JP2001518478A - Glyoxyl compounds containing one or more active ingredients - Google Patents

Abstract

  (57) [Summary] The present invention relates to glyoxyl compounds containing one or more active ingredients. According to the present invention, delayed release of the active ingredient is provided upon contact of the compound with the aqueous medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention relates to glyoxylic compounds containing one or more active ingredients, especially alcohol or mixed alcohol / aldehyde components. More particularly, the present invention relates to glyoxyl compounds comprising one or more active ingredients for use in laundry and cleaning products.

[0002]

[Background Art]

Cleaning and laundry products are well known in the art. However, consumer acceptance of laundry and cleaning products is determined not only by the performance achieved with these products, but also by the aesthetics associated therewith. Therefore, perfume ingredients are an important aspect of the successful formulation of such commercial products.

[0003] It is also desired by consumers to maintain a pleasant aroma of a washed fabric over time. In fact, the fragrance additives make the laundry composition more aesthetically pleasing to the consumer and, in some cases, the fragrance imparts a pleasing fragrance to the fabric treated therewith. However, the amount of perfume carryover from the aqueous washing bath onto the fabric is often trivial and does not last long on the fabric. In addition, fragrances are often very expensive and inefficient use in laundry and cleaning compositions and ineffective delivery to fabrics are very common to both consumers and laundry / cleaning product manufacturers. Incurs high costs. Therefore, the industry continues to urgently seek more efficient and effective fragrance delivery in laundry and cleaning products, especially to improve the long-lasting fragrance delivery of fabrics.

[0004] One solution is to use a carrier mechanism for perfume delivery, such as by encapsulation. This is taught in the prior art and is disclosed in US Pat.
, 753. Yet another solution is to formulate a compound that provides a delayed release of the perfume over a longer period of time than the use of the perfume itself. The disclosure of such compounds is described in WO 95/04809, WO 9/04809.
5/08976 and the pending application EP 95303762.9.

[0005] However, despite advances in the art, there remains a need for compounds that provide delayed release of perfume ingredients.

[0006] The inventors have now found that glyoxyl compounds containing one or more active alcohols also provide a delayed release of active ingredients such as fragrances.

Another advantage of the present invention is that these glyoxyl compounds can be suitably copolymerized with monomer units, of which active aldehyde monomer units can be used as appropriate, including those useful in perfumes. is there. When using active aldehyde monomer units, this results in glyoxyl compounds containing mixed active alcohol / aldehyde groups,
This results in the release of the respective groups, namely the active alcohol groups and the active aldehyde groups.

[0008] Yet another advantage of the present invention is that one or more of these active ingredients, ie, glyoxyl compounds containing active alcohols or mixed active alcohols / aldehydes, do not interfere with the release of the active ingredients during use of the product, The purpose is to provide a sufficient stabilization of the linkage between the active alcohol and / or aldehyde groups and the carrier such that the release of the active ingredient is limited during storage in the product.

[0009] Yet another advantage of the compounds of the present invention is their ease of manufacture, making their use most desirable.

[0010]

DISCLOSURE OF THE INVENTION

The present invention relates to glyoxyl compounds containing one or more active ingredients, wherein said compound is of the following empirical formula:

Embedded image Wherein at least one of R or R2 is an organic chain of an active alcohol and the other (R and / or R2) is hydrogen, alkali metal, ammonium, alkyl,
Alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or at least one other chain having at least one carbon atom, wherein each of R1 and R'1 is independently hydrogen,
Hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR
3, (CR ₄ R ₄ ) _q COOR 3, OR 3, or another chain having at least one carbon atom; R 3 is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, Or at least one other chain having at least one carbon atom, and R4 is each independently hydrogen, hydroxyl, alkyl,
Alkylene, aryl, alkylaryl, COOR3, CH ₂ COOR3, O
Y is a comonomer unit and m is 0-10000, preferably 0-1000, more preferably 0-100.
N is an integer of at least 1, preferably less than 1000, more preferably less than 100, and q is an integer of 0 to 10, preferably 0 to 4, more preferably 0. There is].

In another aspect of the present invention, there is provided a laundry and cleaning or personal cleansing composition comprising said compound.

[0012] Yet another aspect of the present invention provides for contacting a surface with a compound of the present invention or a composition comprising said compound in the presence of a substance such that at least one of the odorants comprising oxygen is hydrolyzed. A method of delivering a characteristic residual aroma to a surface.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

The essential component of the present invention is a compound derived from glyoxylic acid. The compound of the present invention has the following empirical formula

Embedded image Wherein at least one of R or R2 is an organic chain of an active alcohol and the other (R and / or R2) is hydrogen, alkali metal, ammonium, alkyl,
Alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or at least one other chain having at least one carbon atom, wherein each of R1 and R'1 is independently hydrogen,
Hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR
3, (CR ₄ R ₄ ) _q COOR 3, OR 3, or another chain having at least one carbon atom; R 3 is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, Or at least one other chain having at least one carbon atom, and R4 is each independently hydrogen, hydroxyl, alkyl,
Alkylene, aryl, alkylaryl, COOR3, CH ₂ COOR3, O
Y is a comonomer unit and m is 0-10000, preferably 0-1000, more preferably 0-100.
N is an integer of at least 1, preferably less than 1000, more preferably less than 100, and q is an integer of 0 to 10, preferably 0 to 4, more preferably 0. There is].

The alkyl and alkenyl chains are those having at least one carbon atom, preferably one carbon atom.
It is understood that the chain length is ２０20, more preferably methyl or ethyl. It is, of course, also understood that the chains and cycles can be replaced or interrupted, as the case may be. Short alkyl chains, such as methyl, ethyl, or hydroxy groups, represent such substitutions. O, N, CO, OC (O), CO (O), C (O
) N, NC (O) and mixtures thereof represent such interruptions. "Comonomer unit" means a suitable comonomer that can be copolymerized with a glyoxylic acid-based monomer unit. Those which have at least two reactive sites and do not inhibit polymerization or depolymerize the copolymer in an alkaline solution are representative of such comonomers. Preferably, these monomer units are ethylene oxide, propylene oxide, epihalohydrin, epoxy compounds such as epoxy succinate, formaldehyde, aldehydes such as acetaldehyde, active aldehydes such as those commonly used in perfumes, for example, It is selected from octanal, decanal, dodecanal, methylnonylacetaldehyde, benzaldehyde and aldehydes having up to 20 carbon atoms. Of the above, preferred are active aldehydes commonly used in perfumes that release either the mixed active alcohol compound or the aldehyde fragrance compound, or the mixed fragrance aroma of one or more alcohols and one or more aldehydes. There is even the most preferred.

For ease of purpose, the copolymer has been empirically modeled as a block copolymer. However, in general, by copolymerization of two or more different monomers, the resulting copolymer generally exhibits a completely random distribution of monomers along the polymer backbone rather than the block distribution. Will be obvious to those skilled in the art. The possible combinations of different monomers in the copolymer will not affect the total controlled release benefit observed in the case of such a copolymer and are therefore included in the present description. You.

Among the compounds described in the above formula, preferred compounds are those in which n is equal to 1 and m and q are equal to 0. Such compounds that allow for the controlled release of one or more active alcohols have the formula:

Embedded image Wherein R, R1, R'1, and R2 are as previously defined.

Preferred compounds where n is 1 when m and q are 0 are compounds derived from the class of glycolic acid esters and their ethers. Preferred compounds derived from this class of compounds are those wherein R is the organic chain of the active alcohol and R'1 and R1
Is hydrogen, and R 2 is selected from hydrogen, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or another chain having at least one carbon atom;
Preferably hydrogen, -CH2CH2- (OCH2CH2) _p- OCH3, -CH2
CH2-(OCH2 CH2) _p- OH, methyl and ethyl, wherein p is 0
-20, preferably an integer of 0-6. Preferably, R2 is selected from hydrogen, methyl and ethyl.

Still other preferred compounds wherein n is 1 when m and q are 0 are compounds derived from the type of acetal or hemiacetal glyoxylate. Preferred compounds derived from this class are those wherein R1 is OR3 and R'1 is hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, C
OOR3, (CR4R4) COOR3, OR3, or another chain having at least one carbon atom, preferably hydrogen,-(OCH2 CH2) _{p + 1} -OCH3,-(
OCH2 CH2) _{p + 1} selected from -OH, methyl and ethyl, wherein p is from 0 to 20,
It is preferably an integer of 0 to 6. Preferably, R'1 is selected from hydrogen.

Most preferred compounds from the glyoxylate acetal or hemiacetal class are those wherein R is the organic chain of the active alcohol, R'1 is hydrogen,
R1 is OR3, and each of R3 and R2 is independently hydrogen, alkyl, alkylene, aryl, alkylaryl, an organic chain of active alcohol, or at least one carbon atom;
Is a dialkoxy acetate of an active alcohol selected from other chains.

A preferred type of at least one other chain of the dialkoxy acetate of the active alcohol compound is -CH2CH2- (OCH2CH2) _p- OCH3 or -CH2CH2- (OCH2CH2) _p- OH, (formula Wherein p is an integer of 0 to 20, preferably 0 to 6. Most preferably, each R3, R2 is independently selected from methyl and ethyl.

Other most preferred compounds from the class of glyoxylate acetals or hemiacetals are those wherein R 2 is an organic chain of an active alcohol and R is selected from hydrogen, alkali metal, ammonium, alkyl, alkylene, aryl. A 2-hydroxy-2-active oxyacetate alkyl ester wherein R3 is hydrogen, preferably methyl and ethyl, more preferably methyl.

Still other most preferred compounds from the acetal or hemiacetal class of glyoxylates are 2-hydroxy-2-active wherein each R and R 2 are independently the organic chain of an active alcohol and R 3 is hydrogen. Oxyacetate active ester.

Another preferred group of compounds described in the above general formula is polymerized on their own (m = 0 and n ≧ 2) or copolymerized with some active aldehyde (m ≧ 1)
And n ≧ 1) oligomers and polymers of ketocarboxylate R ′ ₁ OC (CR ₄ R ₄ ) _q COOR. A preferred group of ketocarboxylate oligomers and polymers according to the general formula HOC (CR ₄ R ₄ ) _q COOR is
Oligomers and polymers of glyoxylates polymerized by themselves (q = 0, m = 0 and n ≧ 2) or copolymerized with some active aldehydes (q = 0, m ≧ 1 and n ≧ 1) is there.

Self-polymerized (m = 0 and n ≧ 2) ketocarboxylate R ′ ₁ OC (
Preferred oligomers and polymers of CR ₄ R ₄ ) _q COOR are those wherein n is 2 to 10,
000. Preferred compounds n is 2 to 10,000, the keto active alcohol carboxylate _{R '1 OC (CR 4 R} 4) derived from a type of polyacetal _q COOR and below formula

Embedded image Is a compound having

Preferred compounds derived from this class of compounds are those wherein at least one R is an organic chain of an active alcohol and the other (R and R 2) are each independently an organic chain of an active alcohol, hydrogen, an alkali metal, ammonium, Alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol or at least one other chain, wherein R1 and R'1 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, _{COOR3, (CR 4 R 4)} q COO
R3, OR3, or another chain having at least one carbon atom; R3 is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, organic chain of active alcohol, or another chain having at least one carbon atom. Selected from;
R4 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR3, CH ₂ COOR3, OR3 or selected from at least one other chain carbon atoms,, n is 2 to 10,000, preferably 1000 Less, more preferably less than 100, and q is 0-10, preferably 0-4, more preferably 0, 1 or 2.

R′1 is preferably hydrogen, methyl, ethyl, COOR3.

R 4 is preferably hydrogen, methyl, ethyl, phenyl.

R 1 is preferably —OCH (CH 3) —O—C 2 H 5, — (OCH 2 CH
2) _{p + 1} -OCH3 or-(OCH2 CH2) _{p + 1} -OH (where p is 0 to 2)
0, preferably an integer of 0 to 6).

In the case of the aforementioned R2 and R3 groups, -CH (CH3) -OC2H5, -CH
2CH2- (OCH2CH2) _p- OCH3 or -CH2CH2- (OCH2
CH2) _p- OH (wherein p is an integer from 0 to 20, preferably from 0 to 6)
It is a preferable group as the other group having at least one carbon atom.

One preferred group of ketocarboxylate oligomers and polymers is glyoxylate oligomers and polymers (q = 0, m = 0 and n
≧ 2) (n is 2 to 10,000). Preferred compounds wherein n is from 2 to 10,000 are compounds derived from the type of polyacetals of glyoxylates of active alcohols and having the formula:

Embedded image Wherein R1, R'1, R2 and R are as defined above for the polyacetal of ketocarboxylate.

Preferably, R'1 is hydrogen.

Preferred oligomers and polymers of (m ≧ 1 and n ≧ 1) ketocarboxylate R ′ ₁ OC (CR ₄ R ₄ ) _q COOR copolymerized with a suitable comonomer are:
An oligomer and a polymer of some active aldehyde copolymerized with keto carboxylate _{R '1 OC (CR 4 R} 4) q COOR, said copolymer empirical formula

Embedded image Wherein Y is the active aldehyde R'CHO.

Preferably, n and m are independently 1 to 10000, preferably 1 to 1000
, More preferably 1 to 100.

Preferred compounds derived from this class of compounds are those in which at least one R is an organic chain of an active alcohol and the other (R and R 2) are each independently an organic chain of an active alcohol, hydrogen, an alkali metal, ammonium, Alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol or at least one other chain, wherein R1 and R'1 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, _{COOR3, (CR 4 R 4)} q COO
R3 is selected from R3, OR3, or another chain having at least one carbon atom; R3 is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or another chain having at least one carbon atom. Selected from;
R4 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR3, CH ₂ COOR3, OR3 or selected from at least one other chain carbon atoms, q is 0, preferably 0 to 4 , More preferably 0
, 1 or 2.

R′1 is preferably hydrogen, methyl, ethyl, COOR3.

R 4 is preferably hydrogen, methyl, ethyl, phenyl.

R 1 is preferably —OCH (CH 3) —O—C 2 H 5, — (OCH 2 CH
2) _{p + 1} -OCH3 or-(OCH2 CH2) _{p + 1} -OH (where p is 0 to 2)
0, preferably an integer of 0 to 6).

In the case of the R 2 and R 3 groups, —CH (CH 3) —O—C 2 H 5, —CH
2CH2- (OCH2CH2) _p- OCH3 or -CH2CH2- (OCH2
CH2) _p- OH (wherein p is an integer from 0 to 20, preferably from 0 to 6)
It is a preferable group as the other group having at least one carbon atom.

Among the preferred oligomers and polymers of ketocarboxylate R ′ ₁ OC (CR ₄ R ₄ ) _q COOR copolymerized with suitable comonomers (m ≧ 1 and n ≧ 1), some active aldehydes Most preferred are oligomers and polymers of polymerized glyoxylate, wherein the copolymer is of the empirical formula

Embedded image Wherein Y is the active aldehyde R'CHO and R1, R ', R'1, R and R2 are as defined above in the case of the copolymer of ketocarboxylate.

Preferably, n and m are independently 1 to 10,000, preferably 1 to 1000
, More preferably 1 to 100.

In the case of the compounds, the “organic chain” of an active alcohol or an active aldehyde means a chain having at least 1, preferably at least 5, carbon atoms. Preferably, the active alcohol or active aldehyde is selected from a flavor alcohol or aldehyde component, a pharmaceutical alcohol or aldehyde active component, a biocontrol alcohol or aldehyde, a perfume alcohol or aldehyde component, respectively, and mixtures thereof. When more than one organic chain of an active alcohol is present on a compound of the present invention, each organic chain of the active alcohol can be different from the other, for example, there are two organic chains of the active alcohol. Sometimes one can be a biocontrol alcohol agent and the other can be a fragrance alcohol component, or one organic chain of active alcohol is a fragrance alcohol component and the other organic chain of active alcohol is a different fragrance It is an alcohol component. The same applies when the active ingredient is an active aldehyde.

[0042] Flavor components include spices and flavor enhancers that contribute to total flavor perception.

The pharmaceutically active ingredient includes a drug.

As biocontrol agents, biocides, antibacterial agents, bactericides, fungicides,
Examples include algicides, fungicides, disinfectants, preservatives, insecticides, anthelmintics, and plant growth hormones.

As the fragrance alcohol component, a component having aromaticity can be mentioned. Preferably, in the case of said compound, the R group is the organic chain of a perfume alcohol, wherein said alcohol is pentyl alcohol, pentyl-o-hydroxy benzoate, 2-ethyl-4.
-(2,2,3-trimethylcyclopent-3-enyl) -2-buten-1-ol, cis-3-hexenol, 2-methyl-4- (2,2,3-trimethyl-
3-cyclopenten-1-yl) -butanol, 2-norbornanemethanol,
α-3,3-trimethyl-2-methyl-5-isopropylphenol, 3-phenyl-2-propen-1-ol, citronellol (3,7-dimethyl-6-octen-1-ol), p-cymene- 7-ol, 3,7-dimethyl-1-octanol, 2-ethoxy-4-hydroxybenzaldehyde, eugenol (
4-allyl-2-methoxyphenol), farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), 1,3,3-trimethyl-2-norbornanol, geraniol (3 7-dimethyl-2,6-octadien-1-ol), n-hexyl salicylate, 2-phenylpropyl alcohol, 2- (cyclododecyl) -propan-1-ol, 3-methyl-1-butanol, 2,4 , 6-Trimethyl-3-cyclohexene-1-methanol, 2-
Methoxy-4- (1-propenyl) phenol, 2- (5,6,6-trimethyl-2-norbornyl) cyclohexanol isomer, 7-methyl-1-octanol, ethyl 3-hydroxy-3-phenylpropionate, 3- (hydroxymethyl) -2-nonanone, 3-methyl-3-penten-1-ol, 3-methyl-1
-Pentanol, 6,8-dimethyl-2-nonanol, octanol, 4-hydroxytoluene, 4- (p-hydroxyphenyl) butanone, 4-t-butylphenol, 4-t-butylcyclohexanol, phenylethyl alcohol (phenene) Butanol), 3-phenylpropanol, 3,3-dimethyl-5- (2,2
, 3-Trimethyl-3-cyclopenten-1-yl) -4-penten-2-ol, 3,7-dimethyl-7-octenol and 3,7-dimethyl-6-octenol, 9-decen-1-ol, 4-isopropylcyclohexanol, 2-
Methyl-5-phenyl-pentan-1-ol, 5- (2,2,3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol, 2-methyl-5
-(2,3-dimethyltricyclo [2.2.1.0 (2,6)] hept-3-yl) -2-penten-1-ol, 2-isopropyl-5-methylphenol,
Racemic 2,2,6-trimethyl-α-propylcyclohexanepropanol,
Decahydro-2-naphthol, 1,7,7-trimethylbicyclo [1.2.2]
Heptane-2-ol, 3,3,5-trimethylcyclohexanol, undecavertol (4-methyl-3-decene-5-ol), 10-undecene-1-
All, vanillin (4-hydroxy-5-methoxybenzaldehyde), 2-t
-Butylcyclohexanol, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, isopulegol (1-methyl-4-isopropenylcyclohexane-
3-ol), 4- (1-methylethyl) cyclohexanemethanol, phenoxanol (3-methyl-5-phenyl-1-pentanol), 5,6-dimethyl-1-methylethenyl-bicyclo [2.2. 1] Hept-5-ene-2-methanol, 2,4-dimethyl-1-heptanol, 2-isopropenyl-5-methyl-4-hexen-1-ol, 2-methyl-3-phenyl-1-propanol ,
2-benzyl-M-dioxan-5-ol, 1-undecanol, 2- (4-
Methylphenoxy) -ethanol, 2,4-dimethyl-2,6-heptadienol, 2,4-decadien-1-ol, 2-decene-1-ol, 1-hydroxymethyl-4-isopropenyl-1- Cyclohexene, 2,4-dodecadiene-
1-ol, 2-dodecene-1-ol, 2-methyl-3-phenyl-2-propen-1-ol, 6,6-dimethyl-2-oxymethylbicyclo [3.1.1
Hept-2-ene, 2,4-nonadien-1-ol, 2-nonen-1-ol, 2,4-octadien-1-ol and 4-methyl-2,4-heptadien-1-ol, -Octen-1-ol, 3,7,11,15-tetramethylhexadec-2-en-1-ol, 3-methyl-2-buten-1-ol,
2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl)
-2-buten-1-ol, 2-undecene-1-ol, p-methoxybenzyl alcohol, 4-methylbenzyl alcohol, 3,4-methylenedioxybenzyl alcohol, 3-nonanol, β-methylcyclohexaneethanol, −
Phenyl-2-butanol, 1-phenyl-2-pentanol, 1-methyl-4
-Isopropenylcyclohex-6-en-2-ol, 4-phenyl-3-buten-2-ol, 6,6-dimethyl-3-hydroxy-2-methylenebicyclo [3.1.1] heptane, 1 -Phenyl-1-hydroxyethane, 1-phenyl-1-propanol, 2-t-4-methyl-cyclohexanol, 4-ethyl-
2-methoxyphenol, ethyl 2-hydroxybenzoate, 4-allyl-2,6
-Dimethoxyphenol, 3-hydroxy-5-methoxytoluene, pt-butyl-m-cresol, 1-ethoxy-2-hydroxy-4-propenylbenzene, 2-ethoxy-4-methylphenol, 2-methyl-4 -Vinylphenol, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 3,7-dimethyl-7-methoxyoctane-2-ol, 3- (4-methylcyclohexe-
3-ene) butanol, majantol (2,2-dimethyl-3- (3-methylphenyl) -1-propanol), 2-ethyl-2-prenyl-3-hexenol, 4,7-dimethyl-4- Vinyl-6-octen-3-ol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethylbicyclo [3
. 1.1] hept-2-ene-2-ethanol, trans-2-hexenol, 4
-Isopropyl-1-methylcyclohexane-3-ol, 2-isopropyl-
5-methylcyclohexanol, 1- (4-isopropylcyclohexyl) -ethanol, 2,6,9-trimethyl-2,5,9-dodecatrien-1-ol isomer and 2,6,9-trimethyl-2, 5-dodecadien-1-ol isomer, cyclohexaneethanol, 2,4-dimethylcyclohexanemethanol,
Floralol (2,4-dimethyl-3-cyclohexene-1-methanol), o
, M, p-methylphenylethanol, 2-methyl-4-phenyl-1pentanol, cis-3-pentenol, α-n-amylcinnamyl alcohol, 3,3
-Dimethyl-δ-2-β-norbornaneethanol, ethyl 3-hydroxybutyrate, 4-methyl-1-phenyl-2-pentanol, 3,4,5,6,6-pentamethyl-2-heptanol, 1-octene -3-ol, 6-methyl-3-isopropenylcyclohexane-1-ol, 4,7-methano-1H-indene-5
-Ol, 3a, 4,5,6,7,7a-hexahydro-2 (or 3) -4-
Dimethyl, 2-methylbutyl salicylate, n-amyl salicylate, β salicylate
-Phenylethyl, 2-isopropyl-5-methyl-2-hexenol, (1-
Methyl-bicyclo [2.2.1] hepten-2-yl) -2-methyl-pent-
1-en-3-ol, isobornylcyclohexanol isomer, linanol,
Tetrahydrolinanol, 1,2-dihydromyrcenol, hydroxycitronellal, terpineol, 2-phenoxyethanol, menthol, losalva (
9-decene-1-ol) and mixtures thereof.

Preferably, in the case of said compounds, preferred alcohols are 2-phenoxyethanol, phenylethyl alcohol, geraniol, citronellol, phenoxanol, floralol, farnesol, menthol, isopulegol,
Eugenol, vanillin, cis-3-hexenol, undecavertol, majantol, losalva, linalool, tetrahydrolinalool, 1,2-dihydromyrcenol, hydroxycitronellal, terpineol and mixtures thereof. The most preferred R groups for the purposes of the present invention are those wherein the alcohol is selected from geraniol, citronellol, linalool, phenylethyl alcohol, undecavertol, majantol, losalva, 1,2-dihydromyrcenol, and mixtures thereof. Organic chain of active alcohol.

Examples of the flavor aldehyde component include components having aromaticity.

Preferably, in the case of said compound, the R ′ group is the organic chain of a perfume aldehyde, wherein said aldehyde is 2,6,10-trimethyl-9-undecenal, 3-dodecene-1-al, α- n-amylcinnamic aldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3- (4-t-butylphenyl) -propanal, 2-methyl-3- (p-methoxyphenylpropanal, 2-methyl-4
-(2,6,6-trimethyl-2 (1) -cyclohexen-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,
6-octadiene-1-al, 3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl) oxy] acetaldehyde, 4-
Isopropylbenzaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl -3- (isopropylphenyl) propanal, 1-decanal, decylaldehyde, 2,6-dimethyl-5
-Heptenal, 4- (tricyclo [5.2.1.0 (2,6)]-decylidene-8) -butanal, octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy Benzaldehyde, p-ethyl-
α, α-dimethylhydrocinnamaldehyde, α-methyl-3,4- (methylenedioxy) hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, α-n-hexylcinnamic aldehyde, m-cymene-7- Carboxaldehyde, α-methylphenylacetaldehyde, 7-hydroxy-3,7
-Dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3-pentenyl) -3-cyclohexene-carboxaldehyde, 1-dodecanal, 2,
4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde,
7-methoxy-3,7-dimethyloctane-1-al, 2-methylundecanal, 2-methyldecanal, 1-nonanal, 1-octanal, 2,6,1
0-trimethyl-5,9-undecadienal, 2-methyl-3- (4-t-butyl) propanal, phenylacetaldehyde, dihydrocinnamic aldehyde, 1-methyl-4- (4-methyl-3- Pentenyl) -3-cyclohexene-1-carboxaldehyde, 5 or 6-methoxy-hexahydro-4,7-
Methanoindan-1 or 2-carboxaldehyde, 3,7-dimethyloctane-1-al, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 1-undecanal, 10-undecene-1-al, 4- Hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl)-
3-cyclohexenecarboxaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, p-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6
, 6-Trimethyl-1-cyclohexen-1-yl) -2-butenal, o-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde and 2,4,6-trimethyl-3-cyclohexene Carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, paeonylaldehyde (6,10-dimethyl-3-oxa-5,9- Undecadiene-1
-Earl), hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyloctanal, α-methyl-4- (1-methylethyl) benzeneacetaldehyde, 6,6-dimethyl-2-norpinene-2- Propionaldehyde, p-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2
-Propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo [2.2
. 1] -Hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, benzaldehyde, and mixtures thereof.

The most preferred aldehyde is selected from 1-octanal, 1-decanal, 1-dodecanal, methylnonylacetaldehyde, trans-4-decenal, benzaldehyde and mixtures thereof.

For the purposes of the present invention, mixtures of the aforementioned compounds, which contain one or more active alcohols or aldehydes, may also be used.

Mechanism of Release A delayed release of the active ingredient, ie, the alcohol or aldehyde / alcohol mixture, is obtained by the present invention. Without being bound by theory, it is believed that release occurs by the following mechanism.

When m and q are 0 and n = 1, one or more alcohols are
It is released upon hydrolysis of one or more acetal / hemiacetal bonds OR2 and / or OR3 or by hydrolysis of ester bonds.

In the case of dialkoxy acetate of an active alcohol such as dimethoxy acetate, the active ingredient is released upon hydrolysis of the ester bond.

2-Hydroxy-2-active methyl 1-oxyacetate, active 2 2-hydroxy-2
-In the case of a hemiacetal of glyoxylic acid such as active 1 oxyacetate,
The hemiacetal bond first hydrolyzes, releasing active alcohol 1 and active 2 glyoxylate (or its hydrate active 22,2,2-dihydroxyacetate)
Is thought to result in the generation of The ester linkage of active 2 glyoxylate (or its hydrate active 22,2,2-dihydroxyacetate) then hydrolyzes to release active alcohol 2.

When m = 0 and n ≧ 2 (polymer of ketocarboxylate):
Active alcohol is released upon hydrolysis of the ester linkage. This release can occur by hydrolysis of the ester bonds of the polymer itself, or by hydrolysis of the ester bonds of the monomeric ketocarboxylate, which in use is generated by hydrolysis of the acetal bonds on the polymer backbone. .

In the case of a copolymer or oligomer of an active aldehyde and a ketocarboxylate (m ≧ 1, n ≧ 1), the active aldehyde is released upon hydrolysis of an acetal bond constituting a main chain of the polymer. , Resulting in the release of active aldehydes and ketocarboxylates. The active alcohol is released when the ester bond of the polymer is hydrolyzed or the ketocarboxylate released when the acetal bond constituting the main chain of the polymer is hydrolyzed.

The preparation of the process components is carried out in the synthesis examples as follows. In general, the preparation of glyoxyl compounds containing one or more active alcohols comprises reacting the glyoxyl compound with an active alcohol by acetal exchange and / or transesterification.

In the case of poly (ketocarboxylate) compounds containing one or more active alcohols or mixed alcohol / aldehyde components, these compounds have the ketocarboxylate R ′ ₁ OC (CR ₄ R ₄ ) _q COOR It is prepared by polymerizing or copolymerizing with an active aldehyde and then transesterifying the obtained compound with an active alcohol in the presence of a base catalyst.

Preferred features of these general methods of preparing the compounds of the present invention are described below. Glycolic acid ester of active alcohol A preferred method for producing the glycolic acid ester of the active alcohol is methyl glycolate.
Methyl ester of glycolic acid such as
Ter (or methyl 2-methoxyacetate, ethyl 2-ethoxyacetate, etc.)
To 0.01 equivalent, preferably 0.02 equivalent to 0.25 equivalent.
Required in the presence of a catalyst (usually sodium methoxide)
Coal (0.1 equivalent to 10 equivalents, preferably 0.5 equivalent to 4 equivalents, more preferably
Is used at a concentration of 0.9 to 1.1 equivalents). reaction
Methanol or ethanol produced by transesterification to
Tanol is distilled off. This depends on the presence or absence of the required solvent, at atmospheric pressure or
It can be performed under reduced pressure. If a solvent is used, toluene is preferred.

[0060] Acetals of glyoxylic acid esters of active alcohols can also be prepared by the method described above. Glyoxylate hemiacetal of active alcohol 2-hydroxy-2-active methyl oxyacetate, 2-hydroxy-2-active ethyl oxyacetate, and the like. Alkyl 2-alkoxyacetates (methyl 2-hydroxy-2-methoxyacetate, ethyl 2-hydroxy-2-ethoxyacetate) at a concentration of 0.01 to 1 equivalent, preferably 0.02 to 0.1 equivalent. The required active alcohol (in the presence of the catalyst used (generally sodium methoxide))
0.1 equivalent to 10 equivalents, preferably 0.5 equivalent to 4 equivalents, more preferably 0.9 equivalent
(Used at a concentration of 1 to 1.1 equivalents). To complete the reaction, the methanol or ethanol produced by acetal exchange is distilled off. This can be done at atmospheric or reduced pressure, with or without the required solvent. If a solvent is used, toluene is preferred. It has also been found that if the alcohol produced by acetal exchange is distilled off, the catalyst is not actually necessary for the reaction to take place. The reason is that only a trace of an acid catalyst (such as hydrochloric acid or sulfuric acid) or an alkali catalyst (such as sodium hydroxide or sodium methoxide) is sufficient to cause the reaction. However, in order to accelerate the reaction, an acid catalyst (hydrochloric acid, sulfuric acid, etc.) or an alkaline catalyst (
Sodium hydroxide, sodium methoxide, etc.) can be added to the reaction mixture.

Another preferred method of preparing the hemiacetal of a glyoxylate ester of an active alcohol, such as methyl 2-hydroxy-2-active methyl oxyacetate, ethyl 2-hydroxy-2-active oxyacetate, is to use some freshly distilled glyoxylic acid. Alkyl (eg, glyoxylate, ethyl glyoxylate, etc.) is converted into a required active alcohol (0.1 to 10 equivalents, preferably 0.5 to 4 equivalents, more preferably 0.9 to 1 equivalent).
. (Used at a concentration of 1 equivalent). In the case of freshly distilled methyl glyoxylate (obtained by distillation from methyl 2-hydroxy-2-methoxyacetate (in the presence of phosphorus pentoxide)) and primary or secondary alcohols, a catalyst is required. Not found.

Yet another preferred process for preparing the hemiacetal of a glyoxylate of an active alcohol such as a 2-hydroxy-2-active oxyacetate active ester is
An alkyl hydroxy-2-alkoxyacetate (e.g., methyl 2-hydroxy-2-methoxyacetate, ethyl 2-hydroxy-2-ethoxyacetate) is used in an amount of 0.01 to 2 equivalents, preferably 0.02 to 0.4 equivalent. The required active alcohol (or mixture of alcohols) (0.1 to 10 equivalents, preferably 0.5 to 4 equivalents, more preferably 1. 0 equivalents) in the presence of a catalyst (generally sodium methoxide) used in a concentration. (Used at a concentration of 8 equivalents to 2.2 equivalents) and transesterification and acetal exchange. To complete the reaction, the methanol or ethanol produced by transesterification and acetal exchange is distilled off. This means
It can be carried out at atmospheric pressure or under reduced pressure, depending on the presence or absence of the required solvent. If a solvent is used, toluene is preferred.

Yet another preferred process for the preparation of hemiacetals of glyoxylates of active alcohols, such as 2-hydroxy-2-active oxyacetate active esters, is to use some alkyl 2-hydroxy-2-active oxyacetates (2-hydroxy- 2-active methyl oxyacetate, 2-hydroxy-2-active ethyl oxyacetate)
The required active alcohol (0.1 eq to 10 eq, preferably 0.1 eq) in the presence of a catalyst (generally sodium methoxide) used at a concentration of from 1 eq to 1 eq, preferably 0.02 eq to 0.25 eq. 5 equivalents to 4 equivalents, more preferably 0.9 equivalents to 1.
(Used at a concentration of 1 equivalent). To complete the reaction, the methanol or ethanol produced by transesterification is distilled off. This can be done at atmospheric or reduced pressure, with or without the required solvent. If a solvent is used, toluene is preferred. After the preparation of alkyl 2-hydroxy-2-active monooxyacetate from freshly distilled alkyl glyoxylate and the required active alcohol 1, the 2-hydroxy-2-active alkyl monooxyacetate is added to a catalytic amount of sodium methoxide. Transesterification with the required active alcohol 2 below means that both active alcohols 1 and 2 are different 2-hydroxy-
A preferred route for specifically producing glyoxylates of active alcohols such as 2-active 1-oxyacetate-active 2 esters.

The active alcohol or mixed active alcohol / aldehyde ketocarboxylate R ′ ₁ OC (CR ₄ R ₄ ) _q COOR polymer or copolymer is formed from the active alcohol or mixed active alcohol / aldehyde glyoxylate ester polymer. The union or copolymer can be obtained in a two-stage process, exemplified below.

A preferred method of preparing a polymer or copolymer of glyoxylic acid ester is as follows: (A) A slight amount of freshly distilled glyoxylic acid ester (eg, methyl glyoxylate, ethyl glyoxylate, etc.) is converted to a glyoxylic acid such as an epoxy compound. (B) the stability of the polymer in the product is such that excessive depolymerization in the product is caused by the presence of other substances or preferably active aldehydes copolymerizable with the ester, together with the polymerization initiator. End-capping the resulting polymer or copolymer with a suitable chemical group so that it can be optimized for prevention, and (C) subjecting the resulting polymer or copolymer to the presence of a catalyst such as sodium methoxide. This is a method of transesterifying with the required active alcohol (perfume alcohol, etc.) below. It is advantageous to distill off the alcohol (methanol, ethanol, etc.) produced by transesterification in order to provide for transesterification.
It will be known to those skilled in the art that complete transesterification cannot always be achieved such that the final polymer can contain some methyl ester linkages along with the desired active alcohol ester linkages. Preferably, the amount of residual methyl ester bonds should be as low as possible.

Suitable initiators for polymerization are known to those skilled in the art and are described in the art, for example, in US Pat. No. 4,204,052, column 4, lines 3 to 15. Preferred initiators are phosphorus pentoxide, amines, strong Lewis acids, hydroxides or cyanide ions or sodiomalonates or sodiomethylmalonate esters.

Once the polymer or copolymer of the glyoxylate (or more generally the aldehyde ester) has been prepared, any number of chemically reactive groups is preferably provided in US Pat. No. 4,204,052, column 5 As described in line 25 to column 6, line 28, it can be added to the terminal of the polymer or copolymer using an ionic catalyst such as a boron trifluoride etherate compound or trifluoroacetic acid. Particularly suitable end groups include alkyl group, an alkyl group containing oxygen, for example, alkyl groups containing ether, such as methoxy or _{OCH (CH 3) OC 2 H} 5 and carboxylic acids. The chemical nature of the chemically reactive group is not critical to the proper function of the polymer or copolymer in the intended application to release the active alcohol and / or aldehyde. Chemically reactive groups need only stabilize the polymer or copolymer to limit depolymerization prior to use. The end-capping group can be selected such that depolymerization upon use is triggered by either hydrolysis, photochemical cleavage, enzymatic cleavage or oxidative cleavage of the bond attaching the end-capping group to the remainder of the polymer. .

In the same manner, in copolymers, the comonomers are such that the depolymerization in use is triggered by either hydrolysis, photochemical, enzymatic or oxidative cleavage of the bond connecting the comonomer to the rest of the polymer. You can choose to

The polymerization step (A) can be performed with or without a solvent. Suitable solvents include alkyl nitriles, preferably acetonitrile, dimethyl sulfoxide, acetone, halogenated alkanes, preferably dichloromethane or chloroform, tetrahydrofuran, ethyl acetate and the like. When a solvent is used, the choice of solvent is such that it does not interfere with the polymerization and can be separated relatively easily from the obtained polymer. These solvents can also be used in the case of the end capping step (B). Dichloromethane and acetonitrile are preferred solvents for both step (A) and step (B) of the present method.

In the case of the transesterification step (C), suitable solvents are those which dissolve the polymer, do not interfere and can facilitate the distillation of the alcohol produced by transesterification. Toluene is the preferred solvent for step (C) of the method.

Laundry and Cleaning Compositions The compositions of the present invention typically wash fabrics and delay hard surfaces such as tableware, floors, bathrooms, toilets, kitchens and active alcohols or mixed alcohols / aldehydes. Includes both laundry and cleaning compositions used to clean other surfaces that require release. This also includes compositions for use in personal cleansing such as shower gels, deodorants, solids, shampoos and the like.

Laundry compositions that result in contacting the compounds of the present invention with a fabric are preferred. Preferably, for use in such laundry and cleaning products, the active alcohol is a fragrance such as geraniol.

These include not only detergent compositions that provide fabric cleaning benefits, but also rinsed fabric softener compositions that provide softening and / or antistatic benefits and hard surface cleaning, dryer additions. It should be understood that compositions such as compositions (eg, sheets) are also encompassed.

The one or more compounds of the present invention typically comprise from 0.01% to 10% by weight of the composition,
Preferably it accounts for 0.05 to 5% by weight, more preferably 0.1 to 2% by weight. Mixtures of compounds may also be used here.

Optional ingredients useful for formulating such laundry and cleaning compositions according to the present invention include one or more of the following: Fabric Softener The fabric softener component may also be optionally used in the laundry and cleaning compositions of the present invention to impart softness and antistatic properties to the treated fabric. When used, the fabric softener component will typically be present in an amount sufficient to provide softness and antistatic properties.

The fabric softening component includes a cationic fabric softening component, a nonionic fabric softening component,
It may be selected from an amphoteric fabric softening component or an anionic fabric softening component.

A quaternary ammonium compound or an amine precursor thereof as described below represents a cationic softening component.

A) Quaternary Ammonium Fabric Softening Active Compound (1) Preferred quaternary ammonium fabric softening active compounds have the formula

Embedded image Or expression

Embedded image Wherein Q is of the formula

Embedded image Each R unit independently is hydrogen, C ₁ -C ₆ alkyl,
C ₁ -C ₆ hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxyalkyl; each R ¹ unit is independently a linear or branched C ₁₁ -C ₂₂ alkyl, linear or branched C ₁₁ -C ₂₂ alkenyl, and mixtures thereof,
R ² is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and mixtures thereof; X is an anion that is compatible with the fabric softener active and auxiliary components; m is 1-4, preferably 2, and the subscript n is 1-4, preferably 2,).

One example of a preferred fabric softener active ingredient has the formula

Embedded image Wherein R is preferably methyl; R ¹ is a linear or branched alkyl or alkenyl chain having at least 11 carbon atoms, preferably at least 15 carbon atoms.
Is a mixture of quaternized amines having the formula: In the above fabric softener example, the unit
—O ₂ CR ¹ typically represents a fatty acyl unit derived from a triglyceride source. The triglyceride source is preferably tallow, partially hydrogenated tallow, lard,
Partially hydrogenated lard, vegetable oils and / or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, and the like, and mixtures of these oils I do.

Preferred fabric softening actives of the present invention are diester and / or diamide quaternary ammonium (DEQA) compounds of the formula

Embedded image Wherein R, R ¹ , X and n are the same as defined for formulas (1) and (2);

Embedded image And a diester and diamide having the formula:

[0081] These preferred fabric softening actives are prepared by reacting an amine with a fatty acyl unit to form a compound of formula

Embedded image (Wherein, R is preferably a methyl, Z is -OH, -NH ₂ or a is mixture thereof) After generating the amine intermediate having the quaternized final softener active Generate by doing.

Non-limiting examples of preferred amines used to produce the DEQA fabric softening active according to the present invention include those of the formula

Embedded image A methylbis (2-hydroxyethyl) amine having the formula

Embedded image A methylbis (2-hydroxypropyl) amine having the formula

Embedded image (3-aminopropyl) (2-hydroxyethyl) amine having the formula

Embedded image A methylbis (2-aminoethyl) amine having the formula

Embedded image A triethanolamine having the formula

Embedded image Di (2-aminoethyl) ethanolamine having the formula:

The counter ion X ⁽⁻⁾ is a softener-compatible anion, preferably a strong acid anion;
For example, it can be chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, nitrate and the like, more preferably chloride or methyl sulfate. Anions are less preferred, but can also carry double charges (in this case, X ^(-) represents half of the group).

Tallow and canola oils are a convenient source of inexpensive fatty acyl units that are suitable for use in the present invention as R ¹ units. The following are non-limiting examples of quaternary ammonium compounds suitable for use in the compositions of the present invention. The "
Taroiru "The term point out that R ¹ unit is a mixture of from to and fatty acyl units Taroguriserido source. Similarly, the use of the term canolyl is
It refers to a mixture of fatty acyl units derived from canola oil. TABLE II Fabric softener active ingredient N, N-di (tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride; N, N-di (canolyl-oxy-ethyl) -N, N-dimethylammonium chloride; N N, N-di (tallowyl-oxy-ethyl) -N-methyl-N- (2-hydroxyethyl) ammonium chloride; N, N-di (canolyl-oxy-ethyl) -N-methyl-N- (2-hydroxy Ethyl) ammonium chloride; N, N-di (2-tallowyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N-di (2-canolyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N
-Dimethylammonium chloride; N, N-di (2-canolyloxyethylcarbonyloxyethyl) -N, N
-Dimethylammonium chloride; N- (2-tallowoiloxy-2-ethyl) -N- (tallowyloxy-2)
-Oxo-ethyl) -N, N-dimethylammonium chloride; N- (2-canolyloxy-2-ethyl) -N- (canolyloxy-2-
Oxo-ethyl) -N, N-dimethylammonium chloride; N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride; N, N, N-tri (canolyl-oxy-ethyl) -N -Methylammonium chloride; N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl) -N
, N-dimethylammonium chloride; N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N
1,2-Ditallowyloxy-3-N, N, N-trimethylammoniopropane chloride; and 1,2-dicanolyloxy-3-N, N, N-trimethylammonium chloride Opropane chloride; and mixtures of the above active ingredients.

Other examples of quaternary ammonium softening compounds are methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate and methyl bis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate is there. These materials are available under the trade names Varisoft (Varisoft ^R) 222 and Varisoft ^R 110 each from Witco Chemical Company.

N, N-di (tallowoil-oxy-ethyl) -N, N-dimethylammonium chloride wherein the tallow chains are at least partially unsaturated is particularly preferred.

The amount of unsaturation contained in the tallow, canola or other fatty acyl unit chain can be determined by the iodine value (IV) of the corresponding fatty acid, in this case preferably in the range of 5 to 100 And two categories of compounds are distinguished, having an IV of less than or greater than 25.

In fact, when the iodine value is between 5 and 25, preferably between 15 and 20, the formula derived from tallow fatty acids

[0089]

Embedded image In the case of compounds having the formula, it has been found that a cis / trans isomer weight ratio of more than 30/70, preferably more than 50/50, more preferably more than 70-30 gives optimal enrichment.

Unless very high concentrations are required, for such compounds formed from tallow fatty acids having an iodine value of greater than 25, the ratio of cis to trans isomers is less critical. Not found.

Another suitable example of a fabric softener active ingredient is that the terms “tallowyl” and “canolyl” in the above examples correspond to “cocoyl, palmyl, lauryl, oleyl,” which corresponds to the triglyceride source that is the source of fatty acyl units. Lisinorail, stearyl,
It is derived from a fatty acyl group which is replaced by the term "palmityl". These other fatty acyl sources can consist of either fully saturated or, preferably, at least partially unsaturated chains.

As mentioned above, the R units are preferably methyl. However, suitable fabric softener actives include the term "methyl" in the above examples in Table II as "ethyl,
Ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t
-Replaced by the unit butyl.

The counter ion X in the examples of Table II can be replaced by bromide, methyl sulfate, formate, sulfate, nitrate, and mixtures thereof, as appropriate. In fact, the anion X merely exists as a counter ion of the positively charged quaternary ammonium compound. The scope of the present invention is not considered to be limited to any particular anion.

In the case of the previous ester fabric softeners, the pH of the composition is an important parameter of the present invention. In fact, it affects the stability of quaternary ammonium or amine precursor compounds, especially under long-term storage conditions.

[0095] The pH as defined in the present context is measured in neat compositions at 20 ° C.
Although these compositions can be operated at pH below 6.0, for optimal hydrolytic stability of these compositions, the neat pH measured under the above conditions is preferably 2.0
-5, preferably 2.5-4.5, preferably 2.5-3.5.
Must be within the range. The pH of these compositions of the invention can be adjusted by the addition of Bronsted acids.

Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially low molecular weight (C ₁ -C ₅ )
Carboxylic acids, and alkyl sulfonic acids. Suitable inorganic acids include
HCl, H ₂ SO ₄ , HNO ₃ and H ₃ PO ₄ . Suitable organic acids include formic acid, acetic acid, citric acid, methyl sulfonic acid and ethyl sulfonic acid. Preferred acids are citric, hydrochloric, phosphoric, formic, methyl sulfonic,
And benzoic acid.

As used herein, when specifying a diester, it will include the monoesters normally present during manufacture. For softening, under no / low detergent carryover laundry conditions, the percentage of monoester should be as low as possible, preferably no more than 2.5%.
However, under high detergent carryover conditions, some monoesters are preferred. The total ratio of diester to monoester is from 100: 1 to 2: 1, preferably from 50: 1 to 5: 1, more preferably from 13: 1 to 8: 1. Under high detergent carryover conditions, the di / monoester ratio is preferably 11: 1. The amount of monoester present can be controlled in the preparation of the softener compound.

A mixture of the active ingredient of formula (1) and the active ingredient of formula (2) may also be prepared.

2) Still other quaternary ammonium fabric softening compounds suitable for use herein
Represents two or more long-chain acyclic aliphatic C which can be used alone or as part of a mixture. ₈ ~ C_{twenty two}Having a hydrocarbon group or one such group and one arylalkyl group
A cationic nitrogen-containing salt having the formula (i):

Embedded image Wherein R ⁴ is an acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group, R ⁵ is a C ₁ -C ₄ saturated alkyl or hydroxyalkyl group, and R ⁸ is selected from R ⁴ and R ⁵ groups. chosen, a ^- acyclic quaternary ammonium salts having the definitions of anions on);

Formula (ii)

Embedded image Wherein n is equal to 1 to 5 and R ¹ , R ² , R ⁵ and A ⁻ are as defined above; a diaminoalkoxylated quaternary ammonium salt having:

(Iii) mixtures thereof. Examples of cationic nitrogen-containing salts of the type described above include the well-known dialkyldimethylammonium.
Salt, for example, ditallow dimethyl ammonium chloride, ditallow dimethylan
Monium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride
Lido, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium
It is a nickel chloride. Di (hydrogenated tallow) dimethyl ammonium chloride
And ditallow dimethyl ammonium chloride are preferred. Can be used in the present invention
Examples of commercially available dialkyldimethylammonium salts include di (hydrogenated tallow) dimethyl
Luammonium chloride [trade name Adogen^R) 442]
Tilammonium chloride (trade name ADGEN^R470, Praepagen ^R 3445], distearyl dimethyl ammonium chloride [trade name Allosa
Arosurf^R) TA-100] (All purchased from Witco Chemical Company)
You can do it). Dibehenyl dimethyl ammonium chloride is
Brand name by Hamco Chemical Division of Mikal Corporation
It is sold under the name Kemamine Q-2802C. Dimethylstearylben
Zylammonium chloride is a trade name of Witco Chemical Company
Bali soft^RAnnounced under the name of Onyx Chemical Company at SDC
Monix (Ammonyx^R490).

B) Amine Fabric Softening Active Compound Suitable amine fabric softening compounds for use herein, which may be in amine or cationic form, are selected from:

(I) A reaction product of a polyamine selected from hydroxyalkylalkylenediamines, dialkylenetriamines and mixtures thereof and higher fatty acids. These reaction products are mixtures of several compounds in view of the polyfunctional structure of the polyamine. Preferred components (i) are nitrogen-containing compounds selected from the group consisting of the reaction product mixture or some predetermined components of the mixture.

One preferred component (i) has the formula

Embedded image Wherein each R ⁷ is an acyclic aliphatic C _{15 to} C ₂₁ hydrocarbon group, and R ⁸ is a divalent C ₁ to
A substituted imidazoline compound having a C ₃ alkylene group).

[0105] Component (i) materials are commercially available as sold by being Mazuamido (Mazamide ^R) 6 or Sandoz Colors End Chemicals sold by Seranin (Ceranine ^R) HC by Maazel Chemicals, Alkazine ^R S trade name by Alcalle Chemicals, Inc.
T, or hydroxyethylimidazoline stearate sold under the trade name Schercozoline® S by Shah Chemicals, Inc., N, N ″ -ditalowalcoyldiethylenetriamine, ^1- tallowamidoethyl- ^2- tallowimidazoline (Wherein R ¹ is an aliphatic C _15-
A C ₁₇ hydrocarbon group and R ⁸ is a divalent ethylene group).

Some of component (i) can also be first dispersed in a Bronsted acid dispersing aid having a pKa value of 4 or less if the pH of the final composition is 6 or less. Some preferred dispersing aids are hydrochloric acid, phosphoric acid, or methyl sulfonic acid.

N, N ″ -DitallowalcoylDiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are both reaction products of tallow fatty acids and diethylenetriamine, and the cationic fabric softener methyl- It is a precursor of 1-tallowamidoethyl-2-tallowimidazolinium methyl sulfate (
"Cationic surfactants as fabric softeners" R. Egan, Journal of the American Oil Chemistry Society, 11th January 1978
Pages 8 to 121). N, N "-ditalycoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Chemical Company as experimental chemicals. Methyl-1-tallowamidoethyl-2-tallowimidazo Linium methyl sulfate is available from Witco
It is sold under the trade names Varisoft (Varisoft ^R) 475 by Chemical Company.

Formula (ii)

Embedded image Wherein each R ² is a C _1-6 alkylene group, preferably an ethylene group; G is an oxygen atom or a —NR— group; each R, R ¹ , R ² and R ⁵ are as defined above. Having the definition, wherein A ⁻ has the definition given above for X ⁻ ).

One example of the component (ii) is that R ¹ is an acyclic aliphatic C ₁₅ -C ₁₇ hydrocarbon group, R ² is an ethylene group, G is an NH group, R ⁵ is a methyl group, and A ⁻ is a chloride group. 1-Oleylamidoethyl-2-oleylimidazolinium chloride which is an ion.

Formula (iii)

Embedded image Wherein R, R ¹ , R ² , and A ⁻ are defined as above.

One example of the component (iii) is represented by the formula

Embedded image Wherein R ¹ is derived from oleic acid.

[0112] Additional fabric softening materials may be used in addition to or in place of the cationic fabric softener. These may be selected from non-ionic fabric softening materials, amphoteric fabric softening materials or anionic fabric softening materials. The disclosure of such materials is disclosed in U.S. Pat. No. 4,327,133, U.S. Pat.
No. 92, U.S. Pat. No. 4,426,299, U.S. Pat. No. 4,460
U.S. Pat. No. 4,644,203, U.S. Pat.
No. 61,269, U.S. Pat. No. 4,439,335, U.S. Pat.
No. 4,861,870; U.S. Pat. No. 4,308,151; U.S. Pat. No. 3,886,075; U.S. Pat. No. 4,233,164; U.S. Pat. U.S. Pat. No. 3,974,076, U.S. Pat.
It can be found in U.S. Pat. Nos. 4,237,016 and EP 472,178.

Typically, such non-ionic fabric softener materials have an HLB of 2-9, more typically 3-7. Such nonionic fabric softener materials tend to disperse easily when combined with them alone or with other materials described in detail below, such as single long chain alkyl cationic surfactants. Dispersibility can be improved by using more single long chain alkyl cationic surfactant, a mixture with other materials as described below, using hotter water and / or using more agitation. In general,
The material chosen should be relatively crystalline, have a high melting point (eg,> 40 ° C.), and be relatively water-insoluble.

Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols or anhydrides thereof (alcohols or anhydrides have 2 to 18, preferably 2 to 8 carbon atoms and each fatty acid moiety is 12-30, preferably 16-20 carbon atoms). Typically, such softeners contain from 1 to 3, preferably 2 fatty acid groups per molecule.

The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (eg, di-, tri-, tetra, penta- and / or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Can be Sorbitan esters and polyglycerol monostearate are particularly preferred.

The fatty acid part of the ester is usually derived from fatty acids having 12 to 30, preferably 16 to 20, carbon atoms, typical examples of which are lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid. .

[0117] Optional nonionic softeners that are highly preferred for use in the present invention are sorbitan esters, which are esterified dehydration products of sorbitol, and glycerol esters.

Commercially available sorbitan monostearate is a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having a weight ratio of stearate / palmitate of 10: 1 to 1:10, and 1,5-sorbitan esters are also useful.

Glycerol esters and polyglycerol esters, especially glycerol,
Mono- and / or di-esters, preferably monoesters, of diglycerol, triglycerol and polyglycerol are preferred here (for example polyglycerol monostearate with the trade name Radiasurf 7248).

Useful glycerol and polyglycerol esters include monoesters with stearic acid, oleic acid, palmitic acid, lauric acid, isostearic acid, myristic acid and / or behenic acid and stearic acid, oleic acid, palmitic acid, Examples include diesters of lauric, isostearic, behenic and / or myristic acids. It is understood that typical monoesters contain some diesters and triesters and the like.

“Glycerose ester” also includes polyglycerol esters, for example, diglycerol esters to octaglycerol esters. Polyglycerol polyols are prepared by condensing glycerin or epichlorohydrin together and linking the glycerol moieties via ether linkages. Monoesters and / or diesters of polyglycerol polyols are preferred, with the fatty acyl groups typically being those described above for sorbitan and glycerol esters.

Still other fabric softening components suitable for use herein are softening clays, such as, for example,
It has a low ion exchange capacity as described in EP-A 0,150,531.

Of course, the term “softening active ingredient” can also include mixed softening actives.

Among the types of softener compounds, diester or diamide quaternary ammonium fabric softening active compounds (DEQA) are preferred.

The fabric softener compounds of the present invention may comprise from 1% to 80% of the composition, depending on the composition practice.
[The amount is dilutable (the preferred amount of active ingredient is 5 to 15% by weight of the composition) and can be concentrated (the preferred amount of active ingredient is 15 to 50% by weight of the composition, most preferably 15 to 15% by weight of the composition). 35% by weight).

[0126] Fully formulated laundry and cleaning compositions, such as softening compositions, preferably contain, in addition to the above components, one or more of the following components.

(A) Brightener The composition may optionally also contain 0.005-5% by weight of certain hydrophilic optical brighteners which also have a dye transfer inhibiting action. If used, the composition will preferably contain 0.001 to 1% by weight of such an optical brightener.

The hydrophilic optical brightener useful in the present invention has the structural formula

Embedded image Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is N-2-bis-hydroxyethyl, N-2-
Selected from hydroxyethyl-N-methylamino, morpholino, chloro, and amino; M is a salt-forming cation such as sodium, potassium, and the like.

Where R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4′-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is Ciba - are commercially available under the trade name Tinopal (Tinopal) -UNPA-GX ^R by Geigy Corporation. Tinopearl-UNPA-GX is a preferred hydrophilic optical brightener useful in the rinse composition of the present invention.

In the above formula, R ₁ is anilino, and R ₂ is N-2-hydroxyethyl-N-2
-Methylamino and when M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-
Methylamino) -s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid disodium salt. This particular brightener species is Ciba-Geigy.
Commercially available under the trade name Tinopearl 5BM-GX ^R by the Corporation.

In the above formula, when R ₁ is anilino, R ₂ is morpholino and M is a cation such as sodium, the brightener is 4,4′-bis [(4-anilino-
6-Morifolino-s-triazin-2-yl) amino] sodium salt of 2,2'-stilbene disulfonic acid. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX ^R by Ciba-Geigy Corporation.

(B) Dispersing Aid A relatively concentrated composition containing both a saturated diester quaternary ammonium compound and an unsaturated diester quaternary ammonium compound that is stable without the addition of a concentration aid, Can be prepared. However, the compositions of the present invention may require organic and / or inorganic thickening auxiliaries to achieve higher concentrations and / or to meet higher stability standards depending on other ingredients. These thickening aids, which can typically be viscosity modifiers, may be required or preferred to ensure stability under extreme conditions using a particular softener active ingredient amount. Sometimes. The surfactant concentration aid typically comprises (1) a single long chain alkyl cationic surfactant,
(2) nonionic surfactant, (3) amine oxide, (4) fatty acid, and (5)
) Selected from the group consisting of mixtures thereof. These auxiliaries are described in WO 94/20
No. 597, specifically page 14, line 12 to page 20, line 12 (herein incorporated by reference).

When said dispersing aid is present, the total amount is from 2 to 25%, preferably from 3 to 17%, more preferably from 4 to 15%, more preferably from 5 to 1% by weight of the composition.
3% by weight. These materials are active softener raw materials (I), such as mono-long chain alkyl cationic surfactants and / or reactants used to produce biodegradable fabric softener actives as described above. Can be added as part of certain fatty acids,
Or it can be added as a separate component. The total amount of dispersing aid includes any amount that may be present as part of component (I).

(1) Monoalkyl Cationic Quaternary Ammonium Compound The monoalkyl cationic quaternary ammonium compound, when present, is typically 2 to 25%, preferably 3 to 17%, by weight of the composition. , More preferably 4 to
It is present in an amount of 15% by weight, more preferably 5 to 13% by weight (the total monoalkyl cationic quaternary ammonium compound is at least an effective amount).

[0135] Such monoalkyl cation quaternary ammonium compounds useful in the present invention are:
And preferably a compound of the general formula [R^FourN⁺(R^Five)_ThreeX^- [Wherein, R^FourThe group is C₈~ C_{twenty two}An alkyl or alkenyl group, preferably C_Ten~ C ₁₈ An alkyl or alkenyl group, more preferably C_Ten~ C₁₄Or C₁₆~ C₁₈A
Alkyl or alkenyl groups; each R^FiveIs C₁~ C₆Alkyl or substituted al
A kill group (eg, hydroxyalkyl), preferably C₁~ C_ThreeAlkyl group, example
For example, methyl (most preferred), ethyl, propyl and the like, benzyl group, hydrogen, 2
-20 oxyethylene units, preferably 2.5-13 oxyethylene units
Polyethoxylated chain having 3 to 10 oxyethylene units
And mixtures thereof; X^-Is as defined above in the case of formula (I)
A quaternary ammonium salt of

Particularly preferred dispersing aids are those available from Witco under the trade name Adogen.^R) 412
And adgens^RMonolauryltrimethylammonium chloride available at 471
Lido and monotallow trimethylammonium chloride, trade name
Dogen^RMonooleyltrimethylammonium chloride available at 417;
Is monocanola trimethyl ammonium chloride, trade name Adgen from Witco ^R Mono-coconut trimethyl ammonium chloride available at 461;
Trade name Adgen from Itco^RMonosoya trimethyl ammonium available at 415
Um chloride.

The R ⁴ group contains one or more linking groups, such as an ester linking group, an amide linking group, an ether linking group, an amine linking group, which may be desirable for increased concentration of component (I) and the like. It can also be attached to the cationic nitrogen atom through a group. Such linking groups are preferably within 1 to 3 carbon atoms of the nitrogen atom.

The monoalkyl cation quaternary ammonium compounds also include C ₈ -C ₂₂ alkyl choline esters. Preferred dispersing aids of this kind are of the formula R ¹ C (O) —O—CH ₂ CH ₂ N ⁺ (R) ₃ X ⁻ , where R ¹ , R and X ⁻ are as defined above. There is).

Highly preferred dispersing aids include C₁₂~ C₁₄Cococholine ester and C ₁₆ ~ C₁₈Tallow choline esters.

Suitable biodegradable single long chain alkyl dispersing aids containing an ester linkage in the long chain are described in US Pat. No. 4,840,738, which is incorporated herein by reference. It is described in.

When the dispersing aid comprises an alkylcholine ester, preferably the composition also contains a small amount, preferably 2 to 5% by weight of the composition, of an organic acid. Organic acids are EP
No. 404,471 (hereby incorporated by reference). Preferably, the organic acid is selected from the group consisting of glycolic acid, acetic acid, citric acid, and mixtures thereof.

[0142] As the quaternary ammonium compound ethoxylation can serve as the dispersibility aid, trade name Barikuoto from Witco Corporation (Variquat ^R) 6
Available in 6 ethylbis with ethylene oxide 17 mol (polyethoxy ethanol) alkylammonium ethylsulfate, polyethylene glycol (15) available under the trade name Etokuodo (Ethoquad ^R) 0/25 from Akzo oleammonium chloride, and trade name from Akzo Etokuodo ^R polyethylene glycol (15) available at C / 25 Kokomo chloride and the like.

Quaternary compounds having only a single alkyl long chain can protect cationic softeners from interacting with anionic surfactants and / or detersive builders that are carried over from the wash to the rinse. .

(2) Nonionic Surfactants (Alkoxylated Substances) Suitable nonionic surfactants to serve as viscosity / dispersion modifiers include ethylene oxide and optionally propylene oxide and fatty alcohols, fatty acids, fatty amines And the like. They are referred to herein as ethoxylated fatty alcohols, ethoxylated fatty acids, and ethoxylated fatty amines.

Any of the specific types of alkoxylated materials described below can be used as the nonionic surfactant. From a general point of view, the nonionic surfactants of the present invention, when used alone, represent from 0 to 5% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.2 to 5% by weight, in the liquid composition.量 3% by weight. Preferred compounds have the general formula ^{_{R 2 -Y- (C 2 H 4}} O) z -C 2 H 4 OH ( wherein, R ² in the case of both solid and liquid compositions is primary, Secondary and branched alkyl and / or acyl hydrocarbyl groups; primary, secondary and branched alkenyl hydrocarbyl groups; and primary, secondary and branched alkyl substituted phenol hydrocarbyl and alkenyl substituted phenols A hydrocarbyl group; said hydrocarbyl group having a hydrocarbyl chain length of from 8 to 20, preferably from 10 to 18, carbon atoms). More preferably, the hydrocarbyl chain length for liquid compositions is 16-18 carbon atoms and the hydrocarbyl chain length for solid compositions is 10-14 carbon atoms. In the general formula for the ethoxylated nonionic surfactant of the present invention, Y is typically -O-, -C (
O) O -, - C ( O) N (R) -, or -C (O) N (R) R-, preferably -O- (wherein, R ² and R, when present, before Has the meaning given and / or R can be hydrogen), and z is at least 8, preferably at least 10-11. The performance and normal stability of the softener composition is
Decreases when less ethoxylate groups are present.

The nonionic surfactant of the present invention comprises HLB (hydrophilic-lipophilic balance) 7 to 20,
It is preferably characterized by 8-15. Of course, by defining the number of R ² and ethoxylate, the HLB of the surfactant is generally determined. However, it should be noted that non-ionic ethoxylated surfactants useful herein, in the case of concentrated liquid compositions, contain relatively long chain R ² groups and are relatively highly ethoxylated. is there. Shorter alkyl chain surfactants with short ethoxylated groups may have the required HLB, but are not as effective here.

Nonionic surfactants as viscosity / dispersion modifiers are preferred over other modifiers disclosed herein in the case of compositions having high levels of perfume.

Examples of the nonionic surfactant are as follows. The nonionic surfactant of the present invention is not limited to these examples. In the example, the integer is the ethoxy (EO) in the molecule.
) Define the number of groups.

(3) Amine oxide Suitable amine oxides have 8 to 22 carbon atoms, preferably 10 to 1 carbon atoms.
8, more preferably an alkyl or hydroxyalkyl moiety 1 having 8 to 14 carbon atoms
And two alkyl moieties selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups.

Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamineoxide, dimethyldodecylamineoxide, dipropyltetradecylamineoxide, methylethylhexadecylamineoxide, dimethyl- 2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.

(C) Stabilizers Stabilizers can be present in the compositions of the present invention. The term "stabilizer" as used herein includes antioxidants and reducing agents. These agents are 0% to 2% in the case of antioxidants, preferably 0.01% to 0.2%, more preferably 0.035%
To 0.1%, in the case of a reducing agent, more preferably 0.01% to 0.2%. They guarantee good odor stability under long-term storage conditions. Antioxidants and reducing agent stabilizers are particularly critical for unscented or slightly scented products (small or no scents).

[0152] Examples of antioxidants that can be added to the compositions of the present invention, ascorbic acid and ascorbic available from Eastman Chemical Products, Inc. under the trade name Tenox (Tenox ^R) PG and Tenox ^R S-1 Mixture of acid palmitate and propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate and citric acid available from Eastman Chemical Products, Inc. under the trade name Tenox® ^R- 6 a mixture of acid, t available tradename Sasutan (Sustane ^R) butylated hydroxy toluene, available in BHT from UOP process Division, Eastman Chemical products, Inc. as Tenox ^R TBHQ Butylhydroquinone, Eastman Chemical Products,
Tenox from Inc. ^R GT-1 / GT-2 natural available in tocopherol, and Eastman Chemical Products, Inc. available as BHA from butylated hydroxy anisole, long chain esters of gallic acid (C ₈ -C ₂₂ ), For example, dodecyl gallate, Irganox
ox ^R ) 1010, Irganox ^R 1035, Irganox ^R B1171, Irganox ^R 1425, Irganox ^R 3114, Irganox ^R 312
5, and mixtures thereof, preferably Irganox ^R 3125, Irganox ^R 1425, Irganox ^R 3114, and mixtures thereof, more preferably Irganox ^R 3125 alone or other such as citric acid and / or isopropyl citrate a mixture of a chelating agent, Dequest available by chemical name from Monsanto 1-hydroxyethylidene-1,1-diphosphonic acid (etidronate) (Dequest ^R) 2010, and the Kodak 4,5-dihydroxy -m-
Chiron available by chemical name of benzenesulfonic acid / sodium salt (Tiron ^R), and DTP from Aldrich available by chemical name of diethylenetriaminepentaacetic acid
A ^R is mentioned.

(D) Antifouling agent In the present invention, any antifouling agent can be added. Addition of the antifouling agent can occur before or after electrolyte addition, or after preparing the final composition, in combination with a premix, in combination with an acid / water sheet. The softening composition prepared by the method of the present invention can contain 0% to 10%, preferably 0.2% to 5%, of an antifouling agent. Preferably, such an antifouling agent is a polymer. Polymeric antifouling agents useful in the present invention include copolymer blocks of terephthalate and polyethylene oxide or polypropylene oxide.

A preferable antifouling agent is a copolymer having a block of terephthalate and polyethylene oxide. More specifically, these polymers have a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of 25:75 to 35
: Consisting of repeating units of 65 ethylene terephthalate and polyethylene oxide terephthalate (the polyethylene oxide terephthalate has a molecular weight of 300 to
Containing 2000 polyethylene oxide blocks). The molecular weight of this polymeric antifouling agent is in the range of 5,000 to 55,000.

Another preferred polymer antifouling agent is a polyoxyethylene terephthalate unit derived from polyoxyethylene glycol having an average molecular weight of 300 to 6,000.
A crystalline polyester having a repeating unit of ethylene terephthalate units containing 10 to 15% by weight of ethylene terephthalate units together with a weight%, and a molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystalline polymer compound. Is 2: 1 to 6: 1. Examples of this polymer, commercially available materials Zerukon (Zelcon) 4780 ^R (manufactured by DuPont) and Milly's (Mileas
e) T ^R (manufactured by ICI).

Highly preferred antifouling agents have the general formula:

Embedded image Wherein each X can be a suitable capping group, and each X is typically selected from the group consisting of H, and an alkyl or acyl group having 1 to 4 carbon atoms. . p is chosen to be water-soluble and is generally between 6 and 113, preferably between 20 and 50. u is critical for formulation in liquid compositions having relatively high ionic strength. There should be few substances with u higher than 10. Furthermore, there should be at least 20%, preferably at least 40%, of the substances where u is 3-5.

The R ¹⁴ moiety is essentially a 1,4-phenylene moiety. As used herein the term "R ¹⁴ moiety is essentially 1,4-phenylene moieties", R ¹⁴ moieties total 1,4
A phenylene moiety or part of another arylene or alkarylene moiety,
A compound substituted with an alkylene moiety, alkenylene moiety, or a mixture thereof is meant. Arylene and alkarylene moieties that can be partially used in place of 1,4-phenylene include 1,3-phenylene, 1,2-phenylene,
, 8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof. Alkylene and alkenylene moieties that can be partially substituted include 1,2-propylene, 1,4-butylene, 1
, 5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8
-Octamethylene, 1,4-cyclohexylene, and mixtures thereof.

In the case of the R ¹⁴ moiety, the degree of partial substitution at a moiety other than 1,4-phenylene should be such that the antifouling properties of the compound are not adversely affected to a large extent. In general, an acceptable degree of partial substitution will depend on the backbone length of the compound, i.e.,
Longer backbones can have more partial substitutions for the 1,4-phenylene moiety. Usually, R ¹⁴ is 1,4-phenylene moieties 50% to 100% (1,4
A compound consisting of a portion other than phenylene (0 to 50%) has an appropriate antifouling activity. For example, polyesters produced according to the present invention using a molar ratio of isophthalic acid (1,3-phenylene) to terephthalic acid (1,4-phenylene) of 40:60 have suitable antifouling activity. However, since most polyesters used in fiber production consist of ethylene terephthalate units, it is usually desirable to minimize the degree of partial substitution in portions other than 1,4-phenylene for best antifouling activity. . Preferably, R ¹⁴ moieties consist entirely of 1,4-phenylene moieties (i.e.,
100%), that is, each R ¹⁴ moiety is 1,4-phenylene.

For the R ¹⁵ moiety, suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene And mixtures thereof. Preferably,
R ¹⁵ moieties are essentially ethylene moieties, 1,2-propylene moieties or mixtures thereof. Higher proportions of ethylene moieties tend to improve the antifouling activity of the compound. Surprisingly, the incorporation of a higher percentage of the 1,2-propylene moiety tends to improve the solubility of the compound in water.

Therefore, the use of a 1,2-propylene moiety or similar branching equivalent is desirable to incorporate a substantial portion of the antifouling component into the liquid fabric softener composition. Preferably,
75% to 100% are 1,2-propylene moieties.

The value of each p is at least 6, preferably at least 10. The value of each n is typically 12-113. Typically, the value of each p is in the range of 12-43.

A more complete disclosure of antifouling agents is described in US Pat. No. 4,661,267,
711,730, 4,749,596, 4,818,56
No. 9, No. 4,877,896, No. 4,956,447,
And U.S. Pat. No. 4,976,879, all of which are incorporated herein by reference.

These antifouling agents can also act as scum dispersants. (E) Scum dispersant In the present invention, the premix can be combined with any scum dispersant other than the antifouling agent and heated to a temperature equal to or higher than the melting point of the components.

Preferred scum dispersants of the present invention are formed by highly ethoxylating hydrophobic materials. The hydrophobic material can be a fatty alcohol, a fatty acid, a fatty amine, a fatty acid amide, an amine oxide, a quaternary ammonium compound, or a hydrophobic moiety used to form an antifouling polymer. Preferred scum dispersants are highly ethoxylated, for example, on average greater than 17 moles per molecule, preferably 25 moles per molecule.
There is more than moles, more preferably more than 40 moles, of ethylene oxide and the polyethylene oxide portion is between 76% and 97% of the total molecular weight, preferably between 81% and 94%.

The amount of scum dispersant is sufficient to keep the scum acceptable (preferably unrecognizable to the consumer) under the conditions of use, but not enough to adversely affect softening. . For some purposes, it is desirable that no scum be present. Depending on the amount of anionic or non-ionic detergent used in the washing cycle of a typical washing process, the efficiency of the rinsing step before introduction of the composition, and the water hardness, it is trapped in the fabric (laundry). The amount of anionic or nonionic detergent surfactant and detersive builders (particularly phosphates and zeolites) will vary. Normal,
A minimal amount of scum dispersant should be used to avoid adverse effects on flexibility. Typically, the scum dispersant will have at least 2 based on the amount of softener active.
%, Preferably at least 4% (at least 6%, preferably at least 10% for maximum scum avoidance). However, at amounts above 10% (relative to the softener material), there is a risk of loss of the softening efficacy of the product, especially when the fabric contains a high proportion of nonionic surfactant absorbed during the washing operation.

A preferred scum dispersant is Brij 700^R, Varonic U
-250^R, Genapol T-500^R, Genapol T-800^R,
Plurafac A-79^R, And Neodol 25-50 ^R It is.

[0167] (F) killing Examples of bacterial agents bactericides used in the compositions of the present invention, glutaraldehyde, formaldehyde, Pennsylvania Philadelphia trade name by Inolex Chemicals placed in A bronopol (Bronopol ^R) 2-Bromo-2-nitropropane-1,3-diol sold by Rohm and Haas
5-Chloro-2- sold by the company under the trade name Kathon
Methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazoline-3
And mixtures thereof (1-1,000 ppm by weight of drug).

(G) Fragrances The present invention can contain any softener compatible fragrance. Suitable perfumes are disclosed in U.S. Patent No. 5,500,138, which is incorporated herein by reference.

As used herein, perfumes may be aromatic substances or mixtures of substances, such as natural aromatic substances (ie obtained by extraction of flowers, herbs, leaves, roots, bark, wood, fruit flowers or plants), Includes artificial fragrances (ie, a mixture of different natural oils or oil components) and synthetic fragrances (ie, synthetically produced). Such substances are often accompanied by auxiliary substances such as volatile retention agents, extenders, stabilizers, solvents and the like. These adjuvants are also included within the meaning of "perfume" as used herein. Typically, perfumes are complex mixtures of multiple organic compounds.

Examples of perfume ingredients useful in the perfume of the compositions of the present invention include, but are not limited to, hexylcinnamic aldehyde, amyl cinnamic aldehyde, amyl salicylate,
Hexyl salicylate, terpineol, 3,7-dimethyl-cis-2,6-octadien-1-ol, 2,6-dimethyl-2-octanol, 2,6-dimethyl-7-octen-2-ol, 3,7 -Dimethyl-3-octanol, 3,7
-Dimethyl-trans-2,6-octadien-1-ol, 3,7-dimethyl-
6-octen-1-ol, 3,7-dimethyl-1-octanol, 2-methyl-3- (pt-butylphenyl) -propionaldehyde, 4- (4-hydroxy-4-methylpentyl) -3 -Cyclohexene-1-carboxaldehyde, tricyclodecenyl propionate, tricyclodecenyl acetate, anisaldehyde, 2-methyl-2- (p-isopropylphenyl) -propionaldehyde,
Ethyl 3-methyl-3-phenylglycidate, 4- (p-hydroxyphenyl)
-Butan-2-one, 1- (2,6,6-trimethyl-2-cyclohexene-1
-Yl) -2-buten-1-one, p-methoxyacetophenone, p-methoxy-α-phenylpropene, methyl 2-n-hexyl-3-oxo-cyclopentanecarboxylate, γ-undecalactone. .

Additional examples of aromatic substances include, but are not limited to, orange oil, lemon oil, grapefruit oil, bergamot oil, clove oil, γ-dodecalactone, 2- (2-pentyl-3-oxo-cyclopentyl) ) Methyl acetate, β-naphthol methyl ether, methyl-β-naphthyl ketone, coumarin, decylaldehyde, benzaldehyde, 4-t-butylcyclohexyl acetate, α, α-dimethylphenethyl acetate,
Methylphenylcarbinyl acetate, 4- (4-hydroxy-4-methylpentyl)
Schiff base of -3-cyclohexene-1-carboxaldehyde and methyl anthranilate, cyclic ethylene glycol diester of tridecanedioic acid, 3,7-dimethyl-2,6-octadien-1-nitrile, γ-ionone methyl, α- Yonone, β-yonone, petiglen, methyl sedrone, 7-acetyl-1,2,3,4
, 5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene, yononemethyl, methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, 4-acetyl-6-t-butyl-1,1-dimethylindane, benzophenone, 6-acetyl-1,1,2,3 , 3,5-hexamethylindane, 5-acetyl-3-isopropyl-1,1,2,6-tetramethylindane, 1-dodecanal, 7-hydroxy-3,7-dimethyloctanal, 10
-Undecene-1-al, isohexenylcyclohexylcarboxaldehyde, formyltricyclodecane, cyclopentadecanolide, 16-hydroxy-
9-hexadecenoic acid lactone, 1,3,4,6,7,8-hexahydro-4,6
, 6,7,8,8-Hexamethylcyclopenta-γ-2-benzopyran, ambroxane, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b
Furan, cedrol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopentene -1-yl) -2-buten-1-ol, caryophyllene alcohol, cedril acetate, pt-butylcyclohexyl acetate, patchouli, oribanam resinoid, labdanam, betibat, balsam copaiba, filbalsam, and hydroxycitronellal and anthranil Condensates with methyl acid, condensates of hydroxycitronellal and indole, condensates of phenylacetaldehyde and indole, 4- (4-hydroxy-4-methylpentyl)-
A condensate of 3-cyclohexene-1-carboxaldehyde and methyl anthranilate is exemplified.

More examples of perfume ingredients include geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol acetate, terpinyl acetate, nopol , Nopyr acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styralyl acetate, dimethylbenzylcarbinol, trichloromethylphenylcarbinylmethylphenylphenylcarbinyl acetate, isononyl acetate, Vetiveryl acetate, Vetiverol, 2-methyl-3- (pt-butylphenyl) -propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3-
(Pt-butylphenyl) -propanal, 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyltetrahydropyran, methyl dihydrojasmonate, 2-n-heptyl Cyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-
Dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, citronellonitrile, ceryl acetal, 3-isocamphylcyclohexanol, ceryl methyl ether, isolongifolanone , Ovepinnitrile, ovepin, heliotropin, eugenol, vanillin, diphenyloxide, hydroxycitronellalyonone, methylyonone, isomethylyonone, iron, cis-3-hexenol and its esters, indanmusque fragrance, tetralinmusquefragrance, isochromanmusquefragrance , Macrocyclic ketones, macrolactone musk fragrances, ethylene brassates.

The fragrances useful in the compositions of the present invention are substantially free of halogenated substances and nitromsk.

Suitable solvents, diluents or carriers for the perfume ingredients are, for example, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate and the like. The amount of such solvents, diluents or carriers incorporated into the perfume is preferably kept to the minimum required to provide a homogeneous perfume solution.

The fragrance can be present in an amount of 0 to 10%, preferably 0.1 to 5%, more preferably 0.2 to 3% by weight of the finished composition. The fabric softener composition of the present invention provides improved fabric perfume deposition.

(H) Chelating Agents The compositions and methods of the present invention can optionally employ one or more copper and / or nickel chelators (“chelators”). Such water-soluble chelators include aminocarboxylates, aminophosphonates, as defined below,
It can be selected from the group consisting of polyfunctionally substituted aromatic chelators and mixtures thereof. The whiteness and / or whitening of the fabric is substantially improved or restored by such chelating agents and the stability of the material in the composition is improved.

Examples of the aminocarboxylate useful as the chelating agent of the present invention include ethylenediaminetetraacetate (EDTA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate (NTA), ethylenediaminetetrapropionate, and ethylenediamine-N, N ′. -Diglutamate, 2-hydroxypropylenediamine-N, N'-disuccinate, triethylenetetraamine hexaacetate, diethylenetriaminepentaacetate (DETPA)
And water-soluble salts such as ethanol diglycine, for example, their alkali metal salts, ammonium salts, substituted ammonium salts, and the like, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent composition and examples thereof include ethylenediaminetetrakis (methylenephosphonate). ), Diethylenetriamine-N, N, N ', N ", N" -pentakis (methanephosphonate) (DETMP) and 1-hydroxyethane-1,1-diphosphonate (H
EDP). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

[0179] The chelating agent is typically present in the rinse method of the present invention in an amount of from 2 ppm to 25 ppm to 1 ppm.
Used for soaking hours from minutes to hours.

The preferred EDDS chelators used herein (ethylenediamine-N, N ′
-Also known as disuccinate) is a material described in U.S. Patent No. 4,704,233.

As can be seen from the foregoing, various chelating agents can be used here. In fact, simple polycarboxylates, such as citrates, oxydisuccinates, can be used, although not as effective as aminocarboxylates and phosphonates on a weight basis. Thus, the amount used may be adjusted taking into account different chelation efficiencies. The chelators of the present invention will preferably have a stability constant in the case of copper ions (the stability constant of a fully ionized chelator) of at least 5, preferably at least 7. Typically, the chelating agent will comprise from 0.5 to 1 of the composition.
It will account for 0% by weight, more preferably 0.75-5% by weight. Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures thereof.

(I)enzyme The compositions and methods of the present invention may optionally comprise one or more enzymes, such as
Use of protease, cellulase, amylase and peroxidase
Wear. A preferred enzyme for use herein is a cellulase enzyme. In fact, this
Certain enzymes will further impart color care benefits to the treated fabric. Use here
Cellulases that can be used include both bacterial and fungal cellulases.
(Preferably having a pH optimum of 5 to 9.5). US Patent No. 4,43
No. 5,307 describes Humicola insolens or Humicola strain DSM1800.
Or suitable fungal cells from cellulase 212 producing fungi belonging to the genus Aeromonas
And extract from the hepatopancreas of marine molluscs (Dolabella Auricula Solander)
The disclosed cellulase is disclosed. Suitable cellulases are also described in British Patent No. 2
. No. 075.028, British Patent No. 2.095.275 and DE
-OS No. 2.2477.832. Carezyme (CAREZYME ^R ) And CELLUZYME^R) (Novo) is particularly useful. Other suitable cells
Lulase is described in WO 91/17243 to Novo, WO 96/3409.
No. 2, WO 96/34945 and EP-A-0,739,9
No. 82 is also disclosed. For practical use of currently marketed formulations, a typical
The amount is up to 5 mg of active enzyme per gram of detergent composition (by weight), more typically 0.0
1 mg to 3 mg. In other words, the composition typically comprises a commercially available enzyme preparation.
001-5% by weight, preferably 0.01-1% by weight. Enzyme preparation
In certain cases where the activity can be defined in other ways, such as with cellulases, the corresponding activity
Sex units are preferred (eg, CEVU or cellulase equivalent viscosity units). example
If the composition of the present invention has an amount equivalent to 0.5 to 1000 CEVU / g of composition g
Cellulase enzyme. Cell used for formulating the composition of the present invention
Lase enzyme preparations typically have 1,000 to 10,000 C when in liquid form.
It has an activity of EVU / g and 1,000 CEVU / g in solid form.

(J) Liquid Carrier Another optional but preferred component is a liquid carrier. The liquid carrier used in the composition is preferably water, at least primarily for low cost, comparative accessibility, safety, and environmental compatibility. The amount of water in the liquid carrier is preferably at least 50% by weight of the carrier, most preferably at least 60% by weight. Mixtures of water with low molecular weight, eg, <200, organic solvents, eg, lower alcohols such as ethanol, propanol, isopropanol, butanol, are useful as carrier liquids. Low molecular weight alcohols include monohydric alcohols, dihydric alcohols (such as glycols), trihydric alcohols (such as glycerol), and higher polyhydric alcohols (polyols).

(K) Other Optional Components The present invention relates to optional components commonly used in cloth treatment compositions, for example, colorants, preservatives, surfactants, anti-shrinkage agents, fabric refining agents, spotting. (Spotting
) Agents, fungicides, fungicides, antioxidants such as butylated hydroxytoluene,
Corrosion inhibitors and the like can be included.

The present invention relates to other compatible components, such as WO 96/02625, WO
It may also include those as disclosed in WO 96/21714 and WO 96/21715. A variety of other optional auxiliary ingredients may also be used to provide a fully formulated detergent composition. The following ingredients are listed for convenience of the formulator, but are not intended to be limiting.

[0186]Detergent surfactant Non-limiting examples of surfactants useful herein, typically in amounts of 1 to 55% by weight, include:
, Normal C₁₁~ C₁₈Alkylbenzene sulfonates ("LAS") and primary
, Branched and random C_Ten~ C₂₀Alkylsulfate ("AS"), formula CH _Three (CH_Two)_x(CHOSO_Three ^-M⁺) CH_ThreeAnd CH_Three(CH_Two)_y(CH
OSO_Three ^-M⁺) CH_TwoCH_ThreeWherein x and (y + 1) are at least 7, preferably
Preferably, it is an integer of at least 9, and M is a water-soluble cation, especially sodium.
C)_Ten~ C₁₈Secondary (2,3) alkyl sulfate, unsaturated sulfate
For example, oleyl sulfate, C_Ten~ C₁₈Alkyl alkoxy sulfate
("AE_xS "; especially EO ethoxy sulfate in which x is up to 7), C_Ten~ C₁₈A
Alkyl alkoxycarboxylate (especially EO1-5 ethoxycarboxylate)
), C_10-18Glycerol ether, C_Ten~ C₁₈Alkyl polyglycosides and
Their corresponding sulfated polyglycosides, and C₁₂~ C₁₈α-sulfonated fatty acids
Esters are mentioned. If desired, conventional nonionic surfactants and amphoteric surfactants
Activator, for example C₁₂~ C₁₈Alkyl ethoxylates ("AE"), for example
So-called narrow peaked alkyl ethoxylates and C₆~ C₁₂Alkylpheno
Alkoxylates (especially ethoxylates and mixed ethoxy / propoxy)
, C₁₂~ C₁₈Betaine and sulfobetaine ("sultaine"), C_Ten~ C₁₈A
Min oxides, cationic surfactants and the like can also be included in the total composition. C_Ten~ C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used. A typical example is
, C₁₂~ C₁₈N-methylglucamide is exemplified. WO 9,206,154
See specification. Other sugar-derived surfactants include C_Ten~ C₁₈N- (3-methoxyp
N-alkoxy polyhydroxy fatty acid amides such as ropyl) glucamide and the like.
It is. N-propyl C₁₂~ C₁₈Glucamide to N-hexyl C₁₂~ C₁₈Glukami
Until the foam can be used for low foaming. Normal C_Ten~ C₂₀You can use soap
No. If high foaming is desired, the branched C_Ten~ C₁₆Soap may be used. Shadow
Mixtures of surfactants and nonionic surfactants are particularly useful. Other normal
Useful surfactants are described in standard texts.

Builder Detergency A builder may optionally be incorporated into the present compositions to help control mineral hardness. Inorganic and organic builders can be used. Builders are typically used in fabric laundry compositions to help remove particulate soil.

The amount of the builder can vary widely depending on the end use of the composition and the desired physical form. When present, the composition will typically contain at least 1%, preferably 1% to 80%, of the builder. Liquid formulations are typically detergent builders 5
-50% by weight, more typically 5-30% by weight. Granular formulations typically comprise 1 to 80% by weight of detersive builder, more typically 5 to 50% by weight. However, lower or higher amounts of builders are not meant to be excluded.

Inorganic or P-containing detersive builders include, but are not limited to, polyphosphoric acid (exemplified by tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphate), phosphonic acid, phytic acid, silicic acid, carbonic acid (bicarbonate). (Including carbonic acid and sesquicarbonate), sulfuric acid, and alkali metal, ammonium and alkanolammonium salts of aluminosilicate. However, non-phosphate builders are needed in some places. Importantly, the present compositions surprisingly survive in the presence of so-called "weak" builders (compared to phosphates) such as citrate or in the case of zeolites or layered silicate builders. Works well even under "builder shortage" situations.

Examples of silicate builders are alkali metal silicates, especially SiO ₂ : Na ₂ O
Those having a ratio of 1.0: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in US Pat. No. 4,664,839. Na
SKS-6 is a trademark of a crystalline layered silicate marketed by Hoechst (usually abbreviated here as "SKS-6"). Unlike zeolite builder, Na
SKS-6 silicate builder does not contain aluminum. NaSKS-6
Has the form of a layered silicate, δ-Na ₂ SiO ₅ . It can be prepared by methods such as those described in DE-A 3,417,649 and DE-A 3,742,043. SKS-6 is a highly preferred layered silicate for use herein, other such layered silicates, e.g., in the general formula _{NaMSi x O 2x + 1 · yH} 2 O ( wherein, M is sodium or X is a number from 1.9 to 4, preferably 2, and y is 0 to 20, preferably 0
) Can be used here. Various other layered silicates from Hoechst include NaSKS-5, NaSKS as α, β and γ forms
-7 and NaSKS-11. As noted above, δ-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. Other silicates,
For example, magnesium silicates may also be useful, and can serve as a crispness agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component of a foam control system.

Examples of carbonate builders are alkaline earth metal and alkali metal carbonates as disclosed in DE 2,321,001.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions and can also be a significant builder component in liquid detergent formulations.
As an aluminosilicate builder, the empirical formula M _{z / n} [(AlO ₂ ) _z (SiO ₂ ) _y ] · xH ₂ O (where z and y are usually at least integers of 6 and the molar ratio of z to y Is 1.0
And x is an integer from 0 to 264, and M is
And those having a Group A or Group IIA element, such as Na, K, Mg, and Ca.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived. The preparation of the aluminosilicate ion exchange material is disclosed in U.S. Pat. No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O, where x is 20-30, especially 27. Have. This material is known as zeolite A. Dehydrated zeolite (x =
0 to 10) may also be used here. Preferably, the aluminosilicate has a particle size of from 0.1 to 10 μm in diameter.

Suitable organic detersive builders for the purposes of the present invention include, without limitation, various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having multiple carboxylate groups, preferably at least three carboxylate groups. The polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When using in salt form,
Alkali metal salts such as sodium, potassium, lithium salts, or alkanolammonium salts are preferred.

Polycarboxylate builders include various categories of useful agents. One important category of polycarboxylate builders include oxydisuccinates as disclosed in Berg U.S. Pat. Nos. 3,128,287 and 3,635,830. And ether polycarboxylates. See also the "TMS / TDS" builder in U.S. Pat. No. 4,663,071. Suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds, for example, US Pat. No. 3,923,679 and 3,832.
Nos. 5,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful detergency builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether,
Various alkali metal salts, ammonium salts and substituted ammonium salts of 3,5-trihydroxybenzene-2,4,6-trisulfonic acid and polyacetic acids such as carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, and nitrilotriacetic acid; And melitic acid, pyromellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid,
Polycarboxylates such as benzene-1,3,5-tricarboxylic acid and carboxymethyloxysuccinic acid, and soluble salts thereof are also included.

Citric acid-based builders, such as citric acid and its soluble salts, especially the sodium salt, have particular importance in heavy-duty liquid detergent formulations due to availability from renewable sources and biodegradability. It is a polycarboxylate builder.
Citrate can also be used in particulate compositions, especially in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

The 3,3-dicarboxy-4-oxa-1,6-hexanediate and related compounds disclosed in US Pat. No. 4,566,984 are suitable for the detergent composition of the present invention. It is. Useful succinic acid builders include C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-succinic acid
Dodecenyl (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is a preferred builder of this group, EP 0,200,263.
It is described in the specification.

Other suitable polycarboxylates are disclosed in US Pat. No. 4,144,226 and US Pat. No. 3,308,067. US Patent No. 3
723, 322.

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids, such as oleic acid and / or its salts, may also be incorporated in the compositions, alone or in combination with the abovementioned builders, especially citrate and / or succinate builders. To provide additional builder activity. Such use of fatty acids will generally result in reduced foaming which should be considered by the formulator.

In situations where phosphorus-based builders can be used, and especially in the formulation of solids used in hand-washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate, sodium orthophosphate, etc. Salts can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, US Pat.
No. 581, No. 3,213,030, No. 3,422,021, No. 3,400,148 and No. 3,422,137)
Can also be used.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The detergent compositions of the present invention optionally comprise a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleaching activators. Is also good. When present, the bleach will typically be in an amount of 1% to 30%, more typically 5% to 20% of the detergent composition, especially for fabric laundering. If present, the amount of bleach activator typically ranges from 0.1% to 60%, more typically from 0.5% to 60% of the bleaching composition comprising the bleach and the bleach activator. Will be 40%.

The bleaches used herein can be any bleaches useful in detergent compositions for fabric cleaning or other cleaning purposes now known or known. These include oxygen bleaches as well as other bleaches.
Perborate bleaches, such as sodium perborate (eg, monohydrate or 4
Hydrate) can be used here.

Another category of bleaches that can be used without limitation include percarboxylic acid bleaches and their salts. Preferred examples of this type of bleach are magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid,
Nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid are included. Such bleaching agents are disclosed in U.S. Patent No. 4,483,781, U.S. Patent Application No. 740,446, EP 0,133,354, and U.S. Patent No. 4,412,934. In the specification. Highly preferred bleaches also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551.

[0205] Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium hydrogen carbonate peroxide and equivalent "percarbonate" bleaches, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide. Persulfate bleach (eg, OXONE, commercially produced by DuPont) can also be used.

Preferred percarbonate bleaches are from dry particles having an average particle size of from 500 μm to 1,000 μm (less than 10% by weight of the particles are smaller than 200 μm and less than 10% by weight of the particles are larger than 1,250 μm). Become. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactant.
Percarbonates are available from various commercial sources such as FMC, Solvay, Tokai Denka.

[0207] Mixtures of bleaches can also be used.

The peroxygen bleaches, perborates, percarbonates and the like are preferably combined with a bleach activator, which means that the in-situ production in an aqueous solution of the peroxyacid corresponding to the bleach activator (ie the washing process) Time) bring. Various non-limiting examples of activators are described in U.S. Pat. No. 4,915,854 and U.S. Pat.
No. 934. Nonanoyloxybenzenesulfonate (N
OBS), 3,5,5-trimethylhexanoyloxybenzenesulfonate (
ISONOBS), and tetraacetylethylenediamine (TAED) activators are typical and mixtures thereof can also be used. See also U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amide-derived bleach activators are of the formula R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O Wherein L ¹ is an alkyl group having 6 to 12 carbon atoms, R ² is alkylene having 1 to 6 carbon atoms, and R ⁵ is H or alkyl, aryl or alkaryl having 1 to 10 carbon atoms. And L is a suitable leaving group). A leaving group is a group that is displaced from a bleach activator as a result of nucleophilic attack on the bleach activator by a perhydrolytic anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include US Pat. No. 4,634,551.
-(6-Octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzene as described in US Pat. Sulfonates, and mixtures thereof.

Another type of bleach activator comprises a benzoxazine-type activator as disclosed in Hodge et al., US Pat. No. 4,966,723. Highly preferred activators of the benzoxazine type have the formula

Embedded image belongs to.

Yet another class of preferred bleach activators includes acyl lactam activators, especially those of the formula

Embedded image Wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group having 1 to 12 carbon atoms, and acylcaprolactam and acylvalerolactam. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam,
Benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5
5-trimethylhexanoylvalerolactam and mixtures thereof. U.S. Pat. No. 4,545,784 issued Oct. 8, 1985 to Sanderson which discloses acylcaprolactams, including benzoylcaprolactam adsorbed on sodium perborate, incorporated herein by reference. See also.

Bleaches other than oxygen-based bleaches are known in the art and can be used herein. One type of non-oxygen bleach of particular interest includes light activated bleach, such as sulfonated zinc phthalocyanine and / or aluminum phthalocyanine. See U.S. Pat. No. 4,033,718. If used, detergent compositions typically include such bleaching agents, especially sulfonated zinc phthalocyanines.
. It will contain 025-1.25% by weight.

If desired, the bleaching compound can be catalyzed by a manganese compound. Such compounds are well known in the art and are described, for example, in US Pat. No. 5,246,621, US Pat. No. 5,244,594, US Pat. No. 5,194,416, U.S. Pat. No. 5,114,606 and EP 549,271A.
No. 1, 549,272 A1, 544, 440 A2 and 544, 490 A1. Preferred examples of these catalysts include Mn ^IV ₂ (u—O) ₃ (1,4,
7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^{II I} ₂ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4 , _{7-triazacyclononane) 2 - (ClO 4) 2} , Mn IV 4 (u-O) 6 (1,4,7
- _{triazacyclononane) 4 (ClO 4) 4,} Mn III Mn IV 4 (u-O) 1 (
u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-tria _{Zashikurononan) - (OCH 3) 3 (} PF 6), and mixtures thereof. Other metal-based bleach catalysts include U.S. Pat. No. 4,430,243.
And US Pat. No. 5,114,611. The use of manganese in combination with various complexing ligands to enhance bleaching has also been reported in the following U.S. Patents: 4,728,455, 5,284,944,5. , 246,612, 5,256,779, 5
, 280,117, 5,274,147, 5,153,1
No. 61, and No. 5,227,084.

In practice, and without limitation, the compositions and methods of the present invention can be adjusted to provide at least one part per ten million active bleaching catalyst species in an aqueous wash liquor, and preferably the catalyst species in a wash liquor. It will provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm.

Other preferred optional ingredients include enzyme stabilizers, polymeric anti-fouling agents, substances useful in inhibiting the transfer of dye from one fabric to another during the cleaning process (
Dye transfer inhibitors), polymeric dispersants, foam inhibitors, optical brighteners or other brighteners or whitening agents, chelating agents, fabric softening clays, antistatic agents, other active ingredients, carriers , Hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for solid compositions.

The liquid detergent compositions can contain water and other solvents as carriers. methanol,
Low molecular weight primary or secondary alcohols exemplified by ethanol, propanol, and isopropanol are preferred. Monohydric alcohols are preferred for solubilizing surfactants, but polyols, such as those containing 2-6 carbon atoms and 2-6 hydroxy groups (e.g., 1,3-propanediol,
Ethylene glycol, glycerin, and 1,2-propanediol) can also be used. The composition may contain from 5% to 90% of such carriers, typically from 10% to 50%.

The granular detergent may be, for example, spray-dried base granules (final product density 520 g).
Per liter) by agglomeration (final product density greater than 600 g / liter). The remaining dry components can then be mixed with the base granules in particulate or powder form, for example, in a rotating mixing drum, and the liquid components (eg, nonionic surfactants and fragrances) can be sprayed on.

The detergent composition of the present invention will preferably be formulated such that when used in an aqueous cleaning operation, the wash water has a pH of 6.5 to 11, preferably 7.5 to 10.5. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended use levels include the use of buffers, alkalis, acids, and the like, and are well known to those skilled in the art.

Uses There is also provided herein a method for providing delayed release of active alcohols, characterized by contacting the surface to be treated with an aqueous medium containing a substance, preferably a compound or composition of the present invention. .

"Surface" means any surface to which a compound can be attached. Typical examples of such materials are fabrics, hard surfaces, such as tableware, floors, bathrooms, toilets,
Kitchen and other surfaces requiring delayed release of active alcohol, such as litter
er).

“Delayed release” means the release of an active ingredient (eg, perfume) over a longer period of time than use of the active ingredient (eg, perfume) itself.

In the composition examples, the abbreviations for component identification have the following meanings. In the abbreviation detergent compositions used in the examples , the abbreviation component identification has the following meaning.

DEQA: di- (tallowyl-oxy-ethyl) dimethylammonium chloride
Lido DTDMAC: Ditallow dimethyl ammonium chloride Fatty acid: Stearic acid with IV = 0 Electrolyte: Calcium chloride PEG: Polyethylene glycol 4000 Carezyme: Cellulos marketed by Novo Industries A / S
Enzyme LAS: linear C_11-13Sodium alkylbenzene sulfonate TAS: Tallow sodium alkyl sulfate CxyAS: C_1x~ C_1ySodium alkyl sulfate C46SAS: C₁₄~ C₁₆Sodium secondary (2,3) alkyl sulfate CxyEzS: C condensed with z moles of ethylene oxide_1x~ C_1yAlkyl sulfur
Sodium acid CxyEz: C condensed with an average z mole of ethylene oxide_1x~ C_1ymainly
Linear primary alcohol QAS: R_Two・ N⁺(CH_Three)_Two(C_TwoH_FourOH) (wherein R_Two= C₁₂~ C ₁₄ ) QAS1: R_Two・ N⁺(CH_Three)_Two(C_TwoH_FourOH) (wherein R_Two= C₈~
C₁₁APA: C₈~ C_TenAmidopropyl dimethylamine soap: A linear amide derived from an 80/20 mixture of tallow fatty acid and coconut oil fatty acid.
Sodium alkylcarboxylate STS: Sodium toluenesulfonate CFAA: C₁₂~ C₁₄(Coco) alkyl N-methylglucamide TFAA: C₁₆~ C₁₈Alkyl N-methylglucamide TPKFA: C₁₂~ C₁₄Topped all cut fatty acids STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: Formula Na having a primary particle size of 0.1 to 10 μm₁₂(AlO_TwoSi
O_Two)₁₂・ 27H_TwoO hydrated sodium aluminosilicate (weight expressed on an anhydrous basis
) NaSKS-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate of citric acid: anhydrous citric acid borate: sodium borate carbonate: anhydrous sodium carbonate having a particle size of 200 μm to 900 μm: anhydrous bicarbonate having a particle size distribution of 400 μm to 1200 μm
Sodium silicate: amorphous sodium silicate (SiO_Two: Na_TwoO = 2.0: 1) Sulfate: anhydrous sodium sulfate Mg sulfate: anhydrous magnesium sulfate citrate: 86.4% active having a particle size distribution of 425 μm to 850 μm
Trisodium citrate dihydrate MA / AA: maleic acid / acrylic acid 1: 4 copolymer, average molecular weight about 70
000 MA / AA (1): maleic acid / acrylic acid 4: 6 copolymer, average molecular weight
About 10,000 AA: sodium polyacrylate polymer having an average molecular weight of 4,500 CMC: sodium carboxymethylcellulose cellulose ether: methyl having a degree of polymerization of 650 available from Shin-Etsu Chemical
Cellulose ether protease: Trade name Savinase by Novo Industries A / S
Proteolytic enzyme with 3.3% by weight of active enzyme sold Protease 1: WO sold by Genencol Int Inc.
A protein having 4% by weight of active enzyme as described in WO 95/10591
Degradative enzyme Alcalase: an activity sold by Novo Industries A / S
Proteolytic enzyme with 5.3% enzyme by weight Cellulase: marketed by Novo Industries A / S under the trade name Carezyme
Cellulolytic enzyme amylase with 0.23% by weight of active enzyme sold: Termamyl 12 by Novo Industries A / S
Starch degrading enzyme with 1.6% by weight of active enzyme sold under 0T Lipase: sold under the trade name Lipolase by Novo Industries A / S
Lipolytic enzyme with 2.0% by weight active enzyme Lipase 1: trade name Lipolase® by Novo Industries A / S
Lipolytic enzyme with 2.0% by weight of active enzyme sold by Rutra Endase: activity sold by Novo Industries A / S
Endoglunase enzyme with 1.5% enzyme by weight PB4: Nominal formula NaBO_Two・ 3H_TwoOH_TwoO_TwoSodium perborate 4
Hydrate PB1: Nominal formula NaBO_Two・ H_TwoO_TwoOf anhydrous sodium perborate bleach percarbonate: nominal formula 2Na_TwoCO_Three・ 3H_TwoO_TwoSodium percarbonate
NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt NAC-OBS: (6-Nonamimidocaproyl) oxybenzenesulfone
TAED: tetraacetylethylenediamine DTPA: diethylenetriaminepentaacetic acid DTPMP: marketed by Monsanto under the trade name Quest 2060
Diethylenetriaminepenta (methylenephosphonate) EDDS: ethylenediamine-N, N'-disuccinic acid in the form of its sodium salt
(S, S) isomer Photoactivated bleach (1): sulfon encapsulated in dextrin-soluble polymer
Zinc phthalocyanine photoactivated bleach (2): sulfon encapsulated in dextrin-soluble polymer
Halogenated aluminophthalocyanine Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4,4'-bis (2-anilino-6-morpholino-1,3,5-
Triazin-2-yl) amino) stilbene-2: 2'-disulfonic acid dinatri
HEDP: PEG 1,1-hydroxyethanediphosphonic acid_xA polyethylene glyco having a molecular weight x (typically 4,000)
PEO: polyethylene oxide having an average molecular weight of 50,000 TEMPAE: tetraethylenepentamine ethoxylate PVI: polyvinylimidazole having an average molecular weight of 20,000 PVP: polyvinylpyrrolidone polymer having an average molecular weight of 60,000 PVNO: average molecular weight of 50 Polyvinylpyridine N-oxy having 2,000
Polymer PVPVI: Polyvinylpyrrolidone having an average molecular weight of 20,000 and vinyl
Copolymer with Luimidazole QEA: bis ((C_TwoH_FiveO) (C_TwoH_FourO)_n) (CH_Three) -N⁺-C₆ H₁₂-N⁺− (CH_Three) Screw ((C_TwoH_FiveO)-(C_TwoH_FourO))_n(Where n is
20 to 30) SRP1: Anion end-capped polyester SRP2: Diethoxylated poly (1,2-propylene terephthalate) short blow
Polymer PEI: average molecular weight of 1800 and 7 ethyleneoxy residues per nitrogen
Polyethyleneimine with average degree of ethoxylation Silicone defoamer: having a foam control to dispersant ratio of 10: 1 to 100: 1
Polydimethylsiloxane with siloxane-oxyalkylene copolymer as dispersant
Sun Antifoam Emulsifier: Sold under the trade name Lytron 621 by BASF Corporation
-Based water-based monostyrene latex mixtures wax: paraffin wax

The following are synthetic examples of the compounds according to the present invention. I- methyl methoxyacetate and synthetic phenylethyl alcohol main butoxy phenylacetate by transesterification of phenylethyl alcohol (31.6 ml, 0.264 mol, 1.1 eq) methyl methoxyacetate the in toluene (100 ml) ( 25 g, 0.24 mol, 1 equivalent)
And sodium methoxide (1.62 g, 30 mmol, 0.125 eq). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) is added, the mixture is filtered (filter paper 40), stored at -18 DEG C. for 16 hours, and then filtered again (filter paper 42) to recover all the catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil, which is distilled under 3 mm Hg to produce two fractions of a colorless oil.

Fraction 2: 11.5 g, characterized by ¹ H NMR as 60 mol% phenylethyl methoxyacetate and 40 mol% phenylethyl alcohol
(Boiling point 90-110 ° C under 3 mmHg).

Fraction 3: 12.95 g (bp 110 ° C. under 3 mm Hg) characterized as pure phenylethyl methoxyacetate by ¹ H NMR. Synthesis of Losalva Dimethoxyacetate by Transesterification of Methyl II-Dimethoxyacetate with Losalva (9-decene-1-ol)
Mix) with methyl dimethoxyacetate (25 g, 0.187 mol, 1 equiv.) and sodium methoxide (1.26 g, 23.3 mmol, 0.125 equiv.) The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (filter paper 40).
, Stored at -18 ° C for 16 hours, then filtered again (filter paper 42) to recover all catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil,
The crude oil was distilled under 3 mmHg to give a colorless oil (3 mm) characterized by ¹ H NMR as 90 mol% of Losalva dimethoxyacetate and 10 mol% of Losalva.
(Boiling point 130-150 ° C. under Hg) 26.8 g are produced.

III- Synthesis of Geranyl Dimethoxyacetate by Transesterification of Methyl Dimethoxyacetate and Geraniol Geraniol (31.73 g, 0.206 mol, 1.1 equivalents) was added to toluene (1
(25 ml, 0.187 mol, 1 eq.) And sodium methoxide (1.26 g, 23.3 mmol, 0.125 eq.). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over the course of one hour. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (filter paper 4).
0), store at -18 ° C for 16 hours, then filter again (filter paper 42) to recover all catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil, which is distilled under 3 mm Hg. The two fractions of the recovered colorless oil are as follows.

Fraction 2: 6.90 g (boiling point 120-130 ° C. under 3 mm Hg) characterized by 90 mol% of geranyl dimethoxyacetate and 10 mol% of geraniol by ¹ H NMR.

Fraction 3: 34.26 g (bp 130-134 ° C. under 3 mm Hg) characterized as pure geranyl dimethoxyacetate by ¹ H NMR.

IV— Synthesis of Phenylethyl Dimethoxyacetate by Transesterification of Methyl Dimethoxyacetate with Phenylethyl Alcohol Phenylethyl alcohol (25.1 g, 0.206 mol, 1.1 equiv) was treated with dimethoxyacetic acid in toluene (100 ml). Methyl (25 g, 0.187 mol, 1 equivalent) and sodium methoxide (1.26 g, 23.3 mmol, 0.125
(Equivalent). The mixture is (10%) under reduced pressure such that most of the toluene and methanol produced by transesterification are slowly distilled off over the course of 1 hour.
mmHg) Increase the temperature. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (filter paper 40), stored at -18 ° C for 16 hours, and then filtered again (filter paper 42).
), Recover all catalyst. The clear filtrate is then concentrated on a rotary evaporator,
A crude oil is formed, which is distilled under 3 mm Hg to give a colorless oil (bp 155 at 3 mm Hg 155) characterized by ¹ H NMR as 90 mol% phenylethyl dimethoxyacetate and 10 mol% phenyl alcohol. -160 ° C) to produce 28.31 g.

[0232] V- synthetic undecapeptide bell Torr dimethoxyethane carboxymethyl acid Undekaberuchiru by transesterification of dimethoxy methyl acetate and undecalactone bell Torr (35 g, 0.206 mol, 1.1 equiv) in toluene (1
(25 ml, 0.187 mol, 1 eq.) And sodium methoxide (1.26 g, 23.3 mmol, 0.125 eq.). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 3 hours. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (filter paper 4).
0), store at -18 ° C for 16 hours, then filter again (filter paper 42) to recover all catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil, which is distilled under 3 mmHg to give a colorless, characterized by ¹ H NMR as pure undecavertyl dimethoxyacetate. Oil (boiling point under 3mmHg 12
25.6 g).

[0233] VI- dimethoxy methyl acetate and synthetic dihydromyrcenol of dimethyl butoxy acetate dihydro myrcenyl by transesterification of dihydromyrcenol (32.2 g, 0.206 mol, 1.1 equiv) in toluene (100ml ) In methyl dimethoxyacetate (25 g, 0.187 mol, 1 eq)
And sodium methoxide (1.26 g, 23.3 mmol, 0.125 eq). The mixture was reduced under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by the transesterification were
) Raise the temperature. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (
Filter paper 40), stored at −18 ° C. for 16 hours, then filtered again (filter paper 42),
Recover all catalyst. The clear filtrate was then concentrated on a rotary evaporator to produce a crude oil, which was analyzed by ¹ H NMR to convert 70 mol% of the starting methyl dimethoxyacetate to dihydromyrcenyl dimethoxyacetate. Indicates that you have done. The crude oil was fractionated under 3 mm Hg and a colorless oil characterized by ¹ H NMR as pure dihydromyrcenyl dimethoxyacetate (bp 107 ° C. under 3 mm Hg)
) Produce 20.97 g.

[0234] VII - Synthesis of dimethoxy acetic acid linalyl by transesterification of methyl dimethoxy acetate and Linalool Linalool (31.78 g, 0.206 mol, 1.1 equiv) in toluene (10
0 ml) with methyl dimethoxyacetate (25 g, 0.187 mol, 1 eq) and sodium methoxide (1.26 g, 23.3 mmol, 0.125 eq). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) was added and the mixture was filtered (filter paper 40).
), Store at -18 ° C for 16 hours, then filter again (filter paper 42) to recover all catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil, which is fractionated under 3 mm Hg to give a colorless oil characterized by ¹ H NMR as pure linalyl dimethoxyacetate ( (Boiling point 106 ° C. under 3 mmHg) 9.8
Generate g.

[0235] VIII- diethoxy ethyl acetate and synthetic phenylethyl alcohol by that diethoxy phenyl acetate ethyl ester exchange with phenylethyl alcohol (25.1 g, 0.206 mol, 1.1 eq.) In toluene (100ml) Ethyl diethoxyacetate (32.95 g, 0.187 mol, 1 eq) and sodium methoxide (1.26 g, 23.3 mmol, 0.1 g).
125 equivalents). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) is added, the mixture is filtered (filter paper 40), stored at -18 DEG C. for 16 hours, and then filtered again (filter paper 42) to recover all the catalyst. The clear filtrate is then concentrated on a rotary evaporator to produce a crude oil, which is fractionated under 3 mm Hg to give a colorless oil characterized by ¹ H NMR as pure phenylethyl diethoxyacetate. 27.60 g (boiling point 126-130 ° C. under 3 mm Hg) are produced.

[0236] the IX-2-hydroxy-2-methoxyacetic acid methyl ester interchange and acetals 2-hydroxy-2-methoxy acetate off Eniruechiru and 2-hydroxy-2-phenylethoxy phenylacetate by exchange with phenylethyl alcohol Synthesis of the mixture Phenylethyl alcohol (22.83 g, 0.1 mol, 1 eq) in toluene (125 ml) was treated with methyl 2-hydroxy-2-methoxyacetate (22.46 g, 0
. 187 mol, 1 eq) and sodium methoxide (0.38 g, 7 mmol, 0.0375 eq). The mixture is heated under reduced pressure (10 mmHg) such that most of the toluene and methanol produced by transesterification and acetal exchange are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) is added and the mixture is filtered (filter paper 42) to recover all the catalyst. The clear filtrate was then concentrated on a rotary evaporator and 2-H by ¹ H NMR.
Methyl hydroxy-2-phenylethoxyacetate 45 mol%, 2-hydroxy-2
Produces a crude oil characterized as 35 mol% phenylethyl phenylethoxyacetate and 20 mol% phenylethyl alcohol.

[0237] Synthesis geraniol X-2-hydroxy-2-methyl methoxyacetate and 2-hydroxy-2-geranyloxy methyl acetate by acetal exchange with geraniol (35 ml, 0.2 mol, 1 eq) in toluene (150ml 2) in
Mix with methyl hydroxy-2-methoxyacetate (24 g, 0.2 mol, 1 eq) and sodium methoxide (0.38 g, 7 mmol, 0.0375 eq). The mixture is heated under reduced pressure (10 mmHg) such that most of the toluene and methanol produced by acetal exchange are slowly distilled off over 3 hours. After cooling, diethyl ether (200 ml) was added and the mixture was filtered (filter paper 4).
2) recover the catalyst. The clear filtrate was then concentrated on a rotary evaporator to give ¹ H
This produces an oil characterized by NMR as 85 mol% methyl 2-hydroxy-2-geranyloxyacetate and 15 mol% geraniol.

XI Synthesis of Geranyl 2-Hydroxy-2-geranyloxyacetate by Transesterification of Methyl 2-Hydroxy-2-methoxyacetate with Geraniol and Acetal Exchange Geraniol (35 ml, 0.2 mol, 2 equiv.) 2 in (125 ml)
-Mix with methyl hydroxy-2-methoxyacetate (12 g, 0.1 mol, 1 equiv) and sodium methoxide (0.75 g, 14 mmol, 0.14 equiv). The mixture was reduced under reduced pressure so that most of the toluene and methanol produced by transesterification and acetal exchange were slowly distilled off over 2 hours.
10mmHg) Raise the temperature. After cooling, diethyl ether (200 ml) is added and the mixture is filtered twice (filter paper 42) to recover all the catalyst. The clear filtrate was then concentrated on a rotary evaporator to give a crude brown oil (35 g) characterized by ¹ H NMR as 75 mol% methyl 2-hydroxy-2-geranyloxyacetate and 25 mol% geraniol. Generate

XII -Synthesis of methyl 2-hydroxy-2-losalbaoxyacetate by acetal exchange of methyl 2-hydroxy-2-methoxyacetate with Losalva (9- decene-1-ol) in the absence of a catalyst . (0 ml, 0.18 mol, 1 eq) are mixed with methyl 2-hydroxy-2-methoxyacetate (24 g, 0.2 mol, 1 eq) in toluene (100 ml). The mixture is stirred at room temperature under reduced pressure (10 mmHg) for 1 hour before applying gentle heat so that most of the toluene and methanol produced by acetal exchange are slowly distilled off over 2 hours. After complete evaporation of the residual toluene concentrated on a rotary evaporator, the clear oil obtained is characterized by ¹ H NMR and ¹³ C NMR.
Is characterized by 80 mol% methyl 2-hydroxy-2-rosavaoxyacetate and 20 mol% losalva. No starting methyl 2-hydroxy-2-methoxyacetate remains.

[0240] XIII- of using an acid catalyst 2-hydroxy-2-methyl methoxyacetate and Rosaruba (9-decenoic 1-ol) Synthesis of 2-hydroxy-2-b Sarubaokishi methyl acetate by acetal exchange with Rosaruba (37.0 ml, 0.18 mol, 1 equiv.) In toluene (100 ml) and 6 drops of 1N hydrochloric acid in methyl 2-hydroxy-2-methoxyacetate (24 g, 0.2 g).
Mol, 1 equivalent). The mixture is stirred at room temperature under reduced pressure (10 mmHg) for 1 hour before applying gentle heat so that most of the toluene and methanol produced by acetal exchange are slowly distilled off over 2 hours. After complete evaporation of the residual toluene concentrated on a rotary evaporator, the clear oil obtained is ¹ H NMR
And ¹³ C NMR revealed methyl 2-hydroxy-2-rosavaoxyacetate 85.
Mol% and 15 mol% of Losalva. No starting methyl 2-hydroxy-2-methoxyacetate remains.

[0241]XIV-2-Hydroxy-2-methoxide using sodium methoxide as catalyst Acetal exchange between methyl xyacetate and Losalva (9-decene-1-ol) Of methyl 2-hydroxy-2-losalvaoxyacetate Losalva (33.3 ml, 0.18 mol, 0.9 equiv.) In toluene (150 ml)
In methyl 2-hydroxy-2-methoxyacetate (24 g, 0.2 mol, 1 equivalent)
And sodium methoxide (0.38 g, 7 mmol, 0.0375 equivalents)
Mix. The mixture is made by most toluene and acetal exchange
Under reduced pressure (10 mmHg) so that the methanol
Raise the temperature. After cooling, diethyl ether (200 ml) was added and the mixture was filtered (
Filter paper 42) and recover the catalyst. The clear filtrate is then concentrated on a rotary evaporator, ¹ 95 mol of methyl 2-hydroxy-2-losalvaoxyacetate by 1 H NMR
% And 5 mol% of Losalva.

[0242] XV-2-hydroxy-2-methyl methoxyacetate and synthetic undecapeptide bell Torr 2-hydroxy-2-undecalactone bell chill oxy acid methyl according acetals Lumpur exchange with undecalactone bell torr (42.5 ml, 0 .25 mol, 1 equivalent) in toluene (15
Methyl 2-hydroxy-2-methoxyacetate (30.03 g, 0.25
Mol, 1 equiv.) And sodium methoxide (0.5 g, 9.4 mmol, 0.1 mol.
0375 equiv.). The mixture is heated under reduced pressure (10 mmHg) such that most of the toluene and methanol produced by acetal exchange are slowly distilled off over 2 hours. After cooling, diethyl ether (200 ml) is added and the mixture is filtered (filter paper 42) to recover the catalyst. The clear filtrate is then concentrated on a rotary evaporator to give an oil characterized by ¹ H NMR as 50 mol% methyl 2-hydroxy-2-undecavertyloxyacetate and 50 mol% undecavertole. Generate.

XVI-2-Hydroxy-2 from methyl glyoxylate ( generated from methyl 2-hydroxy-2-methoxyacetate and phosphorus pentoxide) and undecavertol (4-methyl-3-decene-5 -ol) - undecalactone Bell chill oxymethyl of synthetic acetic acid 2-hydroxy-2-methyl methoxyacetate (120 g, 1 mole, 1 eq) Bigureukkusu (Vigreux) column, 3-neck round bottom flask 250ml equipped with a thermometer and a funnel Put in (all glassware has been pre-washed with dilute acid and dried). To this, under stirring, slowly add phosphorus pentoxide (71 g, 0.5 mol, 0.5 equiv) in three portions, taking care not to raise the temperature above 90 ° C. At the end of the addition, the mixture is stirred for 1 hour before applying heat and distilling the methyl glyoxylate under a nitrogen blanket. Methyl glyoxylate (boiling point 106-1
(07 ° C.) 67 g are recovered during the distillation. Some of this freshly distilled methyl glyoxylate (12 g, 0.136 mol, 1 equivalent) was added to undecavertole (25.5 g).
, 0.15 mol, 1.1 eq) and the mixture is left for 16 hours. The reaction is initially strongly exothermic. After standing for 16 hours, the crude oil is characterized by ¹ H NMR as 90 mol% methyl 2-hydroxy-2-undecavertyloxyacetate and 10 mol% undecavertole. Only traces of methyl glyoxylate remain.

XVII Synthesis of a Mixture of 2 - Hydroxy-2-Active Methyl Oxyacetate from a Blend of Methyl Glyoxylate and Four Perfume Alcohols The composition of the blend of four perfume alcohols is as follows: Janthol (2,2-dimethyl-3- (3-methylphenyl) -1-propanol): 62.5% by weight Losalva (9-decene-1-ol): 15% by weight L-isopulegol (L-1 methyl) -4-isopropenylcyclohexane-3
-Ol): 15% by weight Undecavertol (4-methyl-3-decene-5-ol): 7.5% by weight Some freshly distilled methyl glyoxylate (12 g, 0.136 mol, 1 equivalent) With the above blend of four perfume alcohols (25.5 g, 0.15 mol, 1.1
And the mixture is allowed to stand for 16 hours. The reaction is initially strongly exothermic. After standing for 16 hours, the crude oil is characterized by ¹ H NMR to contain only traces of the starting methyl glyoxylate. The 2-hydroxy-2-active methyl oxyacetate of each perfume alcohol was clearly detectable in the reaction mixture.

XVIII-Poly (methyl glyoxylate) of geraniol 1) Synthesis of poly (methyl glyoxylate) Freshly distilled methyl glyoxylate (10.2 g) in dichloromethane (5 ml)
, 0.116 mol) is added a freshly prepared solution of dimethyl sodimethylmalonate in THF (0.5 ml of a 0.05 mol / l solution). The mixture was stirred at 15 ° C. for 1 hour, then trifluoroacetic acid (0.18 ml, 2.3 mmol) was added followed by ethyl vinyl ether (3.5 ml, 36.6 mmol). The mixture is stirred at 15 ° C. for 18 hours, then sodium carbonate (0.5 g, 4.6 mmol, 2 equivalents compared to trifluoroacetic acid) is added. The mixture is stirred for 30 minutes before diluting with 30 ml of dichloromethane and washing with water (25 ml). Then the aqueous phase is extracted with dichloromethane (20 ml). The two organic phases are combined and dried over sodium sulfate. After filtration and concentration on a rotary evaporator, a colorless gum (11.2 g) is obtained. 2a) Transesterification of poly (methyl glyoxylate) with geraniol Poly (methyl glyoxylate) obtained in the previous example (11.2 g, 0.1 g of repeating unit).
128 mol) in toluene (150 ml). Then, Geranil (21.
After addition of 9 ml, 0.125 mol), sodium methoxide (0.75 g, 18
. 75 mmol, 0.15 eq.). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 3 hours. After complete removal of the toluene on a rotary evaporator, a dark brown oil (24.15 g) is obtained. 2b) Second further experiment of transesterification of poly (methyl glyoxylate) with geraniol Some poly (methyl glyoxylate) obtained as in Example XVIII (1) above (11.2 g, 0 repeating units) .128 mol) in toluene (150 ml). Geranyl (16 ml, 0.095 mol, about 0.7 eq) was then added followed by sodium methoxide (0.375 g, 9.4 mmol, 0.075 eq).
vs repeat units). The mixture was reduced under reduced pressure so that most of the toluene and methanol produced by transesterification were slowly distilled off over 2 hours.
10mmHg) Raise the temperature. After cooling, diethyl ether (100 ml) is added and the mixture is filtered (filter paper 42). The light brown clear filtrate is then concentrated on a rotary evaporator to produce a light brown oil (20.6 g).

XIX-Synthesis of copolymer of methyl glyoxylate and dodecanal Freshly distilled methyl glyoxylate (10.2) in dichloromethane (10 ml)
g, 0.116 mol) and dodecanal (10.67 g, 0.058 mol) in freshly prepared solution of dimethyl sodiomethylmalonate in THF (0.5 ml of 0.05 mol / l solution) Add. The mixture was stirred at 20 ° C. for 1 hour, then trifluoroacetic acid (0.18 ml, 2.3 mmol) was added followed by ethyl vinyl ether (3.5 ml, 36.6 mmol). The mixture is stirred at 20 ° C. for 18 hours, then sodium carbonate (0.5 g, 4.6 mmol, 2 equivalents compared to trifluoroacetic acid) is added. The mixture is stirred for 30 minutes before diluting with 30 ml of dichloromethane and washing with water (25 ml). The aqueous phase was then washed with dichloromethane (20 ml)
Extract with The two organic phases are combined and dried over sodium sulfate. After filtration and concentration on a rotary evaporator, a colorless gum (15.5 g) is obtained.

[0247] XX- methyl glyoxylate and dodecanal, copolymers and methyl glyoxylate as obtained as by S. Tel exchange in Synthesis Example XIX copolymers of glyoxylic acid geranyl and dodecanal and geraniol (15.5 g, 0.116 mol of methyl glyoxylate repeating unit) of toluene and dodecanal are dissolved in toluene (100 ml). Then, Geraniel (18.1 ml, 0
. After addition of 104 moles, about 0.9 equivalents compared to methyl glyoxylate repeating units), sodium methoxide (1.40 g, 0.026 mmol, 0.25 equivalents)
vs geraniol). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) is added and the mixture is filtered (filter paper 42). The brown filtrate is then concentrated on a rotary evaporator to produce a brown oil.

XXI Synthesis of copolymer of methyl glyoxylate and trans-4-decenal Methyl glyoxylate (30 g, freshly distilled) in dichloromethane (30 ml)
To a solution of 0.349 mol) and trans-4-decenal (2.63 g, 0.017 mol) was added boron trifluoride diethyl etherate (1 ml). The mixture is stirred at 0 ° C. for 1.5 hours before the addition of trifluoroacetic acid (1.08 ml, 14 mmol) / then dropwise addition of ethyl vinyl ether (10.5 ml) at 0 ° C. The mixture is stirred at 20 ° C. for 18 hours, then sodium carbonate (1.5 g, 14 mmol) is added. The mixture is stirred for 30 minutes before diluting with 30 ml of dichloromethane and washing with water (40 ml). The aqueous phase is then extracted with dichloromethane (30ml). The two organic phases are combined and dried over sodium sulfate. After filtration and concentration on a rotary evaporator, a dark brown gum (30 g) is obtained.

[0249] XXII- as in Synthesis Example XXI copolymers of glyoxylic acid, geranyl and trans-4-decenal by transesterification of the copolymer and Geranio Lumpur of methyl glyoxylate and trans-4-decenal Methyl glyoxylate and trans as obtained in
Copolymer with -4-decenal (30 g, methyl glyoxylate repeating unit 0.3
49 mol) in toluene (100 ml). Then, Geraniel (36.3)
ml, 0.21 mol, about 0.6 equivalents compared to methyl glyoxylate repeating units), followed by sodium methoxide (1.13 g, 0.021 mmol, 0.1 equivalents vs geraniol). The mixture is heated under reduced pressure (10 mmHg) so that most of the toluene and methanol produced by transesterification are slowly distilled off over 2 hours. After cooling, diethyl ether (100 ml) is added and the mixture is filtered (filter paper 42). The dark brown filtrate is then concentrated on a rotary evaporator to produce a dark brown oil (51 g).

[0250] XXIII - terpolymer synthesis dichloromethane (30ml) freshly distilled methyl glyoxylate in the methyl glyoxylate and trans-4-decenal and benzaldehyde (30 g,
0.349 mol), a solution of trans-4-decenal (2.63 g, 0.017 mol) and benzaldehyde (0.19 g, 1.75 mmol) at 0 ° C. were mixed with a boron trifluoride diethyl etherate compound (1 ml). ). Trifluoroacetic acid (1.0
8 ml, 14 mmol) followed by ethyl vinyl ether (10.
The mixture is stirred for 1.5 hours at 0 ° C. before the dropwise addition of 5 ml). Sodium carbonate (3g
, 28 mmol) was added and the mixture was stirred at 0 ° C. for 30 min.
Stir at 18 ° C. for 18 hours. The mixture is stirred for 30 minutes before diluting with 30 ml of dichloromethane and washing with water (30 ml). The aqueous phase is then extracted with dichloromethane (30ml). The two organic phases are combined and dried over sodium sulfate. After filtration and concentration on a rotary evaporator, a brown gum (27 g) is obtained.

[0251] XXIV- third methyl glyoxylate and trans-4-decenal and Guriokishi Le acid geranyl and trans-4-decenal and benzaldehyde by transesterification of terpolymer and geraniol and benz aldehyde of Example XXIII Synthesis of the Copolymer Methyl glyoxylate obtained as in Example XXIII above and trans-4
Dissolve the terpolymer of desenal and benzaldehyde (25 g, about 0.28 mol of methyl glyoxylate repeating units) in toluene (100 ml). Geranyl (29.6 ml, 0.17 mol, about 0.6 equivalents compared to methyl glyoxylate repeating units) was then added followed by sodium methoxide (0.92 g, 0.017 mol).
Mmol, 0.1 equivalent vs geraniol). The mixture is heated under reduced pressure so that most of the toluene and methanol produced by transesterification are slowly distilled off at 65 ° C. over 2 hours. After cooling, diethyl ether (100
ml) and the mixture is filtered (filter paper 42). The dark brown filtrate is then concentrated on a rotary evaporator to produce a dark brown oil (47 g).

In the following formulation examples, all amounts are quoted as weight percent of the composition, unless otherwise specified.

[0253]

EXAMPLES Example 1 The following high-density granular laundry detergent compositions A to F according to the present invention were prepared.

ABCDEF LAS 8.0 8.0 8.0 2.0 6.0 6.0 TAS-0.5-0.5 1.0 0.1 C46 (S) AS 2.0 2.5----C25AS---7.0 4.5 5.5 C68AS 2.0 5.0 7.0---C25E5- -3.4 10.0 4.6 4.6 C25E7 3.4 3.4 1.0---C25E3S---2.0 5.0 4.5 QAS-0.8----QAS (I)---0.8 0.5 1.0 Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid---2.5 -2.5 carbonate 13.0 13.0 27.0 10.0 10.0 13.0 SKS-6---10.0-10.0 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Site rate-1.0-3.0--Sulfate 26.1 26.1 26.1 6.0--Mg sulfate 0.3--0.2-0.2 MA / AA 0.3 0.3 0.3 4.0 1.0 1.0 CMC 0.2 0.2 0.2 0.2 0.4 0.4 PB4 9.0 9.0 5.0---Percarbonate----18.0 18.0 TAED 1.5 0.4 1.5-3.9 4.2 NAC-OBS-2.0 1.0---DTPMP 0.25 0.25 0.25 0.25 --SRP1---0.2-0.2 EDDS-0.25 0.4-0.5 0.5 CFA A-1.0-2.0--HEDP 0.3 0.3 0.3 0.3 0.4 0.4 QEA---0.2-0.5 Protease I--0.26 1.0--Protease 0.26 0.26--1.5 1.0 Cellulase 0.3--0.3 0.3 0.3 Amylase 0.1 0.1 0.1 0.4 0.5 0.5 Lipase (1) 0.3--0.5 0.5 0.5 Photoactivated bleach (ppm) 15ppm 15ppm 15ppm-20ppm 20ppm PVNO / PVPVI---0.1--Brightener 1 0.09 0.09 0.09-0.09 0.09 Fragrance 0.3 0.3 0.3 0.4 0.4 0.4 Glyoxylic acid ( ^* ) 0.3 0.3 0.3 0.4 0.4 0.4 Silicone antifoam 0.5 0.5 0.5-0.3 0.3 Miscellaneous / trace components Remainder (assuming 100%) Density (g / liter) 850 850 850 850 850 850 850 ( ^* ) Glyoxyl compounds such as those produced in any one of Synthesis Examples I-XXIV

Example 2 The following granular laundry detergent compositions G to L having specific utility under European machine wash conditions according to the present invention were prepared.

GHIJKLLAS 5.5 7.5 5.0 5.0 6.0 7.0 TAS 1.25 1.86-0.8 0.4 0.3 C24AS / C25AS-2.24 5.0 5.0 5.0 2.2 C25E3S-0.76 1.0 1.5 3.0 1.0 C45E7 3.25----3.0 TFAA--2.0 ---C25E5-5.5----QAS 0.8-----QASII-0.7 1.0 0.5 1.0 0.7 STPP 19.7-----Zeolite A-19.5 25.0 19.5 20.0 17.0 NaSKS6 / citric acid-10.6-10.6--( 79:21) NaSKS-6--9.0-10.0 10.0 Carbonate 6.1 21.4 9.0 10.0 10.0 18.0 Bicarbonate-2.0 7.0 5.0-2.0 Silicate 6.8--0.3 0.5-Site Rate--4.0 4.0--Sulfate 39.8--5.0-12.0 Mg sulfate--0.1 0.2 0.2-MA / AA 0.5 1.6 3.0 4.0 1.0 1.0 CMC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7----Percarbonate----18.0 15.0 TAED 0.5 3.1--5.0-NAC-OBS 1.0 3.5---2.5 DTPMP 0.25 0.2 0.3 0.4-0.2 EDP-0.3-0.3 0.3 0.3 QEA--1.0 1.0 1.0-Protease I---0.5 1.2-Protease 0.26 0.85 0.9 1.0-0.7 Lipase (1) 0.15 0.15 0.3 0.3 0.3 0.2 Cellulase 0.28 0.28 0.2 0.2 0.3 0.3 Amylase 0.1 0.1 0.4 0.4 0.6 0.2 PVNO / PVPVI--0.2 0.2--PVP 0.9 1.3---0.9 SRP1--0.2 0.2 0.2-Light activated bleach (1) (ppm) 15ppm 27ppm--20ppm 20ppm Light activated bleach (2 ) (ppm) 15ppm-----Brightener 1 0.08 0.19--0.09 0.15 Brightener 2-0.04----Fragrance 0.3 0.3 0.4 0.3 0.4 0.3 Glyoxylic acid ( ^* ) 0.3 0.3 0.4 0.3 0.4 0.3 Silicone Defoamer 0.5 2.4 0.3 0.5 0.3 2.0 Trace / miscellaneous components Remainder (assuming 100%) Density (g / liter) 750 750 750 750 750 750 ( ^★ ) Produced by any one of Synthesis Examples I to XXIV Glyoxyl compounds such as

Example 3 The following detergent formulations having particular utility under European machine wash conditions according to the present invention were prepared.

MNOP blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0--2.0 Zeolite A 24.0--20.0 STPP-27.0 24.0-Sulfate 4.0 6.0 13.0-MA / AA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone defoamer 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray-on brightener 0.02--0.02 C45E7---5.0 C45E2 2.5 2.5 2.0-C45E3 2.6 2.5 2.0-Fragrance 0.5 0.3 0.5 0.2 Glyoxylic acid ( ^★ ) 0.5 0.3 0.5 0.2 Silicone defoamer 0.3 0.3 0.3-Dry additive QEA---1.0 EDDS 0.3---Sulfate 2.0 3.0 5.0 10.0 Carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5--2.0 QASII 0.5--0.5 SKS-6 10.0---Percarbonate 18.5---PB4-18.0 10.0 21.5 TAED 2.0 2.0-2.0 NAC-OBS 3.0 2.0 4.0-Protease 1.0 1.0 1.0 1.0 Lipase-0 .4-0.2 Lipase (1) 0.4-0.4-Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05--0.05 Miscellaneous / trace components Remaining (100%) ( ^★ ) Any of Synthesis Examples I to XXIV Glyoxyl compounds such as produced in one

Example 4 The following granular detergent formulation according to the present invention was prepared.

QRSTUV blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS----1.0-C45AS 6.0 6.0 5.0 8.0--C45AES-1.0 1.0 1.0--C45E35----2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA / AA-0.5---2.0 MA / AA (1) 7.0-----AA-3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA-0.9 0.5--0.5 Brightener 2 0.3 0.2 0.3-0.1 0.3 Spray on C45E7-2.0--2.0 2.0 C25E9 3.0-----C23E9--1.5 2.0-2.0 Perfume 0.3 0.3 0.3 2.0 0.3 0.3 Glyoxylic acid type ( ^★ ) 0.3 0.3 0.3 2.0 0.3 0.3 Aggregate C45AS-5.0 5.0 2.0-5.0 LAS-2.0 2.0--2.0 Zeolite A-7.5 7.5 8.0-7.5 Carbonate-4.0 4.0 5.0-4.0 PEG4000-0.5 0.5--0.5 Miscellaneous (Water etc.)-2.0 2.0 2.0-2.0 Dry / dry additive QAS (I)----1.0-Citric acid----2.0-PB4----12.0 1.0 PB1 4.0 1.0 3.0 2.0--Percarbonate-- --2.0 10.0 Carbonate-5.3 1.8-4.0 4.0 NOBS 4.0-6.0--0.6 Methylcellulose 0.2-----SKS-6 8.0-----STS--2.0-1.0-Cumenesulfonic acid-1.0---2.0 Lipase 0.2-0.2-0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0.2-0.1-0.2-Protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI----0.5 0.1 PVP----0.5-PVNO--0.5 0.3--QEA ----1.0-SRP1 0.2 0.5 0.3-0.2-Silicone defoamer 0.2 0.4 0.2 0.4 0.1-Mg sulfate--0.2-0.2-Miscellaneous components / trace components Remainder (assuming 100%) ( ^★ ) Synthesis Example Glyoxyl compounds such as those produced in any one of I-XXIV

Example 5 A bleach-free detergent formulation according to the present invention was prepared which is particularly useful for washing colored clothing.

WXY blown powder zeolite A 15.0 15.0-sulfate 0.0 5.0-LAS 3.0 3.0-DTPMP 0.4 0.5-CMC 0.4 0.4-MA / AA 4.0 4.0-aggregate C45AS--11.0 LAS 6.0 5.0-TAS 3.0 2.0-silicate 4.0 4.0-Zeolite A 10.0 15.0 13.0 CMC--0.5 MA / AA--2.0 Carbonate 9.0 7.0 7.0 Spray-on fragrance 0.3 0.3 0.5 Glyoxylic acid ( ^* ) 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Drying additive MA / AA--3.0 NaSKS-6--12.0 Cytrate 10.0-8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI / PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Dry additive Sulfate 0.0 9.0 0.0 Miscellaneous / trace components Remainder (assuming 100%) dense (G / liter) 700 700 700 ^(★) glyoxylic compounds as produced in any one of Synthesis Example I~XXIV

Example 6 The following granular detergent formulation according to the present invention was prepared.

Z AABB Base Granules Zeolite A 30.0 22.0 24.0 Sulfate 10.0 5.0 10.0 MA / AA 3.0--AA-1.6 2.0 MA / AA (1)-12.0-LAS 14.0 10.0 9.0 C45AS 8.0 7.0 9.0 C45 AES-1.0 1.0 silicate -1.0 0.5 Soap-2.0-Brightener 1 0.2 0.2 0.2 Carbonate 6.0 9.0 10.0 PEG4000-1.0 1.5 DTPA-0.4-Spray-on C25E9---C45E7 1.0 1.0-C23E9-1.0 2.5 Fragrance 0.2 0.3 0.3 Glyoxylic acid ( ^* ) 0.2 0.3 0.3 Drying additive Carbonate 5.0 10.0 18.0 PVPVI / PVNO 0.5-0.3 Protease 1.0 1.0 1.0 Lipase 0.4--Amylase 0.1--Cellulase 0.1 0.2 0.2 NOBS-4.0-PB1 1.0 5.0 1.5 Sulfate 4.0 5.0-SRP1-0.4-Suppressed foam agent - 0.5 0.5 (as 100%) miscellaneous ingredients / trace components balance ^(★) generated in any one of synthesis example I~XXIV Glyoxylic compounds such as

Example 7 The following granular detergent composition according to the present invention was prepared.

CC DD EE blown powder zeolite A 20.0-15.0 STPP-20.0-sulfate--5.0 carbonate--5.0 TAS--1.0 LAS 6.0 6.0 6.0 C68AS 2.0 2.0-silicate 3.0 8.0-MA / AA 4.0 2.0 2.0 CMC 0.6 0.6 0.2 Brightener 1 0.2 0.2 0.1 DTPMP 0.4 0.4 0.1 STS--1.0 Spray-on C45E7 5.0 5.0 4.0 Silicone defoamer 0.3 0.3 0.1 Fragrance 0.2 0.2 0.3 Glyoxylic acid ( ^* ) 0.2 0.2 0.3 Drying additive QEA--1.0 Carbonate 14.0 9.0 10.0 PB1 1.5 2.0-PB4 18.5 13.0 13.0 TAED 2.0 2.0 2.0 QAS (I)--1.0 Photoactivated bleach 15ppm 15ppm 15ppm SKS-6--3.0 Protease 1.0 1.0 0.2 Lipase 0.2 0.2 0.2 Amylase 0.4 0.4 0.2 Cellulase 0.1 0.1 0.2 sulfate 10.0 20.0 5.0 (as 100%) miscellaneous ingredients / trace components balance density (g / liter) 700 700 700 ^(★) Glyoxylic compounds as produced in any one of the adult embodiments I~XXIV

Example 8 The following detergent formulation according to the present invention was prepared.

FF GG HH Blown powder Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS-1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS-0.4 0.2 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Aggregate LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray-on perfume 0.3 0.3 0.3 Glyoxylic acid ( ^* ) 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0--Dry additive Cytorate 5.0-2.0 Bicarbonate- 3.0-Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 PEO--0.2 Bentonite clay--10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Dry additive Sulfuric acid Sodium 0.0 3.0 0.0 Miscellaneous / trace components Remainder (assuming 100%) Degrees (g / liter) 850 850 850 ^(★) glyoxylic compounds as produced in any one of Synthesis Example I~XXIV

Example 9 The following detergent formulation according to the present invention was prepared.

II JJ KK LL LAS 20.0 14.0 24.0 20.0 QAS 0.7 1.0-0.7 TFAA-1.0--C23E56.5--1.0-C45E7-1.0--C45E3S 1.0 2.5 1.0-STPP 36.0 18.0 30.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 13.0 7.5 10.0 5.0 Bicarbonate-7.5--PB1 3.0 1.0--PB4-1.0--NOBS 2.0 1.0--DTPMP-1.0--DTPA 0.5-0.2 0.3 SRP1 0.3 0.2-0.1 MA / AA 1.0 1.5 2.0 0.5 CMC 0.8 0.4 0.4 0.2 PEI--0.4-Sodium sulfate 25.0 10.0 20.0 30.0 Mg sulfate 0.2-0.4 0.9 Protease 0.8 1.0 0.5 0.5 Amylase 0.5 0.4-0.25 Lipase 0.2-0.1-Cellulase 0.15--0.05 Light activated bleach (ppm) 30ppm 20ppm- 10ppm perfume 0.3 0.3 0.1 0.2 glyoxylic acid ^(★) (as 100%) 0.3 0.3 0.1 0.2 brightener 1/2 0.05 0.2 0.08 0.1 Misc component / trace components balance ^(★) synthesis example I~XXIV Glyoxylic compounds as produced in any one

Example 10 The following liquid detergent formulation according to the present invention was prepared (amounts are given as parts by weight).

MMNNOO PP QQ LAS 11.5 8.8-3.9-C25E2.5 S-3.0 18.0-16.0 C45E2.25S 11.5 3.0-15.7-C23E9-2.7 1.8 2.0 1.0 C23E7 3.2----CFAA--5.2-3.1 TPKFA 1.6-2.0 0.5 2.0 Citric acid (50%) 6.5 1.2 2.5 4.4 2.5 Calcium formate 0.1 0.06 0.1--Sodium formate 0.5 0.06 0.1 0.05 0.05 Sodium cumene sulfonate 4.0 1.0 3.0 1.18-Borate 0.6-3.0 2.0 2.9 Sodium hydroxide 5.8 2.0 3.5 3.7 2.7 Ethanol 1.75 1.0 3.6 4.2 2.9 1,2-Propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 0.8 TEPAE 1.6-1.3 1.2 1.2 Protease 1.0 0.3 1.0 0.5 0.7 Lipase--0.1--Cellulase--0.1 0.2 0.05 Amylase---0.1-SRP1 0.2-0.1--DTPA--0.3--PVNO--0.3-0.2 Brightener 1 0.2 0.07 0.1--Silicone defoamer 0.04 0.02 0.1 0.1 0.1 Glio Xylic acid system ( ^* ) 0.04 0.02 0.1 0.1 0.1 Water / trace component balance ( ^* ) Glyoxyl compound such as produced in any one of Synthesis Examples I to XXIV

Example 11 The following liquid detergent formulation according to the present invention was prepared (amounts are given in parts by weight).

RR SS TT UU VV LAS 10.0 13.0-25.0-C25AS 4.0 1.0 10.0-13.0 C25E3S 1.0-3.0-2.0 C25E7 6.0 8.0 2.5--TFAA--4.5-6.0 APA-1.4-3.0 1.0 TPKFA 2.0-7.0-15.0 2.0 3.0 1.5 1.0 1.0 citric acid dodecenyl / tetradecenyl 12.0 10.0-15.0-succinic rapeseed fatty acid 4.0 2.0-1.0-ethanol 4.0 4.0 2.0 7.0 2.0 1,2-propanediol 4.0 4.0 7.0 6.0 8.0 monoethanolamine--5.0--tri Ethanolamine-----TEPAE 0.5-0.2--DTPMP 1.0 1.0 1.0 2.0 1.2 Protease 0.5 0.5 0.25-0.5 Alcalase---1.5-Lipase-0.10 0.01--Amylase 0.25 0.25 0.5 0.25 0.9 Cellulase--0.05--Endase --0.10--SRP2 0.3-0.1--Boric acid 0.1 0.2 2.0 1.0 1.5 Calcium chloride-0.02 0.01--Bentonite clay---4.0 4.0 Brightener 1-0.4-0.1 0.2 Foam suppressant 0.1 0.3 0.1 0.4-Emulsion 0.5 0.4 0.3 0.8 0.7 Glyoxylic acid ( ^* ) 0.5 0.4 0.3 0.8 0.7 Water / trace component balance (100%) NaOH (predetermined pH) 8.0 8.0 7.7 8.0 7.5 ( ^* ) Glyoxyl compound such as produced in any one of Synthesis Examples I-XXIV

Example 12 The following liquid detergent composition according to the present invention was prepared (amounts are given in parts by weight).

WW XX LAS 27.6 18.9 C45AS 13.8 5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citric acid 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium formate 0.2 0.1 Sodium formate-0.5 Ethanol 7.0-Monoethanolamine 16.5 8.0 1,2-Propanediol 5.9 5.5 Xylenesulfonic acid-2.4 TEPAE 1.5 0.8 Protease 1.5 0.6 PEG-0.7 Brightener 2 0.4 0.1 Fragrance 0.5 0.3 Glyoxylic acid ( ^* ) 0.5 0.3 Water / trace component Remainder ( ^* ) Any one of Synthesis Examples I to XXIV Glyoxyl compounds such as produced in one

Example 13 The following laundry solid detergent composition according to the present invention was prepared (amounts are given in parts by weight).

YYZZAB AB AC AD AE LAS--19.0 15.0 21.0-C28AS 30.0 13.5---22.5 Sodium laurate 2.5 9.0----Zeolite A 2.0 1.25---1.25 Carbonate 20.0 3.0 13.0 8.0 10.0 10.0 Calcium carbonate 27.5 39.0 35.0--40.0 Sulfate 5.0 5.0 3.0 5.0 3.0 5.0 TSPP 5.0-----STPP 5.0 15.0 10.0--10.0 Bentonite clay-10.0--5.0-DTPMP-0.7 0.6-0.6 0.7 CMC-1.0 1.0 1.0 1.0 1.0 Talc- -10.0 15.0 10.0-Silicate--4.0 5.0 3.0-PVNO 0.02 0.03-0.01--MA / AA 0.4 1.0--0.2 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 Protease-0.12-0.08 0.08 0.1 Lipase-0.1-0.1--Amylase --0.8---Cellulase-0.15--0.15-PEO-0.2-0.2 0.3 0.3 Fragrance 1.0 0.5 0.3 0.2 0.4 0.4 Glyoxylic acid ( ^★ ) 1.0 0.5 0.3 0.2 0.4 0.4 Mg sulfate--3.0 3.0 3.0-Brightener 0.15 0.10 0 .15--0.1 Light activated bleach (ppm)-15.0 15.0 15.0 15.0 15.0 ( ^* ) Glyoxyl compound such as produced in any one of Synthesis Examples I-XXIV

Example 14 With the exception of composition CC, the following fabric softening compositions relate to the present invention.

Ingredient AF AG AH AI AJ AK CC DTDMAC----4.5 15.0-DEQA 2.6 2.9 18.0 19.0--18.0 Fatty acid 0.3-1.0----Hydrochloric acid 0.02 0.02 0.02 0.02 0.02 0.02 0.02 PEG--0.6 0.6-0.6 -Fragrance 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Silicone defoamer 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Glyoxylic acid ( ^★ ) 0.4 0.6 0.8 0.8 0.6 0.8-Electrolyte (ppm)--600 1200-1200 800 Dye (ppm) 10 10 50 50 10 50 50 Keazyme CEVU / g---50---PEI------2.0 SRP2------0.2 Water / trace component balance (100) ( ^★ ) Synthesis Example I ~ Glyoxyl compounds such as those produced in any one of XXIV

Example 15 The following composition for use as a dryer-added sheet is according to the present invention.

ALAM AN AO AP AQ DOEQA 40 25----DHEQA--20---DTDMAMS---20 12 60 SDASA 30 30 20 30 20-Glicosperse S-20--10---Glycerol mono Stear---20 10-Rate Clay 4 4 3 4 4-Fragrance 0.7 1.1 0.7 1.6 2.6 1.4 Glyoxylic acid ( ^* ) 0.8 0.5 0.8 0.8 0.5 1.20 Stearic acid balance ( ^* ) Any one of Synthesis Examples I to XXIV Glyoxyl compounds such as produced in one

Example 16 The following hard surface cleaning compositions AX to AZ are related to the present invention.

AR AS AT Dovanol 23-3 ^R 3.20 3.20 1.28 Lutensol AO30 ^R 4.80 4.80 1.92 Dovanol C7-11EO6 ^R 8.0 8.0 3.20 Top palm kernel fatty acid, Na salt 0.80 0.80 0.40 C8 alkyl sulfate, Na salt 2.0 2.0 0.8 Paraffin sulfonate , Na salt 3.0 3.0 1.20 Cumene sulfonate, Na salt 3.0 3.0 1.20 Fragrance 0.8 0.8 0.6 Branched alcohol, Isophor 16 ^R --0.30 Glyoxylic acid ( ^★ ) 1.86 2.49 0.6 NaOH (predetermined pH) pH 10 pH 10 pH 10 water / trace component balance (assuming 100%) ( ^* ) glyoxyl compound as produced in any one of Synthesis Examples I to XXIV

Example 17 The following mechanical dishwashing composition according to the present invention was prepared.

[0286] AU AV AW AX AY AZ BA site rate 15.0 15.0 15.0 15.0 15.0 15.0 - 480N 6.0 6.0 6.0 6.0 6.0 6.0 - carbonate 17.5 17.5 17.5 17.5 17.5 17.5 - STPP - - - - - - 38.0 silicate (as SiO ₂₎ 8.0 8.0 8.0 8.0 8.0 8.0 14.0 Metasilicate 1.2 1.2 1.2 1.2 1.2 1.2 2.5 (as SiO ₂ ) PB1 (AvO) 1.2 1.2 1.5 1.5 1.5 2.2 1.2 TAED 2.2 2.2 2.2--2.2 2.2 BzP---0.8---Cation precursor Substance----3.3--Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Bismuth nitrate-0.2 0.2 0.2 0.3 0.4 0.2 BD / MA------0.5 PMT-------0.5 Protease 0.04 0.04 0.04 0.04 0.04 0.04 0.04 amylase 0.03 0.03 0.03 0.03 0.03 0.03 - BSA - - - - - - 0.03 DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 - HEDP 1.0 1.0 1.0 1.0 1.0 1.0 - nonionic surfactant 2.0 2.0 2.0 2.0 2.0 2.0 1.5 glyoxylic acid ^(★ 0.5 0.5 0.5 1.86 1.86 1.86 1.86 sulfate 23.0 22.8 22.4 22.7 22.2 21.5 0.3 Miscellaneous ingredients / water balance ^(★) glyoxylic compounds as produced in any one of Synthesis Example I~XXIV

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Simon, Sawyer, Newcastle, UK Appon, Tyne, Hamstery, Drive, 12 (72) Inventor Robert, Strife Ohio, United States of America, Fairfield, Yorktown, Drive, 2098 (72) Inventor Arnaud, Pierre, Struyrow Newcastle, England, Appon, Tyne, Killingworth, Ashdown, Mano , Ashley, Closed, 30F term (reference) 4H003 AB19 AB27 AB31 AC05 AC08 AE06 BA27 DA01 DA02 DA05 EA12 EA15 EA16 EA20 EA28 EB08 EB09 EB12 EB13 EB19 EB22 EB24 EB26 EB28 EB32 EB34 EB37 EC01 EB37 4J032 AA12

Claims (20)

[Claims] 1. An empirical formula (Wherein at least one of R or R2 is an organic chain of an active alcohol and the other is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or at least one other carbon atom. R1 and R'1 are each independently hydrogen, hydroxyl, alkyl,
Alkylene, aryl, _{alkylaryl, COOR3, (CR 4 R 4} ) q CO
OR3, OR3, or another chain having at least one carbon atom; R3 is hydrogen,
Selected from alkali metals, ammonium, alkyl, alkylene, aryl, alkylaryl, organic chains of active alcohols, or other chains having at least one carbon atom, wherein R4 is each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl , COOR3, CH ₂ COOR3, OR3 or selected from at least one other chain carbon atoms,; Y is a comonomer unit, m is 0 to 10000,
It is preferably an integer having a value of 0 to 1000, more preferably 0 to 100, n is an integer of at least 1, preferably less than 1000, more preferably less than 100, and q is 0 to 10, preferably 0. ~ 4, more preferably an integer having a value of 0)
A compound having: 2. n is 1, m and q are 0, R is an organic chain of an active alcohol,
R'1 and R1 are hydrogen; and R2 is selected from hydrogen, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, and at least one other chain having at least one carbon atom, preferably hydrogen, methyl, ethyl, -CH2CH2- (OCH
2CH2) _p- OCH3, selected from -CH2CH2- (OCH2CH2) _p- OH, more preferably selected from hydrogen, methyl and ethyl, and p is an integer of 0-20, preferably 0-6, A compound according to claim 1. 3. n is 1, m and q are 0, R1 is OR3, R'1 is hydrogen,
Hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR
3, (CR ₄ R ₄ ) _q COOR 3, OR 3 or another chain having at least one carbon atom, preferably hydrogen, methyl, ethyl, — (OCH 2 CH 2) _{p + 1} —O
CH3,-(OCH2 CH2) _{p + 1-} OH; more preferably R'1 is selected from hydrogen, methyl and ethyl; p is an integer from 0 to 20, preferably from 0 to 6. 2. The compound according to 1. 4. R is an organic chain of an active alcohol, R'1 is hydrogen, and each of R3 and R2 is independently hydrogen, alkyl, alkylene, aryl, alkylaryl, an organic chain of the active alcohol, or carbon number. Selected from at least one other chain, preferably -CH
2CH2- (OCH2CH2) _p- OCH3, -CH2CH2- (OCH2CH
2) The compound according to claim 3, wherein the compound is selected from _p- OH, methyl and ethyl, more preferably selected from methyl and ethyl, and p is an integer of 0-20, preferably 0-6. 5. The method according to claim 1, wherein R 2 is an organic chain of an active alcohol, R is selected from alkyl, alkylene, aryl groups, preferably selected from methyl and ethyl, more preferably methyl, and R 3 is hydrogen. 3. The compound according to 3. 6. A compound according to claim 3, wherein each R and R2 is an organic chain of an active alcohol, and R3 is hydrogen. 7. m is 0 and n is at least 2, preferably less than 10000, more preferably less than 1000, most preferably less than 100; q is 0-10, preferably 0-4, more preferably 0, 1 or 2; at least one R is an organic chain of an active alcohol and the other R and R2 are each independently an organic chain of an active alcohol, hydrogen, alkali metal, ammonium, alkyl, alkylene, aryl,
Alkylaryl, organic chain of an active alcohol or selected from other chain of at least 1 carbon atoms,, R1, hydrogen each independently R'1, hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR3, (CR ₄ R ₄ ) _q COOR
R3 is selected from hydrogen, alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or another chain having at least one carbon atom. Selected from; R
4 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, _{alkylaryl, COOR3, CH 2 COOR3, OR3} , or is selected from the other chain of at least 1 carbon atoms, A compound according to claim 1. 8. m and n are each independently at least 1 and preferably each is independently 10,
Less than 000, more preferably less than 1000, most preferably less than 100;
q is 0-10, preferably 0-4, more preferably 0, 1 or 2; Y is an aldehyde R'CHO; R 'is an organic chain of an active aldehyde; at least one R is an active alcohol And the other R and R 2 are each independently an organic chain of an active alcohol, hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or at least one other carbon atom. R1 and R'1 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, alkylaryl, COOR3, (C
R ₄ R ₄ ) _q COOR 3, OR ₃ , or at least one other chain having at least one carbon atom; R 3 is hydrogen, an alkali metal, ammonium, alkyl, alkylene, aryl, alkylaryl, an organic chain of an active alcohol, or carbon number selected from at least one other chain; R4 are each independently hydrogen, hydroxyl, alkyl, alkylene, aryl, _{alkylaryl, COOR3, CH 2 COOR3, OR3} , or is selected from at least one other chain carbon atoms, wherein Item 7. The compound according to Item 1. 9. The compound according to claim 7, wherein q is 0 and R'1 is hydrogen. 10. The compound according to claim 1, wherein the organic chain of the active alcohol is a perfume alcohol organic chain. 11. The fragrance alcohol may be 2-phenoxyethanol, phenylethyl alcohol, geraniol, citronellol, phenoxanol, floralol, farnesol, menthol, isopulegol, eugenol, vanillin, cis-3-hexenol, undecabertol, majan. Toll, Losalva, linalool, tetrahydrolinalool, 1,2-dihydromyrcenol, hydroxycitronellal, terpineol and mixtures thereof, preferably geraniol, citronellol, linalool, phenylethyl alcohol, undecabertol, ma 11. The compound of claim 10, wherein the compound is selected from Jantol, Losalva, 1,2-dihydromyrcenol, and mixtures thereof. 12. The organic chain of an active aldehyde is an organic chain of a perfume aldehyde,
The compound according to any one of claims 8 to 11, wherein the compound is selected from -octanal, 2-decanal, 1-dodecanal, methylnonylacetaldehyde, trans-4-decenal, benzaldehyde and a mixture thereof. 13. A method for producing a glyoxyl compound having one or more active alcohols, wherein the glyoxyl compound is reacted with an active alcohol by acetal exchange and / or transesterification. 14. One or more active alcohols which (i) polymerize or copolymerize methyl glyoxylate with an active aldehyde, and (ii) transesterify the resulting compound with an active alcohol in the presence of a base catalyst. A method for producing a polyglyoxyl compound containing a mixed alcohol / aldehyde component. 15. A laundry and cleaning or personal cleansing composition comprising a compound according to any one of claims 1 to 14. 16. The compound as claimed in claim 10, comprising 0.01 to 10% by weight of the composition, preferably 0.05 to 5%.
The composition according to claim 15, wherein the composition is formulated in an amount of 0.1 to 2% by weight. 17. The composition according to claim 15, wherein the composition is a laundry and cleaning composition selected from a fabric softening composition, a detergent composition, and a hard surface cleaning composition. 18. The composition according to claim 15, wherein the composition further comprises an enzyme, preferably a cellulase.
A composition according to any one of the preceding claims. 19. A compound as claimed in any one of claims 1 to 12 or any of claims 15 to 18 in the presence of a substance such that at least one of the perfumes containing oxygen is hydrolyzed. A method for delivering a residual fragrance to a surface, which is in contact with the composition of claim 1. 20. The method according to claim 19, wherein said substance is water.