CA2202737C - Novel aminopolysiloxanes with hindered 4-amino-3,3-dimethylbutyl groups - Google Patents
Novel aminopolysiloxanes with hindered 4-amino-3,3-dimethylbutyl groups Download PDFInfo
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Abstract
Aminopolysiloxanes of the following structure Q2RSiO- (SiR2O)x-(SiRR1O).gamma.-SiRQ2 wherein R is a monovalent hydrocarbon group having 1 to 10 carbon atoms including alkyl, aryl and aralkyl groups; R1 is CH2-CH2-C-(CH3)2-CH2-NHR2, R2 is hydrogen, an alkyl of C1-C6, an alkyl amine of C1-C6, or an alkanolamine of C1-C6; Q is R, R1, hydroxyl, or an alkoxy of C1-C4, x can be zero or integer; y is an integer, with x + y being less than 1,100, for use in various applications, including softening textiles.
Description
Novel Atni~opolysiloxanes with Hindered 4-Amino-3,3-dimethylbutyi Groups Background It is known to treat fibers and fabrics, both natural and synthetic, with.
organopolysiloxanes to impart tactile properties such as flexibility, smoothness and "hand". Among organopolysiloxanes, aminofunctional organopolysiloxanes have been recognized to provide the most desirable hand. Several examples of such aminoorganopolysiloxane can be found in the prior art.
U.S. Patent No. 4,247,592 to Kalinowski teaches treating synthetic textiles with triorganosiloxy endblocked polydiorganosiloxanes having diamino groups attached through a tower alkylene to a mono or difunctional siloxy units. U.S.
Patent No. 4,661,577 to Lane discloses aminopotysiloxanes with trialkylsiloxy terminal groups having at least one amino, diamino or substituted amino group linked to at least one trifunctional siloxy unit through an alkylene bridge, which may also contain heteroatoms. U.S. Patent No. 5,073,275 to Ona discloses a compos~'~on and method for treating organic fibers with a different type of aminoorganosiloxane, one modified with the SiC bonded N-cyclohexylaminoalkyl radicals.
Surnm of the Invention The present invention provides novel aminofunctionai polysilvxanes particularly useful in the treatment of textiles. These novel polysiloxanes contain hindered, 4-amino- 3,3-dimethylbutyl groups and can be reactive fluids with hydroxy, alkoxy or 4-amino- 3,3-dimethylbutyl terminal functionality or non-reactive, terminated with trialkylsitoxy groups. The potysifoxanes of the present invention contain hindered neohexytamino groups, which are less prone to oxidation and therefore cause less discoloration of any treated textiles. The present invention also provides methods for treating textiles with the aforesaid aminofunetionat silicone compositions.
The present invention is directed to polysiloxanes of general formula (I}
Q2RSi0- (SiR20),~(SiRR'O)y-SiRQa (I) wherein R is selected from the group consisting of monovatent hydrocarbon groups having 1 to 10 carbon atoms including alkyl, aryl and aratkyl groups. The R
groups may be the same or different from one another and are illustrated by methyl, ethyl, butyl, hexyl, phenyl, benzyl and phenethyl. Of these, lower alkyl groups (C,-Ca} are preferred. Most preferably R is methyl.
R' is CH2CH2C(CH3)2CH?N(R2)2, where each RZ is the same or different and each is hydrogen, an alkyl of C,-Cs, an alkyl amine of C,-Cs (i,e. a C,-Cs alkyl group substituted with -NH2) or an alkanolamine of C,-Cs (i.e. a C~-Cs alkyl group substituted with -OH and with -NH2). Specific RZ groups include propylamine, propanolamine, methyl, and most preferably, hydrogen.
The amino group on R1 may be protonated or quaternized.
Q is R, R1, hydroxyl, or an alkoxy of C1-C4. Preferably, the alkoxy group is methoxy or etlaoxy. Most preferably Q is methyl.
"x" can be zero or an integers "y" is an integer greater than zero (with the understanding that for an overall polysiloxane composition, x and y represent average numbers), with x + y being less than 1,100. Preferably x ranges from 20 to 1000 and y ranges from 1 to 50; most preferably x ranges from 50 to 800 or 50 to 500 and y ranges from 1 to 20.
Detailed Description of the Invention Aminopolysiloxanes of the present invention are prepared, for example, by processes analogous to those disclosed in U.S. Patent Nos. 3,033,815, 3,146,250 and 4,247,592 by hydrolyzing the corresponding dialkoxy 4-amino-3,3-dimethylbutyl modified silane (which can be prepared according to U.S. Patent No 5,353,880 to Pepe) in. excess water or water-solvent such as tetrahydrofuran mixture, at 10 to 50°C, preferably, room temperature, for 2 to 5 hours followed by vacuum strip and equilibrating the resulting hydrolyzate with di(alkyl, aralkyl or aryl)cyclopolysiloxane (source of R25i0 groups) and hexamethyldisiloxane, decamethyltetra-siloxane, or other reactants to serve as the source of the terminal RQ2Si0 groups as defined by Formula 1) in the presence of a base catalyst, such as KOH, with heating at about 130 to 150°C for about 5 to 12 hours. A reactive aminopolysiloxane having hydroxy or alkoxy terminal groups can be prepared in a similar and well known manner from the amine containing silane and cyclopolysiloxane.
The protonated form of the polysiloxanes can be prepared by adding a protonic acid in an amount calculated to achieve the desired degree of protonation, that is, complete or less than complete if the amount of acid added: is less than stoichiometric. The quaternized form of the polysiloxane can be prepared by reacting it with a suitable quaternizing agent, such as methyl chloride, benzyl chloride, dimethyl sulfate, or diethyl sulfate. Preferred quaternary substituents include methyl, ethyl, and benzyl. The quaternary forms of the polysiloxane will be in ionic neutrality with a stoichiometric amount of an anion such as chloride, methylsulfate or ethylsulfate.
While the aminopolysiloxanes of the present invention can be used neat, for ease of the application, they are usually applied dissolved, dispersed or emulsified in a suitable liquid medium. Preferably, the aminopolysiloxanes of the present invention can be applied from an aqueous solution, emulsion or dispersion. The aminopolysiloxanes may also be applied as a solution in a non-aqueous solvent such as isopropanol and hexane, or in a liquid in which the aminopolysiloxane is miscible, such as toluene. Most preferably, the aminopolysiloxane is applied to the textile as an aqueous emulsion.
The preparation of aqueous emulsions of aminopolysiloxanes is well known to those skilled in the art.
One such preparation is described, for example, in U.S. Patent No. 5,039,738. To prepare an aqueous emulsion, an aminopolysiloxane is optionally combined with emulsifiers known in the art and diluted to the desired polymer level with water. The polymer content of the aminopolysiloxane emulsion of the present invention ranges from about 10 to 80 percent, preferably 20 to 40 percent.
The emulsion of the aminopolysiloxane of the present invention can be applied to the surface of any desired substrate, such as by spraying, dipping, or kiss roll application. The polysiloxane shoult~ be applied so that the amount of polysiloxane is 0-1 to 5.0, preferably 0.2 to 2.5, weight percent of the textile.
Substrates which can be treated with the aminopolysiloxanes of the present invention include textiles (both woven and nonwoven), hair, and paper.
Textiles are exemplified by (1) natural fibers such as cotton, flax, wool and silk; (ii) synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; (iii) inorganic fibers such as glass and carbon fiber; or (iv) biends of any of the above-mentioned fibers.
Optionally, other additives typically employed in treating the textile or other substrate Can be included with the emulsion or applied separately to the substrate. Such additives can include a durable press resin, curing catalyst, preservatives and biocides, pigments or dyes, fragrances, fillers, pH buffers, antifoamer and defoamers.
Textiles and other substrates treated with the aminopoiysiloxane of the present invention are dried either at room temperature or by heat and cured at a temperature less than the melting or decomposition temperature of the substrate.
Heating can be accomplished by any suitable method, but preferably is done by passing the substrate through a hot air oven. The resulting treated substrate, thus, has properties such as amine-like hand and whiteness.
Moreover, compositions including the amino polysiloxanes of the present invention may be used in personal care formulations, including lotions, creams, shaving cream, hair sprays, conditioners, shampoos, deodorants, moisturizers, and sunblocks, and in adhesive and sealant formulations. Additionally, said aminpolysiloxanes may be used in car wax formulations.
s Exampf_~s The following specific examples are set forth for illustration only and are not to be construed as limiting of the present invention.
In the examples, the test fabric and test procedures used were as follows:
Fabrics Identification (Test Fabrics inc.. Middlesex NJ) - Bleached Cotton interlock Knit, Style 460; Bleached Desized Cott6h Print Cloth, Style 400.
Test Procedures ~ Conditioning Textiles for Testing, ASTM Method D-i 776-79 ~ Absorbency of Bleached Textiles, AATCC Method 79-1992 ~ Softness evaluation was done by the hand panel and the tested fabrics were rated on the scale from 1 to 10, where 1 is very harsh 10 is very soft. Each hand panel involved at least five panelists and reported results are average values.
To evaluate discoloration of the treated textiles caused by the aminopolysiloxanes, whitenesslreflectance data were generated using Colorquest Colorimeter from Hunter I-abs.
~ Reflectance of the fabrics scorched in the curing oven at 200°C for 100 seconds was measured to determine resistance of the aminosilicone finishes to prolonged heating.
Example 1. Preparation of Aminopolysiioxanes Emulsions The aminopolysitoxanes set forth in Table 1 were prepared in accordance with the procedure disclosed in U.S. Patent No. 2,247,592, using 4-amino-3,3-dimethylbutylmethyldimethoxysitane as a source of aminofunctionatity, and formulated into emulsions. To form an emulsion, 40 parts of the aminopolysiloxane was mixed in a vessel with a surfactant blend of 3.6 parts of TERGfTOL~ 15-S-3 surfactant, 2.4 parts of TERGITOL~ 15-S-15 surfactant and 12 parts water to form a premix. The premix was homogenized with a laboratory mixer at 500 to 800 rpm. The remaining water (42 parts) was added slowly white mixing.
Table 1. 4-Amino-3,3-dimethytbutyl Modified Poiysiioxanes besignattv Forrriula ~ . Visco Amore Content.
n " >ity (cps).
, , , : ; 2tS VVf. ./a ',. . s ; ' NH2 a.
AminopofysiloxaneMD~D'2M 105 0.82 t 4minopofysiloxaneMb,~D*~M 21 fi 0.42 1l P.minopofysifoxaneMD~oD*sM 1404 0.43 lil AminopolysitoxaneMD~QO',of~ 1056 0.88 IV
nminopol;~siloxaneMD~D'3M 4632 0.15 V
hmino e!~ siloxaneAAD~~D*.M ~ 3690 0.29 ~!!
' M = O,r2Si(CH3)3 ; D = OSi(CHs)2; D* = OSiCH2CH2C(CH3)aCHzNHa 2 ~1.~,1n~ n~,r,~',W rlnrnrminnl~ by litrwt~~~
1 1111 11~ 11~ V~e~VI ~..
These polysiloxanes were applied to 100% cotton, knit and woven, with and without durable press resin at 1.0 weight percent of polysitoxane. The polysiloxanes improved the hand of the fabric with minimal yellowing after curing.
Example 2. Softness and Discoloration of 100% Cotton Knit Treated with 4-Amino-3,3-dimethylbutyi Modified Polysiloxanes Aminopolysiloxanes I-vt as set forth in Table 1, and two control softeners MAGNASOFT~ Ultra and MAGNASOFTb PLUS ( commercial premium amino softeners modified with 3-(2-(aminoethyl)aminopropyl pendant groups, having amine content of 0.8% and 0.25% as NH2, respectively) were padded onto 100% cotton knit in combination with a durable press resin (methylated dimethyloldihydroxyethyleneurea, which is commercially available) and curing catalyst (magnesium chloride) to simulate typical textile finishing procedure. The softener concentration in the finishing composition was such that the effective actives add-on levels on the fabric were 1.0°/s (BOWF, i.e., based on the weight of the fabric); curing conditions were 171°C for 1.5 minutes. Softness and reflectance data are provided in Table 2.
Tabie 2 Softness and Reflectance of 100% Cotton Knit Treated with ~i-Amino-3,3-dimeihyioutyi i4iodified Poiysiioxatte.~
. . . . : ::~: -: :. i > . Reflectance:
v Softness l~a~ :v. ,.: ;
Des~gnat~ont Amitieng .; ,.
Lori : . x.:____~ . _ , .
~ _. .. , teat as Nw Magnasoft~ Ultra 9.0 64.4 (0.8%) Maonasoftc9 Plus 7.8 72.5 J
(0.25/) Aminopofysiloxane 3.0 72.6 !
(0.82i) A.r,,inopoly si!oxane6.5 74.2 !!
(0.42l0) ~' miriG('.rOlySiloxane7.3 75.3 I!!
(0.43~/0) Amir~opoiysiioxane 5.3 72.8 !V
(o.ss~,o) AfriinOpoiysiioxane6.1 vQ.1 V
(0. i 5l) An~inopoiysiioxane 6.8 %9.6~
vi 0.29l0 Resin Onl 1.0 83-0 dated on the scale 1-10, where 1 is harsh and 10 is very soft Z? higher numbers mean lower discoloration A!f 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less discoloration o!
the textile substrate than aminopolysiloxanes modified with 3-(2-aminoethy!)aminvpropyl groups.
i5 Example 3. Softness and Discoloration of 100°!° Cotton Woven Treated with 4-Amino-3,3-dimethylbutyl Modified Polysiloxancs Aminopolysiloxanes I-VI, as set forth in Table 1, and two control sotteners MAGNASOFT~ Ultra and MAGNASOFT~ PLUS ( commercial premium amino softeners modified with 3-(2-aminoethyl)aminopropyl pendant groups, having amine content of 0.8% and 0.25% as NHZ, respectively) were padded onto 100% cotton print cloth in combination with a durable press resin (methylated dimethyloidihydroxyethyleneurea, which is commercially available} and Curing catalyst (magnesium chloride) to simulate typical textile finishing procedure. The softener concentration in the finishing composition was such that the effective actives add-on levels on the fabric were 1.0% (BOWF}; curing conditions were 171°C for 1.5 minutes.
Softness and reflectance data ace given in Table 3..
20 ._ Table 3. Softness and Retiectaace of 10a% Cotton Print Cloth Treated with 4-Amino-3,3-dimethylbutyi ~ilodil'fed Polyaiioxanes Deslgnariortl~lm~ne';~oftriessR$ting.Ref(eCtat~ce~__ ~
Core to . z . . ; : . . .
. ~ , . ,;
nt as fVH ~ , MagnasoftC~ Ultra 6.6 53.0 (~.$%~
Magnasoft~ Plus 8.0, 58.4 (0.25, ;
Aminnpolysiloxane 8.2 56.4 I
(0.82%) prninn ? .~
,n,QlycilnYana I,I 1, ,7 ~ . ~
(0.42%) . .
Amirnnnlwe~ilnvnr~~5_3 60.0 m l ~ wlrvy amvnm (0.43,0) At l ~SiiG~'IV;yjilviiqivr.~ v~.v ie I~~ ~
(a.sa~i~
111111rIV~Ul51S11I~XQ11C0~2 V3.G' Y ~
(0.55%}
Aminopolysiioxane b.4 62.4 vi 0.29%
Resin Onl 1.0 64.2 '' rated on the scale 1-10, where 1 is harsh and 10 is very soft 2' higher numbers mean lower discoloration All 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less discoloration of the textile substrate than aminopofysiloxanes modified with 3-(2-aminoethyl)aminopropyl groups.
~xampie 4. Reflectance of the Scorched 100% Cotton Print Cloth Fabrics Treated v~rith 4-Amino-3,3-dimethylbutyl Modified Polysi4oxar~es Reflectance of the treated fabrics from Example 3, exposed to scorch Conditions at 200°C for 100 seconds, has been measured to determine yellowing tendency of the inventive potysiloxanes under prolonged heat. Results are summarized in Table 4.
Table 4. Reflectance of the Scorched 100% Print Cloth Treated with with 4-Amino-3,3-dimethylbutyl Modified Polysiloxanes De~ignationlAmi~e.::Reflectance after . ~
;
, ;:...
vcritEnt a~:rZ~-iv-:':...scQ~chin ~) Magnasoft~ Ultra 2&.7 {0.8%) Magnasoftc~ Plus 35.7 (0.25%) Aminopolysiloxane 32.0 I
(0.82%) Aminopolysiloxane 33.5 II
(0.42%) Aminopolysiloxane . 32.6 III
(0.43%) Aminopolysiloxane 31.8 IV
{0.88%) Aminopolysiloxan2 3$,1' V
(0.15%) Aminopolysiloxane 37.4 VI
0.29%
Resin Only 39.5 -'~highes nuraberj mean lower di$~loration At the equivalent amine content, 4-amino-3,3-dimethylbutyl modified polysiloxanes caused less discoloration of the textile substrate than aminopolysiloxanes modified with 3-{2-aminoethyl)aminopropyl groups.
organopolysiloxanes to impart tactile properties such as flexibility, smoothness and "hand". Among organopolysiloxanes, aminofunctional organopolysiloxanes have been recognized to provide the most desirable hand. Several examples of such aminoorganopolysiloxane can be found in the prior art.
U.S. Patent No. 4,247,592 to Kalinowski teaches treating synthetic textiles with triorganosiloxy endblocked polydiorganosiloxanes having diamino groups attached through a tower alkylene to a mono or difunctional siloxy units. U.S.
Patent No. 4,661,577 to Lane discloses aminopotysiloxanes with trialkylsiloxy terminal groups having at least one amino, diamino or substituted amino group linked to at least one trifunctional siloxy unit through an alkylene bridge, which may also contain heteroatoms. U.S. Patent No. 5,073,275 to Ona discloses a compos~'~on and method for treating organic fibers with a different type of aminoorganosiloxane, one modified with the SiC bonded N-cyclohexylaminoalkyl radicals.
Surnm of the Invention The present invention provides novel aminofunctionai polysilvxanes particularly useful in the treatment of textiles. These novel polysiloxanes contain hindered, 4-amino- 3,3-dimethylbutyl groups and can be reactive fluids with hydroxy, alkoxy or 4-amino- 3,3-dimethylbutyl terminal functionality or non-reactive, terminated with trialkylsitoxy groups. The potysifoxanes of the present invention contain hindered neohexytamino groups, which are less prone to oxidation and therefore cause less discoloration of any treated textiles. The present invention also provides methods for treating textiles with the aforesaid aminofunetionat silicone compositions.
The present invention is directed to polysiloxanes of general formula (I}
Q2RSi0- (SiR20),~(SiRR'O)y-SiRQa (I) wherein R is selected from the group consisting of monovatent hydrocarbon groups having 1 to 10 carbon atoms including alkyl, aryl and aratkyl groups. The R
groups may be the same or different from one another and are illustrated by methyl, ethyl, butyl, hexyl, phenyl, benzyl and phenethyl. Of these, lower alkyl groups (C,-Ca} are preferred. Most preferably R is methyl.
R' is CH2CH2C(CH3)2CH?N(R2)2, where each RZ is the same or different and each is hydrogen, an alkyl of C,-Cs, an alkyl amine of C,-Cs (i,e. a C,-Cs alkyl group substituted with -NH2) or an alkanolamine of C,-Cs (i.e. a C~-Cs alkyl group substituted with -OH and with -NH2). Specific RZ groups include propylamine, propanolamine, methyl, and most preferably, hydrogen.
The amino group on R1 may be protonated or quaternized.
Q is R, R1, hydroxyl, or an alkoxy of C1-C4. Preferably, the alkoxy group is methoxy or etlaoxy. Most preferably Q is methyl.
"x" can be zero or an integers "y" is an integer greater than zero (with the understanding that for an overall polysiloxane composition, x and y represent average numbers), with x + y being less than 1,100. Preferably x ranges from 20 to 1000 and y ranges from 1 to 50; most preferably x ranges from 50 to 800 or 50 to 500 and y ranges from 1 to 20.
Detailed Description of the Invention Aminopolysiloxanes of the present invention are prepared, for example, by processes analogous to those disclosed in U.S. Patent Nos. 3,033,815, 3,146,250 and 4,247,592 by hydrolyzing the corresponding dialkoxy 4-amino-3,3-dimethylbutyl modified silane (which can be prepared according to U.S. Patent No 5,353,880 to Pepe) in. excess water or water-solvent such as tetrahydrofuran mixture, at 10 to 50°C, preferably, room temperature, for 2 to 5 hours followed by vacuum strip and equilibrating the resulting hydrolyzate with di(alkyl, aralkyl or aryl)cyclopolysiloxane (source of R25i0 groups) and hexamethyldisiloxane, decamethyltetra-siloxane, or other reactants to serve as the source of the terminal RQ2Si0 groups as defined by Formula 1) in the presence of a base catalyst, such as KOH, with heating at about 130 to 150°C for about 5 to 12 hours. A reactive aminopolysiloxane having hydroxy or alkoxy terminal groups can be prepared in a similar and well known manner from the amine containing silane and cyclopolysiloxane.
The protonated form of the polysiloxanes can be prepared by adding a protonic acid in an amount calculated to achieve the desired degree of protonation, that is, complete or less than complete if the amount of acid added: is less than stoichiometric. The quaternized form of the polysiloxane can be prepared by reacting it with a suitable quaternizing agent, such as methyl chloride, benzyl chloride, dimethyl sulfate, or diethyl sulfate. Preferred quaternary substituents include methyl, ethyl, and benzyl. The quaternary forms of the polysiloxane will be in ionic neutrality with a stoichiometric amount of an anion such as chloride, methylsulfate or ethylsulfate.
While the aminopolysiloxanes of the present invention can be used neat, for ease of the application, they are usually applied dissolved, dispersed or emulsified in a suitable liquid medium. Preferably, the aminopolysiloxanes of the present invention can be applied from an aqueous solution, emulsion or dispersion. The aminopolysiloxanes may also be applied as a solution in a non-aqueous solvent such as isopropanol and hexane, or in a liquid in which the aminopolysiloxane is miscible, such as toluene. Most preferably, the aminopolysiloxane is applied to the textile as an aqueous emulsion.
The preparation of aqueous emulsions of aminopolysiloxanes is well known to those skilled in the art.
One such preparation is described, for example, in U.S. Patent No. 5,039,738. To prepare an aqueous emulsion, an aminopolysiloxane is optionally combined with emulsifiers known in the art and diluted to the desired polymer level with water. The polymer content of the aminopolysiloxane emulsion of the present invention ranges from about 10 to 80 percent, preferably 20 to 40 percent.
The emulsion of the aminopolysiloxane of the present invention can be applied to the surface of any desired substrate, such as by spraying, dipping, or kiss roll application. The polysiloxane shoult~ be applied so that the amount of polysiloxane is 0-1 to 5.0, preferably 0.2 to 2.5, weight percent of the textile.
Substrates which can be treated with the aminopolysiloxanes of the present invention include textiles (both woven and nonwoven), hair, and paper.
Textiles are exemplified by (1) natural fibers such as cotton, flax, wool and silk; (ii) synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; (iii) inorganic fibers such as glass and carbon fiber; or (iv) biends of any of the above-mentioned fibers.
Optionally, other additives typically employed in treating the textile or other substrate Can be included with the emulsion or applied separately to the substrate. Such additives can include a durable press resin, curing catalyst, preservatives and biocides, pigments or dyes, fragrances, fillers, pH buffers, antifoamer and defoamers.
Textiles and other substrates treated with the aminopoiysiloxane of the present invention are dried either at room temperature or by heat and cured at a temperature less than the melting or decomposition temperature of the substrate.
Heating can be accomplished by any suitable method, but preferably is done by passing the substrate through a hot air oven. The resulting treated substrate, thus, has properties such as amine-like hand and whiteness.
Moreover, compositions including the amino polysiloxanes of the present invention may be used in personal care formulations, including lotions, creams, shaving cream, hair sprays, conditioners, shampoos, deodorants, moisturizers, and sunblocks, and in adhesive and sealant formulations. Additionally, said aminpolysiloxanes may be used in car wax formulations.
s Exampf_~s The following specific examples are set forth for illustration only and are not to be construed as limiting of the present invention.
In the examples, the test fabric and test procedures used were as follows:
Fabrics Identification (Test Fabrics inc.. Middlesex NJ) - Bleached Cotton interlock Knit, Style 460; Bleached Desized Cott6h Print Cloth, Style 400.
Test Procedures ~ Conditioning Textiles for Testing, ASTM Method D-i 776-79 ~ Absorbency of Bleached Textiles, AATCC Method 79-1992 ~ Softness evaluation was done by the hand panel and the tested fabrics were rated on the scale from 1 to 10, where 1 is very harsh 10 is very soft. Each hand panel involved at least five panelists and reported results are average values.
To evaluate discoloration of the treated textiles caused by the aminopolysiloxanes, whitenesslreflectance data were generated using Colorquest Colorimeter from Hunter I-abs.
~ Reflectance of the fabrics scorched in the curing oven at 200°C for 100 seconds was measured to determine resistance of the aminosilicone finishes to prolonged heating.
Example 1. Preparation of Aminopolysiioxanes Emulsions The aminopolysitoxanes set forth in Table 1 were prepared in accordance with the procedure disclosed in U.S. Patent No. 2,247,592, using 4-amino-3,3-dimethylbutylmethyldimethoxysitane as a source of aminofunctionatity, and formulated into emulsions. To form an emulsion, 40 parts of the aminopolysiloxane was mixed in a vessel with a surfactant blend of 3.6 parts of TERGfTOL~ 15-S-3 surfactant, 2.4 parts of TERGITOL~ 15-S-15 surfactant and 12 parts water to form a premix. The premix was homogenized with a laboratory mixer at 500 to 800 rpm. The remaining water (42 parts) was added slowly white mixing.
Table 1. 4-Amino-3,3-dimethytbutyl Modified Poiysiioxanes besignattv Forrriula ~ . Visco Amore Content.
n " >ity (cps).
, , , : ; 2tS VVf. ./a ',. . s ; ' NH2 a.
AminopofysiloxaneMD~D'2M 105 0.82 t 4minopofysiloxaneMb,~D*~M 21 fi 0.42 1l P.minopofysifoxaneMD~oD*sM 1404 0.43 lil AminopolysitoxaneMD~QO',of~ 1056 0.88 IV
nminopol;~siloxaneMD~D'3M 4632 0.15 V
hmino e!~ siloxaneAAD~~D*.M ~ 3690 0.29 ~!!
' M = O,r2Si(CH3)3 ; D = OSi(CHs)2; D* = OSiCH2CH2C(CH3)aCHzNHa 2 ~1.~,1n~ n~,r,~',W rlnrnrminnl~ by litrwt~~~
1 1111 11~ 11~ V~e~VI ~..
These polysiloxanes were applied to 100% cotton, knit and woven, with and without durable press resin at 1.0 weight percent of polysitoxane. The polysiloxanes improved the hand of the fabric with minimal yellowing after curing.
Example 2. Softness and Discoloration of 100% Cotton Knit Treated with 4-Amino-3,3-dimethylbutyi Modified Polysiloxanes Aminopolysiloxanes I-vt as set forth in Table 1, and two control softeners MAGNASOFT~ Ultra and MAGNASOFTb PLUS ( commercial premium amino softeners modified with 3-(2-(aminoethyl)aminopropyl pendant groups, having amine content of 0.8% and 0.25% as NH2, respectively) were padded onto 100% cotton knit in combination with a durable press resin (methylated dimethyloldihydroxyethyleneurea, which is commercially available) and curing catalyst (magnesium chloride) to simulate typical textile finishing procedure. The softener concentration in the finishing composition was such that the effective actives add-on levels on the fabric were 1.0°/s (BOWF, i.e., based on the weight of the fabric); curing conditions were 171°C for 1.5 minutes. Softness and reflectance data are provided in Table 2.
Tabie 2 Softness and Reflectance of 100% Cotton Knit Treated with ~i-Amino-3,3-dimeihyioutyi i4iodified Poiysiioxatte.~
. . . . : ::~: -: :. i > . Reflectance:
v Softness l~a~ :v. ,.: ;
Des~gnat~ont Amitieng .; ,.
Lori : . x.:____~ . _ , .
~ _. .. , teat as Nw Magnasoft~ Ultra 9.0 64.4 (0.8%) Maonasoftc9 Plus 7.8 72.5 J
(0.25/) Aminopofysiloxane 3.0 72.6 !
(0.82i) A.r,,inopoly si!oxane6.5 74.2 !!
(0.42l0) ~' miriG('.rOlySiloxane7.3 75.3 I!!
(0.43~/0) Amir~opoiysiioxane 5.3 72.8 !V
(o.ss~,o) AfriinOpoiysiioxane6.1 vQ.1 V
(0. i 5l) An~inopoiysiioxane 6.8 %9.6~
vi 0.29l0 Resin Onl 1.0 83-0 dated on the scale 1-10, where 1 is harsh and 10 is very soft Z? higher numbers mean lower discoloration A!f 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less discoloration o!
the textile substrate than aminopolysiloxanes modified with 3-(2-aminoethy!)aminvpropyl groups.
i5 Example 3. Softness and Discoloration of 100°!° Cotton Woven Treated with 4-Amino-3,3-dimethylbutyl Modified Polysiloxancs Aminopolysiloxanes I-VI, as set forth in Table 1, and two control sotteners MAGNASOFT~ Ultra and MAGNASOFT~ PLUS ( commercial premium amino softeners modified with 3-(2-aminoethyl)aminopropyl pendant groups, having amine content of 0.8% and 0.25% as NHZ, respectively) were padded onto 100% cotton print cloth in combination with a durable press resin (methylated dimethyloidihydroxyethyleneurea, which is commercially available} and Curing catalyst (magnesium chloride) to simulate typical textile finishing procedure. The softener concentration in the finishing composition was such that the effective actives add-on levels on the fabric were 1.0% (BOWF}; curing conditions were 171°C for 1.5 minutes.
Softness and reflectance data ace given in Table 3..
20 ._ Table 3. Softness and Retiectaace of 10a% Cotton Print Cloth Treated with 4-Amino-3,3-dimethylbutyi ~ilodil'fed Polyaiioxanes Deslgnariortl~lm~ne';~oftriessR$ting.Ref(eCtat~ce~__ ~
Core to . z . . ; : . . .
. ~ , . ,;
nt as fVH ~ , MagnasoftC~ Ultra 6.6 53.0 (~.$%~
Magnasoft~ Plus 8.0, 58.4 (0.25, ;
Aminnpolysiloxane 8.2 56.4 I
(0.82%) prninn ? .~
,n,QlycilnYana I,I 1, ,7 ~ . ~
(0.42%) . .
Amirnnnlwe~ilnvnr~~5_3 60.0 m l ~ wlrvy amvnm (0.43,0) At l ~SiiG~'IV;yjilviiqivr.~ v~.v ie I~~ ~
(a.sa~i~
111111rIV~Ul51S11I~XQ11C0~2 V3.G' Y ~
(0.55%}
Aminopolysiioxane b.4 62.4 vi 0.29%
Resin Onl 1.0 64.2 '' rated on the scale 1-10, where 1 is harsh and 10 is very soft 2' higher numbers mean lower discoloration All 4-amino-3,3-dimethylbutyl modified polysiloxanes improved the hand of 100%
cotton knit fabrics and, at the equivalent amine content, caused less discoloration of the textile substrate than aminopofysiloxanes modified with 3-(2-aminoethyl)aminopropyl groups.
~xampie 4. Reflectance of the Scorched 100% Cotton Print Cloth Fabrics Treated v~rith 4-Amino-3,3-dimethylbutyl Modified Polysi4oxar~es Reflectance of the treated fabrics from Example 3, exposed to scorch Conditions at 200°C for 100 seconds, has been measured to determine yellowing tendency of the inventive potysiloxanes under prolonged heat. Results are summarized in Table 4.
Table 4. Reflectance of the Scorched 100% Print Cloth Treated with with 4-Amino-3,3-dimethylbutyl Modified Polysiloxanes De~ignationlAmi~e.::Reflectance after . ~
;
, ;:...
vcritEnt a~:rZ~-iv-:':...scQ~chin ~) Magnasoft~ Ultra 2&.7 {0.8%) Magnasoftc~ Plus 35.7 (0.25%) Aminopolysiloxane 32.0 I
(0.82%) Aminopolysiloxane 33.5 II
(0.42%) Aminopolysiloxane . 32.6 III
(0.43%) Aminopolysiloxane 31.8 IV
{0.88%) Aminopolysiloxan2 3$,1' V
(0.15%) Aminopolysiloxane 37.4 VI
0.29%
Resin Only 39.5 -'~highes nuraberj mean lower di$~loration At the equivalent amine content, 4-amino-3,3-dimethylbutyl modified polysiloxanes caused less discoloration of the textile substrate than aminopolysiloxanes modified with 3-{2-aminoethyl)aminopropyl groups.
Claims (30)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polysiloxane of the formula (I) Q2RSiO-(SiR2O)x-(SiRR1O)y-SiRQ2 (I) wherein each R group is the same or different and each is selected from the group consisting of monovalent alkyl, aryl and aralkyl hydrocarbon groups having 1 to 10 carbon atoms;
R1 is CH2CH2C(CH3)2CH2N(R2)2, wherein each R2 is the same or different and each is hydrogen, a C1-C6 alkyl group, a C1-C6 alkyl amine group, or a C1-C6 alkanolamine group, and each nitrogen atom in an R1 group is optionally protonated or quaternized;
Q is R, R1, hydroxyl, or a C1-C4 alkoxy group;
x is zero or an integer; y is an integer greater than zero, and the sum of (x + y) is less than 1,100.
R1 is CH2CH2C(CH3)2CH2N(R2)2, wherein each R2 is the same or different and each is hydrogen, a C1-C6 alkyl group, a C1-C6 alkyl amine group, or a C1-C6 alkanolamine group, and each nitrogen atom in an R1 group is optionally protonated or quaternized;
Q is R, R1, hydroxyl, or a C1-C4 alkoxy group;
x is zero or an integer; y is an integer greater than zero, and the sum of (x + y) is less than 1,100.
2. A polysiloxane according to claim 1 wherein each R group is selected from the group consisting of phenyl, benzyl, phenethyl, and C1-C6 alkyl groups.
3. A polysiloxane according to claim 1 wherein each R group is methyl.
4. A polysiloxane according to claim 3 wherein R2 is hydrogen.
5. A polysiloxane according to claim 1 wherein R2 is hydrogen.
6. A polysiloxane according to claim 1 wherein each Q is methoxy or ethoxy.
7. A polysiloxane according to claim 1 wherein each Q is methyl.
8. A polysiloxane according to claim 3 wherein each Q is methyl.
9. A polysiloxane according to claim 1 wherein each Q is an R1 group.
10. A polysiloxane according to claim 1 wherein x is 20 to 1,000.
11. A polysiloxane according to claim 1 wherein y is 1 to 20.
12. A liquid composition in which a polysiloxane according to claim 1 is dissolved, dispersed or emulsified.
13. A liquid composition in which a polysiloxane according to claim 3 is dissolved, dispersed or emulsified.
14. A liquid composition in which a polysiloxane according to claim 4 is dissolved, dispersed or emulsified.
15. A liquid composition in which a polysiloxane according to claim 8 is dissolved, dispersed or emulsified.
16. A method of treating a substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, comprising applying thereto a polysiloxane according to claim 1.
17. A method according to claim 16 comprising applying an aqeous emulsion of said polysiloxane.
18. A method of treating a substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, comprising applying thereto a polysiloxane according to claim 3.
19. A method according to claim 18 comprising applying an aqeous emulsion of said polysiloxane.
20. A method of treating a substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, comprising applying thereto a polysiloxane according to claim 4.
21. A method according to claim 20 comprising applying an aqeous emulsion of said polysiloxane.
22. A method of treating a substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, comprising applying thereto a polysiloxane according to claim 8.
23. A method according to claim 22 comprising applying an aqeous emulsion of said polysiloxane.
24. A method of treating a substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, comprising applying thereto a polysiloxane according to claim 9.
25. A method according to claim 24 comprising applying an aqeous emulsion of said polysiloxane.
26. A substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, to at least one surface of which a polysiloxane according to claim 1 has been applied.
27. A substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, to at least one surface of which a polysiloxane according to claim 3 has been applied.
28. A substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, to at least one surface of which a polysiloxane according to claim 4 has been applied.
29. A substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, to at least one surface of which a polysiloxane according to claim 8 has been applied.
30. A substrate selected from the group consisting of woven and nonwoven textiles, hair and paper, to at least one surface of which a polysiloxane according to claim 9 has been applied.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1599796P | 1996-04-15 | 1996-04-15 | |
| US60/015,991 | 1996-04-15 |
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| Publication Number | Publication Date |
|---|---|
| CA2202737A1 CA2202737A1 (en) | 1997-10-15 |
| CA2202737C true CA2202737C (en) | 2003-03-25 |
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| CA002202737A Expired - Fee Related CA2202737C (en) | 1996-04-15 | 1997-04-15 | Novel aminopolysiloxanes with hindered 4-amino-3,3-dimethylbutyl groups |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432270B1 (en) | 2001-02-20 | 2002-08-13 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue |
| US6599393B1 (en) | 2001-11-15 | 2003-07-29 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue containing hydrophilically-modified amino-functional polysiloxanes |
| US6576087B1 (en) | 2001-11-15 | 2003-06-10 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue containing polysiloxanes |
| US6511580B1 (en) | 2001-11-15 | 2003-01-28 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue containing derivitized amino-functional polysiloxanes |
| US6582558B1 (en) | 2001-11-15 | 2003-06-24 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue containing hydrophilic polysiloxanes |
| US6514383B1 (en) | 2001-11-15 | 2003-02-04 | Kimberly-Clark Worldwide, Inc. | Soft absorbent tissue containing derivitized amino-functional polysiloxanes |
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1997
- 1997-04-15 CA CA002202737A patent/CA2202737C/en not_active Expired - Fee Related
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| CA2202737A1 (en) | 1997-10-15 |
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