CA1143888A - Reactants for crosslinking textile fabrics - Google Patents
Reactants for crosslinking textile fabricsInfo
- Publication number
- CA1143888A CA1143888A CA000363341A CA363341A CA1143888A CA 1143888 A CA1143888 A CA 1143888A CA 000363341 A CA000363341 A CA 000363341A CA 363341 A CA363341 A CA 363341A CA 1143888 A CA1143888 A CA 1143888A
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- Prior art keywords
- glyoxal
- product
- reactant
- urea
- cyclic urea
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
Alkylated glyoxal/cyclic urea condensates are excellent formaldehyde-free crosslinking resins for textile fabrics.
Alkylated glyoxal/cyclic urea condensates are excellent formaldehyde-free crosslinking resins for textile fabrics.
Description
Sun 133 - This invention relates to novel textile finishing agents. ~ore particularly it relates to novel finishing resins that impart permanent press characteris-tics to textile fabrics.
BAC~GROUND OF THE INVENTION
The use of thermosetting resins or reactants to impart crease resistance and dimensional stability to textile materials is well-known in the art. These materials, kno-~n as "aminoplast resins", include the products of the reaction o~ formaldehyde with such compounds as urea, thiourea, ethylene urea, dihydroxyethylene urea~
melamines, or ~he like. A serious drawback to the use of such materials is that they contain -free formaldehyde.
This is present during the preparation and storage of the finishing agent and its use in treating textiles, on the treated fabric,~and on the finished garments. Also, when the fabrics or garments made therefrom are stored under humid conditions, additional free formaldehyde is produced.
The presence of even less than one per cent of free formaldehyde, based on the total weight of the product, is undesirable, not only because of its unpleasant odor, - but because it is an allergen and an irritant, causing severe reactions in the operators who manufacture the agent and who treat and handle the treated ~abrics and to persons who handle and ~ear garments fabricated from the treated fabrics.
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3~1~8 These problems associated with ~he presence of free formaldehyde on treated fabrics are well-known and considerable ef~orts have been made to produce -formaldehyde-free textile fabrics. One solution to the problem has been to employ scavengers for the ~ree formaldehyde. In U. S. patent No. 3~590,100 cyclic ethylene urea and propylene urea are disclosed as scavengers. Removal o*
the formaldehyde by reaction with phthalimide is disclosed in U. S. paten-t No. 3,723,058. U. S. patent No. 4,127,382 teaches certain nitrogen-containing heterocyclic compounds as scavengers.
Treating textiles with resin compositions that do not contain or evolve formaldehyde is also known, as in U. S. patent No. 3,260,565 which teaches ~inishing agents formed by the reaction of alkyl or aryl ureas or thioureas with glyoxal. These agents, however, have the disadv~ntage of having marginal permanent press properties. Finishing agents formed by the reaction of ethylene urea with glyoxal are disclosed in Japanese publication 5 304~-567, but they too do not have satisfactory properties.
SUM~LARY OF THE INVENTION
It has now been found that the alkylated products of the reaction of glyoxal and cyclic ureas are excellent crosslinking resins for textile fabrics and do not contain formaldehyde.
DETAILED DESCR~PTION OF THE INVENTION
In accordance with the present invention, novel alkyla-ted glyoxal~cyclic urea condensates are prepared that are useful for crosslinking textile ~abrics.
-30 The cyclic ureas which may be used have the following general formulas:
c \ - / Ic NH NH NH NH
R2RlC ~CR3R~ R2RlC\ CR~5R6 1~ 2~ R3, R~, R5, and R6 may be the same or - different and each may be ~I,OH,COOH,R~ OR, or COOR wherein R is an alkyl or a substituted alkyl group having 1 ~o 4 carbon atoms, and X may be C, O, or N; when X is O, R3 and R4 are each zero; ~hen X is N, R3 or R~ is zero.
Typical examples of such compounds include, but are not limited to, ethylene urea, propylene urea, uron, tetrahydro-5-(2-hydroxye~hyl)-1,3,5-triazin-2-one, 4,5-dihydroxy-2-imidazolidinone and the like, and mixtures of these.
The alkylated condensates can be prepared by any suitable and convenient procedure. The cyclic urea and the glyo~al are generally reacted in stoichiometric amounts, although a slight excess o~ either o-f the reac-tan~s may be empl~yed. The general range of glyoxal:cyclic urea is about 0.8-1.2:1. The reaction may be carried out-within the temperature range of room temperature up to reflux, but preferably is run at about 50 to 60C. for about two hours. The p~l may range from about 2 to 7.0, and preferably it is within the range of about 5.0 to 7Ø
The product is a water-soluble oligomer. These glyoxal/
cyclic urea condensates are then partially or wholly - alkylated~ e.g., by reacting them with an alcohol such as methanol, ethanol, n-propanol, a butanol, and the like, and their mixtures.
- Another method involves reacting glyoxal with an alkylated cyclic urea.
- The *reating agent of this invention is suitable for use with cellulosic textile fabrics~ woven or non-woven, including 100~ cellulosic fabrics, e.g., cotton, rayon, and linen, as well as blends, e.gr, polyester~
cotton or polyester/rayon. Such blends preferably but not necessarily contain at least 20% of cellulose. Both ~ite and colored ~printed, dyed, yarn-dyed, cross-dyed, etc.) fabrics can be effectively treated with the resins o :
.
~ ~ 3~ ~
this invention. It is applicable also to fabrics con-taining fibers wi~h free hydroxyl groups.
~ Vhen applying the resin of this invention to a fabric~ there generally will be present an appropriate catalyst. Typical catalysts include acids (such as hydro-chloric, sulfLIric, fluoboric, acetic, glycolic, maleic, lactic, citric, tartaric, and oxalic acids~, metal salts (such as magnesium chloride, nitrate, fluoborate, or fluosilicate; zinc chloride, nitrate, fluoborate, or fluosilicate; ammonium chloride; zirconium oxychloride;
sodium or potassium bisulfate); amine hydrochlorides (such - as the hydrochloride of 2-amino-2-methyl-1-propanol); and the like, and mixtures thereof. The amount of catalyst generally is about 0.01 to 10 per cent, and pre-ferably about 0.05 to 5 per cent, based on the weightof the padding bath.
The finishing agents may be applied to the textile fabric in any known and convenient manner, e.g., by dipping or padding, and will generally be applied from aqueous or alcoholic solution. The solvent may be water;
an aliphatic alcohol, e.g., methanol, ethanol, or isopropanol; or a mixture of water and an aliphatic alcohol. Other conventional additives such as lubricants, softeners, bodying agents, water repellents, flame retard-ants, soil shedding agents, mildew inhibitorsS anti-wet soiling agents, fluorescent brighteners, and the like may be used in the treating bath in conventional amounts.
Such auxiliaries must not, however, interfere with the proper functioning of the finishing resin, must not them-selves have a deleterious effect on the fabric, anddesirably are free of formaldehyde.
The amount of treating agent which is applied to the fabric will depend upon the type of fabric and its intended application. In general it is about 0.5 to 10 per cent, and preferably about 2 to 5 per cent, based on the weight of the fabric.
3~8 In the process of treatin~ fabrics with the resins of this inventioIl, the abric is impregnated with an aqueous or alcoholic solution of the finishing resin, and the impregnated fabric is then dried and cured; the drying and curing steps may be consecutive or simultaneous, If desired f the textile fabric may be finished by post-curing (also known as d~eferred or delayed curing~.
This consists of impregnating the fabric with a solution of finishing resin and catalyst; drying the impregnated material carefully so that the finishing agent does not react; and then, after a prolonged interval, heating ~he material to a temperature at which the agent reacts under the influence of the catalyst.
Although this invention will be described with the use of the alkylated product of the reaction of a cyclic urea and glyoxal as a textile finishing agent, it is not intended to be limited thereto. It is also suit-able for use as a dry-strength or a wet-strength resin in paper; a hand-builder in textiles; a binder in 2Q particleboard, medium-density fiberboard, plywood, foundry and shell molding, insulation materials including glass fiber mats, friction materials, coated and bonded abrasives, etc.; a component in molding compounds; an adhesive for wood and laminates; a ~ilm-orming resin in coatings and printing inks; an additive i~ fibers, e.g. rayon; an additive in rubber processing; an agent in leather tanning; a textile size; a dry fixative for textiles; an impregnant for filters; e.g., automotive filters; and the liXe.
In order that the present invention may be more fully understood, the following examples are given by way of illustration. No specific details contained therein should be construed as limitations on the present invention ;
`
except insoEar as ~hey appear in the appended claims.
Unless otherl~ise speci~ied, all parts and percentages are by IYeight.
EXAMPL~ 1 290 Parts ~2 moles) of a 40~ aqueous solution of glyoxal was adjusted to pH 6.5 wi~h sodium bicarbonate.
176 Parts ~2 moles) of ethylene urea was a~ded and the temperature raised to 55+5C. The mixture was stirred at this temperature for two hours, maintaining the pH betwee~
6.0 and 7Ø Af~er two hours 200 parts ~6.25 moles) o methanol was added and the pH adjusted to about 3.0 with concentrated sulfuric acid. The reaction was held at reflux for three hours to effect methylation, the resin solution cooled to 30C., and the pH adjusted to about 7.0 with a 25% solution of caustic soda.
The product was a clear viscous liquid, pale yellow, with negligible odor. The reaction was essen~ially complete, as determined by IR and NMR analyses. IR
analysis indicated that methylation had occurred.
EXA~IPLE 2 360 Parts (2.5 moles) of a 40% aqueous solution of glyoxal was added to 905 parts (2.5 moles) of a 44%
methanol solution of dimethyl methoxy propylene urea.
The mixture was heated to 55+5C. for two hours, the pH
being maintained between 6.0 and 7Ø After cooling at 30C. there was obtained a 45%-solids, slightly viscous, water-white solution with no odor of formaldehyde. The reaction was essentially complete, as determined by IR
and NMR analyses.
EXAMP~E 3 The procedure of Example 1 was repeated~except that the glyoxal was reacted with each of the following instead of ethylene urea: propylene urea, uron, tetra-hydro-5-(2-hydroxyethyl)-l~3~5-triazin-2-one~ and 4,5-dihydroxy-2-imidazolidinone. The results were comparable.
3~
The procedure of Example 1 ~as repeated except that each of the following alcohols was used instead of methanol: ethanol, n-propanol, and isopropanol. The results were comparable.
EX~MPLE 5 The resin product of Example 1 was used to treat 100% cotton fabTic. The test results are tabulated below and compared with ~hose of a sample of the same fabric treated with a conventional formaldehyde-containing agent. In each case the solution of resin and catalyst was applied to samples of the fabric by padding with a wet pickup of about 60%, based on the weight of the fabric~
The treated fabrics were dried by heating for 3 minutes at 107C., and the resin cured on the fabrics by heating for 90 seconds at 171DC.
Wrinkle Recovery was measured by AATCC Test Method 66-1978 "Wrinkle Recovery of Pabrics: Recovery Angle Method".
Tensile was measured by ASTM Test Method D-1682-64 (Reapproved 1975) "Tensile-Grab-CRT Pendulum Type".
TABLE I
(a) ~b) ~c) Reactant, parts A 15.0 B 15.0 Catalyst 531~ parts 4.5 4.5 Sulfanole~ RWD, part 0.25 0.25 Tensile warp 40 40 89 fill 16 15 37 Wrinkle Recovery initial 245 286 168 after 5 AHL 245 280_173 A is the product o~ Example 1.
B is 1,3-bishydroxymethyl-4,5-dihydroxy-2-imidazolidinone (45% aqueous solution).
(c) is untreated 100'~ cotton ~abric.
Catalyst 531 (Sun Chemical Corporation) is an activated magnesium chloride catalyst.
Sulfanole~ RWD ~S~m Chemical Corporation) is a non-ionic wetting agent.
AHL is average home :Launderings.
From these data it can be seen that the fabric treated with the product of this invention (a) is comparable in tensile strength and wrinkle recovery to the fabric treated with a commercial formaldehyde-containing agent ~b) and has the advantage of being free of -formaldehyde.
The procedure of Example 5 was repeated with the resin products o Examples 2, 3, and 4. The results were comparable.
An aqueous solution containing 15.0 parts of the resin product of Example 1 and 4.0 parts of Catalyst 531 was applied to samples of 65/35 polyester/cotton fabric by padding. The treated fabrics were dried; the resin cured on the fabrics by heating for 5 minutes at 150C., 5 minutes at 177C., and 1 minute at 193C.; and the ~abric smoothness determined by AATCC Test Method 124-1978 "Appearance of Durable Press Pabrics after Repeated Home Launderings". The results are tabulated below.
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ABLE II
- (a) _ (d) Fabric Smoothness after 1 AHL
150C. 3.7 3.2 177~. 3.6 3.1 193C. 3,4 3.0 after 5 AHL.
150C. 3.5 3.1 177C. 3.7 3.1 193C. 3.6 3.1 a-fter 10 AHL
150C. 3.4 3.2 177C. 3.8 3.2 193C. 3.8 3.2 (d) is untreated 65/35 polyester/cotton fabric, The whiteness o-f the fabric (a) was good, and the fabric showed no chlorine scorch either initially or after 5 launderings.
The following solutions were prepared9 applied - to 100% cotton, and tensile and wrinkle recovery measured as in Example 5:
TABLE III
(a) (e) (c) Reactant, parts A 15.0 C 15.0 Catalyst 531, parts 4.5 4.5 Sulfanole~ RWD, part 0.25 0.25 - Tensile warp 4D 41 89 fill 16 17 37 ~rinkle Recovery initial 245 199 168 after 5 AHL 245 187 173 -':
A is the produc~ o Example 1.
C is the product oE the reaction of stoichio-metric amounts of glyoxal and dimethyl urea (disclosed in U. S. pate~t No. 3,260,565).
(c) is untreated I00% cotton fabric.
~rom these data it can be seen that the fabric treated with the product of this invention ~a) is compa-rable in tensile strength to the fabric treated with the reactant disclosed in U. S. patent No. 3,260,565 ~e) and considerably superior to it in wrinkle recovery.
The procedure of Example 5 was repeated with each of the following fabrics instead of 100% cotton:
50/50 polyester/cotton, 65/35 polyester/cotton, 50/50 polyester/rayon, and 65/35 polyester/rayon. The results were comparable.
EX~fPLE 10 A sample o 65/35 polyester/cotton fabric was impregnated with an aqueous solution containing 20 parts of the product of Example 1, S parts o Catalyst KR ~Sun Chemical Corporation's magnesium chloride catalyst), and 0.25 part o-f Sulfanole RWD. The -fabric was then dried at 100C. and stored at elevated temperature for several weeks. A crease was then pressed into the fabric, and it was cured for 15 minutes at 150C. The fabric was washed and evaluated by AATCC Test Method 8SC-1975 "Appearance of Creases in Wash-and-Wear I-tems after Home Laundering".
It had an appearance rating of 5 as compared with a blank having a rating of 3.
To illustrate the superiority of an alkylated glyoxal/cyclic urea condensate over a nonalkylated glyoxal/
cyclic urea condensate, the following experiments were carried out:
(1) 176 Parts of ethylene urea ~2 moles) was reacted with 320 parts of 40% glyoxal ~2.2 moles) at a , '`' . .
;
3~
pH of 6 and a temperature of 50-60C. for two hours.
The product was then reacted with 200 parts of methanol ~6.25 moles) at pH 3.0, and then adjusted to pH 6.0 and 45% solids. The temperature was lowered to, and held at, 48C., and viscosity measurements were taken at intervals with a Brookfield Viscometer.
~ 2) 176 Parts o:E ethylene urea ~2 moles) was reacted with 320 parts of 40% glyoxal (2.2 moles) at a pH of 6 and a temperature of 50-60C. for two hours. The product was adjusted with water to 45% solids. The temperature was lowered to~ ancL held at, 4BC., and viscosity measurements were tak~n at intervals with a Brookfield Viscometer.
TABLE IV
Viscosity, cps ~ 2) initial 52 26.5 after weeks - 1 65 gelled - - 2 107.5 - 4 127.5 (1) is an alkylated glyoxal/cyclic urea condensate.
~ 2) is a nonalkylated glyoxaltcyclic urea condensate.
From these data it can be seen that the non-alkylated product (2) was unstable, gelling in one week, whereas the alkylated product ~1) remained stable after - 10 weeks at 48C.
EX~IPLE 12 To illustrate ~he superiority o~ an alkylated glyoxal/cyclic urea condensate over a nonalkylated glyoxal/
cyclic urea condensate as a textile treating agent, the following experiments were carri~d out:
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(1) Japanese publication No. 5 3044-567-~xample 1 300 Grams of ethylene urea was charged into a 4-necked flask equipped with a reflux condenser, a thermometer, and a stirrer and dissolved in 450 grams of water. Then 1 kg. of 40% glyoxal (glyoxal:ethylene urea ratio of 2:1) ancl 2 grams of concentrated hydrochloric acid were added. The mixture was reacted for three hours at 40C. After cooling, the pH was adjusted to 5.0 wi~h sodium hydroxide solution. The slightly colored trans-parent product had a solids content of 40%.
~2) Japanese publicatlon No. 5 3044-567-Example 2 300 Grams of ethylene urea was charged into a flask as in (1) and dissolved in 450 grams of water. 750 Grams of 40% glyoxal tglyoxal:ethylene urea ratio of 1.5:1) and 2 grams of concentrated hydrochloric acid were added.
The mixture was reacted for three hours at 40C. After cooling, the pH was adjusted to 5.0 with sodium hydroxide solution. The slightly colored transparent product had a solids content of 40~.
15 Parts o-f each of these products and of the product of Example 1 was each mixed with 3.75 parts of an activated magnesium chloride catalyst and a.25 part of Sulfanole RWD, and the solutions were applied by padding to samples of fabric. The treated fabrics were dried for 3 minutes at 107C. and the resin cured on the fabrics by heating for 90 seconds at 177C.
The blue and whiteness indexes of each were measured by AATCC Test Method 110-1975 and are tabulated as follows:
TABLE V
(a)(f) (g) `~ (h) cotton blue index 81.85 74.83 76.16 85.46 whiteness index 65.53 42.04 47.69 78.23 65/35 polyester/cotton blue index 78.99 70.07 72.51 82.35 whiteness index 57.63 29.51 37.74 67.62 .
~ ~3~
(a) is the product of Example 1 o~ this appli-cation.
(f) is the product of Example 1 of Japanese publication No. 5 3044-5G7.
5~g) is the product of ~xample 2 of Japanese publication No. 5 3044-567.
(h~ is Imtreated fabric.
It is evident from these data that the product of this invention (a) is superior to the products of the Japanese publication (~) and ~g) in both blue index and whiteness index. In addition, it was noted that the dry scorch on the fabrics treated with products ~f) and (g) was extremely severe.
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BAC~GROUND OF THE INVENTION
The use of thermosetting resins or reactants to impart crease resistance and dimensional stability to textile materials is well-known in the art. These materials, kno-~n as "aminoplast resins", include the products of the reaction o~ formaldehyde with such compounds as urea, thiourea, ethylene urea, dihydroxyethylene urea~
melamines, or ~he like. A serious drawback to the use of such materials is that they contain -free formaldehyde.
This is present during the preparation and storage of the finishing agent and its use in treating textiles, on the treated fabric,~and on the finished garments. Also, when the fabrics or garments made therefrom are stored under humid conditions, additional free formaldehyde is produced.
The presence of even less than one per cent of free formaldehyde, based on the total weight of the product, is undesirable, not only because of its unpleasant odor, - but because it is an allergen and an irritant, causing severe reactions in the operators who manufacture the agent and who treat and handle the treated ~abrics and to persons who handle and ~ear garments fabricated from the treated fabrics.
.: . ' `"'~
, . ' ~`
:
3~1~8 These problems associated with ~he presence of free formaldehyde on treated fabrics are well-known and considerable ef~orts have been made to produce -formaldehyde-free textile fabrics. One solution to the problem has been to employ scavengers for the ~ree formaldehyde. In U. S. patent No. 3~590,100 cyclic ethylene urea and propylene urea are disclosed as scavengers. Removal o*
the formaldehyde by reaction with phthalimide is disclosed in U. S. paten-t No. 3,723,058. U. S. patent No. 4,127,382 teaches certain nitrogen-containing heterocyclic compounds as scavengers.
Treating textiles with resin compositions that do not contain or evolve formaldehyde is also known, as in U. S. patent No. 3,260,565 which teaches ~inishing agents formed by the reaction of alkyl or aryl ureas or thioureas with glyoxal. These agents, however, have the disadv~ntage of having marginal permanent press properties. Finishing agents formed by the reaction of ethylene urea with glyoxal are disclosed in Japanese publication 5 304~-567, but they too do not have satisfactory properties.
SUM~LARY OF THE INVENTION
It has now been found that the alkylated products of the reaction of glyoxal and cyclic ureas are excellent crosslinking resins for textile fabrics and do not contain formaldehyde.
DETAILED DESCR~PTION OF THE INVENTION
In accordance with the present invention, novel alkyla-ted glyoxal~cyclic urea condensates are prepared that are useful for crosslinking textile ~abrics.
-30 The cyclic ureas which may be used have the following general formulas:
c \ - / Ic NH NH NH NH
R2RlC ~CR3R~ R2RlC\ CR~5R6 1~ 2~ R3, R~, R5, and R6 may be the same or - different and each may be ~I,OH,COOH,R~ OR, or COOR wherein R is an alkyl or a substituted alkyl group having 1 ~o 4 carbon atoms, and X may be C, O, or N; when X is O, R3 and R4 are each zero; ~hen X is N, R3 or R~ is zero.
Typical examples of such compounds include, but are not limited to, ethylene urea, propylene urea, uron, tetrahydro-5-(2-hydroxye~hyl)-1,3,5-triazin-2-one, 4,5-dihydroxy-2-imidazolidinone and the like, and mixtures of these.
The alkylated condensates can be prepared by any suitable and convenient procedure. The cyclic urea and the glyo~al are generally reacted in stoichiometric amounts, although a slight excess o~ either o-f the reac-tan~s may be empl~yed. The general range of glyoxal:cyclic urea is about 0.8-1.2:1. The reaction may be carried out-within the temperature range of room temperature up to reflux, but preferably is run at about 50 to 60C. for about two hours. The p~l may range from about 2 to 7.0, and preferably it is within the range of about 5.0 to 7Ø
The product is a water-soluble oligomer. These glyoxal/
cyclic urea condensates are then partially or wholly - alkylated~ e.g., by reacting them with an alcohol such as methanol, ethanol, n-propanol, a butanol, and the like, and their mixtures.
- Another method involves reacting glyoxal with an alkylated cyclic urea.
- The *reating agent of this invention is suitable for use with cellulosic textile fabrics~ woven or non-woven, including 100~ cellulosic fabrics, e.g., cotton, rayon, and linen, as well as blends, e.gr, polyester~
cotton or polyester/rayon. Such blends preferably but not necessarily contain at least 20% of cellulose. Both ~ite and colored ~printed, dyed, yarn-dyed, cross-dyed, etc.) fabrics can be effectively treated with the resins o :
.
~ ~ 3~ ~
this invention. It is applicable also to fabrics con-taining fibers wi~h free hydroxyl groups.
~ Vhen applying the resin of this invention to a fabric~ there generally will be present an appropriate catalyst. Typical catalysts include acids (such as hydro-chloric, sulfLIric, fluoboric, acetic, glycolic, maleic, lactic, citric, tartaric, and oxalic acids~, metal salts (such as magnesium chloride, nitrate, fluoborate, or fluosilicate; zinc chloride, nitrate, fluoborate, or fluosilicate; ammonium chloride; zirconium oxychloride;
sodium or potassium bisulfate); amine hydrochlorides (such - as the hydrochloride of 2-amino-2-methyl-1-propanol); and the like, and mixtures thereof. The amount of catalyst generally is about 0.01 to 10 per cent, and pre-ferably about 0.05 to 5 per cent, based on the weightof the padding bath.
The finishing agents may be applied to the textile fabric in any known and convenient manner, e.g., by dipping or padding, and will generally be applied from aqueous or alcoholic solution. The solvent may be water;
an aliphatic alcohol, e.g., methanol, ethanol, or isopropanol; or a mixture of water and an aliphatic alcohol. Other conventional additives such as lubricants, softeners, bodying agents, water repellents, flame retard-ants, soil shedding agents, mildew inhibitorsS anti-wet soiling agents, fluorescent brighteners, and the like may be used in the treating bath in conventional amounts.
Such auxiliaries must not, however, interfere with the proper functioning of the finishing resin, must not them-selves have a deleterious effect on the fabric, anddesirably are free of formaldehyde.
The amount of treating agent which is applied to the fabric will depend upon the type of fabric and its intended application. In general it is about 0.5 to 10 per cent, and preferably about 2 to 5 per cent, based on the weight of the fabric.
3~8 In the process of treatin~ fabrics with the resins of this inventioIl, the abric is impregnated with an aqueous or alcoholic solution of the finishing resin, and the impregnated fabric is then dried and cured; the drying and curing steps may be consecutive or simultaneous, If desired f the textile fabric may be finished by post-curing (also known as d~eferred or delayed curing~.
This consists of impregnating the fabric with a solution of finishing resin and catalyst; drying the impregnated material carefully so that the finishing agent does not react; and then, after a prolonged interval, heating ~he material to a temperature at which the agent reacts under the influence of the catalyst.
Although this invention will be described with the use of the alkylated product of the reaction of a cyclic urea and glyoxal as a textile finishing agent, it is not intended to be limited thereto. It is also suit-able for use as a dry-strength or a wet-strength resin in paper; a hand-builder in textiles; a binder in 2Q particleboard, medium-density fiberboard, plywood, foundry and shell molding, insulation materials including glass fiber mats, friction materials, coated and bonded abrasives, etc.; a component in molding compounds; an adhesive for wood and laminates; a ~ilm-orming resin in coatings and printing inks; an additive i~ fibers, e.g. rayon; an additive in rubber processing; an agent in leather tanning; a textile size; a dry fixative for textiles; an impregnant for filters; e.g., automotive filters; and the liXe.
In order that the present invention may be more fully understood, the following examples are given by way of illustration. No specific details contained therein should be construed as limitations on the present invention ;
`
except insoEar as ~hey appear in the appended claims.
Unless otherl~ise speci~ied, all parts and percentages are by IYeight.
EXAMPL~ 1 290 Parts ~2 moles) of a 40~ aqueous solution of glyoxal was adjusted to pH 6.5 wi~h sodium bicarbonate.
176 Parts ~2 moles) of ethylene urea was a~ded and the temperature raised to 55+5C. The mixture was stirred at this temperature for two hours, maintaining the pH betwee~
6.0 and 7Ø Af~er two hours 200 parts ~6.25 moles) o methanol was added and the pH adjusted to about 3.0 with concentrated sulfuric acid. The reaction was held at reflux for three hours to effect methylation, the resin solution cooled to 30C., and the pH adjusted to about 7.0 with a 25% solution of caustic soda.
The product was a clear viscous liquid, pale yellow, with negligible odor. The reaction was essen~ially complete, as determined by IR and NMR analyses. IR
analysis indicated that methylation had occurred.
EXA~IPLE 2 360 Parts (2.5 moles) of a 40% aqueous solution of glyoxal was added to 905 parts (2.5 moles) of a 44%
methanol solution of dimethyl methoxy propylene urea.
The mixture was heated to 55+5C. for two hours, the pH
being maintained between 6.0 and 7Ø After cooling at 30C. there was obtained a 45%-solids, slightly viscous, water-white solution with no odor of formaldehyde. The reaction was essentially complete, as determined by IR
and NMR analyses.
EXAMP~E 3 The procedure of Example 1 was repeated~except that the glyoxal was reacted with each of the following instead of ethylene urea: propylene urea, uron, tetra-hydro-5-(2-hydroxyethyl)-l~3~5-triazin-2-one~ and 4,5-dihydroxy-2-imidazolidinone. The results were comparable.
3~
The procedure of Example 1 ~as repeated except that each of the following alcohols was used instead of methanol: ethanol, n-propanol, and isopropanol. The results were comparable.
EX~MPLE 5 The resin product of Example 1 was used to treat 100% cotton fabTic. The test results are tabulated below and compared with ~hose of a sample of the same fabric treated with a conventional formaldehyde-containing agent. In each case the solution of resin and catalyst was applied to samples of the fabric by padding with a wet pickup of about 60%, based on the weight of the fabric~
The treated fabrics were dried by heating for 3 minutes at 107C., and the resin cured on the fabrics by heating for 90 seconds at 171DC.
Wrinkle Recovery was measured by AATCC Test Method 66-1978 "Wrinkle Recovery of Pabrics: Recovery Angle Method".
Tensile was measured by ASTM Test Method D-1682-64 (Reapproved 1975) "Tensile-Grab-CRT Pendulum Type".
TABLE I
(a) ~b) ~c) Reactant, parts A 15.0 B 15.0 Catalyst 531~ parts 4.5 4.5 Sulfanole~ RWD, part 0.25 0.25 Tensile warp 40 40 89 fill 16 15 37 Wrinkle Recovery initial 245 286 168 after 5 AHL 245 280_173 A is the product o~ Example 1.
B is 1,3-bishydroxymethyl-4,5-dihydroxy-2-imidazolidinone (45% aqueous solution).
(c) is untreated 100'~ cotton ~abric.
Catalyst 531 (Sun Chemical Corporation) is an activated magnesium chloride catalyst.
Sulfanole~ RWD ~S~m Chemical Corporation) is a non-ionic wetting agent.
AHL is average home :Launderings.
From these data it can be seen that the fabric treated with the product of this invention (a) is comparable in tensile strength and wrinkle recovery to the fabric treated with a commercial formaldehyde-containing agent ~b) and has the advantage of being free of -formaldehyde.
The procedure of Example 5 was repeated with the resin products o Examples 2, 3, and 4. The results were comparable.
An aqueous solution containing 15.0 parts of the resin product of Example 1 and 4.0 parts of Catalyst 531 was applied to samples of 65/35 polyester/cotton fabric by padding. The treated fabrics were dried; the resin cured on the fabrics by heating for 5 minutes at 150C., 5 minutes at 177C., and 1 minute at 193C.; and the ~abric smoothness determined by AATCC Test Method 124-1978 "Appearance of Durable Press Pabrics after Repeated Home Launderings". The results are tabulated below.
:
'~
ABLE II
- (a) _ (d) Fabric Smoothness after 1 AHL
150C. 3.7 3.2 177~. 3.6 3.1 193C. 3,4 3.0 after 5 AHL.
150C. 3.5 3.1 177C. 3.7 3.1 193C. 3.6 3.1 a-fter 10 AHL
150C. 3.4 3.2 177C. 3.8 3.2 193C. 3.8 3.2 (d) is untreated 65/35 polyester/cotton fabric, The whiteness o-f the fabric (a) was good, and the fabric showed no chlorine scorch either initially or after 5 launderings.
The following solutions were prepared9 applied - to 100% cotton, and tensile and wrinkle recovery measured as in Example 5:
TABLE III
(a) (e) (c) Reactant, parts A 15.0 C 15.0 Catalyst 531, parts 4.5 4.5 Sulfanole~ RWD, part 0.25 0.25 - Tensile warp 4D 41 89 fill 16 17 37 ~rinkle Recovery initial 245 199 168 after 5 AHL 245 187 173 -':
A is the produc~ o Example 1.
C is the product oE the reaction of stoichio-metric amounts of glyoxal and dimethyl urea (disclosed in U. S. pate~t No. 3,260,565).
(c) is untreated I00% cotton fabric.
~rom these data it can be seen that the fabric treated with the product of this invention ~a) is compa-rable in tensile strength to the fabric treated with the reactant disclosed in U. S. patent No. 3,260,565 ~e) and considerably superior to it in wrinkle recovery.
The procedure of Example 5 was repeated with each of the following fabrics instead of 100% cotton:
50/50 polyester/cotton, 65/35 polyester/cotton, 50/50 polyester/rayon, and 65/35 polyester/rayon. The results were comparable.
EX~fPLE 10 A sample o 65/35 polyester/cotton fabric was impregnated with an aqueous solution containing 20 parts of the product of Example 1, S parts o Catalyst KR ~Sun Chemical Corporation's magnesium chloride catalyst), and 0.25 part o-f Sulfanole RWD. The -fabric was then dried at 100C. and stored at elevated temperature for several weeks. A crease was then pressed into the fabric, and it was cured for 15 minutes at 150C. The fabric was washed and evaluated by AATCC Test Method 8SC-1975 "Appearance of Creases in Wash-and-Wear I-tems after Home Laundering".
It had an appearance rating of 5 as compared with a blank having a rating of 3.
To illustrate the superiority of an alkylated glyoxal/cyclic urea condensate over a nonalkylated glyoxal/
cyclic urea condensate, the following experiments were carried out:
(1) 176 Parts of ethylene urea ~2 moles) was reacted with 320 parts of 40% glyoxal ~2.2 moles) at a , '`' . .
;
3~
pH of 6 and a temperature of 50-60C. for two hours.
The product was then reacted with 200 parts of methanol ~6.25 moles) at pH 3.0, and then adjusted to pH 6.0 and 45% solids. The temperature was lowered to, and held at, 48C., and viscosity measurements were taken at intervals with a Brookfield Viscometer.
~ 2) 176 Parts o:E ethylene urea ~2 moles) was reacted with 320 parts of 40% glyoxal (2.2 moles) at a pH of 6 and a temperature of 50-60C. for two hours. The product was adjusted with water to 45% solids. The temperature was lowered to~ ancL held at, 4BC., and viscosity measurements were tak~n at intervals with a Brookfield Viscometer.
TABLE IV
Viscosity, cps ~ 2) initial 52 26.5 after weeks - 1 65 gelled - - 2 107.5 - 4 127.5 (1) is an alkylated glyoxal/cyclic urea condensate.
~ 2) is a nonalkylated glyoxaltcyclic urea condensate.
From these data it can be seen that the non-alkylated product (2) was unstable, gelling in one week, whereas the alkylated product ~1) remained stable after - 10 weeks at 48C.
EX~IPLE 12 To illustrate ~he superiority o~ an alkylated glyoxal/cyclic urea condensate over a nonalkylated glyoxal/
cyclic urea condensate as a textile treating agent, the following experiments were carri~d out:
' ' ,:. ' ' '~ ' ' . ' , ;
~ ~ ~ 3~ ~
(1) Japanese publication No. 5 3044-567-~xample 1 300 Grams of ethylene urea was charged into a 4-necked flask equipped with a reflux condenser, a thermometer, and a stirrer and dissolved in 450 grams of water. Then 1 kg. of 40% glyoxal (glyoxal:ethylene urea ratio of 2:1) ancl 2 grams of concentrated hydrochloric acid were added. The mixture was reacted for three hours at 40C. After cooling, the pH was adjusted to 5.0 wi~h sodium hydroxide solution. The slightly colored trans-parent product had a solids content of 40%.
~2) Japanese publicatlon No. 5 3044-567-Example 2 300 Grams of ethylene urea was charged into a flask as in (1) and dissolved in 450 grams of water. 750 Grams of 40% glyoxal tglyoxal:ethylene urea ratio of 1.5:1) and 2 grams of concentrated hydrochloric acid were added.
The mixture was reacted for three hours at 40C. After cooling, the pH was adjusted to 5.0 with sodium hydroxide solution. The slightly colored transparent product had a solids content of 40~.
15 Parts o-f each of these products and of the product of Example 1 was each mixed with 3.75 parts of an activated magnesium chloride catalyst and a.25 part of Sulfanole RWD, and the solutions were applied by padding to samples of fabric. The treated fabrics were dried for 3 minutes at 107C. and the resin cured on the fabrics by heating for 90 seconds at 177C.
The blue and whiteness indexes of each were measured by AATCC Test Method 110-1975 and are tabulated as follows:
TABLE V
(a)(f) (g) `~ (h) cotton blue index 81.85 74.83 76.16 85.46 whiteness index 65.53 42.04 47.69 78.23 65/35 polyester/cotton blue index 78.99 70.07 72.51 82.35 whiteness index 57.63 29.51 37.74 67.62 .
~ ~3~
(a) is the product of Example 1 o~ this appli-cation.
(f) is the product of Example 1 of Japanese publication No. 5 3044-5G7.
5~g) is the product of ~xample 2 of Japanese publication No. 5 3044-567.
(h~ is Imtreated fabric.
It is evident from these data that the product of this invention (a) is superior to the products of the Japanese publication (~) and ~g) in both blue index and whiteness index. In addition, it was noted that the dry scorch on the fabrics treated with products ~f) and (g) was extremely severe.
. :
:
,
Claims (9)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A reactant for imparting permanent press properties to a textile characterized in that said reactant comprises the alkylated product of the reaction of approximately stoichiometric amounts of glycoxal and at least one cycli urea.
2. The reactant of claim 1 wherein the ratio of glyoxal:cyclic urea is about 0.8-1.2:1.
3. The reactant of claim 1 wherein the cyclic urea has the following formula:
or wherein R1, R2, R3, R4, R5, and R6 may be the same or different and each may be H, OH,COOH,R,OR or COOR wherein R is an alkyl or a substituted alkyl group having 1 to 4 carbon atoms, and X may be C, O, or N; when X is O, R3 and R4 are each zero; when X is N, R3 or R4 is zero.
or wherein R1, R2, R3, R4, R5, and R6 may be the same or different and each may be H, OH,COOH,R,OR or COOR wherein R is an alkyl or a substituted alkyl group having 1 to 4 carbon atoms, and X may be C, O, or N; when X is O, R3 and R4 are each zero; when X is N, R3 or R4 is zero.
4. A process for producing crease-resistant textiles which comprises impregnating a textile with a solution of the reactant of claim 1 and a catalyst and heating the impregnated textile to cure the reactant thereon.
5. A crease-resistant textile produced by the process of claim 4.
6. The alkylated product of the reaction of approximately stoichiometric amounts of glyoxal and one or more cyclic ureas.
7. The product of claim 6 wherein the ratio of glyoxal:cyclic urea is about 0.8-1.2:1.
8. A water-soluble resinous product prepared by alkylating the product of the condensation of glyoxal and at least one cyclic urea, the ratio of glyoxal:cyclic urea being about 0.8-1.2:1.
9. The resinous product prepared by condensing glyoxal with at least one alkylated cyclic urea.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9263079A | 1979-11-08 | 1979-11-08 | |
| US92,630 | 1979-11-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143888A true CA1143888A (en) | 1983-03-29 |
Family
ID=22234235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000363341A Expired CA1143888A (en) | 1979-11-08 | 1980-10-27 | Reactants for crosslinking textile fabrics |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS56123478A (en) |
| CA (1) | CA1143888A (en) |
| IN (1) | IN153914B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10155836B2 (en) | 2010-09-30 | 2018-12-18 | Allnex Netherlands B.V. | Reaction product of a cyclic urea and a multifunctional aldehyde |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61173173A (en) * | 1985-01-29 | 1986-08-04 | Shin Etsu Polymer Co Ltd | Burn-in board for testing ic |
| JP2009084316A (en) * | 2007-09-27 | 2009-04-23 | Miki Riken Kogyo Kk | Water-based composition containing vinyl alcohol polymer, and adhesive using the same |
| EP2436709A1 (en) * | 2010-09-30 | 2012-04-04 | Cytec Technology Corp. | Non-etherified reaction product of a cyclic urea and a multifunctional aldehyde |
| EP2436708A1 (en) * | 2010-09-30 | 2012-04-04 | Cytec Technology Corp. | Process for the preparation of a reaction product of a cyclic urea and a multifunctional aldehyde |
| US10115785B1 (en) * | 2017-06-01 | 2018-10-30 | Xerox Corporation | Memory cells and devices |
-
1980
- 1980-10-27 CA CA000363341A patent/CA1143888A/en not_active Expired
- 1980-11-04 JP JP15496880A patent/JPS56123478A/en active Granted
- 1980-11-06 IN IN1257/CAL/80A patent/IN153914B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10155836B2 (en) | 2010-09-30 | 2018-12-18 | Allnex Netherlands B.V. | Reaction product of a cyclic urea and a multifunctional aldehyde |
Also Published As
| Publication number | Publication date |
|---|---|
| IN153914B (en) | 1984-08-25 |
| JPS56123478A (en) | 1981-09-28 |
| JPS6357550B2 (en) | 1988-11-11 |
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