Note: Descriptions are shown in the official language in which they were submitted.
104;Z1S8
TEXTILE FINIS~IING PROCESS
,
- This invention relates to a textile finishing process.
More particularly, this invention relates to an in situ process
for imparting a durable finish to textiles by effectiny on a
textile,free radical polymerization and condensation via
aminoplast functionality to impart durable properties such as
flame re~ardancy, soil resistance, gxease resistance, water re-
sistance, and the like to the textiles.
The concurrence of a tremendous surge in textile
safety regulatory activity and consumer demands for versatility
of textile applications has presented the textile industry with
a severe test of the adequacy of its current textile finishing
technology. Although textile treatments have been develop~d
which are suitable for imparting fire retardance, soil resistance,
; 15 water resistance, and the like to textiles, these treatments
have been generally considered inadequate because of their
- lack of durability. As regulatory activity and the stringency
of stanaards increases , there arises the need for processes
for imparting a variety of durable finishes to textiles. Even
the current mandatory fire safety regulations which confront
, the textile industry present a clear and present need for
, such processes.
Various performed polymers such as polyacrylates,
polyvinyl chloride and the like have heretofore been employed
in textile finishing processes to impart the above-described
properties to textiles. One problem which has been common to
; such finishing processes is that these polymers tend not to
penetrate into fibers, such as cotton, rayon and the like, and
, thus coat the fibers only superficially. Under these circum-
.~ ,~ .
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, ' ~ , ,
104'~1S8
- ~tances, the yolymer is subject to re.~oval ~y l~underi~g and/or
- abrasion during normal use of the textile. Also, when the
polymer is a fairly stiff one, the "hand" ttactile quality)
of the fabric is affected adversely. Mor~over, the polfmsr,
being on th~-~ outer surface of the fibers, tends to cause fiber-
to-fiber attachements which prevent the normally free motion of
the fibers thereby further affecting the hand and sometimes
the strength of the fabric.
Various processes have previously been employed for
preparing polymers in situ in fibers from non-polymer reactants.
- These are reviewed ~y Mark,Wooding and Atlas in "Chemical
., ~
Aftertreatment of Textiles", Wiley-Interscience, New York (1971).
These processes fall into two main classes:
(1) Free radical in situ polymerization.
-~ 15 In these processes, a vinyl monomer such as acrylic
acid or its derivatives on and possibly within the fibers is
polymerized by a free radical catalyst to a vinyl polymer.
- Sometimes grafting onto the textile fiber accompanies such
polymerization especially if means are employed to generate
"graft sites" on the fibers Such processes have found very ~
little actual usage because of the limited variety of monomers ~;
~ and polymers that could thus be formed in practical textile : -
-~ mill operations. The grafting aspect, although much studied,
~ has found little actual use largely because of the expense and
-~. 25 difficulty of inducing sufficient graft sites on the fibers
or getting sufficient grafted polymers to form.
j (2) Aminoplast resin formation.
~ In these processes, -NH and -NCH(OR)- containing
-¦ compounds such as urea-formaldehyde, urea-glyoxal, or melamine-
. 3
. ~ ~ ' ''
~ 104;~1S8
formaldehyde are caused to form resins, usually of a cross-
~; s linked type, by means of acid catalysis which bring~ about
formation of -NCH-N-bonds and/or attachment of NCH- groups to
- the fiber (where the fiber is reactive as in the case of fibers
having -OH or -NH groups to form -NCH-N or -NCH-O links).
Generally, the above-described processes have been
employed as two separate and distinct processes or operations.
For example, it is known to apply N-methylolacrylamide to a
cellulosic fabric, to attach it to the cellulose via acid-
` 10 catalyzed aminoplast resin chemistry, and then, as a separate
~;~ operation, employ the use of high-energy radiation, to induce
.;
~ free radical polymerization of the double bonds. (See, for
-- example, W. Walsh, U.S. 3,434,161). This process has found
no commercial usage to date primarily because of the special
radiation apparatus involved.
It is also known to preattach a desired group, as
for example, (CH30)2P(O)CH2CH2CONHCH20H (as in German Patent
No. 1495383) or a melamine resin (as in British Patent No.
Si 779,231) to a vinyl monomer group by aminoplast resin (acid
~ 20 catalyzed) chemistry, and such monomers could presuma~ly then
- be applied in a free radical curing step on the textile, but
, again, two distinct processes (operations) are involved.
It is also known (Kamogawa et al., Japanese Patent
1 No. 363142, reported by Mark et al., loc. cit. p. 260) that
-¦ N-methylolacrylamide can be both polymerized and condensed in
cotton. No use, however, was made of this reaction scheme
s-: to bind a co-reactant to the fabric to impart a wide variety ;
of finish properties thereto.
The present invention distinguishes itself from the
prior art described above in that it employs both free radical
,.
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` ~0421S8
and acid catalyzed condensation chemistry conjointly, i.e., a
single process step, employing a catalyst or combination of
~ catalyst having both free radical and acid catalysis capabilities,
; to form novel polymeric textile finishes. In the new textile
finishes, the polymeric networks are currently considered to be
7 ' based on C-C linkages formed by the free radica~ polymerization
~ as well as linkages formed by acid-catalyzed condensation poly-
i: ~
merisation between polymer chains and/or between polymer chains
and the fiber and/or between polymer chains and useful side
10 chains. Since the invention employs small molecular weight
~; ~
reactants as contrasted with the polymers of the prior art pro-
cess outlined in (1) above, good fiber penetration is possible
and durable finishes of good hand are obtained. Since the
- - .,
process of the invention requires only one process step, it is
economically advantageous over the two-step or multi-step
~ processes of the prior art. -
-~ Accordingly, it is an object of the present invention
-i to provide a process for imparting a variety of durable finishes
L-~ tQ textiles.
It is another object of the present invention to pro-
vide an in situ, one-step textile finishing process wherein
- by appropriate selection of reactants, a wide variety of
finishes can be durably imparted to textiles.
Thus, in accordance with the present teachings, a ~-
process is provided for producing a wash-durable finish on
a textile which proceæs comprises applying to the textile
an effective amount of:
~ :,
?.,. (a) from about 2 to 50~ based on the weight of
the textile of at least one free radical polymerizable monomer
- 30 selected from the group consisting of
(i) those whose functionality permits them to
! react under acid-catalyzed conditions with an -OH, -O-alkyl or
.;
' 1~3421S~
- -NH group to form C-O or C-N bonds and
(ii) those which contain -OH, -O-alkyl or -NH groups
which undergo acid-catalyzed condensation reactions with
reactive methylol compounds,
(b) at least one co-reactant having a reactive
methylol, hydroxy, alkoxy or amino group capable of undergoing
acid-catalyzed condensation with a reactive methylol group on
` said free radical polymerizable monomer;
(c) from about 0.01 to 10% based on the weight of the
reactants of at least one free radical generating catalyst and at
~, least one acid catalyst, or at least one catalyst having both
'~ free radical generating and acidic characteristics; and
(d) subjecting said textile to curing conditions to
~-~ conjointly effect free radical polymerization and acid-catalyzed
condensation via aminoplast functionality reactions.
i More broadly, the present invention which provides a
.~ process for producing a wash-
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1042158
durable finish on a textile comprising applying to the textilean effective amount of at least one free radical polymerizable
1 monomer having a functional group capable of undergoing an
acid-catalyzed condensation reaction with at least one co-
reactant having reactive methylol, hydroxy, alkoxy or amino
groups capable of undergoing acid-catalyzed condensations with
~ a reactive methylol group on said free radical polymerizable
1-. monomer; along with a free radical generating catalyst and
- ' an acid catalyst or a single catalyst with both free radical
and acid catalyst character and subjecting said textile to
curing conditions to conjointly effect free radical polymeriza-
tion and acid-catalyzed condensation reactions.
~ A solvent, such as water, alcohol, perchloroethylene,
-~ methylchloroform, or the like càn be employed, if desired, as a ~ -
~¦ carrier for these reactants and catalysts.
-j Suitable free radical polymerizable monomers with
~ functional groups capable of reaction under acid-catalyzed
-~ aminoplast resin-forming conditions with a co-reactant having
reactable methylol, hydroxy, alkoxy or amino groups include
acrylamide, methacrylamide, N-methylolacrylamide, N-methylol-
methacrylamide, N-(alkoxymethyl)acrylamide, diacetone-
~3 - -
acrylamide, i.e., CH2=CHCONHC(CH3)2CH2COCH3, the methylolated ~-
products of diacetoneacrylamide, and 2-hydroxyethyl acrylate, -
and 2-hydroxyethyl methacrylate.
The preferred monomer, because of its favorable bal-
ance of low cost, low volatility, and high reactivity, is N- `~ `
3 methylolacrylamide. Within the class of monomers suitable for
use in the process of the invention, two subclasses can be
. distinguished
`
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104;~15~
j (a) those which have suitable functionality to
s permit them to react under acid-catalyzed conditions with an
~''
- -OH, -O-alkyl, or -NH group to form C-O or C-N bonds, such
- functionality being encompassed by the term "reactive methylol
compounds", exemplified by compounds having methylol groups
or ethers or esters thereof (i.e., by -N(CH2OH)-, -N(CH2O-alkoxy)
-N(CH2-O-acyloxy) and C(=O) C-CH2OH groups; and
(b) those which are not per se reactive methylol
compounds, but which contain -OH, -O-alkyl, or -NH groups which
,: ~
` 10 can undergo acid-catalyzed condensation reactions with reactive
methylol compounds.
Subgroup (a) is exemplified by N-methylolacrylamide,
N-methylolmethacrylamide, N-(alkoxymethyl) acrylamide, N-(al-
~j koxymethyl) methacrylamide, and the methylolation products of
diacetoneacrylamide; whereas, subgroup (b) is exemplified by
acrylamide, methacrylamide, diacetoneacrylamide, 2-hydroxy-
ethyl acrylate and 2-hydroxyethyl methacrylate.
. - ,, .
An effective quantity of the free radical polymeriz-- ~ -
able monomer will generally range from about 2 to 50%, and more ;~
q, 20 preferably from about 3 to 40% calculated on the weight of the
textile fabric.
Reactants capable of co-reaction under acid-catalyzed
~ condensation reaction conditions likewise can be subdivided
i~ into two subclasses:
(a) those which have reactable -OH, -O-alkyl or -NH
$~ groups capable of acid-catalyzed condensation reaction with
,
reactive methylol groups, but which are not per se reactive
:~ methylol compounds; and
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10421S~
(b) those which are per .se, re~ctive methylol compounds
and which can r~act both ~ith rcactive m~thylol groups of the
Inonom~r (or i~:~. polym~r) or which can r~ cl: with -011 or -NH
Iroups oE monom~r units not p~r ;o h~vi.n~3 react.iVc Ill~thy10
groups~
Class (a) encompasses alcohols, especially primary
alcohols, primary and secondary amines and amides having -NH
groups, aminoalkyl-substituted polysiloxanes silanols and
; alkoxysilanes which can hydrolize to silanols.
Class (b) encompasses methylolamides, methylolmela-
mines, methylolureas, methylolcarbonates, methylolguanidines,
- methyloldicyandiamides, glyoxal-urea adducts and the ethers
and esters of these, and quaternary alkylating agents of the
type R"3~CH2NHCOR' (wherein R' and R" can both be alkyl or
-~ 15 R"3N may represent a pyridinium ring).
~ An effective quantity of the co-reactant will generally
-7 range from about 2 to 50%, and more preferably, from about 3 to
40% calculated on the weight of the textile fabric.
~ . :
Free radical catalysts which can be employed include -~
organic and inorganic peroxy compounds and azo compounds, for
example, persulfate salts, per~hosphate salts, t-butyl hydro-
peroxide, di-t-butyl peroxide, cumene hydroperoxide, methyl
ethyl ketone peroxide, benzoyl peroxide, t-butyl peroxysuccinate, `
;¦ t-butyl perbenzoate, azobisisobutyronitrile and azobisisovaler-
~3 25 onitrile. Preferred catalysts because of their water solubility
and their ability to serve also in the role of acidic catalysts
j~ are the water soluble persulfate salts, such as ammonium,
:~ sodium and potassium persulfate.
.~ ~cidic catalysts which can be employed include hydro-
$ 30 chloric, sulfuric, fluoboric, ace~ic, lactic, glycolic, citric,
- 8 -
.
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: ;.,. . , - i .
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:-,-, , . - .
~`` 1()42158
tartaric ~nd o~alic acids, acidic salts ~ ch dS magr~e~ium
chloride, ~n~nium chloride, zinc chl~ri.de; m;-gnesium nitrate,
. fluobor~te or ~luosili.cate; ~ C ni~.r~t~, fluoborate, or fluo-
s.ilicate; amine hydrochlorides, sodium bis-llfat~, E~otassium
~~ 5 bisulfate, monoammonium phosphate, and the like.
. - It is, however, considered most preferable to use a
persulfate salt, which supp].ies the acid catalysis as well as
the free radical catalys.is required in the process of the
invention.
~- 10 An effective amount of catalyst generally ranges
~- from about 0.01 to 10% by.weight of the reactants, and prefera-
- bly ranges from about 0.05 to 5%.
Co-reactants of class (a) above include primary
' a].cohols containing phosphorus, such as the pentavalent phos- ~-
15 phorus esters containing primary alcohol groups as disclosed in ~ -
applicant's copending Canadian application S. N. 213,382,
' ~ (HOCH2)3PO,(HOCH2)2P(O)CH2
[OCH2P(O)(CH2OH)CH2]OH, HO-alky~ene-PO(O~ and the liXe, amines
~3 such as NH2CH3-a(CH3)aPO(O-alkyl)2, phosphorus-containing amides
k, ~ 20 such as NH2C(O)CH2CH2P(O)(OCH3)2, (NH-talkyl or 8]1 2P(O)(O-alkyl)~ -
PO(NH2)3, PO(NH-alkyl)3, ~P(O)(CH3)NHCH2 CH2NH-]x~ [P(O)~CH3)
x OCH2CH2NH]X, sulfonamides such as NH2SO2NH2, NH2SO~H, and
NH2SO3NH4, and bromine-containing reactants such as
;: HOCH2NHCOOCH2CHBrCH2Br or HOCH2C~CH2Br)2CH2OH. Preferred examples
b~cause of commercial availability are PO(NHCH3)3, NH2SO3NH4,
- and (HOcH2cH2)2NcH2P~o)(oc2Hs)2~
....
The amounts required to impart flame retardant .
properties are such as to cause from about 0.5 to 5% phosphorus : :
. or sulfur to be attached to the fabric.
~ Co-reactants of class (b) above include hydroxy- -
, ~ .
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104;~1S~
.. methylated or alkoxymethylated triazinylaminoalkyl phosphonates
.~ such as those of applicant's U.S. Patent 3,755,323 or of
~ Tesoro, u.S. Patent 3,551,422 (1970), methylolated amide phos-
.....
. . phonates such as HOCH2NHCOCH2CH2P(O)(OCH3)2 or methylolated
- NH2CO-O-alkylene-PO(O-alkyl)2.
`1 Co-reactants of type (a) which can be employed to
~ impart water repellant and softening properties include long
;~ chain (C6-C22) primary alcohols or amines, such as octyl,.
.~? dodecyl, hexadecyl, and eicosyl alcohol, long chain amides sùch
' 10 as caproamide, or stearamide, fatty acid diethanolamides, mono-
glycerides, polyfluoroalkyl alcohols, or amines, amides of
:
polyfluorinated fatty acids, polyfluorinated alkylsulfonamides,
or silanols or alkoxysilanes which hydrolyze to silanols or ..
aminoalkyl-substituted polysiloxanes. :
Co-reactants of type (b) which can be employed to ..
impart water repellant and softening properties include
. N-methylolated long chain fatty amides; also, N-methylolated
long chain alkylureas, etherified methylolmelamines containing .-.
~l at least one long chain quaternary ammoniomethylated long chain
fatty amides such as N-(stearamidomethyl)pyridinium salts, ~:
quaternary ammoniomethylated long chain alcohols such as
N-(octadecyloxymethyl)pyridinium salts, 3,6-dioxatetracosyloxy-
methylenepyridinium saltq, or stearatoethyoxymethylpyridinium `. -
. .
: saltc, these quaternary salts being water soluble equivalents
. of the corresponding methylol compounds.
Anti-soiling properties can be imparted by employing .
as co-reactants carboxymethyl cellulose, hydroxyethyl cellulose,
hydroxyl-terminated poly(alkylene amides), glycolic acid, .~;
polyfluoroalkylamines, polyfluoroalkanols, or polyfluoroalkan- 'A'
amides.
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ntistatic properties can be imparted by employing
co-reactants hydroxy-terminated poly(alkylene oxide), polyoxy-
ethylated alkylphenols, polyoxyethylated glycerides.
Cross-linking which imparts crease resistance or
durable press properties can be achieved by using as co-reactants
in the process of the invention such reactive methylol compounds
as methylolated ureas, cyclic ureas, urons, triazones, melamines,
dicyandiamides, and urethanes or ethers or esters thereof.
Examples are dimethylolurea, dimethylolethyleneurea, dimethyl-
olpropyleneurea, dimethylolmethyluron, dimethoxymethylethyl-
eneurea, methylolmelamine, dimethylolmelamine, trimethylol-
melamine, pentamethylolmelamine, hexamethylolmelamine (or the
partially or fully etherified derivatives thereof such as
pentamethoxymethylmelamine), dimethylolmethylcarbamate, dimethyl
isobutyl carbamate, tris(N-methylol-2-carbamoylethyl) amine,
trimethylolglyoxaldiurein, dimethyloldihydroxyethyleneurea, -
and dimethyloldicyandiamide
!.- ' .
~; When the free radical curable monomer is one having
., .
reactive methylol groups, such as N-methylolacrylamide or
hydroxymethylated diacetonylacrylamide, the co-reactant can be
~1 of the above type, or can be of the type (a) such as an ~ -
`; unmethylolated urea, ethyleneurea propyleneurea, or other cyclic
.. . . .
urea, melamine, dicyandiamide, cyanamide, urethane, or lact-
amide.
l - .
When employed together with phosphorus or sulfur-
containing flame retardant co-reactants, these nitrogen con-
taining co-reactants synergize the flame retardant action of the
phosphorus or sulfur.
.
! 3o
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104~158
Syn~rgistic flame rct;lrdan~ rJrop~r~ies are also
imparted by using silanols or alkoxysilanes capable of
hydrolyzing to silanols as co-reactants capable of acid
catalyzed co-reaction with monomer units having methylol
reagent character. Especially effective are silanols or 5ili-
cones having primary alcohol groups, ~mino or amido groups.
When the co-reactant methylol compound has two
s types of functional groups differing in their rate of acid-
catalyzed reactivity, the process of the invention can be
employed as the first step of a delayed cure permanent press
process. For example, using N-methylolacrylamide and dimethyl-
oldihydroxyethyleneurea as monomer and co-reactant and employing
low enough temperatures to avoid fully reacting the functional
groups of the dimethyloldihydroxyethyleneurea, a finish is ~ ~ -
obtained which permits the fabric to be cutj and pressed, and
s~ then subject to a final more vigorous cure, thus affording a
permanent press finish.
The process of the present invention can be conducted
by applying the reactants in any of the methods known in textile
finishing, such as padding, spraying, aerosol spraying, appli-
3 cation by a "kiss roll" or printing.
q All types of textiles can be treated by means of the
-~ proce~s of this invention so as to provide them with durable,
finishes. Thus, one may treat textiles derived from natural
~ 2~ fibers such as cotton, wool, silk, sisal, jute, hemp and linen
-~ and from synthetic fibers including nylon and other polyamides;
~¦ polyolefins such as polypropylene; polyesters such as poly-
ethylene terephthalate; cellulosics such as rayon, cellulose
acetate and triacetate; fiber glass; acrylics and modacrylics,
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. 1(~4;~1S8
i.~., fib~ ba;ed on acryl~nitril~ (opolymers; ~an fib~rs,
i.e., fibers based on vinylidene chloride copolymQrs; nytril
fibers, i.e., fibers based on vinylidene dinitrile copolymers;
rubber based fibers, spandex fibers, i.e., fibers based on a
segmented polyurethane; vinyl fibers, i.e., fibers based on
~ vinyl alcohol copolymers; vinyon fibers, i.e., fibers based on
- vinyl chloride copolymers; and metallic fibers. Textiles
derived from blends of any of the above listed natural and/or
-j synthetic fibers may also be treated by means of the process of
this invention. -
As used herein, the term "textile" or "textiles" is
meant to encompass woven or knitted fabrics as well as non-
woven fabrics which consist of continuous and/or discontinuous
~ fibers bonded so as to form a fabric by mechanical entanglement,
,~ 15 thermal interfiber bonding or by the use of adhesive of bonding -
substances.
~t should also be noted, at-this point, that in addi-
tion to being used to impart durable finishes to textiles, the ~ --
finishing process of this invention can be used for imparting
durable finishes to a variety of substrates such as cellulose
in the form of paper, wood, piywood, chipboard, jute, batting
! and the like; urethane foams, rebonded urethane coatings,
:l elastomers; and the like.
Curing can be effected by any means which initiates
both the free-radical and acid-catalyzed reactions. Most
commonly, this will be by application of heat, in the range of
about 50 to 200C. Lower temperatures can be used but the
problem of excessively long cure times, if a very reactive
catalyst is used, the stability of the treating solutions may
'~30 ( ~ -
. ,~
-13-
t. .. i .
J4ZlS8
be inadequate. Higher temperatures can ~e used but may cau~e
~abric dam~lcJe. Curing timei of from a f~w seconds at the
higher temperatures to a fe~ days at ~he lower te~peratures
are used. Those skilled in the ~rt ~lill reali~e that the
` 5 reguired time can be readily determined by routine experimenta-
i tion in any given equipment, wherein the time will be uaried
''-''? upwards until an adequate cure is found to have occurred as
evidenced by wash-durability of the finish. The actual time
will be a function of catalyst choice and amount, fabric type, ~ -
heat-transfer characteristics of the equipment, the presence
of dyes and other ingredients on the fabric or in the finish,
- moisture content of the fabric and other variables well known
~; to the textile finishers.
-~ The conjoint radical-acid catalyzed cure can be also
brought about by application of a catalyst activator, such as
sulfur dioxide which brings about a "redox" reaction with the
~; peroxide-type free radical initiator and also produces an `
-, acidic reaction by virtue of the sulfurous acid and sulfuric
acid formed on the fabric.
When heat is the means employed, it may be applied
~ by radiation (as for example by heat lamps), convection, (as
d` in an oven), conduction (as by means of heated rollers) or by
impinging steam or other heated gas onto or through the fabric.
The free radical portion of the reaction can be assisted by
the conjoint use of actinic radiation such as ultraviolet light,
;3
corona discharge, eleçtron beam, or ga~ma radiation.
To further illustrate the invention, the follo-~ing
examples are presented. These ex~mples are for illustrative
purposes only and are not to be construed as limiting the scope
-14-
'''. .
. i,i . . ~ - : -
1(J421S8
o~ the l~r~n~: invention. Unl~ss oLh~rwjs~ ~tate~, all
,/ pereent~ge~ and parts arc ~y wei~ht. ,,
XAMPLE 1
' This example illustrates the preparation of a water ~ -
repellant and fabric softening finish in situ on cotton:
~ A formulation is made of the following composition:
'; N-methylolacrylamide 10%
.i - .
N-methylolst~aramide or stearamide 5
- ammonium persulfate 0.5%
,' 10 water 3
r isopropyl alcohol 5~%
polyoxyethylated alkylphenol surfactant 1.5
. - - .
~ Cotton cloth is padded to 70% wet uptake and dried at 60 to
-~ 70C. then heated to 150C. for 5 minutes to effect curing.
;-' 15 The resultant fabric exhibits durable water repellant properties ,'-
. ~, . -- -
~'l and soft hand.
' EXAMPLE 2
This example illu5trates imparting a permanent press ~ ' `
finish to cotton broadcloth with a delayed cure.
An aqueous fo,rmulation is made of the following ~;
composition: , , `
N-methylolacrylamide 10~'
dimethyloldihydroxyethyleneure~
, (Sun Chemical Co. Permafresh*183) 10% '
. .. .
~ potassium persulfate 0,
;' 25 zinc nitrate 0.6%
A cotton broadcloth is paddea to 75% wet uptake then heated to ;~
120C. for 2 minutes to effect drying and some curing but very '~
littl,e cross-linkage (as evidenced by ease of cutting and , ~' '
~ sewing). The cloth is then cut and sewn to make garments wbich ~ - `
-~ * Trademark ;~ ' -
~:
--15~
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i04;~158
are pressed at 145 to 150C. ~nd thcn the cure cornpleted to
effect cross linking at 165 to 170C. for 3 minutes. The
finished article retains its press and crease resistance during
normal use and laundering.
EXAMPLE 3
This example illustrates the preparation of a flame
retardant finish in situ on cotton.
Three aqueous finishing solutions are formulated as
follows: A B C
(cH3o)2p(o)cH2cH2coNHcH2oH 28% 28~ 28~ ~ -
N-methylolacrylamide 15% 15~ 15~
potassium persulfate0.5~ - o.5% ~ ~-
ammonium chloride - 0.5% 0.5~ ~
.- ~ . .
n-ionic surfactant 0.01% 0.01~ 0.01%
polyethylene emulsion softener 1% lg 1~ -
Cotton (3.8 oz./yd2 flannel) is padded to 101-102~;
wet pick up, d~ied 1.5 minutes at 250F., cured 1 minute at
350F. After one water washing, the cloth was found to pass the -
Federal Vertical Flammability Test DOC FF-3-71 with 3-4" char
length. After 10 detergent washes, only the cloth treated with
formulations A and C passed tHe test, indicating the necessity
for the free radical polymerization catalyst.
-:,
~ Similar results are obtained by substituting methylol-
..
ated diacetonylacrylamide ~Lubrizol Corp. "HMDAA") for N-methylol
acrylamide, and ammonium persulfate for potassium persulfate.
EXAMPLE 4
~ This example further illustrates the preparation of
-~ a flame retardant finish on cotton.
An aqueous formulation is prepared as follows:
-16-
~ `:
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104Z~S~
N-methylolacrylamide 13.8
tri~(hydroxymethyl)pho;p}line oxide3 21~
potassium persulfate 0.5~ -
ammonium chloride 0.5
non-ionic wetting agent 0.1
~''' . .
Cotton cloth is padded in this solution and dried at 250F. for
.. . . .
1.5 minutes, then cured at 350F. for 1 minute. The flamma-
bility is evaluated by the limiting oxygen index (LOI) method
(ASTM D-2863). Also for application to tèxtiles see Tesoro
and Meiser Text Res. J. 40 430-436 (1970). Initial LOI of the
~' - treated cloth is 30.78%. LOI of the untreated cloth is 17.8%. ~-
After 10 detergent washes, the LOI of the treated cloth is
27.25% indicating that a major par-t of the flame retardant
s finish was retained.
lS A similar experiment using a product derived by acid-catalyzed dehydrative oligomerization of tris(hydroxymethyl)
, . :-.
phosphine oxide, in place of tris(hydroxymethyl~phosphine oxide
~ itself, shows an even hi~her degree of durability, both on
i~ cotton and on cotton-polyester blend.
EXAMPLE 5
This example further illustrates the preparation of
a flame retardant finish on cotton flann~
Aqueous formulations are prepared as follows~
A B
3-(dimethylphosphono)propi~namide 30
~;~ N,N',N"-trimethylphosphoric triamide -
;3 N-methylolacrylamide 18% 18
potassium persulfate 0.5~ 0 5~ ~ 3
3 non-ionic wetting agen~ ~
(Rohm & Haas - Triton*X100) 0.1~ 0.1~ ';
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Cotton flannel (3.8 oz/yd2) is padded, dried and cured a~ in
the preceding example. Both cloths exhibit initial LOI values
. of above 31 and retain a major part of their flame retardancy
j. after vigorous laundering with a commercial phosphate-built
-~ detergent.
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