CA2016833A1 - Method of treating fibrous materials - Google Patents
Method of treating fibrous materialsInfo
- Publication number
- CA2016833A1 CA2016833A1 CA 2016833 CA2016833A CA2016833A1 CA 2016833 A1 CA2016833 A1 CA 2016833A1 CA 2016833 CA2016833 CA 2016833 CA 2016833 A CA2016833 A CA 2016833A CA 2016833 A1 CA2016833 A1 CA 2016833A1
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- group
- reaction product
- amine groups
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Silicon Polymers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Abstract of the Invention A method of treating fibrous materials comprises applying a composition comprising as sole amine containing organosilicon compound the reaction product of an organopolysiloxane having
Description
- 2 ~
MET~OD OF TREATING FI~ROUS MATERIALS
This invention relates to a method o treating fibrous materials and more specifically to a method of treatir)g textile materials.
Wi.th the expression fibrous materials is meant fibres o syr-thet;c or natura].ly occurring materi.als, for example wool, cotton, polyester, carbon and blends of these. The inverltion relates to the treatment of the fi.bres as such as well as to th~ treatment of fabrics or textiles incorporating the fibres.
It is known to treat fibrous materials wi.th composi.-tions comprising amine-containing silicon compounds for imparti,ng desirable properties, e.g. softness, water repellency, lubricity ~ncl crease resistance thereto. G.B.
patent speci,fication 1 491 747 for example provides a compc-sitioll or treatmtrlt of synthttic fibres which comprises 1 part o certain aminosilanes and 1 to 20 parts of certain epoxysiloxanes. G.B. patent specification 1 296 136 provides a process or the treatn)erlt of synthetic organic textile fibres which includes the treatment with a composition comprising either ~) a nlixture of an amino-siloxane and a polyepoxide, b) a mixtur~ o a liquid epoxy-siloxane and a polyamine or c) a mixtur~ of a li.quid epoxy-si.loxalle and ~n aminosiloxane. However, these materials tend t-o give a certain amount: of yel,lowillg of the treated fibres. In U.S. patent 4 757 121 it i.s proposed to over-come the yellowing problem when treating synthetic ibre made waddings by using a composition comprising 100 parts by weight o a combination o two org~nopolysi.1Oxants comp(>sed of rom 5 to 95~ by weight of an aminc)-substi.tuted organopolysiloxane, and 95 to 5% by weight o a second amino-substituted organopolysiloxane, which is a reaction ~o~
- .3 -product of a liquid amino-substituted organopolysiloxane and a l;quid organic epoxy com?ourld, from 1 to 50 parts by weight of an epoxy-containillg alkoxy silane and from 1 to 50 parts by weight of a monoepoxy compound.
We have found ~hat an improved treating composition can be mad~ by restricting tht ami.rle-containing organo-silcxane to those whi.ch ar~ prereac~-ed with a monoepoxide.
Accc>rding to the invtntion th~rt is provided a method of tr~ating fi.brous materials, whi,ch comprises the applica-ti.on to fibrous materials of a composition co~prising as sole amine-containing organosilicon, compound the reaction product of a organopolysiloxane having at least one unit of the general formula O3 aSiXa-R-NH-R' and at least one unit having tht general formula O4 bSi-Xb with one or more mono-epoxid~s, whertin X denotes a monovalent hydrocarbon havin&
up to 8 carbon atoms, R denotes a di.valent alkylene group, R' denotes a hydrogen atom or a group of the formula R-Z, wherein Z is NHX, NH2, NHRNH2 or NHRNHX, a has a value of 1 or 2 and b has a value of 2 or 3.
The organopolysiloxane used in the preparation of the reaction product may be any siloxane polymer having at l.east 1 unit of th~ gentral formula O3 aSiXa-R~NH-R' and at least or,e unit havin~ t~e gerltral for~lu]a O4 bSi-Xb.
Preferably it is a substantially linear polydiorgano-siloxane polymer, although small anlounts Ol Ul-itS which cause branching of the siloxane are possible. Such units, which should not be present in nlore than 5% of the tot~l number o units, have the gerleral structure lSiX. The substituent X may be any hydrocarborl group having up to 8 4 ~Q~ ?~
carbon atoms, for example alkyl, aryl, alkenyl, alkylaryl an~ arylalkyl. Preferably X derlotes a lower alkyl group.
Preferably at least 80% and most preferably subs~antially all X groups are methyl groups. It is, however, possible that small amounts of other substituents are present on silicon at-on!s, for example hydroxyl or alkoxy groups. The ~roup R is a clivalent alkylene group, preferably having up to 8 carborl atonls, most preferably from 3 to 8 carbon atoms Examples of the R group include dimethylene, propy-lene, isobutylene and hexylene. The groups R' may be hydrogen or a group of the formula RZ, wherein Z denotes a primary or secondary amine group or a diamine of the formula NHRNH2 or NHRNHX. a has a value of l or 2, which means that the unit may be located in the siloxane chain or may be an end-urlit of the siloxane chain. Examples of the amine-containing substituent are OSi(CH3)(CH2)3NH2, OSi(C~3)CH2CH(C113)CH2NH2, OSi(CH3)CH2CH(CH3)CH2NH(CH2)2NH2, O~Si(CH3)2CH2CH(CH3)CH2NH(cH~cH3), 3~ 3)2(CH2)3NH(CH2)3NH(CH2)3NH2. The other units of the organopolysiloxane are units of the general formula O4 bSl-Xb wherein b has a value of 2 or 3 and X has the meaning as above. Thi.s means that the units may be preser1t in the siloxane chair-~ or as endgroups of the chain. It is preferred that polydiorganosiloxane havin~ from to 10 to l000 siloxane unit-s, particularly from l00 to 500 units, mcst preferably about 400 units are used. The viscosity of the polydiorgano~iloxane tends to determine the softness which is imparted to the treated materials, the higher the viscosity, the softer the finish However, for reasons of practicality it is pref~rred to use those rrlaterials which are liquid at roorrl temperature. It is also preferred that from 0.l to 20 mole% of all siloxane units are units of the aiy 2~3~
formul~ O3 aSiXa-R-NH-R', preferably from 1 to 10%, most preferably from 1 to 4%. A particularl.y advantageous amount is 2%. Amourlts above 10% are unlikely to contribute additional beneficial effects to the treat,ed materi,als.
Suitable organopolysiloxan~s for the preyaration of the reactioll prc~duct for use in the method o the invention are know~1 in the art ancl many are commercially available. They can be màde by methods known in the art, for example by the condensation of aminofunctional, silanes or hydrolysis products thereof with cyclic siloxanes in the presence of endblocking units, for example those provided by hexa-methyldisiloxanes.
Monoepoxides employed in the preparation of the re~ction product are organic compounds having one epoxy group. By the terrl) epoxy is mear)t a group c~omposed of oxir~ne oxygen attache~d to two vicinal carbon atoms. Mono-~,poxid~s which are suitable for use i.n the present invention are those wherein the substituent of the said vicinal carbon atoms are hydrogen, hydrocarbon groups or ether or ester containing hydrocarbon groups. Preferably one of the carbon atoms has only hydroger- atc)ms whil~ the other carbon atom has an alkyl. group attached to i.t, which may rarlge from methyl to a linear C21 alkyl grou~. Most preferred are those monoepoxides wherein the alkyl group has fron) I l-o ]0 carbon atoms, especiall.y from 1 to 4 carbon atoms. Exanlpl.es o~ suitable mc)noepc)Yides are ethy-lene oxide, propylene oxide, butadiene monoxide, 2,3-epoxy-cyclopentane, substi.tuted olefin oxi des, e.g. 2,3-epoxy-propylbenzene, epoxy alcohols, e.g. glycidol, 2,3-epoxy-cyclopentanol, 3,4-epoxy-6-methylcyclohe-xylmethane, glyci.dyl ethers, e.g. phenyl glycidyl ether, butyl glycidyl ether or glycidyl esters, e.g.glycidyl acetate. Preferred are those monoepoxides of the general formula /o\
H2C - CH-(CH2)r~-CH3, wherein n has a value of from 0 to 20, preferably 0 to 8, most preferably 0 to 3.
The reactiorl product for use in the method of the invt-ntion may be prepared according to known methods. For exanlple, the two reag~nts may be reacted together in the presenct- of a low molecular weight aliphatic alcohol or in the presence of a catalytic armount of water. The reaction can be carried out at room temperature in the presence o~
such catalyst but is preferably carried out at increased temperatures, for example temperatures of 50C or more. In order to make the reaction rr.ore easily handled it may be carried out in the presence of a solvent, which may be the alcohol mer1tioned above or other suitable solvents. The arnount of rnonoepoxide used i,n the reaction should be such that no more than 10% of all aniine groups i,n the organo-polysiloxane are retained unreacted in the reaction product. Where a prirnary arrline group was present in the organopolysiloxane two monoepoxide molecules can react with the amine. It i.s preferrt-d that the majority of the amino groups i.n the reaction product are tertiary amine groups, although the pres~nce of secondary amine groups to the.
exclusion of terti.ary amint- groups i~ also acc~t-ptable. The anline groups in the. reaction product may t:hus be tertiary, 6ect)ndary, a mixture of these, or a mixturt- of eitht-r or both with tlp to a maxinlum of 10% prirmary amitl~ groups.
It i.s important that the reaction product is used in the method of the inverltion, and not a mere ~ixture of the polydior~anosiloxane ant~ the nlonot-poxi.~lt-. ~ert- rrlixtures which contain polydiorganosiloxant-s having relatively high amounts o~ primary amine groups are not sati~factory, si,nce they will still display a yellowirlg of the treated materials. Even a mixture of the two components in the presence of water, e.g. by using an emulsion, is unsatis-factory as the yellowing upon treatn~ent wi~h such mixtures 5 or emulsi ons is wors~ than treatment: according ~o the inventic~n. Preerab]y nc) primary amil~es are retair)ed in the reclctioll product. Most preerably no secondary amines are present either in the reaction product.
The method of the invention comprises the application to fibrous materials of a composition comprising as sole amine-containing compound the reactiot- product as described above. This application may be done in any convenient way.
Applicatiorl nlethods which are suitable include padding, dipping and spraying of a composition cormprising the reaction product. The compositions used may be in any suitable form, e.g. solutions, dispersions or emulsions.
The dispersions may b~ in aqueous or solvent based materials while the elrlulsions ar~ preferably oil-in-water type emulsions. Especially preferred are emulsions, parti-cularly microemulsions according to European patent speci-~ication 138 192. Corllpositions which are useful in the met-hc)d of the invention may conlprise other ingredients which are useful in tre~tment conlpositiolls for fibrous materials, e.g. fatty acid softerltrs. Other ingredients ~5 e g. surfactall~s in t-he emu]sions are also useul. It is, however, preferred t~at the compositiorl comprises no amine-containing compounds other than the reaction product.
The method of the invention is suitable for the treatment o both naturally occurring and synthetic fibres, for example carbon fibres, polyester fibr~s, cot:t()n fibres and blends of cotton and polyester fibres. The apI)]ication may be done at the stage of making the fibres, at t-he stage of producing the fabrics or in a special trec-lting step later, for example during laundering of a textile fabric.
Application may be followed by drying at roo~l temperature or at increased temperatures. After the drying stage a further heat treatment of the fibrous materi,als is pref-erred. The latter i.8 particularly useful when the textilefabrics are treated at the tin~e of their production. The presence of sma~l amt)ul-Zts of prirnary a~ine groups on the reaction product will increase the durability of the finish on the fibrous materials, especially when they are subjected to laundering operations. Fibrous materials and textiles which are treated according to the method of the invention have an improved softener and lubricity, a pleasant feel and handle, without suffering from yellowing due to the treatment.
In a further aspect of the invention there is provi(le~l a fibrous material treated according to the method of the inv~ntiorl. Also included are fabrics or textiles incorporatirlg fibres when treated according to the method of the invention.
There now follow a number of examples illustrating the inventio in which all parts are expressed by weight unless otherwise mentioned.
Examples 1 - 5 1 molar part of a polydiorgallosilo~ane compound of the average formula ( 3)2Si~l(CH3)2SiO~98Si(CH3)2 R K
wherein R denotes -CH2CH(CH3)CH2NHCH2CH3, was reacted with 2 molar parts of a monoepoxide having the average formula /O\
H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 snd 9 respec-tively for Examples 1, 2, 3, 4 and 5 in the presence a mixture of 95 p~rts of methanol,, 3 parts of isopropanol and ~o~
_ 9 _ 2 parts of water at a temperature of 50C. This yielded a reaction product which is believed to have the average formula ( 3)2SiO[CH3)2SiO]98Si(CH3)2 R' R' OH
wherein R denotes CH21CHC 2l 2 ( 2)n 3 prepared with a 2.77% solution in perchloro ethylene of the reaction product prepared in Examples 1 to 5 in which a piece of polyester cotton (65/35) was treated by padding.
The piece was heated to 110C for 1 minute, followed by 2 minutes at 180C after treatment. The piece had picked up 0.5% by weight of the reaction product.
Examples 6 - 10 _ _ _ _ 1 molar part of a polydiorganosiloxane compound of the average formula (CH3)3SiO[(CH3)2SiO]96[(CH3)SiO]2S ( 3 3 wherein R denotes -CH2CH(CH3)CH2NHCH2CH2NH2, was reacted with 6 molar parts of a monoepoxide having the average /o\
formula H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 a re.spectively for Examples 6, 7, 8, 9 and 10 in the presence a mixture of 95 parts of methanol, 3 parts of isopropanol and 2 parts o water at a temperature of 50DC. This yielded a reaction product which is believed to have the average formula (CH3)3SiO[(CH3)2SiO]96[(CH3),SiO]2Si( 3 3 R' OM
i R' denotes -CH2CHcH2N(cH2)2N~cH2 ( 2 n 3 2 CH3 CH2CH(CH2)nCH3 OH
- 10 - ~ "P?.
bath was prepaired with a 2.77~ solution itl perchloro ethylene of the reaction prod~ct prepared in Examples 6 to 10, in which a piece of polyester cotton (65/35) was treated by padding. The piece was heated to 110C for l minut~, followed by 2 minutes at 180C after treatment.
The plece l~acl picked up 0.5% by weight of the reaction pr(J(luct .
Exan~ples 11 - 15 1 molar part of a polydiorganosiloxane compound of the average formula (CH3)3SiO[(CH3)2SiO]386[(CH3)SiO]8Si( 3 3 R
h i R denotes -cH2cH(cH3)cH2NHcH2cH2 2~
with 24 molar ~arts of a monoepoxide having the average 5 formula /o\
H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 and 9 resp~c-tively for Examples 11, 12, 13, 14 and 15 in the presence of a mixture of 95 parts of m~thanol, 3 parts of isopro-0 panol and 2 parts of water at a temperature of 50C. This yielded a r~action product which is believed to have the average for~lula (CH3)3SiO[(CH3)2SiO]386[(CH3)SiO]8Si( 3 3 ~' OH
whereil-l R' d~not~s -CH21CHCH2N(CH2)2N[CH2CH(CH2)nCH3]2. A
CH3 CH2CH(C~2)nCH3 0~1 bath was prepared with a 2.77% solution in perchloro ethylene of the reaction product prepclre(l in Fxamples 11 to 15, in which a piece of polyester cotton (65/35) was treated by p~ddin&. The piece was heated to 110~C for 1 minute, followed by 2 minutes at 180~C after treatment.
J
The piece had picked up 0.5% by weight of the reaction product.
Examples 16 - 20 1 molar par~ of a polydiorganosiloxane compound of the average formula )3sio[(c~3)2sio]392[(cH3)lsio]8si(c 3)3 E~
wherein R denotes -(CH2)3NHCH2CH2NH2, was reacted with 24 molar part-s of a moncJepoxide having the average formula /\
H2C - CH(CH,2)nCH3 wherein n was 0, 1, 3, 7 and 9 respec-tively for Examples 16, 17, 18, 19 and 20 in the presence of a mixture of 95 parts of methanol, 3 parts of isopro-panol and 2 parts of water at a temperature of 50C. This yielded a reaction product which is believecl to have the average formula (CH3)3SiO[(CH3)2SiO]392[(CH3)~iO]8Si( 3 3 OH
i R' denotes -CH2c~2cH2N(cH2)2N[cH2 ( 2 n 3 2 CH2lcH(cH2)ncH3 OH
b~th was prepared with a 2.77% solution ir-l perchloro ethylent of the reaction product prepared irl Examples 16 to 25 20, i,n which a piece c)f polyes~er cotton (65/35) was tr~ated by padding. The piece was heatecl to 110C for 1 minute, followed by heating at 180C for 2 minutes after treatment. The piece had picked up 0.5% by weight of the reaction product.
Examples 21 - 22 1 molar part of a polydiorganosil()~ane conlpound of the average formula (CH3)3SiOE(CH3)2SiO]392~(CH3)SiO]8Si(CH3)3 - 12 ~
wh~rein R denotes -(CH2CH(CH3)CH2)NHCH2CH2NH2, was reacted with 24 molar parts of a monoepoxide having the formula /o~
H2C - CHCH2CH3 in the presence of a mixture of 95 parts of methanol, 3 parts of isopropanol anZ 2 parts of water at a temp~rature of 50C. This yielded a reac~tioll product which ;s believed to have the ~vt!rage formu]a 3 3 [( 3)2siO~392~C~3)sio]8si(c~3)3 wherein R' 1 0 O~f denot~s -CH2CH(CH3)CH2N(CH2)2N[CH2cHcH2cH3]2- A bath was OH
prepared with a microemulsion, containing 1.4% of the reaction product prepared in Example 21, in which a piece of polyester COttOII (65/35) was treated by padding. The piece was heated to 110~C for 90 seconds, followed by heating at 180C for 2 minutes and 150C for S minutes respectively for Examples 21 and 22 after treatment. The pieces had picked up 1~ and 0.5~ by weight of the r~action product respectively.
Example 23 1 mole of (CH3O)2Si(CH3)CH2CH(CH3)CH2NH(C~2)2NH2 and methanol were added to a reaction ves~el. ].~ mole o~ 1,2 butyl~neoxide were added thro~1gh a droppin~ funIlel and the mixture was heated under a nitro~er) blanket to 50C which was mairltained for 1 hour. The product was stripped under r~d~ced pressure on a rotary evaporator. 1 mole of the product was mixed with 3 moles of water and heated to 110C
to allow condensation of th~ silanes. After purificatic-n hexam~thyldisiloxane and cyclic dimethylsi~oxane were added togeth~r with an alkaline catalyst-. The mixture was heat:ed for 5 hours to 140C and then neutralised. The filtered re~ctic,n prdouct had the formul.a 3 3 3)2sio]3g~[(cH3)sio]g~i(cH3)3 wherein R' R' OH
denotes -CH2CH(CH3)CH2NHCH2CHCH2CH3. The reaction product was applied to a piece of polyester cotton according to the methc)d dtscribed for Example 22.
Cc)nlp~rative Examples 1 - 10 . _ _ A bath was prepared wi.th a 2.77% solution in perchloro ethylerle o the amino containing polydiorgano-si.loxane used i,n Examples 11 to 15 on its own, in which a piece of polyester cotton (65/35) was treated by padding.
The piece plcked up 0.5% by weight of the siloxane.
(Comparative Example 1).
As in Comparati.ve Example 1, but usi.g a mixture of 1 mt,lar part of the polydi.organoslloxane of Comparativt Exanlplt 1 wi.th 2 molar parts of propylene oxide, but not reacted. (Comparative Example 2).
Comparative Example 3 was a plece of untreated polyester cotton (blank) as used in Examples 11 to 15.
A bath was prepared with a 2.77% solu~ion iTl p~rchloro ethylene of the am;rlo containing polydiorgano-siloxane used in Examples 16 to 2,~ on its own, in which a plece of polyester cotton (65/35) was t:re~ted by padding.
The pi~ce picked up 0,5% by weight of tht siloxant.
(Cc)lllparative Example, 4).
Comparativ~ Example 5 was a piect of untreated polyestt,~r cotton (blank) as used in Examples 16 to 20.
Con.parative Example 6 was a microenlulsi.on of a mixture of the two reactants of Examp]e 21, in the sanle proportions and with the same concentration, in which ~
piece of polyesttr cotto (6,/35) was treated by padding.
The piece picked up 1% by weight of the siloxane.
Comparative Example 7 was a microemulsion of the arr,ino containing polydiorganosiloxane of Example 21 on its OWtl in the same concentratiorl, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1~ by weight of the si.loxane.
Comp~rative Example 8 was a piece of untreated polyester cotton (blank) as used in Example 21.
Comparative Example 9 was a piece of untreated poly~ster cotton (blank) as used i,n Examples 22 and 23.
Comparative Example 10 was a microemulsion of the amino containirlg polydiorganosiloxane of Example 22 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane.
lS All comparative treate(l pi.eces o polyester-cotton were heated to 110C or 1 minute followed by 2 minutes at 180~C for Comparative Examples 1 to 8 and 5 minutes at 150C for Comparative Examples 9 and 10. The treated pieces of pol.yester cotton of Examples 1 to 23 were compared for softness and yellowing effect. It was found that the increase in molecular weight of the siloxane polymer used gave also an increase in the softness of the treate(l material. Withi.n each series of similar molecu]es the be~l- softness was obtaitled by those materials where _ ?-5 had a value o 0, 1 or 3.
The whiteness index of Examples 16 to 20 were measured using a Hunterlab Optical sensor, Model D25M and were compared with Comparative ~xamples 4 and 5. The following results were obtai.ned.
ExampleWhiteness Index 16 73.2 17 71.6 18 74.8 19 74.0 Colrlparative 4 62.5 Comparative 5 75.7 The whiteness index of Example 11 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 1, 2 and 3. The following results were obtained:
ExampleWhitenes 5 Index 11 68.8 Comparative 1 60.4 Comparative 2 59.7 Comparative 3 69.6 The whiteness index of Example 21 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 6, 7 and 8. The following results were obtained:
ExampleWhitene S 5 _ ndex 21 72.6 Comparative 6 65.1 Comparative 7 58.0 Comparative 8 76.4 The whiteness index of Examples 22 and 23 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 9 and 10. The following results were obtained:
Example Whiteness Index _ .. _ _ _ _ 22 80.8 23 78.3 Comparative 9 81.7 S ComparatLve 10 74.8 It can be seerl from the results that th~ method acc(1rdiT-Ig to the invention yields trecit~d materials which h.lv~. very li.ttle y~llowing in compari.son with materials treated according to th~ prior art, and have a whiteness i.ndex which is very close to that of th~ untreated material.
MET~OD OF TREATING FI~ROUS MATERIALS
This invention relates to a method o treating fibrous materials and more specifically to a method of treatir)g textile materials.
Wi.th the expression fibrous materials is meant fibres o syr-thet;c or natura].ly occurring materi.als, for example wool, cotton, polyester, carbon and blends of these. The inverltion relates to the treatment of the fi.bres as such as well as to th~ treatment of fabrics or textiles incorporating the fibres.
It is known to treat fibrous materials wi.th composi.-tions comprising amine-containing silicon compounds for imparti,ng desirable properties, e.g. softness, water repellency, lubricity ~ncl crease resistance thereto. G.B.
patent speci,fication 1 491 747 for example provides a compc-sitioll or treatmtrlt of synthttic fibres which comprises 1 part o certain aminosilanes and 1 to 20 parts of certain epoxysiloxanes. G.B. patent specification 1 296 136 provides a process or the treatn)erlt of synthetic organic textile fibres which includes the treatment with a composition comprising either ~) a nlixture of an amino-siloxane and a polyepoxide, b) a mixtur~ o a liquid epoxy-siloxane and a polyamine or c) a mixtur~ of a li.quid epoxy-si.loxalle and ~n aminosiloxane. However, these materials tend t-o give a certain amount: of yel,lowillg of the treated fibres. In U.S. patent 4 757 121 it i.s proposed to over-come the yellowing problem when treating synthetic ibre made waddings by using a composition comprising 100 parts by weight o a combination o two org~nopolysi.1Oxants comp(>sed of rom 5 to 95~ by weight of an aminc)-substi.tuted organopolysiloxane, and 95 to 5% by weight o a second amino-substituted organopolysiloxane, which is a reaction ~o~
- .3 -product of a liquid amino-substituted organopolysiloxane and a l;quid organic epoxy com?ourld, from 1 to 50 parts by weight of an epoxy-containillg alkoxy silane and from 1 to 50 parts by weight of a monoepoxy compound.
We have found ~hat an improved treating composition can be mad~ by restricting tht ami.rle-containing organo-silcxane to those whi.ch ar~ prereac~-ed with a monoepoxide.
Accc>rding to the invtntion th~rt is provided a method of tr~ating fi.brous materials, whi,ch comprises the applica-ti.on to fibrous materials of a composition co~prising as sole amine-containing organosilicon, compound the reaction product of a organopolysiloxane having at least one unit of the general formula O3 aSiXa-R-NH-R' and at least one unit having tht general formula O4 bSi-Xb with one or more mono-epoxid~s, whertin X denotes a monovalent hydrocarbon havin&
up to 8 carbon atoms, R denotes a di.valent alkylene group, R' denotes a hydrogen atom or a group of the formula R-Z, wherein Z is NHX, NH2, NHRNH2 or NHRNHX, a has a value of 1 or 2 and b has a value of 2 or 3.
The organopolysiloxane used in the preparation of the reaction product may be any siloxane polymer having at l.east 1 unit of th~ gentral formula O3 aSiXa-R~NH-R' and at least or,e unit havin~ t~e gerltral for~lu]a O4 bSi-Xb.
Preferably it is a substantially linear polydiorgano-siloxane polymer, although small anlounts Ol Ul-itS which cause branching of the siloxane are possible. Such units, which should not be present in nlore than 5% of the tot~l number o units, have the gerleral structure lSiX. The substituent X may be any hydrocarborl group having up to 8 4 ~Q~ ?~
carbon atoms, for example alkyl, aryl, alkenyl, alkylaryl an~ arylalkyl. Preferably X derlotes a lower alkyl group.
Preferably at least 80% and most preferably subs~antially all X groups are methyl groups. It is, however, possible that small amounts of other substituents are present on silicon at-on!s, for example hydroxyl or alkoxy groups. The ~roup R is a clivalent alkylene group, preferably having up to 8 carborl atonls, most preferably from 3 to 8 carbon atoms Examples of the R group include dimethylene, propy-lene, isobutylene and hexylene. The groups R' may be hydrogen or a group of the formula RZ, wherein Z denotes a primary or secondary amine group or a diamine of the formula NHRNH2 or NHRNHX. a has a value of l or 2, which means that the unit may be located in the siloxane chain or may be an end-urlit of the siloxane chain. Examples of the amine-containing substituent are OSi(CH3)(CH2)3NH2, OSi(C~3)CH2CH(C113)CH2NH2, OSi(CH3)CH2CH(CH3)CH2NH(CH2)2NH2, O~Si(CH3)2CH2CH(CH3)CH2NH(cH~cH3), 3~ 3)2(CH2)3NH(CH2)3NH(CH2)3NH2. The other units of the organopolysiloxane are units of the general formula O4 bSl-Xb wherein b has a value of 2 or 3 and X has the meaning as above. Thi.s means that the units may be preser1t in the siloxane chair-~ or as endgroups of the chain. It is preferred that polydiorganosiloxane havin~ from to 10 to l000 siloxane unit-s, particularly from l00 to 500 units, mcst preferably about 400 units are used. The viscosity of the polydiorgano~iloxane tends to determine the softness which is imparted to the treated materials, the higher the viscosity, the softer the finish However, for reasons of practicality it is pref~rred to use those rrlaterials which are liquid at roorrl temperature. It is also preferred that from 0.l to 20 mole% of all siloxane units are units of the aiy 2~3~
formul~ O3 aSiXa-R-NH-R', preferably from 1 to 10%, most preferably from 1 to 4%. A particularl.y advantageous amount is 2%. Amourlts above 10% are unlikely to contribute additional beneficial effects to the treat,ed materi,als.
Suitable organopolysiloxan~s for the preyaration of the reactioll prc~duct for use in the method o the invention are know~1 in the art ancl many are commercially available. They can be màde by methods known in the art, for example by the condensation of aminofunctional, silanes or hydrolysis products thereof with cyclic siloxanes in the presence of endblocking units, for example those provided by hexa-methyldisiloxanes.
Monoepoxides employed in the preparation of the re~ction product are organic compounds having one epoxy group. By the terrl) epoxy is mear)t a group c~omposed of oxir~ne oxygen attache~d to two vicinal carbon atoms. Mono-~,poxid~s which are suitable for use i.n the present invention are those wherein the substituent of the said vicinal carbon atoms are hydrogen, hydrocarbon groups or ether or ester containing hydrocarbon groups. Preferably one of the carbon atoms has only hydroger- atc)ms whil~ the other carbon atom has an alkyl. group attached to i.t, which may rarlge from methyl to a linear C21 alkyl grou~. Most preferred are those monoepoxides wherein the alkyl group has fron) I l-o ]0 carbon atoms, especiall.y from 1 to 4 carbon atoms. Exanlpl.es o~ suitable mc)noepc)Yides are ethy-lene oxide, propylene oxide, butadiene monoxide, 2,3-epoxy-cyclopentane, substi.tuted olefin oxi des, e.g. 2,3-epoxy-propylbenzene, epoxy alcohols, e.g. glycidol, 2,3-epoxy-cyclopentanol, 3,4-epoxy-6-methylcyclohe-xylmethane, glyci.dyl ethers, e.g. phenyl glycidyl ether, butyl glycidyl ether or glycidyl esters, e.g.glycidyl acetate. Preferred are those monoepoxides of the general formula /o\
H2C - CH-(CH2)r~-CH3, wherein n has a value of from 0 to 20, preferably 0 to 8, most preferably 0 to 3.
The reactiorl product for use in the method of the invt-ntion may be prepared according to known methods. For exanlple, the two reag~nts may be reacted together in the presenct- of a low molecular weight aliphatic alcohol or in the presence of a catalytic armount of water. The reaction can be carried out at room temperature in the presence o~
such catalyst but is preferably carried out at increased temperatures, for example temperatures of 50C or more. In order to make the reaction rr.ore easily handled it may be carried out in the presence of a solvent, which may be the alcohol mer1tioned above or other suitable solvents. The arnount of rnonoepoxide used i,n the reaction should be such that no more than 10% of all aniine groups i,n the organo-polysiloxane are retained unreacted in the reaction product. Where a prirnary arrline group was present in the organopolysiloxane two monoepoxide molecules can react with the amine. It i.s preferrt-d that the majority of the amino groups i.n the reaction product are tertiary amine groups, although the pres~nce of secondary amine groups to the.
exclusion of terti.ary amint- groups i~ also acc~t-ptable. The anline groups in the. reaction product may t:hus be tertiary, 6ect)ndary, a mixture of these, or a mixturt- of eitht-r or both with tlp to a maxinlum of 10% prirmary amitl~ groups.
It i.s important that the reaction product is used in the method of the inverltion, and not a mere ~ixture of the polydior~anosiloxane ant~ the nlonot-poxi.~lt-. ~ert- rrlixtures which contain polydiorganosiloxant-s having relatively high amounts o~ primary amine groups are not sati~factory, si,nce they will still display a yellowirlg of the treated materials. Even a mixture of the two components in the presence of water, e.g. by using an emulsion, is unsatis-factory as the yellowing upon treatn~ent wi~h such mixtures 5 or emulsi ons is wors~ than treatment: according ~o the inventic~n. Preerab]y nc) primary amil~es are retair)ed in the reclctioll product. Most preerably no secondary amines are present either in the reaction product.
The method of the invention comprises the application to fibrous materials of a composition comprising as sole amine-containing compound the reactiot- product as described above. This application may be done in any convenient way.
Applicatiorl nlethods which are suitable include padding, dipping and spraying of a composition cormprising the reaction product. The compositions used may be in any suitable form, e.g. solutions, dispersions or emulsions.
The dispersions may b~ in aqueous or solvent based materials while the elrlulsions ar~ preferably oil-in-water type emulsions. Especially preferred are emulsions, parti-cularly microemulsions according to European patent speci-~ication 138 192. Corllpositions which are useful in the met-hc)d of the invention may conlprise other ingredients which are useful in tre~tment conlpositiolls for fibrous materials, e.g. fatty acid softerltrs. Other ingredients ~5 e g. surfactall~s in t-he emu]sions are also useul. It is, however, preferred t~at the compositiorl comprises no amine-containing compounds other than the reaction product.
The method of the invention is suitable for the treatment o both naturally occurring and synthetic fibres, for example carbon fibres, polyester fibr~s, cot:t()n fibres and blends of cotton and polyester fibres. The apI)]ication may be done at the stage of making the fibres, at t-he stage of producing the fabrics or in a special trec-lting step later, for example during laundering of a textile fabric.
Application may be followed by drying at roo~l temperature or at increased temperatures. After the drying stage a further heat treatment of the fibrous materi,als is pref-erred. The latter i.8 particularly useful when the textilefabrics are treated at the tin~e of their production. The presence of sma~l amt)ul-Zts of prirnary a~ine groups on the reaction product will increase the durability of the finish on the fibrous materials, especially when they are subjected to laundering operations. Fibrous materials and textiles which are treated according to the method of the invention have an improved softener and lubricity, a pleasant feel and handle, without suffering from yellowing due to the treatment.
In a further aspect of the invention there is provi(le~l a fibrous material treated according to the method of the inv~ntiorl. Also included are fabrics or textiles incorporatirlg fibres when treated according to the method of the invention.
There now follow a number of examples illustrating the inventio in which all parts are expressed by weight unless otherwise mentioned.
Examples 1 - 5 1 molar part of a polydiorgallosilo~ane compound of the average formula ( 3)2Si~l(CH3)2SiO~98Si(CH3)2 R K
wherein R denotes -CH2CH(CH3)CH2NHCH2CH3, was reacted with 2 molar parts of a monoepoxide having the average formula /O\
H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 snd 9 respec-tively for Examples 1, 2, 3, 4 and 5 in the presence a mixture of 95 p~rts of methanol,, 3 parts of isopropanol and ~o~
_ 9 _ 2 parts of water at a temperature of 50C. This yielded a reaction product which is believed to have the average formula ( 3)2SiO[CH3)2SiO]98Si(CH3)2 R' R' OH
wherein R denotes CH21CHC 2l 2 ( 2)n 3 prepared with a 2.77% solution in perchloro ethylene of the reaction product prepared in Examples 1 to 5 in which a piece of polyester cotton (65/35) was treated by padding.
The piece was heated to 110C for 1 minute, followed by 2 minutes at 180C after treatment. The piece had picked up 0.5% by weight of the reaction product.
Examples 6 - 10 _ _ _ _ 1 molar part of a polydiorganosiloxane compound of the average formula (CH3)3SiO[(CH3)2SiO]96[(CH3)SiO]2S ( 3 3 wherein R denotes -CH2CH(CH3)CH2NHCH2CH2NH2, was reacted with 6 molar parts of a monoepoxide having the average /o\
formula H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 a re.spectively for Examples 6, 7, 8, 9 and 10 in the presence a mixture of 95 parts of methanol, 3 parts of isopropanol and 2 parts o water at a temperature of 50DC. This yielded a reaction product which is believed to have the average formula (CH3)3SiO[(CH3)2SiO]96[(CH3),SiO]2Si( 3 3 R' OM
i R' denotes -CH2CHcH2N(cH2)2N~cH2 ( 2 n 3 2 CH3 CH2CH(CH2)nCH3 OH
- 10 - ~ "P?.
bath was prepaired with a 2.77~ solution itl perchloro ethylene of the reaction prod~ct prepared in Examples 6 to 10, in which a piece of polyester cotton (65/35) was treated by padding. The piece was heated to 110C for l minut~, followed by 2 minutes at 180C after treatment.
The plece l~acl picked up 0.5% by weight of the reaction pr(J(luct .
Exan~ples 11 - 15 1 molar part of a polydiorganosiloxane compound of the average formula (CH3)3SiO[(CH3)2SiO]386[(CH3)SiO]8Si( 3 3 R
h i R denotes -cH2cH(cH3)cH2NHcH2cH2 2~
with 24 molar ~arts of a monoepoxide having the average 5 formula /o\
H2C - CH(CH2)nCH3 wherein n was 0, 1, 3, 7 and 9 resp~c-tively for Examples 11, 12, 13, 14 and 15 in the presence of a mixture of 95 parts of m~thanol, 3 parts of isopro-0 panol and 2 parts of water at a temperature of 50C. This yielded a r~action product which is believed to have the average for~lula (CH3)3SiO[(CH3)2SiO]386[(CH3)SiO]8Si( 3 3 ~' OH
whereil-l R' d~not~s -CH21CHCH2N(CH2)2N[CH2CH(CH2)nCH3]2. A
CH3 CH2CH(C~2)nCH3 0~1 bath was prepared with a 2.77% solution in perchloro ethylene of the reaction product prepclre(l in Fxamples 11 to 15, in which a piece of polyester cotton (65/35) was treated by p~ddin&. The piece was heated to 110~C for 1 minute, followed by 2 minutes at 180~C after treatment.
J
The piece had picked up 0.5% by weight of the reaction product.
Examples 16 - 20 1 molar par~ of a polydiorganosiloxane compound of the average formula )3sio[(c~3)2sio]392[(cH3)lsio]8si(c 3)3 E~
wherein R denotes -(CH2)3NHCH2CH2NH2, was reacted with 24 molar part-s of a moncJepoxide having the average formula /\
H2C - CH(CH,2)nCH3 wherein n was 0, 1, 3, 7 and 9 respec-tively for Examples 16, 17, 18, 19 and 20 in the presence of a mixture of 95 parts of methanol, 3 parts of isopro-panol and 2 parts of water at a temperature of 50C. This yielded a reaction product which is believecl to have the average formula (CH3)3SiO[(CH3)2SiO]392[(CH3)~iO]8Si( 3 3 OH
i R' denotes -CH2c~2cH2N(cH2)2N[cH2 ( 2 n 3 2 CH2lcH(cH2)ncH3 OH
b~th was prepared with a 2.77% solution ir-l perchloro ethylent of the reaction product prepared irl Examples 16 to 25 20, i,n which a piece c)f polyes~er cotton (65/35) was tr~ated by padding. The piece was heatecl to 110C for 1 minute, followed by heating at 180C for 2 minutes after treatment. The piece had picked up 0.5% by weight of the reaction product.
Examples 21 - 22 1 molar part of a polydiorganosil()~ane conlpound of the average formula (CH3)3SiOE(CH3)2SiO]392~(CH3)SiO]8Si(CH3)3 - 12 ~
wh~rein R denotes -(CH2CH(CH3)CH2)NHCH2CH2NH2, was reacted with 24 molar parts of a monoepoxide having the formula /o~
H2C - CHCH2CH3 in the presence of a mixture of 95 parts of methanol, 3 parts of isopropanol anZ 2 parts of water at a temp~rature of 50C. This yielded a reac~tioll product which ;s believed to have the ~vt!rage formu]a 3 3 [( 3)2siO~392~C~3)sio]8si(c~3)3 wherein R' 1 0 O~f denot~s -CH2CH(CH3)CH2N(CH2)2N[CH2cHcH2cH3]2- A bath was OH
prepared with a microemulsion, containing 1.4% of the reaction product prepared in Example 21, in which a piece of polyester COttOII (65/35) was treated by padding. The piece was heated to 110~C for 90 seconds, followed by heating at 180C for 2 minutes and 150C for S minutes respectively for Examples 21 and 22 after treatment. The pieces had picked up 1~ and 0.5~ by weight of the r~action product respectively.
Example 23 1 mole of (CH3O)2Si(CH3)CH2CH(CH3)CH2NH(C~2)2NH2 and methanol were added to a reaction ves~el. ].~ mole o~ 1,2 butyl~neoxide were added thro~1gh a droppin~ funIlel and the mixture was heated under a nitro~er) blanket to 50C which was mairltained for 1 hour. The product was stripped under r~d~ced pressure on a rotary evaporator. 1 mole of the product was mixed with 3 moles of water and heated to 110C
to allow condensation of th~ silanes. After purificatic-n hexam~thyldisiloxane and cyclic dimethylsi~oxane were added togeth~r with an alkaline catalyst-. The mixture was heat:ed for 5 hours to 140C and then neutralised. The filtered re~ctic,n prdouct had the formul.a 3 3 3)2sio]3g~[(cH3)sio]g~i(cH3)3 wherein R' R' OH
denotes -CH2CH(CH3)CH2NHCH2CHCH2CH3. The reaction product was applied to a piece of polyester cotton according to the methc)d dtscribed for Example 22.
Cc)nlp~rative Examples 1 - 10 . _ _ A bath was prepared wi.th a 2.77% solution in perchloro ethylerle o the amino containing polydiorgano-si.loxane used i,n Examples 11 to 15 on its own, in which a piece of polyester cotton (65/35) was treated by padding.
The piece plcked up 0.5% by weight of the siloxane.
(Comparative Example 1).
As in Comparati.ve Example 1, but usi.g a mixture of 1 mt,lar part of the polydi.organoslloxane of Comparativt Exanlplt 1 wi.th 2 molar parts of propylene oxide, but not reacted. (Comparative Example 2).
Comparative Example 3 was a plece of untreated polyester cotton (blank) as used in Examples 11 to 15.
A bath was prepared with a 2.77% solu~ion iTl p~rchloro ethylene of the am;rlo containing polydiorgano-siloxane used in Examples 16 to 2,~ on its own, in which a plece of polyester cotton (65/35) was t:re~ted by padding.
The pi~ce picked up 0,5% by weight of tht siloxant.
(Cc)lllparative Example, 4).
Comparativ~ Example 5 was a piect of untreated polyestt,~r cotton (blank) as used in Examples 16 to 20.
Con.parative Example 6 was a microenlulsi.on of a mixture of the two reactants of Examp]e 21, in the sanle proportions and with the same concentration, in which ~
piece of polyesttr cotto (6,/35) was treated by padding.
The piece picked up 1% by weight of the siloxane.
Comparative Example 7 was a microemulsion of the arr,ino containing polydiorganosiloxane of Example 21 on its OWtl in the same concentratiorl, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 1~ by weight of the si.loxane.
Comp~rative Example 8 was a piece of untreated polyester cotton (blank) as used in Example 21.
Comparative Example 9 was a piece of untreated poly~ster cotton (blank) as used i,n Examples 22 and 23.
Comparative Example 10 was a microemulsion of the amino containirlg polydiorganosiloxane of Example 22 on its own in the same concentration, in which a piece of polyester cotton (65/35) was treated by padding. The piece picked up 0.5% by weight of the siloxane.
lS All comparative treate(l pi.eces o polyester-cotton were heated to 110C or 1 minute followed by 2 minutes at 180~C for Comparative Examples 1 to 8 and 5 minutes at 150C for Comparative Examples 9 and 10. The treated pieces of pol.yester cotton of Examples 1 to 23 were compared for softness and yellowing effect. It was found that the increase in molecular weight of the siloxane polymer used gave also an increase in the softness of the treate(l material. Withi.n each series of similar molecu]es the be~l- softness was obtaitled by those materials where _ ?-5 had a value o 0, 1 or 3.
The whiteness index of Examples 16 to 20 were measured using a Hunterlab Optical sensor, Model D25M and were compared with Comparative ~xamples 4 and 5. The following results were obtai.ned.
ExampleWhiteness Index 16 73.2 17 71.6 18 74.8 19 74.0 Colrlparative 4 62.5 Comparative 5 75.7 The whiteness index of Example 11 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 1, 2 and 3. The following results were obtained:
ExampleWhitenes 5 Index 11 68.8 Comparative 1 60.4 Comparative 2 59.7 Comparative 3 69.6 The whiteness index of Example 21 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 6, 7 and 8. The following results were obtained:
ExampleWhitene S 5 _ ndex 21 72.6 Comparative 6 65.1 Comparative 7 58.0 Comparative 8 76.4 The whiteness index of Examples 22 and 23 was measured using a Hunterlab Optical sensor, Model D25M and compared with Comparative Examples 9 and 10. The following results were obtained:
Example Whiteness Index _ .. _ _ _ _ 22 80.8 23 78.3 Comparative 9 81.7 S ComparatLve 10 74.8 It can be seerl from the results that th~ method acc(1rdiT-Ig to the invention yields trecit~d materials which h.lv~. very li.ttle y~llowing in compari.son with materials treated according to th~ prior art, and have a whiteness i.ndex which is very close to that of th~ untreated material.
Claims (16)
1. A method of treating fibrous materials which comprises the application to the fibrous materials of a composition comprising as sole amine containing organosilicon compound, the reaction product of an organopolysiloxane having at least one unit of the general formula SiXaRNHR' and at least one unit of the general formula SiXb with one or more monoepoxides wherein X
denotes a monovalent hydrocarbon group having up to 8 carbon atoms, R denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ
wherein Z is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a value of
denotes a monovalent hydrocarbon group having up to 8 carbon atoms, R denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ
wherein Z is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a value of
2 or 3.
2. A method according to Claim 1 wherein the organopoly-siloxane is a substantially linear polydiorganosiloxane wherein at least 80% of all X groups are methyl groups.
2. A method according to Claim 1 wherein the organopoly-siloxane is a substantially linear polydiorganosiloxane wherein at least 80% of all X groups are methyl groups.
3. A method according to Claim 2 wherein the organopoly-siloxane comprises from 10 to 1000 siloxane units.
4. A method according to Claim 2 wherein the organopoly-siloxane comprises from 100 to 500 siloxane units.
5. A method according to Claim 1 wherein from 0.1 to 20 mole%
of all siloxane units of the organopolysiloxane have the formula SixaRNHR'.
of all siloxane units of the organopolysiloxane have the formula SixaRNHR'.
6. A method according to Claim 1 wherein from 1 to 10 mole% of all siloxane units of the organopolysiloxane have the formula SiXaRNHR'.
7. A method according to Claim 1 wherein the monoepoxide has the general formula -(CH2)n-CH3 wherein n has a value of from 0 to 8.
8. A method according to Claim 1 wherein the majority of amine groups in the reaction product are tertiary amine groups, no more than 10% of all amine groups present in said reaction product being primary amine groups.
9. A method according to Claim 6 wherein the majority of amine groups in the reaction product are tertiary amine groups, no more than 10% of all amine groups present in said reaction product being primary amine groups.
10. A method according to Claim 8 wherein the reaction product does not contain any primary or secondary amine groups.
11. A method according to Claim 9 wherein the reaction product does not contain any primary or secondary amine groups.
12. A method according to Claim 1 wherein the composition is in the form of an emulsion.
13. A method according to Claim 12 wherein the emulsion is a microemulsion.
14 . A method according to Claim 1 wherein the composition comprises no other amine containing compounds than the reaction product.
15. Fibrous materials treated according to a method which comprises the application of a composition comprising as sole amine containing organosilicon compound the reaction product of an organopolysiloxane having at least one unit of the general formula SiXaRNHR' and at least one unit of the general formula SiXb with one or more monoepoxides wherein X denotes a monovalent hydrocarbon group having up to 8 carbon atoms, R
denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ wherein Z
is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a valuè of 2 or 3.
denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ wherein Z
is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a valuè of 2 or 3.
16. Textile materials incorporating fibres onto which there has been applied a composition comprising as sole amine containing organosilicon compound the reaction product of an organopoly-siloxane having at least one unit of the general formula SiXaRNHR' and at least one unit of the general formula SiXb with one or more monoepoxides, wherein X denotes a monovalent hydrocarbon group having up to 8 carbon atoms, R
denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ, wherein Z
is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a value of 2 or 3.
denotes a divalent alkylene group, R' is selected from the group consisting of hydrogen and a group of the formula RZ, wherein Z
is selected from the group consisting of NHX, NH2, NHRNH2 and NHRNHX, a has a value of 1 or 2 and b has a value of 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB898911970A GB8911970D0 (en) | 1989-05-24 | 1989-05-24 | Method of treating fibrous materials |
| GB8911970.5 | 1989-05-24 |
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| CA2016833A1 true CA2016833A1 (en) | 1990-11-24 |
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| CA 2016833 Abandoned CA2016833A1 (en) | 1989-05-24 | 1990-05-15 | Method of treating fibrous materials |
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| EP (1) | EP0399706B1 (en) |
| JP (1) | JP2846058B2 (en) |
| CA (1) | CA2016833A1 (en) |
| DE (1) | DE69003009T2 (en) |
| ES (1) | ES2043277T3 (en) |
| GB (1) | GB8911970D0 (en) |
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| GB9004627D0 (en) * | 1990-03-01 | 1990-04-25 | Dow Corning | Composition for treating carbon fibre precursors and precursors treated therewith |
| DE4117864A1 (en) * | 1991-05-31 | 1992-12-03 | Pfersee Chem Fab | WAITER DISPERSIONS OF POLYSILOXANES |
| DE4211256A1 (en) * | 1992-04-03 | 1993-10-07 | Wacker Chemie Gmbh | Crosslinkable composition based on aminosilicone |
| EP0577039B1 (en) * | 1992-06-29 | 1999-09-08 | Witco Corporation | Method for treating a textile with an aminopolysiloxane and treated textile |
| JP2590234Y2 (en) * | 1993-11-16 | 1999-02-10 | マリンブルーブロー株式会社 | A hollow fence standing on a flower bed, etc. |
| DE4424914A1 (en) | 1994-07-14 | 1996-01-18 | Wacker Chemie Gmbh | Amino functional organopolysiloxanes |
| US6136215A (en) * | 1999-09-02 | 2000-10-24 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, amide-functional siloxanes |
| US6171515B1 (en) | 1999-09-02 | 2001-01-09 | Dow Corning Corporation | Fiber treatment composition containing amine-, polyol-, functional siloxanes |
| US6255429B1 (en) * | 1999-09-02 | 2001-07-03 | Dow Corning Corporation | Amine-, polyol-, amide-functional siloxane copolymers and methods for their preparation |
| GB0202631D0 (en) * | 2002-02-05 | 2002-03-20 | Dow Corning | Hair care compositions containing polysiloxanes |
| JP4147067B2 (en) * | 2002-08-09 | 2008-09-10 | 花王株式会社 | Cleaning composition |
| US20040053810A1 (en) * | 2002-08-16 | 2004-03-18 | Tully Jo Anne | Liquid laundry compositions comprising silicone additives |
| US7790801B2 (en) | 2007-07-24 | 2010-09-07 | Momentive Performance Materials Inc. | Organo-functional silicone in emulsion systems and process for preparing same |
| US20110243874A1 (en) * | 2010-04-01 | 2011-10-06 | Rajan Keshav Panandiker | Care polymers |
| DE102010062156A1 (en) | 2010-10-25 | 2012-04-26 | Evonik Goldschmidt Gmbh | Polysiloxanes with nitrogen-containing groups |
| DE102010062676A1 (en) | 2010-12-09 | 2012-06-14 | Evonik Goldschmidt Gmbh | Preparations containing polysiloxanes with nitrogen-containing groups |
| DE102011110100A1 (en) | 2011-08-12 | 2013-02-14 | Evonik Goldschmidt Gmbh | Process for the preparation of polysiloxanes with nitrogen-containing groups |
| US9346023B2 (en) | 2012-08-21 | 2016-05-24 | General Electric Company | Flux enhancing agent for improving composite polyamide reverse osmosis membrane performance |
| US9499671B2 (en) | 2014-10-15 | 2016-11-22 | Ramani Narayan | Hydrophilic polysiloxane compositions containing carbinol groups |
| KR101640714B1 (en) * | 2015-06-11 | 2016-07-18 | 치 솅 엔터프라이즈 컴퍼니 엘티디. | Ski shoe binding |
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|---|---|---|---|---|
| GB1547884A (en) * | 1975-08-20 | 1979-06-27 | Nuova San Giorgio Spa | Apparatus for reinserting broken yarn in an open end spinning unit |
| JPS6039792A (en) * | 1983-08-12 | 1985-03-01 | 松下電工株式会社 | Dimmer |
| JPS6110498A (en) * | 1984-06-25 | 1986-01-17 | 大日本塗料株式会社 | Method of forming relief engraving pattern |
| JPS6375184A (en) * | 1986-09-19 | 1988-04-05 | 信越化学工業株式会社 | Treatment agent for synthetic fiber |
| JPS6445466A (en) * | 1987-08-14 | 1989-02-17 | Shinetsu Chemical Co | Textile treating composition |
-
1989
- 1989-05-24 GB GB898911970A patent/GB8911970D0/en active Pending
-
1990
- 1990-05-11 EP EP19900305117 patent/EP0399706B1/en not_active Expired - Lifetime
- 1990-05-11 DE DE1990603009 patent/DE69003009T2/en not_active Expired - Fee Related
- 1990-05-11 ES ES90305117T patent/ES2043277T3/en not_active Expired - Lifetime
- 1990-05-15 CA CA 2016833 patent/CA2016833A1/en not_active Abandoned
- 1990-05-24 JP JP2132750A patent/JP2846058B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69003009T2 (en) | 1994-01-13 |
| JPH0351375A (en) | 1991-03-05 |
| DE69003009D1 (en) | 1993-10-07 |
| JP2846058B2 (en) | 1999-01-13 |
| EP0399706A3 (en) | 1991-03-20 |
| GB8911970D0 (en) | 1989-07-12 |
| EP0399706B1 (en) | 1993-09-01 |
| EP0399706A2 (en) | 1990-11-28 |
| ES2043277T3 (en) | 1993-12-16 |
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| Date | Code | Title | Description |
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| FZDE | Dead |