CN101421100B - Metal foil substrates coated with condensation cured silicon resin compositions - Google Patents

Metal foil substrates coated with condensation cured silicon resin compositions Download PDF

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CN101421100B
CN101421100B CN2007800135488A CN200780013548A CN101421100B CN 101421100 B CN101421100 B CN 101421100B CN 2007800135488 A CN2007800135488 A CN 2007800135488A CN 200780013548 A CN200780013548 A CN 200780013548A CN 101421100 B CN101421100 B CN 101421100B
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coating
organic siliconresin
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CN101421100A (en
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T·巴纳德
伊藤真树
D·卡佐利斯
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DuPont Toray Specialty Materials KK
Dow Silicones Corp
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Dow Corning Toray Co Ltd
Dow Corning Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A product comprises at least one metal foil substrate and a coating on at least one part on one side of the metal foil substrate. In which, the coating comprises (a) condensation solidified silicone resin composition and (b) silicon dioxide nano particulates.

Description

Metal foil substrate with condensation cured organosilicon resin composition coating
The cross reference of related application
According to 35.U.S.C. § 119 (e), the application requires the rights and interests of the U.S. Provisional Application sequence number 60/875995 of submitting on December 20th, 2006 and the U.S. Provisional Application sequence number 60/792770 of submitting on April 18th, 2006.U.S. Provisional Application sequence number 60/875995 and U.S. Provisional Application sequence number 60/792770 are introduced by reference at this.
Background technology
The present invention relates to a kind of manufacturing goods, it comprises (i) at least one metal foil substrate; (ii) coating at least a portion of at least one side of this metal foil substrate, wherein this coating comprises (a) condensation cured organosilicon resin composition and (b) nano SiO 2 particle.It is maximum 4 microns very thick flawless coatings that the organic siliconresin of condensation curable and the unique combination of nano SiO 2 particle provide thickness in the substrate such as can tolerating 700 ℃ the stainless steel foil of temperature.These substrates can be used for two copper indium gallium selenide (CIGS) solar cell.These substrates also can be used as substrates for thin film batteries.
The invention summary
Comprise (i) at least one metal foil substrate; (ii) the manufacturing goods of the coating at least a portion of at least one side of this metal foil substrate, wherein this coating comprises (a) condensation cured organosilicon resin composition and (b) nano SiO 2 particle.
Detailed Description Of The Invention
It is 0.5 micron-1000 microns that metal foil substrate of the present invention typically is thickness range, perhaps 1-500 micron, the perhaps sheet metal of 10-200 micron.The material that is used for paper tinsel can be any metal and alloy thereof.Can by cast, extrude, roll-in and any other available technology prepare them.Surface quality can be the same with casting, with extrude the same, with the same of roll-in or with polishing.Can or adopt any other technology known in the art to realize polishing by electrochemistry, machinery, chemical-mechanical.The physical form of metal forming can be the coiled material of limited length not, perhaps is the cutting sheet-form of certain size.Metal forming can further comprise the surface layer of composition that is different from body, for example oxide skin(coating) of one of body composition interior element.Can for example introduce superficial layer by thermal oxide.Its thickness range can be that several dusts are to several microns.Superficial layer can be fine and close or porous.The instantiation of metal forming can include but not limited to Copper Foil, aluminium foil, molybdenum foil, titanium foil, goldleaf, silver foil, carbon steel paper tinsel, stainless steel foil, nickel foil, zinc paper tinsel or lead foil.
Coating comprises (a) condensation cured organosilicon resin composition and (b) nano SiO 2 particle.Condensation cured organosilicon resin composition typically comprises the cured product of silicon composition, described silicon composition comprise (A) have with the hydrogen atom of silicon bonding, with the hydroxyl of silicon bonding or with the organic siliconresin of the condensation curable of the hydrolyzable groups of silicon bonding, and randomly (B) has and the crosslinking agent of the hydrolyzable groups of silicon bonding and (C) condensation catalyst randomly.Can by comprise solidify contain (A), randomly (B) and randomly the method for the silicon composition of (C) obtain this cured product." curing " that defines refers to that silicon composition of the present invention (it can be its component part, mixture, solution or blend) has been exposed to air at room temperature herein, for example heating under 50-450 ℃ the temperature or under 100-200 ℃ temperature under the rising temperature, perhaps be exposed under ultraviolet light, electron beam or the microwave.Herein the definition " curing " refer to silicon composition of the present invention (it can be its component part, mixture, solution or blend) just be exposed to air at room temperature, at elevated temperatures (for example under 50-450 ℃ temperature, perhaps under 100-200 ℃ temperature) heating, perhaps just be exposed under ultraviolet light, electron beam or the microwave.Can use any known conventional equipment, for example be set under the 50-450 ℃ of temperature or in the air circulation oven under 100-200 ℃ temperature by placing with silicon composition or with the glass of silicon composition coating, thereby heat.
The organic siliconresin of condensation curable (A) contains R typically 1SiO 3/2Unit (being the T unit) and/or SiO 4/2Unit (being the Q unit) is in conjunction with R 1R 2 2SiO 1/2Unit (being the M unit) and/or R 2 2SiO 2/2The copolymer of unit (being the D unit), wherein R 1C 1-C 10Alkyl or C 1-C 10The alkyl that halogen replaces, wherein the two does not all contain aliphatic unsaturated bond, R 2R 1,-H ,-OH or hydrolyzable groups, condition is R 1SiO 3/2Unit and SiO 4/2The unit sum greater than 0 and every a part contain at least two hydrogen atoms with the silicon bonding, at least two hydroxyls with the silicon bonding, or at least two hydrolyzable groups with the silicon bonding.For example, organic siliconresin can be DT resin, MT resin, MDT resin, DTQ resin, MTQ resin and MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.Term as used herein " does not contain aliphatic unsaturated bond " and refers to that the alkyl that alkyl or halogen replace does not contain aliphatic carbon-to-carbon double bond or carbon-to-carbon triple bond.
R 1The C of expression 1-C 10Alkyl and C 1-C 10The alkyl that halogen replaces more typically has 1-6 carbon atom.Contain the acyclic hydrocarbon group of at least 3 carbon atoms and the alkyl of halogen replacement and can have branching or nonbranched structure.R 1The example of the alkyl of expression includes but not limited to: alkyl, for example 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, for example cyclopenta, cyclohexyl and methylcyclohexyl; Aryl, for example phenyl and naphthyl; Alkaryl, for example tolyl and xylyl; And aralkyl, for example benzyl and phenethyl.R 1The example of the alkyl that the halogen of expression replaces 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.
According to an embodiment, the chemical formula of the organic siliconresin of condensation curable (A) is:
(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 1As defined above and exemplify R 2R 1,-H ,-OH or hydrolyzable groups, and w, x, y and z are molar fractions, and the every a part of organic siliconresin (A) on average has at least two hydrogen atoms with the silicon bonding, at least two hydroxyls with the silicon bonding, or at least two with silicon bonding hydrolyzable groups.More specifically, the numerical value of subscript w typically is 0-0.8, perhaps 0.02-0.75, perhaps 0.05-0.3.The numerical value of subscript x typically is 0-0.6, perhaps 0-0.45, perhaps 0-0.25.The numerical value of y typically is 0-0.99, perhaps 0.25-0.8, perhaps 0.5-0.8.The numerical value of subscript z typically is 0-0.35, perhaps 0-0.25, perhaps 0-0.15.In addition, the y+z sum is greater than 0 and typically be 0.2-0.99, perhaps 0.5-0.95, perhaps 0.65-0.9.In addition, the w+x sum can be 0, singly typically is 0.01-0.80, perhaps 0.05-0.5, perhaps 0.1-0.35.
Term as used herein " hydrolyzable groups " refer in the situation that do not exist catalyst, from room temperature (～23 ℃ ± 2 ℃) under any temperature of 100 ℃, for example form silanol (Si-OH) base with group and the water reaction of silicon bonding in 30 minutes at several clocks.R 2The example of hydrolyzable groups of expression includes but not limited to-Cl ,-Br ,-OR 3,-OCH 2CH 2OR 3, CH 3C (=O) O-, Et (Me) C=N-O-, CH 3C (=O) N (CH 3)-and-0NH 2, R wherein 3C 1-C 8Alkyl or C 1-C 8The alkyl that halogen replaces.
R 3The alkyl that the alkyl of expression and halogen replace typically has 1-8 carbon atom, perhaps 3-6 carbon atom.Contain the acyclic hydrocarbon group of at least 3 carbon atoms and the alkyl of halogen replacement and can have branching or nonbranched structure.R 3The example of alkyl of expression includes but not limited to the not alkyl of branching and branching, for example 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, for example cyclopenta, cyclohexyl and methylcyclohexyl; Phenyl; Alkaryl, for example tolyl and xylyl; Aralkyl, for example benzyl and phenethyl; Alkenyl, for example vinyl, pi-allyl and acrylic; Aromatic yl alkenyl, for example styryl and alkynyl, for example acetenyl and propinyl.R 3The example of the alkyl that the halogen of expression replaces includes but not limited to 3,3,3-trifluoro propyl, 3-chloropropyl, chlorphenyl and dichlorophenyl.
Typically, the R of 1-30mo l% or 1-15mo l% in organic siliconresin 2Base is hydrogen, hydroxyl or hydrolyzable groups.The R of mol% as used herein 2Base is defined as in the organic siliconresin (A) at condensation curable and the molal quantity of the group of silicon bonding and R in the organic siliconresin (A) of condensation curable 2The ratio of total mole number multiply by 100.
The example of the organic siliconresin of condensation curable (A) includes 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)(HO)SiO 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, and
(Ph(HO)SiO 2/2) x(PhSiO 3/2) y(MeSiO 3/2) y(PhMeSiO 2/2) x
Wherein Me is methyl, and Ph is phenyl, and wherein w, x, y and z as above define, and the numerical value of subscript y is so that the number-average molecular weight of organic siliconresin is 500-50,000.Sequence of unit in aforementioned chemical formula is never thought and is limited the scope of the invention.
The example of the organic siliconresin of condensation curable (A) includes 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 methyl, and Ph is phenyl, and the numerical value subscript outside bracket represents molar fraction.Sequence of unit in aforementioned chemical formula is never thought and is limited the scope of the invention.
As mentioned above, the number-average molecular weight (Mn) of the organic siliconresin (A) of the condensation curable of usefulness formula (I) expression is 500-50,000.Perhaps, the Mn of the organic siliconresin of condensation curable (A) can be 500-10,000, and perhaps 800-3000 wherein by gel permeation chromatography, uses refractive index detector and organic siliconresin (MQ) reference material, measures this molecular weight.
The viscosity of the organic siliconresin of condensation curable (A) under 25 ℃ typically is 0.01Pa.s to solid, perhaps 0.1-10,000Pa.s, perhaps 1-100Pa.s.Organic siliconresin (A) with the condensation curable of formula (V) expression typically comprises less than 10% (w/w), and perhaps less than 5% (w/w), perhaps less than 2% (w/w) and the hydroxyl silicon bonding, this passes through 29Si NMR measures.
Preparation method with the organic siliconresin (A) of the condensation curable of formula (I) expression is known in the art; Many these resins are commercially available.Typically by at the organic solvent organic siliconresin (A) of the condensation curable of the suitable mixture standby mode processed (I) of cohydrolysis chlorosilane precursor expression in the toluene for example.For example, be R by cohydrolysis chemical formula in toluene 1R 2 2The first compound of SiCl and chemical formula are R 1SiCl 3The second compound, preparation contains R 1R 2 2SiO 1/2Unit and R 2SiO 3/2The organic siliconresin of unit, wherein R 1And R 2As defined above and exemplify, to form aqueous hydrochloric acid and organic siliconresin (it is the hydrolysate of the first and second compounds).Separate aqueous hydrochloric acid and organic siliconresin, wash this organic siliconresin with water removing residual acid, and this organic siliconresin of heating arrives required viscosity with " condensing " this organic siliconresin in the presence of the condensation catalyst of gentleness.
Optionally, can in organic solvent, further process organic siliconresin with condensation catalyst, with the content of reduction with the hydroxyl of silicon bonding.Perhaps, but cohydrolysis contain except chlorine for example-Br ,-I ,-OCH 3,-OC (O) CH 3,-N (CH 3) 2, NHCOCH 3With-SCH 3And so on the first or second compound of hydrolyzable groups, form organic siliconresin.The performance of this organic siliconresin depends on the type of the first and second compounds, the mol ratio of the first and second compounds, condensation level, and processing conditions.
In another embodiment, the organic siliconresin of condensation curable (A) can be at water, (iv) condensation catalyst, and (v) organic solvent exists down, being selected from (i) chemical formula by making is (R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 1SiO 3/2) y(SiO 4/2) zOrganic siliconresin, and (ii) hydrolysable precursors of (i), and (iii) chemical formula is R 4 3SiO (R 1R 4SiO) mSiR 4 3Silicon rubber in the organic siliconresin of modified rubber of organic group silicon compound reaction preparation, R wherein 1And R 2As defined above and exemplify R 4R 1Or hydrolyzable groups, m is 2-1000, perhaps 4-500, perhaps 8-400, with w, x, y and z as defined above and exemplify, and the every a part of organic siliconresin (i) on average has at least two hydroxyl or hydrolyzable groups with the silicon bonding, the every a part of silicon rubber (iii) on average has at least two hydrolyzable groups with the silicon bonding, with in silicon rubber (iii) with the hydrolyzable groups of silicon bonding and organic siliconresin (i) in and the hydroxyl of silicon bonding or the mol ratio of hydrolyzable groups be 0.01-1.5, perhaps 0.05-0.8, perhaps 0.2-0.5.Typically, the R of 1-30mol% or 1-15mol% in organic siliconresin 2Base is hydrogen, hydroxyl or hydrolyzable groups.
The number-average molecular weight (Mn) of organic siliconresin (i) typically is 500-50, and 000, perhaps 500-10,000, perhaps 800-3000 wherein passes through gel permeation chromatography, refractive index detector and organic siliconresin (MQ) reference material is measured this molecular weight.
Be suitable for including but not limited to have as the instantiation of the organic siliconresin of organic siliconresin (i) 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, and
(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 methyl, and Ph is phenyl, wherein x, y and z as defined above, and the numerical value of subscript y is so that the number-average molecular weight of this organic siliconresin is 500-50,000.The order of unit is never thought and is limited the scope of the invention in aforementioned chemical formula.
Be suitable for including but not limited to have as the instantiation of the organic siliconresin of organic siliconresin (i) 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) 0.05With
(CH 3COOSiO 3/2) 0.06(PhSiO 3/2) 0.3(SiO 4/2) 0.04(Me 2SiO 2/2) 02(Ph 2SiO 2/2) 0.4
Wherein Me is methyl, and Ph is phenyl, and the numerical value subscript outside bracket represents molar fraction.Sequence of unit in aforementioned chemical formula is never thought and is limited the scope of the invention.Organic siliconresin (i) can be single organic siliconresin or the mixture that contains two or more different organic siliconresins, the chemical formula that wherein has separately regulation.Organic siliconresin (i) can be single organic siliconresin or the mixture that contains two or more different organic siliconresins, the chemical formula that wherein has separately regulation.
Term as used herein " hydrolysable precursors " refers to have the silane of hydrolyzable groups, and it is suitable for as parent material (precursor) for preparation organic siliconresin (i).The available chemical formula R of hydrolysable precursors (ii) 1R 4 2SiX, R 4 2SiX 2, R 4SiX 3And SiX 4Expression, wherein R 1, R 8With X as defined above and exemplify.
The instantiation of hydrolysable precursors (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 methyl, Et is ethyl, and Ph is phenyl.
The instantiation of silicon rubber (iii) includes but not limited to have the silicon 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 that methyl and Et are ethyls.
Typically under the temperature from room temperature (～23 ℃ ± 2 ℃) to 180 ℃ or room temperature to 100 ℃, react.Reaction time is depended on several factors, comprising structure and the temperature of organic siliconresin (i) and silicon rubber (iii).Typically allow each component reaction to be enough to finish the time period of condensation reaction.This means allow each component reaction until at least 40mol% or at least 65mol% or at least the hydrolyzable groups with the silicon bonding that is present at first in the silicon rubber (iii) of 90mol% in condensation reaction, be consumed, this passes through 29SiNMR spectrum is measured.Under 100 ℃ temperature, the reaction time typically is 1-30 hour in room temperature (～23 ℃ ± 2 ℃).Optimum reacting time can be measured by normal experiment.
Below will describe in further detail suitable condensation catalyst (iv), and in the organic siliconresin part of above modified rubber, describe suitable organic solvent (v).The concentration of condensation catalyst (iv) is enough to the condensation reaction of catalysis organic siliconresin (i) and silicon rubber (iii).Typically, based on the weight of organic siliconresin (i), the concentration of condensation catalyst (iv) is 0.01-5% (w/w), perhaps 0.01-3% (w/w), perhaps 0.05-2.5% (w/w).Based on the gross weight of reactant mixture, the concentration of organic solvent (v) typically is 10-95% (w/w), perhaps 20-85% (w/w), perhaps 50-80% (w/w).
The concentration of water depends on R in the organic group silicon compound in the reactant mixture 8In the character of base and the silicon rubber with the character of the hydrolyzable groups of silicon bonding.When organic siliconresin (i) when containing hydrolyzable groups, the concentration of water is enough to carry out the hydrolysis of organic siliconresin (i) and the interior hydrolyzable groups of silicon rubber (iii).For example, the concentration of water typically is the organic siliconresin (i) of 0.01-3mol or 0.05-1mol/mol combination and the hydrolyzable groups in the silicon rubber (iii).When organic siliconresin (i) when not containing hydrolyzable groups, in reactant mixture, only require for example water of 100ppm of trace.Trace water is present in reactant and/or the solvent usually.
Component (b) nano SiO 2 particle can be to have less than about any earth silicon material of at least one physical size of 200nm (for example, particle diameter, bed thickness).A kind of nano SiO 2 particle of the form that is particularly useful is the pyrogenic silica nano particle.The example of useful commercially available unmodified silica parent material comprises the colloidal silica of nano-scale, its with product grade NALCO1040,1042,1050,1060,2326,2327 and 2329 colloidal silicas available from Nalco Chemical Co., Naperville, Illinois is available from Degussa's
Figure G2007800135488D00081
, available from DuPont's , available from NissanChemical's
Figure G2007800135488D00083
, available from Bayer's
Figure G2007800135488D00084
, or available from Fuji SilysiaChemical's
Figure G2007800135488D00085
Suitable pyrogenic silica comprises the product that for example is available commercially from DeGussaAG (Hanau, Germany) with the trade mark " AerosilseriesOX50 ", and production code member-130 ,-150 and-200.Pyrogenic silica also is available commercially from CabotCorp. with Bade trade mark CABO-SPERSE2095, CAB-O-SPERSEA105 and CAB-O-SILM5, Tuscola, I.Persons skilled in the art will recognize that different known methods can obtain the particle of different grain size, different physical characteristics and different compositions, for example flame-hydrolysis (Aerosil-Process), plasma process, electric arc technique and be used for hot wall reactor technique or the ion-exchange process of gas phase or solid phase reaction and be used for the depositing technology of solution-based reaction.
Nano SiO 2 particle can be the colloidal dispersion form.Therefore nano SiO 2 particle for example can be dispersed in the following polar solvent: methyl alcohol, ethanol, isopropyl alcohol (IPA), ketone is methyl iso-butyl ketone (MIBK) for example, water, acetic acid, two pure and mild triols are propane diols for example, the 2-methyl isophthalic acid, ammediol HOCH2CH (CH3) CH20H, 1,2-hexylene glycol CH3 (CH2) 3CH (OH) CH20H and glycerine, glyceride is glycerol triacetate (glyceryl triacetate) for example, glycerin tripropionate (glyceryl tripropanoate) and glycerin tributyrate (tributyrin), with polyglycols for example polyethylene glycol and polypropylene glycol, especially PPG-14 butyl ether C 4Hg (OCH (CH 3) CH 2) 14OH.
The particle size range of silica typically is the 1-1000 nanometer, perhaps 1-100 nanometer, perhaps 5-30 nanometer.Nano SiO 2 particle can be the nano SiO 2 particle of single type or the mixture that contains at least two kinds of dissimilar nano SiO 2 particles.Known nano SiO 2 particle can be pure silica, and perhaps they can contain a certain amount of impurity, for example A l 2O 3, ZnO and/or cation, for example Na +, K ++, Ca ++, Mg ++Deng.
Based on the gross weight of silicon composition, the concentration of nano SiO 2 particle typically is 0.0001-99wt%, perhaps 0.001-75wt%, perhaps 10-65wt%, perhaps 5-50wt%, perhaps 20-40wt%.Silicon composition can be the single part composition in single part, described single part composition comprises the silicon composition of the organic siliconresin that contains condensation curable, with any optional composition, and nano SiO 2 particle, or many parts composition, described many parts composition comprises these components in two or more parts.
Can be by at ambient temperature, have or organic solvent-free auxiliary lower, in conjunction with the curable organic siliconresin of condensation, nano SiO 2 particle, and any optional composition prepare single part silicon composition with described ratio.In addition, can by in every part in conjunction with each component, preparation many parts silicon composition.But also original position preparation of silicon composition of the present invention, namely nano SiO 2 particle can add in the technical process of the organic siliconresin for preparing above-described condensation curable.Can be by any technology known in the art, for example grinding, blend and stirring are intermittently or with continuous processing to realize mixing.
The silicon composition that contains the organic siliconresin (A) of at least a condensation curable can further comprise crosslinking agent (C).The chemical formula of crosslinking agent (C) can be R 5 qSiX 4-q, R wherein 5C 1-C 8Alkyl or C 1-C 8The alkyl that halogen replaces, X is hydrolyzable groups, and q is 0 or 1.R 5The hydrolyzable groups that the alkyl that the alkyl of expression and halogen replace and X represent as mentioned above and exemplify.
The instantiation of crosslinking agent (C) includes but not limited to alkoxy silane, for example 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) 4Organic group acetoxylsilane, for example CH 3Si (OCOCH 3) 3, CH 3CH 2Si (OCOCH 3) 3And CH 2=CHSi (OCOCH 3) 3Organic group imino group TMOS, for example 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 acetamido silane, for example CH 3Si[NHC (=O) CH 3] 3And C 6H 5Si[NHC (=O) CH 3] 3Amino silane, for example CH 3Si[NH (s-C 4H 9)] 3And CH 3Si (NHC 6H 11) 3With organic group amino oxygen base silane.
Crosslinking agent (C) can be independent silane or the mixture of two or more different silane, wherein separately as mentioned above.In addition, the method for the silane of preparation trifunctional and four senses is well-known in the art, and many these silane are commercially available.
If exist, the concentration of crosslinking agent (C) in silicon composition is enough to solidify the organic siliconresin of (crosslinked) this condensation curable.The definite consumption of crosslinking agent (C) depends on required state of cure, and it increases with the ratio of the molal quantity of hydrogen atom, hydroxyl or the hydrolyzable groups of and silicon bonding interior with the organic siliconresin (A) of condensation curable with the molal quantity of the hydrolyzable groups of silicon bonding in the crosslinking agent (C) usually.Typically, the concentration of crosslinking agent (C) be enough to provide the hydrolyzable groups/mol of 0.2-4mol and silicon bonding in the organic siliconresin (A) of condensation curable with hydrogen atom, hydroxyl or hydrolyzable groups the silicon bonding.The optimum amount of crosslinking agent (C) can easily be determined by normal experiment.
Condensation catalyst (D) can be typically to promote to form the employed any condensation catalyst of Si-O-Si key with hydroxyl (silanol) condensation of silicon bonding.The example of condensation catalyst includes but not limited to the complex compound of amine and lead, tin, zinc and iron and carboxylic acid.Especially, condensation catalyst (D) can be selected from: tin (II) and tin (IV) compound, for example two tin laurates, two tin octoates and tetrabutyltin; And titanium compound, for example four butanols titaniums.
If exist, based on the gross weight of the organic siliconresin (A) of condensation curable, the concentration of condensation catalyst (D) typically is 0.1-10% (w/w), perhaps 0.5-5% (w/w), perhaps 1-3% (w/w).
When silicon composition comprised condensation catalyst (D), silicon composition typically was two parts composition, and wherein the organic siliconresin of condensation curable (A) and condensation catalyst (D) are in the part of separating.
The silicon composition that contains the organic siliconresin of at least a condensation curable of the present invention can comprise extra composition.The example of extra composition includes but not limited to: adhesion promotor, for example adhesion promotor of instruction in United States Patent(USP) Nos. 4087585 and 5194649; Dyestuff; Pigment; Antioxidant; Heat stabilizer; The UV stabilizing agent; Fire retardant; The control additive flows; And diluent, for example organic solvent and reactive diluent.
Applying above-described silicon composition can be any common method that applies a coating on the solid substrate to the method on the metal foil substrate, and for example spin coating, blade coating, flow coat, spraying, brushing, japanning, curtain coating, dip-coating, rod are coated with, scraper plate is coated with, air knife blade coating, intaglio plate coating, forward roller coating and inverse roller coating, slit and extrusion coated, sliding being coated with and curtain coating.As mentioned above, before solidifying or silicon composition after the solid, silicon composition can be coated on the substrate of glass.
At least a portion metal foil substrate must be coated with above-described silicon composition, yet, typically, on the even blend paint metal foil substrate with silicon composition, so that the conforming layer of distribution silicon composition on metal foil substrate, and typically use all obtainable surfaces of silicon composition coated glass substrate.Also think, by the present invention, the both sides of available above-described silicon composition coating metal paper tinsel substrate.The thickness of the organosilicon resin composition of the curing on metal foil substrate typically is the 0.010-20 micron, perhaps 0.050-10 micron, perhaps 0.100-5 micron.
Perhaps, also can use the adhesive that can be used for any routine of bonding coat on the solid substrate, will contain the coating adhesion of above-described silicon composition on metal foil substrate.
Embodiment
Comprise that following embodiment is with explanation the preferred embodiments of the invention.It will be understood by those of skill in the art that disclosed technology represents the good technology in practice of the present invention that the inventor finds in following examples, therefore can be considered the preference pattern that consists of practice.Yet, it will be understood by those skilled in the art that in view of disclosure of the present invention, can in the situation that not break away from the spirit and scope of the present invention, in disclosed specific embodiments, make many variations, and still obtain same or similar result.All percentages are in wt%.
Embodiment 1
In the 500ml three neck round-bottomed flasks of being furnished with mechanical agitator and thermometer, introduce the chilled mixture IPA-ST (available from NissanChemical) of 200g colloidal silica in isopropyl alcohol, and add the 28g deionized water.Stir this mixture and further be quenched to 2 ℃ with ice-water bath.Add 70.72g MTMS and 3.48g acetic acid and hydrolysis.Stirred this mixture other 3.5 hours.Then remove ice-water bath and allow mixture to be warming to room temperature.After being warming to room temperature, stirred the mixture 14 hours, produce final resin.Final resin solution is translucent and solids content is 24.5wt%, and this by measuring at 150 ℃ of lower heating 1g samples in 1 hour.The average composition of the organic siliconresin of condensation curable is ((Me (i-PrO) SiO 2/2) 0.10(MeSiO 3/2) 0.39(SiO 4/2) 0.50), wherein i-PrO represents isopropoxy, and (SiO 4/2) 0.50For the nuclear particle form in resin structure and contain in a small amount cation Na for example +
100 micron thick and the 200mm coiled material of 304 wide type stainless steel foils is provided, and this stainless steel foil is by Nippon Kinzoku production and by the Marubeni-Itochu retail.From this coiled material, cut the sheet of 150mm * 200mm, and flatly be layered on the experimental bench desktop.Adopt adhesion line (bound wire) drawdown rod #18, with embodiment 1) in the resin solution of preparation be applied on the top side of stainless steel foil.Stainless steel foil by will coating placed in the fume hood empty dry coating 1 hour.The sheet that then will be coated with places in the baking oven, to be cured by following temperature sequence: 2 ℃/min to 150 ℃, 150 ℃/1 hour, close baking oven to cooling.Smooth and the flawless of the resin coating film of the curing on stainless steel foil.
Embodiment 2
According to the sheet of same size that is coated with and solidifies the stainless steel foil of same type with the described identical mode of embodiment 1, difference is the coating that applies the resin of preparation among the thicker embodiment 1 with #32 adhesion line drawdown rod.The resin coating film of the curing on stainless steel foil is smooth and flawless also.
Embodiment 3
According to the sheet of same size that is coated with and solidifies the stainless steel foil of same type with the described identical mode of embodiment 1, difference be with #55 adhesion line drawdown rod apply in addition thicker embodiment 1 in the coating of resin of preparation.The resin-coated film of the curing on stainless steel foil is smooth and flawless also.
Embodiment 4
The aluminum foil coiled material of 20 micron thick is available from Pactiv Corporation.Be coated with similarly and solidify its small pieces.Again obtain smooth and flawless coating.
Embodiment 5
The coiled material of 430 type stainless steel foils of wide and 25 micron thick of 300mm is also available from Marubenin-Itochu Steel, Inc..Adopt the intaglio plate spreader and have the groove of 45BCM at coiled material, with a side of identical resin-coated stainless steel foil, and by being set in 4 feet long IR stove curing under 300 ℃.Linear velocity is 0.5 feet per minute clock.Coating layer thickness is approximately 3 microns, and on 25 microns * 25 microns measurement area, the r.m.s. roughness of coating surface (RMS) is 1.55nm.Under 600 ℃, heat treatment coating in nitrogen does not have crackle to form.

Claims (5)

1. the metal forming of a coating is made goods, comprise that (i) at least one thickness is the metal foil substrate of 10-200 μ m and (ii) coating at least a portion of at least one side of this metal foil substrate, wherein this coating comprises (a) condensation cured organosilicon resin composition and (b) nano SiO 2 particle; Wherein condensation cured organosilicon resin composition comprise the organic siliconresin that contains (A) condensation curable, randomly (B) crosslinking agent and randomly (C) be used for promoting hydroxyl condensation with the silicon bonding to form the cured product of silicon composition of the condensation catalyst of Si-0-Si key; Wherein (A) is the organic siliconresin with following formula:
(R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 1SiO 3/2) y(SiO 4/2) z
R wherein 1C 1-C 10Alkyl or C 1-C 10The alkyl that halogen replaces, wherein the two does not all contain aliphatic unsaturated bond, R 2R 1,-H ,-OH or hydrolyzable groups, and the numerical value of w is 0-0.8, the numerical value of x is 0-0.6, the numerical value of y is 0-0.99, the numerical value of z is 0-0.35, the y+z sum is 0.2-0.99, and the w+x sum is 0 or 0.01-0.80, condition be the every a part of organic siliconresin (A) on average have at least two with the hydroxyl of the hydrogen atom of silicon bonding or at least two and silicon bonding or at least two hydrolyzable groups with the silicon bonding; With
(B) be that chemical formula is R 7 qSiX 4-qCrosslinking agent, R wherein 7C 1-C 8Alkyl or C 1-C 8The alkyl that halogen replaces, X is hydrolyzable groups, and q is 0 or 1.
2. the metal forming of the coating of claim 1 is made goods, and wherein (A) is that its chemical formula is selected from following organic siliconresin:
(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)(HO)SiO 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) xOr
(Ph(HO)SiO 2/2) x(PhSiO 3/2) y(MeSiO 3/2) y(PhMeSiO 2/2) x
Wherein Me is methyl, and Ph is phenyl, wherein w, x, y and z as defined above, and the numerical value of subscript y is so that the number-average molecular weight of organic siliconresin is 500-50,000; With
(B) be selected from 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) 4, CH 3Si (OCOCH 3) 3, CH 3CH 2Si (OCOCH 3) 3, CH 2=CHSi (OCOCH 3) 3, CH 3Si[O-N=C (CH 3) CH 2CH 3] 3, Si[O-N=C (CH 3) CH 2CH 3] 4, CH 2=CHSi[O-N=C (CH 3) CH 2CH 3] 3CH 3Si[NHC (=O) CH 3] 3, C 6H 5Si[NHC (=O) CH 3] 3, CH 3Si[NH (S-C 4H 9)] 3Or CH 3Si (NHC 6H 11) 3
3. the metal forming of the coating of claim 1 is made goods, and wherein R1 is methyl, and w is that 0, x is 0, and the numerical value of z is 0-0.15.
4. the metal forming of a coating is made goods, comprise that (i) at least one thickness is the metal foil substrate of 10-200 μ m and (ii) coating at least a portion of at least one side of this metal foil substrate, wherein this coating comprises (a) condensation cured organosilicon resin composition and (b) nano SiO 2 particle, wherein adds nano SiO 2 particle in preparation is included in the technical process of organic siliconresin of the condensation curable in the condensation cured organosilicon resin composition.
5. the metal forming of a coating is made goods, comprise (i) at least one metal foil substrate and (ii) coating at least a portion of at least one side of this metal foil substrate, wherein this coating comprises that average composition is ((Me (i-Pro) SiO 2/2) 0.10(MeSiO 3/2) 0.39(SiO 4/2) 0.50) the organic siliconresin of condensation curable, wherein i-Pro represents isopropoxy, and (SiO 4/2) 0.50For the nuclear particle form in resin structure and contain in a small amount cation.
CN2007800135488A 2006-04-18 2007-04-18 Metal foil substrates coated with condensation cured silicon resin compositions Expired - Fee Related CN101421100B (en)

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