CA2048890C - Silicone textile finishes - Google Patents
Silicone textile finishesInfo
- Publication number
- CA2048890C CA2048890C CA002048890A CA2048890A CA2048890C CA 2048890 C CA2048890 C CA 2048890C CA 002048890 A CA002048890 A CA 002048890A CA 2048890 A CA2048890 A CA 2048890A CA 2048890 C CA2048890 C CA 2048890C
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- Prior art keywords
- group
- silicone
- textile
- finishing agent
- glycol
- Prior art date
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Classifications
-
- 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
- D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
-
- 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
- D06M15/65—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing epoxy 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)
Abstract
A durable hydrophilic silicone textile finish is produced on cellulose-containing textiles to impart durable hydrophilic softness and durable press properties to the textile. The silicone finish is produced from an aqueous solution of glyoxal, a reactive organomodified silicone copolymer, a glycol and an acidic catalyst. The treating composition is applied to the textile and cured by heating at an elevated temperature to bond the silicone to the cellulose.
Description
SIT.ICONF. TExTIT~F FINISHFS
FIELD O~ T~E INVENTION
The present invention is directed to silicone copolymers which can produce durable hydrophilic finishes on cotton te~tiles. More particularly, the invention is directed to a method of treating cotton textiles to impart softness and durable hydrophilic properties to the te~tiles.
BACKGROUND OF THE INV~TION
Te~tiles, and particularly cotton and cotton blend textiles, are often treated with silicone finishing agents to provide softness, improve tear strength, flex abrasion, processibility and wrinkle recovery. These finishing agents are generally applied to the te~tile from aqueous systems in pad-dry-cure operations.
- Commonly employed types of si1icone finishing agents are the polysilo~anes containing pendant organic groups. The silicone finishing agents which have been typically used heretofore have hydrophobic properties and result in the fabrics having little or no water absorbency. When hydrophilic silicone copolymers are used, the te~tiles have improved hydrophilic properties, but these finishes generally have poor dura~ility. To improve the durability of the hydrophilic silicone finishes, reactive or curable organomodified silicones are generally used.
One example of the efforts to produce durable silicone finishes on te~tiles is disclosed in 20~8890 U.S. Patent No. 4,459,383. The fiber-treating composition includes at-least two reactive organosilicones which are able to react with each other and form durable finishes. The organomodified silicones include (1) an epo~y-substitutes silo~a-ne and (2) an amino or carbo~y-substituted and polyether-containing siloxane copolymer. The epoxy silicone is reacted with the amino-containing silo~ane or alternatively the carbo~yl-containing siloxane during curing to crosslink the siloxanes onto the fibers.
Other silicone finishing agents include silicone copolymers having polyo~yalkylene substituents and hydrolyzable di- or trialkoxysilyl groups. The silicones are applied to the fabric in the presence of moisture where the alkoxysilyl groups are hydrolyzed and cured at elevated temperatures.
One example of this form of silicone finishing agent is disclosed in U.S. Patent No. 4,283,519. A
hydrophilic organosilicone includes a trialko~ysilyl pendant group and a polyoxyethylene/polyoxypropylene chain terminated with a hydrogen or an acyl group.
The silicone is applied to the fabric and cured by heating in the presence of a catalyst.
U.S. Patent No. 4,758,646 discloses a bis (alko~ysilyl) polyether copolymer as a fabric sizing agent. The sizing agent is applied to the-fabric and cured by heating to produce a hydrophilic finish having antistatic and soil release properties.
Glyo~al has been known to react with cotton and produce durable press finishes for cotton related fabrics such as that disclosed in U.S. Patent No.
4,472,167. In this patent, an aqueous solution of ~ 3 ~ 20~890 glyo~al, glycol and an acid catalyst is applied to a cellulosic textile and cured by heating. The glyoxal is reported to form acetal crosslinks with cellulose. The glycol is added as a coreactant additive to modify the length of the crosslinks in the network. An optional silanol-terminated silicone is reported to produce a treated fabric having considerable water repellency.
U.S. Patent No. 4,269,603 discloses a durable press treatment for te~tile fabrics using an aqueous solution of glyoxal, a reactive hydrophobic silicone and a catalyst. The treating composition is cured at about 177C to 204C. This curing temperature has the disadvantage of producing a significant loss of tear strength of the fabric. The treating composition is reported to impart wrinkle resistance and smooth drying performance.
The present invention is directed to a method of producing hydrophilic silicone finishes for cellulose-containing te~tiles, using glyoxal to bind silicone copolymers to the te2tile. The resulting silicone finishes are durable to washing and impart soft hydrophilic properties and durable press properties to the treated fabric.
SUMMARY OF THE INV~NTION
The present invention is directed to finished te~ile materials and to a method of imparting durable hydrophilic softness to cellulose-containing te~tile materials. The hydrophilic finishes produced are sufficiently dura~le to withstand repeated washings in water ~889~
and/or home laundering. The textile finish can be used with or without other te~tile finishes.
The hydrophilic finish of the invention is produced by forming a chemical bond between the cellulose portion of a textile substrate and a hydrophilic silicone via acetal formation with glyo~al. The hydrophilic finish-forming composition is a mi~ture of glyoxal, glycol, a reactive hydrophilic silicone and an acid catalyst. The cellulose-containing textile is impregnated with the composition and subjected to reactive conditions, such as heating. The hydrophilic silicone then becomes fixed to the textile to impart durable hydrophilic properties.
The preferred reactive silicones are the hydrophilic silicone random copolymers having a hydro2yl terminated organic polyether substituent.
Preferably the silicone copolymers have primary or`
secondary hydroxyl terminated polyoxyalkylene chains. Preferably the polyoxyalkylene is a polyo~yethylene or a polyo~yethylene/polyo~ypropylene copolymer where the ethyleneo~ide content is such that the silicone is hydrophilic. The silicone copolymer may also be a terpolymer of polysiloxane, polyo~yethylene or polyo~yethylene/polyoxypropylene terminated with a hydroxy-, alko~y-, acetoxy-end group and pendant groups which bear hydro~yl, amine, amide or thiol groups or groups capable of forming hydro~yl gro~ps under reactive conditions. The preferred functional groups which are able to form hydro~yl groups are epo~y-pendant groups.-The reactive hydrophilic silicone whencombined with the glyoxal and glycol provides durable hydrophilic softness to the textile and enhanced durable press performance compared to the glyoxal-glycol system alone. A hydrophilic silicone copolymer, which becomes chemically linked to the textile, provides improved durable wrinkle recovery angles, smooth drying performance and increased tear strength to the treated fabrics.
In accordance with one aspect of the present invention, there is provided a process of forming durable hydrophilic silicone finishes on textiles formed at least partially of cellulosic fibers such finishes withstanding repeated washing in water which process comprises:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5~ glyoxal, about 1% to 15~ glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0~ to 2~ catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) R R
R3SiO...(S:O)n(S )m...SiR3 q ~2 wherein R at each occurrence is a monovalent hydrocarbon radi~al; n is an integer and m is an integer equal to or greater than l; and R2 has the formula -(CH2)~(oR3)y(0R4)zR5 wherein oR3 and oR4 are repeating units; R3 and R4 are the same or different and sele~ted from the group consisting of C2H4 and C3H6; ~, y and z are integers with the proviso that and at least y or z are not zero; R5 is hydro~yl, n, m, ~, y and z are selected such that the silicone is soluble or dispersible in water at room temperature;
and (ii) 2d48890 5a ~ R R
R3siO...(s-o)n(s:o)m(s-o)o---siR3 ~- ~2 ~6 wherein R, n and m are as above, and o is an integer of at least l; R2 at each occurrence has the formula -(CH2-)1~(oR3)y(0R4)zR~
wherein ~, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy-, and R6 is a monovalent organic radicàl having a reactive group selected from the group consisting of epo~ide, hydrosyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is solu~le or dispersible in water at room temperature; and (b) heating the textile to a temperature of 120 -180C to cure the finishing agent.
In accordance with another aspect of the present invention, there is provided a heat curable textile finishing agent for forming durable hydrophilic finishes on textiles formed at least partially of cellulosic fibers, such finishes withstanding repeated washing in water, which finishing agent in the form of an aqueous solution comprising by weight about 1% to 5%
glyoxal, about 1% to 15% glycol, about 1% to 15%
hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) R R
R3sio~(s-o)n(s-o)m~siR3 ~ ~2 wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer, m is an integer 5b equal to or greater than 1; and R2 has the formula -(CH2)~-(oR3)y(0R~)~R5 wherein, oR3 and OR~ are repeating units; R3 and R~ are the same or different and selected from the group consisting of C2H~ and C3H6; x, y, z are integers with the proviso that x and at least y or z are not zero; Rs is hydroxyl, n, m, x, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) ~. R R
R3SiO...(S-O)n(s O)m(s o)o~SiR3 ~ h2 -6 wherein R, m and n are as above and o is an integer of at least 1; R2 at each occurrence has the formula -(CH2)~-(oR3)y(0R~)~Rs wherein x, y, z, R3 and R~ are as above, Rs is hydroxy-, alkoxy- or acetoxy, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are ~uch that the silicone is soluble or dispersible in water at room temperature.
In accordance with yet a further aspect of the present invention, there is provided a textile formed at least partially of cellulosic fibers having a durable hydrophilic finish that withstands repeated w~;ng in water produced by the steps of:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5% glyoxal, about 1% to 15% glycol, about 1%
to 15% hydrophilic silicone copolymer, about 0.1 to 2%
acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) ~' 5c 2048890 R3sio~(s-o)n(s-o)m~siR3 ". R2 wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer and m is an integer equal to or greater than l; and R2 has the formula -(CH2)s-(oR3)y(OR4)zR5 wherein oR3 and oR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; s, y, z are integers with the proviso that s and at least y or z are not zero; R5 i5 hydrosyl, n, m, s, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) R - _ R3SiO...(S-O)n(S O)m(S-O)o...SiR3 ~ ~2 q6 wherein R, m and n are as above a~d o is an integer of at least l; R2 at each occurrence has the formula -(CH2)~(0R3)y(0R4)2R5 wherein s, Yr Z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or aceto~y, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of eposide, hydrosyl, diol, amine, amide and thiol groups and n, m, o, s, y and 2 are such that the silicone is soluble or dispersible in water at room temperature;
and b) heating the textile to a temperature of 120 -180C to cure the finishing agent.
. ~, 'L~
~048890 5d DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a method of applying hydrophilic finishes to the surface of cellulose-containing te~tiles to impart durable hydrophilic properties. The resulting te~tiles have improved softness, wettability, and durable press properties. The hydrophilic finish can be applied to woven and nonwoven testiles containing cellulose fibers, such as for esample cotton, flas, hemp and jute. The testile may be a blend of cellulose fibers and synthetic fibers such as, for esample, a cotton/polyester blend.
The process of the invention applies a finishing agent solution to a testile and cures the finishing agent on the testile. The finishing agent solution includes glyosal, glycol, an acid catalyst and a reactive hydrophilic silicone copolymer having a hydrosyl terminated polyether chain.
Alternatively, the hydrophilic silicone copolymer may ~be a terpolymer with a polyether having hydrosy-, alkosy- or acetosy-end groups and functional pendant groups bearing hydrosyl, amine, amide or thiol group or groups capable of forming reactive hydrosyl groups. The functional pendant group may be, for P~
~3~
_ 6 - ~0~8890 e~ample, an epo~y-pendant group. The hydrophilic silicone having the hydro~yl group or functional group capable of forming hydroxyl groups under reaction conditions is linked to the cellulose substrate to impart durable hydrophilic properties to the te~tile. The chemical linkage between the cellulose and the silicone is formed by the use of the acid catalyzed reaction of glyoxal, silicone and cellulose. The finish is generally produced by applying an aqueous solution of the silicone copolymer, glyo~al, glycol and acid catalyst to the cellulose textile, which is then dried and cured by heating at about 120 to about 180C.
The textiles treated in accordance with the invention possess durable hydrophilic softness. In the presence of an acid catalyst, glyo~al forms acetal links between the cellulose and hydroxyl group of the silicone copolymer.
The silicone copolymers of the invention are preferably random hydrophilic silicone copolymers having a polyoxyalkylene chain, hydroxyl groups or functional groups capable of forming hydro~yl groups under reactive conditions, and are reactive with glyoxal to form linkages between the silicone and the cellulose te~tile via the acetal formation. In a preferred embodiment of the invention, the reactive silicone is a copolymer having a polyether chain with hydro~yl end groups or alternatively a terpolymer with polyether and reactive pendant groups.
The preferred silicone copolymer is represented by the formula:
- 7 - 20~8890 R3 Si(S O)n(S:O)m...SiR3 ~ -2 wherein R at each occurrence is a monovalent hydrocarbon radical. R may be, for e~ample, an alkyl preferably having from 1 to 4 carbon atoms, aryl or arylalkyl. Most preferably R is methyl. In the above formula, n is an integer and m is an integer equal to or greater than 1. For egample, n may be about 10 to about 150. R2 at each occurrence is represented by the formula -(CH2)x(oR3)y(0R9)zR5 with recurring units oR3 and oR4, where R3 and R4 are the same or different and are C2H4 or C3H6. R5 is hydro~yl. In the formula, x, y and z are integers with the proviso that g and at least y or z are not zero. In the formula, n, m, g, y and z are selected such that the silicone is soluble or at least slightly soluble or dispersible in water at room temperature. The amount of ethyleneo~ide in the copolymer is sufficient to impart hydrophilic properties to the silicone copolymer. R2 consisting of oxyethylene and oxypropylene moieties linked in a random chain or in a block chain preferably has a molecular weight of about 150 to about 6,000 most preferably of about 3S0 to about 4,000.
In an alternative preferred embodiment the hydrophilic silicone copolymer has the general formula:
R R R
R3SiO...(SiO)n(SiO)m(SiO)o...SiR3 wherein R, n and m are as above and o is an integer of at least 1. R2 at each occurrence is represented by the formula -(CH2)s(oR3)y(0R4)zRS
wherein s, y, z, R3 and R4 are as above and RS is hydro~y-, alkosy- or acetosy-. The-alkosy preferably has 1 to 4 carbon atoms. In the preferred embodiment, R2 has a molecular weight of about lS0 to 6,000 and most preferably about 3S0 to 4,000. The amount of ethyleneoside in the copolymer is sufficient to impart hydrophilic properties to the silicone copolymer. R6 is a monovalent organic radical having one or more hydrosyl, diol, amine, amide, thiol or eposide groups. Preferably R6 has a pendant group selected from the group consisting of hydro~yl, diol and eposide group. In the preferred embodiment R6 is selected from the group consisting of -R7-CH-CH2, R7 ~ , R7CH20H, R7CH(oH)CH20H and R7 O =, wherein R7 is a divalent organic radical OH
such es methylene, ethylene, propylene, phenylene, -C3H60CH2- and (CH2)3-O-. Most preferably R6 is -(cH2)3ocH2cH-cH2~ -(CH2)2 ~' -C3H60H, ~ _OH
-C3H6-0CH2CIH_CIH2 or C2H4 OH OH
i ~
~S
9- 204~890 In the preferred embodiments, the silicone copolymer is soluble or dispersible in water. The silicone copolymer may be a liquid at room temperature or a wa~y solid. Generally, the water solubility is enhanced by increasing the weight ratio of the polyo~yethylene group to the polyo~ypropylene and to the silicone backbone in the molecule. For moderately water soluble silicone copolymers, a suitable surfactant may be used to disperse the silicone in water.
The glycol employed in the process may be a suitable diol which is able to react with the glyoxal. Glycols suitable for the process of the invention include, for example, straight chain alkanediols having the formula, HOR8OH, wherein R8 is an alkylene group having 2 to 12 carbon atoms or polyoxyalkylenes (polyethylene glycol or polypropylene glycol). The glycols preferably have a molecular weight of less than about 200. The most preferred glycols are diethylene glycol and triethylene glycols. Other glycols which may be used include, for e~ample, ethylene glycol, propylene glycol and dipropylene glycol.
The glyoxal used is suitably a commercial grade material commonly supplied as a 40% aqueous solution. Although less preferred, the glyoxal may be obtained as a solid which is subsequently dissolved in water to form a solution of a desired concentration.
The preferred acidic catalysts are Bronsted or Lewis acids capable of catalyzing the reaction of the glyo~al with the cellulose. Suitable acid catalyst include, for example, p-toluenesulfonic acid, zinc chloride, zinc tetrafluoroborate, aluminum chloride, magnesium chloride, aluminum chlorohydroxide and mi~tures thereof. In the preferred embodiment, the catalyst is a mi~ture of aluminum sulfate and tartaric acid as a catalyst -activator. Other acid catalyst activators which are effective include citric acid, glycolic acid, lactic acid, malic acid and mixtures thereof. The mole ratio of the acid to aluminum sulfate may range from 0.5:1 to 15:1. The preferred range of tartaric acid to aluminum sulfate is about 0.5:1 to 5:1.
In the process of the invention the finishing agent is prepared as an aqueous solution containing about 1% to about 5% glyoxal on a solids basis, about 1% to about 15% by weight of a glycol, about 1% to 15% by weight hydrophilic silicone polymer, about 0.1% to 2% by weight acidic catalyst and 0% to 2% of catalyst activator. Preferably the molar ratio of glyoxal to glycol is about 1:1 to 1:2 in the finishing agent. Suitably the aqueous solution contains from about 3% to 15~ by weight of a 40%
glyoxal solution, 3% to 15% by weight glycol, 1% to 5% by weight hydrophilic silicone copolymer, 0.1% to 1% catalyst and 0% to 0.5% by weight of an optional acid catalyst activator with the balance to 100%
with water.
The cellulose-containing textile is preferably impregnated in a bath with the treating solution and wet pick-up adjusted to 100% of the weight of the dry textile. Alternatively, the treating solution may be applied by spraying or by other suitable applicators. The moisture content of the impregnated textile maybe initially reduced by heating at an elevated temperature for about 2 to about 8 minutes and preferably about 3 minutes prior to substantial curing. The treated textile may then be cured by heating to a sufficient temperature for a sufficient period of time. The drying temperature may vary depending on the te~tile composition but will generally range from about 50C to 110C and is preferably about 85C. The te~tile is then heated to cure the finishing agent on the textile at a temperature of about 110C to 180C. The treated te~tile can be dried and cured in a one step heating process by heating the textile at a temperature of about 110 to about 180C. The heating time to dry and cure the finishing agent is dependent on the amount of water remaining from the treating solution to be evaporated and the curing temperature.
Suitably the curing time is about 0.5 to 5 minutes.
Alternatively the heating step may be initiated, for example, at about 50C and gradually heated to about 180C over a sufficient period of time to dry and cure the finishing agent on the te~tile.
The following e~amples illustrate the preferred embodiments of the invention and are not intended to be limiting. The treated te~tiles were evaluated and compared for properties and characteristics.
The testing methods employed were the standard methods as understood by those skilled in the art and include Wrinkle Recovery Angle by AATCC Method 66-1984, Durable Press Appearance by AATCC Method 124-1984, Wettability Test by AATCC Method 39-1980, Fabric Conditioning by ASTM Method D-1776-74, and Elmendorf Tearing Strength by ASTM D-1682-64.
The fabric used in the following examples was a bleached, desized mercerized cotton print cloth, Style 400M by Testfabric, Inc., Middlesex, N.J. The softness of the treated fabric was evaluated by a hand panel and the tested fabrics were rated using a scale of 1 to 10, where 1 is the softest and 10 is the harshest. In the following - examples, durability is intended to refer to the resistance of the hydrophilic silicone to repeated washing or laundering. The durability of the hydrophilic silicone on the te~tile was assessed by determining the amount of the silicone on the treated fabrics before and after five machine washing cycles as conducted by AATCC standard machine wash conditions with AATCC Detergent 124 and standard drying procedure. Durable press properties are intended to refer to the overall properties of the textile including shrinkage control, wrinkle recovery angle, and smooth drying performance.
F~x~MpT~
A mercerized, 100% cotton print cloth was treated with the aqueous treating composition as set forth in Table I below. Wet pick-up was adjusted to 100% by weight of the dry fabric. The treated fabrics were dried in a forced draft oven for about 3 minutes at B5C. Subsequently, the dried treated fabrics were cured by heating in a forced draft oven at 125C for 2 minutes. The durability of the hydrophilic silicone copolymers was determined by a comparison of the silicone level on treated fabrics before washing and after five washing cycles.
- 13 - 2 048 8~0 Standard AATCC machine wash conditions using AATCC
Detergent 124 and drying were applied. The durability to washing is calculated as the percentage of initial level of the silicone determined on the unwashed fabrics. The accuracy of the analytical method was 10%.
SAMPLE N0. 1 2 Comparative Samples A
Percent by ~e;ght Glyoxal, 40% solution 6.0 12.0 6.0 Diethylene glycol 8.8 8.8 (I) Me3SiO(Me2S;0)13(MeSj0)5SiMe3 2.0 2.0 2.0 2.0 C3H6(C2H4)7H
Aluminum sulfate octadecahydrate 0.770.77 0.77 Tartaric acid hydrate 0.370.37 0-37 ~ater 8Z.0676.06 90.8698.0 Durability of the silicone 65% 72% 33% 12%
The above data show a significant increase in the durability of the hydrophilic silicone copolymer on the cotton fabric from the treating solution containing glyo~al, diethylene glycol, and an acid catalyst compared to a similar treating solution without diethylene glycol or the silicone used alone.
A similar textile treatment was conducted on a mercerized cotton fabric using the process as in Example 1 for different treating solutions containing silicone copolymers having different silicone to -polyethyleneo~ide ratios. The durability of the silicone on the fabric was determined as in E~ample 1. The treating solution and resulting durability are shown in Table 2.
TABLE Z
SAMPLE N0. 1 3 4 S
Percent by ~eight Glyoxal, 40% solution 6.0 6.0 6.0 6.0 Diethylene glycol 8.8 8.8 8.8 8.8 (I) Me3SiO(Me25iO)13(MeSi0)5SiMe3 2.0 - - ~
C3H6(0C2H4)70H
(II) Me35iO(Me25iO)3û(MeSiO)5SiMe3 - 2.0 C3H6(0CzH4)70H
(III) Me3SiO(Me2SiO)45(MeSiO)5SiMe3 - - 2.0 C3H6(0C2H4)70H
(IV) Me3SiO(Me2SiO)75(MelSiO)lOSiMe3 2.0 C3H6(0C2H4)70H
Aluminum sulfate octadecahydrate 0.77 0.77 0.77 0.77 Tartaric acid h~drate 0.37 0.37 0.37 0-37 ~ater 82.06 82.06 82.06 82.06 % ethylene oxide 50 37 28 33 Durabilit~ of the Silicone (%) 65 41 -(spots) 33 - 15 - 2048~90 The above data demonstrate that as the hydro~yl functionality and hydrophilicity increases as represented by the percent of the ethylene o~ide in the copolymer, the durability of the hydrophilic silicone finish increases.
EXAMPT,F. 8 A textile treatment as in E~ample 1 was conducted on 100% cotton fabric using different treating solutions to compare the durability of silicones having a terminal primary or secondary hydroxyl groups on the organic group. The fabric was treated, dried and cured as in Example 1.
~ARLF. 3 SAMPLE N0. 6 7 Glyoxal, 40% solution 6.0 6.0 Diethylene glycol 8.8 8.8 (V) Me3SiO(Me2SiO)40(MefiO)lOSiMe3 2.0 C3H6 (0C2H4 ) 12H
(VI) Me3SiO(Me2siO)4o(Melsio)losiMe3 2.0 (random copolymer) C3H6(0c2H4)s(0c3H6~6oH
Aluminum R-~lfate octadecahydrate . 0.77 0.77 Tartaric acid hydrate 0.37 0.37 Water 82.06 82.06 Durability ~ 50% 2~%
- 16 - 20~8~90 The durability of the hydrophilic silicone on the textile as shown in Table 3 is significantly greater for the silicone of Sample 6 having a primary hydroxyl group on the polyethyleneoxide pendant group. The primary hydro~yl group on the polyo~yethylene is more reactive than the secondary hydroxyl end group on the polyo~yethylene/polyoxypropylene pendant group, and produces a finish that is more durable to repeated washing.
F.~Z~MpT.~ 4 This example considers the differences in durability between silicone copolymers having reactive hydro~yl end groups on the organo group and non-reactive silicone copolymers having methoxy end groups on the polyether organo group. In this e~ample, compound VII is a hydrophilic silicone copolymer with a terminal hydro~yl group on the polyoxyethylene/polyoxypropylene chain. The organic block included about 75% by weight polyo~yethylene.
Compound VIII is a methoxy terminated polyoxyethylene/polyo~ypropylene silicone copolymer.
The organic block of compound VIII included about 75%
by weight polyoxyethylene. The treating solution having the composition as shown in Table 4 was applied to samples of mercerized, 100% cotton fabric. The treated fabric was dried and cured in one step in a forced air oven at 171C for 90 seconds. The fabric samples were washed using standard washing procedures. The durabiLity of the finish is shown in Table 4. This data clearly demonstrate the increased durability of the silicone - 17 - 204~890 finish using the hydroxyl terminated polyether modified silicone compared to a non-reactive silicone. The residual durability of the non-reactive silicone (VIII) is believed to be due to the incomplete capping (85%) of the polyether. The remaining 15% contains hydroxyl functionality which may produce the semi-durable properties of this sample.
SAMPLE N0. 8 9 (% by weight) Glyoxal, 40% ~olution 6.0 6.0 Diethylene glycol 8.8 8.8 Aluminum 6ulfate octadecahydrate 0.125 0.125 Tartaric acid hydrate 0.075 0.075 (VII) Me3SiO(Me2SiO~74(MefiO)9SiMe3 2.0 C3H6(0C2H4)23(0C3H6)60H
(VIII) Me3SiO(Me2SiO)74(MefiO)gSiMe3 - 2.0 C3H6(0C2H4)23(0C3H6)60Me Water 83.0 83.0 Durability 56% 31%
FX~qpt.F. 5 The durability of the epo~y functional hydrophilic silicones was evaluated in this e~ample.
The aqueous treating solutions were prepared as Samples 10-13 according to Table 5. Compound I~ is - 18 - 2 0~ 8 890 silicone terpolymer with a metho~y-terminated polyo~yethylene/polyo~ypropylene and (3,4-eposycyclohe~yl)ethyl functional group. The polyo~yethylene/polyo~ypropylene included about 40%
by weight polyo~yethylene. Compound X is a silicone terpolymer with 3-glycidylo~ypropyl and icetyl-terminated polyo~yethylene/polyo~ypropylene, with higher epo~y content than Compound IX. The polyo~yethylene content in the polyo~yalkylene is about 40% by weight. Compound X~ was a silicone terpolymer of 3-glycidylo~ypropyl and acetyl-terminated polyo~yethylene/polyosypropylene with higher epo~y content than Compound ~. The polyo~yethylene content in the polyo~yalkylene was about 40% by weight. The solutions were applied to the cotton fabric and adjusted to 10~% of the weight of the dry fabric. The fabrics were dried and cured in one step for 90 seconds at 171C in an oven. The durability of each silicone is recorded in Table 5.
The data demonstrate high durability of the silicone bearing epo~ide, which increases with the epo~y content in the molecule.
S~mple No 10 11 12 13 ~X by ~eight) Gl~ox~l 40% 6 6 6 Dieth~lene glycol 8 8 8 8 8 5 Alurinum sulf~t~ oct~dec~hydr~te 0 2 0 2 0 2 T~rt~ric ~cid hydr~te 0 05 S 0 05 (IX) ~k3SiO(~e2SiO)85(~kSiO)~(MeSiO)nSiHe3 1 0 1 0 C2H4~0 C3H6(0~2H4)2s(0c3H6)27o~e3 n~n=7 5 epoxide content 0 25X
lg --(X) Me3sio(Me2sio)85(Mes;o)o(Mes;o)pMesio)qs;Me3 1.0 C3H60CH2-cH-cH2 o C3H6(0C2H4~36(oC3H6)410COCH3 C3H6(0C2H4~13(0C3H6)15Coc 3 o+p~q=7.5 o/p-3:1 epox;de content 0.4%
(XI) Me3SiO(Me2S;0)85(MeSiO)s(MeSiO)sMeSiO)tSiMe3 1.0 o C3H6(0c2H4)36(0c3H6)4loco 3 C3H6(0CzH4)13(0C3H6)15ococ 3 2s+t=7.5 epox;de content 0.7%
Water 83.95 83.95 83.95 99.0 Durab;lit~ ~fter 5 washing cycles 61% 67% 79% 23%
F.XPIMPT.~ 6 The durability of the hydrophilic silicones having diol pendant groups produced from the epo~y-functional silicones is demonstrated in this e~ample as Samples 14 and 15. Compounds IX and ~I from ~ample 5 were reflu~ed in a water/isopropanol solution in the presence of 0.2% trifluoroacetic acid for 2 hours to hydrolyze the epo~y group and form Compounds XII and ~III respectively. The hydrolysis efficiency was determined by titration of the residual epo~ide to be 8~% to gO~. The treating - 20 - 20~8~ 90 solution was prepared as shown in Table 6 accordin~
to the method of Example 1. The treated fabric was dried and cured at 171C for 90 seconds. The durability of the silicone was determined as shown in Table 6. This data shows that the silicones having pendant diol groups have similar durability as the epo~y-pendant silicones.
Sample No. 14 15 (% by we;ght) Glyoxal, 40% 6 6 Diethylene glycol 8.B 8.8 Aluminum sulfate octadecahydrate 0.2 O.Z
Tartaric acid hydrate 0.05 0.05 (XII) Me3SiO(Me25io)8s(Mesio)m(Mesio)nsiMe3 1.0 CzH4~1_ OH
C3H6 ( C2H4 ) 25 ( C3H6 ) 270Me ~n=7.5 (XIII) Me3sio~Me2sio)85(Mesio)s(Mesio)s(Mesio)tsiMe3 1.0 OH OH
C3H6(0C2H4)36(0C3H6)410COcH3 C3H6(0C2H4)13(0C3H6)15CCH3 2s~t=7.5 Hater 83.85 83.95 Durab;l;ty after 5 washing cycles 61% 6~%
- 21 - 204~890 This e~ample evaluates the durable press properties of the glyo~al-glycol-hydrophilic silicone systems. The treating solutions were prepared in accordance with Table 7. The solutions were applied to the cotton fabric samples and adjusted to 100% of the weight of the fabric. The fabrics were dried and cured at 171C for 90 seconds. The properties of the fabrics were determined as shown in Table 7.
Sample No. 16 17 Comparative Sample C
(% by weight) Glyoxal, 40% 6.0 6.0 6.0 Diethylene glycol 8.8 B.8 8.8 Aluminum 6ulfate octadecahydrate 0.125 0.125 0.125 Tartaric acid hydrate 0.075 0.075 0.075 Copolymer IX 2.0 Copolymer VII 2.0 Water 83.0 83.0 85.0 Cond. WRA (f+w degrees) initial 301 300 272 after 3 wa6he~ 295 285 230 tear 6trength 49% 44~ 31%
retention (w) Wetting time (6econd6) initial 9 6 6 after 3 wa6heR 30 10 3 Durable pre66 3.3 3.4 3.1 rating (average) Softne6c 2.5 2.5 6 Copolymer6 VII and IX are a6 in Example 4 and Example 5 respectively.
The data demonstrate that the glyo~al, glycol, hydrophilic silicone, catalyst process results in improved tear strength, wrinkle recovery, durable press rating and softness compared to the glyoxal-glycol system without the silicone.
The above examples are intended to be exemplary of the preferred embodiments of.the invention. It will be readily recognized by those skilled in the art that other modifications and embodiments can be made without departing from the spirit and scope of the invention as set forth in the following claims.
FIELD O~ T~E INVENTION
The present invention is directed to silicone copolymers which can produce durable hydrophilic finishes on cotton te~tiles. More particularly, the invention is directed to a method of treating cotton textiles to impart softness and durable hydrophilic properties to the te~tiles.
BACKGROUND OF THE INV~TION
Te~tiles, and particularly cotton and cotton blend textiles, are often treated with silicone finishing agents to provide softness, improve tear strength, flex abrasion, processibility and wrinkle recovery. These finishing agents are generally applied to the te~tile from aqueous systems in pad-dry-cure operations.
- Commonly employed types of si1icone finishing agents are the polysilo~anes containing pendant organic groups. The silicone finishing agents which have been typically used heretofore have hydrophobic properties and result in the fabrics having little or no water absorbency. When hydrophilic silicone copolymers are used, the te~tiles have improved hydrophilic properties, but these finishes generally have poor dura~ility. To improve the durability of the hydrophilic silicone finishes, reactive or curable organomodified silicones are generally used.
One example of the efforts to produce durable silicone finishes on te~tiles is disclosed in 20~8890 U.S. Patent No. 4,459,383. The fiber-treating composition includes at-least two reactive organosilicones which are able to react with each other and form durable finishes. The organomodified silicones include (1) an epo~y-substitutes silo~a-ne and (2) an amino or carbo~y-substituted and polyether-containing siloxane copolymer. The epoxy silicone is reacted with the amino-containing silo~ane or alternatively the carbo~yl-containing siloxane during curing to crosslink the siloxanes onto the fibers.
Other silicone finishing agents include silicone copolymers having polyo~yalkylene substituents and hydrolyzable di- or trialkoxysilyl groups. The silicones are applied to the fabric in the presence of moisture where the alkoxysilyl groups are hydrolyzed and cured at elevated temperatures.
One example of this form of silicone finishing agent is disclosed in U.S. Patent No. 4,283,519. A
hydrophilic organosilicone includes a trialko~ysilyl pendant group and a polyoxyethylene/polyoxypropylene chain terminated with a hydrogen or an acyl group.
The silicone is applied to the fabric and cured by heating in the presence of a catalyst.
U.S. Patent No. 4,758,646 discloses a bis (alko~ysilyl) polyether copolymer as a fabric sizing agent. The sizing agent is applied to the-fabric and cured by heating to produce a hydrophilic finish having antistatic and soil release properties.
Glyo~al has been known to react with cotton and produce durable press finishes for cotton related fabrics such as that disclosed in U.S. Patent No.
4,472,167. In this patent, an aqueous solution of ~ 3 ~ 20~890 glyo~al, glycol and an acid catalyst is applied to a cellulosic textile and cured by heating. The glyoxal is reported to form acetal crosslinks with cellulose. The glycol is added as a coreactant additive to modify the length of the crosslinks in the network. An optional silanol-terminated silicone is reported to produce a treated fabric having considerable water repellency.
U.S. Patent No. 4,269,603 discloses a durable press treatment for te~tile fabrics using an aqueous solution of glyoxal, a reactive hydrophobic silicone and a catalyst. The treating composition is cured at about 177C to 204C. This curing temperature has the disadvantage of producing a significant loss of tear strength of the fabric. The treating composition is reported to impart wrinkle resistance and smooth drying performance.
The present invention is directed to a method of producing hydrophilic silicone finishes for cellulose-containing te~tiles, using glyoxal to bind silicone copolymers to the te2tile. The resulting silicone finishes are durable to washing and impart soft hydrophilic properties and durable press properties to the treated fabric.
SUMMARY OF THE INV~NTION
The present invention is directed to finished te~ile materials and to a method of imparting durable hydrophilic softness to cellulose-containing te~tile materials. The hydrophilic finishes produced are sufficiently dura~le to withstand repeated washings in water ~889~
and/or home laundering. The textile finish can be used with or without other te~tile finishes.
The hydrophilic finish of the invention is produced by forming a chemical bond between the cellulose portion of a textile substrate and a hydrophilic silicone via acetal formation with glyo~al. The hydrophilic finish-forming composition is a mi~ture of glyoxal, glycol, a reactive hydrophilic silicone and an acid catalyst. The cellulose-containing textile is impregnated with the composition and subjected to reactive conditions, such as heating. The hydrophilic silicone then becomes fixed to the textile to impart durable hydrophilic properties.
The preferred reactive silicones are the hydrophilic silicone random copolymers having a hydro2yl terminated organic polyether substituent.
Preferably the silicone copolymers have primary or`
secondary hydroxyl terminated polyoxyalkylene chains. Preferably the polyoxyalkylene is a polyo~yethylene or a polyo~yethylene/polyo~ypropylene copolymer where the ethyleneo~ide content is such that the silicone is hydrophilic. The silicone copolymer may also be a terpolymer of polysiloxane, polyo~yethylene or polyo~yethylene/polyoxypropylene terminated with a hydroxy-, alko~y-, acetoxy-end group and pendant groups which bear hydro~yl, amine, amide or thiol groups or groups capable of forming hydro~yl gro~ps under reactive conditions. The preferred functional groups which are able to form hydro~yl groups are epo~y-pendant groups.-The reactive hydrophilic silicone whencombined with the glyoxal and glycol provides durable hydrophilic softness to the textile and enhanced durable press performance compared to the glyoxal-glycol system alone. A hydrophilic silicone copolymer, which becomes chemically linked to the textile, provides improved durable wrinkle recovery angles, smooth drying performance and increased tear strength to the treated fabrics.
In accordance with one aspect of the present invention, there is provided a process of forming durable hydrophilic silicone finishes on textiles formed at least partially of cellulosic fibers such finishes withstanding repeated washing in water which process comprises:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5~ glyoxal, about 1% to 15~ glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0~ to 2~ catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) R R
R3SiO...(S:O)n(S )m...SiR3 q ~2 wherein R at each occurrence is a monovalent hydrocarbon radi~al; n is an integer and m is an integer equal to or greater than l; and R2 has the formula -(CH2)~(oR3)y(0R4)zR5 wherein oR3 and oR4 are repeating units; R3 and R4 are the same or different and sele~ted from the group consisting of C2H4 and C3H6; ~, y and z are integers with the proviso that and at least y or z are not zero; R5 is hydro~yl, n, m, ~, y and z are selected such that the silicone is soluble or dispersible in water at room temperature;
and (ii) 2d48890 5a ~ R R
R3siO...(s-o)n(s:o)m(s-o)o---siR3 ~- ~2 ~6 wherein R, n and m are as above, and o is an integer of at least l; R2 at each occurrence has the formula -(CH2-)1~(oR3)y(0R4)zR~
wherein ~, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy-, and R6 is a monovalent organic radicàl having a reactive group selected from the group consisting of epo~ide, hydrosyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is solu~le or dispersible in water at room temperature; and (b) heating the textile to a temperature of 120 -180C to cure the finishing agent.
In accordance with another aspect of the present invention, there is provided a heat curable textile finishing agent for forming durable hydrophilic finishes on textiles formed at least partially of cellulosic fibers, such finishes withstanding repeated washing in water, which finishing agent in the form of an aqueous solution comprising by weight about 1% to 5%
glyoxal, about 1% to 15% glycol, about 1% to 15%
hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) R R
R3sio~(s-o)n(s-o)m~siR3 ~ ~2 wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer, m is an integer 5b equal to or greater than 1; and R2 has the formula -(CH2)~-(oR3)y(0R~)~R5 wherein, oR3 and OR~ are repeating units; R3 and R~ are the same or different and selected from the group consisting of C2H~ and C3H6; x, y, z are integers with the proviso that x and at least y or z are not zero; Rs is hydroxyl, n, m, x, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) ~. R R
R3SiO...(S-O)n(s O)m(s o)o~SiR3 ~ h2 -6 wherein R, m and n are as above and o is an integer of at least 1; R2 at each occurrence has the formula -(CH2)~-(oR3)y(0R~)~Rs wherein x, y, z, R3 and R~ are as above, Rs is hydroxy-, alkoxy- or acetoxy, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are ~uch that the silicone is soluble or dispersible in water at room temperature.
In accordance with yet a further aspect of the present invention, there is provided a textile formed at least partially of cellulosic fibers having a durable hydrophilic finish that withstands repeated w~;ng in water produced by the steps of:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5% glyoxal, about 1% to 15% glycol, about 1%
to 15% hydrophilic silicone copolymer, about 0.1 to 2%
acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, the hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) ~' 5c 2048890 R3sio~(s-o)n(s-o)m~siR3 ". R2 wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer and m is an integer equal to or greater than l; and R2 has the formula -(CH2)s-(oR3)y(OR4)zR5 wherein oR3 and oR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; s, y, z are integers with the proviso that s and at least y or z are not zero; R5 i5 hydrosyl, n, m, s, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) R - _ R3SiO...(S-O)n(S O)m(S-O)o...SiR3 ~ ~2 q6 wherein R, m and n are as above a~d o is an integer of at least l; R2 at each occurrence has the formula -(CH2)~(0R3)y(0R4)2R5 wherein s, Yr Z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or aceto~y, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of eposide, hydrosyl, diol, amine, amide and thiol groups and n, m, o, s, y and 2 are such that the silicone is soluble or dispersible in water at room temperature;
and b) heating the textile to a temperature of 120 -180C to cure the finishing agent.
. ~, 'L~
~048890 5d DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a method of applying hydrophilic finishes to the surface of cellulose-containing te~tiles to impart durable hydrophilic properties. The resulting te~tiles have improved softness, wettability, and durable press properties. The hydrophilic finish can be applied to woven and nonwoven testiles containing cellulose fibers, such as for esample cotton, flas, hemp and jute. The testile may be a blend of cellulose fibers and synthetic fibers such as, for esample, a cotton/polyester blend.
The process of the invention applies a finishing agent solution to a testile and cures the finishing agent on the testile. The finishing agent solution includes glyosal, glycol, an acid catalyst and a reactive hydrophilic silicone copolymer having a hydrosyl terminated polyether chain.
Alternatively, the hydrophilic silicone copolymer may ~be a terpolymer with a polyether having hydrosy-, alkosy- or acetosy-end groups and functional pendant groups bearing hydrosyl, amine, amide or thiol group or groups capable of forming reactive hydrosyl groups. The functional pendant group may be, for P~
~3~
_ 6 - ~0~8890 e~ample, an epo~y-pendant group. The hydrophilic silicone having the hydro~yl group or functional group capable of forming hydroxyl groups under reaction conditions is linked to the cellulose substrate to impart durable hydrophilic properties to the te~tile. The chemical linkage between the cellulose and the silicone is formed by the use of the acid catalyzed reaction of glyoxal, silicone and cellulose. The finish is generally produced by applying an aqueous solution of the silicone copolymer, glyo~al, glycol and acid catalyst to the cellulose textile, which is then dried and cured by heating at about 120 to about 180C.
The textiles treated in accordance with the invention possess durable hydrophilic softness. In the presence of an acid catalyst, glyo~al forms acetal links between the cellulose and hydroxyl group of the silicone copolymer.
The silicone copolymers of the invention are preferably random hydrophilic silicone copolymers having a polyoxyalkylene chain, hydroxyl groups or functional groups capable of forming hydro~yl groups under reactive conditions, and are reactive with glyoxal to form linkages between the silicone and the cellulose te~tile via the acetal formation. In a preferred embodiment of the invention, the reactive silicone is a copolymer having a polyether chain with hydro~yl end groups or alternatively a terpolymer with polyether and reactive pendant groups.
The preferred silicone copolymer is represented by the formula:
- 7 - 20~8890 R3 Si(S O)n(S:O)m...SiR3 ~ -2 wherein R at each occurrence is a monovalent hydrocarbon radical. R may be, for e~ample, an alkyl preferably having from 1 to 4 carbon atoms, aryl or arylalkyl. Most preferably R is methyl. In the above formula, n is an integer and m is an integer equal to or greater than 1. For egample, n may be about 10 to about 150. R2 at each occurrence is represented by the formula -(CH2)x(oR3)y(0R9)zR5 with recurring units oR3 and oR4, where R3 and R4 are the same or different and are C2H4 or C3H6. R5 is hydro~yl. In the formula, x, y and z are integers with the proviso that g and at least y or z are not zero. In the formula, n, m, g, y and z are selected such that the silicone is soluble or at least slightly soluble or dispersible in water at room temperature. The amount of ethyleneo~ide in the copolymer is sufficient to impart hydrophilic properties to the silicone copolymer. R2 consisting of oxyethylene and oxypropylene moieties linked in a random chain or in a block chain preferably has a molecular weight of about 150 to about 6,000 most preferably of about 3S0 to about 4,000.
In an alternative preferred embodiment the hydrophilic silicone copolymer has the general formula:
R R R
R3SiO...(SiO)n(SiO)m(SiO)o...SiR3 wherein R, n and m are as above and o is an integer of at least 1. R2 at each occurrence is represented by the formula -(CH2)s(oR3)y(0R4)zRS
wherein s, y, z, R3 and R4 are as above and RS is hydro~y-, alkosy- or acetosy-. The-alkosy preferably has 1 to 4 carbon atoms. In the preferred embodiment, R2 has a molecular weight of about lS0 to 6,000 and most preferably about 3S0 to 4,000. The amount of ethyleneoside in the copolymer is sufficient to impart hydrophilic properties to the silicone copolymer. R6 is a monovalent organic radical having one or more hydrosyl, diol, amine, amide, thiol or eposide groups. Preferably R6 has a pendant group selected from the group consisting of hydro~yl, diol and eposide group. In the preferred embodiment R6 is selected from the group consisting of -R7-CH-CH2, R7 ~ , R7CH20H, R7CH(oH)CH20H and R7 O =, wherein R7 is a divalent organic radical OH
such es methylene, ethylene, propylene, phenylene, -C3H60CH2- and (CH2)3-O-. Most preferably R6 is -(cH2)3ocH2cH-cH2~ -(CH2)2 ~' -C3H60H, ~ _OH
-C3H6-0CH2CIH_CIH2 or C2H4 OH OH
i ~
~S
9- 204~890 In the preferred embodiments, the silicone copolymer is soluble or dispersible in water. The silicone copolymer may be a liquid at room temperature or a wa~y solid. Generally, the water solubility is enhanced by increasing the weight ratio of the polyo~yethylene group to the polyo~ypropylene and to the silicone backbone in the molecule. For moderately water soluble silicone copolymers, a suitable surfactant may be used to disperse the silicone in water.
The glycol employed in the process may be a suitable diol which is able to react with the glyoxal. Glycols suitable for the process of the invention include, for example, straight chain alkanediols having the formula, HOR8OH, wherein R8 is an alkylene group having 2 to 12 carbon atoms or polyoxyalkylenes (polyethylene glycol or polypropylene glycol). The glycols preferably have a molecular weight of less than about 200. The most preferred glycols are diethylene glycol and triethylene glycols. Other glycols which may be used include, for e~ample, ethylene glycol, propylene glycol and dipropylene glycol.
The glyoxal used is suitably a commercial grade material commonly supplied as a 40% aqueous solution. Although less preferred, the glyoxal may be obtained as a solid which is subsequently dissolved in water to form a solution of a desired concentration.
The preferred acidic catalysts are Bronsted or Lewis acids capable of catalyzing the reaction of the glyo~al with the cellulose. Suitable acid catalyst include, for example, p-toluenesulfonic acid, zinc chloride, zinc tetrafluoroborate, aluminum chloride, magnesium chloride, aluminum chlorohydroxide and mi~tures thereof. In the preferred embodiment, the catalyst is a mi~ture of aluminum sulfate and tartaric acid as a catalyst -activator. Other acid catalyst activators which are effective include citric acid, glycolic acid, lactic acid, malic acid and mixtures thereof. The mole ratio of the acid to aluminum sulfate may range from 0.5:1 to 15:1. The preferred range of tartaric acid to aluminum sulfate is about 0.5:1 to 5:1.
In the process of the invention the finishing agent is prepared as an aqueous solution containing about 1% to about 5% glyoxal on a solids basis, about 1% to about 15% by weight of a glycol, about 1% to 15% by weight hydrophilic silicone polymer, about 0.1% to 2% by weight acidic catalyst and 0% to 2% of catalyst activator. Preferably the molar ratio of glyoxal to glycol is about 1:1 to 1:2 in the finishing agent. Suitably the aqueous solution contains from about 3% to 15~ by weight of a 40%
glyoxal solution, 3% to 15% by weight glycol, 1% to 5% by weight hydrophilic silicone copolymer, 0.1% to 1% catalyst and 0% to 0.5% by weight of an optional acid catalyst activator with the balance to 100%
with water.
The cellulose-containing textile is preferably impregnated in a bath with the treating solution and wet pick-up adjusted to 100% of the weight of the dry textile. Alternatively, the treating solution may be applied by spraying or by other suitable applicators. The moisture content of the impregnated textile maybe initially reduced by heating at an elevated temperature for about 2 to about 8 minutes and preferably about 3 minutes prior to substantial curing. The treated textile may then be cured by heating to a sufficient temperature for a sufficient period of time. The drying temperature may vary depending on the te~tile composition but will generally range from about 50C to 110C and is preferably about 85C. The te~tile is then heated to cure the finishing agent on the textile at a temperature of about 110C to 180C. The treated te~tile can be dried and cured in a one step heating process by heating the textile at a temperature of about 110 to about 180C. The heating time to dry and cure the finishing agent is dependent on the amount of water remaining from the treating solution to be evaporated and the curing temperature.
Suitably the curing time is about 0.5 to 5 minutes.
Alternatively the heating step may be initiated, for example, at about 50C and gradually heated to about 180C over a sufficient period of time to dry and cure the finishing agent on the te~tile.
The following e~amples illustrate the preferred embodiments of the invention and are not intended to be limiting. The treated te~tiles were evaluated and compared for properties and characteristics.
The testing methods employed were the standard methods as understood by those skilled in the art and include Wrinkle Recovery Angle by AATCC Method 66-1984, Durable Press Appearance by AATCC Method 124-1984, Wettability Test by AATCC Method 39-1980, Fabric Conditioning by ASTM Method D-1776-74, and Elmendorf Tearing Strength by ASTM D-1682-64.
The fabric used in the following examples was a bleached, desized mercerized cotton print cloth, Style 400M by Testfabric, Inc., Middlesex, N.J. The softness of the treated fabric was evaluated by a hand panel and the tested fabrics were rated using a scale of 1 to 10, where 1 is the softest and 10 is the harshest. In the following - examples, durability is intended to refer to the resistance of the hydrophilic silicone to repeated washing or laundering. The durability of the hydrophilic silicone on the te~tile was assessed by determining the amount of the silicone on the treated fabrics before and after five machine washing cycles as conducted by AATCC standard machine wash conditions with AATCC Detergent 124 and standard drying procedure. Durable press properties are intended to refer to the overall properties of the textile including shrinkage control, wrinkle recovery angle, and smooth drying performance.
F~x~MpT~
A mercerized, 100% cotton print cloth was treated with the aqueous treating composition as set forth in Table I below. Wet pick-up was adjusted to 100% by weight of the dry fabric. The treated fabrics were dried in a forced draft oven for about 3 minutes at B5C. Subsequently, the dried treated fabrics were cured by heating in a forced draft oven at 125C for 2 minutes. The durability of the hydrophilic silicone copolymers was determined by a comparison of the silicone level on treated fabrics before washing and after five washing cycles.
- 13 - 2 048 8~0 Standard AATCC machine wash conditions using AATCC
Detergent 124 and drying were applied. The durability to washing is calculated as the percentage of initial level of the silicone determined on the unwashed fabrics. The accuracy of the analytical method was 10%.
SAMPLE N0. 1 2 Comparative Samples A
Percent by ~e;ght Glyoxal, 40% solution 6.0 12.0 6.0 Diethylene glycol 8.8 8.8 (I) Me3SiO(Me2S;0)13(MeSj0)5SiMe3 2.0 2.0 2.0 2.0 C3H6(C2H4)7H
Aluminum sulfate octadecahydrate 0.770.77 0.77 Tartaric acid hydrate 0.370.37 0-37 ~ater 8Z.0676.06 90.8698.0 Durability of the silicone 65% 72% 33% 12%
The above data show a significant increase in the durability of the hydrophilic silicone copolymer on the cotton fabric from the treating solution containing glyo~al, diethylene glycol, and an acid catalyst compared to a similar treating solution without diethylene glycol or the silicone used alone.
A similar textile treatment was conducted on a mercerized cotton fabric using the process as in Example 1 for different treating solutions containing silicone copolymers having different silicone to -polyethyleneo~ide ratios. The durability of the silicone on the fabric was determined as in E~ample 1. The treating solution and resulting durability are shown in Table 2.
TABLE Z
SAMPLE N0. 1 3 4 S
Percent by ~eight Glyoxal, 40% solution 6.0 6.0 6.0 6.0 Diethylene glycol 8.8 8.8 8.8 8.8 (I) Me3SiO(Me25iO)13(MeSi0)5SiMe3 2.0 - - ~
C3H6(0C2H4)70H
(II) Me35iO(Me25iO)3û(MeSiO)5SiMe3 - 2.0 C3H6(0CzH4)70H
(III) Me3SiO(Me2SiO)45(MeSiO)5SiMe3 - - 2.0 C3H6(0C2H4)70H
(IV) Me3SiO(Me2SiO)75(MelSiO)lOSiMe3 2.0 C3H6(0C2H4)70H
Aluminum sulfate octadecahydrate 0.77 0.77 0.77 0.77 Tartaric acid h~drate 0.37 0.37 0.37 0-37 ~ater 82.06 82.06 82.06 82.06 % ethylene oxide 50 37 28 33 Durabilit~ of the Silicone (%) 65 41 -(spots) 33 - 15 - 2048~90 The above data demonstrate that as the hydro~yl functionality and hydrophilicity increases as represented by the percent of the ethylene o~ide in the copolymer, the durability of the hydrophilic silicone finish increases.
EXAMPT,F. 8 A textile treatment as in E~ample 1 was conducted on 100% cotton fabric using different treating solutions to compare the durability of silicones having a terminal primary or secondary hydroxyl groups on the organic group. The fabric was treated, dried and cured as in Example 1.
~ARLF. 3 SAMPLE N0. 6 7 Glyoxal, 40% solution 6.0 6.0 Diethylene glycol 8.8 8.8 (V) Me3SiO(Me2SiO)40(MefiO)lOSiMe3 2.0 C3H6 (0C2H4 ) 12H
(VI) Me3SiO(Me2siO)4o(Melsio)losiMe3 2.0 (random copolymer) C3H6(0c2H4)s(0c3H6~6oH
Aluminum R-~lfate octadecahydrate . 0.77 0.77 Tartaric acid hydrate 0.37 0.37 Water 82.06 82.06 Durability ~ 50% 2~%
- 16 - 20~8~90 The durability of the hydrophilic silicone on the textile as shown in Table 3 is significantly greater for the silicone of Sample 6 having a primary hydroxyl group on the polyethyleneoxide pendant group. The primary hydro~yl group on the polyo~yethylene is more reactive than the secondary hydroxyl end group on the polyo~yethylene/polyoxypropylene pendant group, and produces a finish that is more durable to repeated washing.
F.~Z~MpT.~ 4 This example considers the differences in durability between silicone copolymers having reactive hydro~yl end groups on the organo group and non-reactive silicone copolymers having methoxy end groups on the polyether organo group. In this e~ample, compound VII is a hydrophilic silicone copolymer with a terminal hydro~yl group on the polyoxyethylene/polyoxypropylene chain. The organic block included about 75% by weight polyo~yethylene.
Compound VIII is a methoxy terminated polyoxyethylene/polyo~ypropylene silicone copolymer.
The organic block of compound VIII included about 75%
by weight polyoxyethylene. The treating solution having the composition as shown in Table 4 was applied to samples of mercerized, 100% cotton fabric. The treated fabric was dried and cured in one step in a forced air oven at 171C for 90 seconds. The fabric samples were washed using standard washing procedures. The durabiLity of the finish is shown in Table 4. This data clearly demonstrate the increased durability of the silicone - 17 - 204~890 finish using the hydroxyl terminated polyether modified silicone compared to a non-reactive silicone. The residual durability of the non-reactive silicone (VIII) is believed to be due to the incomplete capping (85%) of the polyether. The remaining 15% contains hydroxyl functionality which may produce the semi-durable properties of this sample.
SAMPLE N0. 8 9 (% by weight) Glyoxal, 40% ~olution 6.0 6.0 Diethylene glycol 8.8 8.8 Aluminum 6ulfate octadecahydrate 0.125 0.125 Tartaric acid hydrate 0.075 0.075 (VII) Me3SiO(Me2SiO~74(MefiO)9SiMe3 2.0 C3H6(0C2H4)23(0C3H6)60H
(VIII) Me3SiO(Me2SiO)74(MefiO)gSiMe3 - 2.0 C3H6(0C2H4)23(0C3H6)60Me Water 83.0 83.0 Durability 56% 31%
FX~qpt.F. 5 The durability of the epo~y functional hydrophilic silicones was evaluated in this e~ample.
The aqueous treating solutions were prepared as Samples 10-13 according to Table 5. Compound I~ is - 18 - 2 0~ 8 890 silicone terpolymer with a metho~y-terminated polyo~yethylene/polyo~ypropylene and (3,4-eposycyclohe~yl)ethyl functional group. The polyo~yethylene/polyo~ypropylene included about 40%
by weight polyo~yethylene. Compound X is a silicone terpolymer with 3-glycidylo~ypropyl and icetyl-terminated polyo~yethylene/polyo~ypropylene, with higher epo~y content than Compound IX. The polyo~yethylene content in the polyo~yalkylene is about 40% by weight. Compound X~ was a silicone terpolymer of 3-glycidylo~ypropyl and acetyl-terminated polyo~yethylene/polyosypropylene with higher epo~y content than Compound ~. The polyo~yethylene content in the polyo~yalkylene was about 40% by weight. The solutions were applied to the cotton fabric and adjusted to 10~% of the weight of the dry fabric. The fabrics were dried and cured in one step for 90 seconds at 171C in an oven. The durability of each silicone is recorded in Table 5.
The data demonstrate high durability of the silicone bearing epo~ide, which increases with the epo~y content in the molecule.
S~mple No 10 11 12 13 ~X by ~eight) Gl~ox~l 40% 6 6 6 Dieth~lene glycol 8 8 8 8 8 5 Alurinum sulf~t~ oct~dec~hydr~te 0 2 0 2 0 2 T~rt~ric ~cid hydr~te 0 05 S 0 05 (IX) ~k3SiO(~e2SiO)85(~kSiO)~(MeSiO)nSiHe3 1 0 1 0 C2H4~0 C3H6(0~2H4)2s(0c3H6)27o~e3 n~n=7 5 epoxide content 0 25X
lg --(X) Me3sio(Me2sio)85(Mes;o)o(Mes;o)pMesio)qs;Me3 1.0 C3H60CH2-cH-cH2 o C3H6(0C2H4~36(oC3H6)410COCH3 C3H6(0C2H4~13(0C3H6)15Coc 3 o+p~q=7.5 o/p-3:1 epox;de content 0.4%
(XI) Me3SiO(Me2S;0)85(MeSiO)s(MeSiO)sMeSiO)tSiMe3 1.0 o C3H6(0c2H4)36(0c3H6)4loco 3 C3H6(0CzH4)13(0C3H6)15ococ 3 2s+t=7.5 epox;de content 0.7%
Water 83.95 83.95 83.95 99.0 Durab;lit~ ~fter 5 washing cycles 61% 67% 79% 23%
F.XPIMPT.~ 6 The durability of the hydrophilic silicones having diol pendant groups produced from the epo~y-functional silicones is demonstrated in this e~ample as Samples 14 and 15. Compounds IX and ~I from ~ample 5 were reflu~ed in a water/isopropanol solution in the presence of 0.2% trifluoroacetic acid for 2 hours to hydrolyze the epo~y group and form Compounds XII and ~III respectively. The hydrolysis efficiency was determined by titration of the residual epo~ide to be 8~% to gO~. The treating - 20 - 20~8~ 90 solution was prepared as shown in Table 6 accordin~
to the method of Example 1. The treated fabric was dried and cured at 171C for 90 seconds. The durability of the silicone was determined as shown in Table 6. This data shows that the silicones having pendant diol groups have similar durability as the epo~y-pendant silicones.
Sample No. 14 15 (% by we;ght) Glyoxal, 40% 6 6 Diethylene glycol 8.B 8.8 Aluminum sulfate octadecahydrate 0.2 O.Z
Tartaric acid hydrate 0.05 0.05 (XII) Me3SiO(Me25io)8s(Mesio)m(Mesio)nsiMe3 1.0 CzH4~1_ OH
C3H6 ( C2H4 ) 25 ( C3H6 ) 270Me ~n=7.5 (XIII) Me3sio~Me2sio)85(Mesio)s(Mesio)s(Mesio)tsiMe3 1.0 OH OH
C3H6(0C2H4)36(0C3H6)410COcH3 C3H6(0C2H4)13(0C3H6)15CCH3 2s~t=7.5 Hater 83.85 83.95 Durab;l;ty after 5 washing cycles 61% 6~%
- 21 - 204~890 This e~ample evaluates the durable press properties of the glyo~al-glycol-hydrophilic silicone systems. The treating solutions were prepared in accordance with Table 7. The solutions were applied to the cotton fabric samples and adjusted to 100% of the weight of the fabric. The fabrics were dried and cured at 171C for 90 seconds. The properties of the fabrics were determined as shown in Table 7.
Sample No. 16 17 Comparative Sample C
(% by weight) Glyoxal, 40% 6.0 6.0 6.0 Diethylene glycol 8.8 B.8 8.8 Aluminum 6ulfate octadecahydrate 0.125 0.125 0.125 Tartaric acid hydrate 0.075 0.075 0.075 Copolymer IX 2.0 Copolymer VII 2.0 Water 83.0 83.0 85.0 Cond. WRA (f+w degrees) initial 301 300 272 after 3 wa6he~ 295 285 230 tear 6trength 49% 44~ 31%
retention (w) Wetting time (6econd6) initial 9 6 6 after 3 wa6heR 30 10 3 Durable pre66 3.3 3.4 3.1 rating (average) Softne6c 2.5 2.5 6 Copolymer6 VII and IX are a6 in Example 4 and Example 5 respectively.
The data demonstrate that the glyo~al, glycol, hydrophilic silicone, catalyst process results in improved tear strength, wrinkle recovery, durable press rating and softness compared to the glyoxal-glycol system without the silicone.
The above examples are intended to be exemplary of the preferred embodiments of.the invention. It will be readily recognized by those skilled in the art that other modifications and embodiments can be made without departing from the spirit and scope of the invention as set forth in the following claims.
Claims (21)
1. A process of forming durable hydrophilic silicone finishes on textiles formed at least partially of cellulosic fibers such finishes withstanding repeated washing in water which process comprises:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 15% to 5% glyoxal, about 1% to 15% glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 15% to 5% glyoxal, about 1% to 15% glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to
2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, said hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer and m is an integer equal to or greater than 1; and R2 has the formula -(CH2)x(OR3)y(OR4)zR5 wherein OR3 and OR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; x, y and z are integers with the proviso that and at least y or z are not zero; R5 is hydroxyl, n, m, x, y and z are selected such that the silicone is soluble or dispersible in water at room temperature;
and (ii) wherein R, n and m are as above, and o is an integer of at least l; R2 at each occurrence has the formula -(CH2-)x(0R3)y(OR4)zR5 wherein 2, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy or acetoxy-, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of episode, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature; and b) heating the textile to a temperature of 120 -180°C to cure the finishing agent.
2. The process of claim 1 wherein R is methyl.
and (ii) wherein R, n and m are as above, and o is an integer of at least l; R2 at each occurrence has the formula -(CH2-)x(0R3)y(OR4)zR5 wherein 2, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy or acetoxy-, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of episode, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature; and b) heating the textile to a temperature of 120 -180°C to cure the finishing agent.
2. The process of claim 1 wherein R is methyl.
3. The process of claim l wherein the catalyst is selected from the group consisting of p-toluenesulfonic acid, zinc chloride, zinc tetrafluoroborate, aluminum chloride, magnesium chloride, aluminum chlorohydroxide, aluminum sulfate and mixtures thereof.
4. The process of claim 3 wherein said catalyst further includes a catalyst activator selected from the group consisting of tartaric acid, citric acid, glycolic acid, lactic acid, malic acid and mixtures thereof.
5. The process of claim l wherein the glycol is selected from the group consisting of alkanediols and polyoxyalkylene diols, wherein said glycol has a molecular weight of less than about 200.
6. The process of claim l wherein the molar ratio of glyoxal to glycol is about 1:1 to about 1:2 in the finishing agent.
7. The process of claim l wherein R6 is selected from the group consisting of and wherein R7 is selected from the group consisting of methylene, ethylene, propylene, phenylene, -C3H60CH2-and -(CH2)3O.
8. A heat curable textile finishing agent for forming durable hydrophilic finishes on textiles formed at least partially of cellulosic fibers, such finishes withstanding repeated washing in water, which finishing agent in the form of an aqueous solution comprising by weight about 1% to 5% glyoxal, about 1% to 15% glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, said hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer, m is an integer equal to or greater than 1; and R2 has the formula -(CH2)x-(OR3)y(OR4)zR5 wherein, OR3 and OR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; s, y, z are integers with the proviso that x and at least y or z are not zero; R5 is hydroxyl, n, m, s, y and z are selected such that the silicone is soluble or dispersible in water at room temperature;
and (ii) wherein R, m and n are as above and o is an integer of at least l; R2 at each occurrence has the formula -(CH2)x(OR3)y(OR4)zR5 wherein x, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature.
and (ii) wherein R, m and n are as above and o is an integer of at least l; R2 at each occurrence has the formula -(CH2)x(OR3)y(OR4)zR5 wherein x, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy, and R6 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature.
9. The finishing agent of claim 8 wherein the glycol is selected from the group consisting of an alkanediol and polyoxyalkylene, wherein said glycol has a molecular weight of less than about 200.
10. The finishing agent of claim 8 wherein the catalyst is selected from the group consisting of p-toluenesulfonic acid, zinc chloride, zinc tetrafluoroborate, aluminum chloride, magnesium chloride, aluminum chlorohydroxide, aluminum sulfate and mixtures thereof.
11. The finishing agent of claim 10 wherein said catalyst includes a catalyst activator selected from the group consisting of tartaric acid, citric acid, glycolic acid, lactic acid, malic acid and mixtures thereof.
12. The finishing agent of claim 8 wherein is methyl.
13. The finishing agent of claim 8 wherein the molar ratio of glyoxal to glycol is about 1:1 to about 1:2 in the finishing agent.
14. The finishing agent of claim 8 wherein R6 is selected from the group consisting of , and wherein R7 is selected from the group consisting of methylene, ethylene, propylene, phenylene, -C3H6OCH2-and -(CH2)3O-.
15. A textile formed at least partially of cellulosic fibers having a durable hydrophilic finish that withstands repeated washing in water produced by the steps of:
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5% glyoxal, about 1% to 15% glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, said hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer and m is an integer equal to or greater than 1; and R2 has the formula -(CH2)x-(OR3)y(OR4)zR5 wherein OR3 and OR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; x, y, z are integers with the proviso that x and at least y or z are not zero;
R5 is hydroxyl, n, m, x, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) wherein R, m and n are as above and o is an integer of at least 1; R2 at each occurrence has the formula -(CH2)x-(OR3)y(OR4)zR5 wherein, x, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy, and R5 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature; and b) heating the textile to a temperature of 120 -180°C to cure the finishing agent.
a) impregnating the textile with a finishing agent in the form of an aqueous solution comprising by weight about 1% to 5% glyoxal, about 1% to 15% glycol, about 1% to 15% hydrophilic silicone copolymer, about 0.1 to 2% acid catalyst and 0% to 2% catalyst activator based on the weight of the solution, said hydrophilic silicone copolymer being at least one organomodified silicone copolymer selected from the group consisting of (i) wherein R at each occurrence is a monovalent hydrocarbon radical; n is an integer and m is an integer equal to or greater than 1; and R2 has the formula -(CH2)x-(OR3)y(OR4)zR5 wherein OR3 and OR4 are repeating units; R3 and R4 are the same or different and selected from the group consisting of C2H4 and C3H6; x, y, z are integers with the proviso that x and at least y or z are not zero;
R5 is hydroxyl, n, m, x, y and z are selected such that the silicone is soluble or dispersible in water at room temperature; and (ii) wherein R, m and n are as above and o is an integer of at least 1; R2 at each occurrence has the formula -(CH2)x-(OR3)y(OR4)zR5 wherein, x, y, z, R3 and R4 are as above, R5 is hydroxy-, alkoxy- or acetoxy, and R5 is a monovalent organic radical having a reactive group selected from the group consisting of epoxide, hydroxyl, diol, amine, amide and thiol groups and n, m, o, x, y and z are such that the silicone is soluble or dispersible in water at room temperature; and b) heating the textile to a temperature of 120 -180°C to cure the finishing agent.
16. The textile of claim 15 wherein R is methyl.
17. The textile of claim 15 wherein the catalyst is at least one selected from the group consisting of p-toluenesulfonic acid, zinc chloride, zinc tetrafluoroborate, aluminum chloride, magnesium chloride, aluminum chlorohydroxide, aluminum sulfate and mixtures thereof.
18. The textile of claim 17 wherein said catalyst includes a catalyst activator selected from the group consisting of tartaric acid, citric acid, glycolic acid, lactic acid, malic acid and mixtures thereof.
19. The textile of claim 15 wherein the glycol is selected from the group consisting of alkylene glycols and polyoxyalkenes.
20. The textile of claim 15 wherein the molar ratio of glyoxal to glycol is about 1:1 to about 1:2 in the finishing agent.
21. The textile of claim 15 wherein R6 is selected from the group consisting of and , wherein R7 is selected from the group consisting of methylene, ethylene, propylene, phenylene, -C3H6OCH2-and -(CH2)3O-.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56716390A | 1990-08-10 | 1990-08-10 | |
| US7-567,163 | 1990-08-10 | ||
| US68334291A | 1991-04-10 | 1991-04-10 | |
| US7-683,342 | 1991-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2048890A1 CA2048890A1 (en) | 1992-02-11 |
| CA2048890C true CA2048890C (en) | 1997-07-15 |
Family
ID=27074380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002048890A Expired - Fee Related CA2048890C (en) | 1990-08-10 | 1991-08-09 | Silicone textile finishes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0470613B1 (en) |
| JP (1) | JPH04245979A (en) |
| AT (1) | ATE121473T1 (en) |
| CA (1) | CA2048890C (en) |
| DE (1) | DE69109017T2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0995535A (en) * | 1995-09-29 | 1997-04-08 | Toray Dow Corning Silicone Co Ltd | Diorganopolysiloxane and treatment agent for cloth |
| DE19628018A1 (en) * | 1996-07-11 | 1998-01-15 | Wacker Chemie Gmbh | Hydrophilic, permanent organosilicon compounds |
| KR100281513B1 (en) * | 1997-05-22 | 2001-02-15 | 울프 크라스텐센, 스트라쎄 로텐베르그 | Okano polysiloxanes consisting of polyhydroxyorganyl radicals and polyoxy alkylene radicals, in particular sugar radicals or sugar derivatives |
| DE19724948A1 (en) * | 1997-06-12 | 1998-12-17 | Wacker Chemie Gmbh | Organosilicon compounds containing (meth) acrylate groups and oxyalkylene groups |
| US6495057B1 (en) * | 1999-12-28 | 2002-12-17 | General Electric Company | Wrinkle removing composition and process |
| US20010042276A1 (en) * | 2000-03-30 | 2001-11-22 | Shiseido Co., Ltd. | Hair dye fixatives, hair dyes and hair dyeing methods |
| US7122174B2 (en) | 2002-09-30 | 2006-10-17 | L'oreal S.A. | Compositions comprising at least one silicone compound and at least one amine compound, and methods for using the same |
| US7833541B2 (en) * | 2006-05-01 | 2010-11-16 | Momentive Performance Materials Inc. | Cosmetic compositions utilizing acrylate cross linked silicone copolymer networks |
| WO2008127519A1 (en) | 2007-04-11 | 2008-10-23 | Dow Corning Corporation | Silcone polyether block copolymers having organofunctional endblocking groups |
| US8709959B2 (en) * | 2009-12-28 | 2014-04-29 | Kimberly-Clark Worldwide, Inc. | Puncture resistant fabric |
| CN113717388B (en) * | 2021-08-19 | 2022-11-15 | 浙江三元纺织有限公司 | Preparation of ecological antibacterial finishing agent and method for finishing fabric by using same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269603A (en) * | 1979-05-04 | 1981-05-26 | Riegel Textile Corporation | Non-formaldehyde durable press textile treatment |
| US4283519A (en) * | 1979-12-20 | 1981-08-11 | Union Carbide Corporation | Organosilicone terpolymers |
| US4472167A (en) * | 1983-08-26 | 1984-09-18 | The United States Of America As Represented By The Secretary Of Agriculture | Mild-cure formaldehyde-free durable-press finishing of cotton textiles with glyoxal and glycols |
| US4536422A (en) * | 1984-03-06 | 1985-08-20 | The United States Of America As Represented By The Secretary Of Agriculture | Process to impart smooth-dry and flame retardant properties to cellulosic fabric |
| DE3832089A1 (en) * | 1988-09-21 | 1990-03-29 | Rotta Gmbh & Co Dr | TEXTILE FINISHING AGENT AND METHOD FOR FINISHING CELLULOSE-CONTAINING TEXTILE GOODS |
-
1991
- 1991-08-08 AT AT91113322T patent/ATE121473T1/en active
- 1991-08-08 EP EP91113322A patent/EP0470613B1/en not_active Expired - Lifetime
- 1991-08-08 DE DE69109017T patent/DE69109017T2/en not_active Expired - Fee Related
- 1991-08-09 JP JP3223643A patent/JPH04245979A/en not_active Withdrawn
- 1991-08-09 CA CA002048890A patent/CA2048890C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE69109017D1 (en) | 1995-05-24 |
| ATE121473T1 (en) | 1995-05-15 |
| EP0470613B1 (en) | 1995-04-19 |
| CA2048890A1 (en) | 1992-02-11 |
| JPH04245979A (en) | 1992-09-02 |
| EP0470613A1 (en) | 1992-02-12 |
| DE69109017T2 (en) | 1995-08-31 |
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