CA1214606A - Bleed resistant coloured crepe paper and the method of its preparation - Google Patents
Bleed resistant coloured crepe paper and the method of its preparationInfo
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- CA1214606A CA1214606A CA000443565A CA443565A CA1214606A CA 1214606 A CA1214606 A CA 1214606A CA 000443565 A CA000443565 A CA 000443565A CA 443565 A CA443565 A CA 443565A CA 1214606 A CA1214606 A CA 1214606A
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Abstract
BLEED RESISTANT COLORED CELLULOSICS
AND THE METHOD OF THEIR PREPARATION
ABSTRACT OF THE DISCLOSURE
The invention is concerned with a method of coloring a crepe type paper, which comprises the steps of (a) providing a reactive dye; (b) mixing the dye with a sufficient propor-tion of a cross-linker, to partially cross-link a portion of the dye molecules, the proportion being insufficient to cross-link all of the dye molecules; (c) partially cross-linking the portion of dye molecules; (d) adding addi-tional cross-linker to the mixture of partially cross-linked reactive dye; (e) applying the product of step (d) to the paper; and (f) chemically cross-linking the product to the paper. The method of the invention enables one to obtain bleed resistant, colored crepe type paper.
AND THE METHOD OF THEIR PREPARATION
ABSTRACT OF THE DISCLOSURE
The invention is concerned with a method of coloring a crepe type paper, which comprises the steps of (a) providing a reactive dye; (b) mixing the dye with a sufficient propor-tion of a cross-linker, to partially cross-link a portion of the dye molecules, the proportion being insufficient to cross-link all of the dye molecules; (c) partially cross-linking the portion of dye molecules; (d) adding addi-tional cross-linker to the mixture of partially cross-linked reactive dye; (e) applying the product of step (d) to the paper; and (f) chemically cross-linking the product to the paper. The method of the invention enables one to obtain bleed resistant, colored crepe type paper.
Description
60~; 1 ;-45 PLEED RESISTANT COLORED CELLULOSICS
ve AND THE METHOD OF THEIR PREPARATION
I BACKGROUND OF THE INVENTION
-¦l Field OI the Invention I The invention relates to the coloring of cellulosics, inclusive of color printing techniques, and more I particularly relates to the coloring of cellulosics with ¦ chemically reactive dyes to obtain bleed resistant, colored Il cellulosic articles.
, Brief Description of the Prior Art The U. S. Patents 1,732,540; 1,805,013; 1,863,813;
1,871,647; and 1,871,769 are representative of descriptions ,' of prior art methods and practices for preparing so-called ~ color f~st, colored cellulosic articles. In spite of the I known art for preparing colored cellulosic articles, there is a considerable amount of commercially available articles such as crepe paper, colored with dyes, that "bleed" when put into contact with water. Bv "bleeding" we mean that the ,I color leaches out of the paper and may stain whatever the 20 , ~et paDe- comes into contact with. This effect is ll ~r~
'!
' ~ i .1 ~
17~i4606 considered undesirable for many uses of crepe paper.
Apparently the known prior art methods of preparing color fast dyed cellulosics have not been found practical, sufficient or efficient for present day practices.
5 I Prior to our invention, a class of dyes (reactive dyes -ll for cellulosics) were known, which react with free hydroxyl groups on cellulosic fibers to cause a coloring thereof.
¦¦ However, the fibers must be free of contaminants such as ,' starch, which would also react with the dye to form colored, 10 ~ insoluble particles on the fiber surface. The starch/dye reaction product is readily washed off of the fiber surface, resulting in a waste of dye reactant. Another disadvantage .. I
is found in the long reaction times needed to affect a ,l coloration, i.e.; 20 to 30 minutes at elevated temperatures.
In another way to use such dyes (to dve paper, for example), this class of reactive dye may be added to the paper pulp in the beater stage to per~it reaction with cellulose over a prolonged period of time. The dyed pulp is ~ then made into a paper sheet. The resulting colored paper is color fast (bleed resistant). The disadvantage of this approach is that a considerable amount of a given colored paper has to be made at one time (for economic reasons), and thus an inventory must be maintained until demand depletes it. This is a costly procedure.
, .
1214ti(~6 !
i l By the method of this invention the reactive dyes may 1, be first reacted with a cross-linking agent such as a Il ¦' melamine-formaldehyde resin. The resulting colorant compound is then used to impregnate preformed cellulosic articles such as crepe paper and then further reacted with the paper to chemically crosslink the dye to the crepe paper. The result is a colored crepe paper sheet which resists "bleeding" when placed in contact with water. The method of the invention is economical and may be used in a i conventional plant for commercial coloration without purchasing new equipment or modifying that already in existence. Reaction times required are relatively short, which is an unexpected advantage. The method of the invention may also be carried out at relatively low temperatures, rapidly. Thus there are operating and economic advantages. The coloring approach described above may be used on a wide variety of woven anZ
non-woven disposable cellulosic items where non-bleeding is
ve AND THE METHOD OF THEIR PREPARATION
I BACKGROUND OF THE INVENTION
-¦l Field OI the Invention I The invention relates to the coloring of cellulosics, inclusive of color printing techniques, and more I particularly relates to the coloring of cellulosics with ¦ chemically reactive dyes to obtain bleed resistant, colored Il cellulosic articles.
, Brief Description of the Prior Art The U. S. Patents 1,732,540; 1,805,013; 1,863,813;
1,871,647; and 1,871,769 are representative of descriptions ,' of prior art methods and practices for preparing so-called ~ color f~st, colored cellulosic articles. In spite of the I known art for preparing colored cellulosic articles, there is a considerable amount of commercially available articles such as crepe paper, colored with dyes, that "bleed" when put into contact with water. Bv "bleeding" we mean that the ,I color leaches out of the paper and may stain whatever the 20 , ~et paDe- comes into contact with. This effect is ll ~r~
'!
' ~ i .1 ~
17~i4606 considered undesirable for many uses of crepe paper.
Apparently the known prior art methods of preparing color fast dyed cellulosics have not been found practical, sufficient or efficient for present day practices.
5 I Prior to our invention, a class of dyes (reactive dyes -ll for cellulosics) were known, which react with free hydroxyl groups on cellulosic fibers to cause a coloring thereof.
¦¦ However, the fibers must be free of contaminants such as ,' starch, which would also react with the dye to form colored, 10 ~ insoluble particles on the fiber surface. The starch/dye reaction product is readily washed off of the fiber surface, resulting in a waste of dye reactant. Another disadvantage .. I
is found in the long reaction times needed to affect a ,l coloration, i.e.; 20 to 30 minutes at elevated temperatures.
In another way to use such dyes (to dve paper, for example), this class of reactive dye may be added to the paper pulp in the beater stage to per~it reaction with cellulose over a prolonged period of time. The dyed pulp is ~ then made into a paper sheet. The resulting colored paper is color fast (bleed resistant). The disadvantage of this approach is that a considerable amount of a given colored paper has to be made at one time (for economic reasons), and thus an inventory must be maintained until demand depletes it. This is a costly procedure.
, .
1214ti(~6 !
i l By the method of this invention the reactive dyes may 1, be first reacted with a cross-linking agent such as a Il ¦' melamine-formaldehyde resin. The resulting colorant compound is then used to impregnate preformed cellulosic articles such as crepe paper and then further reacted with the paper to chemically crosslink the dye to the crepe paper. The result is a colored crepe paper sheet which resists "bleeding" when placed in contact with water. The method of the invention is economical and may be used in a i conventional plant for commercial coloration without purchasing new equipment or modifying that already in existence. Reaction times required are relatively short, which is an unexpected advantage. The method of the invention may also be carried out at relatively low temperatures, rapidly. Thus there are operating and economic advantages. The coloring approach described above may be used on a wide variety of woven anZ
non-woven disposable cellulosic items where non-bleeding is
2 useful factor (for example, tissue paper, towelling, rayon ~ sheets, crepe paper and the like).
' Our observations made while coloring crepe paper indicated that the color dispersions used in the method of the invention can be used for printing on the surfaces of cellulosic articles. Prior to the invention, a considerable amount of color printing on low cost substrates was . ' I
accomplished with either resin bonded pigments or solvent based inks. Both of these systems operate on a common principle, that is, attachment of the colorant to a substrate using a binder. Resin bonded systems are comprised of highly dispersed water insoluble pigments in - water based emulsions. An acrylic emulsion is most commonly , used in such systems. Preparation of the print paste involves addition of suitable thickeners to achieve good , definition of the print, then drying to coalesce and adhere the pigment particles to the substrate. Solvent based systems are comprised of solvated dyes and lacquers.
Preparation of the print paste involves addition of suitable thickeners to achieve good definition of print, then drying to evaporate the solvent and permit the lacquer to hold the colorant on a substrate. Both of the above described systems are expensive. For the printing of low cost items such as paper, paperboard, gift wrapping paper, textiles or other disposable items, the method of the invention is advantageous since it adds little to the overall cost of manufacture. The method of the invention is not limited however to the coloring or printing of low cost disposable cellulosics but mav be used to color even more e~:pensive articles such as textile fabrics, including woven, non-woven, knitted, pile and velvet fabrics, webs and varns.
By the method of the invention the printing of cotton i -4-l l l iZlg~06 t~ ~
1. '.
fabrics is particularly advantageous. For example, the i cotton fabric need not of necessity be pre~washed to remove starch contaminants.
Il By the method of our invention a particular class of ,' dyes referred to as "reactive dyes for cellulosics", which ',' will react with cross-linker chemicals containing, for example, amino or hydroxyl groups, are used to form reactive colorant molecules which may be used as a coloring or a 1 printing medium. The advantages are clear in that the 0 ll water-based system used in the method of the invention has produced a good definition of print. This is of economic importance since currently used organic solvent based systems present occupational and fire hazards and problems j of environmental pollution.
In addition, an inert flame retardant may be added to the print pastes or coloring mixtures used in the method of the invention to render the cellu osic articles non-fla~mable.
SU~RY OF THE INVENTION
~ The invention comprises a method of coloring preformed cellulosic articles, which comprises; chemically . .
cross-linking a reactive dye molecule to the cellulosic article. The term "coloring" as used herein includes printing, i.e.; the coloring of selected areas of a cellulosic article. More particularly, the invention is directed to a method of coloring a crepe type paper, which comprises the steps of:
~a) providing a reactive dye;
(b) mixing the dye with a sufficient proportion of a cross-linker, to partially cross-link a portion of the dye molecules, the proportion being in-sufficient to cross-link all of the dye molecules;
(c) partially cross-linking the portion of dye molecules;
(d) adding additional cross-linker to the mixture of partially cross-linked reactive dye;
(e) applying the product of step (d) to the paper;
and (f) chemically cross-linking the product to the paper.
Preferably, the cross-linker is a melamine-formal-dehyde resin or a urea-formaldehyde resin.
The method of the invention enables one to obtain bleed resistant, colored crepe type paper.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing is a block diagram out-lining a preferred embodiment method of the invention.
DETAILED DESCRIPTION OF THE PREFERRED
EMBODIMENTS OF THE INVENTION
In the accompanying diagram, there is illustrated schematically an embodiment method of the invention for coloring crepe paper to obtain a color-fast (bleed resistant) 1214~06 crepe paper. Although the method is described in regard to the coloring of crepe paper it will be appreciated that the method of the invention applies to the coloring of any like cellulosic articles such as tissue paper, towelling, non-wovens and like articles.
Cellulosic articles may be colored by the method of the invention to obtain colored articles which resist color bleeding upon contact with water. The term "cellulosic - 6a -121460~;
~~ article" as used herein means natural or synthetic preformed ', articles made from materials such as those containing a ; polymeric structure with repeating moieties of the formula:-H OH
'' X
; (I) ., wherein x is an integer which is an average of about 3,000.Representative of such cellulosic materials are cotton, paper, rayon and the like. The method of the invention is particularly advantageous for coloring crepe paper to obtain a color fast product, i.e.; colored crepe paper resistant to color bleeding.
The coloring of the cellulosic is carried out by chemically cross-linking to the cellulosic, through its free hydroxyl groups, a reactive dye molecule.
As illustrated in the accompanying drawing, the cellulosic (crepe paper) is impregnated with a mixture of a reactive dye and a chemical cross-linker. The cellulosic . . i ., I
11 1;214~
I . .
can be impregnated with the two reactants separately in any order or sequence or, preferably, the cross-linker is added to the dye component and the impregnation carried out in a single step. In the latter case, the cross-linker is first added to the dye component and may be partially reacted with the dye. Impregnation may be carried out by conventional techniques such as by spraying the impregnants on the cellulosic, dipplng the cellulosic in a bath of impregnant, by kiss roll-pad applicators and like techniques. The impregnants may also include besides the reactive dye and crosslinker, conventional additives such as wetting agents, sizes, fire retardants and the like commonly used in the art to dye or color cellulosic materials.
Following impregnation of the cellulosic, such as crepe paper, the desired cross-linkinc reaction is promoted by heating the impregnated cellulosic to a cross-linking temperature. In general, a cross-linking temperature is one within the range of from about 150F. to 500F. for periods of time between 10 seconds or less and an hour or more, depending on the particular heating techniques that are involved and the heat exchanging efficiencies that are realized. Heating may be carried out by exposure of the impregnated cellulosics to radiant heaters and like heat sources.
Il ~
46Q6;
i , Il .
The proportion of coloring reactants impregnated into the cellulosic for reaction therewith are important in regard to the degree of color fast coloration to be achieved. If a relatively light shade of coloration is ` desired, only a relatively small proportion of the cross-linking reagent is necessary to provide the cross-linked product. Thus, from 5 to 350 percent by weight of the cross-linking reagent, based on the weight of the ,, coloring component, is generally adequate for the , cross-linking purpose. Frequently, an amount of the cross-linking reagent that is between about 100 and 275 percent by weight, based on the weight of the dye component may be emploved with advantage. If precision is desired~
l the exact quantity of the cross-linking reagent for accomplishment of the intended purpose can be calculated using trial and error techniques. For a deeper shade of dyeing, more than 350 percent (by weight of colorant) of cross-linker may be employed.
The cross-linking reaction which occurs may be illustrated in the schematic formula:-A X + 2 B Z + HO - R
; (II) ~III) (IV) :, A M B M R + HX
(V~
wherein ~he compound of formula ~II) is a reactive dye . .
i, Ij _g_ ., , 1.~
!i ~
(described more fully hereinafter), X being representative of a halogen; the compound of formula (III) is a representative polyfunctional cross-linker wherein B is a ' divalent organic moiety and Z is selected from the group consisting of amino and hydroxyl; and the formula (IV) represents a hydroxy containing cellulosic material as , described above wherein R is the residue after removal of a . hydroxy group. The resulting product of formula (V) is one , wherein the dye component (II) is chemically bound to the 10 l, cellulosic (IV) so as to be color fast (bleed resistant), M
representing oxygen or a group of formula NH
The cross-linking reagent employed in the method of the invention may be a di- or polyfunctional compound, provided the functional groups are capable of a cross-linking reaction between the free hydroxyl groups on the cellulosic .(see for example the formula (I) given above) and the reactive, functional groups on the org~nic, reactive dye such as that of formula (II) given above. Representative of such cross-linking reagents are diols and diamines of the formula (III) given above wherein B is selected from the " group consisting of (a) a straight chain, branched chain or cyclic alkylene radical containing from 2 to 12 carbon atoms and in which one or both of the Z groups may be present on a secondary carbon atom, 1. ' ., .
I, --10--~214~Q6 (b) the group: - (CH2)m - - Y - - (CH2)n wherein Y is a divalent radical selected from the class consisting of straight chain alkylene groups, branched chain alkylene groups, cyclic 5 . alkylene groups and oxydialkylene groups and wherein m and n have the value 2 to 4.
~ (c) the group:
,i ., R
,, I
' C3H6 N - C3H6 ;;
wherein R is a lower alkyl or phenyl group, and 10 ; ~d) the group:
CH2 _~3 CH2 --.j The diamines of class (a) above which may be satisfactorily employed in accordance with the invention are represented by ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,3-butanediamine, 1,5-hexanediamine, 1,3-diaminecyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexane-bis (methylamine) and the like.
,1 .
Il .
12146~6 ., .
l~ The diamines of class (b) may be 3,3'-(ethylenedioxy) ,' bis(propylamine), 3,3'-(2,2-dimethyltrimethylenedioxy) bis ; (propylamine), 3,3'-(cyclohexylene-1,4-dimethylenedioxy) bis ~ (propylamine), of the formula:-S H2N(CH2)3 O 2 4 ( 2)3 NH2 and the like.
Likewise the diamines of class (c) may be
' Our observations made while coloring crepe paper indicated that the color dispersions used in the method of the invention can be used for printing on the surfaces of cellulosic articles. Prior to the invention, a considerable amount of color printing on low cost substrates was . ' I
accomplished with either resin bonded pigments or solvent based inks. Both of these systems operate on a common principle, that is, attachment of the colorant to a substrate using a binder. Resin bonded systems are comprised of highly dispersed water insoluble pigments in - water based emulsions. An acrylic emulsion is most commonly , used in such systems. Preparation of the print paste involves addition of suitable thickeners to achieve good , definition of the print, then drying to coalesce and adhere the pigment particles to the substrate. Solvent based systems are comprised of solvated dyes and lacquers.
Preparation of the print paste involves addition of suitable thickeners to achieve good definition of print, then drying to evaporate the solvent and permit the lacquer to hold the colorant on a substrate. Both of the above described systems are expensive. For the printing of low cost items such as paper, paperboard, gift wrapping paper, textiles or other disposable items, the method of the invention is advantageous since it adds little to the overall cost of manufacture. The method of the invention is not limited however to the coloring or printing of low cost disposable cellulosics but mav be used to color even more e~:pensive articles such as textile fabrics, including woven, non-woven, knitted, pile and velvet fabrics, webs and varns.
By the method of the invention the printing of cotton i -4-l l l iZlg~06 t~ ~
1. '.
fabrics is particularly advantageous. For example, the i cotton fabric need not of necessity be pre~washed to remove starch contaminants.
Il By the method of our invention a particular class of ,' dyes referred to as "reactive dyes for cellulosics", which ',' will react with cross-linker chemicals containing, for example, amino or hydroxyl groups, are used to form reactive colorant molecules which may be used as a coloring or a 1 printing medium. The advantages are clear in that the 0 ll water-based system used in the method of the invention has produced a good definition of print. This is of economic importance since currently used organic solvent based systems present occupational and fire hazards and problems j of environmental pollution.
In addition, an inert flame retardant may be added to the print pastes or coloring mixtures used in the method of the invention to render the cellu osic articles non-fla~mable.
SU~RY OF THE INVENTION
~ The invention comprises a method of coloring preformed cellulosic articles, which comprises; chemically . .
cross-linking a reactive dye molecule to the cellulosic article. The term "coloring" as used herein includes printing, i.e.; the coloring of selected areas of a cellulosic article. More particularly, the invention is directed to a method of coloring a crepe type paper, which comprises the steps of:
~a) providing a reactive dye;
(b) mixing the dye with a sufficient proportion of a cross-linker, to partially cross-link a portion of the dye molecules, the proportion being in-sufficient to cross-link all of the dye molecules;
(c) partially cross-linking the portion of dye molecules;
(d) adding additional cross-linker to the mixture of partially cross-linked reactive dye;
(e) applying the product of step (d) to the paper;
and (f) chemically cross-linking the product to the paper.
Preferably, the cross-linker is a melamine-formal-dehyde resin or a urea-formaldehyde resin.
The method of the invention enables one to obtain bleed resistant, colored crepe type paper.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing is a block diagram out-lining a preferred embodiment method of the invention.
DETAILED DESCRIPTION OF THE PREFERRED
EMBODIMENTS OF THE INVENTION
In the accompanying diagram, there is illustrated schematically an embodiment method of the invention for coloring crepe paper to obtain a color-fast (bleed resistant) 1214~06 crepe paper. Although the method is described in regard to the coloring of crepe paper it will be appreciated that the method of the invention applies to the coloring of any like cellulosic articles such as tissue paper, towelling, non-wovens and like articles.
Cellulosic articles may be colored by the method of the invention to obtain colored articles which resist color bleeding upon contact with water. The term "cellulosic - 6a -121460~;
~~ article" as used herein means natural or synthetic preformed ', articles made from materials such as those containing a ; polymeric structure with repeating moieties of the formula:-H OH
'' X
; (I) ., wherein x is an integer which is an average of about 3,000.Representative of such cellulosic materials are cotton, paper, rayon and the like. The method of the invention is particularly advantageous for coloring crepe paper to obtain a color fast product, i.e.; colored crepe paper resistant to color bleeding.
The coloring of the cellulosic is carried out by chemically cross-linking to the cellulosic, through its free hydroxyl groups, a reactive dye molecule.
As illustrated in the accompanying drawing, the cellulosic (crepe paper) is impregnated with a mixture of a reactive dye and a chemical cross-linker. The cellulosic . . i ., I
11 1;214~
I . .
can be impregnated with the two reactants separately in any order or sequence or, preferably, the cross-linker is added to the dye component and the impregnation carried out in a single step. In the latter case, the cross-linker is first added to the dye component and may be partially reacted with the dye. Impregnation may be carried out by conventional techniques such as by spraying the impregnants on the cellulosic, dipplng the cellulosic in a bath of impregnant, by kiss roll-pad applicators and like techniques. The impregnants may also include besides the reactive dye and crosslinker, conventional additives such as wetting agents, sizes, fire retardants and the like commonly used in the art to dye or color cellulosic materials.
Following impregnation of the cellulosic, such as crepe paper, the desired cross-linkinc reaction is promoted by heating the impregnated cellulosic to a cross-linking temperature. In general, a cross-linking temperature is one within the range of from about 150F. to 500F. for periods of time between 10 seconds or less and an hour or more, depending on the particular heating techniques that are involved and the heat exchanging efficiencies that are realized. Heating may be carried out by exposure of the impregnated cellulosics to radiant heaters and like heat sources.
Il ~
46Q6;
i , Il .
The proportion of coloring reactants impregnated into the cellulosic for reaction therewith are important in regard to the degree of color fast coloration to be achieved. If a relatively light shade of coloration is ` desired, only a relatively small proportion of the cross-linking reagent is necessary to provide the cross-linked product. Thus, from 5 to 350 percent by weight of the cross-linking reagent, based on the weight of the ,, coloring component, is generally adequate for the , cross-linking purpose. Frequently, an amount of the cross-linking reagent that is between about 100 and 275 percent by weight, based on the weight of the dye component may be emploved with advantage. If precision is desired~
l the exact quantity of the cross-linking reagent for accomplishment of the intended purpose can be calculated using trial and error techniques. For a deeper shade of dyeing, more than 350 percent (by weight of colorant) of cross-linker may be employed.
The cross-linking reaction which occurs may be illustrated in the schematic formula:-A X + 2 B Z + HO - R
; (II) ~III) (IV) :, A M B M R + HX
(V~
wherein ~he compound of formula ~II) is a reactive dye . .
i, Ij _g_ ., , 1.~
!i ~
(described more fully hereinafter), X being representative of a halogen; the compound of formula (III) is a representative polyfunctional cross-linker wherein B is a ' divalent organic moiety and Z is selected from the group consisting of amino and hydroxyl; and the formula (IV) represents a hydroxy containing cellulosic material as , described above wherein R is the residue after removal of a . hydroxy group. The resulting product of formula (V) is one , wherein the dye component (II) is chemically bound to the 10 l, cellulosic (IV) so as to be color fast (bleed resistant), M
representing oxygen or a group of formula NH
The cross-linking reagent employed in the method of the invention may be a di- or polyfunctional compound, provided the functional groups are capable of a cross-linking reaction between the free hydroxyl groups on the cellulosic .(see for example the formula (I) given above) and the reactive, functional groups on the org~nic, reactive dye such as that of formula (II) given above. Representative of such cross-linking reagents are diols and diamines of the formula (III) given above wherein B is selected from the " group consisting of (a) a straight chain, branched chain or cyclic alkylene radical containing from 2 to 12 carbon atoms and in which one or both of the Z groups may be present on a secondary carbon atom, 1. ' ., .
I, --10--~214~Q6 (b) the group: - (CH2)m - - Y - - (CH2)n wherein Y is a divalent radical selected from the class consisting of straight chain alkylene groups, branched chain alkylene groups, cyclic 5 . alkylene groups and oxydialkylene groups and wherein m and n have the value 2 to 4.
~ (c) the group:
,i ., R
,, I
' C3H6 N - C3H6 ;;
wherein R is a lower alkyl or phenyl group, and 10 ; ~d) the group:
CH2 _~3 CH2 --.j The diamines of class (a) above which may be satisfactorily employed in accordance with the invention are represented by ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, 1,3-butanediamine, 1,5-hexanediamine, 1,3-diaminecyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexane-bis (methylamine) and the like.
,1 .
Il .
12146~6 ., .
l~ The diamines of class (b) may be 3,3'-(ethylenedioxy) ,' bis(propylamine), 3,3'-(2,2-dimethyltrimethylenedioxy) bis ; (propylamine), 3,3'-(cyclohexylene-1,4-dimethylenedioxy) bis ~ (propylamine), of the formula:-S H2N(CH2)3 O 2 4 ( 2)3 NH2 and the like.
Likewise the diamines of class (c) may be
3,3'-ethyliminobis (propylamine) 3,3'-phenyliminobis ; (propylamine) and the like.
Similarly, the diamines of class (d) may be o-, m-, and o-xylene-diamines and the like.
Diols of class (a) above are represented by ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-dihydroxycyclohexane and the like.
The diols of class (b) above may be a poly (alkylene oxide) glycol or the like.
Diols of the class (c) given above are represented by 3,3'-ethyliminobis (propanol~ and the ]ike.
I, Diols of the class (d) given above are represented by o-, m-, p-xylene diols and the like.
, -12-j~ lZ14606 ¦ Preferred cross-linkers (III) of the diol class are ¦~ represented by dimethylol urea, dimethylol melamine, dimethylol methyltriazine, dimethylol cyclic ethylene urea l~, (DCEU) and the like. The cross-linking reagents may also be 5 1i represented by polyamines of the formula:-2 (CNH )n ~H2 wherein G may be any C2 to C10 aliphatic or C6 to C14 Il aromatic radical and n is a whole integer of at least 1.
il Polyamines that may be included in this category include for ~~ example hexamethylene tetramine, diethylene triamine,triethylene tetra~ine and the like. Other functionally equivalent polyamine compounds such as piperazine and the " various substituted piperazines and melamine, in which the nitrogen atoms are part of a heterocyclic molecular structure, may also be utilized as cross-linking reagents in the method of the invention.
Advantageously, the cross-linking reagent may be an aldehyde type of material such as furfural or glyoxal and Il the like, or a urea-formaldehyde or melamine formaldehyde polymer condensate of the usual resin precursor varietv, i.e.; mono-or dimethylolurea and the like. It is generally desirable to employ as the cross-linking reagent a polvmer which is a urea-formaldehyde or melamine-formaldehyde ., .
I polymer condensate such as those which have been previously ,¦ used in the treatment of paper to increase or impart wet strength to the paper fibers. It is believed that such ~ resin cross-linkers form hydrogen bonds between the polymer ~ chains, thereby increasing further the chemical bond strength; see Kirk Othmer, Encyclopedia of Chemistry, Vol.
2, pages 254-255. These urea-formaldehyde and melamine-formaldehyde polymer condensates contain (generally) both free hydroxyl and free amino groups which !
, may function in the desired cross-linking reaction.
Although we are not to be bound by any theory of the mechanism involved, it is believed that the free hydroxyl groups predominate in the cross-linking reaction.
~ The colored cellulosic of formula (V) is bleed resistant.
The reactive dye of formula (II) described above is an acid halide. Reactive dyes o~ the formula (II) are a class Oc dves having active, functional, halogen groups which will react with active hydrogen atoms on the cross-linking agents described above to form chemical bonds between the dye moiety and the cross-linker. Representative of reactive dyes are those described in U. S. Patents 3,290,282 and 3,503,953 which also describe their preparation. Preferred reactive dyes are those of the formulae:-il ' ' ' ~, ! !
i i! , 12~46Q6 .
Cl ~C~
N N
S13Na ll ¦
~ r N
S03Na ( Procion Yellow) ,, Cl '.
' C
',', - /~
N N
S03Na H0 NH--C C.Ci ~N= N-- ~ ~I N
.~ So3N a S03Na (Procion ~ed) O NH ~ 03Na \ N
( Procion Blu e) ., and the li ke .
An important advantage of the method and the articles ! of the invention is found in their compatibility with the ' presence of conventional, inert flame retardants. Thus, 1, inert flame retardants conventionally used to impregnate cellulosic articles may be added to the coloring compositions used to color cellulosics in the method of the invention. The term "inert flame retar~ant" means a flame , retardant compound or composition which does not enter into , the above-described cross-linking reaction or otherwise , adversely affect the desired course of the cross-linking.
The process of the invention as described above may be used for printing on cellulosics and the coloring compositions are basically the same as used for dyeing crepe paper except that alkali such as soda ash is added to the impregnant to produce a desired viscosity. Any desired viscosity can be achieved by varying the proportion of alkali, as those skilled in the art will appreciate ~viscosity increases as the pH is raised). In printing operations, the colorants are very suitable for use in the thermal process wherein the printing paste contains both the colorant and alkali and the print is cured by heating above 270C. for 30 seconds or more. Thermal printing is a well known process and the techniques and apparatus are known and readily available.
, 12~46Q6 !` I
1, 1 The following examples describe the manner and process ¦ of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the !~ invention, but are not to be construed as limiting. Bleed resistance is determined by immersing a representative portion of the colored cellulosic article (crepe paper) in tàp water and sandwiching the wet article between a top and a bottom layer of white tissue paper which layers are ' subsequently saturated with tap water. After a period of i! i , about lO minutes the sandwich is opened and the amount of bleed, i.e.; migration of colorant from the colored article to the upper and lower tissue layers noted. The article is deemed "bleed resistant" if no color migration is seen.
~. i ! EXAMPLE 1 ;
A suitable vessel is charged with 5 gms of a melamine-formaldehyde resin (Berset 808-B, Bersen Chemical Co.) in 30 ml of water. The charge is heated with stirring to a temperature of 140~F. To the heated charge there is Il added with stirring 4 gms of Procion Blue I~X-2GA (I.C.I.
Z0 Americas Inc., Wilmington, Delaware) dissolved in 20 ml of hot (140F.) water. The resulting mix,ure is mixed for 30 I minutes while maintaining the temperature of 140~F. At the end of this period, the mixture is allowed to cool to room , .
.
l -17-Il ~
1 lZ146Q6 temperature and then 40 gms of a fire retardant (Apex Flameproof #736, Apex Chemical Co~) in 10 ml of water is added with stirring. To the resulting mixture there is , added an additional 5 gms. of the melamineformaldehyde ~ resin. Crepe paper is immersed in the resulting mixture and then removed. Excess dye solution is removed by passing the dye immersed paper between the rolls of a padder. The paper is cured at a temperature of 300~F. for one minute to obtain a bleed resistant, colored crepe paper.
A dye solution is prepared as described in Example 1, supra. except that the dye solution obtained is not used for immersion of crepe paper. Instead, there is added to the dye solution with stirring 0.8 gms. soda ash. The resulting lS viscous mixture is a printing paste. The printing paste is ap?lied by screen to paper stock znd the prints are cured by exposure to radiant heaters (temperature circa 350F.) for l.S minutes. The resulting print is well defined and is bleed resistant.
! -18-
Similarly, the diamines of class (d) may be o-, m-, and o-xylene-diamines and the like.
Diols of class (a) above are represented by ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-dihydroxycyclohexane and the like.
The diols of class (b) above may be a poly (alkylene oxide) glycol or the like.
Diols of the class (c) given above are represented by 3,3'-ethyliminobis (propanol~ and the ]ike.
I, Diols of the class (d) given above are represented by o-, m-, p-xylene diols and the like.
, -12-j~ lZ14606 ¦ Preferred cross-linkers (III) of the diol class are ¦~ represented by dimethylol urea, dimethylol melamine, dimethylol methyltriazine, dimethylol cyclic ethylene urea l~, (DCEU) and the like. The cross-linking reagents may also be 5 1i represented by polyamines of the formula:-2 (CNH )n ~H2 wherein G may be any C2 to C10 aliphatic or C6 to C14 Il aromatic radical and n is a whole integer of at least 1.
il Polyamines that may be included in this category include for ~~ example hexamethylene tetramine, diethylene triamine,triethylene tetra~ine and the like. Other functionally equivalent polyamine compounds such as piperazine and the " various substituted piperazines and melamine, in which the nitrogen atoms are part of a heterocyclic molecular structure, may also be utilized as cross-linking reagents in the method of the invention.
Advantageously, the cross-linking reagent may be an aldehyde type of material such as furfural or glyoxal and Il the like, or a urea-formaldehyde or melamine formaldehyde polymer condensate of the usual resin precursor varietv, i.e.; mono-or dimethylolurea and the like. It is generally desirable to employ as the cross-linking reagent a polvmer which is a urea-formaldehyde or melamine-formaldehyde ., .
I polymer condensate such as those which have been previously ,¦ used in the treatment of paper to increase or impart wet strength to the paper fibers. It is believed that such ~ resin cross-linkers form hydrogen bonds between the polymer ~ chains, thereby increasing further the chemical bond strength; see Kirk Othmer, Encyclopedia of Chemistry, Vol.
2, pages 254-255. These urea-formaldehyde and melamine-formaldehyde polymer condensates contain (generally) both free hydroxyl and free amino groups which !
, may function in the desired cross-linking reaction.
Although we are not to be bound by any theory of the mechanism involved, it is believed that the free hydroxyl groups predominate in the cross-linking reaction.
~ The colored cellulosic of formula (V) is bleed resistant.
The reactive dye of formula (II) described above is an acid halide. Reactive dyes o~ the formula (II) are a class Oc dves having active, functional, halogen groups which will react with active hydrogen atoms on the cross-linking agents described above to form chemical bonds between the dye moiety and the cross-linker. Representative of reactive dyes are those described in U. S. Patents 3,290,282 and 3,503,953 which also describe their preparation. Preferred reactive dyes are those of the formulae:-il ' ' ' ~, ! !
i i! , 12~46Q6 .
Cl ~C~
N N
S13Na ll ¦
~ r N
S03Na ( Procion Yellow) ,, Cl '.
' C
',', - /~
N N
S03Na H0 NH--C C.Ci ~N= N-- ~ ~I N
.~ So3N a S03Na (Procion ~ed) O NH ~ 03Na \ N
( Procion Blu e) ., and the li ke .
An important advantage of the method and the articles ! of the invention is found in their compatibility with the ' presence of conventional, inert flame retardants. Thus, 1, inert flame retardants conventionally used to impregnate cellulosic articles may be added to the coloring compositions used to color cellulosics in the method of the invention. The term "inert flame retar~ant" means a flame , retardant compound or composition which does not enter into , the above-described cross-linking reaction or otherwise , adversely affect the desired course of the cross-linking.
The process of the invention as described above may be used for printing on cellulosics and the coloring compositions are basically the same as used for dyeing crepe paper except that alkali such as soda ash is added to the impregnant to produce a desired viscosity. Any desired viscosity can be achieved by varying the proportion of alkali, as those skilled in the art will appreciate ~viscosity increases as the pH is raised). In printing operations, the colorants are very suitable for use in the thermal process wherein the printing paste contains both the colorant and alkali and the print is cured by heating above 270C. for 30 seconds or more. Thermal printing is a well known process and the techniques and apparatus are known and readily available.
, 12~46Q6 !` I
1, 1 The following examples describe the manner and process ¦ of making and using the invention and set forth the best mode contemplated by the inventors of carrying out the !~ invention, but are not to be construed as limiting. Bleed resistance is determined by immersing a representative portion of the colored cellulosic article (crepe paper) in tàp water and sandwiching the wet article between a top and a bottom layer of white tissue paper which layers are ' subsequently saturated with tap water. After a period of i! i , about lO minutes the sandwich is opened and the amount of bleed, i.e.; migration of colorant from the colored article to the upper and lower tissue layers noted. The article is deemed "bleed resistant" if no color migration is seen.
~. i ! EXAMPLE 1 ;
A suitable vessel is charged with 5 gms of a melamine-formaldehyde resin (Berset 808-B, Bersen Chemical Co.) in 30 ml of water. The charge is heated with stirring to a temperature of 140~F. To the heated charge there is Il added with stirring 4 gms of Procion Blue I~X-2GA (I.C.I.
Z0 Americas Inc., Wilmington, Delaware) dissolved in 20 ml of hot (140F.) water. The resulting mix,ure is mixed for 30 I minutes while maintaining the temperature of 140~F. At the end of this period, the mixture is allowed to cool to room , .
.
l -17-Il ~
1 lZ146Q6 temperature and then 40 gms of a fire retardant (Apex Flameproof #736, Apex Chemical Co~) in 10 ml of water is added with stirring. To the resulting mixture there is , added an additional 5 gms. of the melamineformaldehyde ~ resin. Crepe paper is immersed in the resulting mixture and then removed. Excess dye solution is removed by passing the dye immersed paper between the rolls of a padder. The paper is cured at a temperature of 300~F. for one minute to obtain a bleed resistant, colored crepe paper.
A dye solution is prepared as described in Example 1, supra. except that the dye solution obtained is not used for immersion of crepe paper. Instead, there is added to the dye solution with stirring 0.8 gms. soda ash. The resulting lS viscous mixture is a printing paste. The printing paste is ap?lied by screen to paper stock znd the prints are cured by exposure to radiant heaters (temperature circa 350F.) for l.S minutes. The resulting print is well defined and is bleed resistant.
! -18-
Claims (3)
1. A method of coloring a crepe type paper, which comprises:
(a) providing a reactive dye;
(b) mixing said dye with a sufficient proportion of a cross-linker, to partially cross-link a portion of the dye molecules, said proportion being insufficient to cross-link all of the dye molecules;
(c) partially cross-linking the portion of dye molecules;
(d) adding additional cross-linker to the mixture of partially cross-linked reactive dye;
(e) applying the product of step (d) above to the paper; and (f) chemically cross-linking said product to the paper.
(a) providing a reactive dye;
(b) mixing said dye with a sufficient proportion of a cross-linker, to partially cross-link a portion of the dye molecules, said proportion being insufficient to cross-link all of the dye molecules;
(c) partially cross-linking the portion of dye molecules;
(d) adding additional cross-linker to the mixture of partially cross-linked reactive dye;
(e) applying the product of step (d) above to the paper; and (f) chemically cross-linking said product to the paper.
2. The method of claim 1 wherein the cross-linker is a melamine-formaldehyde resin.
3. The method of claim 1 wherein the cross-linker is a urea-formaldehyde resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000443565A CA1214606A (en) | 1983-12-16 | 1983-12-16 | Bleed resistant coloured crepe paper and the method of its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000443565A CA1214606A (en) | 1983-12-16 | 1983-12-16 | Bleed resistant coloured crepe paper and the method of its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1214606A true CA1214606A (en) | 1986-12-02 |
Family
ID=4126769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443565A Expired CA1214606A (en) | 1983-12-16 | 1983-12-16 | Bleed resistant coloured crepe paper and the method of its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1214606A (en) |
-
1983
- 1983-12-16 CA CA000443565A patent/CA1214606A/en not_active Expired
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