CA1051144A - Method of eliminating or preventing the brightening effect on fibrous materials of anionic optical brightening agents - Google Patents
Method of eliminating or preventing the brightening effect on fibrous materials of anionic optical brightening agentsInfo
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- CA1051144A CA1051144A CA211,769A CA211769A CA1051144A CA 1051144 A CA1051144 A CA 1051144A CA 211769 A CA211769 A CA 211769A CA 1051144 A CA1051144 A CA 1051144A
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract of the Disclosure A method for eliminating or preventing the brighten-ing effect on materials, particularly fibrous materials such as textiles and paper, of anionic optical bright-ening agents involving the use of hydrosoluble acid addition salts or quaternary ammonium salts of compounds containing the group of formula:
Description
5A~ADA
~ase 150~3546 - ` 10~ 4 IM~ROVE~!E~TS IN OR RELATING TO O`RGA~IC COMPO~NDS
The present invention ralate~ to a method for e~imina~lng or preventina the bri~htening effect on .aterials of anionic optical briqhtening aaents in~olving the use of hydrosoluble acid addition salts or quaternary ammonium salts of compounds containing the qroup of formula, -C}~2~CH2~
IJ
wherein the benzene radical is attached to the other two par~s of the group at its m- or p-positions.
lb The brighteniny effects on materials, particulariy - -fibrous materials, obta~ned by treatment of the materials with optical ~rightenLng agents are not always r~quired r and accordingly, there exists a need ~or substances possessing the property of eliminating the brightening efects cn such materials previously undesirably br~.ghtened, or preventing such efrects from occurring.
This si~ua~ion arises particularly in the paper industry, ~Iherein it is often desire~ to produce a ~atch of non-~rigntened paper in a ~achine previously :~0 used to produce briahtened paper~ Between the production ,' "' ' ' ' ~ :
.
.
.. . . . .. ~.
Ch~AD~
~ase 150~3546 - ` 10~ 4 IM~ROVE~!E~TS IN OR RELATING TO O`RGA~IC COMPO~NDS
The present invention ralate~ to a method for e~imina~lng or preventina the bri~htening effect on .aterials of anionic optical briqhtening aaents in~olving the use of hydrosoluble acid addition salts or quaternary ammonium salts of compounds containing the qroup of formula, -C}~2~CH2~
IJ
wherein the benzene radical is attached to the other two par~s of the group at its m- or p-positions.
lb The brighteniny effects on materials, particulariy - -fibrous materials, obta~ned by treatment of the materials with optical ~rightenLng agents are not always r~quired r and accordingly, there exists a need ~or substances possessing the property of eliminating the brightening efects cn such materials previously undesirably br~.ghtened, or preventing such efrects from occurring.
This si~ua~ion arises particularly in the paper industry, ~Iherein it is often desire~ to produce a ~atch of non-~rigntened paper in a ~achine previously :~0 used to produce briahtened paper~ Between the production ,' "' ' ' ' ~ :
.
.
.. . . . .. ~.
Ch~AD~
- 2 ~ 35~6 ,. ;
5~
~ ~he two sorts -oE pap~r, the machine and its ~7hole reverse run system must nonmally ~e thoroughly cleaned in oraer that the residues of optical brigh~eners ~e ~emoved, and thus preventing the subsequent batch of paper from being undesirably brightened. Such a cleaning operation is costly, time-consuming and so reduces the paper production capacity. It is more economical -to avoid the need for such a cleaning operation by using some form o brightening eliminator during or after the paper formation, such that any bri~htener undesirably incorporated in the paper during production is "neutralised". Amongst other applications, the present invention is directed at a method of eliminating or pre~enting the unwanted brightening effects involving the addition of the previously ~entioned salts to the paper at an appropriate stage in its production.
Included amongst the situations wherein the present invention is of benefit is that where it is desired to produce non-brightened paper from waste paper containing an optical brightener.
More particularly, the present invention has for ~ts purpose the elimination from a material of brightening efects produced by optical brighteners containing anionic groups, e.g. those derived from sulphonic acid groups, or the prevention in a material of brightening effects from being produced by such optical brighteners.
.
- , . . .
... ~ ,, . . . .... ~
CANADA
`" - 3 _ ~ ~ 5~ 150-3546 Accordingly, it provides a method o~ eliminating the brigh-taning effect produced by or preventing the brightening effect from being produced by an anionic optical brightener on fibrous material by the application to the fibrous material substrate of a water-soluble acid addition salt or quaternary am~onium ~alt of a compound containing the group of formula, --C112-CH~ ~N-- ~
wherein the benzene radical is attached to the other two parts of the group at its .
m- or p-positions, which compound is proauced by the acylation of an excess of a polyethylenepolyamine of formula II, H(~IN-CH2-CH2)p-NH2 . II :
in which p is an integer 2 to 5, by isophthalic or terephthalic acid or an anhydride, acid halide or ester thereof in a molar ratio exceeding 1.5 ~
subsequently cyclising the product to afford imidazoline groups, and optionally reaoting the product further, by way of alkylation with an alkylating agent yielding a methyl, ethyl or phenyl- or naphthyl-substituted methyl or ethyl group and/or acylation in a molar ratio o~ initial to present acylating agent of 1:0.3 to 1:1.0, wlth a bifunctional acylating agent which is a saturated aliphatic dicarboxylic acLd of formula III, _ 4 _ ~ ~ ~ ~ ~ ~ CANADA
~ v ~ ~ ~ ~ 150-3546 HOOC (CH2)q~cOoH III
in which q is an integer 1 to 6, or a diester thereof, a halide, ester or mixed halide-ester of carbonic acid, or urea, and which quaternary ammonium salt does not contain a nitrogen atom bearing more than two S phenyl- or naphthyl-substituted methyl ox ethyl groups.
The compounds produced in the above described process have the effect, in said salt form, o eliminating or preventin~ the brightenlng effects of anionic optical brighteners on fibrous material su~strates, and are herein~
after referred to as the "brlghtening-eliminating" compounds.
In the above method, preferred diesters of the saturated aliphatic dicarboxylic acids of ~ormula III axe the dimethyl esters. Examples of halides, esters and mixed halide-esters of car~onic acid are phosgene, diethyl carbonate and ethyl chlorocarbonate. Acids from which the acid addition salts of the brightening-eliminating compounds ~, . . . :CA~A~A
5 - 15~-3~4 - ` ` 10511~4 ~an be produced i~cl~de inorganic acid~, ~.g~ ~ydrochloric, hydrobromic and sulphuric acids, aromatic ~ulphonic ~cids, e.g. benzenesulphonic and ~toluenesulphonic acids, and Cl 2 alkylsulph-uric acids. The anions of the acid addition salts, and also of the ~uaternary ammonium :
salts are preferably those of a strons inorganic acid, e.g. Cl , Br and SO~ , or of a strong mixed organic-inorganic acid, e.g. C~3S04, C~H5SO~ and the benzene-and toluenesulphonic acid anions~ Especially preferred :
are anions of strong inorganic acids, particularly Cl , and the preferred salts are the acid addition sal~s, especiall~ ~ith hydrochloric acid.
It is believed that the brightening-eliminating compounds possess the general formula I, R ~N-CH -CH-~- N ~
1 1 2 2 n ~ N ~ Y~x~cH2-c~2 1 ~ 5 in which X is the group of formula, - -CH2-CE~
wherein the benzene radical is attached to the other t~lo " ' ' ' "'' .CA~AD~
~05~
. . parts o~ the gro~p at its m- or p-positions;
n is an integer 1 to 4, Y is, when n is lt ~he group -CO-NH-, .or, when n is 2 to 4, the group of ~ormula, -~N~CH~-CH~ IN~2 either each of Rl, R2, R3, R4 and R5, independently is hydrogen, methyl, ethyl or methyl or ethyl substituted by phen~l or naphthyl, or R2, R3 and R4 are as defined above, ~1 is a bond, and R5 is the group or -C-(CH2) -O O O
wherein ~ is an integer 1 to 6, and the group of formula I is the repeating unit or an oligomerous or polymeric compound, and the benzene radicals are attac~ed to the oth~r -parts of the compound or group at 2D theLr m- or p-positions.
.
.
' ' - . , ~ ~ ~ ~ 7 ~ ~05~144 Of ~he brightening-eliminating compounds of formula I, an especially preferred class is constituted by those compounds which contain the repeating unit of formula Ia or Ib as hereinafter disclosed.
Accordingly, the present invention also provides an acid addition or quaternary ammonium salt of the compound containing the repeating unit of formula, ~IN-(CH2)2-N /~
I ~ C-~IN-CH -CII - ~
~~" O 2 2 '~ W ~ ~ -cH2-cH2-NH-co-(cH2)q-co ~
Ia in which q is an integer 1 to 6.
and the benzene nuclei are linked at their m- or p-positions, which sal~
is produced by the acylation of an excess of diethylene triamine by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester ex-ceeding 1.5:1, subsequently cyclising the product to afford imidazoline groups, acylating the product with the ester CH300C-(CH2) -COOCH3 in a molar ratio of the ester to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1, and converting the product into a salt. More preferably, the compounds contain the repeating unit of formula Ia in which q is ~.
The invention also provides an acid additi.on or quaternary ammonium salt of a compound containing the repeating unit of formula ~HN-(CH2)2 ~ ,", HN-CH2-CH2- ~ -C~12-C~12-N~I-CO w Ib ..
in which the benzene nuclei are linked at their m- or p-positions, ~
which salt is producted by the acylation of an excess of diethylene triamine :
by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester exceeding 1.5:1, subsequently cyclising the product to afford imida-zoline groups, acylating the product with urea in a molar ratio of urea to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1, and con-verting the product into a salt.
~ ; .
- 7a - 105114 In each of the above two classes of compounds, the ben~ene nuclei in the units of formulae Ia and Ib are linked at their m- or p-positions, preferably at their p-positions.
~ . .- -- :
CANAD~
5~4~
The first stage in produciny the brightening-eliminating compounds usea as their acid additi~n or quaternary ammon~um salts in the method o the present in~ention, consists in acylating a polyethylene polyamine of formula II, as given above, with isoph~hali~ or terephthalic acid, or a functional derivative thereo, in a molar ratio o polyamine to acylating `agent in excess o 1.5 : 1. In carrying out such acylation, the cyclisatlon ~ollows. Depending on ~hether the ~ree acid, an ester or an acid halide is used, there will be elimination of ater) water and alcohol, or ~ater and hydro~en halide, respectively, as the reaction proceeds, and it is often advantageous to allo~l the rapld removal of such by-products ~rom the reaction medium by the use of appropriate distillation apparatus. The acylation/cyclisatio generally proceeds satisfactorily at a temperature ~ithin the range 150 to 250C, optionally in a reaction~inert organic solvent, e.g. toluene or an xylene. Once the reaction has gone substantially to completion, generally af~er several hours reaction time, any solvent and excess polyamine may be removed by distillation, preferably under reduced pressure.
The product of the aforedescribed acylation and cyclisation procedure is believed to be of the formula IV, H-tHN-CH -CH ) -N ~ -~ 2 n ~ ~ Y-x-(cH2-c~2-NH)n-H IV
--in which X, n and Y are as defined above.
.. . :.,......... . , . . . . :
OANADA
-` - -- 9 - 1SO-3~46 Preferably, ~he starting material of formula II
~n the above described acylation and cyclisation procedure r for reasons of economy and simplicity in use, is that wherein p is 2, i.e. is aiethylene triamineO
- 5The next stage consists in either converting ~he product of the previous acylati.on and cyclisation stage directly into an acid addition salt/ or alkylating or acylating it. The purpose o the bifunctional acylating agent, which as hereinbefore indicated is either a saturated aliphatic dicarboxylic acid of formula III or a functional derivative thereor or a functional derivative of carbonic acidl is to link together two or more molecules of the product o the previous stage per molecule of sucn bifunctional acylating agent, thus affording a polymeric product which may have cross-linking. However, the reaction should be so controlled as to prevent excess polymerisation leading to insufficient water solubility of the ultimate salt product used in the method of the present invention.
The extent of polymerlsation tolerable will naturally depend, amongst other factors, on the value of X in the starting material of formula II and the quantity of ~cylating agent used, but in general suitable conditions for the acylation reaction are afforded by .
, . ~ CANADA
- lo- ~5~ 150-3546 reacting the product of the initial acylation and cyclisation stage with the bifunctional acylating agent agent ln a molar ratio of the amount of isophthalic or terephthalic acid or anhydride, acid halide or ester thereof used to the amount of bifunctional acylating agent within the range 1-0.3 to 1:1.0, preferably 1:0.4 to 1:0.7, or more preferably 1:0.5, in a reaction inert solvent, preferably propylene glycol, and at an elevated temperature, preferably 150 to 180C.
A preferred bifunctional acylating agent is adipic acid, or more pr.eferably a bi.~unctlonal derivative thereof, in particular a diester, of which adipic acld - . ~ .. ..
dimethyl ester is a preferred example. Also preferred as bifunctional acylating agents are phosgene and urea.
It is preferred to acylate the product of the initial ..
acylation and cyclisation stage, than to convert the latter directly into an acid addition salt. ..
: As an alternative to acylatin~ with a bifunctional acylating agent the product of the initial acylation and cyclisation stage, the latter may be alkylated. This may be ef~ected by well-known procedures using such alkylating a~ents as dimPthyl sulphate, diethyl sulphate, benzyl chloride, benzene- or toluenes~llphonic acid methyl or ethyl ester, l-chloromethyl-naphthalene or p-chloroethyl~benzene, which provide the required al~yl :.... ..
groups, viz~ methy.l or ethyl, optionally substi.tuted by a phenyl or naphthyl group.
~ ' ' . ,~ .
- ;
- - OANAD~
~150-3546 5~
If incomplete alkylation has been achieved, ~.e.
there ~s present in the alk~lation product at least one xeplaceable hydrogen atom bound to a ni~rogen atom, the product may optionally be acylated with a bifunctional S acylating agent as hereinbefore indicated. The acylation may be performed as described before for the acylat~on - of the product of the initial acylation and cyclisation stage~ Alkylation may also follow incomplete acylation.
If it is desired to produce a quaternary am~onium salt of the brightening~eliminating compound, the latter is reacted by well known procedures with the same sort of alkylating agent as hereinbefore described for use only as an alkYlating agent. Thus, if such salt of an ~lkylated compound is desired~ the alkylation and quaternary am.monium salt formation may be effected i.n a single stage using an amount of alkylating agent in excess of that required solely for al~ylation. When a1kylation and quaternary a~nonium salt formation are contemplatea, the quaternary a~.~onium salt used in the method of the invention may not contain a nitrogen atom bearing more than two phenyl- or naphthyl-substituted methyl or ethyl groups. Preferably, any alkyl yroup introduced by way of alkylation and/or by quaternary ammonium salt formation, is unsubstituted methyl or ethyl.
.
OANADA
- 12 150-3~6 ~ ~ 5~
The hydrosoluble acid addition salt forms of the bri~htening-eliminating compounds used in the method of the present invention, may be produced either directly from the init~al acylation and cyclisation product or from the product of the reaction between the latter product and a bifunctional acylating agent and/or an alkylating agent. Such salts may be produced by well known procedures by reacting the free bases with inorganic, organic or aliphatic or aromatic sulphonic acids, as exemplified hereinbefore~ in li~uid medium which ls at least partially aqueous.
According to the method of the present invention, the salt is preferably applied to the ~ibrous ~aterial substrate by lmpregnating the latter with an aqueous solution of the salt. The optical hriyhtener may already be present in the fibrcus material substrate, or it may be undesirably introduced at the same or a subsequent stage of the pxocessing, such that the brightening-eliminating compound is being used respectively for elimination or ~0 preven~ion of the brightening e~fects. The method is prefer-ably applied to the treatment of a textile substrate consti-tuted by fibres of natural or regenerated cellulose or of poly- -vinyl alcohol, and more preferably to the treatment of a paper - CANADA
i~5~
substratel An optical brightener whose efect is eliminated or prevented by the method is anionic in nature, and more partieularly bears sulphonic acid groups 5 - Such optical brighteners of the stilbene series are especially susceptible to subjection to the method. Since these particular optical brigh~eners are generally used in the treatment o~ fibrous materials of natural or synthetic origin contalning hydroxyl groups, the treatment o~ these same materlals is o~ con~iderahle importance in the method of the present invention.
In a particular embodiment of the method of the present invention, an aqueous solution o~ the salt is applied to paper in the stock before sheet formation.
The opkical brightener may have been in the stock before the salt addition, may be undesirably introduced simultaneously, or may be undesirably introduced at a subseauent stage in the processing of the stock. In another embodiment, paper, e.s. in sheet ~orm, is coated with a paste containing the brightening eliminating salt. The paste, for example, may be based on starch, and the coating operation, for example, may be a padding process.
The hydrosoluhle acicl additlon or auaternary ammonium salt is preferably applied to the fibrous material . .
, .~ ' ' .
, .. . .
.. . . . . . . . . . . . . . . ... . . . ... ...
:GANAD~
14 - . ..~5~3~6 ~ . .
~51~
~substrate in an amount by weigh~ from O.S to 50 times that of the optical brightener whose effect is to be -suppressed.
In the following Examples, which illustrate.
S the production of the brightening-eliminating salts ~nd their use in the process of the present invention, the parts and percentages are by weight..
.. . . ..
.. . . . ....
.. ChNADh --- 15 .~o-3~41;
' - '--` .
~315~L4 ~RODUCTION EX~lPI,E 1: .
194.2 Parts of ~erephthalic acid aimethyl ester are ~ntroduced at ~5C with stirring into 1031 parts of ~ethylene triamine (molar ratio of ester to amine = 1:10~.
The mixture is heated to 180C over the course of 3 hours under an atmosphere o nitrogen. During this period, 52 parts of distillate, having a boiling point o~ from 80C to 162C, are collected. The distillate consists mainly of methanol.
The mixture is stirred at temperatures ranging from 187 to 19~C over the course of 7F~ hours, during ~hich the water formed in the reaction together with the diethylene tria~ine is distilled off. The excess diethylene triamine is subsequently removed by vacuwm dis~illation. 255.5 Parts of a product are obtained as residue. This product is dissolved in 115 parts of propylene glycol and 26.3 parts or urea (molar ratio of terephthalic acid to urea = 1:0.5~ are ad~ed thereto.
The reaction mixture is stirred at 155-170C over the course of 2 hours. The reaction product is ~hen cooled to 80C and neutralized with cooling ~tith 211 parts of 26.6% hydrochloric acid. After cooling, a 50~ slightly viscous, brown solution of the hydrochloride salt of the pol~eric co~po~nd, whereln the group of formula Ib, ..... .. . .
- O~N~DA
~ 150-3~46 ~ L05~4 as herein~efore given, is the repeating unlt, is obtainea.
PRODUCTION EXAMPLE 2:
194 Parts of terephthalic acid dimethyl ester are introduced with stirring into 877 parts of diethylene triamine (molar ratio of ester to amine = 1:8.5). The mixture is heated to 187C over the course o~ 1~ hours, during which time 64 parts of distillate having a ~oiling point o from 60C to 148C are collected. The distillate consists mainly of methanol.
During a period of 30 minutes, the temperature is raised to 200C and the ~ater for~ed in the reaction and the excess diethylenetriamine distills off from 160C. On decreasing the distillation rate, the temperature of the reaction mi~ture is raised to 225C within 3 hours~ After this time, a vacuum of 12 to 13 Torr is applied and distillation is continued for a further hour, 758 parts of a second distillate thereby being collected~
The apparatus i5 flushed ~ith nitrogen and ~he residue is dissolved in 1~0 parts of ethylene glycol at 190-220C, after which the solution is cooled to 130C and treated with 27 parts of urea (~.olar ratio of terephthalic acid to urea = 1:0.5). The ammonia produced is taken up in dilute hydrochloric acid. After cessation , .
.' . ,'' ,' . , '' ~ .
- . .CANA~A
- ~7 - 1~0-3~46 ,.. - ~ . . . .
~5~L44 he gas pro~uction, the temperature is raised to 150C
and the reaction mixture is stirred for a ~urther 3 hours at this temperature.
Th~reafter the mixture is ccoled to 90-95C and 167 parts of 33~ hydrochloric acid are added dropwise at such a rate that the temperature, without external cooling, remains between 90C and 100C. Stirring for a ~urther ~ hour is efected after the acid addition, the product solution then displa~ing a pH of 5.5~ The pol~meric compound produced contains the group of formula Ib, as hereinbefore given, as the repeating unit.
PRODUCTIO~I E~IPLE 3:
The process is effected in accordance with - Production Exa~.ple ~, except that to 255.5 parts of the resi.due, dissolved in 115 parts o~ propylene ~lycol, 74 parts of ac'ipic acid dimethyl ester are added and ~he reaction mixture is stirred at 155-~75C over the course of 2 hours. During this period, the methanol formed in ~he reaction is distilled off. The reaction product is ~0 subsequently cooled to 80C and neutralized with cooling with 296 parts of 19.8~ hydrochloric acid. A 50%, slightly viscous solution of the hydrochloride salt of the compound, ~7herein the group of formula Ia, as here inbefore given and wherein (CH2)q is tetramethylene, ls ` : :
- CANADA
,~ .
S~
the repeating unit, is obtained.
APPLICATION E~IPLES
=. .
t. A 2.5~ cellulose suspension, consisting of 50% of bleached beech cellulose and 50~ of bleached sulphite cellulose, is brightened with the optical brightener of formula _ :C~ H ~ ~ N
$ C2 4 V
NH ~ SO3Na 2 -in an amount 0.1% of the ~eiyht of the cellulose~ The optical brightener displays its maxim~r. effect within 10 minutes. The suspension is sized with 2% of resin size and 3% of hydrated aluminium sulphate 1A12(SO4)3.18 H2O], based on the weight of the cellulose.
To parts of th}s suspension are added 1% aqueous solutions containing the hydrochloride salts pxoduced acco~ding to Production E~amples 1 and 3. In each case, 1% of eliminating agent is added, this rigure being based upon the weights of solid elirninating material a~d ce]lulose substrate.
" ' , '-.
, . : - . ,, . , ~ .....
- CANADA
~ 19 - ~50-3546 S~L~44~
5 Minutes after the addition o~ the eliminating solutions a sheet is formed from the suspensions by means of the Rapid-Kothen apparatus. This sheet is pressed and dried at gO-100C. For comparison reasons a sized cellulose sheet and a sized brightened cellulose sheet are produced, in both of which cases no eliminating agent is present.
The elimination of the brightening effect obtained with the optical briyhteners is determined according to fluorometry. The hydrochloride salt as produced in - Production Example 1 shows the better elimination effect.
2. ~ry paper is padded with a bath con~aining 80 g o starch and 0.6 g of the optical bri~htener of formula V per litre and expressed to a pick up of 100~.
The paper briyhtened in this wa~ is dried, subsequently padded with a bath containing 1% of the hydrochloride salt as produced in Production Example 1, expressed to a pick up of 100% and dried.
The ~rightening effect of the optical brightenar ~0 is thereby almost cor.lpletely eliminated.
.
,
5~
~ ~he two sorts -oE pap~r, the machine and its ~7hole reverse run system must nonmally ~e thoroughly cleaned in oraer that the residues of optical brigh~eners ~e ~emoved, and thus preventing the subsequent batch of paper from being undesirably brightened. Such a cleaning operation is costly, time-consuming and so reduces the paper production capacity. It is more economical -to avoid the need for such a cleaning operation by using some form o brightening eliminator during or after the paper formation, such that any bri~htener undesirably incorporated in the paper during production is "neutralised". Amongst other applications, the present invention is directed at a method of eliminating or pre~enting the unwanted brightening effects involving the addition of the previously ~entioned salts to the paper at an appropriate stage in its production.
Included amongst the situations wherein the present invention is of benefit is that where it is desired to produce non-brightened paper from waste paper containing an optical brightener.
More particularly, the present invention has for ~ts purpose the elimination from a material of brightening efects produced by optical brighteners containing anionic groups, e.g. those derived from sulphonic acid groups, or the prevention in a material of brightening effects from being produced by such optical brighteners.
.
- , . . .
... ~ ,, . . . .... ~
CANADA
`" - 3 _ ~ ~ 5~ 150-3546 Accordingly, it provides a method o~ eliminating the brigh-taning effect produced by or preventing the brightening effect from being produced by an anionic optical brightener on fibrous material by the application to the fibrous material substrate of a water-soluble acid addition salt or quaternary am~onium ~alt of a compound containing the group of formula, --C112-CH~ ~N-- ~
wherein the benzene radical is attached to the other two parts of the group at its .
m- or p-positions, which compound is proauced by the acylation of an excess of a polyethylenepolyamine of formula II, H(~IN-CH2-CH2)p-NH2 . II :
in which p is an integer 2 to 5, by isophthalic or terephthalic acid or an anhydride, acid halide or ester thereof in a molar ratio exceeding 1.5 ~
subsequently cyclising the product to afford imidazoline groups, and optionally reaoting the product further, by way of alkylation with an alkylating agent yielding a methyl, ethyl or phenyl- or naphthyl-substituted methyl or ethyl group and/or acylation in a molar ratio o~ initial to present acylating agent of 1:0.3 to 1:1.0, wlth a bifunctional acylating agent which is a saturated aliphatic dicarboxylic acLd of formula III, _ 4 _ ~ ~ ~ ~ ~ ~ CANADA
~ v ~ ~ ~ ~ 150-3546 HOOC (CH2)q~cOoH III
in which q is an integer 1 to 6, or a diester thereof, a halide, ester or mixed halide-ester of carbonic acid, or urea, and which quaternary ammonium salt does not contain a nitrogen atom bearing more than two S phenyl- or naphthyl-substituted methyl ox ethyl groups.
The compounds produced in the above described process have the effect, in said salt form, o eliminating or preventin~ the brightenlng effects of anionic optical brighteners on fibrous material su~strates, and are herein~
after referred to as the "brlghtening-eliminating" compounds.
In the above method, preferred diesters of the saturated aliphatic dicarboxylic acids of ~ormula III axe the dimethyl esters. Examples of halides, esters and mixed halide-esters of car~onic acid are phosgene, diethyl carbonate and ethyl chlorocarbonate. Acids from which the acid addition salts of the brightening-eliminating compounds ~, . . . :CA~A~A
5 - 15~-3~4 - ` ` 10511~4 ~an be produced i~cl~de inorganic acid~, ~.g~ ~ydrochloric, hydrobromic and sulphuric acids, aromatic ~ulphonic ~cids, e.g. benzenesulphonic and ~toluenesulphonic acids, and Cl 2 alkylsulph-uric acids. The anions of the acid addition salts, and also of the ~uaternary ammonium :
salts are preferably those of a strons inorganic acid, e.g. Cl , Br and SO~ , or of a strong mixed organic-inorganic acid, e.g. C~3S04, C~H5SO~ and the benzene-and toluenesulphonic acid anions~ Especially preferred :
are anions of strong inorganic acids, particularly Cl , and the preferred salts are the acid addition sal~s, especiall~ ~ith hydrochloric acid.
It is believed that the brightening-eliminating compounds possess the general formula I, R ~N-CH -CH-~- N ~
1 1 2 2 n ~ N ~ Y~x~cH2-c~2 1 ~ 5 in which X is the group of formula, - -CH2-CE~
wherein the benzene radical is attached to the other t~lo " ' ' ' "'' .CA~AD~
~05~
. . parts o~ the gro~p at its m- or p-positions;
n is an integer 1 to 4, Y is, when n is lt ~he group -CO-NH-, .or, when n is 2 to 4, the group of ~ormula, -~N~CH~-CH~ IN~2 either each of Rl, R2, R3, R4 and R5, independently is hydrogen, methyl, ethyl or methyl or ethyl substituted by phen~l or naphthyl, or R2, R3 and R4 are as defined above, ~1 is a bond, and R5 is the group or -C-(CH2) -O O O
wherein ~ is an integer 1 to 6, and the group of formula I is the repeating unit or an oligomerous or polymeric compound, and the benzene radicals are attac~ed to the oth~r -parts of the compound or group at 2D theLr m- or p-positions.
.
.
' ' - . , ~ ~ ~ ~ 7 ~ ~05~144 Of ~he brightening-eliminating compounds of formula I, an especially preferred class is constituted by those compounds which contain the repeating unit of formula Ia or Ib as hereinafter disclosed.
Accordingly, the present invention also provides an acid addition or quaternary ammonium salt of the compound containing the repeating unit of formula, ~IN-(CH2)2-N /~
I ~ C-~IN-CH -CII - ~
~~" O 2 2 '~ W ~ ~ -cH2-cH2-NH-co-(cH2)q-co ~
Ia in which q is an integer 1 to 6.
and the benzene nuclei are linked at their m- or p-positions, which sal~
is produced by the acylation of an excess of diethylene triamine by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester ex-ceeding 1.5:1, subsequently cyclising the product to afford imidazoline groups, acylating the product with the ester CH300C-(CH2) -COOCH3 in a molar ratio of the ester to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1, and converting the product into a salt. More preferably, the compounds contain the repeating unit of formula Ia in which q is ~.
The invention also provides an acid additi.on or quaternary ammonium salt of a compound containing the repeating unit of formula ~HN-(CH2)2 ~ ,", HN-CH2-CH2- ~ -C~12-C~12-N~I-CO w Ib ..
in which the benzene nuclei are linked at their m- or p-positions, ~
which salt is producted by the acylation of an excess of diethylene triamine :
by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester exceeding 1.5:1, subsequently cyclising the product to afford imida-zoline groups, acylating the product with urea in a molar ratio of urea to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1, and con-verting the product into a salt.
~ ; .
- 7a - 105114 In each of the above two classes of compounds, the ben~ene nuclei in the units of formulae Ia and Ib are linked at their m- or p-positions, preferably at their p-positions.
~ . .- -- :
CANAD~
5~4~
The first stage in produciny the brightening-eliminating compounds usea as their acid additi~n or quaternary ammon~um salts in the method o the present in~ention, consists in acylating a polyethylene polyamine of formula II, as given above, with isoph~hali~ or terephthalic acid, or a functional derivative thereo, in a molar ratio o polyamine to acylating `agent in excess o 1.5 : 1. In carrying out such acylation, the cyclisatlon ~ollows. Depending on ~hether the ~ree acid, an ester or an acid halide is used, there will be elimination of ater) water and alcohol, or ~ater and hydro~en halide, respectively, as the reaction proceeds, and it is often advantageous to allo~l the rapld removal of such by-products ~rom the reaction medium by the use of appropriate distillation apparatus. The acylation/cyclisatio generally proceeds satisfactorily at a temperature ~ithin the range 150 to 250C, optionally in a reaction~inert organic solvent, e.g. toluene or an xylene. Once the reaction has gone substantially to completion, generally af~er several hours reaction time, any solvent and excess polyamine may be removed by distillation, preferably under reduced pressure.
The product of the aforedescribed acylation and cyclisation procedure is believed to be of the formula IV, H-tHN-CH -CH ) -N ~ -~ 2 n ~ ~ Y-x-(cH2-c~2-NH)n-H IV
--in which X, n and Y are as defined above.
.. . :.,......... . , . . . . :
OANADA
-` - -- 9 - 1SO-3~46 Preferably, ~he starting material of formula II
~n the above described acylation and cyclisation procedure r for reasons of economy and simplicity in use, is that wherein p is 2, i.e. is aiethylene triamineO
- 5The next stage consists in either converting ~he product of the previous acylati.on and cyclisation stage directly into an acid addition salt/ or alkylating or acylating it. The purpose o the bifunctional acylating agent, which as hereinbefore indicated is either a saturated aliphatic dicarboxylic acid of formula III or a functional derivative thereor or a functional derivative of carbonic acidl is to link together two or more molecules of the product o the previous stage per molecule of sucn bifunctional acylating agent, thus affording a polymeric product which may have cross-linking. However, the reaction should be so controlled as to prevent excess polymerisation leading to insufficient water solubility of the ultimate salt product used in the method of the present invention.
The extent of polymerlsation tolerable will naturally depend, amongst other factors, on the value of X in the starting material of formula II and the quantity of ~cylating agent used, but in general suitable conditions for the acylation reaction are afforded by .
, . ~ CANADA
- lo- ~5~ 150-3546 reacting the product of the initial acylation and cyclisation stage with the bifunctional acylating agent agent ln a molar ratio of the amount of isophthalic or terephthalic acid or anhydride, acid halide or ester thereof used to the amount of bifunctional acylating agent within the range 1-0.3 to 1:1.0, preferably 1:0.4 to 1:0.7, or more preferably 1:0.5, in a reaction inert solvent, preferably propylene glycol, and at an elevated temperature, preferably 150 to 180C.
A preferred bifunctional acylating agent is adipic acid, or more pr.eferably a bi.~unctlonal derivative thereof, in particular a diester, of which adipic acld - . ~ .. ..
dimethyl ester is a preferred example. Also preferred as bifunctional acylating agents are phosgene and urea.
It is preferred to acylate the product of the initial ..
acylation and cyclisation stage, than to convert the latter directly into an acid addition salt. ..
: As an alternative to acylatin~ with a bifunctional acylating agent the product of the initial acylation and cyclisation stage, the latter may be alkylated. This may be ef~ected by well-known procedures using such alkylating a~ents as dimPthyl sulphate, diethyl sulphate, benzyl chloride, benzene- or toluenes~llphonic acid methyl or ethyl ester, l-chloromethyl-naphthalene or p-chloroethyl~benzene, which provide the required al~yl :.... ..
groups, viz~ methy.l or ethyl, optionally substi.tuted by a phenyl or naphthyl group.
~ ' ' . ,~ .
- ;
- - OANAD~
~150-3546 5~
If incomplete alkylation has been achieved, ~.e.
there ~s present in the alk~lation product at least one xeplaceable hydrogen atom bound to a ni~rogen atom, the product may optionally be acylated with a bifunctional S acylating agent as hereinbefore indicated. The acylation may be performed as described before for the acylat~on - of the product of the initial acylation and cyclisation stage~ Alkylation may also follow incomplete acylation.
If it is desired to produce a quaternary am~onium salt of the brightening~eliminating compound, the latter is reacted by well known procedures with the same sort of alkylating agent as hereinbefore described for use only as an alkYlating agent. Thus, if such salt of an ~lkylated compound is desired~ the alkylation and quaternary am.monium salt formation may be effected i.n a single stage using an amount of alkylating agent in excess of that required solely for al~ylation. When a1kylation and quaternary a~nonium salt formation are contemplatea, the quaternary a~.~onium salt used in the method of the invention may not contain a nitrogen atom bearing more than two phenyl- or naphthyl-substituted methyl or ethyl groups. Preferably, any alkyl yroup introduced by way of alkylation and/or by quaternary ammonium salt formation, is unsubstituted methyl or ethyl.
.
OANADA
- 12 150-3~6 ~ ~ 5~
The hydrosoluble acid addition salt forms of the bri~htening-eliminating compounds used in the method of the present invention, may be produced either directly from the init~al acylation and cyclisation product or from the product of the reaction between the latter product and a bifunctional acylating agent and/or an alkylating agent. Such salts may be produced by well known procedures by reacting the free bases with inorganic, organic or aliphatic or aromatic sulphonic acids, as exemplified hereinbefore~ in li~uid medium which ls at least partially aqueous.
According to the method of the present invention, the salt is preferably applied to the ~ibrous ~aterial substrate by lmpregnating the latter with an aqueous solution of the salt. The optical hriyhtener may already be present in the fibrcus material substrate, or it may be undesirably introduced at the same or a subsequent stage of the pxocessing, such that the brightening-eliminating compound is being used respectively for elimination or ~0 preven~ion of the brightening e~fects. The method is prefer-ably applied to the treatment of a textile substrate consti-tuted by fibres of natural or regenerated cellulose or of poly- -vinyl alcohol, and more preferably to the treatment of a paper - CANADA
i~5~
substratel An optical brightener whose efect is eliminated or prevented by the method is anionic in nature, and more partieularly bears sulphonic acid groups 5 - Such optical brighteners of the stilbene series are especially susceptible to subjection to the method. Since these particular optical brigh~eners are generally used in the treatment o~ fibrous materials of natural or synthetic origin contalning hydroxyl groups, the treatment o~ these same materlals is o~ con~iderahle importance in the method of the present invention.
In a particular embodiment of the method of the present invention, an aqueous solution o~ the salt is applied to paper in the stock before sheet formation.
The opkical brightener may have been in the stock before the salt addition, may be undesirably introduced simultaneously, or may be undesirably introduced at a subseauent stage in the processing of the stock. In another embodiment, paper, e.s. in sheet ~orm, is coated with a paste containing the brightening eliminating salt. The paste, for example, may be based on starch, and the coating operation, for example, may be a padding process.
The hydrosoluhle acicl additlon or auaternary ammonium salt is preferably applied to the fibrous material . .
, .~ ' ' .
, .. . .
.. . . . . . . . . . . . . . . ... . . . ... ...
:GANAD~
14 - . ..~5~3~6 ~ . .
~51~
~substrate in an amount by weigh~ from O.S to 50 times that of the optical brightener whose effect is to be -suppressed.
In the following Examples, which illustrate.
S the production of the brightening-eliminating salts ~nd their use in the process of the present invention, the parts and percentages are by weight..
.. . . ..
.. . . . ....
.. ChNADh --- 15 .~o-3~41;
' - '--` .
~315~L4 ~RODUCTION EX~lPI,E 1: .
194.2 Parts of ~erephthalic acid aimethyl ester are ~ntroduced at ~5C with stirring into 1031 parts of ~ethylene triamine (molar ratio of ester to amine = 1:10~.
The mixture is heated to 180C over the course of 3 hours under an atmosphere o nitrogen. During this period, 52 parts of distillate, having a boiling point o~ from 80C to 162C, are collected. The distillate consists mainly of methanol.
The mixture is stirred at temperatures ranging from 187 to 19~C over the course of 7F~ hours, during ~hich the water formed in the reaction together with the diethylene tria~ine is distilled off. The excess diethylene triamine is subsequently removed by vacuwm dis~illation. 255.5 Parts of a product are obtained as residue. This product is dissolved in 115 parts of propylene glycol and 26.3 parts or urea (molar ratio of terephthalic acid to urea = 1:0.5~ are ad~ed thereto.
The reaction mixture is stirred at 155-170C over the course of 2 hours. The reaction product is ~hen cooled to 80C and neutralized with cooling ~tith 211 parts of 26.6% hydrochloric acid. After cooling, a 50~ slightly viscous, brown solution of the hydrochloride salt of the pol~eric co~po~nd, whereln the group of formula Ib, ..... .. . .
- O~N~DA
~ 150-3~46 ~ L05~4 as herein~efore given, is the repeating unlt, is obtainea.
PRODUCTION EXAMPLE 2:
194 Parts of terephthalic acid dimethyl ester are introduced with stirring into 877 parts of diethylene triamine (molar ratio of ester to amine = 1:8.5). The mixture is heated to 187C over the course o~ 1~ hours, during which time 64 parts of distillate having a ~oiling point o from 60C to 148C are collected. The distillate consists mainly of methanol.
During a period of 30 minutes, the temperature is raised to 200C and the ~ater for~ed in the reaction and the excess diethylenetriamine distills off from 160C. On decreasing the distillation rate, the temperature of the reaction mi~ture is raised to 225C within 3 hours~ After this time, a vacuum of 12 to 13 Torr is applied and distillation is continued for a further hour, 758 parts of a second distillate thereby being collected~
The apparatus i5 flushed ~ith nitrogen and ~he residue is dissolved in 1~0 parts of ethylene glycol at 190-220C, after which the solution is cooled to 130C and treated with 27 parts of urea (~.olar ratio of terephthalic acid to urea = 1:0.5). The ammonia produced is taken up in dilute hydrochloric acid. After cessation , .
.' . ,'' ,' . , '' ~ .
- . .CANA~A
- ~7 - 1~0-3~46 ,.. - ~ . . . .
~5~L44 he gas pro~uction, the temperature is raised to 150C
and the reaction mixture is stirred for a ~urther 3 hours at this temperature.
Th~reafter the mixture is ccoled to 90-95C and 167 parts of 33~ hydrochloric acid are added dropwise at such a rate that the temperature, without external cooling, remains between 90C and 100C. Stirring for a ~urther ~ hour is efected after the acid addition, the product solution then displa~ing a pH of 5.5~ The pol~meric compound produced contains the group of formula Ib, as hereinbefore given, as the repeating unit.
PRODUCTIO~I E~IPLE 3:
The process is effected in accordance with - Production Exa~.ple ~, except that to 255.5 parts of the resi.due, dissolved in 115 parts o~ propylene ~lycol, 74 parts of ac'ipic acid dimethyl ester are added and ~he reaction mixture is stirred at 155-~75C over the course of 2 hours. During this period, the methanol formed in ~he reaction is distilled off. The reaction product is ~0 subsequently cooled to 80C and neutralized with cooling with 296 parts of 19.8~ hydrochloric acid. A 50%, slightly viscous solution of the hydrochloride salt of the compound, ~7herein the group of formula Ia, as here inbefore given and wherein (CH2)q is tetramethylene, ls ` : :
- CANADA
,~ .
S~
the repeating unit, is obtained.
APPLICATION E~IPLES
=. .
t. A 2.5~ cellulose suspension, consisting of 50% of bleached beech cellulose and 50~ of bleached sulphite cellulose, is brightened with the optical brightener of formula _ :C~ H ~ ~ N
$ C2 4 V
NH ~ SO3Na 2 -in an amount 0.1% of the ~eiyht of the cellulose~ The optical brightener displays its maxim~r. effect within 10 minutes. The suspension is sized with 2% of resin size and 3% of hydrated aluminium sulphate 1A12(SO4)3.18 H2O], based on the weight of the cellulose.
To parts of th}s suspension are added 1% aqueous solutions containing the hydrochloride salts pxoduced acco~ding to Production E~amples 1 and 3. In each case, 1% of eliminating agent is added, this rigure being based upon the weights of solid elirninating material a~d ce]lulose substrate.
" ' , '-.
, . : - . ,, . , ~ .....
- CANADA
~ 19 - ~50-3546 S~L~44~
5 Minutes after the addition o~ the eliminating solutions a sheet is formed from the suspensions by means of the Rapid-Kothen apparatus. This sheet is pressed and dried at gO-100C. For comparison reasons a sized cellulose sheet and a sized brightened cellulose sheet are produced, in both of which cases no eliminating agent is present.
The elimination of the brightening effect obtained with the optical briyhteners is determined according to fluorometry. The hydrochloride salt as produced in - Production Example 1 shows the better elimination effect.
2. ~ry paper is padded with a bath con~aining 80 g o starch and 0.6 g of the optical bri~htener of formula V per litre and expressed to a pick up of 100~.
The paper briyhtened in this wa~ is dried, subsequently padded with a bath containing 1% of the hydrochloride salt as produced in Production Example 1, expressed to a pick up of 100% and dried.
The ~rightening effect of the optical brightenar ~0 is thereby almost cor.lpletely eliminated.
.
,
Claims (31)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS :
1. A method of eliminating the brightening effect produced by or preventing the brightening effect from being produced by an anionic optical brightener on fibrous material by the application to the fibrous material substrate of a water-soluble acid addition salt or quaternary ammonium salt of a compound containing the group of formula, wherein the benzene radical is attached to the other two parts of the group at its m- or p-positions, which compund is produced by the acylation of an excess of a polyethylenepolyamine of formula II, H(HN-CH2-CH2)p-NH2 II
in which p is an integer 2 to 5, by isophthalic or terephthalic acid or an anhydride, acid halide or ester thereof in a molar ratio exceeding 1.5:1, subsequently cyclising the product to afford imidazoline groups, and optionally reacting the product further, by way of alkylation with an alkylating agent yielding a methyl, ethyl or phenyl- or naphthyl-substituted methyl or ethyl group and/or acylation in a molar ratio of initial to present acylating agent of 1:0.3 to 1:1.0, with a bifunctional acylating agent which is a saturated aliphatic dicarboxylic acid of formula III, HOOC-(CH2)q-COOH III
in which q is an integer 1 to 6, or a diester thereof, a halide, ester or mixed halide-ester of carbonic acid, or urea, and whicih quaternary ammonium salt does not contain a nitrogen atom bearing more than two phenyl- or naphthyl-substituted methyl or ethyl groups.
in which p is an integer 2 to 5, by isophthalic or terephthalic acid or an anhydride, acid halide or ester thereof in a molar ratio exceeding 1.5:1, subsequently cyclising the product to afford imidazoline groups, and optionally reacting the product further, by way of alkylation with an alkylating agent yielding a methyl, ethyl or phenyl- or naphthyl-substituted methyl or ethyl group and/or acylation in a molar ratio of initial to present acylating agent of 1:0.3 to 1:1.0, with a bifunctional acylating agent which is a saturated aliphatic dicarboxylic acid of formula III, HOOC-(CH2)q-COOH III
in which q is an integer 1 to 6, or a diester thereof, a halide, ester or mixed halide-ester of carbonic acid, or urea, and whicih quaternary ammonium salt does not contain a nitrogen atom bearing more than two phenyl- or naphthyl-substituted methyl or ethyl groups.
2. A method according to Claim 1, in which the anion of the salt is that of a strong inorganic acid or of a strong mixed organic-inorganic acid.
3. A method according to Claim 2, in which the anion of the salt is a chloride anion.
4. A method according to Claim 3, in which the salt is an acid addition salt with hydrochloric acid.
5. A method according to Claim 1, in which the salt is one of a compound which contains the repeating unit of formula Ia, Ia in which q is an integer 1 to 6, and the benzene nuclei are linked at their m- or p-positions.
6. A method according to Claim 5, in which q in the repeating unit of formula Ia is 4.
7. A method according to Claim 1, in which the salt is one of a compound which contains the repeating unit of formula Ib, Ib in which the benzene nuclei are linked at their m- or p-positions.
8. A method according to any one of Claims 5 to 7, in which the benzene nuclei in the repeating unit are linked at their p-positions.
9. A method according to Claim 1, in which the poly-ethylenepolyamine of formula II is diethylene triamine.
10. A method according to Claim 1, in which the cyclised product of the reaction between the compound of formula II and isophthalic acid, terephthalic acid or an anhydride, acid halide or ester thereof is acylated with the bifunctional acylating agent.
11. A method according to Claim 1, in which the cyclised product of the reaction between the compound of formula II
and isophthalic acid, terephthalic acid or an anhydride, acid halide or ester thereof, or a partially methylated, ethylated or phenyl- or naphthyl-methylated or -ethylated derivative of such cyclised reaction product, is acylated with a bifunctional acylating agent in a molar ratio of the amount of isophthalic or terephthalic acid or anhydride, acid halide or ester thereof used to the amount of bifunctional acylating agent within the range 1:0.4 to 1:0.7.
and isophthalic acid, terephthalic acid or an anhydride, acid halide or ester thereof, or a partially methylated, ethylated or phenyl- or naphthyl-methylated or -ethylated derivative of such cyclised reaction product, is acylated with a bifunctional acylating agent in a molar ratio of the amount of isophthalic or terephthalic acid or anhydride, acid halide or ester thereof used to the amount of bifunctional acylating agent within the range 1:0.4 to 1:0.7.
12. A method according to Claim 11, in which the molar ratio is 1:0.5.
13. A method according to Claim 10, in which the bifunctional acylating agent is adipic acid.
14. A method according to Claim 10, in which the bifunctional acylating agent is a diester of adipic acid.
15. A method according to Claim 14, in which the diester of adipic acid is dimethyl adipate.
16. A method according to Claim 10, in which the bifunctional acylating agent is phosgene or urea.
17. A method according to Claim 1, in which any alkyl group introduced by way of alkylation and/or quaternary ammonium salt formation is unsubstituted methyl or ethyl.
18. A method according to Claim 1, in which the salt is applied to the fibrous material substrate by impregnating the latter with an aqueous solution of the salt.
19. A method according to Claim 1, in which the fibrous material substrate is of natural or synthetic origin and contains hydroxyl groups.
20. A method according to Claim 1, in which the fibrous material substrate is a textile substrate constituted by fibres of natural or regenerated cellulose or of polyvinyl alcohol.
21. A method according to Claim 1, in which the fibrous material substrate is a paper substrate.
22. A method according to Claim 1, in which the optical brightener whose effect is eliminated or prevented bears sulphonic acid groups.
23. A method according to Claim 22, in which the optical brightener bearing sulphonic acid groups is of the stilbene series.
24. A method according to Claim 21, in which an aqueous solution of the salt is applied to paper in the stock before sheet formation.
25. A method according to Claim 21, in which paper is coated with a paste containing the brightening-eliminating salt.
26. A method according to Claim 25, in which the paste is based on starch.
27. A method according to Claim 25 or Claim 26, in which the coating operation is a padding process.
28. A method according to Claim 1, in which the salt is applied to the fibrous material substrate in an amount by weight from 0.5 to 50 times that of the optical brightener whose effect is to be suppressed.
29. A fibrous material substrate whenever treated according to the method as claimed in Claim 1.
30. An acid addition or quaternary ammonium salt of a compound containing the repeating unit of formula, in which the benzene nuclei are linked at their m- or p-positions, which salt is produced by the acylation of an excess of diethylene triamine by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester exceeding 1.5:1, subsequently cyclising the product to afford imida-zoline groups, acylating the product with urea in a molar ratio of urea to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1,and converting the product into a salt.
31. An acid addition or quaternary ammonium salt or the compound containing the repeating unit of formula, in which q is an integer 1 to 6, and the benzene nuclei are linked at their m- or p-positions, which salt is produced by the acylation of an excess of diethylene triamine by isophthalic or terephthalic acid dimethyl ester in a molar ratio of amine to ester exceeding 1.5:1, subsequently cyclising the product to afford imida-zoline groups, acylating the product with the ester CH3OOC-(CH2)q-COOCH3 in a molar ratio of the ester to isophthalic or terephthalic acid dimethyl ester of 0.3:1 to 1.0:1,and converting the product into a salt.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1480873A CH572128A5 (en) | 1973-10-19 | 1973-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051144A true CA1051144A (en) | 1979-03-20 |
Family
ID=4403990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA211,769A Expired CA1051144A (en) | 1973-10-19 | 1974-10-18 | Method of eliminating or preventing the brightening effect on fibrous materials of anionic optical brightening agents |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5414205B2 (en) |
| BE (1) | BE821261A (en) |
| BR (1) | BR7408687D0 (en) |
| CA (1) | CA1051144A (en) |
| CH (1) | CH572128A5 (en) |
| DD (1) | DD114109A5 (en) |
| DE (1) | DE2448293C3 (en) |
| FI (1) | FI58363C (en) |
| FR (1) | FR2248365B1 (en) |
| GB (1) | GB1490077A (en) |
| IT (1) | IT1023126B (en) |
| NL (1) | NL174749C (en) |
| NO (1) | NO145886C (en) |
| SE (1) | SE415043B (en) |
| SU (1) | SU878203A3 (en) |
| ZA (1) | ZA746641B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2916656A1 (en) * | 1979-04-25 | 1980-11-06 | Henkel Kgaa | Optical brightener-free textile detergent compsn. - contg. aliphatic polyglycol ether(s), alkyl-pyridinium salt and standard additives |
| IT1127312B (en) * | 1979-12-21 | 1986-05-21 | Apital Prod Ind | PROCEDURE FOR THE ELIMINATION OF THE FLUORESCENCE OF OPTICAL BANDS |
| DE3415103A1 (en) * | 1984-04-21 | 1985-10-31 | Bayer Ag, 5090 Leverkusen | METHOD FOR FLUORESCENT EXTINGUISHING AND NEW CATIONIC AROMATIC NITRO COMPOUNDS |
| CH677167B5 (en) * | 1985-05-08 | 1991-10-31 | Sandoz Ag | |
| GB8518489D0 (en) * | 1985-07-22 | 1985-08-29 | Sandoz Ltd | Organic compounds |
| DE3535496A1 (en) | 1985-10-04 | 1987-04-16 | Bayer Ag | METHOD FOR FLUORESCENT EXTINGUISHING AND NEW CATIONIC NAPHTHALINE PERI DICARBONIC ACID IMID DERIVATIVES |
| JP4728646B2 (en) * | 2005-01-06 | 2011-07-20 | 大王製紙株式会社 | Non-fluorescent board |
| RU2495973C2 (en) * | 2008-03-26 | 2013-10-20 | Клариант Финанс (Бви) Лимитед | Improved optical bleaching compositions |
-
1973
- 1973-10-19 CH CH1480873A patent/CH572128A5/xx not_active IP Right Cessation
-
1974
- 1974-10-10 DE DE2448293A patent/DE2448293C3/en not_active Expired
- 1974-10-10 FI FI2950/74A patent/FI58363C/en active
- 1974-10-10 NO NO743648A patent/NO145886C/en unknown
- 1974-10-10 SE SE7412745A patent/SE415043B/en not_active IP Right Cessation
- 1974-10-15 NL NLAANVRAGE7413523,A patent/NL174749C/en not_active IP Right Cessation
- 1974-10-17 GB GB45025/74A patent/GB1490077A/en not_active Expired
- 1974-10-17 DD DD181766A patent/DD114109A5/xx unknown
- 1974-10-17 JP JP11878074A patent/JPS5414205B2/ja not_active Expired
- 1974-10-18 BR BR8687/74A patent/BR7408687D0/en unknown
- 1974-10-18 CA CA211,769A patent/CA1051144A/en not_active Expired
- 1974-10-18 BE BE149697A patent/BE821261A/en not_active IP Right Cessation
- 1974-10-18 ZA ZA00746641A patent/ZA746641B/en unknown
- 1974-10-18 SU SU742071223A patent/SU878203A3/en active
- 1974-10-18 IT IT53617/74A patent/IT1023126B/en active
- 1974-10-21 FR FR7435326A patent/FR2248365B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL174749C (en) | 1984-08-01 |
| JPS5414205B2 (en) | 1979-06-05 |
| IT1023126B (en) | 1978-05-10 |
| BE821261A (en) | 1975-04-18 |
| NO145886C (en) | 1982-06-16 |
| DE2448293B2 (en) | 1979-03-29 |
| GB1490077A (en) | 1977-10-26 |
| FI58363C (en) | 1981-01-12 |
| NL7413523A (en) | 1975-04-22 |
| CH572128A5 (en) | 1976-01-30 |
| FI58363B (en) | 1980-09-30 |
| FI295074A (en) | 1975-04-20 |
| BR7408687D0 (en) | 1975-09-16 |
| JPS5065610A (en) | 1975-06-03 |
| FR2248365A1 (en) | 1975-05-16 |
| SU878203A3 (en) | 1981-10-30 |
| NO145886B (en) | 1982-03-08 |
| SE415043B (en) | 1980-09-01 |
| FR2248365B1 (en) | 1978-04-28 |
| SE7412745L (en) | 1975-04-21 |
| NO743648L (en) | 1975-05-20 |
| NL174749B (en) | 1984-03-01 |
| DE2448293C3 (en) | 1979-11-15 |
| AU7445074A (en) | 1976-04-29 |
| DE2448293A1 (en) | 1975-04-24 |
| ZA746641B (en) | 1976-05-26 |
| DD114109A5 (en) | 1975-07-12 |
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