MXPA97008478A - Silicone aminopolyalkyleneoxide block copolymers. - Google Patents

Abstract

The present invention discloses non-hydrolyzable, block, (AB)nA type, copolymers comprising alternating units of polysiloxane and amino-polyalkyleneoxide and provides a method for the preparation of these copolymers. Also provided is the use of these copolymers as softeners, in particular durable, hydrophilic textile softeners, which improve tactile properties of the textiles substrates treated with the commercial soil release finishes, without substantially detracting from their properties. The copolymers of the present invention have alternating units of polysiloxane [X(CaH2aO)bR<2>[(SiO(R<1>)2]cSi(R<1>)2R<2>(CaH2aO)bX] and polyalkyleneoxides [YO(CaH2aO)dY] wherein R<1> is a C1 to C4 alkyl, preferably methyl, R<2> is a divalent organic moiety, X and Y are divalent organic groups selected from a secondary or tertiary amine and a ring opened epoxide, such that when X is a ring opened epoxide, Y is an amine and vice versa, a = 2 to 4, preferably 2 to 3, b = 0 to 100, d = 0 to 100, b + d = 1 to 100, preferably 10 to 50, and c = 1 to 500, preferably 10 to 100.

Description

COPOLYMERS OF AMINOPOLIALOUILENOXIDE SILICONE BLOCK The present application claims priority of the U.S. Provisional Application. No. 60 / 012,732 filed March 4, 1996. BACKGROUND OF THE INVENTION Non-hydrolyzable siloxane-polyalkyleneoxide block copolymers of the (AB) nA type, ie with alternating siloxane and organic blocks, primarily polyether, are known in the prior art. Methods for preparing these copolymers are provided in U.S. Pat. No. 4,242,466. The patent of the U.S.A. No. 4,833,225 describes silicone polyquats type (AB) "A derived from a polysiloxane terminated in epoxy block and low molecular weight diamines with tertiary amino end groups. The resulting copolymers are polyquaternary and do not contain polyalkylenoxide units in the structure. The patent of the U.S.A. No. 4,101,272, provides a method for improving properties of fibrous materials, wherein these materials are treated with a composition of polyorganosiloxanes modified with epoxy and polyamines with two or more primary and / or secondary amino groups, which react in situ to form a network non-linear interlaced. Network formation is essential to achieve desirable dryness shrinkage and / or durability control. It is also known that fluorochemical products such as SCOTCHGARD ™ FC-248 (3), are effective treatments for soil release for textile substrates. However, fabrics treated with SCOTCHGARE / "* FC-248, especially in combination with permanent ironing finishes, become very stiff and unpleasant to use, although the improvement in" feel to touch "in accordance with the Prospectus is advisable. SCOTCHGARD Product "* FC-248, polysiloxanes are considered to severely affect the performance properties of the fluorochemical product. SUMMARY OF THE INVENTION The present invention discloses non-hydrolysable block copolymers type (AB) "A comprising alternating units of polysiloxane and amino polyalkylenoxide and provides a method for the preparation of these copolymers. Also provided is the use of these copolymers as softeners, in particular durable hydrophilic textile fabric softeners that improve the tactile properties of textile substrates treated with commercial finishes for release of dirt, without deteriorating these properties. Other uses include treating relatively hydrophobic substrates such as woven and nonwoven substrates to impart durable softness and hydrophilicity. Other uses include personal care formulations containing these copolymers and substrates that have been treated with these copolymers. DESCRIPTION DET¾T.T.¾r > A r > E INVENTION A. Copolymer Structure The copolymers of the present invention have alternating polysiloxane units [X (CaH2a0) "R2 [(SiO (R1) 2] cSi (R1) 2 R2 (0CaH2a) bX] and polyalkylenoxides [Y0 ( CaH2a0), jY], wherein R1 is an alkyl with 1 to 4 carbon atoms, preferably methyl, R2 is a divalent organic moiety, X and Y are divalent organic groups selected from secondary or tertiary amine and an open ring epoxide , such that when X is an open ring epoxide, Y is an amine and vice versa, a is 2 a, preferably 2 to 3, each occurrence of b is 0 to 100, d is 0 to 100, (b + d) is 1 to 100, preferably 10 to 50 and c is 1 to 500, preferably 10 to 100. The total number of repetitive units is only limited by the ability to handle high viscosity material, since the viscosity is increased as the number of units, but practically there must be at least two of each unit and there may be up to 1000 units It is preferred that the unit containing the amine should be the end groups of the copolymer, ie the A in (AB) nA.

The open ring epoxides, represented by either X or Y, can be aliphatic, cycloaliphatic and may contain aromatic rings. They can also contain hydroxy groups, and may contain an ether link. Preferably, the open ring epoxide is chosen from the following: -CH2CH (0H) (CH2) vCH (0H) CH2-, CH [CH20H] (CH2) VCH [CH20H] -, -CH2CH (OH) (CH2) VCH [CH2OH] -, (CH2) v-OCH2CH (OH) CH2-, - (CH2) v-0CH2CH (CH2 [0H]) - with v = 2 to 6. Alternatively, the ring-opened epoxides may be derived of the following groups epoxycyclohexyl alkylene, omega- (3,4-epoxycyclohexyl) alkylene, β- (3,4-epoxycyclohexyl) ethylene, β- (3,4-epoxycyclohexyl) -β-methylethylene, and β- (3, 4) -epoxy-4-methylcyclohexyl) -fi-methylethylene. The amines, represented by either X or Y, are secondary or tertiary amines. More specifically, the amines can be of the type -R * N (R3) (R *) q-, wherein R3 can be an alkyl group with 1 to 4 carbon atoms or hydrogen, more preferably methyl, and R * is a alkylene, cycloaliphatic alkylene or an aralkylene group, which may include heteroatoms, although an alkylene with less than 10 carbon atoms is preferred and g may be 0 or 1. R 2 is a divalent hydrocarbon group with at least one carbon atom, which may have substitutions hydroxy and / or include an ether linkage. It is preferred that it contains less than 10 carbon atoms. Within a particular molecule (AB) "A, each R1, R2, R3 and R" may be the same or different.The polyoxyalkylene blocks represented by (CaH2a0) or (OC "H2a) may be constituted by ethylene oxide (a) = 2), propylene oxide (a = 3) and butylene oxide (a = 4) randomly or blockwise The relationship between these oxides is not of particular importance, but can be adjusted as required for the solubility parameters The molecular weight of the copolymer can be modified by varying the molar ratio of the epoxy component to the amino component, by varying the number of oxyalkylene units and the number of siloxy groups within the polysiloxane blocks. Molecular weight due to properties essential to the application, such as softness and durability, depend on the molecular weight of the polymer, it is also essential to produce non-interlaced structures, ie only linear molecules. Another important factor that controls the properties of the copolymers is the relative content of silicone in the molecule, ie the values of c and (b + d). Copolymers of higher silicone content are usually more hydrophobic and therefore less soluble in water and impart better smoothness. A preferred ratio of c a (b + d) is 10: 1 to 1:10 and more preferably 2: 1. The copolymers are terminated with hydrogen, when the end groups are open ring epoxides. When the terminal groups are amines as described herein, the co-polymers are terminated with primary and secondary amine groups. A particularly preferred copolymer can be one of the following formula: HN (R3) (CaH2a0) bCH (C¾CH2N (R3) [CH2CH (OH) CH20 (CH2) 2 (SiO (R1) 2 (CH2) 30CH2- CH (0H) CH2-N (R3) (CaH2a0) bCH2CH (CH3) N (R3)] and H (1) "and" is at least two and may be as high as is allowed within the technique for manufacturing commutations of high viscosity and thus can be in the range of 2 to about 1,000, depending on the values of b and c in formula (1). B. Manufacturing Method The preparation of the compounds of the present invention is by reacting two species .Q (C¾.0) bi [(SiO (R1),] cSi (R1) aRa (Oq.Ha «) bQ and polyalkylene oxides [ ZO (CbH2t, 0) "Z], which are the same as the above formulas except that each Q and Z are already a primary or secondary amine or an epoxide-containing group, with the proviso that if Q contains an amine, Z contains a epoxide and vice versa These species can be manufactured as known in the art or are commercially available In an exemplary process, omega-hydrogenpolysiloxanes of the general formula H (SiO (R1) 2) xSi (RI) 2H are reacted with unsaturated epoxides with a terminal olefinic bond, such as allyl glycidyl ether, in the presence of a hydrosilation catalyst, such as for example hexachloroplatinic acid, at elevated temperature to produce polyesiloxanes terminated at the epoxy end These methods are known in the art as indicated in p U.S. Patent No. 3,761,444 or British Patent No. 1,213,779. Examples of suitable epoxides with terminal olefinic groups are given below. CH2 = CH-CH2-0-CH-CH2 \ / In the second step, the epoxy end block polysiloxanes are reacted with polyalkylene oxides terminated with primary or secondary amino groups. These aminopolyalkylenoxides are represented by JEFFAMINEMB ED-900 and JEFFAMINEMR BD-200I available from Hunst an Co.f and may be of the following structure: H2 CH (CH,) CH2 (0CeH2a) b0CH2CH (CH3) NH2 (II). The reaction is carried out in a convenient solvent such as alcohol or a mixture of alcohol and water at reflux. Typically, end-block epoxy polysiloxanes are added to the solution of the amine in the reaction solvent. Similarly, a, omega-hydrogenosiloxane can be hydrosylated with a polyoxyalkylene oxide terminated with allyl initiated epoxy as is known in the art. These epoxy-terminated compositions can then be reacted with diamines (for example ethylene diamine, 1,6-diaminohexane, piperazine) to link polyether siloxane units together. Other methods for manufacturing the present structures will be clear to a person skilled in the art. For practical purposes, the reaction is carried out with 1 to 30%, preferably 1 to 10% excess of the amine-containing species. Despite the fact that the excess amine is used, during the preparation of the copolymers and most of the end groups are expected to be amines, it is possible that the epoxy end group in the polysiloxane may be subjected to side reactions with the solvent, water or alcohol to form the corresponding dibl or ether alcohol. After the reaction, the copolymer solution can be neutralized by a direct addition of the Bronstedt acid such as acetic acid, citric acid or tartaric acid, to exchange solvents with a non-flammable solvent such as water, propylene glycol, dipropylene glycol and dipropylene glycol methyl ether. A reaction product can also be isolated by distilling off the solvent at atmospheric or reduced pressure; depending on the molecular weight and ethylene oxide content of the copolymer it can be a viscous oil or a wax. C. Copolymer Uses The copolymers of the present invention are primarily intended as softeners for substrates, especially fiber, hair and textiles, and particularly in formulations for release of stains incorporating a fluorochemical product. While the copolymers of the present invention can be employed as such, for ease of application they are usually applied to dissolved substrates, dispersed or emulsified to a convenient liquid medium. Preferably, the copolymers of the present invention are applied to a substrate of an aqueous solution, emulsion or suspension. They can also be applied as a solution in a non-aqueous solvent such as isopropanol, or in a liquid in which the copolymer is miscible. More preferably, the copolymer is applied to a substrate as an aqueous dispersion. Aqueous emulsions of the copolymers are prepared by combining the copolymer with one or more emulsifiers such as nonionic surfactants and diluted with water to the desired concentration. Nonionic surfactants commonly employed in such emulsions may include, for example, TERGITOL "* surfactants available from Union Carbide Chemicals and Plastics Co., Inc. Stable aqueous dispersions of the copolymers, for example, may be prepared by directly mixing or formulating a solution of the copolymer at the water-miscible solvent such as isopropanol, propylene glycol, dipropylene glycol and dipropylene glycol methyl ether with water to obtain the desired level of copolymer In this way dispersions, emulsions or solutions prepared can be applied to the substrate such as by spray, immersion or kiss roller application or other application method typically employed in the treatment of fibers, hair or textiles The substrate that can be treated with the copolymers of the present invention is exemplified by natural fibers such as hair, cotton, silk, linen, cellulose , paper (including tissue paper), and wool; synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; and inorganic fibers such as glass or carbon fibers. The fabric substrate 5 that can be treated with the copolymers of the present invention is exemplified by the fabric produced from the aforementioned fibrous materials or mixtures thereof. In general, the dispersion is applied on skin, hair, fibers or textiles such as up to 5%, preferably 0.25 to 2.5% copolymer by weight of the dry substrate remaining on the substrate. Optionally, other additives commonly used to treat hair or textile substrates can be used together with the copolymers of the present invention, including but not limited to additional surfactants, curing resins, preservatives, colorants, dyes, formulations and / or perfluorinated finishes for soil / stain release. Even more, compositions that include The copolymers [AB] nA of the present invention can be used in personal care formulations, including cleansers, body washes, soaps, lotions, creams, shaving cream for hair sprays, conditioners, shampoos, deodorants, humectants and sunblocks.

«JilSÍái-ii | i '· líj -íi -Mi-rii ii -ftlS' '* - rififl-rf' tÉntfSi || - * '· **" * The copolymers of the present invention can be formulated in these or other products in combination with one or more anionic surfactants, one or more amphoteric surfactants, one or more nonionic surfactants and / or one or more thickeners Suitable anionic surfactants include sulphonated sulphonated sulphonated anionic, aralkyl and alkaryl alkaryl compounds; alkyl succinates; alkyl sulfosuccinates; and N-alkanoyl sarcosinates The sodium, magnesium, ammonium, and mono-, di-, and triethanolamine salts of alkyl ¾58B £ &omanates are preferred.The alkyl groups preferably contain from 8 to 22 carbon atoms. preferably containing 1 to 10 units of ethylene oxide and / or propylene oxide are preferred Preferred examples of anionic surfactants include sodium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl sulfate, trie lauryl sulfate tanolamine, C14-16 sodium olefin sulfonate, paret-25 ammonium sulfate, myristyl ether sodium sulfate, ammonium lauryl ether sulfate, disodium monooleamido sulfosuccinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate and N -lauroyl sarcosinate sodium.

Examples of amphoteric surfactants from which the copolymers of the present invention can be formulated include cocoanfocarboxiglycinate, cocoanfocarboxipropionate, cocobetaine, N-cocoamido-propyl dimethylglycine and N-lauryl-N * -carboxymethyl-Nx- (2-hydroxyethyl) ethylenediamine, as well as betaine and sultaine compounds described in the CTFA Dictionary as useful in personal care products. Examples of useful nonionic surfactants with which the copolymers of the present invention can be formulated, include mono- and dialkanolamides of fatty acids, wherein the fatty portion preferably contains ~3-? to 21 carbon atoms and amine oxides such as N-alkyl amine oxides. A shampoo formulation typically contains about 3 to 30 weight percent of an anionic and / or amphoteric surfactant component, 0.1 to 10 weight percent of a nonionic surfactant component, together with 0.1 to 20 weight percent of one or more copolymers of the present invention, and water. Preferably also with an effective amount in the order of 0.1 to 5 weight percent of a thickener; Examples of thickeners include sodium alginate, gum arabic, polyoxyethylene, guar gum, hydroxypropyl guar gum, cellulosics such as methyl cellulose, methylhydroxypropyl cellulose and hydroxypropylcellulose, starch derivatives such as hydroxyethyl amylose, algaroba gum and polysaccharides. EXAMPLES Synthetic procedures for the preparation of the copolymers of the invention, as well as their application, are described in the following examples, which are provided by way of illustration and not by way of limitation. EXAMPLE 1 Preparation of the Copolymers (AB) "A of the Invention In a 4-necked flask, of 1 liter capacity, equipped with stirrer, addition funnel and reflux condenser, a, omega-hydrogenosiloxane (charges provided in Table 1 corresponding to a molar excess of the epoxide) of the general formula HSi (CH3) 20 [Si (CH3) 20] pSi (CH3) 2H is heated to 80 ° C. A slow addition of the allyl glycidyl ether starts at 80 ° C after chloroplatinic acid is added to the vessel (5 to 10 ppm as Pt). The temperature is maintained at 80 to 9 ° C until SiH can not be detected. The excess of allyl glycidyl ether is removed by stripping in vacuo at 50 mm Hg and 120 ° C. the resulting epoxy end fluid is characterized by its epoxy equivalent weight.Table 1 - Loads for the Preparation of Blocked Polysiloxanes in Epoxy End Load Ally Load Designation Weight Equivalen-P of SiH piicidil Eter Fluid Epoxy te Epoxy (g) (g) (g) 20 500 91.7 A-20 781.3 50 500 31.2 A-50 2127 75 500 21.0 A-75 3030 100 500 15.9 A-100 3703 150 500 11.2 A-150 4761 In a second stage, the aminopolyalkyleneoxide (5% molar excess) [JEFFAMINE ** ED-900 according to with Formula II above with a = 2.5 and b = 15.5 and JEFFAMINE "R ED 2001 according to Formula II above with a = 2.5 and b = 40.5] detailed charges are given in Table 2 and a sufficient amount of 2-propanol for To produce a 50% solution of the final copolymer, they were placed in a four-necked flask with 1 liter capacity, equipped with stirrer, addition funnel, reflux condenser and thermometer.The temperature of the reaction mixture is adjusted to 80 °. C and an a, omega-diepoxysiloxane is added from an addition funnel in three portions, allowing 1.2 hours between additions.The reaction is completed when the epoxy functionality determined by titration is consumed.

Table 2. Charges for the Preparation of the Copolymers (AB) -A Epoxy Fluid Silica Load JEFFAMINE "* JEFFAMINE *" * of Start with Epoxy ED-900 ED-2001 (g) (g) (g) A-20 50 30.5 A-20 50 69.8 A-50 100 30.0 A-50 100 61.0 A-75 200 75.5 A-100 300 40.1 A-100 300 94.5 A-150 200 49.0 TABLE 2 CONTINUOUS Epoxy Fluid Designation of the Part Copolymer A-20 AB-20-18 A-20 AB-20-43 A-50 AB-50-18 A-50 AB-50-43 A-75 AB-75-43 A-100 AB-100-18 A- 100 AB-100-43 A-150 AB-150-43 EXAMPLE 2 Copolymer Softening Properties Test (AB) "A In this example, the test and test cloth procedures used were as follows: Blanched Cotton Interleaved Fabric , Style 460 (Test Fabrics Inc., Middlesex NJ) Test Procedures Textile Conditioning for Test, Method ASTM D-1776-79 Absorbency of Bleached Textiles, AATCC Method 79-1992 Evaluation of softness is carried out by the test panel for hand and the tested goods were rated from the softest to the hardest (1 is the softest). Selected copolymers of the present invention (as solutions in isopropanol), MAGNASOFT "* PLUS (control, commercial premium amino softener from OSi Specialties, Inc., of Danbury, CT) and MAGNASOFT ™ HSSD (control, hydrophilic softener with polyalkylene oxide and amino groups) secondary of OSi Specialties) were applied in 100% cotton fabric of the waterproofing bath, a durable ironing resin (methylated dimethyloldihydroxyethylene urea, which is commercially available) and curing catalyst (magnesium chloride), were used with all treatments to simulate a typical textile finishing process The concentration of softener in the finishing composition is such that the effective addition level in the fabric was 1%, the curing conditions were 171 ° C for 1.5 minutes. Absorbency is summarized in Table 3. Table 3 Smoothness and Humidity Rating Humidity Smoothing Smoothing Time Rating ( sec) AB-150-43 3 3.5 AB-100-43 2 4.0 AB-75-43 4 7.0 MAGNASOFTm Plus 1 66.0 MAGNASOFTKR HSSD 5 1.0 1 Higher reflectance values correspond to whiter textiles. 2 Lower ranges correspond to softer textiles. Table 3 shows that copolymers (AB) nA in the presence of durable ironing resin provide softening properties superior to silicone MAGNASOFTMR HSSD and wetting properties superior to silicone AGNASOFT "" PLUS. EXAMPLE 3. Hair Conditioning Properties Test In a side-side comparison test, half of a quantity of human hair was washed with a control shampoo and the other half was washed using a conditioning shampoo containing the described product I presented. The susceptibility data for combing, appearance and flight are summarized in Table 4. PREPARATION OF SHAMPOO Conditioning Shampoo for Conditioning Control (% weight) (% by weight) Lauryl Sulfate Ammonium, 28% 35.0 35.0 Lauramide DEA 3.0 3.0 Methyl Glucose Dioleate PEG-120"Glucamate" DOE-120a 2.0 2.0 AB-100-43 (25% in dipropylene glycol) 12.0 Citrus acid, anhydrous 0.4 0.4 Cocamidopropyl Betaine, 35 % 10.0 10.0 Dimethicone Copolyol, 2.5 2.5 SILWET "* surfactant L-7657" Deionized water cs c.s. Conservative c.s. c.s. a: Amerchol b: OSi Specialties, Inc. Procedure: Water was mixed with ammonium lauryl sulfate. The solution was heated to 45 ° C and the remaining ingredients were added in the order listed, waiting for each ingredient to dissolve before adding the next. Conservative was added after cooling the formulation to room temperature. Table 4. Hair Properties Treated with Copolymer AB- 100-43 SUSCEPTIBILITY SUSCEPTIBILITY TREATMENT TO HAIRSTYLE IN WET TO DRY HAIR CM (INCHES) CM (INCHES) Control 6.9 (2.7) 12.7 (5.0) Conditioning Shampoo. 12.2 (4.8) 22.9 (9.0) TABLE 4 CONTINUE FLIGHT APPEARANCE TREATMENT CM (INCHES) Control 25.4 (10.0) smooth, dul Conditioning Shampoo. 12.7 (5.0) soft, silky, shiny The hair washed with the conditioning shampoo had improved combing ability in wet and dry, provided better brightness and reduced electrostatic charge. EXAMPLE 4: Copolymer Test (AB) "A in Combination with Stain Release Agent In this example, the stain release agent, the test cloth, and the test procedures employed were as follows: * Release Agent Fluorocarbon Spots - SCOTCHGARD "* FC-248 Fluorocarbide 30% in aqueous dispersion (3M). * Fabric Identification Í est Fabrics Inc., Middlesex NJ1 - Interwoven Cotton Fabric Bleached Style 460; 65/35 Cotton Poplin or Poplin Cotton Bleach rayon, Style 7409 Test Procedures * Grime Release: Oily Stain Release AATCC Method 13.0-1990 * Textile Conditioning for Test, ASTM Method D-1776-79 * Reflectance, Blue and Bleach Fabric Bleached, AATCC Method 110-1979 * Evaluation of Softness is done by the test panel by hand and the fabrics tested were rated from the softest to the hardest (1 is the softest). selected copolymers of the invention, MAGNASOFTMR PLUS (control, commercial premium amino softener) and MAGNASOFT * "* HSSD (control, hydrophilic softener with polyalkylene oxide and amino side groups) silicones were filled on 100% cotton knitted fabric and woven fabric. 100% cotton, in combination with SCOTCHGARDMR FC-248. A durable ironing resin (methylated dimethyloldihydroxyethyleneurea, which is commercially available) and curing catalyst (magnesium chloride) were used with all treatments to stimulate typical textile finishing processes. The concentrations of softener and stain release agent in the finish composition were such that the levels of effective active agent addition in the fabric were 0.5% (BOWF); Curing conditions were 171 ° C for 1.5 minutes. The whiteness of the treated textiles was determined using a Hunter Lab spectrocolorimeter. The reflectance softness data are given in Table 5. Table 5. Reflectance and Softness Data for Fabrics Treated with Copolymers (AB) "A and Control Softeners 100% COTTON POINT FABRIC FINISH Reflectancex Smoothness Range2 AB-20-18 63.8 5 AB-20-43 73.2 9 AB-50-18 65.9 8 AB-75-43 68.6 1 AB-100-18 71.0 6 Table 5 Reflectance and Softness Data for Fabrics Treated with Copolymers (AB) -A and Control Softeners 100% COTTON POINT FABRIC FINISH Reflectance1 Softness Range2 AB-100-43 71.1 2 AB-150-43 72.0 3 MAGNASOFTHR PLUS- (control) 69.8 4 MAGNASOFT "" HSSD- (control) 75.7 6 Silicon Free 72.9 10 1 Higher values correspond to whiter fabrics 2 Minor ranges correspond to softer fabrics Based on the data contained in Table 5, all copolymers of the present invention improved the "feel to the touch" of the fabrics treated with the perfluoro stain release finish, without discolouring the fabrics . Treated fabrics were subsequently stained with dirty engine oil, mineral oil and corn oil, in accordance with ASTM 130-1990, washed once and evaluated. The ratings for stain release for dirty engine oil stain are summarized in Table 6.

Table 6. Qualifications for Release of Stains from Fabrics Treated with Scotchgard in combination with Copolymers (AB) "A and Control Softeners QUALIFICATION QUALIFICATION OF RELEASE OF RELEASE STAIN FINISH1 STAIN 65/35 100% woven 65/35 knit Cotton Polyester Cotton AB-20-18 3.0 3.75 AB-20-43 3.5 3.5 AB-50-18 3.5 3.75 AB-75-43 3.0 3.5 AB-100-18 3.5 4.0 AB-100-43 2.5 3.75 AB-150-43 3.0 3.5 MAGNASOFTMR PLUS 1.5 .5 MAGNASOFTMR HSSD 2.5 .5 Without Silicone 3.75 3.75 Rating of dirt release: 1 = more visible; 5 = invisible As shown in Table 6, the copolymers of the present inventions are useful as softeners for the stain release finishes, since, unlike traditional hydrophobic softeners, _ "J 1" '' only have minimal effect on perfluorochemical performance EXAMPLE 5. Copolymer Test (AB) "A for Softening and Dabbing Facial Tissue Aqueous solutions or dispersions of the copolymers of the present invention identified in Table 7 was applied by spray on both sides of conventional 3-ply tissue paper such that 2.0 weight percent of silicone solids were present in the tissue after air drying Blind samples (including controls) were evaluated by 5 panelists and graded for softness, and the average of the scores of each sample is recorded and reported in Table 7. The grading scale or in the range of 1 (softest) to 14 (harder). according to the AATCC test protocol 79-1995 Table 7. Evaluation of Copolymers (??) ,, in 3-layer Facial Tissue Paper PRODUCT TESTED HUMANTABILITY, QUALIFICATION OF SOFTNESS AB-20-43 4 4.4 AB-100- 43> 180 5.6 AB-20-18 4 3.4 AB-50-43 15 8.6 AB-50-18 14 3.8 Table 7. Evaluation of Copolymers (AB) nA in 3-layer Facial Tissue Paper (Continued) PRODUCT TESTED HUMANTABILITY, QUALIFICATION SEC OF SOFTNESS Silicone Softener 2 12.3 Water Control 1 14 All the materials according to the present invention that were tested, showed excellent softness properties, superior to an existing commercial product and most showed good wetting characteristics. EXAMPLE 6. Hydrophilic Durability of Copolymers (AB) nA in Nonwoven Polypropylene Another use for the copolymers of the present invention is in surface application to normally hydrophobic substrates such as nonwoven polypropylene, in order to increase the wettability of the substrate. A product that will be used for this purpose should be able to resist being washed from the substrate when aqueous fluids are applied to the substrate. An established technique to estimate the ability of surface treatments to resist flushing is to apply the product, and subject it to repeated treatments ("attacks") with an aqueous solution, and to measure the amount of the product remaining on the substrate after each attack. This technique is used in this example. Aqueous solutions or dispersions of the copolymers (AB) "A" of the present invention identified in Table 8, were prepared and spray applied on one side of 100% polypropylene nonwoven fabric (22.03 gr / m2 (0.65 oz / yd2) )) such that 0.5% silicone solids were present in the nonwoven after air drying. Samples and controls were estimated for hydrophilic durability to repeated attacks (using aqueous 0.9% NaCl solution) using the EDANA test method 150.3-96 (Capillary Liquid Absorption Time). The results are reported in Table 8. Keeping in mind that the objective is to continue imparting wettability even after repeated attacks, a smaller number is preferred in the table representing a shorter time required to wet the substrate and in accordance with this, a higher proportion of the product that remains in the substrate. Table 8. Evaluate Copolymers (AB) "A in 100% Polypropylene Non Woven Time in Seconds Required to Moisten the Substrate After Each Attack No. of Attacks = 1 2 3 4 5 Product Tested: AB-20-18 14.6 9.9 11.1 12.1 11.3 Silicon Copolymer with Secondary Polialcoxi Chains 2.8 4.0 43.1 67.7 93.2 AB-20-43 42 32 30.4 15.0 23.1 Untreated > 180 > 180 > 180 > 180 > 180 The data in Table 8 show that the copolymers of the present invention are more hydrophilically durable after repeated attacks than conventional silicone copolymers with secondary polyalkylene oxide side chains.

Claims (21)

1. CLAIMS 1. A copolymer composed of alternating polysiloxane units of the formula (1) (X (CaH2a0) bR2 (SiO (R1) 2) 6Si (R1) 2R2 (0CaH2a) bX) (1) and polyalkylenoxide of the formula (2) ) (YOIC ^ O ^ Y) (2) wherein each R1 independently is an alkyl group with 1 to 4 carbon atoms, R2 is a divalent organic moiety, X and Y are divalent organic groups selected from the group consisting of secondary amines and tertiary and open-ring epoxies, such that when X is an open ring epoxide, Y is an amine and vice versa, a is 2 to 4, each occurrence of b is 0 to 100, d is 0 to 100, (b + d) is 1 to 100, and c is 1 to 500.
2. 2. A copolymer according to claim 1, characterized in that the secondary and tertiary amines correspond to the structure -R * N (R3) (R4) "in where R3 is an alkyl group with 1 to 4 carbon atoms or hydrogen, R * is alkylene, a cyliphatic alkylene group or an aralkylene which may include heteroat or os and g can be 0 or 1.
3. 3. A copolymer according to claim 1, characterized in that X is a secondary or tertiary amine and Y is an open ring epoxide.
4. 4. A copolymer according to claim 1, characterized in that Y is a secondary or tertiary amine and X is an open ring epoxide.
5. A copolymer according to claim 1, characterized in that it is of the formula (AB) "A wherein each A is a unit of the formula (1) which is terminated with secondary or tertiary amine, each B is a unit of Formula (2) which is terminated with open ring epoxide and n is 2 to 1,000.
6. 6. A copolymer according to claim 1, characterized in that it is of the formula (AB) "A wherein each A is a unit of the formula (2) which is terminated with secondary or tertiary amine, each B is a unit of Formula (1) which is terminated with open ring epoxide and n is 2 to 1,000.
7. 7. A copolymer according to claim 1, characterized in that a is 2 or 3.
8. 8. A copolymer according to claim 1, characterized in that (b + d) is 10 to 50.
9. 9. A copolymer in accordance with claim 1, characterized in that R1 is methyl.
10. 10. A copolymer according to claim 1, characterized in that the ratio of c a (b + d) is 10: 1 to 1:10.
11. 11. A copolymer according to claim 1, characterized in that the open ring epoxide is selected from the group consisting of -CH2CH (0H) (CH2) vCH (0H) CH2-, -CH (CH2OH) (CH2) vCH. { CH20H) -, -CH2CH (OH) (CH2) vCH. { CH20H} , - (CH2) v-0CH2CH (OH) CH2-, and - (CH2) vOCH2OCH2CH (CH2 { OH)) - in each of which v is 2 to 6, and omega- (3, 4- ^ epoxycyexyl) alkylene, β- (3,4-epoxycyexyl) ethylene, β- (3, 4-epoxycyexyl) -β-methylethylene and R- (3,4-epoxy-4-methylcyexyl) -β-methylethylene.
12. 12. A copolymer according to claim 1, characterized in that the formula H N (R 3) (C a H 2 a O) b C H (C H 3) C H 2 N (R 3) -. { CH2CH (0H) CHa0 (CH2) 7 (SiO (RI) a (CHa) 3QCH2CH (OH) CH2-N (R3) (C2a0) bCH2CH (CH3) N (R3).} YH where y is 2 to 1,000
13. 13. A substrate comprising at least one surface a copolymer according to claim 1.
14. 14. A substrate according to claim 13, characterized in that the substrate is selected from the group consisting of natural and synthetic fibers and non-woven materials
15. 15. A method for imparting durable hydrophilicity to a substrate, comprising applying to the substrate a copolymer according to claim 1.
16. 16. A method according to claim 15, characterized in that the substrate is selected from the group consisting of natural and synthetic fibers and nonwoven materials.
17. 17. A method for imparting durable softness to a substrate comprising applying to the substrate a copolymer according to claim 1.
18. 18. A method according to claim 17, characterized in that the substrate is selected from the group consisting of natural and synthetic fibers and materials not "fabrics"
19. 19. A personal care formulation comprising a copolymer according to claim 1, a surfactant component and water
20. 20. A personal care formulation according to claim 19, further comprising a thickener. A personal care formulation which is a shampoo comprising a polymer according to claim 1, a surfactant component selected from the group consisting of anionic surfactants, amphoteric surfactants and mixtures thereof, a nonionic surfactant, a thickener component and water.