US3135710A

US3135710A - Aqueous dispersion of aminoplast and butene-2-diol-1, 4

Info

Publication number: US3135710A
Application number: US57636A
Authority: US
Inventors: Benneville Peter L De
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1960-09-22
Filing date: 1960-09-22
Publication date: 1964-06-02
Anticipated expiration: 1981-06-02

Description

United States Patent 3,135,710 BlSEEREiION 0F AMINGPLAST AND BUTENE-Z-DIGL-lfl Peter L. de Benneville, Philadelphia, Pa, assignor to Robin dz Haas Company, Philadelphia, Pa, :1 corporaof Delaware No Drawing. Filed Sept. 22, 1950, Ser. No. 57,636 8 Claims. (Cl. 26tl29.4)

" "derivatives, such as N,N'-ethyleneurea and methylol melamines and ureas and their alkylated derivatives and also N,N-trimethyleneurea, have been applied to Wool and cellulosic fabrics, such as cotton, for the purpose of imparting crush-resistance and reduced shrinkage on laundering. However, fabrics treated with these condensates pick up chlorine during bleaching operations using chlorine, such as those using it in the form of a hypochlorite. On ironing the fabrics that have been bleached in this manner, severe discoloration and/or loss in tensile and/or tear strengths have generally resulted. in those cases where severe discoloration is encountered, the treatment with these condensates is unsuitable, especially when a White fabric is desired. In some cases, as much as 90% loss in strength is encountered as a result of the action of heat, as in ironing, on fabrics treated with these condensates and bleached with chlorine. The presence on a fabric of a thermoset condensate of formaldehyde with melamine frequently gives rise to some discoloration of the fabric on the mere treatment with a hypochlorite bleach unless care is taken to avoid excess chlorine and elevated temperatures. Ironing in such cases serves to aggravate the discoloration.

U.S. Patent 2,794,754 discloses the use of a mixture of an aminoplast condensate with a compound containing a plurality of vie-epoxy groups. The compounds of this patent, however, are comparatively inefficient in protecting the fabric from chlorine damage by certain nitrogen containing condensates, and especially those of formaldehyde with N,N-ethyleneurea and melamine, when used in admixture therewith. In addition, the vie-epoxy compounds tend to pick up iron in hard Water and thereby produce a discoloration on washing of the fabric which cannot be removed by normal bleaching operations.

It has been found in accordance with the invention that the incorporation of a minor proportion of butene-Z-diol- 1,4 in aqueous solutions of water-soluble aminoplast condensates selected from the group consisting of condensates of formaldehyde with aminotriazines, certain triazones, N,N'-trimethyleneurea, and N,N-ethyleneurea, and their alkylated derivatives serves to eliminate, or reduce to within practical limits, the chlorine damage that would otherwise occur as a result of the treatment with such aminoplasts. Surprisingly, the improvement is accomplished without the necessity to apply excessive quantities of the shrink-proofing or crease-proofing composition in spite of the fact that the diol is incapable of creaseproofing cellulosic fabrics when applied without an aminoplast under conditions similar to those under which. the mixture is applied. The diol of the present invention is from five to ten times as efficient as the Vic-epoxy compounds of the U.S. Patent 2,794,754 in reducing chlorine damage by discoloration and degradation caused by the "ice aminoplast condensates and have little or no tendency to pick up iron from hard waters as the Vic-epoxy compounds do.

The aminoplast constitutes the major or predominant part of the shrink-proofing, crease-proofing, or crushproofing components of the composition. The diol component constitutes from about 5% to about 40% by weight of the effective components, that is the total weight of the aminoplast and diol. For most purposes, from the standpoint of cost, efficiency, optimum freedom from discoloration, and minimum tensile loss on ironing or heating after chlorination, it is preferred to use from 5% to 20% by weight of diol and 95 to by weight respectively of aminoplast.

in accordance with the present invention, the aminoplast compositions with which the invention is concerned are water-soluble in character and include the simple condensates of N,N-ethyleneurea, certain triazones described hereinafter and aminotriazines, such as melamine or its derivatives including N-(C -C )alkylmelamines, N,N-di- (Cf-CQalkylmelamines, and N,N'-di-(C C )alkylmelamines, with formaldehyde as well as the alkylated methylol derivatives thereof, in which the alkylation is effected with lower alcohols from 1 to 3 carbons or with small proportions of higher alcohols, such as the butyl alcohols or with mixtures of such higher alcohols with the lower alcohols, so that in any event the alkylated methylol derivatives are water-soluble or self-dispersible readily in water. Any Water-soluble condensate of formaldehyde with melamine, N,N-ethyleneurea, or N,N'-tri.rnethyleneurea may be employed. Examples of specific compounds that may be used include tn'methylolmelamine, dimethylol-N,N'-ethyleneurea, and dimethylol-N,N-trimethyleneurea. The triazones that may be used include the polymethylol tetrahydro-s-triazones substituted in the 5- position by an alkyl or hydroxyalkyl group. These triazones have the Formula I:

, I i 1) where R is selected from the group consisting of 2-hydroxyethyl, 2-hydroxypropyl, and alkyl groups having 1 to 4 carbon atoms. In addition, the alkylated derivatives of these polymethylol condensates obtained from the lower alcohols from methyl through butyl maybe employed. Examples include dimethoxymethyl-N,N-dimethylmelamine, dimethoxymethyl N,N ethyleneurea,

dimethoxymethyl '5 ([3 hydroxymethyl)tetrahydro-striazone-Z, and so on. Again, it should be noted that the condensates employed as component A may be fairly sharply defined compounds including those just named as Well as others, or it may comprise mixtures of compounds of varying degrees of substitution wherein the number of methylol groups or alkoxymethyl groups may be different in the several compounds within the mixture. For the most efficient action, the aminoplasts derived from N,N'- ethyleneurea and from melamine are preferred.

The aqueous solution of the water-dispersible compouents, including the aminoplast and the diol, may contain each of such components in a concentration in about 2 to 25% or more by weight. The particular concentration applied in any given instance may depend on the purpose'for which the mixture is applied and on the particular substrate or fabricto which it is applied; In case of cotton, the concentration is preferably from 2 to 12%, whereas in application to rayon the concentration I is preferably 5 to 20%, when the purpose of the application is to impart crease-resistance, crush-resistance, or shrinkage stabilization. In the case of WOOl, the concentration is preferably from to 15%. While it is gen-' erally unnecessary, the aminoplast condensate and the diol may be reacted together provided any such reaction leaves'the final condensate in'a water-soluble Condition. However, for most purposes, it is preferred not to coreact these components. The solution containing the mixture of the aminoplast and diol components or the co-reac'ted components is stable when subjected to ordinary conditions of storage and can be soldfshipped and stored as such. Shortly be fore use, an acidic catalyst may beadded, if desired, as pointed out hereinafter.

' "An acidic catalyst for catalyzing the condensation of the ,aminoplast and the reaction of the cellulose with the diol and the aminoplast is applied'to the fabric either simultaneously with the aminoplast condensate and diol or before'or after the'mixture thereof is applied. Prefe'r ably, the'acidic catalyst is dissolved in the aoueous solution of the mixture of aminoplast condensate and diol. Suitable catalysts include phosphate, ammonium fluoborate, ammonium thiocyanate, hydrochloric or other acid salts of a hydroxy aliphatic amine including 2- methyl -2 amino l 'propanol, 2 methyl- 2 amino- 1,3 propandiol, tris- (hydroxymethyl) aminomethane, 2 phenyla 2 .amino 1 propanol, 2- methyl 1 J methylamino 1 pentanol, 2 aminobutainol, triethanolamine, Z-amiho-Z-ethyl-l-butanol, and. also ammonium chloride,v pyridine hydrochloride, aluminum chloride,

benzyldimethylammonium oxalate, magnesium perchlorate, zinc silico-fluoride, zinc perchlorate, magnesium thio cyanate, zincv thiocyanate; Zinc iiuoborate, zinc nitrate, boron fluoride, and especially the boron fluoride ether complex of the boron fluoride water complex, hydrogen fluoride, hydrochloric acid, ammonium chloride, am noacid'fluoride, phosphoric aci.., 'oxalicacid, tartaric acid, citric acid, sulfuric acid, and sodium bisulfate. The preferred catalysts whichseem to be outstanding in their eihciency ofaction and freedom from detrimentaleffect 1 on fabrics, especially with cellulosic types of fabrics, are the zinc salts such asv zinc fiuoborate and zinc nitrate.

The catalyst is generally introduced, into the aqueous solution of the condensates at a concentration of about 0.1 to 2% and preferably approximately 1%. The catalyst may be presentin an amount from about /2 to about on the total weight of aminoplast condensate and diol.

The compositions of the present invention may be ap- 7 plied to fibers filaments, yarns, or fabrics of wool or cellulosic type and especially those of cotton or rayon for various purposes. For example, they maybe applied 7 simply; to modify thefeel or texture of the surtaceof the-fabrics. When applied in greater quantities, the composition of the present inventionmay be used to make the .fabrics wrinkle-resistant, crush-resistant and crease-resistant; composition: serves to provide proportionately increased reduction in shrinkage of the treated fabric on launderingyand when =about3 to 7% by weight ofthe composition, based 'onithe weightof the fabric, is applied, the

The application of increasing amounts'of the Wool or'cellulosic fabric isigenerally substantially stabilized a'g'ainstgshrinkage on laundering. The application of the composition of the present invention may be employedifor .the purpose of-aiding embossing operations. It also may be applied to fabrics as'part. ofa process for theirconversion' to plisse fabrics andembossed fabrics.

. The aqueous solution of the aminoplast condensate and diol may be applied. by spraying, brushingpdipping, as in f paddinggor'by roller-coating; Afterjtheapplication, ex-

' icess may bel-removed, as by squeezing or squeegeeingi t The treated fabric is then dried, such 'as by rairdryingi-at room temperature or by the treatment with heated ain under conventional conditions 1 Afterthe fabric has been dried-,; the composition is baked or cured on the fabric at a temperature of about 220 to 450 F. or higher, depending on the particular substrate. The time may be varied generally in inverse proportions to the temperature. For example, the time may vary from about five seconds to half an hour. A

time of 30 seconds at 400 Pris quite practical and a time of 15 to 30 minutes'at 220 F. is generally satisfactory. The baking operation may simply be a continuation of the drying operation so that drying and curing may be efiected in essentially a one-stage procedure.

The drying and/orthe baking may be eifected by any suitable means for applying the heat, such as by'the application of heated air currents, by infra-red radiation or by high frequency electric induction.

in the following examples, which are illustrative of the invention, the parts and percentages are given by weight unless otherwise noted; 'Ihechlorination test method referred to in the examples follows the A.A.T.C.C. (69-.

1952) procedure in general except the temperature of chlorination and that of ironing indicated hereinafter. The actual procedure used involves the treatment with. a

hypochlorite solution containing 0.25% available chlorine at a temperature of 140 F.i2 F. for 15 minutes with intermittent stirring. This treatment is followed by rinses in'six freshwater baths at 70to P. with a'squeeze between rinses and drying in air atroom temperature.

The drying is'followed by conditioning for at least four hours at 70 Rand 65% relative humidity; The sample is 'iroued'at 400'F. (iron temperature) for 30 seconds.

The chlorine'damage referred to hereinbelow is the percentage loss in tensile strength referred to hereinbelow I andfis calculated by the. formula is... V, 7

t is the tensile strength after chlorination only, -and where t the tensile strength after both chlorination and ironing (or scorch test). H V

ExAivirLE t 7 r (a) An aqueous solution is prepared containing 1% of butene-2 diol-L4, 5% of dimethylol-N,N-ethyleneurea, and 0.4% of Zinc nitrate as a catalystf A white cotton fabric is padded through this solution, dried at 220 F for 5 minutes, and'then 'heatied at 320 F."for 3.minutes to f cure the resin.

" :(bi) Another piece ofthe same cotton fabric is treated in the same way except that the diol was reduced to'0.5%.

'(c) 'Another-pieceof the same cotton fabricis treated '7 in the same way except that the diol was'reduced to. 0.25% Q '(d) Another piece of the same cotton fabric-is treated in the 'sam e way exceptthat thediol was reduced to zero. After-five full Sanforize washes, thefabricsare sub- '-3'ected to the chlorinationtest above. In all'cases, yellowing after ironing is either non-existent or negligible. The results of-testingxfor, crease-proofing and chlorine damageare shown in the following'table (wherein the values given for: crease-re'co "S'nilar results are also obtainedwhen the urea de-. rivative is replaced with dimetlioxymethyl-l LNkthylenevery are theaverage of the EXAMPLE 2 An aqueous solution is prepared containing 1.0% butene-2-diol-l,4, 5% of dimethylol-N,N'-trirnethyleneurea, and 0.5% of zinc fiuoborate as a catalyst. A white cotton fabric is padded through this solution, dried at 240 F. for 5 minutes, and then heated at 340 F. for 5 minutes to cure the resin.

After five full Sanforize washes, the fabric is subjected to the chlorination test with negligible discoloration.

EXAMPLE 3 (a) An aqueous solution is prepared containing 0.5% of butene-2-diol-1,4, 5% of dimethylol trimethoxymethyl melamine, and 0.5% of zinc fluoborate as a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same way except the diol is omitted. After five full Sanforize washes and subjection to the chlorination test EXAMPLE 4 (a) An aqueous solution is prepared containing 1% of butene-2-diol-1,4, 6% of dimethylol-S-ethyl-tetrahydrotriazone-Z, and 1.0% of zinc nitrate as a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same way except the diol is omitted, After five full Sanforize washes and subjection to the chlorination test, the results are as listed in Table 111:

Table III Chlorine Damage Diseoloration on Chlorination and Ironing Percent Loss in Tensile Strength Example Slight. Yellow.

(c) Similar results are obtained when the triazone is replaced with dimethylol-S-(fi-hydroxyethyl)-tetrahydIo-striazone-Z.

I claim:

1. A composition comprising an aqueous dispersion of a mixture of to by weight of a water-dispersible aniinoplast condensate selected from the group consisting of condensates of formaldehyde with a compound selected from the group consisting of N,N-ethyleneurea, N,N-trimefliyleneiuea, a tetrahydro-s-triazone-Z substituted in the 5-position with a group selected from the group consisting of 13-hydroxyethyl, ,B-hydroxypropyl, and (C -C -alltyl groups, and a melamine and 5 to 40% by weight of butene-2-diol-1,4.

2. A composition comprising an aqueous dispersion of a mixture of 60 to 95% by weight of a water-dispersible aminoplast condensate of formaldehyde with N,N'-ethyleneurea and 5 to 40% by weight of butene-2-diol-1,4.

3. A composition as defined in claim 2 in which the aminoplast is a water-disnersible dimethylol-N,N'-ethyleneurea.

4. A composition as defined in claim 2 in which the aminoplast is a dimethoxymethyl-N,N'-ethyleneurea.

5. A composition comprising an aqueous dispersion of a mixture of 60 to 95% by weight of a water-dispersible aminoplast condensate of formaldehyde with melamine and 5 to 40% by weight of butene-2-diol-1,4.

6. A composition as defined in claim 5 in which the aminoplast is a water-dispersible methylated polyrnethylolelarnine.

7. A composition as defined in claim 5 in which the aminoplast is a dimethylol trimethoxymethylmelarnine.

8. A composition as defined in claim 5 in which the aminoplast is a dimethylol-5-ethyl-tetrahydro-s-triazone-Z.

References Cited in the file of this patent UNITED STATES PATENTS 2,596,268 Meiier May 13, 1952 2,640,041 Bruner et al. May 26, 1953 2,794,754 Schroeder June 4, 1957 2,890,242 Kress June 9, 1959 2,950,553 Hurwitz Aug. 30, 1960 2,965,436 Domenico et al. Dec. 20, 1960 2,966,473 Biefeld et a1 Dec. 27, 1960 3,005,792 Craig et al. Oct. 24, 1961

Claims

1. A COMPOSITION COMPRISING AN AQUEOUS DISPERSION OF A MIXTURE OF 60 TO 95% BY WEIGHT OF A WATER-DISPERSIBLE AMINOPLAST CONDENSATE SELECTED FROM THEGROUP CONSISTING OF CONDENSATES OF FORMALDEHYDE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N,N''-ETHYLENEUREA, N,N''-TRIMETHYLENEUREA, A TETRAHYDRO-S-TRIAZONE-2 SUBSTITUTED IN THE 5-POSITION WITH A GROUP SELECTED FROM THE GROUP CONSISTING OF B-HYDROXYETHYL, N-HYDROXYPROPYL, AND (C1-C4)-ALKYL GROUPS, AND A MELAMINE AND 5 TO 40% BY WEIGHT OF BUTENE-2-DIOL-1,4.