MeSiO 3/2) 0.4(PhSiO 3/2) 0.4，
Wherein Me is a methyl, and Ph is a phenyl, and the numeric suffix outside round parentheses is represented molar fraction.The order of unit is considered limitation of the scope of the invention never in any form in the aforementioned formula.
[0023] organic siliconresin of being represented by formula (I) has from 500 to 50,000 number-average molecular weight (M usually n), alternatively from 500 to 10,000, alternatively from 1,000 to 3,000, wherein molecular weight is to use low angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, measures by gel permeation chromatography.
[0024] under 25 ℃, be generally from 0.01 to 100,000 handkerchief second (Pas) by the viscosity of the organic siliconresin of formula (I) expression, alternatively from 0.1 to 10,000Pas, alternatively from 1 to 100Pas.
[0025] generally includes following, following, the following silicon bonded hydroxy of 2% (w/w) alternatively of 5% (w/w) alternatively of 10% (w/w) by the organic siliconresin of formula (I) expression, as pass through 29Si NMR measures.
[0026] preparation method by the organic siliconresin of formula (I) expression is as known in the art; Many these resins are that commerce can get.Normally suitable mixture by cohydrolysis chlorosilane parent in organic solution such as toluene is prepared by the organic siliconresin of formula (I) expression.For example, comprise R 1R 2 2SiO 1/2Unit and R 2SiO 3/2The organic siliconresin of unit can have formula R by cohydrolysis in toluene 1R 2 2First compound of SiCl and have a formula R 2SiCl 3Second compound---R wherein 1And R 2As hereinbefore defined and exemplify---be prepared to form aqueous hydrochloric acid and organic siliconresin, this organic siliconresin is the hydrolysate of first and second compounds.Aqueous hydrochloric acid and organic siliconresin are separated, wash organic siliconresin with water removing residual acid, and organic siliconresin is heated in the presence of appropriate condensation catalyst, so that this organic siliconresin " multiviscosisty (body) " is to the viscosity of expectation.
[0027] if desired, organic siliconresin can further be handled with condensation catalyst in organic solvent, to reduce the content of silicon bonded hydroxy.Alternatively, first or second compound---it contains the hydrolyzable groups except that cl radical, as-Br ,-I ,-OCH 3,-OC (O) CH 3,-N (CH 3) 2, NHCOCH 3With-SCH 3---can be formed organic siliconresin by cohydrolysis.The character of organic siliconresin depends on the type of first and second compounds, the mol ratio of first and second compounds, the degree and the processing conditions of condensation.
[0028] the hydrosilylation curable silicone compositions further comprises crosslinking agent (B), described crosslinking agent (B) have can with the silicon bonded hydrogen atom or the silicon bonding thiazolinyl of silicon bonding thiazolinyl in the organic siliconresin or silicon bonded hydrogen atom reaction.Each molecule of crosslinking agent (B) on average has at least two silicon bonded hydrogen atoms, alternatively at least three silicon bonded hydrogen atoms of per molecule.Usually be understandable that, in organic silicones (A) the silicon bonded hydrogen atom average of the thiazolinyl average of per molecule and the middle per molecule of crosslinking agent (B) and greater than four the time, take place crosslinked.Crosslinking agent (B) exists with the amount that is enough to cured silicone resin (A).
[0029] crosslinking agent (B) organo-silicon compound normally, and can be further defined to organic hydride silane, Organhydridosiloxaneresins or their combination.The structure of organo-silicon compound can be linear, branching, ring-type or resin.In acyclic polysilane and polysiloxanes, silicon bonded hydrogen atom can be positioned at end, side chain, or endways with two places, side chain position.Cyclosilane and cyclosiloxane have 3 to 12 silicon atoms usually, alternatively 3 to 10 silicon atoms, 3 to 4 silicon atoms alternatively.
[0030] organic hydride silane can be monosilane, disilane, trisilalkane or polysilane.When R2 mainly is thiazolinyl, the instantiation that is suitable for the organic hydride silane of the object of the invention comprises, but be not limited to, diphenyl silane, 2-chloroethyl silane, two [(to dimetylsilyl) phenyl] ether, 1,4-dimethylformamide dimethyl silylation ethane, 1,3,5-three (dimetylsilyl) benzene, 1,3,5-trimethyl-1,3,5-trisilalkane, poly-(methyl silylene) phenylene (poly (methylsilylene) phenylene) and poly-(methyl silylene) methylene (poly (methylsilylene) methylene).When R2 mainly was hydrogen, the instantiation that is suitable for the organic hydride silane of the object of the invention included, but not limited to have the silane of following formula: Vi 4Si, PhSiVi 3, MeSiVi 3, PhMeSiVi 2, Ph 2SiVi 2And PhSi (CH 2CH=CH 2) 3, wherein Me is a methyl, and Ph is a phenyl, and Vi is a vinyl.
[0031] organic hydride silane also can have following formula:
HR 1 2Si-R 3-SiR 1 2H (III)
R wherein 1As hereinbefore defined and example, R 3Be the undersaturated alkylene of not fatty family (hydrocarbylenegroup), this alkylene has the formula that is selected from down array structure:
Figure A200780022327D00101
Figure A200780022327D00102
With
Figure A200780022327D00103
Wherein " g " is from 1 to 6.
[0032] have the instantiation of the organic hydride silane of formula (III)---R wherein 1And R 3As top description and example, the organic hydride silane that includes, but not limited to have the formula that is selected from down array structure:
Figure A200780022327D00112
With
Figure A200780022327D00113
[0033] method for preparing organic hydride silane is known in the art.For example, organic hydride silane can prepare by RMgBr and alkyl or aryl halide reaction.Particularly, has formula HR 1 2Si-R 3-SiR 1 2The organic hydride silane of H can so prepare: by have formula R with the magnesium processing in ether 3X 2The aryl dihalide, to produce corresponding RMgBr, then with having formula HR 1 2The chlorosilane of SiCl is handled RMgBr, wherein R 1And R 3As top description and example.
[0034] Organhydridosiloxaneresins can be disiloxane, trisiloxanes or polysiloxanes.Work as R 2When mainly being hydrogen, the example that is suitable as the organosiloxane of crosslinking agent (B) includes, but not limited to have the siloxanes of following formula: PhSi (OSiMe 2H) 3, Si (OSiMe 2H) 4, MeSi (OSiMe 2H) 3And Ph 2Si (OSiMe 2H) 2, wherein, Me is a methyl, Ph is a phenyl.
[0035] works as R 2When mainly being thiazolinyl, the instantiation that is fit to the Organhydridosiloxaneresins of the object of the invention comprises, but be not limited to, 1,1,3,3-tetramethyl disiloxane, 1,1,3,3-tetraphenyl disiloxane, phenyl three (dimethyl silane oxygen base) silane, 1,3, poly-(the hydrogenated methyl siloxanes) of poly-(the hydrogenated methyl siloxanes) of 5-trimethyl cyclotrisiloxane, trimethylsiloxy end-blocking, poly-(dimethyl siloxane/hydrogenated methyl siloxanes) of trimethylsiloxy end-blocking, dimethyl hydrogenation siloxy end-blocking and comprise HMe 2SiO 1/2Unit, Me 3SiO 1/2Unit and SiO 4/2The resin of unit, wherein Me is a methyl.
[0036] Organhydridosiloxaneresins also can be the organic hydride polyorganosiloxane resin.The organic hydride polyorganosiloxane resin is copolymer normally, and it comprises R 4SiO 3/2The unit is T unit and/or SiO 4/2The unit is the Q unit, together with R 1R 4 2SiO 1/2The unit is M unit and/or R 4 2SiO 2/2The unit is the D unit, wherein, and R 1As mentioned above and example.For example, the organic hydride polyorganosiloxane resin can be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.
[0037] by R 4The group of expression is R1 or the Organosilyl with at least one silicon bonded hydrogen atom.By R 4The group that the example of the Organosilyl of expression includes, but not limited to have the formula that is selected from down array structure:
Figure A200780022327D00121
-CH 2CH 2SiMe 2H ,-CH 2CH 2SiMe 2C nH 2nSiMe 2H ,-CH 2CH 2SiMe 2C nH 2nSiMePhH ,-CH 2CH 2SiMePhH ,-CH 2CH 2SiPh 2H ,-CH 2CH 2SiMePhC nH 2nSiPh 2H ,-CH 2CH 2SiMePhC nH 2nSiMe 2H ,-CH 2CH 2SiMePhOSiMePhH and-CH 2CH 2SiMePhOSiPh (OSiMePhH) 2, wherein Me is a methyl, Ph is a phenyl, and subscript n has 2 to 10 value.Usually, at least 50 moles of %, at least 65 moles of %, at least 80 moles of %'s by R alternatively alternatively in the organic hydride polyorganosiloxane resin 4The group of expression is the Organosilyl with at least one silicon bonded hydrogen atom.As used herein, at R 4The molar percentage of middle Organosilyl (mole %) is restricted to: R in the molal quantity of the Organosilyl of the silicon bonding in organic siliconresin and this resin 4The ratio of the total mole number of group multiply by 100.
[0038] the organic hydride polyorganosiloxane resin has formula usually:
(R 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z (IV)
Wherein, R 1, R 4, w, x, y and z each as top definition and example.
[0039] include, but not limited to have the resin of following formula by the instantiation of the organic hydride polyorganosiloxane resin of above-mentioned formula (IV) expression:
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.12(PhSiO 3/2) 0.88、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(PhSiO 3/2) 0.83、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(MeSiO 3/2) 0.17(PhSiO 3/2) 0.66、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.10, and
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.08((HMe 2SiC 6H 4SiMe 2CH 2CH 2) Me 2SiO 1/2) 0.0 6(PhSiO 3/2) 0.86, wherein Me is a methyl, Ph is a phenyl, C 6H 4Represent right-phenylene, the outer numeric suffix of bracket is represented molar fraction.The order of unit is considered limitation of the scope of the invention never in any form in the aforementioned formula.
[0040] instantiation of organic hydride polyorganosiloxane resin includes, but not limited to have the resin of following formula:
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.12(PhSiO 3/2) 0.88、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(PhSiO 3/2) 0.83、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(MeSiO 3/2) 0.17(PhSiO 3/2) 0.66、
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.10, and
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.08((HMe 2SiC 6H 4SiMe 2CH 2CH 2) Me 2SiO 1/2) 0.0 6(PhSiO 3/2) 0.86, wherein Me is a methyl, Ph is a phenyl, C 6H 4Represent right-phenylene, the outer numeric suffix of bracket is represented molar fraction.The order of unit is considered limitation of the scope of the invention never in any form in the aforementioned formula.
[0041] the organic hydride polyorganosiloxane resin with formula (IV) can prepare by reactant mixture is reacted, and described reactant mixture comprises (a) organic siliconresin, and it has the molecular formula (R by following formula (I) expression 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) zAnd organo-silicon compound (b), its per molecule on average has 2 to 4 silicon bonded hydrogen atoms and molecular weight below 1,000, and this is reflected under the existence of (c) hydrosilylation catalysts and optional (d) organic solvent and carries out, wherein R 1, R 2, w, x, y and z each all as surface defined and example, condition is that organic siliconresin (a) per molecule on average has at least two silicon bonding thiazolinyls, and the mol ratio of the silicon bonded hydrogen atom in (b) and thiazolinyl in (a) is 1.5 to 5.Organic siliconresin (a) can be with identical or different as the concrete organic siliconresin of the component (A) in the hydrosilylation curable silicone compositions.
[0042] as mentioned above, organo-silicon compound (b) per molecule on average has 2 to 4 silicon bonded hydrogen atoms.Alternatively, organo-silicon compound (b) per molecule on average has 2 to 3 silicon bonded hydrogen atoms.Also as mentioned above, organo-silicon compound (b) have usually at the molecular weight below 1,000, alternatively below 750, alternatively below 500.Organo-silicon compound (b) further comprise silicon bonding organic group, and this silicon bonding organic group can be selected from alkyl and halo hydrocarbyl group, and it is unsaturated neither to comprise aliphat, as above for R 1Describe and example.
[0043] organo-silicon compound (b) can be organic hydride silane or Organhydridosiloxaneresins, and each all limits and example in the above in detail.
[0044] organo-silicon compound (b) can be single organo-silicon compound or the mixture that comprises two or more different organo-silicon compound, and each is all as top description.For example, organo-silicon compound (B) can be the mixture of the mixture of single organic hydride silane, two kinds of different organic hydride silane, single Organhydridosiloxaneresins, two kinds of different Organhydridosiloxaneresins or the mixture of organic hydride silane and Organhydridosiloxaneresins.The mol ratio of thiazolinyl normally 1.5 to 5 in silicon bonded hydrogen atom in the organo-silicon compound (b) and the organic siliconresin (a), and alternatively 1.75 to 3, alternatively 2 to 2.5.
[0045] hydrosilylation catalysts (c) can be any known hydrosilylation catalysts, the compound that it comprises platinum group metal (being platinum, rhodium, ruthenium, palladium, osmium and indium) or comprises the platinum group metal.Usually, the platinum group metal is a platinum, and this is based on its high activity in hydrosilylation reactions.
[0046] the concrete hydrosilylation catalysts that is suitable for (c) comprises, by Willing at United States Patent (USP) 3,419, disclosed chloro-platinic acid and some contain the complex compound of the organosiloxane of vinyl in 593, and the part that relates to hydrosilylation catalysts in this patent is introduced into by reference thus.Such catalyst is chloro-platinic acid and 1,3-divinyl-1,1,3, the product of 3-tetramethyl disiloxane.
[0047] hydrosilylation catalysts also can be the hydrosilylation catalysts on the carrier, and it is included in the solid carrier that its surface has the platinum group metal.Supported catalyst can separate with the organic hydride polyorganosiloxane resin of being represented by formula (IV) easily, for example, separates by filter reaction mixture.The example of supported catalyst includes, but not limited to platinum/carbon, palladium/carbon, ruthenium/carbon, rhodium/carbon, platinum/silica, palladium/silica, platinum/aluminium oxide, palladium/aluminium oxide and ruthenium/aluminium oxide.
[0048] concentration of hydrosilylation catalysts (c) is enough to the addition reaction of catalysis organic siliconresin (a) and organo-silicon compound (b).Usually, combination weight based on organic siliconresin (a) and organo-silicon compound (b), the concentration of hydrosilylation catalysts (c) is enough to provide 0.1 to 1000ppm platinum group metal, and 1 to 500ppm platinum group metal alternatively is alternatively from 5 to 150ppm platinum group metal.Be lower than under the 0.1ppm platinum group metal, reaction rate is very slow.Use the platinum group metal that surpasses 1000ppm, reaction rate can not perceptiblely increase, and is uneconomic therefore.
[0049] organic solvent (d) comprises at least a organic solvent.Organic solvent (d) can be any non-proton or dipolar aprotic organic solvent, it does not react with organic siliconresin (a), organo-silicon compound (b) or resulting organic hydride polyorganosiloxane resin under the condition of this method, and can mix with component (a) and (b) and organic hydride polyorganosiloxane resin.
[0050] example of the organic solvent (d) of suitable the object of the invention includes, but not limited to saturated aliphatic hydrocarbon, as pentane, hexane, normal heptane, isooctane and dodecane; Cycloaliphatic hydrocarbon such as pentamethylene and cyclohexane; Aromatic hydrocarbon such as benzene,toluene,xylene and Lay; Cyclic ethers, (THF) is with diox as oxolane; Ketone such as methyl iso-butyl ketone (MIBK) (MIBK); Halogenation alkane is as trichloroethanes; With halogenation aromatic hydrocarbon, as bromobenzene and chlorobenzene.Organic solvent (d) can be single organic solvent or the mixture that comprises two or more different organic solvents, and every kind as mentioned above.Based on the total weight of reactant mixture, the concentration of organic solvent (d) is from 0 to 99% (w/w) normally, alternatively from 30 to 80% (w/w), from 45 to 60% (w/w) alternatively.
[0051] reaction that forms the organic hydride polyorganosiloxane resin of being represented by formula (IV) can be carried out in any standard reaction device that is fit to hydrosilylation reactions.The reactor that is fit to comprises the glass reactor of glass reactor and Teflon liner.Usually, reactor is equipped with the stirring instrument, as blender.In addition, usually, be reflected under inert atmosphere such as nitrogen or argon, the no moisture and carry out.
[0052] organic siliconresin (a), organo-silicon compound (b), hydrosilylation catalysts (c) and optional organic solvent (d) can be with any sequential combination.Usually, organo-silicon compound (b) and hydrosilylation catalysts (c) are to make up before at the organic solvent (d) of introducing organic siliconresin (a) and choose wantonly.The reaction under 0 to 150 ℃ temperature, carry out usually, alternatively from room temperature (～23 ± 2 ℃) to 115 ℃.When temperature was lower than 0 ℃, reaction rate was very slow usually.Reaction time depends on Several Factors, as the structure and the temperature of organic silicones (a) and organo-silicon compound (b).To 150 ℃ temperature, the reaction time is generally 1 to 24 hour in room temperature (～23 ± 2 ℃).The optimal reaction time can be determined by normal experiment.
[0053] the organic hydride polyorganosiloxane resin of being represented by formula (IV) can not need isolated or purified and uses, and perhaps the organic hydride polyorganosiloxane resin can separate from most of organic solvents (d) by conventional method of evaporating.For example, reactant mixture can under reduced pressure heat.And, when hydrosilylation catalysts (c) when being aforesaid supported catalyst, can pass through filter reaction mixture, the organic hydride polyorganosiloxane resin is easily separated with hydrosilylation catalysts.Yet hydrosilylation catalysts can keep mixing with the organic hydride polyorganosiloxane resin, and can be used as hydrosilylation catalysts (C).
[0054] crosslinking agent (B) can be single organo-silicon compound, or comprises the mixture of two or more different organo-silicon compound, and every kind all as mentioned above.For example, crosslinking agent (B) can be the mixture of the mixture of single organic hydride silane, two kinds of different organic hydride silane, single Organhydridosiloxaneresins, two kinds of different Organhydridosiloxaneresins or the mixture of organic hydride silane and Organhydridosiloxaneresins.Particularly, crosslinking agent (B) can be to comprise the have formula mixture of organic hydride polyorganosiloxane resin of (IV), based on the total weight of crosslinking agent (B), this amount with organic hydride polyorganosiloxane resin of formula (IV) is at least 0.5% (w/w), at least 50% (w/w), at least 75% (w/w) alternatively alternatively; Wherein crosslinking agent (B) further comprises organic hydrosilanes and/or Organhydridosiloxaneresins, and the latter is different from the organic hydride polyorganosiloxane resin.
[0055] concentration of crosslinking agent (B) is enough to solidify (crosslinked) organic siliconresin (A).The accurate amount of crosslinking agent (B) depends on required state of cure.In organic siliconresin (A), the concentration of crosslinking agent (B) enough provides the silicon bonded hydrogen atom of 0.4 to 2 mole of every mole of thiazolinyl, 0.8 to 1.5 mole silicon bonded hydrogen atom, 0.9 to 1.1 mole silicon bonded hydrogen atom alternatively alternatively usually.
[0056] hydrosilylation catalysts (C) comprises at least a hydrosilylation catalysts, and it promotes the reaction between organic siliconresin (A) and the crosslinking agent (B).In one embodiment, hydrosilylation catalysts (C) can be identical with the above-mentioned hydrosilylation catalysts (c) that is used to generate the organic hydride polyorganosiloxane resin.In addition, hydrosilylation catalysts (C) also can be the microencapsulation platinum group metal, and it contains the platinum group metal of microencapsulation in thermoplastic resin.It is stable that the hydrosilylation curable silicone compositions that comprises the microencapsulation hydrosilylation catalysts is long-term under environmental condition---normally some months or longer time---, and solidify rapid relatively under the temperature of fusing point that is higher than thermoplastic resin (one or more) or softening point.Microencapsulation hydrosilylation catalysts and their method of preparation are well known in the art, as at United States Patent (USP) 4,766,176 and the list of references wherein quoted in and United States Patent (USP) 5,017,654 exemplified.Hydrosilylation catalysts (C) can be single catalyst or the mixture that comprises two or more different catalysts, and these catalyst are at least a kind of different in nature, as structure, form, platinum group metal, complex compound part and thermoplastic resin.
[0057] in another embodiment, hydrosilylation catalysts (C) can be at least a photoactivation hydrosilylation catalysts.The photoactivation hydrosilylation catalysts can be can catalysis organic siliconresin (A) after being exposed to the irradiation with wavelength of 150 to 800nm and any hydrosilylation catalysts of the hydrosilylation of crosslinking agent (B).The photoactivation hydrosilylation catalysts can be any known hydrosilylation catalysts, and it comprises the compound of platinum group metal or platinum group metal.The platinum group metal comprises platinum, rhodium, ruthenium, palladium, osmium and indium.Usually, the platinum group metal is a platinum, and this is based on its high activity in hydrosilylation reactions.For the adaptability of employed concrete photoactivation hydrosilylation catalysts in silicone composition of the present invention, can easily be determined by normal experiment.
[0058] instantiation of the photoactivation hydrosilylation catalysts of suitable purpose of the present invention comprises, but be not limited to, platinum (II) beta-diketon complex compound, as platinum (II) two (2, the 4-pentanedione) (platinum (II) bis (2,4-pentanedioate)), platinum (II) two (2, the 4-acetyl butyryl), platinum (II) two (2, the 4-heptadione), two (the 1-phenyl-1 of platinum (II), the 3-diacetyl), platinum (II) two (1,3-diphenyl-1,3-propanedione), platinum (II) two (1,1,1,5,5,5-hexafluoro-2, the 4-pentanedione); (η-cyclopentadienyl group) trialkyl platinum complex is as (Cp) trimethyl platinum, (Cp) ethyl dimethyl platinum, (Cp) triethyl group platinum, (chloro-Cp) trimethyl platinum and (trimethyl silyl-Cp) trimethyl platinum, wherein Cp representative ring pentadienyl; Triazenes oxide-transition metal complex is as Pt[C 6H 5NNNOCH 3] 4, Pt[p-CN-C 6H 4NNNOC 6H 11] 4, Pt[p-H 3COC 6H 4NNNOC 6H 11] 4, Pt[p-CH 3(CH 2) X-C 6H 4NNNOCH 3] 4, 1,5-cyclo-octadiene .Pt[p-CN-C 6H 4NNNOC 6H 11] 2, 1,5-cyclo-octadiene .Pt[p-CH 3O-C 6H 4NNNOCH 3] 2, [(C 6H 5) 3P] 3Rh[p-CN-C 6H 4NNNOC 6H 11] and Pd[p-CH 3(CH 2) X-C 6H 4NNNOCH 3] 2, wherein x is 1,3,5,11 or 17; (η-alkadienes) (σ-aryl) platinum complex is as (η 4-1,5-cyclo-octadiene base) diphenyl platinum, (η 4-1,3,5,7-cyclo-octatetraene base) diphenyl platinum, (η 4-2,5-norbornadiene base) diphenyl platinum, (η 4-1,5-cyclo-octadiene base) two-(4-dimethylaminophenyl) platinum, (η 4-1,5-cyclo-octadiene base) two-(4-acetylphenyl) platinum and (η 4-1,5-cyclo-octadiene base) two-(4-trifluoromethyl) platinum.Generally speaking, the photoactivation hydrosilylation catalysts is platinum (II) beta diketone complex compound, and more generally speaking, described catalyst is platinum (II) two (2, the 4-pentanedione).Hydrosilylation catalysts (C) can be single photoactivation hydrosilylation catalysts or the mixture that comprises two or more different photoactivation hydrosilylation catalysts.
[0059] method for preparing the photoactivation hydrosilylation catalysts is well-known in the art.For example, and people such as Guo (Chemistry of Materials, 1998,10,531-536) reported the method for preparing platinum (II) beta-diketon.The method of preparation (η-cyclopentadienyl group) trialkyl platinum complex is by United States Patent (USP) 4,510, and 094 is open.The method for preparing triazenes oxide-transition metal complex is by United States Patent (USP) 5,496, and 961 is open.The method of preparation (η-alkadienes) (σ-aryl) platinum complex is by United States Patent (USP) 4,530, and 879 instruct.
[0060] concentration of hydrosilylation catalysts (C) is enough to the addition reaction of catalysis organic siliconresin (A) and crosslinking agent (B).Based on the combination weight of organic siliconresin (A) and crosslinking agent (B), the concentration of hydrosilylation catalysts (C) is enough to provide common 0.1 to 1000ppm platinum group metal, alternatively 0.5 to 100ppm platinum group metal, 1 to 25ppm platinum group metal alternatively.
[0061] randomly, the hydrosilylation curable silicone compositions further comprises (D) silicone rubber, and described silicone rubber (D) has and is selected from (i) R 1R 2 2SiO (R 2 2SiO) aSiR 2 2R 1(ii) R 5R 1 2SiO (R 1R 5SiO) bSiR 1 2R 5Molecular formula; R wherein 1And R 2As top definition and example, R 5Be R 1Or-H, subscript a and b have 1 to 4 numerical value separately, and alternatively 2 to 4, alternatively 2 to 3; And w, x, y and z are also as top definition and example, condition is that organic siliconresin and silicone rubber (D) (i) have on average at least two silicon bonding thiazolinyls of per molecule separately, silicone rubber (D) has at least two silicon bonded hydrogen atoms for (ii) average every mole, and the mol ratio of the silicon bonding thiazolinyl in silicon bonding thiazolinyl or silicon bonded hydrogen atom and the organic siliconresin (A) is 0.01 to 0.5 in silicone rubber (D).
[0062] instantiation that is suitable as component (D) silicone rubber (i) includes, but not limited to have the silicone rubber of following formula: ViMe 2SiO (Me 2SiO) aSiMe 2Vi, ViMe 2SiO (Ph 2SiO) aSiMe 2Vi and ViMe 2SiO (PhMeSiO) aSiMe 2Vi, wherein Me is a methyl, and Ph is a phenyl, and Vi is a vinyl, and subscript a has from 1 to 4 numerical value.Silicone rubber (D) can be single silicone rubber (i), or comprises the mixture of two or more different silicone rubbers, and each all meets (D) molecular formula (i).
[0063] instantiation that is suitable as silicone rubber (D) silicone rubber (ii) includes, but not limited to have the silicone rubber of following formula: HMe 2SiO (Me 2SiO) bSiMe 2H, HMe 2SiO (Ph 2SiO) bSiMe 2H, HMe 2SiO (PhMeSiO) bSiMe 2H and HMe 2SiO (Ph 2SiO) 2(Me 2SiO) 2SiMe 2H, wherein Me is a methyl, Ph is a phenyl, and subscript b has from 1 to 4 numerical value.Component (D) can be single silicone rubber (ii), or comprises the mixture of two or more different silicone rubbers, and each all meets formula (D) molecular formula (ii).
[0064] mol ratio of the silicon bonding thiazolinyl in silicon bonding thiazolinyl in the silicone rubber (D) or silicon bonded hydrogen atom and the organic siliconresin (A) normally from 0.01 to 0.5, and alternatively from 0.05 to 0.4, alternatively from 0.1 to 0.3.[0065] when silicone rubber (D) be that (D) is (i) time, the concentration of crosslinking agent (B) make the silicon bonded hydrogen atom in crosslinking agent (B) molal quantity with the molal quantity of organic siliconresin (A) and silicone rubber (D) the silicon bonding thiazolinyl in (i) with ratio be generally from 0.4 to 2, alternatively from 0.8 to 1.5, alternatively from 0.9 to 1.1.And, when silicone rubber (D) is that (D) is (ii) the time, the concentration of crosslinking agent (B) make crosslinking agent (B) and silicone rubber (D) the silicon bonded hydrogen atom molal quantity in (ii) and with the ratio of the molal quantity of silicon bonding thiazolinyl in organic siliconresin (A), normally from 0.4 to 2, alternatively from 0.8 to 1.5, alternatively from 0.9 to 1.1.
[0066] to comprise the method for silicone rubber of silicon bonding thiazolinyl or silicon bonded hydrogen atom be well-known in the art in preparation; A lot of these compounds are that commerce can get.
[0067] in yet another embodiment of the present invention, the hydrosilylation curable silicone compositions comprises (A 1) the modified rubber organic siliconresin, described (A 1) the modified rubber organic siliconresin prepares by organic siliconresin (A) and at least a silicone rubber (D) are (iii) reacted, this silicone rubber (D) (iii) is selected from the rubber with following formula: R 5R 1 2SiO (R 1R 5SiO) cSiR 1 2R 5And R 1R 2 2SiO (R 2 2SiO) dSiR 2 2R 1, R wherein 1And R 5As surface defined and example, and c and d all have 4 to 1000 numerical value, alternatively from 10 to 500, alternatively from 10 to 50, this is reflected under the existence of hydrosilylation catalysts (c) and optional organic solvent and carries out, condition is that organic siliconresin (A) per molecule on average has at least two silicon bonding thiazolinyls, silicone rubber (D) (iii) has on average at least two silicon bonded hydrogen atoms of per molecule, and silicone rubber (D) in (iii) silicon bonded hydrogen atom and the mol ratio of the silicon bonding thiazolinyl in the organic siliconresin (A) be from 0.01 to 0.5." at least a silicone rubber " be meant for (D) (iii), and only the rubber that need be represented by this formula is a kind of, and can use the combination of the rubber of being represented by this formula.When having organic solvent, modified rubber organic siliconresin (A 1) can mix in this organic solvent, and do not form precipitation or suspension.
[0068] organic siliconresin (A), silicone rubber (D) are (iii), hydrosilylation catalysts (c) and organic solvent can be with any sequential combination.Usually, organic siliconresin (A), silicone rubber (D) are (iii) being introduced the preceding combination of hydrosilylation catalysts (c) with organic solvent.
[0069] reaction is being carried out to 150 ℃ temperature from room temperature (～23 ± 2 ℃) usually, alternatively from room temperature to 100 ℃.Reaction time depends on Several Factors, comprises organic siliconresin (A) and silicone rubber (D) structure and temperature (iii).Usually allow one period that is enough to finish hydrosilylation reactions of described component reaction.This means the described component reaction of common permission, up to silicone rubber (D) (iii) in the initial silicon bonded hydrogen atom that exists at least 95 moles of %, alternatively at least 98 moles of %, at least 99 moles of % are consumed in hydrosilylation reactions alternatively, measure as the FTIR spectrometry.To 100 ℃ temperature, the reaction time is from 0.5 to 24 hour (h) normally in room temperature (～23 ± 2 ℃).The optimal reaction time can be determined by normal experiment.
[0070] silicon bonded hydrogen atom and the mol ratio of silicon bonding thiazolinyl in organic siliconresin (A) normally from 0.01 to 0.5, alternatively from 0.05 to 0.4, alternatively from 0.1 to 0.3 of silicone rubber (D) in (iii).
[0071] concentration of hydrosilylation catalysts (c) is enough to catalysis organic siliconresin (A) and silicone rubber (D) addition reaction (iii).Usually, based on the combination weight of resin and rubber, the concentration of hydrosilylation catalysts (c) is enough to provide the platinum group metal from 0.1 to 1000ppm.
[0072] based on the total weight of reactant mixture, the concentration of organic solvent is from 0 to 95% (w/w) normally, alternatively from 10 to 75% (w/w), from 40 to 60% (w/w) alternatively.
[0073] modified rubber organic siliconresin (A 1) can not need isolated or purified and use, perhaps modified rubber organic siliconresin (A1) can be by traditional method of evaporating and most of separated from solvent.For example, reactant mixture can heat under reduced pressure.And, when hydrosilylation catalysts (c) when being aforesaid supported catalyst, modified rubber organic siliconresin (A 1) can easily separate with hydrosilylation catalysts (c) by filter reaction mixture.Yet, as modified rubber organic siliconresin (A 1) not be used to prepare modified rubber organic siliconresin (A 1) hydrosilylation catalysts (c) when separating, this hydrosilylation catalysts (c) can be used as hydrosilylation catalysts (C) and uses.
[0074] as known in the art, hydrosilylation curable silicone compositions of the present invention can comprise supplementary element.The example of supplementary element comprises, but be not limited to, the hydrosilylation catalysts inhibitor, as 3-methyl-pirylene, 3,5-dimethyl-3-hexene-1-alkynes, 3,5-dimethyl-1-hexin-3-alcohol, 1-acetylene-1-cyclohexanol, 2-phenyl-3-butyne-2-alcohol, vinyl cyclosiloxane and triphenylphosphine; Adhesion promoter, as at United States Patent (USP) 4,087, the adhesion promoter of being instructed in 585 and 5,194,649; Dyestuff; Pigment; Antioxidant; Heat stabilizer; The UV stabilizer; Fire retardant; Flow control additive; And diluent, as organic solvent and reactive diluent.
[0075] as the alternative of hydrosilylation curable silicone compositions, the condensation curable silicone compositions also is suitable for silicone composition of the present invention.
[0076] the condensation curable silicone compositions generally includes: the organic siliconresin (A with silicon bonded hydrogen atom, silicon bonded hydroxy or silicon bonding hydrolyzable groups 2), choose wantonly, have the crosslinking agent (B of silicon bonding hydrolyzable groups 1), and optional, condensation catalyst (C 1).Condensation curable organosilicon resin (A 2) copolymer normally, it comprises R 1SiO 3/2The unit is T unit and/or SiO 4/2The unit is the Q unit, together with R 1R 6SiO 1/2The unit is M unit and/or R 6 2SiO 2/2The unit is D unit, wherein R 1As described above, R 6Be R 1,-H ,-OH or hydrolyzable groups.For example, organic siliconresin can be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin, MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.
[0077] according to an execution mode, organic siliconresin (A 2) have a formula:
(R 1R 6 2SiO 1/2) w’(R 6 2SiO 2/2) x’(R 6SiO 3/2) y’(SiO 4/2) z’ (V)
R wherein 1And R 6In above definition and example, w ' is from 0 to 0.8, alternatively from 0.02 to 0.75, alternatively from 0.05 to 0.3; X ' is from 0 to 0.95, alternatively from 0.05 to 0.8, alternatively from 0.1 to 0.3; Y ' is from 0 to 1, alternatively from 0.25 to 0.8, alternatively from 0.5 to 0.8; And z ' is from 0 to 0.99, alternatively from 0.2 to 0.8, alternatively from 0.4 to 0.6.Organic siliconresin (A 2) have at least two silicon bonded hydrogen atoms of average per molecule, hydroxyl or a hydrolyzable groups.As used herein, term " hydrolyzable groups " mean from room temperature (～23 ± 2 ℃) to any temperature of 100 ℃, the silicon binding groups is lacking under the situation of catalyst and water reaction some minutes, for example 30 minutes, to form silanol (Si-OH) group.By R 6The example of hydrolyzable groups of expression includes, but not limited to-Cl ,-Br ,-OR 7,-OCH 2CH 2OR 7, CH 3C (=O) O-, Et (Me) C=N-O-, CH 3C (=O) N (CH 3)-and-ONH 2, R wherein 7Be C 1To C 8Alkyl or C 1To C 8The halo alkyl.
[0078] by R 7The alkyl and the halo hydrocarbyl group of expression have 1 to 8 carbon atom usually, alternatively 3 to 6 carbon atoms.The acyclic hydrocarbon group and the halo hydrocarbyl group that comprise at least 3 carbon atoms can have branching or non-branching structure.By R 7The example of the hydrocarbyl group of expression comprises, but be not limited to, non-branching and branched-alkyl, as methyl, ethyl, propyl group, 1-Methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, amyl group, 1-methyl butyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl and octyl group; Cycloalkyl is as pentamethylene, cyclohexane and methylcyclohexyl; Phenyl; Alkaryl is as tolyl and xylyl; Aralkyl is as benzyl and phenethyl; Thiazolinyl is as vinyl, pi-allyl and acrylic; Arylalkenyl is as styryl; And alkynyl, as acetenyl and propinyl.By R 7The halo alkyl examples of groups of expression includes, but not limited to 3,3,3-trifluoro propyl, 3-chloropropyl, chlorphenyl and dichlorophenyl.
[0079] common, at organic siliconresin (A 2) in, 1mol%, 5mol%, the R of 10mol% at least alternatively at least alternatively at least 6Group is hydrogen, hydroxyl or hydrolyzable groups.As used herein, R 6The mol% of middle group is defined as: organic siliconresin (A 2) in the silicon binding groups molal quantity with at organic siliconresin (A 2) middle R 6The ratio of the total mole number of group multiply by 100.
[0080] by organic siliconresin (A 2) instantiation of the cured silicone resin that forms includes, but not limited to have the cured silicone resin of following formula: (MeSiO 3/2) 0.9(Me (HO) SiO 2/2) 0.1, (PhSiO 3/2) 0.7(Ph (MeO) SiO 2/2) 0.3, (Me 3SiO 1/2) 0.8(SiO 4/2) 0.15(HOSiO 3/2) 0.05, (MeSiO 3/2) 0.67(PhSiO 3/2) 0.23(Ph (HO) SiO 2/2) 0.1, (MeSiO 3/2) 0.45(PhSiO 3/2) 0.24(Ph (HO) SiO 2/2) 0.16(Ph 2SiO 2/2) 0.1(PhMeSiO 2/2) 0.05, (PhSiO 3/2) 0.3(Ph (HO) SiO 2/2) 0.1(MeSiO 3/2) 0.4(Me (HO) SiO 2/2) 0.05(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05(PhSiO 3/2) 0.3(Ph (MeO) SiO 2/2) 0.1(MeSiO 3/2) 0.1(PhMeSiO 2/2) 0.5, wherein Me is a methyl, and Ph is a phenyl, and the outer numeric suffix of bracket is represented molar fraction, and subscript n has such value, so that organic siliconresin has from 500 to 50,000 number-average molecular weight usually.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.
[0081] as mentioned above, the organic siliconresin (A that represents by formula (V) 2) have 500 to 50,000 number-average molecular weight (M usually n).Alternatively, organic siliconresin (A 2) can have at least 300 M n, alternatively 1,000 to 3,000, wherein molecular weight is to use low angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, measures by gel permeation chromatography.
Under [0082] 25 ℃, the viscosity of organic siliconresin (A2) is generally from 0.01 handkerchief second (PaS) to solid, and alternatively from 0.1 to 100,000PaS, alternatively from 1 to 1,000PaS.
[0083] in second execution mode, organic siliconresin (A 2) can have and identical as mentioned above formula (V), but have different values for subscript x and z, and condition is R 6SiO 3/2Unit and SiO 4/2The unit and greater than zero, and further condition is the organic siliconresin (A of second execution mode 2) per molecule comprises at least two silicon bonded hydrogen atoms, at least two silicon bonded hydroxy groups or at least two silicon bonding hydrolyzable groups.More specifically, for the organic siliconresin (A of second execution mode 2), w ', y ', R 1And R 6Keep same as described above, x ' has from 0 to 0.6 numerical value usually, and alternatively from 0 to 0.45, alternatively from 0 to 0.25, z ' has from 0 to 0.35 value usually, and alternatively from 0 to 0.25, alternatively from 0 to 0.15; And y '+z's ' and greater than zero, and be generally 0.2 to 0.99, alternatively from 0.5 to 0.95, alternatively from 0.65 to 0.9.Further, w '+x's ' and can be zero, but be generally 0.01 to 0.80, alternatively from 0.05 to 0.5, alternatively from 0.1 to 0.35.Usually, at the organic siliconresin (A of second execution mode 2) in, 1 mole of % to 30 mole of %, the R of 1 to 15 mole of % alternatively 6Group is hydrogen, hydroxyl or hydrolyzable groups.
The condensation curable organosilicon resin (A of [0084] second execution mode 2) example include, but not limited to have the organic siliconresin of following formula: (Me (MeO) Si 2/2) X '(MeSiO 3/2) Y ', (Ph (HO) SiO 2/2) X '(PhSiO 3/2) Y ', (Me 3SiO 1/2) W '(CH 3COOSiO 3/2) Y '(SiO 4/2) Z ', (Ph (MeO) SiO 2/2) X '(MeSiO 3/2) Y '(PhSiO 3/2) Y ', (Ph (MeO) is SiO (HO) 1/2) W '(MeSiO 3/2) Y '(PhSiO 3/2) Y '(Ph 2SiO 2/2) X '(PhMeSiO 2/2) X ', (PhMe (MeO) SiO 1/2) W '(Ph (HO) SiO 2/2) X '(MeSiO 3/2) Y '(PhSiO 3/2) Y '(PhMeSiO 2/2) X '(Ph (HO) SiO 2/2) X '(PhSiO 3/2) Y '(MeSiO 3/2) Y '(PhMeSiO 2/2) X ', wherein Me is a methyl, Ph is a phenyl, wherein w ', x ', y ' and z ' as surface defined, and subscript y ' has numerical value like this, so that organic siliconresin has from 500 to 50,000 number-average molecular weight.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.
The condensation curable organosilicon resin (A of [0085] second execution mode 2) instantiation include, but not limited to have the organic siliconresin of following formula: (Me (MeO) Si 2/2) 0.05(Me 3SiO 1/2) 0.75(SiO 4/2) 0.2, (Ph (HO) SiO 2/2) 0.09(MeSiO 3/2) 0.67(PhSiO 3/2) 0.24, (Ph (MeO) SiO 2/2) 0.05(MeSiO 3/2) 0.45(PhSiO 3/2) 0.35(Ph 2SiO 2/2) 0.1(PhMeSiO 2/2) 0.05, (PhMe (MeO) SiO 1/2) 0.02(PhSiO 3/2) 0.4(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.03(Ph (HO) SiO 2/2) 0.04(PhMe (MeO) SiO 1/2) 0.03(PhSiO 3/2) 0.36(MeSiO 3/2) 0.1(PhMeSiO 2/2) 0.47, wherein Me is a methyl, and Ph is a phenyl, and the outer numeric suffix of bracket is represented molar fraction.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.
[0086] as mentioned above, the condensation curable organosilicon resin (A of second execution mode 2) have from 500 to 50,000 number average component (M usually n).Alternatively, condensation curable organosilicon resin (A) can have from 500 to 10,000 M n, alternatively from 800 to 3,000, wherein molecular weight is to use refractive index detector and organic siliconresin (MQ) reference material, measures by gel permeation chromatography.
Under [0087] 25 ℃, the condensation curable organosilicon resin (A of second execution mode 2) viscosity, normally from 0.01PaS to solid, alternatively from 0.1 to 10,000PaS, alternatively from 1 to 100PaS.Condensation curable organosilicon resin (A) by formula (V) expression generally includes, below 20% (w/w), alternatively below 10% (w/w), the silicon bonded hydroxy below 2% (w/w) alternatively, as pass through 29Si NMR measures.
[0088] organic siliconresin (A that represents by formula (V) 2) the preparation method be well-known in the art; A lot of these resins are that commerce can get.Organic siliconresin (A by formula (V) expression 2) be prepared by following usually: in organic solvent such as toluene, the suitable mixture of cohydrolysis chlorosilane parent.For example, comprise R 1R 6 2SiO 1/2Unit and R 6SiO 3/2The organic siliconresin of unit can have formula R by cohydrolysis in toluene 1R 6 2First compound of SiCl and have a formula R 6SiCl 3Second compound be prepared R wherein 1And R 6As top qualification and example.The cohydrolysis process aspect the hydrosilylation curable silicone compositions in above being described.The reactant of cohydrolysis can be by further " multiviscosisty (bodied) " to required degree, with the quantity and the viscosity of control crosslinkable groups.
[0089] if expects, by the organic siliconresin (A of formula (V) expression 2), can in organic solvent, further handle, to reduce the content of silicon bonded hydroxy group with condensation catalyst.Alternatively, contain except that the chloro group hydrolyzable groups as-Br ,-I ,-OCH 3,-OC (O) CH 3,-N (CH 3) 2, NHCOCH 3With-SCH 3First or second compound, can be by cohydrolysis, to form organic siliconresin (A 2).Organic siliconresin (A 2) characteristic depend on the type of first and second compounds, the mol ratio of first and second compounds, the degree and the treatment conditions of condensation.
[0090] the Q unit in the formula (V) is at organic siliconresin (A 2) in can be the form of discrete particle (or discrete particle (discrete particles)).Granular size is normally from 1nm to 20 μ m.The example of these particles includes, but not limited to the silicon dioxide (SiO of diameter 15nm 4/2) particle.
[0091] in another embodiment, the condensation curable silicone compositions comprises modified rubber organic siliconresin (A 3), described modified rubber organic siliconresin (A 3) by making organo-silicon compound---it is selected from (i) and has formula (R 1R 6 2SiO 1/2) W '(R 6 2SiO 2/2) X '(R 6SiO 3/2) Y '(SiO 4/2) Z 'Organic siliconresin, (ii) (i) the hydrolyzable parent and (iii) have formula R 8 3SiO (R 1R 8SiO) mSiR 8 3Silicone rubber---have water, (iv) condensation catalyst and (v) react under the situation of organic solvent and prepare, wherein R 1And R 6As surface defined and example, R 8Be R 1Or hydrolyzable groups, m is from 2 to 1,000, alternatively from 4 to 500, alternatively from 8 to 400, and w ', x ', y ' and z ' are as surface defined and example.Organic siliconresin (i) has at least two silicon bonded hydroxies of average per molecule or hydrolyzable groups.Silicone rubber (iii) has at least two silicon bondings of average per molecule hydrolyzable groups.Silicone rubber (iii) in silicon bonded hydroxy in silicon bonding hydrolyzable groups and the organic siliconresin (i) or the mol ratio of hydrolyzable groups, be from 0.01 to 1.5, alternatively from 0.05 to 0.8, alternatively from 0.2 to 0.5.
[0092] in the first embodiment, in organic siliconresin (i), usually at least 1 mole of %, at least 5 moles of %, the R of at least 10 moles of % alternatively alternatively 6Group is hydroxyl or hydrolyzable groups.In second execution mode, in organic siliconresin (i), common 1 mole of % to 30 mole of % or the R of 1 to 15 mole of % alternatively 6Group is hydrogen, hydroxyl or hydrolyzable groups.
The organic siliconresin of [0093] first execution mode (i) has at least 300 number-average molecular weight (M usually n), alternatively from 500 to 50,000, alternatively from 800 to 3,000, wherein molecular weight is to use low angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, measures by gel permeation chromatography.
[0094] instantiation that is suitable as the organic siliconresin of organic siliconresin (i) includes, but not limited to have the resin of following formula: (Me (MeO) Si 2/2) X '(MeSiO 3/2) Y ', (Ph (HO) SiO 2/2) X '(PhSiO 3/2) Y ', (Ph (MeO) SiO 2/2) X '(PhSiO 3/2) Y '(MeSiO 3/2) Y '(PhSiO 3/2) Y '(PhMeSiO 2/2) X '(CH 3COOSiO 3/2) Y '(PhSiO 3/2) Y '(SiO 4/2) Z '(Me 2SiO 2/2) X '(Ph 2SiO 2/2) X ', wherein Me is a methyl, and Ph is a phenyl, and wherein x ', y ' and z ' be as top definition, and subscript y ' has numerical value like this, makes organic siliconresin have from 500 to 50,000 number-average molecular weight.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.
[0095] other instantiation that is suitable as the organic siliconresin of organic siliconresin (i) includes but not limited to have the resin of following formula: (Ph (HO) SiO 2/2) 0.03(PhSiO 3/2) 0.37(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05(CH 3COOSiO 3/2) 0.06(PhSiO 3/2) 0.3(SiO 4/2) 0.04(Me 2SiO 2/2) 0.2(Ph 2SiO 2/2) 0.4, wherein Me is a methyl, and Ph is a phenyl, and the outer numeric suffix of bracket is represented molar fraction.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.Organic siliconresin (i) can be single organic siliconresin or the mixture that comprises two or more different organic siliconresins, has pointed formula separately.Organic siliconresin (i) can be single organic siliconresin or the mixture that comprises two or more different organic siliconresins, has pointed formula separately.
[0096] as used herein, term " hydrolyzable parent " is meant the silane with hydrolyzable groups, and it is suitable as the raw material (parent) of preparation organic siliconresin (i).The hydrolyzable parent (ii) can be by formula R 1R 8 2SiX, R 8 2SiX 2, R 8SiX 3And SiX 4Expression, wherein R 1, R 8With X as surface defined and example.
[0097] hydrolyzable parent instantiation (ii) includes, but not limited to have the silane of following formula: Me 2ViSiCl, Me 3SiCl, MeSi (OEt) 3, PhSiCl 3, MeSiCl 3, Me 2SiCl 2, PhMeSiCl 2, SiCl 4, Ph 2SiCl 2, PhSi (OMe) 3, MeSi (OMe) 3, PhMeSi (OMe) 2And Si (OEt) 4, wherein Me is a methyl, Et is an ethyl, and Ph is a phenyl.
[0098] silicone rubber instantiation (iii) includes, but not limited to have the silicone rubber of following formula: (EtO) 3SiO (Me 2SiO) 55Si (OEt) 3, (EtO) 3SiO (Me 2SiO) 16Si (OEt) 3, (EtO) 3SiO (Me 2SiO) 386Si (OEt) 3(EtO) 2MeSiO (PhMeSiO) 10SiMe (OEt) 2, wherein Me is a methyl, Et is an ethyl.
[0099] reaction is being carried out to 180 ℃ temperature from room temperature (～23 ± 2 ℃) usually, alternatively from room temperature to 100 ℃.
[00100] reaction time depends on Several Factors, comprises organic siliconresin (i) and silicone rubber structure (iii), and temperature.Usually allow one period that is enough to finish condensation reaction of component reaction.This means the permission component reaction, up to silicone rubber (iii) in the initial silicon bonding hydrolyzable groups that exists at least 40 moles of %, alternatively at least 65 moles of %, at least 90 moles of % are consumed in condensation reaction alternatively, as pass through 29Si NMR is measured.Room temperature (～23 ± 2 ℃) to 100 ℃ under, the reaction time is generally 1 to 30 hour (h).The optimal reaction time can be determined by normal experiment.
[00101] condensation catalyst of Shi Heing (iv) is discussed in further detail below, and the organic solvent that is fit to is (v) above in modified rubber organic siliconresin (A 1) content in be described.Condensation catalyst concentration (iv) is enough to catalysis organic siliconresin (i) and silicone rubber condensation reaction (iii).Usually, based on the weight of silicones (i), condensation catalyst concentration (iv) is from 0.01 to 5% (w/w), alternatively from 0.01 to 3% (w/w), from 0.05 to 2.5% (w/w) alternatively.Based on the total weight of reactant mixture, (concentration v) is from 10 to 95% (w/w) normally, alternatively from 20 to 85% (w/w), from 50 to 80% (w/w) alternatively for organic solvent.
[00102] concentration of the water in reactant mixture depends on R in the organo-silicon compound 8The character of silicon bonding hydrolyzable groups in the character of group and the silicone rubber.When organic silicones (i) when comprising hydrolyzable groups, the concentration of water is enough to be implemented in the hydrolysis of organic siliconresin (i) and the silicone rubber hydrolyzable groups in (iii).For example, the organic siliconresin (i) of combination and silicone rubber (iii) in, the concentration of water is 0.01 to 3 mole, 0.05 to 1 mole alternatively of every mole of hydrolyzable groups normally.When organic silicones (i) when not containing hydrolyzable groups, only the water of trace such as 100ppm is present in reactant mixture usually.Under the normal condition, the water of trace is present in reactant and/or the solvent.
[00103] as mentioned above, the condensation curable silicone compositions can further comprise crosslinking agent (B 1).Crosslinking agent (B 1) can have formula R 7 qSiX 4-q, R wherein 7Be C 1To C 8Alkyl or C 1To C 8The halo alkyl, X is a hydrolyzable groups, and q is 0 or 1.By R 7The alkyl of expression and halo hydrocarbyl group and the hydrolyzable groups represented by X are as mentioned above and exemplify.
[00104] crosslinking agent (B 1) instantiation include, but not limited to alkoxy silane, as MeSi (OCH 3) 3, CH 3Si (OCH 2CH 3) 3, CH 3Si (OCH 2CH 2CH 3) 3, CH 3Si[O (CH 2) 3CH 3] 3, CH 3CH 2Si (OCH 2CH 3) 3, C 6H 5Si (OCH 3) 3, C 6H 5CH 2Si (OCH 3) 3, C 6H 5Si (OCH 2CH 3) 3, CH 2=CHSi (OCH 3) 3, CH 2=CHCH 2Si (OCH 3) 3, CF 3CH 2CH 2Si (OCH 3) 3, CH 3Si (OCH 2CH 2OCH 3) 3, CF 3CH 2CH 2Si (OCH 2CH 2OCH 3) 3, CH 2=CHSi (OCH 2CH 2OCH 3) 3, CH 2=CHCH 2Si (OCH 2CH 2OCH 3) 3, C 6H 5Si (OCH 2CH 2OCH 3) 3, Si (OCH 3) 4, Si (OC 2H 5) 4And Si (OC 3H 7) 4Organoacetoxysilane is as CH 3Si (OCOCH 3) 3, CH 3CH 2Si (OCOCH 3) 3And CH 2=CHSi (OCOCH 3) 3Organic imino group oxosilane (organoiminooxysilanes) is as CH 3Si[O-N=C (CH 3) CH 2CH 3] 3, Si[O-N=C (CH 3) CH 2CH 3] 4And CH 2=CHSi[O-N=C (CH 3) CH 2CH 3] 3Organic acetylamino silane is as CH 3Si[NHC (=O) CH 3] 3And C 6H 5Si[NHC (=O) CH 3] 3Amino silane is as CH 3Si[NH (s-C 4H 9)] 3And CH 3Si (NHC 6H 11) 3With organic amino oxosilane.
[00105] crosslinking agent (B 1) can be the mixture of single silane or two or more different silane, every kind of silane is as mentioned above.Equally, the method for preparing trifunctional and four functional silanes is known in this area, and many in these silane are that commerce can get.
[00106] when it exists, crosslinking agent (B 1) concentration in the condensation curable silicone compositions is enough to solidify (crosslinked) condensation curable organosilicon resin.Crosslinking agent (B 1) accurate amount depend on required state of cure, it is usually along with crosslinking agent (B 1) in the molal quantity and the organic siliconresin (A of silicon bonding hydrolyzable groups 2) in silicon bonded hydrogen atom, hydroxyl or hydrolyzable groups molal quantity ratio increase and increase.Usually, crosslinking agent (B 1) concentration be enough at organic siliconresin (A 2) in the silicon bonding hydrolyzable groups of 0.2 to 4 mole of every mole of silicon bonded hydrogen atom, oh group or hydrolyzable groups is provided.Crosslinking agent (B 1) optimal dose can easily be measured by normal experiment.
[00107] condensation catalyst (C 1) can be to be generally used for promoting the condensation of silicon bonded hydroxy (silanol) group to form any condensation catalyst of Si-O-Si key.The example of condensation catalyst includes, but not limited to amine; The complex compound of lead, tin, zinc and iron and carboxylic acid.Particularly, condensation catalyst (C 1) can be selected from tin (II) and tin (IV) compound, as two laurate tin, two tin octoates and tetrabutyltin; And titanium compound is as four fourth oxygen titaniums.
[00108] when it exists, based on organic siliconresin (A 2) gross weight, condensation catalyst (C 1) concentration normally from 0.1 to 10% (w/w), optionally from 0.5 to 5% (w/w), optionally from 1 to 3% (w/w).
[00109] comprises condensation catalyst (C when the condensation curable silicone compositions 1) time, this condensation curable silicone compositions is two parts composition normally, wherein organic siliconresin (A 2) and condensation catalyst (C 1) be in dividing other part.
[00110] the condensation curable silicone compositions can further comprise granular inorganic filler, as silicon dioxide, aluminium oxide, calcium carbonate and mica.In one embodiment, for example, the condensation curable silicone compositions further comprises nano SiO 2 particle.This nano particle can help to reduce the thermal coefficient of expansion of substrate 106.Low thermal coefficient of expansion can improve the manufacturability of CdTe based photovoltaic device 104.Nano particle also can increase the mechanical strength of substrate 106.Nano SiO 2 particle can be any have at least one overall dimension below about 200nm (as, particle diameter, layer thickness) earth silicon material.A useful especially form of nano SiO 2 particle is the fumed silica nano particle.The raw-material example of non-improved silica that useful commerce can get comprises, the colloidal silica of nano-scale, it can be with name of product NALCO1040,1042,1050,1060,2326,2327 and 2329 colloidal silicas from Nalco Chemical Co., Naperville, Illinois obtains, with Aerosil
Figure A200780022327D0024151225QIETU
Obtain from Degussa, with Ludox
Figure A200780022327D0024151225QIETU
Obtain from DuPont, with Snowtex
Figure A200780022327D0024151225QIETU
Obtain from Nissan Chemical, with Levasil
Figure A200780022327D0024151225QIETU
Obtain from Bayer, or with Sylysia
Figure A200780022327D0024151225QIETU
Obtain from Fuji Silysia Chemical.The fumed silica that is fit to comprises, for example, from DeGussa AG, (Hanau, Germany) commerce can get, commodity " Aerosil series OX 50 " by name and production code member be-130 ,-150 and-200 product.Fumed silica also can be from Cabot Corp., Tuscola, and I is with Bade name " CABO-SPERSE 2095 ", " CAB-O-SPERSE A105 " and " CAB-O-SIL M5 " commercial acquisition.Those skilled in the art will know that the different methods of having established, obtaining having different physical properties and different size particle with different compositions, as the flame hydrolysis (flame-hydrolysis) that is used for gas phase or solid phase reaction (Aerosil-Process), plasma method (plasma-process), arc process (arc-process) and hot wall reactor method (hot-wallreactor-process) or be used for the ion-exchange and the precipitation method that solution-based is reacted.
[00111] nano SiO 2 particle can be the colloidal dispersion form.Therefore nano SiO 2 particle can be dispersed in the polar solvent, as methyl alcohol, ethanol, isopropyl alcohol (IPA), ketone such as methyl iso-butyl ketone (MIBK), water, acetate, glycol; And can attempt as propylene glycol, 2-methyl isophthalic acid, ammediol HOCH 2CH (CH 3) CH 2OH, 1,2-hexylene glycol CH 3(CH 2) 3CH (OH) CH 2OH and glycerol; Glyceride is glyceryl triacetate (glyceryl triacetate), glyceryl tripropanoate (glyceryl tripropionate or tripropionin) and tributyrin (tributyorin) for example; Polyethylene glycols (polyglycols) is as polyethylene glycol and polypropylene glycol, wherein PPG-14 butyl ether C 4Hg (OCH (CH 3) CH 2) 14OH.Alternatively, nano SiO 2 particle also can be scattered in the non-polar solven, as toluene, benzene, dimethylbenzene etc.
[00112] the common scope of silica particle sizes is 1 to 1000nm, or alternatively from 1 to 100nm, or alternatively from 5 to 30nm.Nano SiO 2 particle can be the nano SiO 2 particle of single type, or comprises the mixture of at least two kinds of dissimilar nano SiO 2 particles.Known nano SiO 2 particle can be pure silicon dioxide, or it can comprise a certain amount of impurity, as Al 2O 3, ZnO and/or cation such as Na +, K ++, Ca ++, Mg ++Deng.
[00113] based on the gross weight of condensation curable silicone compositions, the concentration of nano SiO 2 particle is normally from 0.0001 to 99wt%, alternatively from 0.001 to 75wt%, alternatively from 10 to 65wt%, alternatively from 5 to 50wt%, alternatively from 20 to 40wt%.The condensation curable silicone compositions can be one-component (one-part) composition, and it comprises condensation curable organosilicon resin (A in single component 2Or A 3) and any optional ingredients and nano SiO 2 particle; Perhaps, alternatively, can be many components (muliti-part) compositions, it comprises these components in two or more components.
[00114] one-component condensation curable silicone compositions can so prepare: by at ambient temperature, under the help that is with or without organic solvent, make up condensation curable organosilicon resin (A in certain proportion 2Or A 3), nano SiO 2 particle and any optional ingredients.Equally, silicone composition can be prepared by the component that makes up in each component.The condensation curable silicone compositions that comprises nano SiO 2 particle also can in situ preparation, and promptly nano SiO 2 particle can be at above-mentioned manufacturing condensation curable organosilicon resin (A 2Or A 3) process in add.Mixing can realize by any technology as known in the art, for example grinds, mixes and stir, and carries out with batch (-type) or continuity method.
[00115] condensation curable silicone compositions of the present invention can comprise other composition, as known in the art and described for the hydrosilylation curable silicone compositions as mentioned.
[00116] in another embodiment, silicone composition can be the free radical curable silicone compositions.The example of free radical curable silicone compositions comprises, peroxide-curable silicone composition, the radiation curable silicone composition that contains free radical photo-initiation and high-energy radiation curable silicone compositions.Usually, the free radical curable silicone compositions comprises organic siliconresin (A 4) and optional crosslinking agent (B 2) and/or radical initiator (C 2) (for example, free radical photo-initiation or organic peroxide).
[00117] organic siliconresin (A 4) can be to be selected from any organic siliconresin that following method is solidified (that is, crosslinked) by at least a: (i) in the presence of free radical photo-initiation, organic siliconresin is exposed to the irradiation that has from 150 to 800nm wavelength; (ii) in the presence of organic peroxide, heat organic siliconresin (A 4); (iii) with organic siliconresin (A 4) be exposed to electron beam.Organic siliconresin (A 4) copolymer normally, described copolymer contain T siloxane unit and/or Q siloxane unit and with M and/or D unit combination.
[00118] for example, organic siliconresin (A 4) can have formula: (R 1R 9 2SiO 1/2) W "(R 9 2SiO 2/2) X "(R 9SiO 3/2) Y " (SiO 4/2) Z ", R wherein 1As surface defined and example, R 9Be R 1, alkenyl or alkynyl, w ＂ is from 0 to 0.99, x ＂ is from 0 to 0.99, y ＂ is from 0 to 0.99, z ＂ is from 0 to 0.85, and w ＂+x ＂+y ＂+z ＂=1.
[00119] by R 9The alkenyl group of expression, it can be identical or different, as in the above to R 2Description defined in and example.
[00120] by R 9The alkynyl group of expression, it can be identical or different, has 2 usually to about 10 carbon atoms, from 2 to 6 carbon atoms alternatively, and be example with acetenyl, propinyl, butynyl, hexin base and octyne base, but be not limited thereto.
[00121] organic siliconresin (A 4) have at least 300 number-average molecular weight (M usually n), alternatively from 500 to 10,000, alternatively from 1,000 to 3,000, wherein molecular weight is to use refractive index detector and organic siliconresin (MQ) reference material, measures by gel permeation chromatography.
[00122] organic siliconresin (A 4) can contain the following silicon bonded hydroxy group of 10% (w/w), alternatively below 5% (w/w), alternatively below 2% (w/w), as pass through 29Si NMR measures.
[00123] organic siliconresin (A of suitable purpose of the present invention 4) instantiation include, but not limited to have the organic siliconresin of following formula: (Vi 2MeSiO 1/2) 0.25(PhSiO 3/2) 0.75, (ViMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75, (ViMe 2SiO 1/2) 0.25(MeSiO 3/2) 0.25(PhSiO 3/2) 0.50, (ViMe 2SiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.1(Vi 2MeSiO 1/2) 0.15(ViMe 2SiO 1/2) 0.1(PhSiO 3/2) 0.75, wherein Me is a methyl, and Vi is a vinyl, and Ph is a phenyl, and the outer numeric suffix of bracket is represented molar fraction.The order of unit is not considered by any way and limits the scope of the invention in the aforementioned formula.
[00124] the free radical curable silicone compositions of this method can comprise other composition, and it includes, but not limited to silicone rubber; Unsaturated compound; Radical initiator; Organic solvent; The UV stabilizer; Sensitizer; Dyestuff; Fire retardant; Antioxidant; Filler is as reinforced filling, compatibilization filler (extendingfiller) and conductive filler; And adhesion promoter.
[00125] the free radical curable silicone compositions can further comprise and is selected from following unsaturated compound: (i) at least a organo-silicon compound, its per molecule have at least one silicon bonding alkenyl group; (ii) at least a organic compound, its per molecule have at least one aliphat carbon-carbon double bond; (iii) contain (i) and mixture (ii); Wherein said unsaturated compound has the molecular weight below 500.Alternatively, unsaturated compound has below 400 or 300 following molecular weight.Similarly, unsaturated compound can have straight chain, side chain or circulus.
[00126] organo-silicon compound (i) can be organosilan or organosiloxane.Organosilan can be monosilane, disilane, trisilalkane or polysilane.Similarly, organosiloxane can be disiloxane, trisiloxanes or polysiloxanes.Cyclosilane and cyclosiloxane have 3 to 12 silicon atoms usually, alternatively 3 to 10 silicon atoms, 3 to 4 silicon atoms alternatively.In acyclic polysilane and polysiloxanes, silicon bonding thiazolinyl (one or more) can be positioned at end, side chain or end and side chain position.
[00127] instantiation of organosilan includes, but not limited to have the silane of following formula: Vi 4Si, PhSiVi 3, MeSiVi 3, PhMeSiVi 2, Ph 2SiVi 2And PhSi (CH 2CH=CH 2) 3, wherein Me is a methyl, Ph is a phenyl, and Vi is a vinyl.
[00128] instantiation of organosiloxane includes, but not limited to have the siloxanes of following formula: PhSi (OSiMe 2Vi) 3, Si (OSiMe 2Vi) 4, MeSi (OSiMe 2Vi) 3And Ph 2Si (OSiMe 2Vi) 2, wherein Me is a methyl, Vi is a vinyl, and Ph is a phenyl.
[00129] organic compound can be any organic compound that per molecule contains at least one aliphatic carbon-carbon double bond, and condition is that compound does not stop organic siliconresin (A 4) solidify to form silicone resin.Organic compound can be alkene, diene, triolefin or polyenoid.Further, in acyclic organic cpd, carbon-carbon double bond (one or more) can be positioned at end, side chain or end and side chain position.
[00130] organic compound can contain one or more functional groups except that aliphatic carbon-carbon double bond.The example of the functional group that is fit to includes, but not limited to-O-, C=O ,-CHO ,-CO 2-,-C ≡ N ,-NO 2, C=C＜,-C ≡ C-,-F ,-Cl ,-Br and-I.The suitability that is used for the concrete unsaturated organic compound of free radical curable silicone compositions of the present invention can easily be determined by normal experiment.
[00131] under the room temperature, organic compound can be liquid or solid-state.Equally, in the free radical curable silicone compositions, organic compound can be soluble, partly soluble or insoluble.The normal boiling point of organic compound can change on wide region, and this depends on the number and the character of molecular weight, structure and the functional group of compound.Usually, organic compound has the normal boiling point greater than the curing temperature of composition.In addition, when solidifying, can remove the organic compound of appreciable amount by volatilization.
[00132] example that contains the organic compound of aliphatic carbon-carbon double bond includes, but not limited to 1,4-divinylbenzene, 1,3-hexadienyl benzene and 1,2-divinyl cyclobutane.
[00133] unsaturated compound can be single unsaturated compound or the mixture that contains two or more different unsaturated compounds, and every kind as mentioned above.For example, unsaturated compound can be the mixture of mixture, organosilan and organic compound of the mixture of mixture, organosilan and the organosiloxane of the mixture of single organosilan, two kinds of different organosilans, single organosiloxane, two kinds of different organosiloxanes, single organic compound, two kinds of different organic compounds or the mixture of organosiloxane and organic compound.
[00134] based on the gross weight of free radical curable silicone compositions, the concentration of unsaturated compound is from 0 to 70% (w/w) normally, alternatively from 10 to 50% (w/w), from 20 to 40% (w/w) alternatively.
[00135] preparation contains the organosilan and the organosiloxane of silicon bonding alkenyl group and the method that contains the organic compound of aliphatic carbon-carbon double bond, is well known in the art; A lot of these compounds are that commerce can get.
[00136] normally free radical photo-initiation or organic peroxide of radical initiator.Further, free radical photo-initiation can be to be exposed to wavelength can cause the curing (crosslinked) of organic siliconresin down from 200 to 800nm irradiation free radical photo-initiation arbitrarily.
[00137] example of free radical photo-initiation includes, but not limited to benzophenone; 4,4 '-two (dimethylamino) benzophenone; Halogenated benzophenone; Acetophenone; The Alpha-hydroxy acetophenone; Chloroacetophenone is as dichloroacetophenone and trichloroacetophenone; The dialkoxy acetophenone, as 2, the 2-diethoxy acetophenone; Alpha-hydroxy alkyl benzene ketone is as 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxy-cyclohexyl benzophenone; Alpha-aminoalkyl benzene ketone is as 2-methyl-4 '-(methyl mercapto)-2-morpholino phenyl ethyl ketone; Benzoin; Benzoin ether is as benzoin methyl ether, benzoin ethylether and benzoin isobutyl ether; Benzil ketals, as 2,2-dimethoxy-2-phenyl acetophenone; The acylphosphine oxide class is as diphenyl (2,4, the 6-trimethylbenzoyl) phosphine oxide; The xanthene ketone derivatives; The thio-xanthene-one derivative; Fluorenone derivatives; The aminomethyl phenyl glyoxalic acid; Acetonaphthone; Anthraquinone derivative; The sulfonic acid chloride aromatic compound; With O-acyl alpha-oximinoketone, as 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime.
[00138] free radical photo-initiation also can be a polysilane, as West at United States Patent (USP) 4,260, the polyphenyl methyl polysilane of definition in 780, the disclosure that this United States Patent (USP) 4,260,780 relates to the phenyl methyl polysilane is incorporated into by reference thus; People such as Baney are at United States Patent (USP) 4,314, the amination methyl polysilicon alkane of definition in 956, and the disclosure that this United States Patent (USP) 4,314,956 relates to amination methyl polysilicon alkane is incorporated into by reference thus; People such as Peterson are at United States Patent (USP) 4,276, the methyl polysilicon alkane of definition in 424, and the disclosure that this United States Patent (USP) 4,276,424 relates to methyl polysilicon alkane is incorporated into by reference thus; And people such as West is at United States Patent (USP) 4,324, the poly-silicon styrene (polysilastyrene) of definition in 901, and this United States Patent (USP) 4,324,901 relates to the poly-cinnamic disclosure of silicon and incorporates into thus by reference.
[00139] free radical photo-initiation can be single free radical photo-initiation or the mixture that contains two or more different free radical photo-initiations.Based on organic siliconresin (A 4) weight, the concentration of free radical photo-initiation is from 0.1 to 6% (w/w) normally, alternatively from 1 to 3% (w/w).
[00140] radical initiator also can be an organic peroxide.The example of organic peroxide comprises: two aroly peroxides, and as the dibenzoyl peroxide, two-right-chlorobenzoyl peroxide and two-2,4-dichloro-benzoyl peroxide; Dialkyl peroxide, as di-tert-butyl peroxide and 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane; Two aromatic alkyl superoxides are as dicumyl peroxide; The alkyl aralkyl peroxide is tert-butyl group cumyl peroxide and 1 for example, two (t-butyl peroxy isopropyl) benzene of 4-; And the alkyl aroly peroxide, as t-butyl perbenzoate, t-butyl peroxy-acetate and the sad tert-butyl ester of mistake.
[00141] organic peroxide can be single peroxide or the mixture that contains two or more different organic peroxides.Based on organic siliconresin (A 4) weight, the concentration of organic peroxide is from 0.1 to 5% (w/w) normally, alternatively from 0.2 to 2% (w/w).
[00142] the free radical curable silicone compositions can further comprise at least a organic solvent.Organic solvent can be any non-proton or dipolar aprotic organic solvent, its not with organic siliconresin (A 4) or other composition (one or more) reaction, and with organic siliconresin (A 4) can mix.The example of organic solvent include but not limited to: saturated aliphatic hydrocarbon, as pentane, hexane, normal heptane, isooctane and dodecane; Cycloaliphatic hydrocarbon is as pentamethylene and cyclohexane; Aromatic hydrocarbon is as benzene,toluene,xylene and Lay; Cyclic ethers, (THF) is with diox as oxolane; Ketone is as methyl iso-butyl ketone (MIBK) (MIBK); Halogenated alkane is as trichloroethanes; And halogenated aromatic, as bromobenzene and chlorobenzene.As mentioned above, organic solvent can be single organic solvent or the mixture that contains two or more different organic solvents.
[00143] based on the gross weight of free radical curable silicone compositions, the concentration of organic solvent is from 0 to 99% (w/w) normally, alternatively from 30 to 80% (w/w), from 45 to 60% (w/w) alternatively.
[00144] when free radical curable silicone compositions mentioned above comprises one or more other compositions such as radical initiator, described composition can be the one-component composition, and it comprises organic siliconresin and optional ingredients (one or more) in single component; Perhaps can be multicomponent composition, it contains described composition in two components or many components.
[00145] the another kind of silicone composition that is fit to comprises ring-type dihydro polysiloxanes, and it has from 1,500 to 1,000, and the weight average molecular weight of 000 number range is liquid under room temperature (～23 ± 2 ℃), and comprises H 2SiO 2/2The unit.Ring-type dihydro polysiloxanes can so be produced: make dichlorosilane (H 2SiCl 2) hydrolyzing in the mixture of non-polar organic solvent and water, and from formed ring-type dihydro polysiloxanes, remove volatile cyclic dihydro polysiloxanes.
[00146] non-polar organic solvent used herein illustrates by aromatic hydrocarbon organic solvent and aliphatic hydrocarbon organic solvent, wherein aromatic hydrocarbon organic solvent illustrates by toluene and dimethylbenzene, and the aliphatic hydrocarbon organic solvent illustrates by hexane, heptane, octane and cyclohexane.
[00147] usually by slowly dropwise adding the non-polar organic solvent solution of dichlorosilane, stirring non-polar organic solvent and water simultaneously, is hydrolyzed/condensation reaction.Preferably drip not being higher than under 5 ℃ the temperature, to prevent the volatilization of dihydro polysiloxanes.
[00148] hydrolyzing is normally carried out mutually and in the mixture of water at non-polar organic solvent, wash the non-polar organic solvent phase that contains formed ring-type dihydro polysiloxanes subsequently with water, be dried, then wash-out non-polar organic solvent and volatile cyclic dihydro polysiloxanes.
[00149] in a single day be added dropwise to complete, place solution, make it be divided into non-polar organic solvent layer and water layer, the non-polar organic solvent layer is moved out of and washes with water then.Usually, the non-polar organic solvent layer is washed, and becomes neutrality or up to no longer detecting chloride ion up to it.The non-polar organic solvent layer also can be washed to a certain degree, and uses weak base, and neutralization washes formed salt subsequently with water---as calcium carbonate, sodium carbonate or sodium acid carbonate---.Non-polar organic solvent layer through washing can be dried, and non-polar organic solvent and volatile cyclic dihydro polysiloxanes are usually by wash-out.Although, only otherwise change ring-type dihydro polysiloxanes, be not particularly limited about being used for the method for dry non-polar organic solvent layer through washing, can add powder or granulated dried agent, as anhydrous magnesium sulfate, anhydrous sodium sulfate or molecular sieve.The mixture that stirring obtains, the elimination drier.Only otherwise change ring-type dihydro polysiloxanes, the wash-out about non-polar organic solvent and ring-type dihydro polysiloxanes also is not particularly limited.It is example that wash-out can be dried in drying nitrogen down with reduce pressure down heating or heating.The volatile cyclic dihydro polysiloxanes that this paper mentions is that the 3-aggressiveness is to the 15-aggressiveness.By when using FT-IR to analyze, do not exist silanol groups to absorb, determined that product is this fact of ring-type dihydro polysiloxanes.
[00150] ring-type dihydro polysiloxanes also can produce like this: by make dichlorosilane cohydrolysis/condensation in the mixture of non-polar organic solvent, hydrochloric acid and ionic surface active agent, then as mentioned above, from the dihydro polysiloxanes that forms, remove volatile cyclic dihydro polysiloxanes.Hydrochloric acid is concentrated hydrochloric acid normally, and more generally speaking, hydrochloric acid has the hydrogen chloride content of 15wt% to 37wt%.Ionic surface active agent can comprise anion surfactant, cationic surfactant and amphoteric surfactant, wherein anion surfactant is exemplified below: the alkali metal salt of aliphatic hydrocarbon sulfonic acid, for example alkali metal salt of the alkene sulfonic acid of the alkali metal salt of the alkyl sulfonic acid of 6 to 20 carbon atoms, 6 to 20 carbon atoms and the alkali metal salt of alkyl benzene sulphonate; Aliphatic hydrocarbon sulfonic acid, for example alkene sulfonic acid of the alkyl sulfonic acid of 6 to 20 carbon atoms, 6 to 20 carbon atoms; Alkyl benzene sulphonate; The alkali metal salt of alkyl sulfonic ester; Alkali metal salt with higher fatty acids.Preferred sodium and potassium are as alkali metal used herein.Cationic surfactant is exemplified below: quaternary ammonium salt, for example tetramethyl ammonium chloride, benzyl tributyl ammonium chloride, cetyl ammonio methacrylate and tetrabutylammonium chloride; Alkylamine hydrochloride, for example decyl amine hydrochloride.The use amount of ionic surface active agent in being contained in the water of hydrochloric acid is generally 0.01-50wt%, is more typically 0.1-1.0wt%.
[00151] common, the hydrolyzing reaction is to carry out to mixture by the non-polar organic solvent solution that dropping contains dichlorosilane, and described mixture comprises non-polar organic solvent, hydrochloric acid and ionic surface active agent.Usually, in the dropping process, continue to stir.The hydrolyzing reaction usually occurs under the temperature that is not higher than 5 ℃, in order to avoid the dichlorosilane volatilization.
[00152] another silicone composition that is fit to comprises the hydrogenation polysiloxanes, and it has siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " '[SiO 4/2] Z " ', x wherein " and ', y " ' and z " ' the expression molar fraction, 0.12≤x " '≤1.0,0≤y " '≤0.88,0≤z " '≤0.30, y " ' and z " ' be not 0 simultaneously, and x " '+y " '+z " '=1.The hydrogenation polysiloxanes has from 500 to 1,000 usually, the weight average molecular weight of 000 number range, and under 120 ℃ or lower temperature, be liquid.
[00153] when at siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " '[SiO 4/2] Z " 'Middle z " '=0 o'clock, hydrogenation polysiloxanes siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " 'Be described, wherein x " ' and y " ' represent aforesaid molar fraction, and x " '+y " '=1.As z " '=0 time, common 0.15≤x " '≤1.0 and 0＜y " less than 0.15 the time, degree of branching increases '≤0.85, because as x " ', and cracking becomes when solidifying and more may take place.
[00154] when at siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " '[SiO 4/2] Z " 'Middle y " '=0 o'clock, hydrogenation polysiloxanes siloxane unit molecular formula [H 2SiO 2/2] X " '[SiO 4/2] Z " 'Be described, wherein x " ' and z " ' represent aforesaid molar fraction, and x " '+z " '=1.As y " '=0 time, common 0.15≤x " '≤1.0, because as x " ' less than 0.15 the time, degree of branching increases, and cracking becomes when solidifying and more may take place; And 0＜z " greater than 0.15 the time, degree of branching increases '≤0.15, because as z " ', and cracking becomes when solidifying and more may take place.
[00155] on average, it is x that the hydrogenation polysiloxanes has above-mentioned molar fraction " ', y " ' and z " ' the siloxane unit molecular formula, this does not mean that with the order of above-mentioned siloxane unit and arranges.When siloxane unit during random arrangement, have some block parts in some situation, but remaining the unit arranges with random form in the hydrogenation polysiloxanes.Because [H 2SiO 2/2] unit exists always, so there is linearity block, but owing to always have [HSiO 3/2] unit and/or [SiO 4/2] unit, molecular structure is branching at least, and also can be netted or cage shape, promptly it can be a resin.When the hydrogenation polysiloxanes has [SiO 4/2] during the unit, degree of branching even increase more.
[00156] the hydrogenation polysiloxanes can produce by such method, wherein make (A ') dichlorosilane (H 2SiO 2), (B ') trichlorosilane (HSiCl 3) and (C) tetraalkoxysilane (Si (OR) 4) or tetrachloro silicane (SiCl 4) in the mixture of non-polar organic solvent, hydrochloric acid and ionic surface active agent, carry out cohydrolysis/condensation with mol ratio like this, this mol ratio makes 0.12≤(A ')＜1.0,0≤(B ')≤0.88,0≤(C ')≤0.30, (A ') and (B ') not 0 simultaneously, and (A ')+(B ')+(C ')=1, thus, the formed non-polar organic solvent layer that contains the hydrogenation polysiloxanes washes with water, drying, and non-polar organic solvent is with volatility hydrogenation polysiloxanes wash-out.In this case, R represents alkyl group, ethyl normally, and it can also be methyl or propyl group.The concrete grammar step with above carry out for the described identical mode of ring-type dihydro polysiloxanes.
[00157] in addition, has siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " 'The hydrogenation polysiloxanes can be by (A ') dichlorosilane (H 2SiCl 2) and (B ') trichlorosilane (H 2SiCl 3) cohydrolysis and produce, and have siloxane unit molecular formula [H 2SiO 2/2] X " '[SiO 4/2] Z " '(wherein, x " ' and z " ' expression molar fraction, 0.12≤x " '≤1.0,0≤z " '≤0.30, and x " '+z " '=1) the hydrogenation polysiloxanes, can be by (A ') dichlorosilane (H 2SiCl 2) and (C ') tetraalkoxysilane (Si (OR) 4) or tetrachloro silicane (H 2SiCl 4) cohydrolysis and produce.
[00158] hydrochloric acid concentrated hydrochloric acid normally, and, even more generally, hydrochloric acid has the hydrogen chloride content of 15wt% to 37wt%.Be used to (A ') dichlorosilane (H owing to be included in water in the hydrochloric acid 2SiCl 2), (B ') trichlorosilane (H 2SiCl 3) and (C ') tetraalkoxysilane (Si (OR) 4) or tetrachloro silicane (H 2SiCl 4) hydrolysis, hydrochloric acid is usually to be equal to or higher than (A ') dichlorosilane (H 2SiCl 2), (B ') trichlorosilane (H 2SiCl 3) and (C ') tetraalkoxysilane (Si (OR) 4) or tetrachloro silicane (H 2SiCl 4) the required equimolar amounts use of hydrolysis.
[00159] ionic surface active agent is described in the above, and ionic surface active agent owing to the independent condensation of trichlorosilane and rapidly hydrolyzing suppress gelatification, and described ionic surface active agent promotes the cohydrolysis/condensation of itself and dichlorosilane.
[00160] when ring-type dihydro polysiloxanes and have siloxane unit molecular formula [H 2SiO 2/2] X " '[HSiO 3/2] Y " '[SiO 4/2] Z " 'Hydrogenation polysiloxanes when being heated to 120 ℃ or higher temperature, hydrogen bonding by silicon changes hydroxyl into by oxidation reaction, and as taking place crosslinked with the result of the dehydration condensation of silicon bonded hydrogen atom.In other words, crosslinked and curing takes place as the result who forms the Si-O-Si key.In wet ammonia, Direct Bonding to the hydrogen atom of silicon is activated, and is transformed into hydroxyl by easily reacting with airborne moisture, therefore causes the dehydration condensation with silicon bonded hydrogen atom, and crosslinked.As a result, silicon dioxide (silica) is formed.Yet, do not need to eliminate in the molecule of above-mentioned ring-type dihydro polysiloxanes and above-mentioned hydrogenation polysiloxanes all hydrogen atoms with the silicon atom Direct Bonding, and, some hydrogen atoms for example, 60 moles of % or still less can be held former state.
[00161] heating can take place in oxygen atmosphere.Air is the representative example of oxygen atmosphere.Oxygen atmosphere can be oxygenous nitrogen or helium alternatively, and its oxygen concentration is lower than airborne oxygen concentration.Alternatively, be exposed to the reaction that ozone, nitrous oxide or wet ammonia can be used to reduce ring-type dihydro polysiloxanes and hydrogenation polysiloxanes.Ozone is example with pure ozone, ozone-containing air, the ozone that contains steam and nitrogen ozoniferous, wherein any can being used.With the reacting phase ratio of inducing by aerial oxygen, when use was ozone-induced, reaction took place in more effective mode.Nitrous oxide is an example with single nitrous oxide gas, the nitrogen that contains the air of nitrous oxide and contain nitrous oxide, wherein any can being used.Wet ammonia is with the air, the ammonium hydroxide gas that contain ammonia and contain ammonia and the nitrogen of steam is example, wherein any can being used.Ozone exposure, nitrous oxide expose or ammonia exposes and can carry out under heating condition.
[00162] ring-type dihydro polysiloxanes mentioned above and hydrogenation polysiloxanes also can be cured by high-energy irradiation.Electron beam and X ray are the representative instances of this irradiation.The amount of electron beam irradiation is no less than 3Gry usually.
[00163] referring to Fig. 3, substrate 106 further comprises metal foil layer 312.Usually, siloxane layer 306 and metal foil layer 312 mutual laminations.Metal foil layer is formed by metal usually, for example stainless steel, titanium, kovar (iron nickel cobalt) expansion alloy (covar), invar, tantalum, brass, niobium and their combination altogether.
[00164] comprises that the substrate 106 of siloxane layer 306 and metal foil layer 312 has the thickness of from 2 to 1006 microns (μ m) usually, alternatively from 15 to 500 μ m.In substrate 106, siloxane layer 306 has the thickness of from 0.5 to 6 μ m usually, and metal foil layer 312 has the thickness of from 12.5 to 1000 μ m usually.
[00165] in other excellent physical property, the substrate 106 that comprises siloxane layer 306 and metal foil layer 312 has flexible usually, it is crooked to make that substrate 106 can not have cracking ground along the cylindrical steel axle, described cylindrical steel axle has the diameter that is less than or equal to 3.2mm, wherein, measure flexible described in the Method B as at ASTM Standard D522-93a.
[00166] substrate 106 has low coefficient of linear thermal expansion (CTE), high tensile and high-modulus usually.For example, to 200 ℃ temperature, substrate 106 has from 0 to 20 μ m/m ℃ CTE usually in room temperature (～23 ± 2 ℃), and from 0 to 15 μ m/m ℃ alternatively, from 2 to 10 μ m/m ℃ alternatively.The hot strength and the Young's modulus of substrate 106 are controlled by metal forming.
[00167] referring to Fig. 4, CIS-based photovoltaic device 104 comprises the thin layer of common four to seven vertical stackings, and it forms on substrate 106.Therefore, although in Fig. 4 only four layers be indicated on the substrate 106, be appreciated that the other optional layer that will be described below also can be included in.Various floor are deposited or modify in independent chamber usually.
[00168] in order to make CIS based photovoltaic device 104, provides substrate 106.Substrate 106 can be provided by making aforesaid substrate 106.Alternatively, can obtain substrate 106 from the third party.Usually, naked initial volume of substrate 106 (bare starterroll) or band can provide from propping up make the test (pay-out roll).This substrate 106 has thickness and the about 300 meters length of Ke Da of the width of about 33cm, about 0.005cm usually.Certainly, the size of width, thickness and length is the problem of selecting, and it depends on the final intended use of CIS based photovoltaic device 104.
[00169] intermediate layer, stress flexible metal (not shown)---it is selected to have the intermediate heat diffusion property between the molybdenum layer (one or more layers) 504 of substrate 106 and formation subsequently, can randomly be used as the ground floor that is formed at substrate 106 end faces 512.Metal intermediate layer can be formed at the material that is selected from nickel vanadium, copper, brass, indium tin oxide (ITO), and other material that is known in the art, if CIS base device 104 is had minimum adverse effect---described diffuse other layer to the device 104.Metal intermediate layer can be used to strengthen breaking of adhesiveness and the molybdenum layer (one or more layers) 504 that minimizes formation subsequently.
[00170] after forming ground floor, such molybdenum (Mo) layer 504 of one deck is formed at least optionally, and it has the internal compression stresses of the expectation of certain level, and randomly contains the oxygen of carrying secretly.When described ground floor does not exist, molybdenum layer (one or more layers) 504 can directly be formed at the end face 512 of substrate 106 alternatively, in this case, molybdenum layer (one or more layers) 504 contains the oxygen of carrying secretly usually, with the characteristic of change molybdenum layer (one or more layers) 504, and reduce breaking of molybdenum layer (one or more layers) 504.Molybdenum layer (one or more layers) 504 works as the back contact layer of CIS base device 104.Molybdenum layer (one or more layers) 504 can be that about 0.5 μ m is thick.Randomly, other stress-relieving interlayer (not shown) is formed by molybdenum, the side opposite with molybdenum layer (one or more layers) 504 that other another kind of inert metal can be formed on substrate 106.
[00171] then, CIS base solar absorbed layer 506 forms on substrate 106.More specifically, CIS base solar absorbed layer 506 is formed on the end face 514 of molybdenum layer (one or more layers) 504 by methods known in the art usually.As used herein, CIS is meant copper-indium-diselenide (or copper indium diselenide), and it has or do not have metal alloy, as gallium, aluminium, boron, tellurium or sulphur.For example, CIS base solar absorbed layer 506 can be copper-indium-gallium-diselenide (or copper indium callium diselenide (CIGS), CIGS).Inter alia, these different compositions can be basically interchangeably as absorbed layer, this depends on the required specific nature of CIS based photovoltaic device 104.By way of example and nonrestrictive mode, CIS base solar absorbed layer 506 can be that about 2.0 μ m are thick.As known in the art, CIS base solar absorbed layer is formed best by above heating under 500 ℃ the temperature 25 to 30 minutes.More generally speaking, the device experience heats under about 575 ℃ temperature, so that layer annealing.Because substrate 106 of the present invention can stand to surpass 500 ℃ temperature, so the transformation efficiency of CIS base device in generating is maximized.
[00172] heterojunction partner (heterojunction partner) or Window layer 508 are formed on the end face 516 of CIS base solar absorbed layer 506.Window layer 508 usually by cadmium sulfide (CdS), with CdS (ZnCdS), zinc sulphide, the zinc oxide of kirsite with zinc hydroxide forms or formed by zinc-magnesium oxide and magnesium hydroxide or zinc.Generally (chemical bath deposition CBD) forms Window layer 508, but also can form by non-wetness technique, as sputter by chemical bath deposition.The nonrestrictive mode by example, Window layer 508 can be that about 0.05 μ m is thick.
[00173] randomly, the electric insulation layer (not shown) is formed at the end face 518 of Window layer 508.The nonrestrictive mode by example, electric insulation layer can be that about 0.05 μ m is thick, and can by intrinsic zinc oxide (intrinsiczinc-oxide, i-ZnO), zinc-magnesium oxide alloy or tin oxide forms.The application of layer like this is known in the art.
[00174] form is the last contact layer 510 of translucent, conductive oxide or on the top layer 518 that directly is formed at Window layer 508 under the situation of not using electric insulation layer, perhaps directly is formed on the electric insulation layer when having electric insulation layer.Last contact layer 510 usually by doped stannum oxide, indium tin oxide (ITO) alloy, use aluminium or gallium doping zinc-oxide (ZnO:Al, Ga) or tin oxide form.The nonrestrictive mode by example, last contact layer 510 can be that about 0.6 μ m is thick.
[00175] in one embodiment, back contact interface layer (not shown) can form between molybdenum layer (one or more layers) 504 and CIS base solar absorbed layer 506.Back contact interface layer can be formed by doping zinc tellurium (ZnTe).In this execution mode, electric insulation layer and last contact layer can be formed by tin oxide.About comprise back contact interface layer and form the last contact layer made by tin oxide and the other details of electric insulation layer at IlvydasMatulionis, Sijin Han, Jennifer A.Drayton, Kent J.Price and Alvin D.Compaan, Mat.Res.Soc.Symp.Proc.Vol.668, p.H8.23.1, April instructs in (2001), and it incorporates this paper into its full content by reference.
[00176] in an embodiment of the invention, wire netting (not shown)---it generally includes a thin Ni layer and a thicker Al or an Ag layer---is formed on the including transparent conducting oxide layer.
[00177] a variety of depositing operations can be used to form various layers on substrate 106.For example, depositing operation can be plasma sputtering (RF, AC, DQ, randomly plasma strengthens) technology, evaporation (heat, electron beam or cathode arc) processing, chemical vapour deposition (CVD) (low pressure, atmospheric pressure or plasma strengthen), sublimation process, physical vapor deposition technology and/or heated filament technology.
[00178] sputter can carried out under the pressure limit of about one to 20 millitorr.Hollow cathode sputter or cathode arc technology can carried out under the pressure limit of about 1/10th to 20 millitorrs.The scope that evaporation is pressed can be from about 0.01 to 0.1 millitorr.The scope that the chemical vapour deposition (CVD) that chemical vapour deposition (CVD) pressure and plasma strengthen is pressed can be to atmospheric pressure from about 10 millitorrs.The nonrestrictive mode by example, on about 60 square centimeters target, the power supply of RF, AQ and DC sputter can be from about 50 watts to 5,000 watts scope.Rotating shaft can be about 2.25 inches apart from (axisof rotation distance).The nonrestrictive mode by example, pocket source of independent or multiple electron beam (pocket sources) or single straight type evaporator tank (single linear beamevaportation trough) can be utilized.
[00179] in an embodiment, under the pressure of about one to 20 millitorr, use the DC sputtering technology in scope, molybdenum layer (one or more layers) 504 can form on substrate 106 or boundary layer.The nonrestrictive mode by example, on about 60 square centimeters target, the power supply that is used for the DC sputter can have from about 500 to 5,000 watts scope.During sputter deposition craft, oxygen can mix molybdenum layer (one or more layers) 504, as people such as Shafarman in September, 2005 at Space Photovoltaic Research and TechnologyConference at NASA Glenn in Cleveland, OH is last disclosed.
[00180] in an embodiment, use hot coevaporation technology (therma co-evaporationprocess), on molybdenum layer (one or more layers) 504, form CIS base solar absorbed layer 506.Use the whole bag of tricks known in the art,, can carry out hot coevaporation technology as those disclosed method in people's such as people's such as Noufi United States Patent (USP) 5,441,897 or Mickelsen United States Patent (USP) 4,335,226.
[00181] in an embodiment, use chemical bath deposition technology, chemical surface depositing operation or non-wetting technology such as sputter, on CIS base solar absorbed layer 506, form Window layer 508.Chemical bath deposition technology can be finished by the whole bag of tricks known in the art.For example, people's such as McCandless United States Patent (USP) 6,537,845 discloses and CdS is bathed solution has been applied on the first surface 516 of CIS base solar absorbed layer.In addition, as known in the art, when being formed by CdS, Window layer 508 can be formed on the CIS base solar absorbed layer 506 by immersing by the aqueous chemical bath.Such chemical bath is formed and is generally included cadmium salt and/or zinc salt, (NH 2) 2CS (it generally is called as thiocarbamide), hydroxide agent and water.Exemplary salt comprises cadmium sulfate and zinc sulfate, and the example of hydroxide agent is ammonium hydroxide (NH 4OH).Bathe temperature usually in 60 to 85 ℃ scope.Usually, the time that the end face 516 of CIS base solar absorbed layer 506 is at first immersed the one section q.s of solution that contains salt (one or more) and hydroxide agent (for example, 1 minute) reach temperature required so that comprise the substrate 106 of CIS base solar absorbed layer 506.Use thiocarbamide then, and chemical reaction was taken place several minutes.The substrate 106 that comprises CIS base solar absorbed layer 506 is shifted out from chemical bath, and unreacted bath solution is rinsed out by the first surface 516 from solar absorbing layer 506.The thickness of the Window layer 508 that obtains is usually in 10 to 100nm scope.
[00182] in one embodiment, to connecting material (as solar absorbing layer 506/ Window layer 508 heterojunction) or separately solar absorbing layer 506 being carried out high temeperature chemistry and handle.It can be wet or dried CdCl that such high temeperature chemistry is handled 2The coating and to having CdCl 2Substrate use high temperature (as 350 to 450 ℃) 5 to 30 minutes subsequently.
[00183] in an embodiment, be under the pressure of about one to 20 millitorr in scope, use pulsed D C or RF sputter, on Window layer 508, form electric insulation layer.The nonrestrictive mode by example, on about 60 square centimeters target, the power supply of pulsed D C sputter can be in about 50 to 500 watts scope.The electric insulation layer that forms by such sputter can have scope for from 10 to 100nm thickness.
[00184] in an embodiment, be downforce in scope from about one to 20 millitorr, use pulsed D C sputter, can form contact layer 510 on Window layer 506 or the electric insulation layer.The nonrestrictive mode by example, on about 60 square centimeters target, the power supply of pulsed D C sputter can be in about 500 to 1500 watts scope.The typical membrane thickness degree of the last contact layer that forms by such sputter is the scope from 200 to 500nm.
[00185] in an embodiment of the invention, as shown in Figure 5, the CIS based photovoltaic device can be on common substrate 106 " monolithic integrated form ".Particularly, monolithic integrates array 102, and it has monolithic and is integrated in a plurality of photovoltaic device 502A, 502B, 502C on the substrate 106.Be appreciated that array 102 can comprise any amount of photovoltaic device that comprises a plurality of knots.
[00186] in Fig. 5, although all CIS base devices 502 have common substrate 106, by first line 604, each CIS based photovoltaic device 502 separates with one or more adjacent C IS based photovoltaic device 502 electricity.Each first line 604 can be filled with resistance filler 612, isolates two parts of for example given CIS based photovoltaic device 502 with electricity.In other words, each CIS based photovoltaic device 502 comprises the part of molybdenum layer (one or more layers) 504, solar absorbing layer 506, Window layer 508 and last contact layer 510, and wherein substrate 106 is that each device 502 is total.And each device 502 comprises, rules 604 down to first of substrate 106, and each first line, 604 usefulness resistance fillers filling, makes first line 604 can improve the electricity isolation between device 502.The nonrestrictive mode by example, resistance filler can be resistance printing ink or oxide.
[00187] in one embodiment, photovoltaic device 502A, 502B, 502C are electrically connected, and make electric current 610 Continuous Flow flow through photovoltaic device 502.As shown in Figure 5, electric current 610 can enter array 102 by terminals 608.In the execution mode shown in Fig. 5, electric current 610, flows along photovoltaic device 502A top through last contact layer 510 from terminals 608.Then, electric current 610 flow to molybdenum layer (one or more layers) 504 from last contact layer 510 via second line 602, and described second chemistry is to be used for forming the electric conducting material filling of contact layer 510.Then, electric current 610 molybdenum layer (one or more layers) 504 of flowing through arrives next photovoltaic device, i.e. photovoltaic device 502B.Then, electric current 610 flows to the last contact layer 510 of photovoltaic device 502B through CIS base solar absorbed layer 506 and Window layer 508 from molybdenum layer (one or more layers) 504.Electric current 610 continues mobile remainder through photovoltaic device 502B with its same way as in photovoltaic device 502A, flows through photovoltaic device 502C in the same manner then.Electric current finally withdraws from array 102 via another terminals 614.Although show photovoltaic device 502A, 502B, the 502C of series connection, be appreciated that photovoltaic device 502A, 502B, 502C can be by in parallel or can be series connection and combination in parallel at the execution mode shown in Fig. 5.
[00188] be the array 102 shown in the shop drawings 5, a series of line of interspersed above-mentioned electroless copper deposition operation and printing operation can be used to form a series of monolithic integrated photovoltaic devices 104 on the single part of substrate 106, thereby form array 102.
[00189] after molybdenum layer (one or more layers) 504, CIS base solar absorbed layer 506, the Window layer of choosing wantonly 508 and aforesaid other optional layer form, substrate 106 is proceeded sequence of operations usually, it is designed at first zoning, and series connects " being divided " zone of adjacency then.First line is operated all sedimentary deposits of scribing, is exposed uncoated naked substrate 106, thereby forms first line 604.This first line operation is divided into a plurality of independent parts with sedimentary deposit on function, thereby each part electricity is isolated.By the substrate 106 that is kept perfectly, various piece is held togather.Used ruling is the thing of design alternative, and wherein this paper preferable methods uses high power density laser to be realized.
[00190] second selectivity line operation is carried out in next-door neighbour's first line operation usually, to form second line 602.With first line, 604 contrasts, the end face 514 that second line 602 only is cut to molybdenum layer (one or more layers) 504, thereby molybdenum layer (one or more layers) 504 keeps complete under the firm sedimentation state condition.This second selectivity line operation forms second line 602, and it will filled with conductive oxide of selecting or material subsequently, and the conductive oxide of described selection or material are used to form contact layer 510.As shown in Figure 5, first line is extended down to substrate 106 604 times, and second line 602 only extends to molybdenum layer (one or more layers) 504.
[00191] be to prevent that the conductive oxide in last contact layer " is packed into " first line, and effective molybdenum layer 504, the first line 604 that connect adjacent division are again filled with insulator usually.Generally, this realizes that by the UV curable ink described UV curable ink is used and the simultaneous commercial self adaptation ink-jet dispensing head deposition of high power density laser.In optional step, electric insulation layer is formed on the Window layer 508, if perhaps Window layer 508 is not to form, electric insulation layer is formed on the CIS base solar absorbed layer 506.
[00192] then, after line, last contact layer 510 is formed up to three-dimensional end face 616.At last, the 3rd line 606 is cut.As seen in fig. 5, the 3rd line 606 extends to the end face 514 of molybdenum layer (one or more layers) 504.The 3rd line 606 also provides electricity to isolate, with the formation of the array 102 of finishing photovoltaic device 502A, 502B, 502C.
[00193] CIS based photovoltaic device 104 of the present invention can have the efficient up to 19%, and can surpass 19%.Though use substrate 106 of the present invention can realize efficient, but still need experiment to obtain to produce the process conditions of maximum efficiency up to 19%.
[00194] Yi Xia embodiment is used to illustrate the present invention, and is considered limitation of the scope of the invention never in any form.
Embodiment 1
The substrate of the siloxane layer that comprises the stainless steel foil layer and form by DowCorning FOX resin
[00195] on the rotary coating machine,, that Dow Corning 9-5101Hydrogen Silsesquioxane is resin-coated in 6 with 2000 commentaries on classics/per minutes (rpm) " * 6 " stainless steel foil layer last 30 second.The stainless steel foil layer is 430 stainless steels of 25 micron thickness, and can be from Marubeni Corporation, Tokyo, and Japan obtains.Resin on the stainless steel foil layer solidified 2 hours down at 200 ℃ in air dry oven, to form siloxane layer on the paper tinsel layer.The thickness of siloxane layer is about 1 micron.
Embodiment 2
The substrate of the siloxane layer that comprises the stainless steel foil layer and form by the hydrogenation polyorganosiloxane resin
[00196] becomes (H by cohydrolysis trichlorosilane and dichlorosilane, washing and hydrolytic condensation product to generate average group 2SiO 2/2) 0.29(HSiO 3/2) 0.71Resin, preparation hydrogenation polyorganosiloxane resin.This resin is coated on the stainless steel foil layer as described in embodiment 1.Resin on the stainless steel foil layer solidified 2 hours down at 200 ℃ in air dry oven, to form siloxane layer on the paper tinsel layer.
Embodiment 3
Be included in the manufacturing and the performance of CIGS (copper indium callium diselenide (CIGS)) photovoltaic device of the substrate of making among the embodiment 1
[00197] molybdenum is sputtered on the substrate of making among the embodiment 1, to form the molybdenum layer of about 0.5 micron thickness.Copper, indium and gallium under selenium atmosphere by coevaporation on molybdenum layer, to form CIS base solar absorbed layer, it has about two microns thickness.Then, CdS is deposited on the CIS base solar absorbed layer by wet type CBD bath process, forms Window layer, and it has the thickness of about 50nm.ITO is sputtered onto on this Window layer by RF, and to form contact layer, copper grid (copper grid) is evaporated to contact layer then.This battery performance detects under the AM1.5 illuminate condition, and measures 5 to 7% efficient.
Embodiment 4
Be included in the Computer-Assisted Design, Manufacture And Test of the CIS based photovoltaic device of the substrate of making among the embodiment 2
[00198] to make the CIS based photovoltaic device as embodiment 3 described same way as, it is included in the substrate of making among the embodiment 2.The CIS based photovoltaic device is tested under the same terms shown in embodiment 3.Measure 6 to 14% efficient.
Embodiment 5
The substrate of the siloxane layer that comprises the stainless steel foil layer and form by MP101 Crystal Coat resin
[00199] MP101 Crystal Coat resin is from SDC Coating Technologies, and Inc obtains.Resin is 31wt%.Resin is coated on the stainless steel foil layer, and with embodiment 1 described identical mode solidified coating.
Embodiment 6
The Computer-Assisted Design, Manufacture And Test of the CIS based photovoltaic device on the substrate of in embodiment 5, making
[00200], makes the CIS based photovoltaic device on the substrate of in embodiment 5, making with embodiment 3 described same way as.The CIS based photovoltaic device is tested under the same terms shown in embodiment 3.Measure 6 to 9% efficient.
[00201] the present invention is described in illustrational mode, and is appreciated that employed term is intended to have the character of descriptive words rather than restricted word.Apparently, because above-mentioned instruction, many modifications and variations of the present invention are possible.Therefore, be appreciated that except as specifically described that the present invention can put into practice within the scope of the claims.

Claims (20)

1. copper indium diselenide (CIS) based photovoltaic device (104), it comprises:
CIS base solar absorbed layer (506), it comprises copper, indium and selenium; With
Substrate (106), it comprises siloxane layer (306) and the metal foil layer (312) that is formed by silicone composition.
2. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said metal foil layer (312) is formed by the metal that is selected from stainless steel, titanium, covar, invar, tantalum, brass, niobium and their combination.
3. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said metal foil layer (312) has the thickness of 12.5 to 1000 μ m.
4. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said CIS base solar absorbed layer (506) further comprises the metal that is selected from gallium, aluminium, boron, tellurium, sulphur and their combination.
5. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition further is restricted to the hydrosilylation curable silicone compositions, and it comprises:
(A) organic siliconresin, it has silicon bonding alkenyl group or hydrogen bonding by silicon;
(B) organo-silicon compound, it has per molecule on average at least two silicon bonded hydrogen atoms or silicon bonding alkenyl group, and exists with the amount that is enough to solidify described organic siliconresin; With
(C) hydrosilylation catalysts of catalytic amount.
6. copper indium diselenide-based photovoltaic device according to claim 5 (104), wherein said organic siliconresin has following formula:
(R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z
R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, neither fatty family is unsaturated, R 2Be R 1, alkenyl group or hydrogen, w is from 0 to 0.9, x is from 0 to 0.9, y is from 0 to 0.99, z is from 0 to 0.85, w+x+y+z=1, and y+z/ (w+x+y+z) is from 0.1 to 0.99, and w+x/ (w+x+y+z) is from 0.01 to 0.9, and condition is that described organic siliconresin has on average at least two silicon bonding thiazolinyls of per molecule.
7. copper indium diselenide-based photovoltaic device according to claim 6 (104), wherein said organic siliconresin further is restricted to the modified rubber organic siliconresin, and it comprises the product of following material:
(A) have the described organic siliconresin of following formula:
(R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) zAnd
(D) (iii) at least a silicone rubber, it is selected from the rubber with following formula:
R 5R 1 2SiO (R 1R 5SiO) cSiR 1 2R 5With
R 1R 2 2SiO(R 2 2SiO) dSiR 2 2R 1，
Wherein c and d have 4 to 1000 value separately,
In the presence of described hydrosilylation catalysts (c) and
Randomly, in the presence of organic solvent, condition is when described organic siliconresin (A) has silicon bonding alkenyl group, (D) (iii) has silicon bonded hydrogen atom, and, (D) (iii) has silicon bonding thiazolinyl when described organic siliconresin (A) when having silicon bonded hydrogen atom.
8. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition is further defined to the condensation curable silicone compositions, and it comprises:
(A 2) organic siliconresin, it has silicon bonded hydroxy group or hydrolyzable groups at least two;
Randomly, (B 1) crosslinking agent, it has silicon bonding hydrolyzable groups; With
Randomly, (C 1) condensation catalyst of catalytic amount.
9. copper indium diselenide-based photovoltaic device according to claim 8 (104), wherein said organic siliconresin has following formula:
(R 1R 2 2SiO 1/2) w’(R 6 2SiO 2/2) x’(R 6SiO 3/2) y’(SiO 4/2) z’
R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, neither fatty family is unsaturated, R 6Be R 1,-H ,-OH or hydrolyzable groups, w ' is from 0 to 0.8, and x ' is from 0 to 0.95, and y ' is from 0 to 1, and z ' is from 0 to 0.99, w '+x '+y '+z '=1, condition is described organic siliconresin (A 2) per molecule has on average at least two silicon bonded hydrogen atoms, oh group or hydrolyzable groups.
10. copper indium diselenide-based photovoltaic device according to claim 8 (104), wherein said organic siliconresin has following formula:
(R 1R 6 2SiO 1/2) w’(R 6 2SiO 2/2) x’(R 6SiO 3/2) y’(SiO 4/2) z’
R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, neither fatty family is unsaturated, R 6Be R 1,-H ,-OH or hydrolyzable groups, w ' is from 0 to 0.8, and x ' is from 0 to 0.95, and y ' is from 0 to 1, and z ' is from 0 to 0.99, w '+x '+y '+z '=1, condition is described organic siliconresin (A 2) per molecule has on average at least two silicon bonded hydrogen atoms, oh group or hydrolyzable groups, wherein limits R 1SiO 3/2Unit and SiO 4/2The unit sum is greater than zero.
11. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition further is restricted to the condensation curable silicone compositions, and it comprises:
(A 3) the modified rubber organic siliconresin, it so prepares: be selected from following organo-silicon compound by making:
(i) organic siliconresin, it has formula (R 1R 6 2SiO 1/2) W '(R 6 2SiO 2/2) X '(R 6SiO 3/2) Y '(SiO 4/2) Z ',
(ii) the hydrolyzable parent of (i) and
(iii) silicone rubber, it has formula R 8 3SiO (R 1R 8SiO) mSiR 8 3
Water, (iv) condensation catalyst and (v) organic solvent in the presence of reaction, R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, neither fatty family is unsaturated, R 6Be R 1,-H ,-OH or hydrolyzable groups, R 8Be R 1Or hydrolyzable groups, m is from 2 to 1000, and w ' is from 0 to 0.8, and x ' is from 0 to 0.95, and y ' is from 0 to 1, z ' is from 0 to 0.99, w '+x '+y '+z '=1,
Randomly, (B 1) crosslinking agent, its have silicon bonding hydrolyzable groups and
Randomly, (C 1) condensation catalyst of catalytic amount.
12. copper indium diselenide-based photovoltaic device according to claim 8 (104), wherein said silicone composition further comprises the inorganic filler of particle form.
13. further being restricted to, copper indium diselenide-based photovoltaic device according to claim 12 (104), wherein said inorganic filler have the nano silicon particles of at least one overall dimension below about 200nm.
14. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition is further defined to the free radical curable silicone compositions.
15. copper indium diselenide-based photovoltaic device according to claim 14 (104), wherein said free radical curable silicone compositions comprises the organic siliconresin with following formula:
(R 1R 9 2SiO 1/2) w”(R 9 2SiO 2/2) x”(R 9SiO 3/2) y”(SiO 4/2) z”，
R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, neither fatty family is unsaturated; R 9Be R 1, alkenyl or alkynyl; W " be from 0 to 0.99; X " be from 0 to 0.99; Y " be from 0 to 0.99; Z " be from 0 to 0.85; And w "+x "+y "+z "=1.
16. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition comprise ring-type dihydro polysiloxanes, described ring-type dihydro polysiloxanes comprises H 2SiO 2/2The unit also has value range from 1,500 to 1,000,000 weight average molecular weight, and it at room temperature is a liquid.
17. copper indium diselenide-based photovoltaic device according to claim 1 (104), wherein said silicone composition comprises the hydrogenation polysiloxanes, and it has the siloxane unit molecular formula:
[H 2SiO 2/2] X " '[H 2SiO 3/2] Y " '[SiO 4/2] Z " ', x wherein " and ', y " ' and z " ' the expression molar fraction, 0.12≤x " '≤1.0,0≤y " '≤0.88,0≤z " '≤0.30, y " ' and z " ' be not 0 simultaneously, and x " '+y " '+z " '=1.
18. array (102), it comprises a plurality of copper indium diselenide-based photovoltaic devices according to claim 1 (104).
19. array according to claim 18 (102), wherein said CIS based photovoltaic device (104) is integrated on the described substrate (106) by monolithic.
20. make the method for copper indium diselenide-based photovoltaic device (104), it comprises step:
Substrate (106) is provided, and it comprises the siloxane layer (306) that is formed by silicone composition, and metal foil layer (312);
Go up the CIS base solar absorbed layer (506) that formation comprises copper, indium and selenium at described substrate (106).
CN2007800223277A 2006-04-18 2007-04-18 Copper indium selenide-based photovoltaic device and method of making same Expired - Fee Related CN101473447B (en)

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