US3919449A - Acid-modified poly(vinyl acetate) textile sizes - Google Patents

Acid-modified poly(vinyl acetate) textile sizes Download PDF

Info

Publication number
US3919449A
US3919449A US40650873A US3919449A US 3919449 A US3919449 A US 3919449A US 40650873 A US40650873 A US 40650873A US 3919449 A US3919449 A US 3919449A
Authority
US
United States
Prior art keywords
solution
percent
maleate
weight
interpolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Other languages
English (en)
Inventor
Albert E Corey
Donald D Donermeyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
Original Assignee
Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to US05406508 priority Critical patent/US3919449A/en
Priority to CA211,322A priority patent/CA1018691A/en
Priority to DE19742448886 priority patent/DE2448886A1/de
Priority to JP11722374A priority patent/JPS5231474B2/ja
Priority to IT2840774A priority patent/IT1022859B/it
Priority to AU74269/74A priority patent/AU7426974A/en
Priority to FR7434481A priority patent/FR2247575B3/fr
Priority to US05/614,827 priority patent/US4013805A/en
Application granted granted Critical
Publication of US3919449A publication Critical patent/US3919449A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2402—Coating or impregnation specified as a size

Definitions

  • the present invention relates to textile sizes. More particularly, it relates to acid-modified poly(vinyl acetate) textile sizes and to textiles, especially spun polyester textiles sized with these materials.
  • yarn is sized with an aqueous solution of a watersoluble material woven into cloth on a conventional loom with a mechanical shuttle and then the size is removed in a water bath.
  • Many water-soluble compositions are used as textile sizes, for example, poly( vinyl alcohols), carboxymethyl cellulose, starch, styrene-maleic anhydride copolymers, acrylic copolymers and vinyl acetate copolymers. While these sizes have been adequate for natural textile fibers and for many of the synthetic textile fibers, they exhibit deficiencies in the sizing of yarns of spun polyester and spun polyester blended with natural fibers.
  • Poly(vinyl alcohols) lack ease of removability from the sized yarn and are difficult to recover or eliminate from the waste stream.
  • Carboxymethyl cellulose is low in Sizing efficiency and difficult to recover from the waste stream.
  • Starch is similar to carboxymethyl cellulose in sizing efficiency and recoverability and is a stronger pollutant because it has a high biochemical oxygen demand.
  • Styrene-maleic anhydride copolymers are deficient in adhesion to spun polyester, being easily shed, leaving the textile fiber unprotected.
  • Acrylic copolymer sizes have good adhesion but are deficient in strength and low in efficiency.
  • Vinyl acetate copolymers are, in general, low in efficiency, and lack ease of removability from the sized yarn.
  • the textile sizes of the present invention have excellent solubility characteristics, film properties and adhesion to yarns of spun polyester and polyester fiber blends. Moreover, these sizes are easily removed from sized yarns or the resulting fabric using water or aqueous solutions of inorganic or organic monovalent bases and are readily recovered from the wash solution.
  • One embodiment of the invention comprises a textile sizing solution of an interpolymer of from 90.5 to 95.5 percent by weight of vinyl acetate, from 4.0 to 7.5 percent by weight of acrylic acid and from 0.5 to 2 percent by weight of a monoalkyl ester of maleic, fumaric, or citraconic acids.
  • Another embodiment of the invention comprises a process of sizing textile materials by applying to the textile material a textile sizing solution of the abovedescribed interpolymer.
  • Another embodiment of the invention comprises textile materials sized with the above-described interpolymer.
  • the sizes of the present invention are prepared by interpolymerizing vinyl acetate, acrylic acid and a monoalkyl ester of maleic, fumaric, or citraconic acids in which the alkyl group contains from 1 to 8 carbon atoms.
  • monoalkyl esters examples include monomethyl maleate, monomethyl fumarate, monomethyl citraconate, monoethyl maleate, monoethyl fumarate, mono-n-propyl maleate, mono-iso-propyl fumarate, mono-n-butyl maleate, mono-iso-butyl fumarate, mono-t-butyl citraconate, mono-n-hexyl maleate, mono-iso-hexyl fumarate, mono-n-octyl maleate, mono-n-octyl fumarate, mono-n-octyl citraconate, mono-iso-octyl maleate, mono-Z-ethyl hexyl maleate and mono-2-ethyl hexyl fumarate.
  • Preferred monoalkyl esters are monoalkyl maleates or fumarates in which the alkyl group contains from l to 4 carbon atoms, such as monomethyl maleate, monoethyl fumarate, mono-npropyl maleate and mono-n-butyl maleate since these monoalkyl esters are associated with acceptable rates of interpolymerization and more rapid solution of the resulting interpolymers.
  • the interpolymers contain between 90.5 and 95.5 percent by weight of vinyl acetate, between 4.0 and 7.5 percent by weight of acrylic acid and between 0.5 and 2 percent by weight of the monoalkyl ester. Thus, the total acid monomer is in the range from 4.5 to 9.5 percent by weight. Below 4.5 percent by weight, the solubility or the rate of solution of the interpolymer is unsatisfactory. Above 9.5 percent by weight, the interpolymer lacks water resistance.
  • a minor fraction comprises the monoalkyl esters set forth hereinbefore.
  • This minor fraction of monoalkyl ester has been found to impart improved solubility and improved rate of solution to the interpolymer composition thus improving the efficiency of removal of the interpolymer size from woven goods, when the size is used as a warp yarn size.
  • This improved solubility is achieved with between 0.5 and 2 parts by weight of monoalkyl ester per parts by weight of interpolymer.
  • the monomers are preferably polymerized using latex polymerization methods at a temperature in the range of from 40 to 60C. and preferably at a temperatui'e in the range of from 40 to 45C. At temperatures below about 40C. the polymerization rate is too slow and the reaction mass tends to coagulate. At polymerization temperatures above 60C., the product tends to low molecular weight and lacks the tensile strength and elongation required in the sizes of the present invention.
  • the molecular weight of the interpolymer should be such that the specific viscosity of a 1 percent solution of interpolymer in dimethyl sulfoxide at 25C.
  • Solubility is in the range from L5 to l2 .0 and more preferably for adequate strength and solubility, it should be such that the specific viscosity is in the range from 1.8 to 6.0. Solubility is determined by the solution rate of a film of interpolymer as described herein.
  • the interpolymerization is carried out using a surfactant which comprises a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from 7 to ll carbon atoms.
  • a surfactant which comprises a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from 7 to ll carbon atoms.
  • a surfactant which comprises a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from 7 to ll carbon atoms.
  • PEOPEO phosphate esters of tertiary octyl phenolethylene oxide condensates
  • PENPEO nonyl phenolethylene oxide condensates
  • These preferred surfactants are available commercially as Triton XQS surfactants (Rohm and Haas Company) and GAFAC surfactants (General Aniline and Film Company), respectively.
  • the latex interpolymerization of the monomers is carried out using an anionic co-surfactant in combination with the phosphate esters of an alkyl phenolethylene oxide condensate.
  • the use of the co-surfactant reduces the amount of coagulum in the resulting latex and provides a better product.
  • the preferred co-surfactants used in the present invention include alkyl sulfonates such as sodium dodecyl benzene sulfonate', fatty alcohol sulfates such as sodium lauryl sulfate; dialkyl sulfosuccinates such as sodium dihexyl sulfosuccinate; etc.
  • the amount of co-surfactant used is in the range of 0.3 to 1.0 percent by weight and more preferably 0.40 to 0.60 percent by weight based on the total weight of the latex.
  • the co-surfactant is preferably added continuously during the polymerization reaction.
  • the latex polymerization processes are initiated by a two component redox free radical initiator system.
  • Suitable oxidizing components for the system are the inorganic peracid salts such as ammonium, potassium and sodium persulfates. perborates. and hydrogen peroxide.
  • Preferred, however. are the oil soluble organic hydroperoxides such as t-butyl hydroperoxide. cumene hydroperoxide. p-menthane hydroperoxide, etc. and esters of the t-butyl perbenzoate type.
  • the useful reducing components include compounds like the sulfites. bisulfites. hydrosulfites and thiosulfates; ethyl and other alkyl sulfites'.
  • the sulfoxylates such as sodium formaldehyde sulfoxylate; and the like.
  • initiator systems based on t butyl hydroperoxide and sodium formaldehyde sulfoxylate; and redox combinations such as mixtures of hydrogen peroxide and an iron salt.
  • hydrogen peroxide and zinc formaldehyde sulfoxylate or other similar reducing agent hydrogen peroxide and a titanous salt
  • potassium persulfate and sodium bisulfite and a bromate mixed with a bisulfite are particularly preferred.
  • equimolar amounts of initiator system components is generally preferred although the amount of each component as well as the total amount of catalyst used depends on the type of component used as well as on other polymerization conditions and may range between .02 and 0.4 percent by weight of the total polymerization system, the preferred range being 0.03 to 0.20 percent for the oxidizing component and 0.04 to 0.20 for the reducing component.
  • the solids contents of the interpolymer latices can be varied over a wide range.
  • the preferred latices having a solids content in the range of from to 65 percent by weight and more preferably from 35 to 55 percent by weight, based on the total weight of the latex.
  • a conventional base such as ammonium hydroxide or sodium hydroxide is used to buffer the latex to a pH in the range of 4.0 to 6.0.
  • the textile size solution may be prepared from an interpolymer latex in several ways.
  • an aqueous solution of base is mixed with the latex to dissolve the interpolymer by formation of the water soluble interpolymer carboxylate.
  • Suitable bases include the hydroxides, carbonates and bicarbonates of alkali metals such as sodium hydroxide. sodium carbonate and sodium bicarbonate; ammonia. organic bases such as methylamine. dimethylamine. trimethylamine, ethylamine. diethylamine, triethylamine, morpholine. etc.
  • the preferred base in the preparation of a loom finish size is ammonium hydroxide since it contributes to good adhesion and resistance to water. water spotting and dry cleaning.
  • the preferred base in the preparation of removable warp yarn size is sodium carbonate since it contributes to rapid solution of the interpolymer. good adhesion of the interpolymer size to spun polyester yarn and rapid removability of the size from the woven goods.
  • a particular advantage of the interpolymer latex is that the fine size of the interpolymer particles allows rapid solubility of the interpolymer in aqueous base to form the size solution.
  • Another method for preparation of the textile size solution comprises the recovery of the interpolymer from the latex by conventional means and solution of the interpolymer in an organic solvent.
  • the size is then applied to the textile yarn as an organic solution and may be removed from the woven goods with aqueous base or organic solvent.
  • Preferred organic solvents for preparation of size solutions and removal of size are alcohols. ketones, esters and aromatic solvents.
  • chlorinated aliphatic hydrocarbons such as methylene chloride, methylene bromide, chloroform. bromoform, ethylene dichloride, ethylene dibromide. ethylidene chloride. ethylidene bromide, s-tetra-chloroethane, hexachloroethane, s-dichloroethylene. l l l -trichloroethane, l,l,2-trichloroethane. trichloroethylene.
  • a further advantage of the interpolymer compositions lies in their recoverability.
  • the aqueous solutions of the interpolymer obtained by scouring of the sized goods are acidified with strong acid to a pH less than about 3.5.
  • the interpolymer is precipitated and recovered by conventional means such as filtration or centrifugation. It is then redissolved in aqueous alkaline solution or organic solvent to form fresh sizing solution.
  • a latex is prepared in a conventional latex polymerization kettle equipped with an agitator and a heating and cooling system. The charges listed in Table l are used.
  • Charge A Water and sodium hydroxide are charged to the reaction vessel. The solution is purged for IS minutes to remove oxygen. The PEOPEO surfactant and sodium formaldehyde sulfoxylate are added to form Charge A.
  • Charges B and C are prepared by adding t-butyl hydroperoxide solution and sodium dihexyl sulfosuccinate to the respective quantities of monomers. Charge B is then dispersed in Charge A. The batch is mildly agitated and maintained at 42 to 44C. while Charge C is added over 2 /2 hours.
  • the resulting latex has a total solids of 43.0 percent. a pH of 4.9 and a Brookfield viscosity of 27 cps. at C.
  • the coagulum is 0.1 l weight percent of the solids.
  • the interpolymer has a specific viscosity of 2.30 in dimethyl sulfoxide at a concentration of l g. per 1011 ml.
  • the properties of the latex interpolymer are tabulated in Table 1 below.
  • Example 2 to 6 The following Examples 2 to 6 are set forth to illustrate variations in the latex polymerization of the present invention. 1n each case. the general procedures of Example 1 are followed except for the noted changes. Polymerization temperatures are maintained in the range from 41 to C. The resulting latices have solids contents in the range of 40 to 47 percent by weight. pH in the range of 4.5 to 5.5, and Brookfield EXAMPLES 7 to 11 The following examples are set forth to illustrate the use of various acid comonomers in the preparation of the interpolymer latices. The latices are prepared by the procedure described in Example 1. Composition data for the interpolymers are presented in Table 11. la
  • the latices prepared in Examples 1 to 5 are tested in order to determine their suitability as yarn sizes in conventional weaving processes.
  • the sizes are prepared by dissolving the latex in a basic solution such as aqueous sodium carbonate. aqueous sodium hydroxide or aqueous ammonia.
  • Sizing solutions prepared from the latices of Exam ples l to 6 by solution in aqueous ammonia, sodium hydroxide or sodium carbonate have Brookfield viscosities in the range of from 5 to 500 centipoises at 5 to percent solids at a temperature of 170F. allowing easy application and control of the amount of size added to the yarn.
  • V iscosities determined at C. on solutions containing 10 weight percent of interpolymer are used for comparison of the interpolymers.
  • a viscosity of at least 200 cps. at 25C. in a 10 weight percent solution is preferred to provide adequate viscosity in the sizing solution at the higher temperatures conventionally used in sizing textile yarns.
  • Adhesion solutions of the latex interpolymers of Examples l6 have been tested and are found to have good adhesion to the following yarns Filaments: polyester, acetate, rayon and texturized polyester; Spun: polyester, rayon, cotton, wool, and blends of polyester with rayon, cotton and wool.
  • Solubility in Organic Solvent size solutions of interpolymer latex in aqueous ammonia are applied to yarn and dried.
  • the dried films are readily soluble in chlorinated hydrocarbons.
  • Solubility in Aqueous Solvent 5 mil films are cast either from ammonia or sodium carbonate solutions of interpolymer. Two square inch samples of film are weighed. The samples are immersed in 100 g. of solvent and stirred with a magnetic stirrer at a rate sufficient to create a slight vortex. The time taken for the samples to dissolve at 80t2C. is detemiined.
  • the solvent is water; for films cast from ammonium hydroxide, the solvent is 025 Weight percent aqueous sodium hydroxide. Based on the assumption that the rate of solution is constant over the time taken for solution, rates are calculated and are given as milligrams per square centimeter minute.
  • Size Efficiency is a measure of the amount of size add-on required in a given operation.
  • the add-on is the amount of size that must be applied to the yarn in order to permit it to be woven on a loom. in general, the less size add-on required. the more efficient the size. Sizes prepared from the latices of the present invention have high efficiency as is indicated by the following Examples 12-15.
  • Weaving Efficiency is a measure of efficiency of weaving of the sized warp yarn into a cloth or sheet construction. It is expressed as a percentage ratio of the number of yards woven in unit time versus the number of yards which would be woven if the loom had no stops in the unit of time.
  • EXAMPLE 13 A 9.5 percent solution of the interpolymer latex of Example 4 is made by dissolving 380 pounds of latex (41%) with 20 pounds of NH OH (28%) to pH 9.2. Seven pounds of mill wax and one'half pound defoamer are added after solution of the interpolymer is complete. The solution is diluted with water to yield 200 gallons of sizing solution. The sizing solution is applied to a 39/1, 65/35 Polyester/Rayon blend on a 9-can West Point Slasher. Cans 18 are run at 235F., the 9th can at ambient temperature. The Slasher is run at 45 yards per minute at 170F. Size add-on is 10.8% The warp is free of can sticking or ends out during leasing.
  • the solution is free of skinning during slashing.
  • the warp is woven at 93% efficiency in a 88 X 60 bastiste weave.
  • the warp is desized in /17r NaOH at 180F.
  • the woven goods are uniformly receptive to dye and give the same dye shade as goods obtained from warp sized with easily removed carboxymethyl cellulose.
  • EXAMPLE 14 A 9.7% solution is prepared by dissolving 210 pounds of the latex of Example 3 in five pounds of sodium carbonate dissolved in gallons of water. Five pounds of a mill wax and 1 pound of defoamer are added after the latex has dissolved. The mix is diluted to gallons. Size solution is applied to a 26/1. 50/50 polyester/cotton warp at 175F. on a 9can Cocker Slasher run at 75 yards per minute. Can temperatures are 250F. except for first can which is set at 220F. The split is easy with no can sticking, skinning or ends out during leasing. Size add-on is 11.8%. The warp is woven into a sheet construction on a DSL loom at high efficiency.
  • EXAMPLE 15 An eight percent solution is prepared by dissolving 275 pounds of a 46% latex of composition similar to Example 4 in six pounds of sodium carbonate dissolved in gallons of water and finished to 200 gallons. The size is applied to 30/1 spun polyester yarn at 11% addon. The warp weaves at high efficiency and is desized readily in water containing the usual wetting agents employed in textile desizing.
  • Sizes which are obtained from polymers prepared by the process of the present invention are compared to commercially available textile sizes.
  • the sizes are prepared in the form of aqueous solutions of the sodium salt or ammonium salt and are cast as films.
  • the films are dried and tested at 65 percent relative humidity at 72F. for tensile strength and elongation. Solubility rates are determined by the method set forth above. Data are presented in Table 111.
  • Sizes A and B are obtained from latices prepared in the manner described in Examples 1 and 6. respectively. Sizes C to H are commercially available sizes representative of the prior art. Sizes A and B exhibit high solution viscosity necessary for controlled add-on to spun polyester yarns and high solution rates for eco nomic desizing. The solution viscosity of Size C is too low for economical addon of size to span polyester, while the solution rates of Sizes D. E. F, and G are too low for economic desizing. Carboxymethyl Cellulose has an acceptable solution rate. However. it is inefficient as a size because of low adhesion to polyester and it is difficult to recover from waste water.
  • EXAMPLE 16 A latex composition is prepared as in Example 1 and coagulated by addition of acetone. The interpolymer is recovered and dried. It is then dissolved in trichloroethylene to give a 8.0 percent solution. The solution is used to size spun polyester yarn.
  • EXAMPLE 17 A latex composition is prepared as in Example l. The resulting latex is dissolved in aqueous ammonia to give a 8.0 percent solution of interpolymer having a pH of 9.0. The solution is used to size spun polyester yarn. The sized warp yarn is woven on a conventional loom. Size is removed from the woven goods by extraction with 1.1 l -trichloroethylene.
  • the sizes of the present invention may be formulated with lubricants. defoamers, humectants. plasticizers. softening agents and other adjuncts without departing from the scope of the invention.
  • a method for sizing textiles which comprises ap plying to the textile material a solution of the interpolymerization product of from 90.5 to 95.5 weight percent of vinyl acetate. from 4.0 to 7.5 weight percent of acrylic acid and from 05 to 2.0 weight percent of a monoalkyl ester of maleic. fumaric. or citraconic acids in which the alkyl group contains from i to 8 carbon atoms.
  • the monoalkyl ester is monomethyl maleate. monomethyl fumarate. monoethyl maleate or monoethyl fumarate.
  • the size contains from i to 25 percent by weight of interpolymer based on the total weight of the aqueous solution.
  • a sized textile material wherein the size is the interpolymerization product of from 90.5 to 95.5 weight percent of vinyl acetate. from 4.0 to 7 .5 weight percent of acrylic acid and from 0.5 to 2.0 weight percent of a monoalkyl ester of maleic acid. fumaric acid. or citraconic acid in which the alkyl group contains from 1 to 8 carbon atoms,
  • the sized textile material as in claim 9 wherein the monoalkyl ester is monomethyl maleate, monomethyl fumarate. monoethyl maleate or monoethyl fu marate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US05406508 1973-10-15 1973-10-15 Acid-modified poly(vinyl acetate) textile sizes Expired - Lifetime US3919449A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US05406508 US3919449A (en) 1973-10-15 1973-10-15 Acid-modified poly(vinyl acetate) textile sizes
CA211,322A CA1018691A (en) 1973-10-15 1974-10-11 Acid-modified poly (vinyl acetate) textile sizes
JP11722374A JPS5231474B2 (enrdf_load_stackoverflow) 1973-10-15 1974-10-14
IT2840774A IT1022859B (it) 1973-10-15 1974-10-14 Bozzime tessili di acetato di polivinile modificato con acido
DE19742448886 DE2448886A1 (de) 1973-10-15 1974-10-14 Saeure-modifizierte poly-(vinylacetat)- textil-schlichten und appreturen
AU74269/74A AU7426974A (en) 1973-10-15 1974-10-14 Polyvinvyl acetate textile sizes and use
FR7434481A FR2247575B3 (enrdf_load_stackoverflow) 1973-10-15 1974-10-14
US05/614,827 US4013805A (en) 1973-10-15 1975-09-19 Acid-modified poly(vinyl acetate) textile sizes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05406508 US3919449A (en) 1973-10-15 1973-10-15 Acid-modified poly(vinyl acetate) textile sizes

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US05/614,827 Division US4013805A (en) 1973-10-15 1975-09-19 Acid-modified poly(vinyl acetate) textile sizes

Publications (1)

Publication Number Publication Date
US3919449A true US3919449A (en) 1975-11-11

Family

ID=23608283

Family Applications (1)

Application Number Title Priority Date Filing Date
US05406508 Expired - Lifetime US3919449A (en) 1973-10-15 1973-10-15 Acid-modified poly(vinyl acetate) textile sizes

Country Status (7)

Country Link
US (1) US3919449A (enrdf_load_stackoverflow)
JP (1) JPS5231474B2 (enrdf_load_stackoverflow)
AU (1) AU7426974A (enrdf_load_stackoverflow)
CA (1) CA1018691A (enrdf_load_stackoverflow)
DE (1) DE2448886A1 (enrdf_load_stackoverflow)
FR (1) FR2247575B3 (enrdf_load_stackoverflow)
IT (1) IT1022859B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013805A (en) * 1973-10-15 1977-03-22 Monsanto Company Acid-modified poly(vinyl acetate) textile sizes
US4073994A (en) * 1977-03-14 1978-02-14 Monsanto Company Acid modified polyvinyl acetate textile sizes
US4073995A (en) * 1977-03-14 1978-02-14 Monsanto Company Acid modified polyvinyl acetate textile sizes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0455526U (enrdf_load_stackoverflow) * 1990-09-18 1992-05-13

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716547A (en) * 1970-12-16 1973-02-13 Monsanto Co Process for the preparation of a poly(vinyl acetate-dialkyl maleaee-acrylic acid) textile sizes
US3759858A (en) * 1971-10-04 1973-09-18 Monsanto Co Acid modified poly vinyl acetate vinyl propionate textile
US3770679A (en) * 1970-12-16 1973-11-06 Monsanto Co Process for the preparation of a poly(vinyl acetate-dialkyl maleateacrylic acid) latex

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716547A (en) * 1970-12-16 1973-02-13 Monsanto Co Process for the preparation of a poly(vinyl acetate-dialkyl maleaee-acrylic acid) textile sizes
US3723381A (en) * 1970-12-16 1973-03-27 Monsanto Co Poly(vinyl acetate-dialkyl maleate acrylic acid) textile sizes
US3770679A (en) * 1970-12-16 1973-11-06 Monsanto Co Process for the preparation of a poly(vinyl acetate-dialkyl maleateacrylic acid) latex
US3759858A (en) * 1971-10-04 1973-09-18 Monsanto Co Acid modified poly vinyl acetate vinyl propionate textile

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013805A (en) * 1973-10-15 1977-03-22 Monsanto Company Acid-modified poly(vinyl acetate) textile sizes
US4073994A (en) * 1977-03-14 1978-02-14 Monsanto Company Acid modified polyvinyl acetate textile sizes
US4073995A (en) * 1977-03-14 1978-02-14 Monsanto Company Acid modified polyvinyl acetate textile sizes

Also Published As

Publication number Publication date
JPS5231474B2 (enrdf_load_stackoverflow) 1977-08-15
CA1018691A (en) 1977-10-04
DE2448886A1 (de) 1975-04-17
FR2247575B3 (enrdf_load_stackoverflow) 1977-07-22
JPS5070687A (enrdf_load_stackoverflow) 1975-06-12
IT1022859B (it) 1978-04-20
FR2247575A1 (enrdf_load_stackoverflow) 1975-05-09
AU7426974A (en) 1976-04-15

Similar Documents

Publication Publication Date Title
US3321819A (en) Process for sizing and desizing textile fibers
JPH075692B2 (ja) 新規のグラフト重合されたスルホン化ポリエステル、それらの製造方法並びに紡織糸及び繊維のサイジングへのそれらの使用
US3242123A (en) Glycidyl acrylate-styrene-ethyl acrylate-itaconic acid interpolymers
US4013805A (en) Acid-modified poly(vinyl acetate) textile sizes
US3960485A (en) Process for recovery and reuse of textile size
US3919449A (en) Acid-modified poly(vinyl acetate) textile sizes
US3854990A (en) Process for sizing textile materials
US3459716A (en) Polyalkylene glycol ester-unsaturated acid-methylalamide terpolymers
US3922461A (en) Acid-modified poly(vinyl acetate-vinyl propionate) textile sizes
DE2707150C2 (de) Verfahren zum Schlichten von Textilfasern
US4073995A (en) Acid modified polyvinyl acetate textile sizes
US2798047A (en) Detergent compositions for laundering textile fabrics, containing a copolymer of a lower nu-alkyl acrylamide and vinyl alcohol
US3770679A (en) Process for the preparation of a poly(vinyl acetate-dialkyl maleateacrylic acid) latex
US5082896A (en) Polymeric materials useful for sizing synthetic yarns to be used in water jet weaving
US3909477A (en) Warp-sizing compositions and yarns sized therewith
US4073994A (en) Acid modified polyvinyl acetate textile sizes
US2819189A (en) Process of sizing textile yarn and product thereof
US2909447A (en) Process of treating textile yarns
US3366509A (en) Textile process and composition
CA1128249A (en) Water-soluble alkaline earth metal salts of polymers of acrylic acid, and their use as sizes
US2845689A (en) Warp size containing dicyandiamide and a polyacrylate salt
WO1998000449A1 (en) Waterborne polymer composition having a small particle size
US2616867A (en) Composition for and method of sizing yarns
JPS61201079A (ja) 経糸糊剤
US3728299A (en) Textile sizing solution comprising an interpolymer of a hydrophobic monomer and an unsaturated organic carboxylic monomer and a halogenated hydrocarbon solvent