NZ233651A - N,n'-(cyanomethyl)-n,n,n',n',-tetraalkyl alkylene diamine salts and their preparation - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £33651 2336 Under the provisions of Reflation 23 (i) the Specification has been ansxiated to St.. 19 tt- Initials Patents Form No. 5 HQ DRAWINGS Priority Dete(s): /v. 4 95* ^ • Complete Specification Filed: &..Z3Z Class: • • • • • • • • r» A • w Publication Date: P.O. Journal. No: , ...Vi 2BAPR 1991 ii«/X /%*■ (aJ "\ I . f5,! !lZt 1 MAY 1990 je E This is a divisional out of application number 225815 dated 12 August 1988 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION A PEROXIDE PERACID PRECURSOR WE, KAO COPORATION, of 14—10, Nihonbashi-Kayabacho 1—chome, Chuo-ku, Tokyo, Japan, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: la 23365 1 This invention relates to a peroxide peracid precursor which is useful as a textile softener, an antistatic agent, a fungicide and a bleaching activator.

A chlorinated bleaching agent has disadvantages in that it is limited in the kind of fibers to which it is applicable, can not be applied to colored or patterned cloths, and has a peculiar odor. Recently, therefore, an oxygenic bleaching agent free from these disadvantages has been widely spread.

Particularly, sodium percarbonate and sodium perborate are generally used as such an oxygenic bleaching agent owing to their excellent bleaching performance and stability.

An oxygenic bleaching agent exhibits a poorer bleaching power than that of a chlorinated bleaching agent, so that various bleach activators are used simultaneously therewith. Further, studies have been made on various activators and examples of them include nitriles such as acetonitrile, malononitrile, (followed by Page 2) 23 36 51 phthalonitrile and benzoyliminodiacetonitrile; 0-acetates such as glucose pentaacetate, octaacetyl-sucrose, triacetin, sorbitol hexaacetate, acetoxy-benzenesulfonates, triacetyl cyanurate and isethyl chloroformate; N-acylates such as N,N,N',N'-tetra-acetylethylenediamine, tetraacetylglycolyluril, N-benzylimidazole, di-N-acetvldimethylglyoxirne, 1-phenyl-3-acefcylhycantoin, N/N-diacetylaniline/ N-acetyldiglycolimide and diacetylmethylenediformaraide; acid anhydrides such as phthalic anhydride, succinic anhydride, benzoic anhydride, glutaric anhydride, alkylsulfuric anhydride and mixed anhydrides of carboxylic acids and organic sulfonic acids; sulfonyl oximes such as di(methanesulfonyl)dimethylglyoxime; acyl phosphates such as diethyl benzoyl phosphate; phenvlsulfonates; organophosphoric azide such as diphenylphosphinic azide; aisulfones such as diphenyl-disulfone; N-sulfonylimidazole, cyansmide, halogenated triazine and N,N-diniethyl-N-octyl-N-10-carbophenoxy-dodecylami-nonium chloride. However, the bleaching power of an oxygenic bleaching agent was poor even when it was used together with an activator described above. o 233651 I /r\ Known compounds having -N^-CH^CN groups in the molecule include the following compounds: n ch3 ...

Ig g ca5 — X-C3 = CM CI I ch3 (J.Org.Chem-, 1977, Vol. 42, No.2, pp. 26 ^ 32), Et !g g Et-H-CHsCJi I i Et (J.Chem.Soc.Perkin Trans., 2, 1978- No.8, pp. 786 -v 793) , C CHsCN Ig q HO-CHsCSz-N -CSzCM N03 I c h 2 c m • (U.S. Patent No. 3281452), and CH;CM lg g HsC=CHCHs-N-CHsCH-CHs CI I CH3 (British Patent No. 1178371).

This invention provides a compound having the generic formula (l>—7) R1 *3 I© I© 0 NCCH2N (CH2)nN CH2CN 2X (b-7) I I R2 *4 in which R^, Rjr R^ and R^ are each a to Cg alkyl; n is an integer of 1 to 16; and X~is an anion.

The compound of the formula (b-7) is useful in a bleaching composition which comprises (a) a peroxide and (b) the compound. The bleaching composition may also have a detergent component.

In the composition, it is preferred that the mole ratio of (a) to (b) ranges from 99.9/0.1 to 20/80 and the component (b) is contained in the composition in the form of granules of a blend of 100 parts by weight of (b) an 5 to 20 parts by weight of a binder.

Preferably R1, R2, R^f and R4 each represent an alkyl group having 1 to 3 carbon atoms, especially a methyl group, and n is an integer of 1 to 9.

The compound of the general formula (b-7) can be prepared, for example, according to the process described below. Namely, the compound of the formula (b-7) can be easily prepared by reacting a tertiary alkylenediamine with a halide of acetonitrile as in the quaternization of ,an ordinary amine, as shown by the following reaction formi Rl\ /R3 , * ^N(CH2)nNi +2X - CH_.CN R, r4 R1 R3 IQ 10 NCCH2N (CH2)nN CH2CN I I R2 R4 233651 The compound (b-7) is useful as a textile softener, an antistatic agent, a fungicide and a bleaching activator.

When used in a bleaching composition, the compound of formula (b-7) is easy to adhere on articles to bleach, owing to its cationic group. In addition, the carbon atom in the group -CN is easy to be positive electrically and active to the bleaching effect since the quaternary nitrogen is electron-attractive. This way the component (b) serves to provide for sites where bleaching take place to the effect and enhance the bleaching power of the composition.

Component (b) in the bleaching composition can be granulated by an ordinary method prior to its addition to a peroxide. For example, 5 to 200 parts by weight, preferably 10 to 100 parts by weight, of one or more binders exhibiting a fluidity at 5 to 60°C, preferably 10 to 40°C, is added to 100 parts by weight of an activator and the obtained mixture is granulated. 233651 c The birder to be used may be one or more members r selected from among nonionic surfactants polyethylene glycol, polypropylene glycol, liquid paraffins and higher alcohols which exhibit a fluidity at 5 to 60°C, preferably 10 to 40°C.

The granulation may be carried out by a method selected depending upon the kinds of the organic per acid precursor and binder used from among conventional methods such as extruding granulation, tumbling granulation or compression granulation. For example, according to the extruding granulation, an organic per acid precursor which has been finely ground into a size of 150 ym or below is homogeneously mixed by means of an ordinary mixer and a binder is gradually added to the ground precursor, followed by ^ sufficient kneading. Then, the kneaded mixture was fed into an extruding granulator to obtain a granulate, followed by screening. If necessary, the granulate may be coated, prior to the screening, with a fine ^ inorganic powder having an average primary particle size of 0.1 um or below, such as finely powdered silica, for the purpose of improving the granular characteristics. 23365 1 The peroxide to be used in the composition is preferably hydrogen peroxide or a peroxide which generates hydrogen peroxide in an aqueous solution.

Examples of the peroxide which generates hydrogen peroxide in an aqueous solution include sodium carbonate-hydrogen peroxide acduct, sodium tripoly— phosphate—hydrogen peroxide adduct, sodium pyrophosphate-hydrogen peroxide adduct, urea-hydrogen peroxide adduct, 4Na2SO^•2H2O2*NaCl, sodium perborate monohvdrate, sodium perborate tetrahydrate, sodium peroxide and calcium peroxide, among which sodium carbonate-hydrogen peroxide adduct, sodium perborate monohvdrate and sodium perborate tetrahydrate are particularly preferred.

In the composition a peroxide and a specified activator as defined above are generally used in a molar ratio of said peroxide to said activator of between 99.1 : 0.1 and 20 : 80, preferably between 99 : 1 and 50 : 50. It is preferable that the composition comprises 1 to 99 percent by weight of the component (a). 233651 The bleaching detergent composition-- may comprise - the following in addition to the bleaching agents described above.

Surfactants: (1) Straight-chain or branched alkylben2enesulfonate salts having an alkyl group of 10-16 carbon atoms in average. (2) Alkyl or alkenyl ether sulfate salts having a straight-chain or branched alkyl or alkenyl group of 10-20 carbon atoms in average, 0.5-8 mol in average of ethylene oxide, propylene oxide or butylene oxide in the-.-molecule and an addition ratio of ethylene oxide/propylene oxide of 0.1/9.9-9-9/0.1 or ethylene oxide/butylene oxide of 0.1/9.9-9.9/0.1. (3) Alkyl or alkenyl sulfate salts having an alkyl or alkenyl group of 10-20 carbon atoms in average. (4) Olefinsulfonate salts having 10-20 carbon atoms . in average in the molecule. (5) Alkanesulfonate salts having 10-20 carbon atoms in average in the molecule. (6) Saturated or unsaturated fatty acid salts having <=\ 23365 1 -24 carbon atoms in average in the molecule. (7) Alkyl or alkenyl ether carboxylate salts having an alkyl or alkenyl group of 10-20 carbon atoms in average, 0.5-3 mol in average of ethylene oxide, propylene oxide or butylene oxide in the molecule and an addition ratio of ethylene oxide/propylene oxide of 0.1/9.9-9.9/0.1 or ethylene oxide/butylene oxide of 0.1/9.9 to 9-9/0.1. * • (8) a-Sulfo fatty acid salts or esters of the general formula: R-CHCO-Y I 2 so^z D wherein Y represents an alkyl group having 1-3 carbon atoms or a counter-ion, Z represents a counter-ion and R represents an alkyl or alkenyl group having 10-20 carbon atoms.

As the counter-ions of anionic surfactants, there may be mentioned, for example, ions of alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, ammonium, al-ks^olaniines containing 1-3 alkanol groups having 2 or 3 carbon atoms such as 23 36 5 1; iO J* monoethanolamine, diethanolamine, triethanolamine and triisopropanolaniine. (9) Amino acid-type surfactants of the general formulae: No. 1 FL -CO-N-CH-COOX 1 i \ R2 R3 wherein R^ represents an alkyl or alkenyl group having 8-24 carbon atoms, R£ represents hydrogen or an alkyl group having 1—2 carbon atoms, R- represents an amino acid residue and X represents an alkali metal or alkaline earth metal ion.

No. 2 R-,-CO-N-(CH-) -COOX • JL j Z n R2 wherein R^, and X have the same meanings as above and n represents an integer of 1-5.

No. 3 R1V x >N-(CHO -COOX ri wherein has the same meaning as above and m represents an integer of 1-8.

No. 4 R,-N-CH-COOX A I \ R4R3 wherein R^, R^ and X have the same meaning as above and R^ represents hydrogen, or an alkyl or hydroxyalkyl group having 1-2 carbon atoms.

No. 5 Re-N-CK-COOX I \ R2 R- « S* 23 36 5 1 wherein R£, R^ and X have the same neaning as above and represents a p-hyaroxyalkyl or p-hydroxyalkenyl group having 6-23 carbon atoms.

No. 6 R.v > N-CH-COOX R5 1 R3 wherein R~, and X have the same meaning as above. (10) Phosphate ester surfactants: No. 1 Acid alkyl (or alkenyl) phosphates: 0 n (R'0)n,-P-(OH)mI wherein R1 represents an alkyl or alkenyl group having 8-24 carbon atoms, n'+ra* Represents 3 and n' represents a number of 1-2.

No. 2 Alkyl (or alkenyl) phosphates: 0 II (R'0)nll-?-(OH)mll wherein R1 has the same meaning as above, n"+ni" represents a number of 3 and n" represents a number of 1-3- No. 3 Alkyl (or alkenyl) phosphate salts: 0 II (R'0)nll-P-(OK)tnI, wherein R*, n" and «n" have the same meaning as above and M represents Na, K or Ca. (11) Sulfonic acid-type amphoteric surfactants of the 11 -**" 23 365 1 general formulae: No. 1 ^13 R11C0NH~R12_r^""R14~S°3^ R13 wherein represents an alkyl or alkenyl group having 8-24 carbon atoms, R12 represents an alkylene group having 1-4 carbon atoms, R^- represents an alkyl group having 1-5 carbon atoms, represents an alkylene or hydro-xyalkylene group having 1-4 carbon atoms. No. 2 R15 R —\^^-R —SO ® Rn y R14 3 R16 wherein R-q and R-, ^ have the same meaning as above and R^^ and R^g each represent an alkyl or alkenyl group having 8-24 or 1-5 carbon atoms.

No. 3 • rii"^rICso30 wherein R^ and R^ have the same meaning as above and nl represents an integer of 1-20. (12) Betaine—type, amphoteric surfactants of the general formulae: No. 1 R22 r21-^-r23-coo® R22 a ^»365 wherein R21 represents an alkyl, alkenyl, p-hvdroxyalkyl or g-hydroxyalkenyl group having 8-24 carbon atoms, R22 represents an alkyl group having 1-4 carbon atoms and R2^ represents an alkylene or hydroxyalkylene group having 1-6 carbon atoms.

No. 2 (C2H40)n2H R,, -ffS-R„-CCo3 21 | 23 <C2V>n2H wherein R2^ and R2~ have the same meaning as above and n2 represents an integer of 1-20.

Mo. 3 Rzh R21-flR23-C0C^ R. 24 wherein R2^ and have the same meaning as above and R2^ represents a carboxy'alkyl or hydroxyalkyl group having 2-5 carbon atoms. (13) Polyoxyethylene alkyl or alkenyl ethers having an alkyl or alkenyl group of 10-20 carbon atoms in average and 1-30 Qol of ethylene oxide added. (14) Polyoxyethylene alkylphenyl ethers having an alkyl group of 6-12 carbon atoms in average and 1-25 mol of ethylene oxide added. (15) Polyoxypropylene alkyl or alkenyl ethers having an alkyl or alkenyl group of 10-20 carbon atoms in average and 1-20 mol of propylene oxide added. lit " ^ 23 3 657 (16) Polyoxybutylene alkyl or alkenyl ethers having an alkyl or alkenyl group of 10-20 carbon atoms in average and 1-20 mol of butylene oxide added. (17) Nonionic surfactants having an alkyl or alkenyl group of 10-20 carbon atoms in average and 1-30 mol in total of ethylene oxide and propylene oxide .added or ethylene oxide and butylene oxide added (ratio of ethylene oxide to propylene oxide or butylene oxide being 0.1/9.9 to 9.9/0.1). (18) Higher fatty acid alkanolamides or alkylene oxide adducts thereof of the general formula: - «'12 ' (CHCH,0) -H R'^CON* t R"1 2 n3 (CHCH2°)m5H 12 wherein R'-j^ represents an alkyl or alkenyl group having 10-20 carbon atoms, R'^2 rePresen"^s H or CH^, n3 represents an integer of 1-3 and m3 represents an integer of 0-3. (19) Sucrose/fatty acid esters con-prising fatty acids having 10-20 carbon atoms in average and sucrose. (20) Fatty acid/glycerol monoesters comprising fatty acids having 10-20 carbon atoms in average and glycerol. (21) Alkylamine oxides of the- general formula: ,<f 23365 1 RXi, i 14 —» o •° i R,15 wherein R1-^ represents an alkyl or alkenyl group having 10-20 carbon atoms ana R'-^ ^'^5 each represent an alkyl group having 1-3 carbon ato:ns. (22) Cationic surfactants of the general formulae: No. 1 R' I [ R»,-^R* ] X'® .1 .

R,3 wherein at least one of R'-j_» R*2» ^'3 ^*4 represents an alkyl or alkenyl group having 8-24 carbon atoms and r the remainder represents an alkyl group having 1—5 carbon atoms and X1 represents a halogen.

No. 2 R' I ^ [ R' -^©-CHgCgH- ] X'® wherein R1.^* R*2» ^'3 ^ave ^e" same meaning as above.

No. 3 (R'5°)nlU [ R^-N^-R^ ] Xl<^ " ^R'50)n4H wherein R'^* R*2 ^avs "^'ne sane meaning as above, R'^ represents an alkylene group having 2-3 carbon atoms and n4 represents an integer of 1-20. ,fc 233651 The composition probably contains at least one of the above surfactants in an amount of at least 10 wt.

As preferred surfactants, there may be mentioned above surfactants 1), 2), 3), 4), 5), 6), ll)-No. 2, 12)-No. 1, 13), 14), 13), 17) and IS). [2] Divalent metal ion sequestering agents: The composition nay contain 0-50 wt. % of one or more builder components selected from the group consisting of alkali metal salts or alkanolamine salts of the f ollowing _ compound s: 1) Salts of phosphoric acids such as orthophosphpric acid, pyrophosphoric acid, tripolyphosphoric acid, meta.-phosphoric acid, hexarnetaphosphoric acid and phytic acid. 2) Salts of phosphonic acids such as ethane-1,1-diphosphonic acid, ethane—1,1,2-triphosphonic acid, ethane-l-hydroxy-l,l-diphosphonic acid and its derivatives, ethane-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-l,2-diphosphonic acid and methanehydroxyphos-phonic acid. 3) Salts of phosphono carboxylic acids such as 2-phospho-nobutane-1,2-cicarboxylic acids, l-phosphonobutane-2,3,4-tricarboxylic acids and a-aethylphosphonosuccinic acid. 4) Salts of amino acids such as aspartic acid, glutamic acid and glycine.

) Salts of aininopolyacetic acids such as nitrilotri- ar- 23 36 5 1 * acetic acid, iminodiacetic acid, ethylenediaminetetra— acetic acid, diethylenetriaminepentaacetatic acid, glycol ether diaminetetraacetic acid, hydroxyethylimino— diacetic acid, triethylenetetraminehexaacetic acid and dienkolic acid. 6) High --.olecular electrolytes such as polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymesaconic acid, poly-c-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride/diisobutylene copolymer, maleic anhydride/styrene copolymer, maleic anhydride/methyl vinyl ether copolymer, nalei'c anhydride/ ethylene copolymer, maleic anhydride/ethylene cross-linked copolymer, maleic anhydride/vinyl acetate copolymer, maleic anhydride/acrylonitrile copolymer, maleic anhydride/acrylate ester copolymer, maleic anhydride/ "butadiene copolymer, maleic anhydride/isoprene copolymer, poly-p-keto carboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid/ethylene copolymer, itaconic acid/aconitic acid copolymer, itaconic acid/ maleic acid copolymer, itaconic acid/acrylic acid copolymer, malonic acid/methylene copolymer, mesaconic acid/fumaric acid copolymer, ethylene glycol/ethylene terephthalate copolymer, vinylpyrrolidone/vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid/ 23 36 5 1 itaconic acid/acrylic acid copolymer, quaternary amnoniurn group-containing polyester polyaldshyde carboxylic acids, cis-isomer of epoxysuccinic acid, poly[N,N-bis(car"ooxy-methyl)acryla.T.ide], poly(hydroxy carboxylic acid), starch succinate, starch ir.alea.te, starch terechtalate ^ starch phosphate ester, dicarboxystarch, dicarboxymethylstarch and cellulose succinate esters. 7) Non-dissociating high-rr.olecular compounds such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and cold water-soluble, urethanated polyvinyl alcohol. • 8) Salts of dicarboxylic acids such as' oxalic.acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid.and aecane-1,10-dicarboxylic acid; salts of diglycolic acid, thiodiglycolic acid, oxalacetic acid, hydroxydisuccinic acid, carboxy- rae thy Ihydroxy succinic acid and carboxymethyltartronic acid; salts of hydroxy carboxylic acids such as glycolic acid, malic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid, mucic acid, glucuronic acid and diaidehydostarch oxide; salts of itaconic acid, metnylsuccinic acid, 3-~'ethylglutaric acid, 2,2-dinetnylmalonic acid, maleic acid, fumaric acid, glutamic acid, 1,2,3-propanetricarboxylic acid, aconitic acid, 3-butene-l,2,3-tricarboxylic acid, {°i . 23 3 6 5 1 butane-1,2,3,4—tetracarboxylic acid, ethanetetracarboxy-lic acid, ethenetetricarboxylic acid, n-alkenyl-aconitic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, phthalic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenehexacarboxylic acid, tetrahydrofuran-l,2,3,4-tetracarboxylic acid and tetrahydrofuran-2,2,5,5-tetracarboxylic acid; salts of sulfonated carboxylic acids such as sulfoitaconic acid, sulfotricarballylic acid, cysteic acid, sulfoacetic acid and sulfosuccinic acid; carboxymethylated sucrose, lactose and raffinose, carboxymethylated pentaerythritol, carboxymethylated gluconic acid, condensates of polyhyaric alcohols or saccharides with maleic anhydride or succinic anhydride, condensates of hydroxy carboxylic acids with maleic anhydride or succinic anhydride, and organic acid salts such as CMOS and Builder M. 9) Aluminosiiicates: No. 1 Crystalline aluminosilicates of the formula: x' (M'20 or M" 0) .A-S^-y' (Si02) -w' (H20) wherein >1' represents an alkali metal atom, M" represents an alkaline earth metal atom exchangeable with calcium, and x' , y' and v' represent mole numbers of the respective .components and generally, they are as follows: 0.7 <! x' £ 1-5, 0.8 <£ y' 6 and w1 being a positive number. &sr 23365 1 No. 2 Detergent builders having the following general formula are particularly preferred: Na_0-A-OX, -nSi0o-wHo0 < £ j 2 2 wherein n represents a number of 1.8-3.0 and w represents a number of 1-6.

No. 3 Amorphous aluminosilicates of the formula: x(M2O)-A-02O3-y(SiO2)-w(H20) wherein M represents sodium and/or potassium atom, and x, y and w represent mole numbers of the respective components within the following ranges: 0.7 < X <; 1.2 1.6 ^ y <: 2.8 w: any positive number including 0.

No. 4 A.morphous aluminosilicates of the formula: X(K20) -A^203-Y(Si02) -Z(P20_) -w(H20) wherein M represents Na or K and X, Y, Z and w represent mole numbers of the respective components within the following ranges: 0_20< X^l.10 0.20 ^ Y4.00 0.001 Z < 0.80 uj : any positive number including 0. [3] Alkalis or inorganic electrolytes: The composition may contain also 1-50 wt. 56, preferably 5-30 wt. 5$, of one or more alkali metal salts ^ 233651 selected from the following compounds as the alkali or inorganic electrolyte: silicates, carbonates and sulfates. Further, the composition may contain organic alkalis such as triethanolamine, diethanolamine, monoethanolamine and triisopropanolamine.

Antiredeposition agents: The composition may contain 0.1-5 % of one or more of the following compounds as antiredeposition agent(s): polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and carboxym'ethylcellulose. [5J Enzymes (enzymes which exhibits the essential enzymatic effects thereof in the deterging step): As the enzymes, the following enzymes may be mentioned (classified with respect to their enzymatic reactivities): Hydrolases, hydrases, oxido-reductases, desmolases, trans-ferases and isomerases. All of these enzymes may be used 233651 in the compisition. Particularly preferred enzymes are hydrolases auch as proteases, esterases, carbohydrolases and nucleases.- Examples of proteases are pepsin, trypsin, chymo-. trypsin, collagenase, keratinase, elastase, subtilisin, BPN, papain, bromelin, carboxypeptidases A and B, amino-peptidase and aspergillopeptidases A and B-.

Examples of esterases are gastric lipase, pancreatic lipase, vegetable lipases, phospholipases, cholinesterases and phosphotases.

(^Lrbohydrolases include alkali cellulases, maltase, saccharase, amylase, pectinase, lysozyme, a-glucosidase and p-glucosidase. [6] Bluing agents and fluorescent dyes: Various bluing agents and fluorescent dyes may be incorporated in the composition, if necessary. For example, compounds of the following structures are is recommended: NH 0 CH = SO,Na 5 f>CH = CH-^ CH = CH-^^ SO^Na S03Na " rl )<> = CH^>/ 1 SO-Na SO-Na 0 and bluing agents of the general formulae: <2.u 23 365 1 D - NR - C VC I! I M N I vherein D represents a residue of blue or purple, monoazo, disazo or anthraquinone dye, X and Y each represent hydroxyl group, amino group, an aliphatic amino group vhich nay be substituted with hydroxyl, sulfonic acid, carboxylic acid or alkoxyl group, or an aromatic or ali-cyclic amino group vhich may-be substituted with a halogen atom or hydroxyl, sulfonic acid, carboxylic acid, lower alkyl or lower alkoxyl group, R represents a hydrogen atom or a lower alkyl group but excluding cases whereiri.-. (1) R represents a hydrogen atom and both X and Y represent*: a hydroxyl group or an alkanolamine at the sase time and (2) R represents a hydrogen atom, one of X and Y represents a hydroxyl group and the other represents an alkanolamine group, and n represents an integer of at least 2, and - Y (SO,H) n ^ 23 3 6 5 1j wherein D represents a residue of a blue or purple, azo or anthraquinone dye, and X and Y may be the same or different and represent an alkanolamine residue or a hydroxyl group. [7] Caking-preventing agents: The following caking-preventing agents may be incorporated in powdery detergent composition: p-toluenesulfo-nate salts, xylenesulfonate salts, acetate salts, sulfo-succinate salts, talc, finely pulverized silica, clay, calcium silicates (such as Micro-CelLof Johns-Manvill Co.), calcium carbonate and magnesium oxide. [8] Antioxidants: The antioxidants include, for example, tert-butyl-hydroxytoluene, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol) , 2,2'-butylidenebis(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol and 1,1' -bi s ( 4-hydroxyphenyl) cyclohexane. ao, 23 36 51 [9] Stabilizer for the peroxide arid an adduct to hydrogen peroxide A stabilizer may be used in the bleaching detergent composition, including a magnesium salt such as magnesium sulfatef magnesium silicate, magnesium chloride, magnesium silicofluoride, magnesium oxide and magnesium hydroxide and a silicate such as sodium silicate.

[10] Fragrant matter and Coloring matter Process examples by which the compounds of the formula (b-7) may be manufactured are now described. m on 23 36 51 n Example 1 c c:-:3 ch i lei© q ncc'hsm ch;chjn chxcm 2c1 (IV-a) I I ca3 ch3 In 100-m£ of acetone was dissolved 20 g (172 ircnol) of chloroacetonitrile and, while the solution was stirred at room temperature in a 300-m£ two-necked flask equipped with a reflux tube by means of a magnetic stirrer, a solution of 39 g (516 mmol) of N,N,N' ,N'-tetra.nethylethylene-diamine in 100-m£. of acetone was dropped into the solution. After the completion of the dropwise addition, the mixture was heated at 9Q°C and reacted for 90 minutes, followed by concentration and cooling. The formed crystal was recovered by filtration to give 39.37 g of the compound (I-a). The yield was 85.6%.

Melting point: 195 to 200°C (dec.).

V K3r (cm"1): 3022, 2944, 1482, 1455, 1410, 981, 918, 906, 792. ifi—NMR: 3.52 (12H, s), 4.33 (4H, s), 4.95 (4H, brs). 23 36 51 -2.T.43" Example 2 ca5 CH 3 IG I© 0 NCCH:N CH:CH;CH:CH=CH=CH:H CH:CN 2C1 I I ch3 ch3 W (IV-b) The procedure set out in example 1 was "followed in the same manner except that 57.8 g (516 mmol) of N/NjN',N*-tetramethyl-1,6-hexanediamine was used instead of 39 g of tetramethylethylenediamine, whereby 102.8 g of the compound (IV-b) was prepared in the form of a white crystal. The yield was 80.3%. Melting point: 201 to 203°C (dec.).

C VKBr {cm 1}: 2962, 2920, 1488, 1455. 1.05-2.25 (8H, m), 3.35 (12H, s), 3.40-3.80 (4H, m) , 4.75 (4H, s).

OPi 233651 Examples 1 to 8 of Composition Bleaching compositions were prepared, shown in Table 1, using the organic peracid precursors IV-a and IV-b IV-c, with control compositions 1 to 4, and tested on their bleaching effect in terms of a bleaching rate or a bleaching extent. Results are shown in Table 1. <Dip bleaching effect (Table 1) > Sodium percarbonate was dissolved in 300 ml of water of 20°C to prepare a solution having an active oxygen content of 0.05%. An activator was added to the solution in such a way that one sixteenth of the equivalent amount of the hvdrocen peroxide contained in the solution was equal to the equivalent amount of the C=N group of the activator. Thus, a bleach composition was obtained. Five black tea-stained 2 cloths (8 x 8 cm ) which had been prepared by the method which will be described below were soaked in the bleach composition for 30 minutes, washed with water and dried. The rate of bleaching was calculated by the following equation: rate of bleaching with respect to black tea-stained cloth: reflectance _reflectance rate of after bleaching before bleaching bleaching = — —— x 100 (%) reflectance of reflectance white cloth before bleaching 23 3 6 5 1 These reflectances were determined with NDR-IOIDP mfd. by Nippon Denshcku Kogyo X.K. by the use of a filter of 460 nra. Black tea-stained cloth: 80 g of NITTOH black tea (yellow package) was boiled in 3 i of ion-exchanged water for about 15 minutes and the resulting mixture was filtered through a desized bleached cotton cloth. A cotton shirting cloth #2003 was immersed in the obtained filtrate and boiled for about 15 minutes. The cloth immersed in the filtrate was taken off as such from fire and allowed to stand for about 2 hours. The resulting cloth was spontaneously cried and washed with water until the washings became .colorless. The resulting cloth was dehydrated and pressed to form a test piece (8x8 cm).

In Table 1, the compound shown (1) has the formula: TAED shown (2) is tetraacetylethylenediamine being available from Hoechst. The compound shown (3) is available Interox. The bleaching extent shown (4) is measured with a solution having an active oxygen concentration of 0.05%. 233651 Examples 9 and 10 of Composition Bleaching method: Hydrogen peroxide was added to 300 mi of water at 20°C so that the effective oxygen concentration was 0.05%, and 1 g of sodium carbonate was further added thereto. The compound (IV-a) or (IV-b) was added to the solution in an amount equimolar to hydrogen peroxide. A black tea stained cloth prepared in the same way as before, having a sire of 10 cm and 10 cm, was immersed in the solution for 30 minutes to effect bleaching. The cloth was washed with water and dried, and the bleaching ratio was calculatsd according to the formula described below. Sodium hypochlorite as a comparative product was evaluated at an effective chlorine concentration of 0.061. Results are shown in Table 2. Examples 11 to 18 of Detergent Composition Sodium percarbonate and cationic compounds shown in Table 3 were added to a solution of a heavyduty detergent comprising a nonionic surfactant as a base, not containing an anionic one, being available in the commertial market, to prepare a detergent solution having a composition given in Table 5. Five black tea-stained cloths (Sx8 cm") ,4T3> 23 36 51 prepared by the above-mentioned procedure were washed with the detergent solution in a Terg-O-Tcmeter at 20°C for 10 minutes, washed with water dried and examined for the rate of bleaching according to the above mentioned method. Results are shown in Table 3, together with data of control compositions 7 to 10.

Example 19 The three bleaching compositions, containing no phosphorus, a small amount of phosphorus and a considerable amount of phosphorus, respectively, were obtained in the below shown formulations- Percent is based on weight.

The composition containing no phosphorus was obtained from 14% of sodium linear dodecylbenzene sulfonate, 6% of polyoxyethylene (10 moles of EO) CI 2 to CI 3 alkyl ether, 2% of sodium salt of hardened beef tallow aliphatic acid, 5% of sodium silicate of 2 go, 10% of sodium carbonate, 25% of zeolite of the 4A type, 10% of sodium percarbonate, % of the cationic compound (IV-a) , 2% of polyethylene glycol having a molecular weight of 6,000, 2% of protease, 4% of water and the balance of sodium sulfate. 2336 5 1 The compound having a small amount of phosphorus was obtained from 10% of sodium linear dodecylbenzene sulfonate, 2% of sodium dodecylsulfate, 8% of polyoxyethylene(7.7 moles of EO) CI 2 to C13 alkyl ether, 2% of sodiuni salt of hardened beef tallow aliphatic acid, 5% of sodium silicate of 1 go, 10% of sodium carbonate, 20% of zeolite of the 4A type, 15% of sodiuni pyrophosphate, 10% of sodiuni perborate, 5% of the it compound (IV-a), 1% of polyethylene glycol having a molecular weight of 11,000, 1% of sodium sulfite, 2% of protease, 4% of water and the balance of sodium sulfate.

The compound containing a considerable amount of phosphorus was obtained from 20% of polyoxyethylene(8 - 6 moles of EO) beef tallow alcohol ether, 2% of sodiuni salt of hardened beef tallow aliphatic acid, 30% of sodium tripolyphosphate, 10% of sodiuni perborate, 5% of the compound CIV-a), 5% of sodium silicate of 2 go, 10% of sodium carbonate, 1% of sodium sulfite, 2% of polyethylene glycol having a molecular weight of 6,000, 2% of protease, 6% of water and the balance of sodium sulfate. ( i o Table 1 the invention control 1 2 3 4 6 7 8 1 2 3 1 4 composition (percent by weight) Sodium pcrca'rbona tc 13 n 89 V V cjo yy.5" <57 1 OO IV-a - ~ — - — \ — 1 - — — — — IV-c - — - — — - — —- — — - methyl-2-cyano-• pyridinium iodide^ ' — — — — — •— .

- II.S* - - - TAI-D (2) — - — __ - — — — — & ■— — magnesiiun mono?,-, pcrphthalatc ^ J /3 — blcaching extent (%) J 37,o \ 7 37.i U6 ^O.o W3 W. I 13. 2. 2I.V If.-5 1 -fch CM CD cn Table 2 3 the invention control • 9 6 11 2 0 2 0.106 0. 106 0. 106 f—> If- a 0.417 — <u 17- b — • 0.505 C X O ja • H M 4-> •M C NaOCl — — 0.063 1/1 <U O U CU ^ E flj O O.

N a 2 C 0 3 0.333 0.333 0. 333 —— U v—' NaOH 1 ■ ■* 0.01 concentration of available oxygen ($) 0.05 0.05 0.05 concentration of available chlorine (1) — — — 0.06 bleaching extent 77 73 21 63 % ro 04 CM o> U1 Tabic 3 the invention control 11 12 13 14 16 17 18 7 8 9 detergent 0.& o 0.^ o.k 0. b 6,k O.k o} o.t O. ^ O ,<» 0. ^ IV-a — — — — o.oli — — .

— — IV-c — — — — — 0>ol3 — — methyl-2-cyano-pyr illinium iodide — — — — — — — o.°'3 — — TAHI) magnesium inono-perphthalate — Ool2 — blcaching extent (?„) lo,' *\° |o ,9 I0.3 /*.» I.3 2.^ it i.5" " no CM <y> Cn 'J rJ O.T .< u»1bo

Claims (6)

WHAT WE CLAIM IS:

1. A compound having the generic formula (b-7) 0 (b-7) NCCH2N (CH2)nN CH2CN 2X R. 2 R 4 in which R^, R2, and R4 are each a Cj to Cg alkyl; n is an integer of 1 to 16; and X~is an anion.

2. A compound as claimed in claim 1 in which R^f R2, Rg an<* R4 are each an alkyl of 1 to 3 carbon atoms and n is an integer of 1 to 9.

3. A compound as claimed in claim 1 in which R^, R2, and R^ are each a methyl and n is an integer of 1 to 9.

4. A compound according to claim 1 and specifically identified in this specification with reference to example 1 or example 2.

5. A process for the production of a compound according to claim 1 sxibstantially as described in this specification with reference to example 1 or example 2.

6. A compound of formula (b-7) whenever p^riuroH vy a _ process according to claim 5. bj >meys BALDWIN, SON & CAREY KAO CORPORATION