|Publication number||US2262771 A|
|Publication date||Nov 18, 1941|
|Filing date||Jan 3, 1940|
|Priority date||Jan 3, 1940|
|Publication number||US 2262771 A, US 2262771A, US-A-2262771, US2262771 A, US2262771A|
|Inventors||La Piana Fred G|
|Original Assignee||Stein Hail & Company Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (10), Classifications (10)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Patented Nov. 18', lQl
No Drawing. Application January 3, 1940, Serial No. 312,229
This invention relates to sizing and finishing compositions, and has. particular reference to compositions suitable for treating textile materials, such as natural or synthetic yarns, filaments, fibers, and fabrics of animal or vegetable origin. The invention also relates to a method of applying the compositions.
Sizes and finishes are widely used in the textile industry for such purposes as imparting desired body to fibers and to loosely woven cloths, to strengthen and to lubricate them, particularly in the case of warp and weft for weaving operations. Fibers and fabrics properly sized and-finished have a more desirable feel, are more resistant to wear anddirt and may be handled with greater facility in many operations.
Many fibers and fabrics, particularly delicate fibers, are advantageously treated with sizing and finishing composition sufiiciently soluble in water to permit subsequent removal thereof by immersing the material in mild aqueous baths. Again, other textile materials exhibit superior qualities when treated with compositions which are not intended to'be removed or are insoluble in water, particularly when the material will be subjected to excessive moisture or humid atmospheres. In the case of a large class of organic fibers it is also desirable to apply the composition in an unheated condition. In still other instances, after a definite sizing or finishing characteristic has been imparted to a fiber or fabric, it is desirable to alter this characteristic to meet the requirements of different uses to which the material may be put from that originally contemplated.
It is an object of the invention to provide sizing and finishing compositions that fulfill the above and other requirements, and that have superior and desirable properties in sizing yarns and finishing fabrics.
It is also an object of this invention to provide compositions easily applied to textile material in a cold state, thereby allowing treatment 1 of materialswhose fibers are injuriously affected by subjection to high temperatures.
Another object of the invention is to provide compositions particularly adaptable for the treatment of organic derivatives of cellulose, such as viscose rayon fibers and. cellulose esters, to
render the fibers more amenable to textile operathe composition can be readily washed out of the material in cold aqueous baths.
It is a further object of this invention to provide sizing and finishing compositions having water solubility characteristics which may be modified, if desired, after their application to flbers or fabrics to provide a water-insoluble tions by increasing their strength, flexibility and main in a water-soluble form if desired, so that composition.
In accordance with anembodiment 'of the present invention, it has been discovered that an finishing composition to impart a smooth liquid consistency thereto.
A composition of this type may be applied to warp or fabric in a cold condition, thus eliminating the necessity of heating the composition or maintaining it at a critical temperature during application. The composition is a relatively clear solution or dispersion and is free from slimy adhesive qualities often found in compositions containing casein or protein; it dries readily to a smooth and resistant surface, and enables its use with a. large class of artificial organic fibers which react unfavorably with sizing and finishingcompositions applicable'only in a heated condition;
A modification of the present invention, and one that is usually preferred, comprises the addition of a hardening agent, such as an aldehyde, to the composition above described. If desired, the hardening agent may be mixed in with the other ingredients in the aqueous dispersion or it may be applied after application of the composition to the material to be treated. In most instances it is preferable to include the hardening agent as an ingredient of the composition. If
the composition containing the hardening agent as an ingredient thereof is applied, or if the composition without the hardening agent is applied and the hardening agent applied to the sized or finished material in a separate operation, and the material is then dried at a moderate temperature, it remains substantially soluble in water. However, if the fabric thus treated is subjected to temperatures of about 250 to 280 13., or above, during drying or later, the constituents of the composition react chemically to render the same insoluble in water.
Ifit is desired to avoid the use of high temperatures, the composition comprising a hardening agent, which has been applied to the textile material, may be insolublized by subjecting the treated material to an acid bath treatment at ordinary temperatures which will insolubilize forming a solution, preferably dilute, of any commercially available mineral or organic acid or 1 acid reacting salt. After immersion in the bath 1 the fabric is preferably'washed and soaped to l remove excess acid.
Referring primarily to the size or finishing composition of the invention not containing 1 the hardening agent, it is comprised primarily of protein from a vegetable source such as soya The following example of a sizing and finishning composition in accordance with the inven- The proven particularly suitable for use in the sizing composition because of its action with the casein in softening and dispersing the same, and its commercial availability. Monoethanolamine is suitable, and if used, alesser amount is required due to its greater alkalinity.
ishing composition without causing undesirable precipitation.
Although the casein is capable of reacting with both the alkylolamineand the urea in the comthe composition. The bath may be prepared by position, the reaction is-preferential in nature and tends to take place between the casein and the alkylolamine probably because of the greater alkaline characteristics of this latter material. Accordingly, because suificient alkylolamine is present in the composition to react with all of the casein, the reaction between these two materials willbe substantiallycomplete and substanbean, or an animal source, such as milk, and an alkylolamine, such as triethanolamine, and urea, which are in thoroughly mixed aqueous solution. An organic wetting or thinning agent may be included.
- 1 tion is given merely as illustrative. The parts 3 are by weight.
I Parts Casein 15 to 30 Triethanolamine 10 to 2'0 lUrea- 20 to Water 30 to 55 Octyl alcohol .2 to .4?
The use of a suflicient quantity of an alkylolamine to solubilize all of the casein is 'important. The casein, which is acidic, is believed to tially all of the urea present will remain in an uncombin'ed state. It will be apparent that in order to. insure the presence of suflicient alkylolamine to react with all of the casein, it is possible toadd the alkylolamine in excess, but
such an excess serves no useful purpose in 'the composition and therefore is avoided for economical reasons. In general, in order to fully neutralize the casein with triethanolamine, for
example, it isnecessary to use from about to of triethanolamine based on the weight of thedry casein. It will be apparent that this amount may vary, depending upon the acidity of the casein. As a specific example, a composition prepared in accordance with the invention may-comprise casein and triethanolamine in the ratio of 15.6 grams of casein and, 9.5 grams of triethanolamine. The amount of ,urea added is.
not regarded as critical.
The urea present in the composition acts as a plasticizer for the amine caseinate when the composition is used in this form. When a hardening aldehyde is added, the urea reacts chemically with the aldehyde to impart additional and des'irable characteristics to the composition, as will be described'more fully hereinafter.
One of the higher boiling point alcohols, such as butyl or octyl alcohol, an alkyl ether of a monoor di-alkylene glycol, an ester or a ketone is preferably added to the composition to insure a V smooth liquid consistency. Other ingredients, such as sulfonated wetting agents, emulsifying agents and the like, may be added to the com- .position, the desirability of these added constituents being determined primarily according to the purpose for which the composition is to be used.
In preparing-the sizing and finishing composition of' the invention, the protein and ethanola'mine are added to the water and mixed. The urea is then added and the substances thoroughly mixed by a suitable stirring device. The comporeact with theMbasic alkylolamine to form an alkylolaminecaseinate, which is a salt that is soluble in any concentrationof water. Accordingly, the composition may be diluted readily to the extent required for its use as a sizing or finishing composition. The amount of dilution, in general, will vary from 4 ounces to 3 pounds of the composition per gallon of water, depending' upon the type of product desired." It is well known that casein reacts with urea to become .solubilized thereby, but, probably because of the weak basic characteristics of the urea, the reaction product of casein and urea is not soluble in dilute solutions. Heretofore, it has been usual to form glues and adhesives comprising casein and urea, or casein, urea and a.
small amount of an alkylolamine, but in such compositions there is not sufiicient alkylolamine present to solubilize all of the casein. As a consition thus prepared is soluble in anyamount of water, which may be addedin amounts determined by the viscosity of the composition which is desired. The composition prepared in accordadaptable for sizing delicate fibers and fabrics,
sequence, part of the casein is solubilized by the urea, and compositions of this type may not be diluted to the extent required in a sizing or anance with the example given is particularly being applicable thereto in a cold state, and easily washed from the woven fabric with a wash solution of cold water. v
In'another preferred embodiment of the invention, in which a hardening agent is employed,
an aldehyde, such as formaldehyde, is added to the above described composition. While-other aldehydes may be used, such as crotonaldehyde and acrylicaldehyde, formaldehyde .has been found to be particularly suitable as a hardening agent and is readily available. When formalde-' hyde is used it is gradually added to the composition in the proportion of parts by weight of the above described composition to 20 to 55 parts by weight of a 40% solution of formaldehyde.
As the formaldehyde is added to the compobrushes or applicator rolls. It can be applied to 1 action of the formaldehyde on the constituents of the solution has gone to completion.
It is believed that the formaldehyde combines chemically with the .amine caseinate in the composition to coagulate or polymerize the same and that the reaction is analogous to the'reaction of any aldehyde with a caseinate.
The above reaction being preferential in nature, the formaldehyde added to the composition tends to react with the caseinate present until all such caseinate is combined with formaldehyde. Any formaldehyde added in excess of that required to combine with the caseinate may then react with the urea present in the composition to form a urea. formaldehyde initial condensation product. In accordance with the invention, it ispreferred to add sufficient formaldehyde to the composition to react with all of the caseinate and to add an additional or excess amount to react with the urea. In the example given above of a mixture comprising 15.6 grams of casein and 9.5 grams of triethanolamine, it is necessary to add the material in the cold state and may be dried thereon at ordinary temperatures or by moderate heating at preferably not over a temperature of 150 F. The fiber or fabric thus treated carries the size or finish in a water-soluble condition, and the material may be washed substantially free therefrom.
When it is.desired to impart to the material a permanent finish that is substantially water resistant, the composition containing the hardening agent is applied as above described. The
treated material is then heated to a temperature I of about 250 F. to 280 F. or above, in a suitable drying chamber or by the application of an iron or mangle. This heating step apparently induces a chemical reaction in the composition on the treated material which renders the composition fixed to the treated material in a water-insoluble condition. I That'a reaction takes place is indicated by the fact that formaldehydeis liberated during the heating.
A modification of the method of insolublizing the textile material impregnated with a compositionformed in accordance with my invention is to subject the impregnated material prepared as described above to the action of an acid bath.
- In this manner hardening of the finish on the 15 cc. of formaldehyde to insure that sufiicient formaldehyde is present to combine with all of the 'ethanolamine caseinate. When more than 15' cc. of formaldehyde is added, the excess combines with the urea as set forth'above.
The composition formed by. .the combination of formaldehyde with an alkylolamine caseinate is soluble in dilute solutions in the presence of urea or the urea formaldehyde condensation product. Accordingly, the composition comprising casein or alkylolamine, ureaand formaldehyde, formed in accordance with the invention, may be diluted to the extent required for sizing and finishing operations without any appreciable precipitation from the solution.
If the composition is to be compounded prior to use it is preferable to add enough formaldehyde to react with all. of the caseinate and to add the remainder of the formaldehyde,. that product is accomplished at ordinary temperatures and does not require expensive heating equipment. However the material which has been treated in an acid bath should be soaked .subsequently and washed to remove excess acid and because of the difllculties involved in this step, the hardening method utilizing an acid bath is not preferred. A suitable hardening acid bath may be formed by preparinga dilute solution of a mineral or organic acid or acid reacting salt, such as hydrochloric acid, acetic acid, and the like. harden the 'composition'prepared in accordance with the invention and the exact nature of the bath is not regarded as critical.
Another significant modification of the process includes the treatment of the material with a composition not containing formaldehyde, after which the formaldehyde may be applied to the sized or finished material to react chemically with 1 the composition in s'itu instead of being added which is to react with the urea, prior to the application of the composition to the textile.
The amount of formaldehyde to be used depends primarily upon the type of finish desired.
The larger the amount, the more permanent will be the finish, particularly in its resistance to washing. amounts also will have more resilience. The min- The finish obtained by the larger imum amount of formaldehyde mentioned heretofore will be effective-for obtaining a clear solution of all the ingredients and will give a finish.
that is acceptable for many purposes. The composition containing the smaller amount of formaldehyde is also more stable and resists deterioration, particularly'in hot weather. For this reason it may be desirable to make the solution with the minimum amount if it is to stand before using and then to add an additional amount 'of formaldehyde before the composition is applied to the fabric or yarn.
The sizing or finishing composition may be applied to the fibers or textile fabrics in any conventional manner: known to the art, such as originally to the composition. The treated material may then be subjected to the heat or acid conversion processes above described, if a waterinsoluble size or finish is desired.
Thus it is possible in accordance with the invention to apply directly to the yarn or fabric "a size or finish containing or not containing a hardening agent depending on the final properties desired in the sized or finished material.
But if the size or finish not containing the hardening agent is used and it is later desired to alter its properties, the sized or finished material may be treated with formaldehyde to yield a sized or finished material which has difierent properties. If this size or finish in turn is to be insolubilized,
' the material can be treated as described. This flexibility is a very desirable feature since it enables a single composition to be used to obtain a variety of sized or finished effects.
The composition is essentially a sizing or finishing composition which, when. used in treating yarns, is applied upon the surface of the yarns. for example, to form a smooth surface and faciltate weaving operations. When the composition is used in treating woven or knitted fabrics, it is I applied on the surface of or in between the yarns In 'general, any acid reacting medium will or threads of which the fabric is composed, for
the purpose of filling the fabric, rendering it more resistant to dirt and imparting a desirable hand. 1
The "composition also may be mixed and is entirely compatible with starch in any proportion. The starch may be'added for the purpose of obtaining a modified finish or for achieving greater economies. The starch is preferably first gela tinized in any convenient way and then mixed with the composition; The viscosity of the gela tinized starch should be such that upon mixing with the composition the desired viscosity of the mixture will be obtained. The starch is more permanent in such a' finish than is usually the case in starch-containing finishes. As an explanation of this, it is quite probable that a thin film of the composition is formed around the starch granules and assists in preventing their removal. While the compositions of the present invention have been described with reference to specific. v
ingredients, it is to be understood that other ingredients, which are the equivalent of those set forth, may be used in preparing the size. It is my intention to include all equivalent ingredients and steps in the process of this invention to be within the scope thereof as set forth in the appended claims.
This application is a continuation-in-part of my application Serial No. 277,889, filed June I claim: 1. A composition of matter, comprising urea,
' an aqueous dispersion of a protein soluble in an alkylolamine, and a suflicient quantity of an alkylolamine to disperse substantially all of 'said protein.
25A composition of matter, comprising urea, and an aqueous dispersion of casein reacted with a sufficient quantity of an ethanolamine'to disperse substantially all of the casein.
3. A composition of matter, comprising urea, an aqueous dispersion of casein reacted with a sufficient quantity of an ethanolamine to disperse substantially all of the casein, and a partly water-soluble lower aliphatic alcohol.
4. A composition of matter comprising an aqueous dispersion of about 15 to 30 parts of a protein soluble in an alkylolamine, about to 20 parts of an alkylolamine and about 20 to 35 parts of urea.
5."A composition of matter comprising an .aqueous dispersion, in about 125 to 150 parts of water, of about 92.5 parts of casein, about 55 parts of triethanolamine, about 115 parts of urea, and-about 1 part of octyl alcohol.
. 6. A composition of matter comprising an aqueous dispersion of about to 30 parts of casein, about 10 to parts of an ethanolamine and about 20 to 30 parts of urea.
7. A composition of matter comprising an aqueous dispersion containing urea, a protein soluble in an' alkylolamine, and an alkylolamine, said alkylolamine being in .a' quantity suflicient to disperse substantially all of said protein, and said composition being reacted with an aldehyde selected from the group consisting of formaldehyde. crotonaldehyde, and acrylicaldehyde. said aldehyde being in a quantity suflicient to combine said alkylolamine being in a quantity sufilcient to disperse substantially all of said protein, and.
said composition being reacted with formaldehyde in a quantity sufficient to combine with substantially all of the protein and alkylolamine 'reaction product.
of the casein, and said composition being reacted? with formaldehyde in a quantity suflicient to combine with substantially all of the casein and.
ethanolamine reaction product.
10. A composition. of matter comprising an aqueous dispersion containing urea, .a protein soluble in an alkylolamine, and an alkylolamine, said alkylolamine being in a quantity suflicient to disperse substantially all of said protein, and to which dispersion is added formaldehyde in a-quantity sufficient to combine with substantially all of said protein and alkylolamine reaction product and with a material portion of said urea;
11. A composition of matter comprising an aqueous dispersion containing urea, casein, and
; ethanolamine, said ,ethanolamine being in a quantity sufficient to disperse substantially all of the casein, and to which dispersion is added formadding an aldehyde selected from the group consisting of formaldehyde, crotonaldehyde and acrylicaldehyde to said solution in an amount such that the protein-alkylolamine reaction product is precipitated and subsequently redissolved so that all of the ingredients are in solution.
13. A composition'of matter comprising an aqueous dispersion, in about 30 to parts of water, of about 15 to 30 parts of casein; about 10 to 20 parts of triethanolamine, about 20 to 35 parts of urea, about .2 to .4 part of octyl alcohol, and about 20 to 55 parts of formaldehyde,
14. A composition of matter comprising an aqueous dispersion of about 15 to 30 parts of casein, about 10 to 20 parts of an ethanolamine, about 20 to 35 parts of urea, and based upon a composition of the above ingredients, about'20 amount of higher boiling alcohol, and based on with substantially all of the protein and alkylolamine reaction product.
8. A composition of matter comprising an aqueous dispersion containing urea, a "protein soluble in an alkylolamine, and an alkylolamine' the composition of the above ingredients about 20 to 55% of about a 40%,solution of formaldehyde..
16. A composition of matter comprising a gelatinized starch paste in admixture with an aqueous dispersion of about 15 to 30 parts of casein, about'l0 to 20 parts of an ethanolamine, about 20 to 35.parts of urea,.and based on the composition of the-above ingredients about 20 to 55% of about'a 40% solution of formaldehyde.
17 A composition of matter comprising a disperson of substantially 92.5 parts of casein, 55
20. A process for producing a composition of parts of'triethanolamine, 115 parts of urea, and 136.5 parts of water to whichdispersion has been added about 80 to 220 parts of about a 40% solution of a formaldehyde.
18. A process for producing a composition of matter which comprises dissolving casein, urea and an alkylolamine in water, said casein and alkylolamine being proportioned so that substantially all of the casein is dispersed by the alkylolamine, and adding formaldehyde to said mixture in an amount to precipitate initially the casein-alkylolamine reaction product and subsequently to redissolve the same.
19. A process of producing a composition of matter which comprises dissolving a protein soluble in an alkylolamine, urea and an alkylolamine in water, said protein and said alkylolamine being proportioned so that substantially all of the protein is dispersed by the alkylolamine and adding formaldehyde to said solution in an amount that is at least sufficient tocombine with all of the protein-alkylolamine reaction product.
matter which comprises dissolving casein, urea and an ethanolamine in water, said casein and ethanolamine being proportioned so that substantially all of the casein is dispersed by the ethanolamine, and adding formaldehyde to said mixture in an amount in excess of that necessary to combine with the casein-ethanolamine reaction product. V
21. A process for producing a composition of matter which comprises dissolving casein, urea and an ,ethanolamine in water, said casein and ethanolamine being proportioned so that the casein is solubilized entirely by the ethanolamine, and adding formaldehyde to said mixture in an amount suflicient to combine with both the casein-ethanolamine reaction product and the urea.
. FRED G. LA PIANA.
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US2448571 *||Jul 18, 1945||Sep 7, 1948||Celanese Corp||Sized organic derivative of cellulose yarn|
|US2511113 *||May 16, 1947||Jun 13, 1950||Stein Hall & Company Inc||Pigment binders|
|US2636829 *||Sep 27, 1949||Apr 28, 1953||Sherwin Williams Co||Protein emulsion coating composition|
|US2848342 *||Mar 3, 1955||Aug 19, 1958||The Buckeye Cellulose Corporation||Protein compositions|
|US5494744 *||Oct 12, 1994||Feb 27, 1996||Kimberly-Clark Corporation||Method of applying a protein coating to a substrate and article thereof|
|US5855788 *||Feb 7, 1996||Jan 5, 1999||Kimberly-Clark Worldwide, Inc.||Chemically charged-modified filter for removing particles from a liquid and method thereof|
|US5858503 *||Oct 26, 1995||Jan 12, 1999||Kimberly-Clark Worldwide, Inc.||Method of applying chemical charge modifiers to a substrate and article thereof|
|US5912194 *||Aug 30, 1996||Jun 15, 1999||Kimberly Clark Corp.||Permeable liquid flow control material|
|US6046378 *||Mar 12, 1997||Apr 4, 2000||Kimberly-Clark Worldwide, Inc.||Wettable article|
|US6403858||Mar 25, 1999||Jun 11, 2002||Kimberly-Clark Worldwide, Inc.||Wettable article|
|U.S. Classification||524/704, 106/155.21, 524/18, 527/205, 524/22, 524/25|
|International Classification||D06M15/15, D06M15/01|