CN1268127A - Pro-fragrance cyclic acetals - Google Patents
Pro-fragrance cyclic acetals Download PDFInfo
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- CN1268127A CN1268127A CN 98808557 CN98808557A CN1268127A CN 1268127 A CN1268127 A CN 1268127A CN 98808557 CN98808557 CN 98808557 CN 98808557 A CN98808557 A CN 98808557A CN 1268127 A CN1268127 A CN 1268127A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to a fragrance delivery system for use in laundry detergent compositions including rinse-added and dryer-added fabric conditioning compositions which provides a long lasting 'freshness' or 'clean' scent to fabric. The compositions described herein deliver highly fabric substantive furanyl or pyranyl pro-fragrances to the fabric surface during laundering wherein the pro-fragrances release their fragrance raw materials over a period of up to two weeks. The present invention also relates to a method for delivering a pleasurable scent to fabric which has a lasting freshness quality by contacting the fabric with a laundry detergent composition which comprises the fragrance-releasable pro-fragrances.
Description
Invention field
The present invention relates to be used for the fragrance precursors of laundry detergent composition.This fragrance precursors comprises a kind of perfume material composition and a kind of solvability or affinity composition, and they can be conditioned independently to satisfy prescription teacher's specific requirement.This fragrance precursors is specially adapted to provide the fragrance seemingly pure and fresh or that seemingly clean of " experience washing process " to fabric, and it can be retained on the fabric and can long-time continuous release after finishing wash(ing)cycle.
Background of invention
Except getting on from fabric except that spot, dirty dirt, dirt, dust and dirt and grease, the prescription teacher of detergent for washing clothes also attempts providing the smell of " pure and fresh " or " cleaning " to the clothes that is washed, a kind of sense of smell aesthetic effect to be provided and to be effective a kind of indicator signal as product.Laundry detergent composition, the matrix thing that adds when fabric softener that adds when comprising rinsing and use moisture eliminator, usually be furnished with spices and aroma constituent, they make the human consumer that happy aesthetic feeling be arranged, but they provide " fragrance " or " pleasant smell " for a long time can not for final washed fabric.
Wherein the spices of the most easily discovering be spices " top " fragrant and " in " perfume (or spice), they are highly volatile compounds and just can detect under low amount usually.Yet, generally can lose in the long-time heating process that these highly volatile materials take place in automatic dryer, or they lack and deposit to needed affinity on the fabric face, therefore in the rinsing clothes process, lose.
People have attempted providing the perfume composition that can preserve at rinsing clothes with in drying cycle and therefore residual " pure and fresh " or " cleaning " smell is provided to the material of washing to fabric.Yet none was fit to provide after washing to fabric the perfume material of the long-time release of " pure and fresh " or " cleaning " smell that reached for 2 weeks during these were attempted.Particularly have recognized the need to provide some tertiary alcohol perfume material, especially phantol and dihydromyrcenol for a long time.
Therefore, keep the demand of fragrance system is provided in this area, the mode of composition that adds when wherein perfume base is by detergent for washing clothes, rinsing or the goods that add when using moisture eliminator offers fabric, and it gives the smell that the clothes that is cleaned or fabric provide " pure and fresh " or " cleaning " that reached for 2 weeks after washing.In addition, need provide the compound of the release spices of " pure and fresh " or " cleaning " fragrance, the solvability of wherein said compound and affine character can and provide parameter to change with various prescriptions, especially with the consistency of surfactivity subsidiary and fabric type.In addition, need a kind of fragrance system that provides, it is fit to give various personal-care supplies and personal hygiene article, especially reodorant, human body washing lotion or frost and shampoo that lasting discharge or weather resistance enhanced fragrance is provided.
Background technology
Below relate to the perfume composition theme.The U.S. Pat 5232612 of the Trinh that on August 3rd, 1996 authorized etc.; The U.S. Pat 5506201 of the McDermott that on April 9th, 1996 authorized etc.; The U.S. Pat 5378468 of the Suffis that authorize January 3 nineteen ninety-five etc.; The U.S. Pat 5266592 of the Grub that on November 30th, 1993 authorized etc.; The U.S. Pat 5081111 of the Akimoto that on January 14th, 1992 authorized etc.; The U.S. Pat 4994266 of the Wells that on February 19th, 1991 authorized; The U.S. Pat 4524018 of the Yemoto that on June 18th, 1985 authorized etc.; The U.S. Pat 3849326 of the Jaggers that on November 19th, 1974 authorized etc.; The U.S. Pat 3779932 of the Jaggers that on December 18th, 1973 authorized etc.; July 18 nineteen ninety-five disclosed JP07-179328; On September 7th, 1993 disclosed JP05-230496; On May 23rd, 1996 disclosed WO96/14827; February 16 nineteen ninety-five disclosed WO95/04809; With disclosed WO95/16660 on June 22 nineteen ninety-five.In addition, P.M.Muller, D.Lamparsky spices technological sciences and technology Blackie Academic﹠amp; Professional, (New York, 1994) comprise for referencial use in the present invention.
Summary of the invention
The present invention has satisfied the demand, find that surprisingly some cyclic acetal can be used for providing on the fabric in " washing process " spices or the perfume material from single fragrance precursor molecule, described fragrance precursor molecule has different fabric affinities, different solvability and different fragrance rates of release.These fragrance precursors can be used for providing tertiary alcohol raw material and primary and secondary perfume material, it is given fabric or gives the human skin aesthetic feeling odor effect that (when skin contact comprises personal-care supplies or personal hygiene article, especially reodorant, the human body washing lotion of fragrance precursor of the present invention or frost and shampoo) gives " pure and fresh " or " cleaning ".According to fragrance precursor of the present invention, except pleasant smell effect, can also continue to discharge their perfume material that reaches several weeks according to the structure of fragrance precursor with short period of time.
But fragrance precursor described herein comprises the perfume material of stable releasing pattern.The laundry detergent composition that the present invention contains fragrance precursor can comprise the fragrance precursor of any number, and is suitable for providing the fragrance " characteristic " of any kind of prescription Shi Suoxu.
A first aspect of the present invention relates to the fragrance precursors with following formula:
Wherein R is a perfume material alcohol, preferred phantol or dihydromyrcenol; R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Respectively be independently selected from:
A) hydrogen;
B) C
1-C
22The straight or branched alkyl;
C) C
2-C
22The straight or branched alkenyl;
D) C
1-C
22The straight or branched alkoxyl group;
E) C
6-C
20Replace or unsubstituted aryl;
F) C
2-C
20Replace or unsubstituted alkylene oxide group;
G) C
3-C
20Replace or unsubstituted alkylene oxide group alkyl;
H) C
6-C
20Replace or unsubstituted alkylidene aryl;
I) C
6-C
20Replace or unsubstituted aryloxy;
J) C
7-C
20Replace or unsubstituted alkylene oxide group aryl;
K) C
6-C
20The oxyalkylene aryl;
1) C
1-C
20The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-
R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12Straight or branched alkyl, M are hydrogen or salifiable positively charged ion, and x is the integer of 0-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, or its mixture; Y is the integer of 1-about 22;
P) and its mixture;
The invention still further relates to the laundry detergent composition that comprises pro-fragrance cyclic acetals as herein described." freshener " of the present invention after also an aspect is to use pro-fragrance cyclic acetals of the present invention as laundry, be used in be washed but do not wear and be with on the long fabric.The present invention also aspect is a use fragrance precursor of the present invention in the composition that adds when rinsing and the composition that adds during with moisture eliminator.Fragrance precursors of the present invention provides lasting discharge or weather resistance enhanced fragrance can also for various personal-care supplies and personal hygiene article, especially reodorant, human body washing lotion or frost and shampoo.By reading the following detailed description and appended claim, for the person of ordinary skill of the art, these and other objects, feature and advantage are conspicuous.
Unless otherwise indicated, all percentage ratios of this paper, ratio and ratio are by weight.Unless otherwise indicated, all temperature be meant degree centigrade (℃).The relevant portion of all documents of quoting is quoted for referencial use at this paper.
Detailed Description Of The Invention
Fragrance precursor of the present invention comprises perfume material composition and affinity or solvability composition.The perfume material composition can be that the prescription teacher is desirable to provide to fabric face to be used for any spices or any " the perfume material alcohol " that the later stage discharges after wash(ing)cycle.In addition, fragrance precursor comprises affinity or solvability composition, wherein suitably selects this composition to divide to make the prescription teacher can control the solvability of fragrance precursor in water, the fragrance precursor bulk property to affinity or this material of fabric.The bulk property of control fragrance precursor can make the fragrance precursor in the easier laundry composition of sneaking into particular type of prescription teachers and students output, that described laundry composition adds when for example being liquid, granular, high-density, encapsulated ingredient, rinsing, add when using moisture eliminator etc.
In case washing process is finished and fragrance precursor is suitably offered fabric, then fragrance precursor begins to discharge perfume material, because the release of this material is for a long time, so fabric keeps " pure and fresh " and " cleaning " smell of longer time.Yet, also can be designed to change being activated or wet activation or " thermal activation " are given fabric " pure and fresh fragrance " so that discharge in drying process by pH according to fragrance precursor of the present invention.Therefore the fragrance precursor of thermal activation can be offered fabric face.Lower " cleaning " and " pure and fresh " fragrance that this causes fabric to have high " initial flavor " and obtained by the long-time release of inactive fragrance precursor." thermal activation " fragrance precursor meaning here is the compound that has higher spices release rate after being exposed to high temperature.Therefore, prescription teacher's high fragrance that can obtain initially to provide and the lasting release of longer time.
Therefore fragrance precursor of the present invention is to be used for perfume material that provides required on fabric and a kind of reagent that longer time and more lasting " pure and fresh " or " cleaning " smell are provided to fabric thus.For the object of the invention, as if " provide feature happy on fragrance, fragrance, taste, smell or the general sense organ have usually the alcohol of molecular weight more than or equal to 100g/mol " is provided term " perfume material alcohol ".
Most perfume material, comprise fragrance precursor of the present invention, can not be as independent compound by passing to fabric wash(ing)cycle, this is (can not fully attached to fabric face) or volatility factor (evaporating in drying cycle) because solubility factor (lose or rinse in the laundry cycles process), affinity factor.Therefore, provide before can not be effectively or the reagent of some perfume material of fully discharging to fabric for fragrance precursor described herein.In fact, fragrance precursor of the present invention is more suitable for providing tertiary alcohol perfume material than conventional fragrance precursor.
" perfume material " comprises preferred examples, is perfume material alcohol.The catalogue of common " perfume material alcohol " is found in various reference, " spices and flavor chemistry product " (Perfume andFlavor Chemicals) for example, I and II volume; Steffen Arctander AlluredPub.Co. (1994) and " spices: technology, science and technology " (Pefumes:Art, Scienceand Technology); Muller, P.M. and Lamparsky, D., Blackie Academic and Professional (1994), all these documents are quoted for referencial use at this paper.
The technician in detergent composition field will appreciate that term " affine " and " affinity " are meant that compound adheres to, is connected or is deposited on surface, the lip-deep proneness of preferred fabric.Therefore, the compound that affinity is strong more, easier of on the fabric face.But the compound of affinity does not generally react with their sedimentary surfaces.
Fragrance precursor
Fragrance precursor of the present invention is replacement and the unsubstituted 2-hydroxyl tetrahydrofuran derivative with following formula:
With replacement with following formula and unsubstituted 2-hydroxy tetrahydro pyran derivate:
Wherein R is 2,4 dimethyl-3-tetrahydrobenzene-1-methyl (Floralol), 2,4-dimethyl cyclohexane methyl (Dihydro floralol), 5,6-dimethyl-1-methyl ethylene dicyclo [2.2.1] heptan-5-alkene-2-methyl (Arbozol), 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-methyl (different ring geranyl), 4-(1-methylethyl) cyclohexyl methyl (Mayol), α-3,3-trimethylammonium-2-norbornane ylmethyl, 1,1-dimethyl-1-(4-methyl cyclohexane-3-thiazolinyl) methyl, the 2-phenylethyl, 2-cyclohexyl ethyl, 2-(o-methyl-phenyl-) ethyl, 2-(aminomethyl phenyl) ethyl, 2-(p-methylphenyl) ethyl, 6,6-dimethyl dicyclo-[3.1.1] hept-2-ene"-2-ethyl (nopyl), 2-(4-methylphenoxy) ethyl, 3,3-dimethyl-D
2-b-norborneol alkyl ethyl, 2-methyl-2-cyclohexyl ethyl, 1-(4-isopropylcyclohexyl-) ethyl, 1-phenyl-1-hydroxyethyl, 1,1-dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-aminomethyl phenyl) ethyl, the 1-phenyl propyl, the 3-phenyl propyl, 2-phenyl propyl (alcohol of lyotropy), 2-(cyclo-dodecyl) third-1-base (hydroxyl ambran), 2,2-dimethyl-3-(3-aminomethyl phenyl) third-1-base (Majantol), 2-methyl-3-phenyl propyl, 3-phenyl-2-propylene-1-base (styryl carbinol), 2-methyl-3-phenyl-2-propylene-1-base (methyl styryl carbinol), α-n-pentyl-3-phenyl-2-propylene-1-base (α-Wu Jirouguichun), 3-hydroxyl-3-phenylpropionic acid ethyl ester, 2-(4-aminomethyl phenyl)-2-propyl group, 3-(4-methyl cyclohexane-3-alkene) butyl, 2-methyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl) butyl, 2-ethyl-4-(2,2,3-front three basic ring penta-3-thiazolinyl)-2-butylene-1-base, 3-methyl-2-butene-1-base, 2-methyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-base, 3-hydroxyl-2-butanone, ethyl 3-hydroxybutanoate, 4-phenyl-3-butene-2-Ji, 2-methyl-4-phenyl fourth-2-base, 4-(4-hydroxy phenyl) fourth-2-ketone, 4-(4-hydroxy 3-methoxybenzene base) fourth-2-ketone, cis-3-pentenyl, 3-methyl-amyl group, 3-methyl-3-amylene-1-base, 2-methyl-4-phenylpentyl (Pamplefleur), 3-methyl-5-phenylpentyl (Phenoxanyl), 2-methyl-5-phenylpentyl, 2-methyl-5-(2,3-dimethyl three ring [2.2.1.0 (2,6)] heptan-3-yl)-2-amylene-1-base (santalyl), 4-methyl isophthalic acid-phenyl-2-amyl group, (1-methyl bicycle [2.1.1] heptene-2-yl)-2-methylpent-1-alkene-3-base, 3-methyl isophthalic acid-phenyl penta-3-base, 1,2-dimethyl-3-(1-methyl ethylene) ring penta-1-base, 2-sec.-propyl-4-methyl-2-hexenyl, suitable-3-hexene-1-base, trans-2-hexene-1-base, 2-pseudoallyl-5-methyl-4-hexene-1-base (Lavandulyl), 2-ethyl-2-isopentene group-3-hexenyl (silwanol), the 2-ethylhexyl, 1-hydroxymethyl-4-pseudoallyl-1-cyclohexenyl (dihydro cuminyl alcohol), 1-methyl-4-pseudoallyl hexamethylene-6-alkene-2-base (Sheep's-parsley thiazolinyl), 6-methyl-3-pseudoallyl hexamethylene-1-base, 1-methyl-4-pseudoallyl hexamethylene-3-base, 4-sec.-propyl-1-methyl cyclohexane-3-base, 4-tertiary butyl ring-hexyl, the 2-tert-butylcyclohexyl, the 2-tertiary butyl-4-methylcyclohexyl, the 4-isopropylcyclohexyl-, 4-methyl isophthalic acid-(1-methylethyl)-3-tetrahydrobenzene-1-base, 2-(5,6,6-trimethylammonium-2-norcamphyl) cyclohexyl, the isobornyl cyclohexyl, 3,3, the 5-trimethylcyclohexyl, 1-methyl-4-sec.-propyl hexamethylene-3-base (menthol), 1,2-dimethyl-3-(1-methylethyl) hexanaphthene-1-base, heptyl, 2,4-dimethyl-g-1-base, 2,4-dimethyl-2,6-heptadiene base, 6,6-dimethyl-2-oxygen methyl-dicyclo [3.1.1] hept-2-ene"-1-base (myrtenyl), 4-methyl-2,4-heptadiene-1-base, 3,4,5,6,6-pentamethyl--2-heptyl, 3,6-dimethyl-3-vinyl-5-heptene-2-base, 6,6-dimethyl-3-hydroxyl-2-methylene radical dicyclo [3.1.1] heptyl, 1,7,7-trimethylammonium dicyclo [2.2.1] heptan-2-base, 2,6-dimethyl-g-2-base, 2,6,6-trimethylammonium dicyclo [1.3.3] heptan-2-base, octyl group, the 2-octenyl, 2-methyl suffering-2-base, 2-methyl-6-methylene radical-7-octene-2-base (myrcenyl), 7-methyl suffering-1-base, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 3,7-dimethyl-6-octene-1-Ji (citronellyl), 3,7-dimethyl-2,6-octadiene-1-base (geranyl), 3,7-dimethyl-2,6-octadiene-1-base (neryl C10H17-), 3,7-dimethyl-1,6-octadiene-3-base (linalyl), 3,7-dimethyl-octa-1-base (Flos Pelargonii base), 3,7-dimethyl oct-3-yl (tetrahydrochysene linalyl), 2,4-octadiene-1-base, 3,7-dimethyl-6-octene-3-base, 2,6-dimethyl-7-octene-2-base, 2,6-dimethyl-5,7-octadiene-2-base, 4,7-dimethyl-4-vinyl-6-octene-3-base, 3-methyl oct-3-yl, 2,6-dimethyl-octa-2-base, 2,6-dimethyl oct-3-yl, 3,6-dimethyl oct-3-yl, 2,6-dimethyl-7-octene-2-base, 2,6-dimethyl-3,5-octadiene-2-base (alloocimene base), 3-methyl isophthalic acid-octene-3-base, 7-hydroxyl-3,7-dimethyl-octa aldehyde radical, the 3-nonyl, 6,8-dimethyl ninth of the ten Heavenly Stems-2-base, 3-(hydroxymethyl)-methyl n-heptyl ketone, 2-nonylene-1-Ji, 2,4-nonadiene-1-base, 2,6-nonadiene-1-base, cis-6-nonylene-1-Ji, 3,7-dimethyl-1,6-nonadiene-3-base, decyl, 9-decene base, 2-benzyl-M-two oxa-s-5-base, 2-decylene-1-Ji, 2,4-decadiene-1-base, 4-methyl-3-decene-5-base, 3,7,9-trimethylammonium-1,6-decadiene-3-base (isobutyl-linalyl), undecyl, 2-undecene-1-Ji, 10-undecene-1-Ji, 2-dodecylene-1-base, 2,4-12 carbon diene-1-base, 2,7,11-trimethylammonium-2,6,10-12 carbon triolefin-1-base (farnesyl), 3,7,11-trimethylammonium-1,6,10-12 carbon triolefin-3-base, 3,7,11,15-tetramethyl-16 carbon-2-alkene-1-base (phytol base), 3,7,11,15-tetramethyl-16 carbon-1-alkene-3-base (isophytol base), to methoxy-benzyl (anisyl), to umbrella flower-7-base (p-isopropylbenzyl), the 4-methyl-benzyl, 3,4-methylene radical dioxy base benzyl, 2-(methyl) carboxyl-1-hydroxyphenyl, 2-(benzyl) carboxyl-1-hydroxyphenyl, 2-(cis-3-hexenyl) carboxyl-1-hydroxyphenyl, 2-(n-pentyl) carboxyl-1-hydroxyphenyl, 2-(2-phenylethyl) carboxyl-1-hydroxyphenyl, 2-(n-hexyl) carboxyl-1-hydroxyphenyl, 2-methyl-5-sec.-propyl-1-hydroxy phenyl, 4-ethyl-2-p-methoxy-phenyl, 4-allyl group-2-methoxyl group-1-hydroxy phenyl (Syzygium aromaticum phenolic group), 2-methoxyl group-4-(1-propenyl)-1-hydroxy phenyl (isoeugenol base), 4-allyl group-2,6-dimethoxy-1-hydroxy phenyl, the 4-tertiary butyl-1-hydroxy phenyl, 2-oxyethyl group-4-methyl isophthalic acid-hydroxy phenyl, 2-methyl-4-vinyl-1-hydroxy phenyl, 2-sec.-propyl-5-methyl isophthalic acid-hydroxy phenyl (thymol base), 2-(isopentyl) carboxyl-1-hydroxy phenyl, 2-(ethyl) carboxyl-1-hydroxy phenyl, 6-(methyl) carboxyl-2,5-dimethyl-1, the 3-dihydroxy phenyl, 5-methoxyl group-3-methyl isophthalic acid-hydroxy phenyl, the 2-tertiary butyl-4-methyl isophthalic acid-hydroxy phenyl, 1-oxyethyl group-2-hydroxyl-4-propenyl phenyl, 4-methyl isophthalic acid-hydroxy phenyl, 4-hydroxy 3-methoxybenzene formaldehyde, the 2-bourbonal, decahydro-2-naphthyl, 2,5,5-trimethylammonium octahydro-2-naphthyl, 1,3,3-trimethylammonium-2-norborneol alkyl (sweet fennel alcohol radical), 3a, 4,5,6,7,7a-six hydrogen-2,4-dimethyl-4,7-methylene radical-1H-indenes-5-base, 3a, 4,5,6,7,7a-six hydrogen-3,4-dimethyl-4,7-methylene radical-1H-indenes-5-base, 2-methyl-2-vinyl-5-(1-hydroxyl-1-methylethyl) tetrahydrofuran base, b-China pink thiazolinyl and their mixture.
Preferred R is 3,7-dimethyl-1,6-octadiene-3-alcohol (phantol, for racemic mixture or respectively be independent optically active isomer), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol, for racemic mixture or respectively be independent optically active isomer) and its mixture.
R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The unit each be independently:
A) hydrogen;
B) C
1-C
22, preferred C
1-C
12, more preferably C
1-C
6The straight or branched alkyl;
C) C
2-C
22, preferred C
2-C
12, more preferably C
2-C
6The straight or branched alkenyl;
D) C
1-C
22, preferred C
1-C
12, more preferably C
1-C
6The straight or branched alkoxyl group;
E) C
6-C
20, preferred C
6-C
10, more preferably C
6Replace or unsubstituted aryl;
F) C
2-C
20, preferred C
2-C
12, more preferably C
2-C
6Replace or unsubstituted alkylene oxide group;
G) C
3-C
20, preferred C
3-C
12, more preferably C
3-C
6Replace or unsubstituted alkylene oxide group alkyl;
H) C
7-C
20, preferred C
7-C
12, more preferably C
7Replace or unsubstituted alkylidene aryl;
I) C
6-C
20, preferred C
6-C
10, more preferably C
6Replace or unsubstituted aryloxy;
J) C
7-C
20, preferred C
8-C
12, more preferably C
8Replace or unsubstituted alkylene oxide group aryl;
K) C
7-C
20, preferred C
7-C
11, more preferably C
7The oxyalkylene aryl;
L) C
2-C
20, preferred C
2-C
12, more preferably C
2-C
6The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-
R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12The straight or branched alkyl, preferable methyl or ethyl; M is hydrogen or salifiable positively charged ion, preferred sodium or potassium; X is the integer of 0-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, preferred sodium or potassium; Or its mixture; Y is the integer of 1-about 22;
P) and its mixture.
For the object of the invention, replacement or unsubstituted alkylene oxide group unit are defined as having the segment of following formula:
R wherein
13Be hydrogen; R
14Be hydrogen, methyl, ethyl and their mixture; Subscript x is 1-about 10.
For the object of the invention, replacement or unsubstituted alkylidene group oxyalkyl are defined as having the segment of following formula:
R wherein
13Be hydrogen, C
1-C
18Alkyl, C
1-C
4Alkoxyl group and its mixture; R
14Be hydrogen, methyl, ethyl and their mixture; Subscript x is that 1-is about 9, and subscript y is 1-about 18.
For the object of the invention, replacement or unsubstituted alkylidene aryl unit are defined as having the segment of following formula:
R wherein
13And R
14Be hydrogen, hydroxyl, C independently of one another
1-C
4Alkoxyl group, nitrilo, halogen, nitro, carboxyl (CHO;-CO
2H;-CO
2R ';-CONH
2-CONHR ';-CONR '
2, wherein R ' is C
1-C
12The straight or branched alkyl), amino, alkylamino and their mixture, p is 1-about 14.
For the object of the invention, replacement or unsubstituted aryloxy unit are defined as having the segment of following formula:
R wherein
13And R
14Be hydrogen, hydroxyl, C independently of one another
1-C
4Alkyl, C
1-C
4Alkoxyl group, nitrilo, halogen, nitro, carboxyl (CHO;-CO
2H;-CO
2R ';-CONH
2-CONHR ';-CONR '
2, wherein R ' is C
1-C
15The straight or branched alkyl), amino, alkylamino and their mixture.
For the object of the invention, replacement or unsubstituted alkylidene group oxygen aryl unit are defined as having the segment of following formula:
R wherein
13And R
14Be hydrogen, hydroxyl, C independently of one another
1-C
4Alkyl, C
1-C
4Alkoxyl group, nitrilo, halogen, nitro, carboxyl (CHO;-CO
2H;-CO
2R ';-CONH
2-CONHR ';-CONR '
2, wherein R ' is C
1-C
12The straight or branched alkyl), amino, alkylamino and their mixture, q is 1-about 14.
For the object of the invention, replacement or unsubstituted oxyalkylene aryl unit are defined as having the segment of following formula:
R wherein
13And R
14Be hydrogen, hydroxyl, C independently of one another
1-C
4Alkyl, C
1-C
4Alkoxyl group, nitrilo, halogen, nitro, carboxyl (CHO;-CO
2H;-CO
2R ';-CONH
2-CONHR ';-CONR '
2, wherein R ' is C
1-C
12The straight or branched alkyl), amino, alkylamino and their mixture, w is 1-about 14.
Above-mentioned as this paper, any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom; Those skilled in the art will appreciate that under the situation of fused aromatic rings, to have only a R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can be present on the carbon atom that constitutes an aromatic ring part, other R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit will not exist.For example, as the R of THP trtrahydropyranyl fragrance precursor
1And R
3The unit combines when forming hexa-atomic fused aromatic rings (ring that comprises 6 carbon atoms), and the compound that obtains has general formula:
Wherein because there is not unit R in the needs of chemical bonding
2And R
4This is suitable for equally if form the situation of the fused aromatic rings of two other carbon atoms that comprise the tetrahydropyrans basic ring, even R
3Combine formation fused aromatic rings, R with R5
4And R
6To not exist.Same replacement with become key to require to be applicable to fragrance precursor based on tetrahydrofuran (THF).
In addition, can need to use two substituting groups on carbon atom to form this part in the replacement on ring carbon atom part.For example, need R
3And R
4The exocyclic double bond of two substituting group formation as following general formula:
Above-mentioned as this paper, any two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom.R wherein
1And R
7The unit combines the example that forms dicyclo [2.2.2] and can be represented by following general formula:
In addition, two R on same ring carbon atom
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine formation volution, wherein R
5And R
6The example that the unit combines the THP trtrahydropyranyl fragrance precursor that forms cyclohexane ring has general formula:
Fragrance precursor of the present invention discharges " perfume material alcohol ", and it provides pleasant " pure and fresh " and/or " cleaning " flavor or fragrance for the fabric of using fragrance precursor.Unrestricted example by the suitable alcohol that discharges of this ortho ester fragrant-inner agent precursor (pro-accords) hydrolysis comprises methyl alcohol, 2,4 dimethyl-3-tetrahydrobenzene-1-methyl alcohol (Floralol), 2,4-dimethyl cyclohexane methyl alcohol (Dihydro floralol), 5,6-dimethyl-1-methyl ethylene dicyclo [2.2.1] heptan-5-alkene-2-methyl alcohol (Arbozol), 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-methyl alcohol (different cyclogeraniol), 4-(1-methylethyl) cyclohexane methanol (Mayol), α-3,3-trimethylammonium-2-norbornane methyl alcohol, 1,1-dimethyl-1-(4-methyl cyclohexane-3-thiazolinyl) methyl alcohol, ethanol, the 2-phenylethyl alcohol, the 2-cyclohexyl ethyl alcohol, 2-(o-methyl-phenyl-) ethanol, 2-(aminomethyl phenyl) ethanol, 2-(p-methylphenyl) ethanol, 6,6-dimethyl dicyclo-[3.1.1] hept-2-ene"-2-ethanol (nopol), 2-(4-methylphenoxy) ethanol, 3,3-dimethyl-D
2-b-norbornane ethanol, 2-methyl-2-cyclohexyl ethyl alcohol, 1-(4-isopropylcyclohexyl-) ethanol, the 1-phenylethyl alcohol, 1,1-dimethyl-2-phenylethyl alcohol, 1,1-dimethyl-2-(4-aminomethyl phenyl) ethanol, n-propyl alcohol, the 2-propyl alcohol, the 1-phenyl propanol, the 3-phenyl propanol, 2-phenyl propanol (alcohol of lyotropy), 2-(cyclo-dodecyl) third-1-alcohol (hydroxyl ambran), 2,2-dimethyl-3-(3-aminomethyl phenyl) third-1-alcohol (Majantol), 2-methyl-3-phenyl propanol, 3-phenyl-2-propylene-1-alcohol (styryl carbinol), 2-methyl-3-phenyl-2-propylene-1-alcohol (methyl styryl carbinol), α-n-pentyl-3-phenyl-2-propylene-1-alcohol (α-Wu Jirouguichun), 3-hydroxyl-3-phenylpropionic acid ethyl ester, 2-(4-aminomethyl phenyl)-2-propyl alcohol, propyl carbinol, the 2-butanols, the 3-methyl butanol, 3-(4-methyl cyclohexane-3-alkene) butanols, 2-methyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl) butanols, 2-ethyl-4-(2,2,3-front three basic ring penta-3-thiazolinyl)-2-butylene-1-alcohol, 3-methyl-2-butene-1-alcohol, 2-methyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol, 3-hydroxyl-2-butanone, ethyl 3-hydroxybutanoate, 4-phenyl-3-butene-2-alcohol, 2-methyl-4-phenyl fourth-2-alcohol, 4-(4-hydroxy phenyl) fourth-2-ketone, 4-(4-hydroxy 3-methoxybenzene base) fourth-2-ketone, amylalcohol, suitable-the 3-pentenol, 3-methyl-amylalcohol, 3-methyl-3-amylene-1-ol, 2-methyl-4-phenyl amylalcohol (Pamplefleur), 3-methyl-5-phenyl amylalcohol (Phenoxanol), 2-methyl-5-phenyl amylalcohol, 2-methyl-5-(2,3-dimethyl three ring [2.2.1.0 (2,6)] heptan-3-yl)-2-amylene-1-ol (santalol), 4-methyl isophthalic acid-phenyl-2-amylalcohol, (1-methyl bicycle [2.1.1] heptene-2-yl)-2-methylpent-1-alkene-3-alcohol, 3-methyl isophthalic acid-phenyl penta-3-alcohol, 1,2-dimethyl-3-(1-methyl ethylene) ring penta-1-alcohol, 2-sec.-propyl-5-methyl-2-is enol, suitable-blatter alcohol, trans-the 2-hexen-1-ol, 2-pseudoallyl-4-methyl-4-hexen-1-ol (Lavandulol), 2-ethyl-2-isopentene group-3-hexenol, 1-hydroxymethyl-4-pseudoallyl-1-tetrahydrobenzene (dihydro cuminyl alcohol), 1-methyl-4-pseudoallyl hexamethylene-6-alkene-2-alcohol (carvenol), 6-methyl-3-pseudoallyl hexamethylene-1-alcohol, 1-methyl-4-pseudoallyl hexamethylene-3-alcohol, 4-sec.-propyl-1-methyl cyclohexane-3-alcohol, 4-tertiary butyl ring-hexanol, 2-tertiary butyl hexalin, the 2-tertiary butyl-4 methyl cyclohexanol, the 4-isopropyl cyclohexanol, 4-methyl isophthalic acid-(1-methylethyl)-3-tetrahydrobenzene-1-alcohol, 2-(5,6,6-trimethylammonium-2-norcamphyl) hexalin, the isobornyl hexalin, 3,3, the 5-cyclonol, 1-methyl-4-sec.-propyl hexamethylene-3-alcohol, 1,2-dimethyl-3-(1-methylethyl) hexanaphthene-1-alcohol, enanthol, 2,4-dimethyl-g-1-alcohol, 2,4-dimethyl-2,6-heptadiene alcohol, 6,6-dimethyl-2-oxygen methyl-dicyclo [3.1.1] hept-2-ene" (myrthenol), 4-methyl-2,4-heptadiene-1-alcohol, 3,4,5,6,6-pentamethyl--2-enanthol, 3,6-dimethyl-3-vinyl-5-heptene-2-alcohol, 6,6-dimethyl-3-hydroxyl-2-methylene radical dicyclo [3.1.1] heptane, 1,7,7-trimethylammonium dicyclo [2.2.1] heptan-2-alcohol, 2,6-dimethyl-g-2-alcohol, 2,6,6-trimethylammonium dicyclo [1.3.3] heptan-2-alcohol, octanol, the 2-octenol, 2-methyl suffering-2-alcohol, 2-methyl-6-methylene radical-7-octen-2-ol (myrcenol), 7-methyl suffering-1-alcohol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-1-ol (geraniol), 3,7-dimethyl-2,6-octadiene-1-alcohol (Geraniol), 3,7-dimethyl-2,6-octadiene-1-alcohol (vernol), 3,7-dimethyl-1,6-octadiene-3-alcohol (phantol), 3,7-dimethyl-octa-1-alcohol (Flos Pelargonii alcohol), 3,7-dimethyl-octa-3-alcohol (tetrahydrolinalool), 2,4-octadiene-1-alcohol, 3,7-dimethyl-6-octene-3-alcohol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-octadiene-2-alcohol, 4,7-dimethyl-4-vinyl-6-octene-3-alcohol, 3-methyl suffering-3-alcohol, 2,6-dimethyl-octa-2-alcohol, 2,6-dimethyl-octa-3-alcohol, 3,6-dimethyl-octa-3-alcohol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadiene-2-alcohol (muguol), 3-methyl isophthalic acid-octene-3-alcohol, 7-hydroxyl-3,7-dimethyl octanal, the 3-nonyl alcohol, 2,6-nonadiene-1-alcohol, suitable-6-nonylene-1-alcohol, 6,8-dimethyl ninth of the ten Heavenly Stems-2-alcohol, 3-(hydroxymethyl)-methyl n-heptyl ketone, 2-nonylene-1-alcohol, 2,4-nonadiene-1-alcohol, 3,7-dimethyl-1,6-nonadiene-3-alcohol, decyl alcohol, the 9-decenol, 2-benzyl-M-two oxa-s-5-alcohol, the 2-decen-1-ol, 2,4-decadiene-1-alcohol, 4-methyl-3-decene-5-alcohol, 3,7,9-trimethylammonium-1,6-decadiene-3-alcohol (isobutyl linalool), hendecanol, 2-undecene-1-alcohol, 10-undecene-1-alcohol, 2-dodecylene-1-alcohol, 2,4-12 carbon diene-1-alcohol, 2,7,11-trimethylammonium-2,6,10-12 carbon triolefin-1-alcohol (farnesol), 3,7,11-trimethylammonium-1,6,10-12 carbon triolefin-3-alcohol, 3,7,11,15-tetramethyl-16 carbon-2-alkene-1-alcohol (phytol), 3,7,11,15-tetramethyl-16 carbon-1-alkene-3-alcohol (isophytol), benzylalcohol, p-methoxybenzyl alcohol (pmethoxybenzyl alcohol), to umbrella flower-7-alcohol (cuminyl alcohol), the 4-methyl-benzyl alcohol, 3,4-methylene radical dioxo benzylalcohol, wintergreen oil, benzyl salicylate, Whitfield's ointment is suitable-3-hexene ester, the Whitfield's ointment n-pentyl ester, Whitfield's ointment 2-phenyl chlorocarbonate, the just own ester of Whitfield's ointment, 2-methyl-5-isopropyl-phenol, 4-ethyl-2-methoxyphenol, 4-allyl group-2-methoxyphenol (oxymethoxyallylbenzene), 2-methoxyl group-4-(1-propenyl) phenol (isoeugenol), 4-allyl group-2, the 6-syringol, the 4-tert.-butyl phenol, 2-oxyethyl group-4-methylphenol, 2-methyl-4-vinylphenol, 2-sec.-propyl-5-methylphenol (thymol), the salicylic acid pentyl ester, the 2 hydroxybenzoic acid ethyl ester, 2,4-dihydroxyl-3,6-mesitylenic acid methyl esters, 3-hydroxy-5-methyl Oxy-1-methylbenzene, the 2-tertiary butyl-4-methyl isophthalic acid-hydroxybenzene, 1-oxyethyl group-2-hydroxyl-4-propenylbenzene, the 4-hydroxytoluene, 4-hydroxy 3-methoxybenzene formaldehyde, the 2-bourbonal, decahydro-beta naphthal, 2,5,5-trimethylammonium octahydro-beta naphthal, 1,3,3-trimethylammonium-2-norbornanol (fenchyl alcohol), 3a, 4,5,6,7,7a-six hydrogen-2,4-dimethyl-4,7-methylene radical-1H-indenes-5-phenol, 3a, 4,5,6,7,7a-six hydrogen-3,4-dimethyl-4,7-methylene radical-1H-indenes-5-phenol, 2-methyl-2-vinyl-5-(1-hydroxyl-1-methylethyl) tetrahydrofuran (THF), b-caryophyllenol and their mixture.
The preferred alcohols that is discharged by The compounds of this invention is 4-(1-methylethyl) cyclohexane methanol (mayol), 2,4 dimethyl-3-tetrahydrobenzene-1-base methyl alcohol (floralol), 2,4-dimethyl hexamethylene-1-base methyl alcohol (dihydrofloralol), 2,4,6-trimethylammonium-3-tetrahydrobenzene-1-base methyl alcohol (different cyclogeraniol), the 2-phenylethyl alcohol, 1-(4-isopropylcyclohexyl-) ethanol (mugetanol), 2-(o-methyl-phenyl-) ethanol (former-hawthanol), 2-(aminomethyl phenyl) ethanol (partially-hawthanol), 2-(p-methylphenyl) ethanol (right-hawthanol), 2,2-dimethyl-3-(3-aminomethyl phenyl) third-1-alcohol (majantol), 3-phenyl-2-propylene-1-alcohol (styryl carbinol), 2-methyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol (santalaire), 3-methyl-5-phenyl penta-1-alcohol (phenoxanol), 3-methyl-5-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-4-amylene-2-alcohol (ebanol), 2-methyl-4-phenyl penta-1-alcohol (pamplefleur), cis-blatter alcohol, 3,7-dimethyl-6-octen-1-ol (geraniol), 3,7-dimethyl-2,6-octadiene-1-alcohol (Geraniol, vernol or their mixture), 7-methoxyl group-3,7-dimethyl-octa-2-alcohol (osyrol), 3,7-dimethyl-1,6-octadiene-3-alcohol (phantol), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 6,8-dimethyl ninth of the ten Heavenly Stems-2-alcohol, cis-6-nonylene-1-alcohol, 2,6-nonadiene-1-alcohol, 4-methyl-3-decene-5-alcohol (undecavertol), benzylalcohol, 2-methoxyl group-4-(1-propenyl) phenol (isoeugenol), 2-methoxyl group-4-(2-propenyl) phenol (oxymethoxyallylbenzene), 4-hydroxy 3-methoxybenzene formaldehyde (vanillin food grade,1000.000000ine mesh) and their mixture; More preferably 3,7-dimethyl-1,6-octadiene-3-alcohol (phantol), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol) and its mixture.
According to the present invention, no matter all perfume material isomer are fragrance precursor or d/d perfume material form, all are suitable for the present invention.In the time may having optically active isomer, perfume material can comprise in the present invention with independent chemical isomerization body or blended racemic mixture form.For example 3,7-dimethyl-6-octen-1-ol, those of ordinary skills are commonly referred to as b-geraniol or cephrol, and it comprises a pair of optically active isomer, R-(+)-b-geraniol and S-(-)-b-geraniol.Each of these materials all is suitable as perfume material of the present invention separately or as a pair of racemic modification.But the technician of field of perfumery should consider any sense of smell difference that each optically active isomer has when application is of the present invention.For example, Karvon, promptly there are two kinds of isomer in 2-methyl-5-(1-methyl ethylene)-2-tetrahydrobenzene-1-ketone: d-Karvon and l-Karvon.The d-Karvon of finding in caraway oil provides diverse fragrance with the l-Karvon of finding in spearmint oil.According to the present invention, the fragrance precursor that discharges the d-Karvon will obtain different fragrance than the fragrance precursor that discharges the l-Karvon.This is suitable for the l-Karvon equally.
Similarly, tetrahydrofuran base and THP trtrahydropyranyl fragrance precursor respectively have at least one chiral centre, it is the C-1 carbon atom that is contained in furans or the pyranoid ring, and when it combined with the perfume alcohol with chiral centre, it is right that fragrance precursor of the present invention can form diastereomer.According to the present invention, there are not single isomer or isomer right to being better than other single isomer or isomer, but because fragrance " feature " or other bulk property, if the prescription teacher has selected a kind of isomer or isomer right, and do not select other, then for the object of the invention, this selection can not slacken and keep other isomer or the right value of isomer.
The spices of the fabric-conditioning compositions that adds when using moisture eliminator that adds when in addition, the present invention relates to be used for laundry detergent composition and rinsing provides system.Spices of the present invention provides system to provide slowly, continued the perfume material of release, and they provide pleasant " pure and fresh " or " cleaning " fragrance for clothes or fabric.In addition, above-mentioned as this paper, the pyranyl or the furyl part of prescription teacher correctability fragrance precursor material are so that the affinity or the raising that improve fabric constitute the solvability of compound in washing liquid that spices provides system.
Generally, the laundry detergent composition of the present invention with enhanced fragrance retention and fragrance weather resistance comprises:
A) at least about 0.01%, preferably about 0.01%-10%, more preferably from about 0.1%-1% weight spices provides system, and this system comprises:
Ii) one or more fragrance precursors of the present invention;
Iii) randomly fragrance carrier provides the subsidiary of fragrance with other;
Iv) randomly, the material of one or more non-pyranyls or non-furyl fragrance precursor;
B) at least about 0.01%, preferred about 0.1%-60%, 0.1%-30% weight detersive surfactant more preferably from about, it is selected from anionic, cationic, non-ionic type, zwitter-ion, amphoterics and its mixture, and preferred described tensio-active agent is an anion surfactant; With
C) carrier of equal amount and annexing ingredient, described annexing ingredient are selected from washing assistant, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleaching catalyst, bleach-activating agent, free dirt polymkeric substance, dye-transfer, dispersion agent, enzyme, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent, enzyme, photosensitizers, fluorescent agent, fabric conditioner, hydrolyzable tensio-active agent, sanitas, antioxidant, sequestrant, stablizer, antishrinking agent, anti wrinkling agent, sterilant, mycocide, corrosion inhibitor and its mixture.
For the object of the invention, term " material of one or more non-pyranyls or non-furyl fragrance precursor " is defined as can suiting to discharge other compound of perfume material, for example disclosed in the U.S. Pat 5378468 of the Suffis that authorizes in January 3 nineteen ninety-five etc., it quotes for referencial use at this paper.
The fabric sofetening composition that adds when generally, having the rinsing of the present invention of enhanced fragrance retention and fragrance weather resistance comprises:
A) at least about 0.01%, preferably about 0.01%-10%, more preferably from about 0.1%-1% weight spices provides system, and this system comprises:
I) one or more are according to fragrance precursors of the present invention;
Ii) randomly, one or more perfume materials;
Iii) randomly fragrance carrier provides the subsidiary of fragrance with other;
B) by the weight of composition, about 99.99%, preferred about 85%-99.9% is used to prepare the component of fabric sofetening composition, described component is selected from cationic fabric softener, nonionic fabric softener, liquid vehicle, concentrated assistant, dirt release agent, spices and sanitas/stablizer and its mixture;
C) at least about 50% liquid vehicle; With
D) randomly, the concentrated assistant of about 0.01%-15% weight;
The pH of wherein said in addition composition under 20 ℃ is lower than about 6.
Generally, by a kind of goods that add in the moisture eliminator, matrix thing for example, preferred flexible matrix thing provide the fabric sofetening composition that adds when using moisture eliminator and the composition favourable to appearance of fabrics, and described goods comprise:
A) at least about 0.01%, preferably about 0.01%-10%, more preferably from about 0.1%-1% weight spices provides system, and this system comprises:
I) one or more are according to fragrance precursors of the present invention;
Ii) randomly, one or more perfume materials;
Iii) randomly fragrance carrier provides the subsidiary of fragrance with other;
B) fabric treating component comprises:
A) about 1%-60% weight has the polyamine of following formula:
I) have the polyamine of following formula skeleton:
Wherein R is C
2-C
8Alkylidene group, C
3-C
8The alkylidene group that alkyl replaces and its mixture, preferred ethylidene, propylene, trimethylene, more preferably ethylidene;
The polyamine that ii) has the following formula skeleton:
Wherein y is 5-about 10000; With
Iii) randomly, 0%-100% polyamine backbone NH unit is had one or more unit replacement of following formula:
-(R
1O)
xR
2
R wherein
1Be C
2-C
6Alkylidene group, C
3-C
6Alkylidene group and its mixture that alkyl replaces; R
2Be hydrogen, C
1-C
4Alkyl and its mixture; Preferred hydrogen and methyl; Wherein m is 2-about 700; N is 0-about 350; X is 1-12, preferred 1-about 4; Y is 5-5000;
B) about 40%-99% weight carboxylic acid carrier;
Wherein the viscosity of fabric treatment composition under 100 ℃ is lower than about 2000 centipoises, and fusing point is about 25 ℃-95 ℃; With
C) in order to discharge the described polyamine (i) of significant quantity and the distribution device that the carboxylic acid carrier is (ii) established to fabric in the automatic laundry dryer under service temperature.
Surfactant system
Cleaning combination of the present invention can contain the tensio-active agent at least about 0.01% weight, and it is selected from anionic, cationic, non-ionic type, both sexes and zwitterionics.In the semisolid of preferred solid of the present invention (promptly granular) and viscosity (being gel, the lotion etc.) system, by the weight of said composition, the content of tensio-active agent is preferably about 0.1%-60%, and more preferably 0.1%-about 30%.
The general content of unrestricted example that is applicable to tensio-active agent of the present invention is about 1%-55% (weight), comprises conventional C
11-C
18The uncle and the random C of alkylbenzene sulfonate (" LAS ") and side chain
10-C
20Alkyl-sulphate (" AS "), formula CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3C
10-C
18Secondary (2,3) alkyl-sulphate, x and (y+1) be integer wherein at least about 7, preferably at least about 9, M is water miscible positively charged ion, particularly sodium, unsaturation vitriol is oleyl sulfate for example, C
10-C
18Alkyl alkoxy sulfate (" AExS "; EO 1-7 ethoxy sulfate particularly), C
10-C
18Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate), C
10-C
18Glyceryl ether, C
10-C
18Alkyl polyglycoside and the many glycosides of they corresponding sulfations, and C
12-C
18A-sulfonated fatty acid ester.If necessary, in total composition of the present invention, also can comprise for example C of conventional nonionic and amphoterics
12-C
18Alkylethoxylate (" AE ") comprises alkylethoxylate and C that so-called narrow peak distributes
6-C
12Alkyl phenolic alkoxy thing (particularly ethoxylate and blended ethoxylate/propoxylated glycerine), C
12-C
18Trimethyl-glycine and sultaine, C
10-C
18Amine oxide etc.C
10-C
18N-alkyl polyhydroxy fatty acid amide is highly preferred, particularly C
12-C
18The N-methyl glucose amide.Referring to WO9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxy-propyl) glucamide.When the low foaming of needs, can use the N-propyl group to N-hexyl C
12-C
18Glucamide.Also can use C
10-C
20Conventional soap.High if desired foaming effect can use side chain C
10-C
16Soap.The mixture of negatively charged ion and nonionogenic tenside is useful especially.Other conventional useful tensio-active agent is further described and is listed in the standard textbook at this paper.
Anion surfactant can extensively be described as the water-soluble salt, particularly an alkali metal salt of organosulfur acid-respons product, has to contain about 8 alkyl and the group that is selected from sulfonic acid and sulfuric ester to about 22 carbon atoms in its molecular structure.(the moieties that in the term alkyl, comprises senior acyl group.) important example of anion synthetic detergent that can constitute the surface active agent composition of the present composition is sodium alkyl sulfate or potassium, those sodium alkyl sulfates or the potassium that obtains by sulfation higher alcohols (C8-18 carbon atom) particularly, these higher alcoholss are that the glyceryl ester by reduction butter or Oleum Cocois obtains; Sodium alkyl benzene sulfonate or potassium, wherein alkyl contains and has an appointment 9 to about 15 carbon atoms, (alkyl can be the aliphatic chain of straight or branched); Alkyl glycerylether sodium sulfonate, particularly those ethers of the higher alcohols that obtains by butter and Oleum Cocois; Single coco-nut oil fatty acid glyceryl ester sodium sulfate and sodium sulfonate; 1 mole of high fatty alcohol (for example butter or coconut oleyl alcohol) and about 1 sodium or sylvite to the sulfuric ester of the reaction product of about 10 moles of ethylene oxide; Per molecule has about 1 alkylphenol oxyethane ether sodium sulfate or potassium to about 10 unit loop oxidative ethanes, and wherein alkyl contains 8 to 12 carbon atoms; The reaction product of the lipid acid that obtains by Oleum Cocois; The sodium of the fatty acid amide of methyl taurate or sylvite, wherein lipid acid is for example obtained by Oleum Cocois, and β-acetoxyl or β-kharophen alkane sulfonic acid sodium or potassium, and wherein alkyl has 8 to 22 carbon atoms.
In addition, the prescription teacher can only use secondary alkyl sulfate or be used in combination with other surfactant materials, below points out and illustrated the difference between Sulfated tensio-active agent and other the conventional alkyl sulfate surfactant.The non-limiting example of this component is as follows.
Conventional primary alkyl sulphates (AS), for example those of above explanation have general formula: ROSO
3 -M
+, wherein R is generally the C of straight chain
8-22Alkyl, M are water-soluble cationic.Chain primary alkyl sulfate tensio-active agent (being side chain " PAS ") with 8-20 carbon atom also is known, referring to for example, and the european patent application 439,316 of application in people's such as Smith 21 days January in 1991.
Conventional secondary alkyl sulfate surfactant is those materials with sulfate radical part of the irregular distribution of alkyl " skeleton " along molecule.These materials can be used following structrual description:
CH
3(CH
2)
n(CHOSO
3 -M
+)(CH
2)
mCH
3
Wherein m and n are 2 or greater than 2 integer, the summation of m+n is generally about 9-17, and M is a water-soluble cationic.
Above-mentioned secondary alkyl sulfate is to pass through H
2SO
4With those of alkene addition preparation.In the U.S. Pat 5075041 of the Lutz that uses alpha-olefin and the general synthetic method of vitriolic to be disclosed in the U.S. Pat 3234258 of the Morris that authorized on February 8th, 1966 or authorized on December 24th, 1991.The U.S. Pat 5349101 of authorizing also referring to September in 1994 20 of Lutz etc.; The U.S. Pat 5389277 that authorize the February 14 nineteen ninety-five of Prieto.
Preferred surfactants of the present invention is an anion surfactant, but has followingly also described other tensio-active agent that this paper is suitable for.
The present composition also comprises at least about 0.01%, and preferably at least 0.1%, the non-ionic detersive surfactant of 1%-30% more preferably from about.Preferred nonionic is C for example
12-C
18Alkylethoxylate (" AE ") comprises alkylethoxylate and C that so-called narrow peak distributes
6-C
12Alkyl phenolic alkoxy thing (particularly ethoxylate and blended ethoxylate/propoxylated glycerine), C
6-C
12The block oxyalkylene condenses of alkylphenol, C
8-C
22The oxyalkylene condenses of alkanol and ethylene oxide/propylene oxide block polymer (Pluronic
TM-BASF AG), and semi-polar nonionic surfactants (for example amine oxide and phosphine oxide) all can be used for the present invention.The detailed description of the tensio-active agent of these types sees in the people's such as Laughlin that authorized on December 30th, 1975 the U.S. Pat 3929678, and the document is quoted for referencial use at this paper.
For example disclosed alkyl polysaccharide also is a present composition preferred nonionic in the U.S. Pat 4565647 (this paper quotes for referencial use) of Llenado.
Preferred nonionogenic tenside is the polyhydroxy fatty acid amide with following formula:
R wherein
7Be C
5-C
31Alkyl, preferred straight chain C
7-C
19Alkyl or alkenyl, more preferably straight chain C
9-C
17Alkyl or alkenyl, most preferably straight chain C
11-C
15Alkyl or alkenyl or its mixture; R
8Be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, preferable methyl or ethyl, more preferably methyl.Q is the polyhydroxy alkyl part with the linear alkyl chain that is connected directly to few 3 hydroxyls, or its alkoxy derivative, and preferred alkoxyl group is oxyethyl group or propoxy-and its mixture.Preferred Q is derived by the reducing sugar in the reductive amination process to obtain; More preferably Q is a glycosyl part.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, can use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and above listed single sugar.These maize treacle can obtain the sugar component mixture as Q.Will be appreciated that and do not mean that other suitable raw material of eliminating here.Q more preferably is selected from-CH
2(CHOH)
n-CH
2OH ,-CH (CH
2OH) (CHOH)
N-1-CH
2OH ,-CH
2-(CHOH)
2(CHOR ') (CHOH)-CH
2OH and its alkoxy derivative, wherein n is 3 to 5 integer, comprises 3 and 5, R ' is the monose of H or cyclic or aliphatic series.The most preferred substituting group of Q part is that n is 4 glycosyl, particularly-and CH
2-(CHOH)
4-CH
2OH.
R
7-CO-N＜can be is Oleum Cocois acid amides, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.
R
8Can be for example methyl, ethyl, propyl group, sec.-propyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl.
Q can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
Being used for the desirable especially such tensio-active agent of the present composition is alkyl-N-methyl glucose amide, i.e. R wherein
7Be alkyl (preferred C
11-C
17), R
8Be that methyl and Q are the following formula compounds of 1-deoxy-glucose base.
Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxy-propyl) glucamide.When the low foaming of needs, can use the N-propyl group to N-hexyl C
12-C
18Glucamide.Also can use C
10-C
20Conventional soap.High if desired foaming can be used side chain C
10-C
16Soap.
Annexing ingredient
Washing assistant-detergent builder compound optionally is included in the present composition to help control mineral substance hardness.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition to help removing particulate fouling.
The content of washing assistant can change in wide region according to end-use and its required physical form of composition.When using washing assistant, generally comprise washing assistant in the composition at least about 1%.Generally comprise about 5%-50% in the prescription, the washing assistant of more typically about 5%-30% (weight).Granular recipe generally comprises about 10%-80%, more typically about 15%-50% weight detergent builder compound.But this does not mean that the lower and more high-load washing assistant of eliminating.
Inorganic or phosphorous washing assistant comprises, but be not limited to: following basic metal, ammonium and alkanol ammonium salt: poly-phosphate (tri-polyphosphate for example, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.But, need non-phosphorus Cleaning Aid Agent in certain areas.Importantly, in addition so-called " weak " washing assistant (with phosphate ratio) as Citrate trianion down, or under generable what is called " hanged down " situation composite when use zeolite or layered silicate washing assistant, the performance of the present composition was good unexpectedly.
The example of silicate-like builder is an alkalimetal silicate, and particularly those have SiO
2: Na
2Silicate and the layered silicate of the ratio of O in 1.6: 1 to 3.2: 1 scopes, the lamina sodium silicate of describing in the U.S. Pat 4664839 as the H.P.Rieck that authorizes on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, Na SKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na
2SiO
5The layered silicate of morphological form.It can be by the method preparation as describing in DE-A-3417649 and DE-A-3742043.SKS-6 is a layered silicate very preferably used herein, but the present invention can use other layered silicate, has general formula NaMSi as those
xO
2x+1YH
2The layered silicate of O, wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, is preferably 0.Various other layered silicates of buying from Hoechst comprise NaSKS-5, NaSKS-7, and NaSKS-11, and they are with α, β and γ form.As mentioned above, δ-Na
2SiO
5(NaSKS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as crisp dose of granular recipe, as the stablizer of oxygen bleaching agent with as the component of control foam system.
The example of carbonate builders is alkaline-earth metal and the alkaline carbonate on November 15th, 1973 disclosed German patent application 2321001.
The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant is most important in the most common commercially available heavy duty type granular detergent composition, and also can be builder component important in the liquid detergent formula.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula:
[M
z(zAlO
2)
y].xH
2O
Wherein z and y are at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.
Useful aluminosilicate ion exchange material is commercial the purchase.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the U.S. Pat 3985669.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper can be that zeolite A, zeolite P (B), zeolite MAP and X zeolite buy by registered trademark.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:
Na
12[(AlO
2)
12(SiO
2)
12].xH
2O
Wherein x is about 20 to about 30, especially about 27.This material is called zeolite A.Dehydration zeolite (x=0-10) also can use in this article.Silico-aluminate preferably has the granularity of diameter for about 0.1-10 micron.
The organic detergent builder compound that is fit to the object of the invention includes, but are not limited to: various multi-carboxylate's compounds." multi-carboxylate " used herein refers to has many carboxylate group, the compound of preferred at least 3 carboxylate group.The multi-carboxy acid salt washing agent generally can add in the composition with sour form, but also can add with the form of neutralized salt.When using with the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salt.
In the multi-carboxy acid salt washing agent, comprise multiple useful material.A kind of multi-carboxy acid salt washing agent of important kind comprises the ether multi-carboxylate, comprise oxygen di-succinate, as those disclosed in the U.S. Pat 3128287 of the Berg that authorizes on April 7th, 1964 and the people's such as Lamberti that authorized on January 18th, 1972 the U.S. Pat 3635830.Also referring to " TMS/TDS " washing assistant in the people's such as Bush that authorized on May 5th, 1987 the U.S. Pat 4663071.The ether multi-carboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as in U.S. Pat 3923679; US3835163; US4158635; Described in US4120874 and the US4102903 those.
Other useful washing assistants comprise ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxyl methoxyl group succsinic acid, various polyacetic acids, as basic metal, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and poly carboxylic acid such as mellitic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and their soluble salt.
The Citrate trianion washing assistant, for example, citric acid and its soluble salt (particularly sodium salt) they are the multi-carboxy acid salt washing agents of particularly important in the heavy duty liquid laundry detergent prescription, reason is that they can obtain having biodegradability with them by renewable resource.Citrate trianion also can be used in the particulate composition, particularly is used in combination with zeolite and/or layered silicate washing assistant.Oxygen di-succinate is also particularly useful in this composition and mixture.
Be suitable in the U.S. Pat 4566984 that also has the Bush that authorizes on January 28th, 1986 of detergent composition of the present invention disclosed 3,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C
5-C
20Alkyl and alkenyl succinic and their salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, nutmeg base succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.
Other multi-carboxylates that are fit to be disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 U.S. Pat 4144226 and the U.S. Pat 3308067 of the Diehl that authorized on March 7th, 1967 in.Also referring to U.S. Pat 3723322.
Lipid acid, for example C
12-C
18Monocarboxylic acid also can mix in the composition individually, or mixes in the composition with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant, so that extra washing assistant activity to be provided.Use lipid acid generally can cause slackening foaming, this prescription teacher should consider.
Under the situation that can use phosphorous washing assistant, especially, can use various alkali metal phosphates tri-polyphosphate, trisodium phosphate and sodium orthophosphate as is well known at the stick prescription that is used for hand-washing operation.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonates (referring to, for example, U.S. Pat 3159581; 3213030; 3422021; 3400148 and 3422137).
Remove great soil group dirt/anti redeposition agent
Composition of the present invention can also optionally contain the water-soluble ethoxylated amine with removal great soil group dirt and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of the 0.01%-10.0% that has an appointment (weight); Liquid detergent composition generally contains the water-soluble ethoxylated amine of the 0.01%-5% that has an appointment (weight).
Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine further is described in the U.S. Pat 4597898 of the VanderMeer of mandate on July 1st, 1986.Another kind of preferred removal great soil group dirt-anti redeposition agent is a disclosed cation compound in the European patent application EP 111965 of the Oh of announcement on June 27th, 1984 and Gosselink.Spendable other are removed disclosed ethoxylated amine polymer in the european patent application 111984 that great soil group dirt/anti redeposition agents are included in the Gosselink that announced on June 27th, 1984; Disclosed amphoteric ion polymer in the European patent application EP 112592 of the Gosselink that on July 4th, 1984 announced; With disclosed amine oxide in the U.S. Pat 4548744 of the Connor that authorizes on October 22nd, 1985.As known in the art other remove the great soil group dirt and/or anti redeposition agent also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
Other components-can be included in various other components useful in the detergent composition in the present composition comprise other active ingredients, carrier, and hydrotropic agent, processing aid, dyestuff or pigment are used for the solid packing of bar composition etc.Other optional components comprises enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photosensitizers, dyestuff, fluorescent agent, fabric conditioner, hydrolyzable tensio-active agent, white dyes, sanitas, antioxidant, sequestrant, stablizer, antishrinking agent, anti wrinkling agent, dirt release agent, sterilant, mycocide and corrosion inhibitor.High if desired foam then can mix suds booster such as C in said composition
10-16Alkanolamide, its content is generally 1%-10%.C
10-14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble additional surfactant, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine, sultaine use together.If necessary, also can add as MgCl
2, MgSO
4Deng the solubility magnesium salts obtaining more foam and strengthen to remove the grease performance, their usage quantity is generally 0.1%-2%.
The various scrubbed component of using in the present composition can also be optionally by these components are adsorbed on the porous hydrophobic matrix, and then apply agent with hydrophobicity and apply this matrix further to make its stabilization.Preferably before adsorbing, this scrubbed component is mixed with tensio-active agent with porous matrix.In use, this scrubbed component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washing soln.
In order to illustrate in greater detail this technology, (trade mark SIPERNAT D10 is DeGussa) with the C that contains 3%-5% with porous hydrophobic silicon-dioxide
13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol (EO7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion emulsification of gained or with it.By this method, enzyme as the aforementioned, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photosensitizers, dyestuff, fluorescent agent, fabric conditioner and hydrolyzable surface active agent composition can be used for washing composition with " protected " form.
Detergent composition of the present invention preferably is formulated into and is being used for aqueous washing operation, and the pH value of washing water is about 6.5-11, is preferably about 7.5-10.5.Laundry product general pH value is 9-11.Control pH is to use buffer reagent in the method under the use value of recommending, alkali, and acid etc., these all are that those skilled in the art are familiar with.
Particulate composition
The particulate composition neutralization that fragrant-inner agent precursor of the present invention can be used for low density (being lower than 550 grams per liters) is used for the high density granular composition that pellet density is 550 grams per liters at least.Particulate composition generally is made into to be in the suds, and pH is provided is about 7.5-11.5, more preferably from about 9.5-10.5.Low-density compositions can be by the spraying-drying means preparation of standard.Can make in all sorts of ways and equipment prepare high-density composition.Use spraying-drying tower to produce in the commercial at present enforcement in this area and have the composition that density is lower than about 500 grams per liters.Therefore, if spraying drying is used as the part of whole technology, the spraying-dried particles that then obtains must be further closely knit with the method and apparatus of hereinafter describing.On the other hand, the prescription teacher omits the spraying drying step by using commercial commercially available mixing, closely knit and granulating equipment.It below is the non restrictive description that is applicable to equipment of the present invention to this.
Various devices and equipment be can buy and high-density of the present invention (promptly, being preferably greater than about 650g/l), high resolution, runny granular detergent composition prepared greater than about 550.The general industrial implementation in this area is to use spray-drying tower to prepare to have the granular laundry detergent that density is lower than about 500g/l usually.In the method, the hydrous slurry with heat-staple various components in the final detergent composition passes through spray-drying tower, uses routine techniques, makes homogeneous granules under about 175 ℃-225 ℃.If but spraying drying is as the part of overall process here, then must use other processing step as described below, (promptly＞650g/l) with the desired level of density of Betengent product that makes fine and close now low usage quantity.
For example, derive from spray-drying tower spray-dried granules can by with liquid for example water or nonionogenic tenside load in this particulate hole, and/or make their come further closely knit through one or more high-speed mixers/closely knit device.High-speed mixer/closely knit the device that is fit to that is used for this method is the equipment of buying by trade(brand)name " Lodige CB 30 " or " Lodige CB 30 Recycler ", it comprises a static round shape mixing drum, it has centre rotational axis, and mixing/cutting blade is housed on this axle.In use, in the component adding cylinder with detergent composition, axle/blade part rotates thoroughly to mix/densification with 100-2500rpm speed.United States Patent (USP) 5149455 referring to the Jacobs that authorized on September 22nd, 1992 etc.The preferred residence time in high-speed mixer/closely knit device is about 1-60 second.The equipment that other this equipment bag is buied by trade(brand)name " Shugi Granulator " and " Drais K-TTP80 ".
The other processing step that is used for further closely knit spray-dried granules is included in middling speed mixing machine/closely knit device grinding, the spray-dired particle of agglomeration or makes it distortion, so that obtain having the particle of lower particle internal porosity.For example mixing machine/closely knit device equipment of buying by trade(brand)name " Lodige KM " (series 300 or 600) or " Lodige Ploughshare " is applicable to this processing step.This equipment is generally operated under 40-160rpm.The residence time of detergent component in middling speed mixing machine/closely knit device is about 0.1-12 minute.Other equipment that is fit to comprises the equipment of buying by trade(brand)name " Drais K-T 160 ".Use this processing step of middling speed mixing machine/closely knit device (for example Lodige KM) itself to use separately or be used in combination with above-mentioned high-speed mixer/closely knit device (for example Lodige CB) in order, to obtain required density.The facility for granulating of other type that the present invention is suitable for is included in disclosed equipment in the U.S. Pat 2306898 of the G.L.Heller that authorizes December 29 nineteen forty-two.
Though use high-speed mixer/closely knit device, use low speed mixer/closely knit device to be more suitable for then, the present invention has also expected the mixing machine/closely knit device operation of reverse order.Can use a kind of or combination in the following various parameter so that the closely knit optimizing of the spray-dried granules in the inventive method, described parameter comprises: the residence time in mixing machine/closely knit device, the service temperature of equipment, particulate temperature and/or composition, annexing ingredient be the use of liquid adhesive and flow promotor for example.For example, referring to the U.S. Pat 5133924 (before closely knit, making particle become deformable state) of the Appel that authorizes on July 28th, 1992 etc.; The U.S. Pat 4637891 of the Delwel that on January 20th, 1987 authorized etc. (spray-dired particle being granulated) with liquid adhesive and silico-aluminate; The U.S. Pat 4726908 of the Kruse that on February 23rd, 1988 authorized etc. (spray-dired particle being granulated) with liquid adhesive and silico-aluminate; With the technology in the U.S. Pat 5160657 (applying closely knit particle) of the Bortolotti that authorized on November 3rd, 1992 etc. with liquid adhesive and silico-aluminate.
To heat responsive especially or high-volatile detergent component or fragrant-inner agent precursor be incorporated under those situations of final detergent composition, the technology that does not comprise spray-drying tower is preferred.The prescription teacher can save the spraying drying step by with continuous or intermittent mode initial detergent component being fed directly in commercially available mixing/closely knit equipment.A kind of particularly preferred embodiment comprises surfactant paste and anhydrous washing assistant material is added in high-speed mixer/closely knit device (for example Lodige CB), add then in middling speed mixing machine/closely knit device (for example LodigeKM), to form highdensity detergent agglomerate.U.S. Pat 5486303 referring to the U.S. Pat 5366652 of the Capeci that authorized on November 22nd, 1994 etc. and the Capeci that authorized on January 23rd, 1996 etc.Randomly, in this technology, can select the liquid/solid ratio of initial detergent component, to obtain more runny and crisp high-density agglomerate.
Randomly, this technology can comprise one or more recycle streams of the undersized grain that is produced by this technology, and their are sent back in mixing machine/closely knit device, with further agglomeration or gather.The oversize particle that this technology produces can be delivered to grinding plant, returns mixing/closely knit equipment then.These other circulation technology steps are impelled initial detergent component accumulation agglomeration, cause final composition have equally distributed desired particle size (400-700 micron) and density (＞550g/l).U.S. Pat 5489392 referring to the U.S. Pat 5516448 of the Capeci that authorized on May 14th, 1996 etc. and the Capeci that authorized on February 6th, 1996 etc.The U.S. Pat 4828721 of the Bollier that other does not need to use the suitable technology of spray-drying tower to be described in to authorize on May 9th, 1989 etc.; The U.S. Pat 5108646 of the Beerse that on April 28th, 1992 authorized etc.; In the U.S. Pat 5178798 of the Jolicoeur that authorized on January 12nd, 1993.
In another embodiment, high density detergent composition of the present invention can use the fluidized-bed mixing machine to produce.In the method, the various components of final composition are blended in (general 80% solids content) in the hydrous slurry, and spray in the fluidized-bed to obtain final detergent particles.Before fluidized-bed, this method alternative comprises uses above-mentioned Lodige CB mixing machine/closely knit device or " Flexomix 160 " mixing machine/closely knit device bought from Shugi to come the step of mixed slurry.In this method, can use fluidized-bed or the moving-bed equipment buied by trade(brand)name " Escher Wyss ".
The technology that the another kind that the present invention uses is fit to comprises the liquid acids precursor of anion surfactant, alkaline inorganic material (for example yellow soda ash) and other optional detergent component is added in high-speed mixer/closely knit device (residence time is 5-30 minute), so that make the agglomerate that contains part or all of neutralize anionic surfactant salt and other initial detergent component.Randomly, the material in high-speed mixer/closely knit device can be sent in middling speed mixing machine/closely knit device (for example Lodige KM), with further agglomeration, obtains final high density detergent composition.U.S. Pat 5164108 referring to the Appel that authorized on November 17th, 1992 etc.
Optional fabric conditioner and subsidiary
Auxiliary cation opsonizing agent
The present composition can contain the 5%-95% that has an appointment, preferably about 15%-90%, 25%-85% more preferably from about, even more preferably from about 25%-55% Biodegradable cationic softening agent, preferably ester quat compound (EQA).
The component of optional conditioning fabric is fabric soft compound preferably, and it is ester quat (EQA) compound or its precursor amine with following formula:
[(R
1)
4-p-N
+-((CH
2)
v-Y-R
2)
p]X
-
Formula I
Wherein Y is the carboxy moiety with following formula:
Subscript p is 1-3, and subscript v is 1-4 and its mixture; R
1Be C
1-C
6Alkyl, C
1-C
4Hydroxyalkyl or benzyl, preferred C
1-C
3Alkyl, for example methyl, ethyl, propyl group most preferably are methyl; A preferred R
1Part is a short-chain alkyl, preferable methyl; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl, preferred C
14-C
18Saturated alkyl or C
14-C
18Unsaturated alkyl, C
14-C
18The alkyl or the C that replace
14-C
18Unsubstituted alkyl, more preferably straight chain C
14-C
18Saturated alkyl, wherein each R of Shi Yonging
2Part has iodine number and is about 3-60; Counter ion X
-Can be the compatible negatively charged ion of any softening agent, preferred methyl-sulfuric acid root, etherosulfuric acid root, chlorine, bromine, formate, sulfate radical, lactate, nitrate radical, benzoate anion, more preferably methyl-sulfuric acid root.
Butter are suitable and cheap raw materials of chain alkyl and alkenyl material.
Be appreciated that the substituent R of formula I
1And R
2Optionally by various groups, for example alkoxyl group or hydroxyl replace.Preferred compound is considered to diester (DEQA) variant of ditallow Dimethyl Ammonium Methylsulfate (DTDMAMS), and it is widely used as fabric softener.At least 80%DEQA is a diester form, and 0%-is about 20%, preferably is less than approximately 10%, can be EQA monoesters (one-Y-R only for example more preferably less than about 5%
2Group).
Below be the limiting examples (wherein all chain alkyl substituting groups are straight chains) of the EQA of formula I:
Saturated
[C
2H
5]
2 +N[CH
2CH
2OC(O)C
17H
35]
2(CH
3SO
4)
-
[CH
3][C
2H
5]
+N[CH
2CH
2OC(O)C
13H
27]
2[HC(O)O]
-
[C
3H
7][C
2H
5]
+N[CH
2CH
2OC(O)C
11H
23]
2(CH
3SO
4)
[CH
3]
2 +N-[CH
2CH
2OC(O)C
17H
35]CH
2CH
2OC(O)C
15H
31(CH
3SO
4)
-
[CH
3]
2 +N[CH
2CH
2OC(O)R
2]
2(CH
3SO
4)
-
Wherein-C (O) R
2Obtain by saturated butter.
Undersaturated
[CH
3]
2 +N[CH
2CH
2OC(O)C
17H
33]
2(CH
3SO
4)
-
[C
2H
5]
2 +N[CH
2CH
2OC(O)C
17H
33]
2Cl
-
[CH
3][C
2H
5]
+N[CH
2CH
2OC(O)C
13H
25]
2[C
6H
5C(O)O]
[CH
3]
2 +N-[CH
2CH
2OC(O)C
17H
33]CH
2CH
2OC(O)C
15H
29(CH
3CH
2SO
4)
[CH
3]
2 +N[CH
2CH
2OC(O)R
2]
2(CH
3SO
4)
Wherein-C (O) R
2Obtain by partially hydrogenated butter or modification butter with feature described herein.
Other specific examples that is applicable to the biodegradable formula I compound of fabric sofetening composition of the present invention is:
N-methyl-N, N-two-(2-C
14-C
18The acyloxy ethyl);
N-2-hydroxyethyl ammonium Methylsulfate;
[HOCH(CH
3)CH
2][CH
3]
+N[CH
2CH
2OC(O)C
15H
31]
2Br
-
[HOCH (CH
3) CH
2] [CH
3]
+N[CH
2CH
2OC (O) C
15H
29]
2[HC (O) O]
-With
[CH
2CH
2OH][CH
3]
+N[CH
2CH
2OC(O)R
2]
2(CH
3SO
4)
-。Preferred compound is the N-methyl, N, N-two-(2-oil acyloxy ethyl) N-2-hydroxyethyl ammonium Methylsulfate.
Also the fabric soft compound of Shi Heing is the quaternary ammonium compound with following formula:
[(R
1)
4-p-N
+-((CH
2)
v-Y”-R
2)
p]X
-
Formula II
Y wherein " be carboxy moiety and its mixture with following formula:
Wherein, at least one Y " group is:
Subscript p is 1-3, and subscript v is 1-4 and its mixture; R
1Be C
1-C
6Alkyl or benzyl, preferred C
1-C
3Alkyl, for example methyl, ethyl, propyl group most preferably are methyl; A preferred R
1Part is a short-chain alkyl, preferable methyl; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl, preferred C
14-C
18Saturated alkyl or C
14-C
18Unsaturated alkyl, C
14-C
18The alkyl or the C that replace
14-C
18Unsubstituted alkyl, more preferably straight chain C
14-C
18Saturated alkyl, wherein each R of Shi Yonging
2Part has iodine number and is about 3-60; R
3Be R or H; Counter ion X
-Can be the compatible negatively charged ion of any softening agent, preferred methyl-sulfuric acid root, etherosulfuric acid root, chlorine, bromine, formate, sulfate radical, lactate, nitrate radical, benzoate anion, more preferably methyl-sulfuric acid root.
Be appreciated that substituent R and the R of formula II
2Optionally by various groups, for example alkoxyl group or hydroxyl replace.
The compound (DEQA) that preferred ester connects can be considered to the diester variations of ditallow dimethyl ammonium chloride (DTDMAC), and it is widely used as fabric softener.Preferably, be diester form at least about 80%DEQA, 0%-is about 20%, preferably is less than approximately 10%, can be DEQA monoesters (one-Y-R only for example more preferably less than about 5%
2Group).In order to obtain best antistatic property, monoesters is should content low, preferably is less than about 2.5%.The content of may command monoesters in preparation DEQA.
When some condition satisfies, have to the quaternary ammonium softening compound thing of small part unsaturated alkyl or acyl group and have advantage (being antistatic property) and be that the consumer's goods are the most acceptable.When fabric is dry in rotary drum dryer and/or when using generation electrostatic synthetic materials, antistatic property is a particularly important.The IV value of hereinafter mentioning is meant the IV of aliphatic alkyl or acyl group, rather than refers to the quaternary ammonium that obtains, for example the IV value of DEQA compound.Along with the raising of IV, has the smell problem.
For undersaturated softening agent actives, guarantee that stability and mobile best storing temp depend on the concrete IV value and/or the selected quantity of solvent/type of the lipid acid that for example is used to prepare DEQA.Should avoid being exposed to oxygen as far as possible, to prevent the unsaturated group oxidation.Therefore be important under the nitrogen atmosphere with this material storage for example under the hypoxic atmosphere.Importantly has good fusion stability in storage, to provide the raw material of viable commercial, not obvious degraded in the normal carriage/storage/processing of this raw material in production operation.
Below be the limiting examples (wherein all chain alkyl substituting groups are straight chains) of the DEQA of formula II:
Saturated
[C
2H
5]
2 (+)N[CH
2CH
2OC(O)C
17H
35]
2SO
4(CH
3)
-
[C
3H
7][C
2H
5]
(+)N[CH
2CH
2OC(O)C
11H
23]
2SO
4 (-)CH
3
[CH
3]
2 (+)N[CH
2CH
2OC(O)R
2]
2SO
4CH
3 (-)
Wherein-C (O) R
2Obtain by saturated butter.
Undersaturated
[CH
3]
2 (+)N[CH
2CH
2OC(O)C
17H
33]
2SO
4 (-)CH
3
[C
2H
5]
2 (+)N[CH
2CH
2OC(O)C
17H
33]
2Cl
(-)
[CH
2CH
2OH][CH
3]
(+)N[CH
2CH
2OC(O)R
2]
2CH
3SO
4 (-)
[CH
3]
2 (+)N[CH
2CH
2OC(O)R
2]
2CH
3SO
4 (-)
Wherein-C (O) R
2Obtain by partially hydrogenated butter or modification butter with feature described herein.
The fabric soft compound that also is fit to according to the present invention is the ester quat compound with following formula:
Formula III wherein Q is the carboxy moiety with following formula:
Subscript v is 1-4 and its mixture; R
1Be C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, preferable methyl; A preferred R
1Part is a short-chain alkyl, preferable methyl; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl, preferred C
14-C
18Saturated alkyl or C
14-C
18Unsaturated alkyl, C
14-C
18The alkyl or the C that replace
14-C
18Unsubstituted alkyl, more preferably straight chain C
14-C
18Saturated alkyl, wherein each R of Shi Yonging
2Part has iodine number and is about 3-60; Counter ion X
-It is the methyl-sulfuric acid root.
The example that is suitable as the above-mentioned ester quaternary ammonium compound of fabric soft compound of the present invention is 1,2-two (butter acyloxy)-3-trimethyl ammonium propane Methylsulfate (DTTMAPMS).Other example that is fit to is 1,2-two (cocounut oil acyloxy)-3-trimethyl ammonium propane Methylsulfate, 1,2-two (bay acyloxy)-3-trimethyl ammonium propane Methylsulfate, 1,2-two (oily acyloxy)-3-trimethyl ammonium propane Methylsulfate and 1,2-two (stearoyl-oxy)-3-trimethyl ammonium propane Methylsulfate.Replace the one or more or methyl moiety in the above example can produce with ethyl, propyl group, sec.-propyl, butyl, isobutyl-or its mixture according to suitable fabric soft compound of the present invention.In addition, can use other negatively charged ion of non-methylsulfate.
Other example of the formula III EQA compound that the present invention is suitable is by for example, obtains with " tallow " in the alternative above-claimed cpds such as coco group, lauryl, oil base, stearyl, palmityl for example; The similar group that replaces with the hydroxyl of ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl or these groups substitutes that methyl in the above-claimed cpd obtains; With chlorion, ethyl sulphate, bromide anion, formate, sulfate radical, lactate, nitrate radical etc., " methylsulfate " in the above-claimed cpd obtain but the preferable methyl sulfate radical substitutes.
The fabric soft compound that also is fit to according to the present invention is the ester quat compound with following formula:
Formula IV wherein Y is the carboxy moiety with following formula:
Subscript p is 2; Subscript v is 1-4 and its mixture; R
1Be C
1-C
4Alkyl or hydroxyalkyl, preferred C
1-C
3Alkyl, for example methyl, ethyl, propyl group, most preferable; R
2Be C
8-C
30Saturated or unsaturated, replacement or unsubstituted alkyl, it has iodine number and is about 3-60; Preferred R
2Be C
8-C
14Straight or branched alkyl, more preferably C
8-C
14Straight chained alkyl; R
4Be C
1-C
4Alcohol; Counter ion X can be the compatible negatively charged ion of any softening agent, preferred methyl-sulfuric acid root, etherosulfuric acid root, chlorine, bromine, formate, sulfate radical, lactate, nitrate radical, benzoate anion, more preferably methyl-sulfuric acid root.
Most preferably, quaternary ammonium compound is complete saturated compound, for example dimethyl two that is obtained by hardened tallow (butter acyloxy ethyl) ammonium methyl sulphate.That also be fit to is C
8-C
30The dimethyl two of lipid acid (acyloxy ethyl) ammonium methyl sulphate derivative, for example dimethyl two (butter acyloxy ethyl) ammonium methyl sulphate; Dimethyl two (oily acyloxy ethyl) ammonium methyl sulphate or dimethyl two (cocounut oil acyloxy ethyl) ammonium methyl sulphate.The present composition can comprise these quaternary ammonium compounds of about 15%-90%.
The example that is suitable as the above-mentioned ester quaternary ammonium compound of fabric soft compound of the present invention is N-methyl-N, N-two-(2-C
14-C
18Acyloxy) ethyl-N-2-hydroxyethyl ammonium Methylsulfate.Preferred examples is N-methyl-N, N-two (2-oil acyloxy ethyl)-N-(2-hydroxyethyl) ammonium methyl sulphate.
Fabric-conditioning compositions can be prior art known those and/or by those disclosed in other people the former patent application.The composition that is fit to is disclosed in the U.S. Pat 3944694 of McQueary; The US4073996 of Bedenk etc.; The US4237155 of Kardouche; The US4711730 of Gosselink etc.; The US4749596 of Evans etc.; The US4808086 of Evans etc.; The US4818569 of Trinh etc.; The US4877896 of Maldonado etc.; The US4976879 of Maldonado etc.; Borcher, the US5041230 of Sr. etc.; The US5094761 of Trinh etc.; US5102564 such as Gardlik; The US5234610 of Gardlik etc., all described patents are quoted for referencial use at this paper.
The above-claimed cpd of this paper can pass through standard esterification and quaterisation, uses facile feedstock production.General preparation method is disclosed among the US4137180, and it quotes for referencial use at this paper.
As described herein, when explanation two ester quats, it comprises the monoesters quaternary ammonium salt of common existence.In order to obtain best antistatic property, the percentage ratio of monoesters quaternary ammonium salt should be low as far as possible, preferably is lower than about 20%.The amount of the monoesters quaternary ammonium salt that may command exists in preparation EQA.
But with the EQA compound fast degraded biologically of fully saturated acyl group preparation and be excellent softening agent.Yet, find, when some condition satisfies, use to the compound of small part unsaturated acyl base preparation to have advantage (being antistatic property) and be that the consumer's goods are the most acceptable.
For obtaining using the benefit of unsaturated acyl group, the variable that must regulate comprises the smell of iodine number (IV), raw material of fatty acid and/or the EQA of lipid acid.Any IV value of hereinafter mentioning is meant the IV of fatty acyl group, is not the IV of the EQA compound that obtains.
When fabric is dry in rotary drum dryer and/or when using generation electrostatic synthetic materials, antistatic property is a particularly important.Along with the raising of IV, has the smell problem.
Some is highly desirable, facile fatty acid source, and for example butter have unpleasant odor, although through the raw material butter being converted into chemistry and the mechanical processing steps of final EQA, it still is retained among the compd E QA.This raw material must for example be deodorized by absorbing, distill technology well known in the prior art such as (comprising stripping, for example steam stripped).In addition, should carefully reduce the unfavorable result that the fatty acyl group of generation contacts with oxygen and/or bacterium by adding antioxidant, antiseptic-germicide etc.Prove the additional cost of relevant unsaturated fatty acyl group and make great efforts to be worthwhile by this good performance.
Be generally the hydrogenation that reduces many degrees of unsaturation and reduce the lipid acid that IV carries out to guarantee good color and odor stable causes having height in molecule transconfiguration.Thereby, can mix complete hydrogenant lipid acid by ratio and a little hydrogenant lipid acid prepares the diester compound that is obtained by the fatty acyl group with low IV value with IV that about 3-60 is provided.It is about 5% that the how unsaturated content of a little hardened lipid acid should be lower than, and preferably is lower than about 1%.In a little process of setting, the weight ratio of suitable/trans isomer can for example mix, uses special catalyzer, high hydrogen availability etc. is provided by the best by currently known methods control of the prior art.
We also find, be to obtain the good chemical stability of diester quat in fusion stores, the water-content in the raw material must be reduced to preferably be less than about 1%, more preferably less than about 0.5%.Storing temp should keep low as much as possible and still keep fluid materials, ideally in about 49 ℃ of-75 ℃ of scopes.For guaranteeing stability and flowability, best storing temp depends on the concrete IV of the lipid acid that is used to prepare diester quat and the content/type of selected solvent.In addition, should avoid being exposed to oxygen as far as possible to prevent the unsaturated group oxidation.Therefore, importantly material is stored under the oxygen atmosphere of reduction, for example under the nitrogen atmosphere.Importantly has good fusion stability in storage, to provide the raw material of viable commercial, not obvious degraded in the normal carriage/storage/processing of this raw material in production operation.
Be used for auxiliary fabric sofetening composition of the present invention and contain as the tertiary amine with following formula of optional components and/or the carboxylate salt of ester amine, its content is about 0%-95%, preferably about 20%-75%, more preferably from about 20%-60%:
R wherein
5It is the long-chain aliphatic group that contains 8-30 the carbon atom of having an appointment; R
4And R
6Be identical or different group and be independently selected from aliphatic group, the formula R that contains 1-30 the carbon atom of having an appointment
8The hydroxyalkyl of OH, wherein R
8Be the alkylidene group and the formula R of about 2-30 carbon atom
9O (R
10O)
m-the polyalkylene oxide base section, R wherein
9Be hydrogen, C
1-C
30Alkyl, C
1-C
30Alkenyl and its mixture; R
10Be ethylidene, propylene, trimethylene and its mixture; M is about 2-10; Wherein other R
4, R
5, R
6, R
8And R
9Chain is inserted with the group of ester group; And R
7Be selected from C
2-C
30Straight chained alkyl, C
2-C
30Straight alkenyl, C
8-C
30Aryl, C
8-C
30Alkaryl and C
8-C
30Aralkyl; The C that replaces
1-C
30Straight chained alkyl, C
1-C
30Straight alkenyl, C
8-C
30Aryl, C
8-C
30Alkaryl and C
8-C
30Aralkyl, wherein substituting group is selected from halogen, carboxyl and hydroxyl, and described composition has about 35 ℃-100 ℃ thermal softening point.
R
5Preferably contain the C that has an appointment
12-C
30The aliphatic chain of straight chained alkyl, R
6Be C
12-C
30Straight chained alkyl, and R
4Be C
1-C
30Straight chained alkyl.
Being used between amine and the carboxylic acid reaction with the example as the preferred tertiary amine of raw material that forms tertiary ammonium salt is: lauryl dimethyl amine, myristyl dimethyl amine, stearyl dimethyl amine, tallow dimethyl amine, coco dimethyl amine, dilauryl methylamine, distearyl methylamine, ditallow methylamine, oil base dimethyl amine, two oil base methylamine, lauryl two (3-hydroxypropyl) amine, stearyl two (2-hydroxyethyl) amine, three lauryl amines, lauryl ethylmethylamine and
Preferred lipid acid is R wherein
7Be C
8-C
30Straight chained alkyl, more preferably C
11-C
17Those of straight chained alkyl.
The example that is used as the specific carboxylic acid of raw material is: formic acid, acetate, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, oxalic acid, hexanodioic acid, 12-oxystearic acid, phenylformic acid, 4-hydroxy-benzoic acid, 3-chloro-benzoic acid, 4-nitrobenzoic acid, 4-ethyl benzoate, 4-(2-chloroethyl) phenylformic acid, phenylacetic acid, (4-chloro-phenyl-) acetate, (4-hydroxy phenyl) acetate and terephthalic acid.
Preferred carboxylic acid is stearic acid, oleic acid, lauric acid, tetradecanoic acid, palmitinic acid and their mixture.
Amine salt can form by simple addition reaction well known in the prior art, and this method is open in the US4237155 of the Kardouche of promulgation on December 2nd, 1980, and it quotes for referencial use at this paper.Excessive unhindered amina can cause the smell problem, compares with amine salt, and unhindered amina provides relatively poor softness usually.
The preferred amine salt as optional components that is used for this paper is that wherein amine moiety is C
8-C
30Alkyl or alkenyl dimethyl amine or two-C
8-C
30Alkyl or alkenyl methylamine and acid moieties are C
8-C
30The compound of alkyl or alkenyl monocarboxylic acid.The amine and the acid that are used to form amine salt have the mixing chain length usually respectively, rather than single chain length, because these materials are obtained by natural fat and oil usually, or synthetic obtaining, it produces the mixture of chain length.Usually need to use physics or the performance characteristic of mixture to improve soft compound of different chain length in addition.
Being used for concrete preferred amine salt of the present invention is oil base dimethyl amine stearate, stearyl dimethyl amine stearate, stearyl dimethyl amine myristate, stearyl dimethyl amine oleate, stearyl dimethyl amine palmitate, distearyl methylamine palmitate, distearyl methylamine lauroleate and their mixture.Especially preferred mixture is that ratio is 1: 10-10: 1, and preferred about 1: 1 oil base dimethyl amine stearate and distearyl methylamine myristate.
Auxiliary nonionic amendment
The softening agent that the present invention chooses wantonly is a nonionic fabric softener material.Generally, it is about 2-9 that this nonionic fabric sofetening agent material has HLB, more generally is about 3-7.Usually, selected this material should be relative crystalline, and high melt point is arranged, (for example＞25 ℃).
The content of the optional NON IONIC SOFTNER in solids composition is generally about 10%-50%, preferably about 15%-40%.
Preferred NON IONIC SOFTNER is the partial fatty acid ester of polyvalent alcohol or their acid anhydride, and wherein alcohol or acid anhydride contain the 2-18 that has an appointment, preferably about 2-8 carbon atom, and each fatty acid part contains the 8-30 that has an appointment, preferably about 12-20 carbon atom.Generally, this softening agent per molecule contains the 1-3 that has an appointment, preferred about 2 fatty acid groups.
The polyol moiety of ester can be ethylene glycol, glycerine, poly-(for example two-, three-, four-, five-and/or six-) glycerine, Xylitol, sucrose, tetrahydroxybutane, tetramethylolmethane, Sorbitol Powder or sorbitan.
Usually by containing the 8-30 that has an appointment, the lipid acid of preferably about 12-22 carbon atom obtains the fatty acid part of ester.The representative instance of described lipid acid is lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid He docosoic.
Being used for highly preferred optional NON IONIC SOFTNER of the present invention is C
10-C
26Acyl group sorbitan ester and Polyglycerine monostearate.Sorbitan ester is the esterification dewatered product of Sorbitol Powder.Preferred sorbitol ester contains and is selected from C
10-C
26Acyl group sorbitan monoesters and C
10-C
26The material of the ethoxylate of acyl group sorbitan diester and described ester, wherein the one or more no esterification hydroxyls in described ester contain about 6 oxygen ethylene unit of 1-and their mixture.For the object of the invention, can use the sorbitan ester (for example dehydrated sorbitol mono-fatty acid ester) that contains degree of unsaturation.
The general Sorbitol Powder that is prepared by the catalytic hydrogenation of glucose can dewater to form 1,4-and 1, the mixture of 5-sorbitan and a small amount of Isosorbide acid anhydride (isosorbide) by known method.(referring to the US2322821 of the Brown that issues June 29 nineteen forty-three, it quotes for referencial use at this paper).
The complex mixture of the above-mentioned type of sorbitan is referred to as " sorbitan " in this article.Be appreciated that this " sorbitan " mixture will contain also that some is free, the Sorbitol Powder of cyclisation not.
The preferred sorbitan softening agent that is used for the type of the present invention can be by using fatty acyl group with standard method esterification " sorbitan " mixture, for example by preparing with fatty carboxylic acid halides, fatty acid ester and/or fatty acid response.Esterification can occur on any available hydroxyl and can prepare various lists-, two-etc. ester.In fact, almost always can obtain by this reaction single-, the mixture of two, three esters etc., the stoichiometric ratio of conditioned reaction thing is to help required reaction product simply.
In the industrial production of sorbitan ester material, usually in same procedure of processing by Sorbitol Powder directly and fatty acid response finish etherificate and esterification.The preparation method of this sorbitan ester more completely is described in MacDonald; " emulsifying agent: processing and quality control "; " american petroleum chemistry meeting will ", 45 volumes, October nineteen sixty-eight.
The detailed description of preferred sorbitan ester comprises that chemical formula can be referring to US4128484, and it quotes for referencial use at this paper.
Some derivative of preferred sorbitan ester of the present invention, especially their " rudimentary " ethoxylate (promptly single-, two-and three-ester, wherein one or more nonesterified-OH groups contain about 20 the oxyethylene group groups of 1-(Tweens )) also be applicable to composition of the present invention.Therefore, for the object of the invention, term " sorbitan ester " comprises this derivative.
That the industrial this material of selling as sorbitan monoesters (for example monostearate) in fact contains is a large amount of two-and three-ester, the general analysis of sorbitan monostearate shows that it contains 27% monoesters of having an appointment, 32% diester and 30% 3 ester and four esters.Therefore industrial sorbitan monostearate is preferred material.Has stearate/cetylate weight ratio 10: 1-1: 10 the sorbitan stearate and the mixture and 1 of dehydrated sorbitol palmitate, the 5-sorbitan ester is useful, 1,4-and 1,5-sorbitan ester are useful in the present invention.
Other the useful alkyl sorbitan ester that is used for soft compound of the present invention comprises sorbitan monolaurate, sorbitan list myristinate, the sorbitan monopalmitate, sorbitan Dan docosoic ester, dehydrated sorbitol mono-fatty acid ester, the sorbitan dilaurate, sorbitan two myristinates, the sorbitan dipalmitate, dehydrated sorbitol distearate, sorbitan Er docosoic ester, sorbitan dioleate and their mixture and blended tallow alkyl sorbitan list-and two-ester.This mixture can be easily by the sorbitan that above-mentioned hydroxyl is replaced, especially 1,4-and 1, the 5-sorbitan is carrying out prepared in reaction with corresponding acid, ester or carboxylic acid halides in simple esterification.Certainly, it should be understood that the industrial material with this method preparation will contain mixture, it contains a spot of not cyclisation Sorbitol Powder, lipid acid, polymkeric substance, Isosorbide acid anhydride works etc. usually.In the present invention, this impurity preferably exists with alap content.
Be used for preferred sorbitan ester of the present invention and can contain by weight C up to about 15%
20-C
26The more ester of high-grade lipid acid and a spot of C
8Fatty acid ester with even lower level.
Glycerine and polyglycerol ester, especially glycerine, two glycerine, triglycerin and Polyglycerine list-and/two-ester, preferred monoesters also is the present invention's preferred (for example Polyglycerine monostearate of commodity Radiasurf 7248 by name).Glyceryl ester can be by naturally occurring triglyceride by normal extraction, purifying and/or Lactonization method or by the above-mentioned esterification process preparation that is used for sorbitan ester.The part ester of glycerine also can be by ethoxylation to be formed with the derivative in the term " glyceryl ester " of being included in of usefulness.
Useful glycerine and polyglycerol ester comprise and stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, tetradecanoic acid and/or the monoesters of docosoic and the diester of stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, docosoic and/or tetradecanoic acid.Can understand, general monoesters contains some two-and three-esters etc.
" glyceryl ester " also comprises Polyglycerine, for example two glycerine to eight glyceryl ester.The Polyglycerine polyvalent alcohol connects glycerine through ehter bond and partly forms by condensating glycerine or Epicholorohydrin together.The list of preferred Polyglycerine polyvalent alcohol-and/or diester, fatty acyl group is generally above-mentioned those fatty acyl groups that are used for sorbitan and glyceryl ester.
Moisture eliminator activatory fabric sofetening composition of the present invention also can comprise auxiliary softening agent.Should assist softening agent can comprise carboxylate salt, tertiary amine ester or its mixture of tertiary amine.Should assist the anionicsite that forms carboxylate salt in the softening agent can be selected from lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid and its mixture.Should assist the amine salt of softening agent can be selected from oil base dimethyl amine stearate, two oil base methylamine stearate, inferior oil base dimethyl amine stearate, two inferior oil base methylamine stearate, stearyl dimethyl amine stearate, distearyl methylamine myristate, stearyl dimethyl amine palmitate, distearyl methylamine palmitate, distearyl methylamine myristate, distearyl methylamine palmitate, distearyl methylamine lauroleate, two oil base distearyl methylamine oleates, distearyl methylamine oleate and its mixture.
Optional cyclodextrin/complex flavor and free spice
Product of the present invention also can contain the 0.5%-60% that has an appointment, preferred about 1%-50% cyclodextrin/spices inclusion complex and/or free spice, described in the US5234610 of the US5139687 of the Borcher of on August 18th, 1992 promulgation etc. and the Gardlik of promulgation on August 10th, 1993 etc., it quotes for referencial use at this paper.Spices is highly required, and it is favourable protecting usually, and can cooperate with cyclodextrin.The fabric sofetening product generally contains spices, the sense of smell aesthetic effect to be provided and/or to be effective a kind of indicator signal as product.
Optional perfume composition of the present invention and composition are known conventional perfume composition of prior art and composition.The selection of any perfume composition or flavour content only is based on aesthetic feeling and considers.Suitable flavor compounds and composition can be referring to prior aries, the US4152272 of the Young that comprises the US4515705 of the Moeddel that the US4209417 of the Whyte that the Brain of promulgation on March 20th, 1979 and the US4145184 of Cummins, on June 24th, 1980 issue, on May 7th, 1985 issue and issued on May 1st, 1979, all patents are quoted document for referencial use at this paper.The known flavor compositions of many prior aries is relative affinity, and its smell is at utmost acted on the substrate.But it is particularly advantageous providing spices through spices/beta-cyclodextrin composition, and it makes that the spices of non-affinity also is effective.
Contain spices free and that cooperate as fruit product, the spices of sealing with title complex can strengthen total fragrance scent intensity, therefore produces longer long lasting fragrance effect.
Described in the US5234610 of the Gardlik/Trinh/Banks/Benvegnu of on August 3rd, 1993 promulgation, described patent is quoted document for referencial use at this paper, by regulating the content of free spice and spices/CD title complex, can be provided in the good aroma profile of time (release) and/or spices individual character (characteristic) aspect wide region.Solid-state moisture eliminator activatory fabric-conditioning compositions is a kind of unique ideal style that applies cyclodextrin, because later stage of the fabric treating state that they can be when cleaning fabric and ought almost not have to provide under other the processing of the cyclodextrin removed.
Stablizer
In the present composition, can there be stablizer.The term " stablizer " that the present invention uses comprises antioxidant and reductive agent.The amount of these reagent is 0% to about 2%, is preferably about 0.01% to about 0.2%, and for antioxidant, more preferably from about 0.05% to about 0.1%, for reductive agent, and more preferably about 0.01% to 0.2%.This has guaranteed that composition has good odor stable under the condition of storage for a long time.It is particularly advantageous using antioxidant and reductive agent stablizer for low fragrance product (low spices).
The example that can add the antioxidant in the present composition comprises the mixture of xitix, Quicifal, Tenox PG, and by Eastman ChemicalProducts, Inc. buys, and commodity are called Tenox
PG and Tenox S-1; The mixture of BHT, BHA, Tenox PG and citric acid, by Eastman ChemicalProducts, Inc. buys, and commodity are called Tenox-6; Butylated hydroxytoluene is buied by UOPProcess Division, and commodity are called Sustane
BHT; Tertiary butylated hydroquinone, Eastman Chemical Products, Inc. is Tenox TBHQ; Natural tocopherol, Eastman Chemical Products, Inc. is Tenox GT-1/GT-2; With butylated BHA, Eastman Chemical Products, Inc. is BHA.
The example of reductive agent comprises sodium borohydride, Hypophosporous Acid, 50 and their mixture.
Other auxiliary component
The present invention can comprise that routine is used for other auxiliary component (minor component) of fabric treatment composition, for example for example guar gum and polyoxyethylene glycol, antishrinking agent, anti wrinkling agent, fabric stiffener, spotting agent, sterilant, mycocide, corrosion inhibitor, defoamer etc. of tinting material, spices, perfume systems, sanitas, white dyes, opalizer, stablizer.
The matrix article
In preferred embodiments, the present invention includes goods.Representational goods are to be suitable for those of in automatic laundry dryer soft fabric, and its type is disclosed in the U.S. Pat 3989631 of the Marsan that authorized on November 2nd, 1976; The U.S. Pat 4055248 of the Marsan that on October 25th, 1977 authorized; The U.S. Pat 4073996 of the Bedenk that on February 14th, 1978 authorized etc.; The U.S. Pat 4022938 of the Zaki that on May 10th, 1977 authorized etc.; The U.S. Pat 4764289 of the Trinh that on August 16th, 1988 authorized; The U.S. Pat 4808086 of the Evans that on February 28th, 1989 authorized etc.; The U.S. Pat 4000340 of the Murphy that on December 28th, 1976 authorized etc.; The U.S. Pat 4103047 of the Zaki that on July 25th, 1978 authorized etc.; The U.S. Pat 3736668 of the Dillarstone that on June 5th, 1973 authorized; The U.S. Pat 3701202 of the Compa that on October 31st, 1972 authorized etc.; The U.S. Pat 3634947 of the Furgal that on January 18th, 1972 authorized etc.; The U.S. Pat 3633538 of the Hoeflin that on January 11st, 1972 authorized; The U.S. Pat 3435537 of the Rumsey that on April 1st, 1969 authorized; All described patents are quoted for referencial use at this paper.
Embodiment 1
3-O THP trtrahydropyranyl 3,7-dimethyl-1, the preparation of 6-octadiene-3-alcohol (THP of phantol)
In flask at the bottom of the 250ml state that argon gas inlet tube and condenser are housed, add phantol (6.62g, 41.6mmol).With 2, (5.41g 62.4mmol) is dissolved in the methylene dichloride (100ml) the 3-dihydropyrane, and the solution that obtains adds and contains in the flask of phantol.(1.07g, 4.2mmol), this fixture at room temperature stirred about 4 hours to add the tosic acid pyridine.To separating funnel, with diethyl ether (150ml) dilution, with saturated NaCl extraction, organic phase is through MgSO with the substance transfer in the reaction vessel
4Dry.Go down to desolventize in vacuum,, obtain colorless oil by thick material is also carried out purifying with sherwood oil/2% eluent ethyl acetate with the oily matter that obtains through silica gel.
Embodiment 2
3-O-THP trtrahydropyranyl 2, the preparation of 6-dimethyl-7-octen-2-ol (THP of dihydromyrcenol)
In the 250ml round-bottomed flask that argon gas inlet tube and condenser are housed, add phantol (10.0g, 64.0mmol).With 2, (8.07g 96.0mmol) is dissolved in the methylene dichloride (75ml) the 3-dihydropyrane, and the solution that obtains adds and contains in the flask of phantol.(1.07g, 4.2mmol), this fixture at room temperature stirred about 4 hours to add the tosic acid pyridine.Substance transfer in the reaction vessel to separating funnel, with diethyl ether (150ml) dilution, with saturated NaCl extraction, is washed with water then, and organic phase is through MgSO
4Dry.Go down to desolventize in vacuum,, obtain colorless oil by thick material is also carried out purifying with sherwood oil/2% eluent ethyl acetate with the oily matter that obtains through silica gel.
Embodiment 3
3-O-tetrahydrofuran base 3,7-dimethyl-1, the preparation of 6-octadiene-3-alcohol (THF of phantol)
In the 250ml round-bottomed flask that argon gas inlet tube and condenser are housed, add phantol (7.09g, 44.6mmol).(3.16g 44.6mmol) is dissolved in the methylene dichloride (100ml), and the solution that obtains adds and contains in the flask of phantol with 2,3 dihydro furan.(1.07g, 4.2mmol), this fixture at room temperature stirred about 6 hours to add the tosic acid pyridine.To separating funnel, with diethyl ether (150ml) dilution, with saturated NaCl extraction, organic phase is through MgSO with the substance transfer in the reaction vessel
4Dry.Go down to desolventize in vacuum,, obtain colorless oil by thick material is also carried out purifying with sherwood oil/2% eluent ethyl acetate with the oily matter that obtains through silica gel.
Embodiment 4
3-O-tetrahydrofuran base 2, the preparation of 6-dimethyl-7-octen-2-ol (THF of dihydromyrcenol)
In the 250ml round-bottomed flask that argon gas inlet tube and condenser are housed, add phantol (6.9g, 44.2mmol).(3.13g 44.2mmol) is dissolved in the methylene dichloride (75ml), and the solution that obtains adds and contains in the flask of phantol with 2,3 dihydro furan.Add tosic acid pyridine (trace), this fixture at room temperature stirred about 6 hours.Substance transfer in the reaction vessel to separating funnel, with diethyl ether (150ml) dilution, with saturated NaCl extraction, is washed with water then, and organic phase is through MgSO
4Dry.Go down to desolventize in vacuum,, obtain colorless oil by thick material is also carried out purifying with sherwood oil/2% eluent ethyl acetate with the oily matter that obtains through silica gel.
Embodiment 5-13
It below is the example that comprises the granular detergent composition of fragrance precursor of the present invention.
Table 1 weight % component 5678
| C 11-C 13Sodium alkyl benzene sulfonate | ????13.3 | ????13.7 | ????10.4 | ????11.1 |
| C 14-C 15Alcohol sodium sulfate | ????3.9 | ????4.0 | ????4.5 | ????11.2 |
| C 14-C 15Alcohol ethoxylate (0.5) sodium sulfate | ????2.0 | ????2.0 | ????0.0 | ????0.0 |
| C 14-C 15Alcohol ethoxylate (6.5) sodium sulfate | ????0.5 | ????0.5 | ????0.5 | ????1.0 |
| Tallow fatty acid | ????0.0 | ????0.0 | ????0.0 | ????1.1 |
| Tripoly phosphate sodium STPP | ????0.0 | ????41.0 | ????0.0 | ????0.0 |
| Zeolite A, hydrate (0.1-10 micron) | ????26.3 | ????0.0 | ????21.3 | ????28.0 |
| Yellow soda ash | ????23.9 | ????12.4 | ????25.2 | ????16.1 |
| Sodium polyacrylate (45%) | ????3.4 | ????0.0 | ????2.7 | ????3.4 |
| Water glass (NaO/SiO 2Ratio 1: 6) (46%) | ????2.4 | ????6.4 | ????2.1 | ????2.6 |
| Sodium sulfate | ????10.5 | ????10.9 | ????8.2 | ????15.0 |
| Sodium peroxoborate | ????1.0 | ????1.0 | ????5.0 | ????0.0 |
| Poly-(ethylene glycol), MW～4000 (50%) | ????1.7 | ????0.4 | ????1.0 | ????1.1 |
| Citric acid | ????0.0 | ????0.0 | ????3.0 | ????0.0 |
| The nonyl ester of p-hydroxy benzenyl sulfonate sodium | ????0.0 | ????0.0 | ????5.9 | ????0.0 |
| Soil release polymers 1 | ????1.5 | ????0.0 | ????0.0 | ????0.0 |
| Soil release polymers 2 | ????0.0 | ????1.5 | ????0.0 | ????0.0 |
| Soil release polymers 3 | ????0.0 | ????0.5 | ????0.5 | ????0.5 |
| Fragrance precursor 4 | ????1.0 | ????1.5 | ????0.0 | ????0.0 |
| Fragrance precursor 5 | ????0.0 | ????0.0 | ????2.5 | ????1.5 |
| Minor component 6 | ????7.0 | ????2.1 | ????4.1 | ????6.3 |
1. according to the soil release polymers of the U.S. Pat 4968451 of the Scheibel that authorizes November 6 nineteen ninety etc.
2. according to the Gosselink that authorizes May 16 nineteen ninety-five, Pan, the soil release polymers of the U.S. Pat 5415807 of Kellett and Hall.
3. according to the soil release polymers of the U.S. Pat 4702857 of the Gosselink that authorized on October 27th, 1987.
4. according to the fragrance precursor of embodiment 1.
5. according to the fragrance precursor of embodiment 2.
6. equal amount to 100% can for example comprise such as white dyes, spices, suds suppressor, dirt dispersant, proteolytic enzyme, lipase, cellulase, sequestrant, dye transfer inhibitor, additional water and filler, comprises CaCO
3, talcum, silicate etc. minor component.
It below is the example that comprises the liquid laundry detergent compositions of fragrance precursor of the present invention.
Table II
Composition weight %
9???????????10????????????11????????????12??????????13
| Poly-hydroxy fatty acid distribution of coconut oil acid amides | ???3.50 | ???3.50 | ???3.15 | ???3.50 | ???3.00 |
| NEODOL?23-9 1 | ???2.00 | ???0.60 | ???2.00 | ???0.60 | ???0.60 |
| C 25Alkyl ethoxylate sulfate | ???19.00 | ???19.40 | ???19.00 | ???17.40 | ???14.00 |
| C 25Alkyl-sulphate | ???- | ???- | ???- | ???2.85 | ???2.30 |
| C 10The aminopropyl acid amides | ???- | ???- | ???- | ???0.75 | ???0.50 |
| Citric acid | ???3.00 | ???3.00 | ???3.00 | ???3.00 | ???3.00 |
| Tallow fatty acid | ???2.00 | ???2.00 | ???2.00 | ???2.00 | ???2.00 |
| Ethanol | ???3.41 | ???3.47 | ???3.34 | ???3.59 | ???2.93 |
| Propylene glycol | ???6.22 | ???6.35 | ???6.21 | ???6.56 | ???5.75 |
| Monoethanolamine | ???1.00 | ???0.50 | ???0.50 | ???0.50 | ???0.50 |
| Sodium hydroxide | ???3.05 | ???2.40 | ???2.40 | ???2.40 | ???2.40 |
| Paratoluenesulfonic acid sodium salt | ???2.50 | ???2.25 | ???2.25 | ???2.25 | ???2.25 |
| Borax | ???2.50 | ???2.50 | ???2.50 | ???2.50 | ???2.50 |
| Proteolytic enzyme 2 | ???0.88 | ???0.88 | ???0.88 | ???0.88 | ???0.88 |
| Lipase 3 | ???0.04 | ???0.12 | ???0.12 | ???0.12 | ???0.12 |
| Duramyl 4 | ???0.10 | ???0.10 | ???0.10 | ???0.10 | ???0.40 |
| CAREZYME | ???0.053 | ???0.053 | ???0.053 | ???0.053 | ???0.053 |
| White dyes | ???0.15 | ???0.15 | ???0.15 | ???0.15 | ???0.15 |
| Fragrance precursor 5 | ???1.18 | ???1.18 | ???1.18 | ???1.18 | ???1.75 |
| Dirt release agent 6 | ???0.22 | ???0.15 | ???0.15 | ???0.15 | ???0.15 |
| Forge the silicon-dioxide of system | ???0.119 | ???0.119 | ???0.119 | ???0.119 | ???0.119 |
| Minor component, aesthstic reagent, water | Equal amount | Equal amount | Equal amount | Equal amount | Equal amount |
1. the C that sells by Shell Oil company
12-C
13Alkyl E9 ethoxylate.
2.Genencor the bacillus amyloliquefaciens subtilysin that International describes in the WO95/10615 that announces April 20 nineteen ninety-five.
3. by also can being purchased that fetal hair humicola lanuginosa (Humicola lanuginosa) obtains from Novo.
4. be disclosed among the WO9510603A and also can buy from Novo.
5. according to the fragrance precursor of embodiment 3.
6. disclosed terephthalic acid ester copolymer in the U.S. Pat 4968451 of the Scheibel that authorizes in November 6 nineteen ninety etc.
Embodiment 14
It below is the example that comprises the solid bleach composition of fragrance precursor of the present invention.
Table III
Composition weight %
| Nonanoly acyloxy benzene sulfonate | ????7.0 |
| Sodium peroxoborate | ????20.0 |
| DTPA 1 | ????10.0 |
| Citric acid (coating) | ????20.0 |
| Spices 2 | ????1.0 |
| Fragrance precursor 3 | ????2.0 |
| Sodium sulfate | Equal amount |
1. diethylene triaminepentaacetic acid(DTPA).
2. dihydromyrcenol.
3. according to the fragrance precursor of embodiment 4.
Embodiment 15
It below is the example that comprises the liquid bleaching composition packed of fragrant-inner agent precursor of the present invention.
Table IV
Composition weight %
| Clorox | ????5.25 |
| C 12Dimethyl oxidation amine | ????0.9 |
| White dyes 1 | ????0.3 |
| Spices 2 | ????1.0 |
| Fragrance precursor 3 | ????2.0 |
| Sodium hydroxide | ????1.0 |
| Water | Equal amount |
1.4,4-two (4-phenyl-2-H-1,2,3-triazolyl)-(2)-stilbene-2,2-disulfonic acid di-potassium.
2. the mixture of phantol (20%), tetrahydrolinalool (30%), galaxolide (Galaxolide) (30%) and citral dimethylacetal (20%).
3. according to the fragrance precursor (1: 1 mixture) of embodiment 1 and 3.
Table V
It below is the example that comprises the fabric-conditioning compositions of fragrance precursor of the present invention.
Weight %
Component 16 17 18 19 20
| DEQA | ???2.6 | ???2.9 | ???18.0 | ???19.0 | ???19.0 |
| Lipid acid | ???0.3 | ???- | ???1.0 | ???- | ???- |
| Hydrochloric acid | ???0.02 | ???0.02 | ???0.02 | ???0.02 | ???0.02 |
| PEG | ???- | ???- | ???0.6 | ???0.6 | ???0.6 |
| Fragrance precursor 1 | ???1.0 | ???1.0 | ???1.0 | ???1.0 | ???1.0 |
| Polysiloxane defoamers | ???0.01 | ???0.01 | ???0.01 | ???0.01 | ???0.01 |
| PEI?1200?E1 2 | ???2.0 | ???2.0 | ???1.0 | ???1.5 | ???2.5 |
| Dyestuff (ppm) | ???10 | ???10 | ???50 | ???50 | ???50 |
| Water and minor component | Equal amount | Equal amount | Equal amount | Equal amount | Equal amount |
1. according to the fragrance precursor of embodiment 1.
2. according to the United States Patent (USP) of the Watson that authorized on October 15th, 1996 etc.
PE 1200 EI of US5565145.
Table VI
It below is the example that comprises the fabric-conditioning compositions of fragrance precursor of the present invention.
Weight %
Component 21 22 23 24
| Poly-hydroxy fatty acid distribution of coconut oil acid amides | ???3.65 | ???3.50 | ???- | ???- |
| C 12-C 13Alcohol ethoxylate E 9 | ???3.65 | ???0.80 | ???- | ???- |
| C 12-C 15Alcohol sodium sulfate | ???6.03 | ???2.50 | ???- | ???- |
| DTDMAMS | ???1.00 | ???1.00 | ???3.00 | ???3.00 |
| PEI?1200?E1 1 | ???4.00 | ???4.00 | ???4.00 | ???4.00 |
| Fragrance precursor 2 | ???1 | ???1 | ???1 | ???1 |
| Spices/beta-cyclodextrin composition | ???- | ???20 | ???- | ???20 |
| Succsinic acid two geranyl esters | ???1 | ???0.50 | ???1 | ???1 |
| Carrier and minor component | Equal amount | Equal amount | Equal amount | Equal amount |
1. according to PE 1200 E1 of the U.S. Pat 5565145 of the Watson that authorized on October 15th, 1996 etc.
2. according to the fragrance precursor of embodiment 2.
Claims (9)
1. fragrance precursors, it has formula:
Wherein R is a perfume material alcohol, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Each is independently:
A) hydrogen;
B) C
1-C
22The straight or branched alkyl;
C) C
2-C
22The straight or branched alkenyl;
D) C
1-C
22The straight or branched alkoxyl group;
E) C
6-C
20Replace or unsubstituted aryl;
F) C
2-C
20Replace or unsubstituted alkylene oxide group;
G) C
3-C
20Replace or unsubstituted alkylene oxide group alkyl;
H) C
7-C
20Replace or unsubstituted alkylidene aryl;
I) C
6-C
20Replace or unsubstituted aryloxy;
J) C
7-C
20Replace or unsubstituted alkylene oxide group aryl;
K) C
7-C
20The oxyalkylene aryl;
L) C
2-C
20The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-
R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12Straight or branched alkyl, M are hydrogen or salifiable positively charged ion, and x is the integer of 1-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, or its mixture; Y is the integer of 1-22; With
P) its mixture.
2. according to the compound of claim 1, R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8The hydrogen of respectively doing for oneself.
3. according to the compound of claim 2, wherein R is selected from phantol, tetrahydrolinalool, dihydromyrcenol, myrcenol and its mixture.
4. laundry detergent composition with enhanced fragrance retention and fragrance weather resistance, it comprises:
A) spices of at least 0.01% weight provides system, and this system comprises:
I) has the fragrance precursors of following formula;
Wherein R is a perfume material alcohol, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Each is independently: a) hydrogen; B) C
1-C
22The straight or branched alkyl; C) C
2-C
22The straight or branched alkenyl; D) C
1-C
22The straight or branched alkoxyl group; E) C
6-C
20Replace or unsubstituted aryl; F) C
2-C
20Replace or unsubstituted alkylene oxide group; G) C
3-C
20Replace or unsubstituted alkylene oxide group alkyl; H) C
7-C
20Replace or unsubstituted alkylidene aryl; I) C
6-C
20Replace or unsubstituted aryloxy; J) C
7-C
20Replace or unsubstituted alkylene oxide group aryl; K) C
7-C
20The oxyalkylene aryl; L) C
2-C
20The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12Straight or branched alkyl, M are hydrogen or salifiable positively charged ion, and x is the integer of 1-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, or its mixture; Y is the integer of 1-22;
P) and its mixture;
Ii) one or more perfume materials randomly;
Iii) randomly fragrance carrier provides the subsidiary of fragrance with other;
B) at least 0.01% weight detersive surfactant, it is selected from anionic, cationic, non-ionic type, zwitter-ion, amphoterics and its mixture; With
C) carrier of equal amount and annexing ingredient, described annexing ingredient are selected from washing assistant, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleaching catalyst, bleach-activating agent, free dirt polymkeric substance, dye-transfer, dispersion agent, enzyme, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent, enzyme, photosensitizers, fluorescent agent, fabric conditioner, hydrolyzable tensio-active agent, sanitas, antioxidant, sequestrant, stablizer, antishrinking agent, anti wrinkling agent, sterilant, mycocide, corrosion inhibitor and its mixture.
5. according to the composition of claim 4, wherein said cationic fabric softener has formula:
[(R
1)
4-p-N
+-((CH
2)
v-Y-R
2)
p]X
-
Wherein Y is:
R
1Be C
1-C
6Alkyl, C
1-C
4Hydroxyalkyl, benzyl and its mixture; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl and its mixture; X
-It is the compatible negatively charged ion of softening agent; Subscript p is 1-3; Subscript v is 1-4.
6. the fabric sofetening composition that adds during the rinsing that has enhanced fragrance retention and fragrance weather resistance, it comprises:
A) at least 0.01% weight spices provides system, and this system comprises:
I) has the fragrance precursors of following formula;
Wherein R is a perfume material alcohol, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Each is independently:
A) hydrogen;
B) C
1-C
22The straight or branched alkyl;
C) C
2-C
22The straight or branched alkenyl;
D) C
1-C
22The straight or branched alkoxyl group;
E) C
6-C
20Replace or unsubstituted aryl;
F) C
2-C
20Replace or unsubstituted alkylene oxide group;
G) C
3-C
20Replace or unsubstituted alkylene oxide group alkyl;
H) C
7-C
20Replace or unsubstituted alkylidene aryl;
I) C
6-C
20Replace or unsubstituted aryloxy;
J) C
7-C
20Replace or unsubstituted alkylene oxide group aryl;
K) C
7-C
20The oxyalkylene aryl;
L) C
2-C
20The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-
R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12Straight or branched alkyl, M are hydrogen or salifiable positively charged ion, and x is the integer of 1-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, or its mixture; Y is the integer of 1-22; With
P) its mixture;
Ii) randomly, one or more perfume materials;
Iii) randomly fragrance carrier provides the subsidiary of fragrance with other;
B) by the weight of composition, high to 99.99% component that is used to prepare fabric sofetening composition, described component is selected from cationic fabric softener, nonionic fabric softener, liquid vehicle, concentrated assistant, dirt release agent, spices and sanitas/stablizer and its mixture;
C) at least 50% liquid vehicle; With
D) randomly, the concentrated assistant of 0.01%-15% weight;
The pH of wherein said in addition composition under 20 ℃ is lower than 6.
7. according to the composition of claim 6, wherein said cationic fabric softener has formula:
[(R
1)
4-p-N
+-((CH
2)
v-Y-R
2)
p]X
-
Wherein Y is:
R
1Be C
1-C
6Alkyl, C
1-C
4Hydroxyalkyl, benzyl and its mixture; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl and its mixture; X is the compatible negatively charged ion of softening agent; Subscript p is 1-3; Subscript v is 1-4.
8. one kind is applicable to the goods that appearance effect is provided to fabric in automatic laundry dryer, and it comprises:
A) at least 0.01% spices provides system, and this system comprises:
I) has the fragrance precursors of following formula;
Wherein R is a perfume material alcohol, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Each is independently:
A) hydrogen;
B) C
1-C
22The straight or branched alkyl;
C) C
2-C
22The straight or branched alkenyl;
D) C
1-C
22The straight or branched alkoxyl group;
E) C
6-C
20Replace or unsubstituted aryl;
F) C
2-C
20Replace or unsubstituted alkylene oxide group;
G) C
3-C
20Replace or unsubstituted alkylene oxide group alkyl;
H) C
7-C
20Replace or unsubstituted alkylidene aryl;
I) C
6-C
20Replace or unsubstituted aryloxy;
J) C
7-C
20Replace or unsubstituted alkylene oxide group aryl;
K) C
7-C
20The oxyalkylene aryl;
L) C
2-C
20The alkylidene group carboxyl, it has formula:
-(CH
2)
xR
9-
R wherein
9Be-CHO ,-CO
2M;-CO
2R
10,-CONH
2,-CONHR
10,-CONR
10R
11With its mixture; R wherein
10And R
11Each is C independently
1-C
12Straight or branched alkyl, M are hydrogen or salifiable positively charged ion, and x is the integer of 1-19;
M) any two R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine fused aromatic rings or the non-aromatic ring that formation comprises 4-7 carbon atom;
N) two or more R
1, R
2, R
3, R
4, R
5, R
6, R
7Or R
8The unit can combine dicyclo, three ring or the volutions that formation comprises 5-8 carbon atom;
O) have the anionic units of following formula:
-(CH
2)
yR
12
R wherein
12Be-SO
3M ,-OSO
3M ,-PO
3M ,-OPO
3M or its mixture; Wherein M is a hydrogen, one or more are enough to satisfy the salt-forming cation of charge balance, or its mixture; Y is the integer of 1-22; And p) its mixture; Ii) randomly, one or more perfume materials; Iii) randomly fragrance carrier provides the subsidiary of fragrance with other; B) fabric treating component comprises: a) 1%-60% weight has the polyamine of following formula: the polyamine that i) has the following formula skeleton:
Wherein R is C
2-C
8Alkylidene group, C
3-C
8The alkylidene group that alkyl replaces and its mixture; The polyamine that ii) has the following formula skeleton:
Wherein y is 5-10000; With
Iii) randomly, 0%-100% polyamine backbone NH unit is had one or more unit replacement of following formula:
-(R
1O)
xR
2
R wherein
1Be C
2-C
6Alkylidene group, C
3-C
6Alkylidene group and its mixture that alkyl replaces; R
2Be hydrogen, C
1-C
4Alkyl and its mixture; Preferred hydrogen and methyl; Wherein m is 2-700; N is 0-350; X is 1-12, preferred 1-4; Y is 5-5000;
B) 40%-99% weight carboxylic acid carrier;
Wherein the viscosity of fabric treatment composition under 100 ℃ is lower than 2000 centipoises, and fusing point is 25 ℃-95 ℃; With
C) in order to discharge the described polyamine (i) of significant quantity and the distribution device that the carboxylic acid carrier is (ii) established to fabric in the automatic laundry dryer under service temperature.
9. composition according to Claim 8, it also comprises the cationic fabric softener with following formula of at least 0.01% weight:
[(R
1)
4-p-N
+-((CH
2)
v-Y-R
2)
p] X
-Wherein Y is:
R wherein
1Be C
1-C
6Alkyl, C
1-C
4Hydroxyalkyl, benzyl and its mixture; R
2Be C
8-C
30Saturated alkyl or C
8-C
30Unsaturated alkyl, C
8-C
30The alkyl or the C that replace
8-C
30Unsubstituted alkyl and its mixture; X
-It is the compatible negatively charged ion of softening agent; Subscript p is 1-3; Subscript v is 1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5116897P | 1997-06-27 | 1997-06-27 | |
| US60/051,168 | 1997-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1268127A true CN1268127A (en) | 2000-09-27 |
Family
ID=21969746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98808557 Pending CN1268127A (en) | 1997-06-27 | 1998-06-26 | Pro-fragrance cyclic acetals |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0991635A1 (en) |
| JP (1) | JP2002507212A (en) |
| CN (1) | CN1268127A (en) |
| AR (1) | AR013142A1 (en) |
| BR (1) | BR9810946A (en) |
| CA (1) | CA2295110A1 (en) |
| WO (1) | WO1999000377A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188172A (en) * | 2016-07-13 | 2016-12-07 | 上海应用技术学院 | A kind of glucoside compounds with Lignum Santali Albi fragrance and preparation method thereof |
| CN107325273A (en) * | 2017-06-22 | 2017-11-07 | 温州大学 | High molecular polymer and preparation method thereof and the application in acid-sensitive type amphiphilic nano micella |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7524809B2 (en) * | 2004-02-27 | 2009-04-28 | The Procter & Gamble Company | Multiple use fabric conditioning composition with improved perfume |
| AU2009323766B2 (en) | 2008-12-02 | 2016-10-06 | Wave Life Sciences Ltd. | Method for the synthesis of phosphorus atom modified nucleic acids |
| SG177564A1 (en) | 2009-07-06 | 2012-02-28 | Ontorii Inc | Novel nucleic acid prodrugs and methods of use thereof |
| DK2620428T3 (en) | 2010-09-24 | 2019-07-01 | Wave Life Sciences Ltd | Asymmetric help group |
| BR112014001244A2 (en) | 2011-07-19 | 2017-02-21 | Wave Life Sciences Pte Ltd | methods for the synthesis of functionalized nucleic acids |
| EP3812370A1 (en) | 2012-07-13 | 2021-04-28 | Wave Life Sciences Ltd. | Asymmetric auxiliary group |
| WO2014202416A1 (en) * | 2013-06-17 | 2014-12-24 | Firmenich Sa | Compounds for a controlled release of active molecules |
| EP4137572A1 (en) | 2014-01-16 | 2023-02-22 | Wave Life Sciences Ltd. | Chiral design |
| US9737628B2 (en) * | 2014-09-25 | 2017-08-22 | International Flavors & Fragrances Inc. | High-coverage, low oder malodor counteractant compounds and methods of use |
| CA3165320A1 (en) | 2020-02-13 | 2021-08-19 | Glycoscience, S.L. | 3'-ketoglycoside compound for the slow release of a volatile alcohol |
| AU2022399868A1 (en) | 2021-11-30 | 2024-06-20 | Glycoscience, S.L. | Slow-release formulation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1277135A (en) * | 1968-09-27 | 1972-06-07 | Unilever Ltd | Detergent compositions |
| US3624106A (en) * | 1970-04-06 | 1971-11-30 | Wayne I Fanta | Tetrahydropyranyl ether of 3-endo-methyl-3-exo(4{40 -methyl-5{40 -hydroxypentyl) norcamphor |
| US4663468A (en) * | 1984-03-14 | 1987-05-05 | Kuraray Company, Ltd. | Hydroformylation of 3-methyl-3-buten-1-ol and analogs thereof and use of such hydroformylation products |
| US5500138A (en) * | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Fabric softener compositions with improved environmental impact |
| US5562847A (en) * | 1995-11-03 | 1996-10-08 | The Procter & Gamble Company | Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity |
| WO1997042290A1 (en) * | 1996-05-03 | 1997-11-13 | The Procter & Gamble Company | Polyamines having fabric appearance enhancement benefits |
-
1998
- 1998-06-26 EP EP98931617A patent/EP0991635A1/en not_active Withdrawn
- 1998-06-26 BR BR9810946-4A patent/BR9810946A/en not_active IP Right Cessation
- 1998-06-26 AR ARP980103114 patent/AR013142A1/en not_active Application Discontinuation
- 1998-06-26 WO PCT/US1998/013278 patent/WO1999000377A1/en not_active Application Discontinuation
- 1998-06-26 CN CN 98808557 patent/CN1268127A/en active Pending
- 1998-06-26 JP JP50575299A patent/JP2002507212A/en active Pending
- 1998-06-26 CA CA002295110A patent/CA2295110A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188172A (en) * | 2016-07-13 | 2016-12-07 | 上海应用技术学院 | A kind of glucoside compounds with Lignum Santali Albi fragrance and preparation method thereof |
| CN107325273A (en) * | 2017-06-22 | 2017-11-07 | 温州大学 | High molecular polymer and preparation method thereof and the application in acid-sensitive type amphiphilic nano micella |
| CN107325273B (en) * | 2017-06-22 | 2019-09-20 | 温州大学 | High molecular polymer and preparation method thereof and application in acid-sensitive type amphiphilic nano micella |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9810946A (en) | 2000-09-26 |
| EP0991635A1 (en) | 2000-04-12 |
| AR013142A1 (en) | 2000-12-13 |
| WO1999000377A1 (en) | 1999-01-07 |
| CA2295110A1 (en) | 1999-01-07 |
| JP2002507212A (en) | 2002-03-05 |
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