JP2002522651A - Fabric protection composition - Google Patents

Abstract

There is provided a method for preventing or reducing the fading of colour on fabric by means of a divalent salt. Compositions which provide care to the color of fabrics and comprising a dye fixing agent and the divalent salt are also herein provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD OF THE INVENTION The present invention provides a composition for protecting treated fabrics, especially for protecting colors even after a number of washing cycles.

BACKGROUND OF THE INVENTION The home treatment of colored fabrics is a problem known to formulators of laundry compositions in the field. It is well known that alternating cycles of use and washing of fabrics and fabrics, e.g., worn clothing and clothing, necessarily adversely affect the appearance and integrity of the fabrics and fabrics so used and washed. I have. Fabrics and fabrics simply wear over time and use. Washing of fabrics and fabrics is necessary to remove dirt and stains that accumulate therein and thereon during normal use. However, the washing operation itself contributes to the deterioration of the integrity and appearance of such fabrics and fabrics over many cycles.

[0003] Deterioration of the condition and appearance of the fabric manifests in several ways. The mechanical action of washing removes short fibers from the woven and sewn fabric / woven structure. These removed fibers can form lint, fluff or "hair balls", which are visible on the surface of the fabric, causing the fabric to lose its appearance freshness. In addition, repeated washing of fabrics and fabrics, especially with bleach-containing laundry products, removes dye from the fabrics and fabrics, resulting in reduced color intensity, and often results in a change in hue or shade, May give a faded, worn out appearance.

[0004] The problem of formulating laundry compositions that reduce the amount of dye released from colored fabrics by wet processing is therefore a particularly challenging and challenging problem for formulators.
This problem is exacerbated by the tendency of consumers toward more colored fabrics.

In this field, to solve this problem, European Patent 0,341,2
No. 5,033,815, with a dye scavenger during the washing process, or polyvinyl as exemplified in WO 94/11482. Many solutions have been proposed, such as treating fabrics with substances. However, all these solutions have the end result of dye breathing,
That is, the focus is on preventing the dye from redepositing on the fabric. Thus, another object of the present invention is to address the problem of dyes at one of its sources, i.e. to solve the fading resulting from dye bleeding due to poor adhesion of the dye to the fabric, especially after several launderings. It is to be.

[0006] Solutions can be found for use in industrial processing. However, it is generally not possible to apply these solutions to home processing. In fact, industrial processes allow for strict control of parameters such as pH, electrolyte concentration, water hardness, temperature, etc., but such high levels of control are not possible with home washing machines.

[0007] Furthermore, it is not practical to rely on high processing temperatures, such as those used in industrial processes, ie temperatures above 40 ° C., in domestic treatments, especially in household rinsing. Moreover, industrial processes use high concentrations of fixatives required for industrial-scale processes, while low levels are most preferred for domestic processes for economic reasons.

[0008] Thus, despite advances in this field, there remains a need for effective and economical compositions that effectively reduce the amount of dye released from colored fabrics in wet processing at home.

[0009] EP 462806 provides a method for using cationic dye fixatives in home treatments that enhance the binding of loosely retained dyes to fabrics. However, although effective, it has been found that some fading of the fabric still occurs, especially after many wash cycles.

Thus, an advantage of the present invention is to provide a composition having effective dye fixing properties.

[0011] Another advantage of the present invention is that such compositions synergistically increase the above properties.

[0012] Yet another advantage of the present invention is that the treated fabric has a reduced tendency to release dye on subsequent washings. Such properties are more pronounced after many wash cycles (eg, 20 wash cycles).

SUMMARY OF THE INVENTION The present invention is directed to a color protection composition comprising a dye fixative and a divalent salt.

In another aspect of the present invention, there is provided the use and method of a composition for preventing or inhibiting the fading of a fabric by using a divalent salt.

Dye fixative A dye fixative is an essential component of the composition of the present invention. Dye fixatives, or "fixers", are well-known, commercially available materials designed to improve the appearance of dyed fabrics by minimizing dye loss from the fabric upon washing. is there. Materials described below as fabric softeners or amino-functional polymers are not included in this definition.

Many dye fixatives are cationic and are based on various quaternized or cationically charged organic nitrogen compounds. Cationic fixatives are commercially available from several suppliers under various trade names. Typical examples include Crossfield to C
ROSCOLOR PMF (July 1981, code number 7894) and CROSCOLOR NOFF (
INDOSOL E-50 from Sandoz (January 1988, code no. 8544), Feb. 27, 1984, reference no.
Commercially available from Sandoz, it is the preferred polycationic fixative for use here
SANDOFIX TPS and SANDOFIX SWE (cationic resinous compound), CHT-Beitlich G
REWIN SRF, REWIN SRF-O and REWIN DWR commercially available from MBH, commercially available from Ciba-Geigy
Tinofix (trade name) ECO, Tinofix (trade name) ERD, and Solfin (trade name). Other cationic dye fixatives are described in "Aftertreatme" by Christopher C. Cook.
nts for improving the fastness of dyes on textile fibres ”(REV.PROG.COL
ORATION Vol. 12, 1982). Dye fixatives suitable for use in the present invention include ammonium compounds, such as fatty acid diamine condensates, such as hydrochloride, acetate, methosulfate and benzyl hydrochloride of oleyldiethylaminoethylamide, oleylmethyl-diethylenediaminemethosulfate, Oxidation products of stearyl-ethylenediaminotrimethylammonium methosulphate and tertiary amines, derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrin.

Preferred dye fixatives are: It is a cellulose reactive dye fixing agent.

“Cellulose-reactive dye fixative” means that the reagent reacts with the cellulose fibers by heat treatment. Suitable agents for use herein can be confirmed by the following test procedure, the so-called cellulose reactivity test measurement.

Cellulose reactivity test measurement Two dyed fabrics (eg 10 × 10 cm knitted cotton, dyed with Direct Red 80)
Is immersed in a 1% (w / w) aqueous solution of a test cellulose-reactive dye fixing agent for 20 minutes.
The pH of the solution is the pH obtained at this concentration.

Next, the cloth is dried. One of the dried pieces of cloth, as well as the piece of cloth that has not been soaked (Comparative 1), are passed ten times through an iron calender with linen setting.

[0021] Comparative 2 cloth pieces, which were not soaked and not ironed, are also used for this measurement.

Four pieces of cloth are individually washed in a Launder-o-meter pots under typical conditions, using a commercially available detergent at the recommended usage, at 60 ° C. for 1/2 hour, followed by Rinse thoroughly with 200 ml of cold water four times, then hang in a row and dry.

The washing fastness of the fabric pieces is then determined by the so-called Delta-E for fresh untreated fabric pieces.
Measure by determining the value. Delta-E is, for example, ASTM D2244
Stipulated. Delta-E is the color difference calculated as specified in ASTM D2244, ie, the CIE 1976 CIELAB counter color space, Hunter counter color space, Friele-Mac Adam-Chickering color space or any equivalent color space. The magnitude of the difference between two psychophysical color stimuli, defined by tristimulus values or by chromaticity coordinates and nominal reflectance, calculated using a specific set of color difference equations defined in And direction.

Thus, the lower the Delta E value for a new product, the better the improvement in washing fastness. Ironing-If the improvement in wash fastness of the dipped cloth is better than that of the non-ironed, dipped cloth and better than each of the two comparisons 1 and 2, then the test agent. Is a cellulose-reactive dye fixing agent that can be used for the purpose of the present invention.

Typical cellulose-reactive dye fixatives include halogeno-triazine compounds, vinyl sulfone compounds, epichlorohydrin derivatives, hydroxyethylene urea derivatives, formaldehyde condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives and the like. Is a compound containing a reactive group of a reactive dye category selected from the mixture of

Other reactive functionalities for cellulose are described in Textile processing and properties., Elsevier from Tyrone L. Vigo (1997), pp. 120-121, using specific electrophilic groups with cellulose affinity. Have been.

[0027] Preferred hydroxyethylene urea derivatives include dimethylol dihydroxyethylene, urea, and dimethyl urea glyoxal.

Preferred formaldehyde condensation products include formaldehyde and condensation products derived from groups selected from amino, imino, phenol, urea, cyanamide and aromatic groups. Commercially available compounds in this group include Clar
Sandofix WE 56 from iant, Zetex E from Zeneca and Levogen BF from Bayer.

Preferred polycarboxylate derivatives include butanetetracarboxylic acid derivatives,
Citric acid derivatives, polyacrylates, and derivatives thereof.

The most preferred cellulose-reactive dye fixative is one of the hydroxyethylene urea derivatives commercially available from Clariant under the trade name Indosol CR. Still other most preferred cellulose reactive dye fixatives are commercially available from CHT R. Beitlich under the trade names REWIN DWR and REWIN WBS.

Among the above dye fixatives, preferred agents for use in the present invention are cationic, especially polycationic, dye fixatives.

[0032] Typical amounts of dye fixative used in the compositions of the present invention are from 0.01 to 5 parts of the composition.
0% by weight, preferably 0.01 to 25% by weight, more preferably 1 to 10% by weight,
Most preferably 1.5 to 5% by weight of active ingredient.

Divalent Salt A divalent salt is an essential component of the present invention. The use of this component improves the appearance of the fabric, especially the color protection properties of the fabric. Without theoretical support, it is believed that salts act by reducing the solubility of the dye.

A divalent salt is defined as a salt that dissociates in water and releases a divalent metal ion.

Salts useful in the present invention are compounds formed from alkaline earth metals and capable of forming hydrates upon crystallization. Typically, the salts used in the present invention have the formula:

AM In the formula, A is a cation. The cation is an alkaline earth metal, preferably selected from magnesium, calcium, more preferably magnesium, and M is sulfate, chloride, nitrate, carbonate, borate,
And carboxylate.

Preferred salts are those selected from magnesium, calcium and mixtures thereof, more preferably magnesium salts.

Particularly preferred salts for use herein are selected from magnesium sulfate, magnesium bicarbonate, magnesium chloride, magnesium borate, magnesium citrate, and mixtures thereof, more preferably magnesium sulfate, magnesium chloride and their mixtures. Selected from a mixture of

Typical amounts of divalent salts used in the compositions of the invention are from 0.01 to 90%, preferably from 0.5 to 90%, more preferably from 1 to 20% by weight of the composition , Most preferably 3 to 10% by weight.

For the purposes of the present invention, the weight ratio of divalent salt to dye fixing agent is greater than 1: 1.

Color Protecting Components The fabric protecting composition can also comprise one or more of the following color protecting components. Amino-functional polymers Amino-functional polymers effectively protect the color of the fabric. Components which are polymers described above or below as dye fixatives do not fall under this definition.

[0042] Suitable amino-functional polymers for use in the present invention are water-soluble or dispersible polyamines. Typically, the amino functional polymers for use herein have a molecular weight from 150 to 10 ^6, preferably 600 to 20,000, most preferably 1000 to
10,000. These polyamines comprise a skeleton that may be linear or cyclic. The polyamine backbone can also comprise more or less polyamine branches. Preferably, the polyamine backbone described herein is defined below with respect to units in which at least one, preferably each nitrogen, of the polyamine chain is substituted, quaternized, oxidized, or a combination thereof. Modified as described. For the purposes of the present invention, the term "modified" relates to the chemical structure of a polyamine and refers to the backbone-
Replacing the hydrogen atom of NH with an R ′ unit (substitution), quaternizing the skeleton nitrogen (quaternization), or oxidizing the skeleton nitrogen to N-oxide (oxidation)
Is defined as The terms "denaturation" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a skeletal nitrogen with an R 'unit. The quaternization or oxidation may optionally occur without substitution, but preferably the substitution involves oxidation or quaternization of at least one skeletal nitrogen.

The linear or acyclic polyamine skeleton constituting the amino-functional polymer has the following general formula

Embedded image The cyclic polyamine skeleton constituting the amino-functional polymer has the following general formula.

[0044]

Embedded image The backbone described above may have an R "
Comprising primary, secondary and tertiary amine nitrogens connected by a "bond" unit.

For purposes of the present invention, the primary amine nitrogens that make up the backbone or branch are defined as V or Z “terminal” units after being modified. For example, located at the end of the main polyamine backbone or branching chain structure H 2 _N- [R] - If a primary amine moiety having being modified by the present invention, then V "terminal"
Defined as units or simply V units. However, for purposes of the present invention, some or all of the primary amine moiety may remain unmodified, subject to the limitations described below. These unmodified primary amine moieties remain "terminal" units due to their position in the backbone. Similarly, located at the end of the main polyamine backbone, if primary amine moiety having the structure -NH ₂ is modified according to the present invention, then Z "terminal"
Defined as units or simply Z units. This unit may be left unmodified, subject to the restrictions described below.

Similarly, the secondary amine nitrogen constituting the skeleton or the branched chain, after being modified,
Defined as a "skeleton" unit. For example, if a secondary amine moiety having the structure H |-[NR]-, which is a major component of the backbone and branch chains of the present invention, is modified according to the present invention, then the W "backbone"
Defined as units or simply as W units. However, for the purposes of the present invention, some or all of the secondary amine moiety may remain unmodified. These unmodified secondary amine moieties remain "backbone" units because of their position in the backbone.

Similarly, the tertiary amine nitrogens that make up the backbone or branch are defined as Y “branched” units after modification. For example, if a tertiary amine moiety having the structure |-[NR]-, which is the branch point of a chain of a polyamine backbone or other branch or ring, is modified according to the present invention, then the Y "branch""
Defined as units or simply as Y units. However, for the purposes of the present invention, some or all of the tertiary amine moiety may remain unmodified. These unmodified tertiary amine moieties remain "branched" units because of their position in the backbone. The R units associated with the nitrogens of the V, W and Y units and serving to connect the polyamine nitrogen are described below.

[0048] Thus, the final modified structure of the polyamines of the present invention, with respect to the linear amino-functional polymer of the general formula V _{(n + 1)} expressed in W _m Y _n Z, with respect to the cyclic amino-functional polymer, formula V _(n-k + ₁₎ can be represented by _{W m Y n Y 'k Z} . In the case of a polyamine comprising a ring, the Y 'unit of the formula | R |-[NR]-serves as a skeleton or branch point of a branched ring. For each Y 'unit, there is a Y unit having the formula |-[NR]-, which forms the point connecting the ring to the polymer backbone or branch. In the special case where the backbone is a complete ring, the polyamine backbone has the formula

Embedded image Has, therefore free of Z terminal unit has the formula _{V n-k W m Y n} Y 'k, where, k is the number of branching units forming the ring. Preferably, the polyamine backbone of the present invention does not contain a ring.

In the case of acyclic polyamines, the ratio of the index n to the index m is related to the relative degree of branching.
The completely unbranched linear modified polyamines of the present invention have the formula: VW _m Z, that is, n is 0. The greater the number of n (the smaller the ratio of m to n), the greater the degree of branching in the molecule. Typically, the value of m is a minimum of 2 to 700, preferably 4 to 40
A value of 0, but a larger value of m is also preferred, especially if the value of the index n is very small or close to 0.

Each polyamine nitrogen, whether primary, secondary or tertiary, after being modified according to the present invention, has three general classes: simple substituted, quaternized, Or oxidized. These unmodified polyamine nitrogen units are classified as V, W, Y, Y 'or Z units, depending on whether they are primary, secondary or tertiary nitrogen. That is, for the purpose of the present invention,
Unmodified primary amine nitrogen is a V or Z unit, unmodified secondary amine nitrogen is a W unit or Y 'unit, and unmodified tertiary amine nitrogen is a Y unit.

The modified primary amine moiety has three forms: a) a simply substituted unit having the structure: R′—N—R— | R ′ b) quaternized units ^{having, R 'X - | R'-} N + -R- | R' ( wherein, X is a suitable counter ion providing charge balance), and c) the following structure O'R'-NR- | R 'is defined as a V "terminal" unit having one of the following oxidized units:

The modified secondary amine moiety has three forms: a) a simply substituted unit having the structure: —N—R— | R ′ b) a compound having the structure: quaternized units ^{R 'X - | -N + -R-} | R' is oxidized with a (wherein, X is a suitable counter-ion is to provide a balance of electric charge), and c) the following structure It is defined as a W "skeleton" unit having one of the units O ↑ -NR- | R '.

Other modified secondary amine moieties have the following three forms: a) a simply substituted unit having the structure: —N—R— | R b) having the structure: quaternized units ^{R 'X - | -N + -R-} | R oxidized with a (wherein, X is a suitable counter-ion is to provide a balance of electric charge), and c) the following structure It is defined as a Y 'unit having one of the units O ↑ -NR- | R.

The modified tertiary amine moiety has three forms: a) an unmodified unit having the following structure: —NR— | b) a quaternized unit having the structure Wherein X is a suitable counter-ion that provides charge balance; and c) an oxidized unit O ↑ -N- having the following structure ^: R ′ X ⁻ | −N ⁺ −R− | R- | is defined as a Y "branch" unit having one of the following:

Certain modified primary amine moieties have three forms: a) a simply substituted unit having the structure: —N—R ′ | R ′ b) the structure: quaternized units ^{having, R 'X - | -N +} -R' | R '( wherein, X is a suitable counter ion providing charge balance), and c) the following structure Is defined as a Z “terminal” unit having one of the oxidized units O ↑ —NR ′ | R ′.

If any position on the nitrogen is unsubstituted or unmodified, then, of course,
Replace For example, primary amine unit comprising one R 'unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula _{(HOCH 2} CH ₂₎ HN-.

For the purposes of the present invention, there are two types of chain termination units, V and Z units. Z "terminal" unit, derived from the end primary amino moiety of the structure -NH _2. The acyclic polyamine skeleton of the present invention has only one Z unit, whereas the cyclic polyamine may not contain a Z unit. Unless the Z unit has been modified to form an N-oxide, the Z "terminal" unit can be replaced with any of the R 'units described further below. If the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified, and thus R 'cannot be hydrogen.

The polyamines of the present invention have a skeleton R “bond” that serves to connect the nitrogen atoms of the skeleton.
Comprising units. R units comprise units referred to as "hydrocarbyl R" units and "oxy R" units for the purposes of the present invention. The “hydrocarbyl R” unit is
C ₂ -C _{12 alkylene,} C 4 _{-C 12 alkenylene,} C 3 _{-C 12} hydroxyalkylene (hydroxyl moieties, with the exception of the carbon atom directly attached to the polyamine backbone nitrogen, take any position on the R unit chain it is), C ₄ -C ₁₂ dihydroxy alkylene (hydroxyl moieties, with the exception of the carbon atom directly attached to the polyamine backbone nitrogen, can also occupy any two of the carbon atoms of R unit chain)
(This, for the purposes of the present invention, an arylene moiety is having two alkyl substituent as part of the linking chain) C ₈ -C ₁₂ dialkyl arylene is. For example, a dialkylarylene unit has the formula

Embedded imageBut this unit need not be 1,4-substituted, but 1,2 or 1
, 3 substituted C₂~ C₁₂It may be alkylene, preferably ethylene, 1,2
-Propylene, and mixtures thereof, more preferably ethylene. "Oki
The "R" unit is-(R¹O)_xR⁵(OR¹)_x-,-(CH₂CH (OR²)
-CH₂O)_z− (R¹O)_yR¹(OCH₂CH (OR²) CH₂)_w−, −
CH₂CH (OR²) CH₂-,-(R¹O)_xR¹-And mixtures thereof
Comprising. Preferred R units are C₂~ C₁₂Alkylene, C₃~ C₁₂Hydro
Xyalkylene, C₄~ C₁₂Dihydroxyalkylene, C₈~ C₁₂Dialki
Luarylene,-(R¹O)_xR¹-, -CH₂CH (OR²) CH₂-,-(
CH₂CH (OH) CH₂O)_z− (R¹O)_yR¹(OCH₂CH- (OH)
CH₂)_w-,-(R¹O)_xR⁵(OR¹)_xAnd more preferably R
Rank is C₂~ C₁₂Alkylene, C₃~ C₁₂Hydroxy-alkylene, C₄~ C ₁₂ Dihydroxyalkylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵−
(OR¹)_x-,-(CH₂CH (OH) CH₂O)_z− (R¹O)_yR¹(O
CH₂CH- (OH) CH₂)_w-, And mixtures thereof; and
Preferably the R units are C₂~ C₁₂Alkylene, C₃Hydroxyalkylene, and
And mixtures thereof, most preferably C₂~ C₆Alkylene. The present invention
The most preferred backbone of comprises at least 50% of R units that are ethylene.
You.

The R ¹ unit is a C ₂ -C ₆ alkylene, and mixtures thereof, preferably ethylene.

R ² is hydrogen and — (R ¹ O) _x B, preferably hydrogen.

[0061] R ³ is a _C 1 _{-C 18 alkyl,} C 7 _{-C 12 arylalkylene,} C 7 _{-C 1 2} alkyl substituted _aryl, C 6 _{-C 12} aryl, and mixtures thereof, preferably C ₁ -C _{12 alkyl,} C 7 _{-C 12} arylalkylene,
More preferably C ₁ -C ₁₂ alkyl, most preferably methyl. The R ³ unit serves as part of the R ′ unit described below.

R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene, preferably C ₁ -C ₁₀ alkylene, C ₈ -C ₁₂ aryl alkylene, more preferably _C 2 -C ₈ alkylene,
Most preferably, it is ethylene or butylene.

R⁵Is C₁~ C₁₂Alkylene, C₃~ C₁₂Hydroxyalkylene, C₄~
C₁₂Dihydroxyalkylene, C₈~ C₁₂Dialkylarylene, -C (O
)-, -C (O) NHR⁶NHC (O)-, -C (O) (R⁴)_rC (O)-
, -R¹(OR¹)-, -CH₂CH (OH) CH₂O (R¹O)_yR¹OCH ₂ CH (OH) CH₂-, -C (O) (R⁴)_rC (O)-, -CH₂CH (O
H) CH₂-And R⁵Is preferably ethylene, -C (O)-, -C (O) N
HR⁶NHC (O)-, -R¹(OR¹)-, -CH₂CH (OH) CH₂−,
-CH₂CH (OH) CH₂O (R¹O)_yR¹OCH₂CH- (OH) CH₂ -, More preferably -CH₂CH (OH) CH₂-.

R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene.

Preferred “oxy” R units are further defined with respect to R ¹ , R ² , and R ⁵ units. Preferred "oxy" R units comprise the preferred ^R 1, ^{R 2,} and ^{R 5} units. A preferred cotton soil releaser of the present invention comprises at least 50% of R ¹ units which are ethylene. Preferred R ¹ , R ² , and R ⁵ units are combined with “oxy” R units to form preferred “oxy” R units in the following manner.

I) More preferable R ⁵ is substituted in — (CH ₂ CH ₂ O) _x R ⁵ (OCH ₂ CH ₂ ) _x —, and — (CH ₂ CH ₂ O) _x CH ₂ CHOHCH ₂ (OCH ₂ CH ₂ ) _x −
Get.

Ii) Preferred R ¹ and R ² are — (CH ₂ CH (OR ² ) CH ₂ O) _z — (R ¹ O) _y R ¹ O (CH ₂ CH (OR ² ) CH ₂ ) _w — And-(CH ₂ C
_{H (OH) CH 2 O)} z - (CH 2 CH 2 O) y CH 2 CH 2 O (CH 2 CH (
_{OH) CH} 2) _w - obtained. substituting _{in, -CH 2 CH (OH) CH} 2 - - iii) preferably the _{^{R 2 -CH 2 CH (OR 2}} ) CH 2 obtained.

R ′ unit is hydrogen, C₁~ C₂₂Alkyl, C₃~ C₂₂Alkenyl, C₇~
C₂₂Arylalkyl, C₂~ C₂₂Hydroxyalkyl,-(CH₂)_pC
O₂M, (CH₂)_qSO₃M, -CH (CH₂CO₂M) CO₂M,-(CH ₂ )_pPO₃M,-(R¹O)_mB, -C (O) R³, Preferably hydrogen, C₂~
C₂₂Hydroxyalkylene, benzyl, C₁~ C₂₂Alkylene,-(R¹O
)_mB, -C (O) R³,-(CH₂)_pCO₂M,-(CH₂)_qSO₃M,
-CH (CH₂CO₂M) CO₂M, more preferably C₁~ C₂₂Alkylene,
− (R¹O)_xB, -C (O) R³,-(CH₂)_pCO₂M,-(CH₂)_q SO₃M, -CH (CH₂CO₂M) CO₂M, most preferably C₁~ C₂₂A
Lucylene,-(R¹O)_xB and -C (O) R³Selected from the group consisting of Nitrification
When no modification or substitution is performed on the element, the hydrogen atom is replaced with a moiety representing R '.
And remain. The most preferred R 'units are (R¹O)_xB. V, W or Z units
Is oxidized, i.e., when the nitrogen is an N-oxide, the R 'unit is a hydrogen atom.
Does not include children. For example, the backbone chain or the branched chain does not include a unit having the following structure.
No.

H O H O In addition, the V, W or Z units are oxidized, ie, the nitrogen is an N-oxide. Where the R 'unit does not include a carbonyl moiety directly attached to the nitrogen atom.
In the present invention, R 'unit -C (O) R ³ moiety is not bonded to the nitrogen which is N- oxide-modified, i.e. N- oxide amides having the structure or combinations thereof below absent.

[0070]

Embedded image B is hydrogen, C₁~ C₆Alkyl,-(CH₂)_qSO₃M,-(CH₂)_p−
CO₂M,-(CH₂)_q(CHSO₃M) CH₂SO₃M,-(CH₂)_q−
(CHSO₂M) CH₂SO₃M,-(CH₂)_pPO₃M, -PO₃M, preferred
Or hydrogen,-(CH₂)_qSO₃M,-(CH₂)_q(CHSO₃M) CH₂ SO₃M,-(CH₂)_q− (CHSO₂M) CH₂SO₃M, more preferably
Hydrogen or-(CH₂)_qSO₃M. M satisfies the charge balance
Sufficient amount of hydrogen or a water-soluble cation. For example, the sodium cation
− (CH₂)_pCO₂M, and-(CH₂)_qSO₃Satisfies M equally, it
By-(CH₂)_pCO₂Na, and-(CH₂)_qSO₃Shape the Na part
To achieve. Combining two or more monovalent cations (sodium, potassium, etc.)
The required chemical charge balance can be satisfied. However, the charge of the polyanion group
To meet the loading requirements, two or more anionic groups must be
The charge may be balanced or two or more monovalent cations may be required. example
For example,-(CH substituted with a sodium atom₂)_pPO₃The M part is represented by the formula-(CH₂) _p PO₃Na₃Having. Divalent cations such as calcium (Ca²⁺)Also
Is magnesium (Mg²⁺) Is replaced by another suitable monovalent water-soluble cation.
Or can be combined with them. The preferred cation is sodium
And potassium, with sodium being more preferred.

X is a water-soluble anion such as chlorine (Cl ⁻ ), bromine (Br ⁻ ) and iodine (
I ⁻ ), or X is any negatively charged group such as sulfate (
SO ₄ ^2-) and methosulfate _{(CH 3} SO 3 ^-), it may be.

The exponents of the formula have the following values: p has a value of 1 to 6, q has a value of 0 to 6, r has a value of 0 or 1, w is 0 Or has the value 1 and x is 1 to 1
Has a value of 00, y has a value of 0 to 100, z has a value of 0 or 1, m has a value of 2 to 700, preferably 4 to 400, and n has a value of 0 to 100. 350, preferably 0
Has a value of ２００200, and m + n has a value of at least 5. Preferably, x is 1
It has a value of -20, preferably 1-10.

Preferred amino-functional polymers of the present invention comprise a polyamine backbone, wherein less than 50%, preferably less than 20%, more preferably less than 5% of the R groups have “oxy” R units. And most preferably the R units are completely free of "oxy" R units.

The most preferred amino-functional polymer that does not contain an “oxy” R unit has a 50
% Comprises a polyamine skeleton having 4 or more carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene have 3 or more carbon atoms,
Preferred "hydrocarbyl" R units. That is, if the backbone R units are _C 2 _{-C 1 2 alkylene,} C 2 -C ₃ alkylene is preferred, ethylene being most preferred.

The amino-functional polymers according to the invention comprise modified homogeneous and heterogeneous polyamine backbones, wherein not more than 100% of the —NH units are modified. For the purposes of the present invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having the same R units (ie all ethylene). However, this definition of identity does not exclude other polyamines that contain extraneous units that make up the polyamine backbone that are present because they are artifacts of the chosen chemical synthesis method. For example, as will be apparent to those skilled in the art, ethanolamine can be used as an "initiator" for the synthesis of polyethyleneimine, and thus the resulting 1
A sample of polyethyleneimine comprising a single hydroxyethyl moiety is considered, for the purposes of the present invention, to comprise a homogeneous polyamine backbone. A polyamine skeleton comprising all ethylene R units and no branching Y units is a homogeneous skeleton. The polyamine skeleton comprising all ethylene R units is a homogeneous skeleton, regardless of the degree of branching or the number of cyclic branches present.

For the purposes of the present invention, the term “heterogeneous polymer backbone” means a polyamine backbone that is a composite material consisting of different lengths of R units and types of R units. For example, a heterogeneous skeleton comprises R units, which is a mixture of ethylene and 1,2-propylene units. For purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" R units is not required to provide a heterogeneous backbone.

[0077] Preferred amino-functional polymers of the present invention include homogeneous polyamine backbones completely or partially substituted by polyethyleneoxy moieties, fully or partially quaternized amines, fully Or nitrogen partially oxidized to N-oxide, and mixtures thereof. However, not all backbone amine nitrogens need to be modified in the same manner, and the formulator can make the choice of modification according to the particular needs. The degree of ethoxylation is also determined by the conditions specifically required by the prescriber.

Preferred polyamines comprising the skeleton of the compounds of the present invention are generally polyalkyleneimines (PAI), preferably polyethyleneimines (PEI), or moieties having R units longer than the parent PAI or PEI. The connected PEI.

A preferred amine polymer backbone comprises R units which are C ₂ alkylene (ethylene) units and is also called polyethylene imine (PEI). Preferred PEIs have at least moderate branching, i.e., the ratio of m to n is less than 4: 1;
Most preferred is a PEI having a ratio of 2: 1 to n. Preferred backbones have the following formula before modification:

[0080]

Embedded image Wherein R ′, m and n are as defined above. Preferred PEIs have a molecular weight of greater than about 200 daltons.

The relative proportions of primary, secondary and tertiary amine units in the polyamine skeleton depend on the mode of production, especially in the case of PEI. Each hydrogen atom added to each nitrogen atom of the polyamine backbone represents a point where subsequent substitution, quaternization or oxidation is possible.

These polyamines can be produced, for example, by polymerizing ethylene imine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. Specific methods for producing these polyamine backbones are described in U.S. Pat. No. 2,182,306, Ul.
Rich et al., issued on December 5, 1939, U.S. Pat. No. 3,033,746, Mayle et al., issued on May 8, 1962, U.S. Pat. No. 2,208,095.
Specification, Esselmann et al., Promulgated July 16, 1940, U.S. Pat. No. 2,80
No. 6,839, Crowther, issued Sep. 17, 1957, and U.S. Pat. No. 2,553,696, Wilson, issued May 21, 1951.

According to the present invention, the prescriber can ethoxylate some of the secondary amine nitrogens and
Secondary amine nitrogens can be oxidized to N-oxides. This is because the formulator can choose to modify all or part of the primary amine nitrogen before oxidation or quaternization with one or more substituents. This is also true. With the exception of the above restrictions, any possible combination of R 'groups can be substituted on the primary and secondary amine nitrogens.

Commercially available amino-functional polymers suitable for use herein include poly (ethylene imine) having a molecular weight of 1200, hydroxyethylated poly (ethylene imine) having a molecular weight of 2000 available from Polysciences, and commercially available from Aldrich. 80% hydroxyethylated poly (ethylene imine). Still other preferred amino-functional polymers are low molecular weight oligoamines. The most preferred materials here are 1,4-bis (3-aminopropyl) piperazine, N, N'-bis (3-aminopropyl) 1
, 3-propanediamine, and mixtures thereof.

Typical amounts of amino-functional polymer used in the compositions of the present invention are preferably up to 90% by weight of the composition, preferably 0.01 to 50% by weight of active ingredient, more preferably 0.1 to 50%. It is 1 to 20% by weight, most preferably 0.5 to 15% by weight.

Crystal Growth Inhibitor Component The composition of the present invention comprises a crystal growth inhibitor component, preferably an organodiphosphonic acid component, and / or an organomonophosphonic acid, preferably 0.01% of the composition.
-5% by weight, more preferably 0.1-2% by weight. Organodiphosphonic acid means here an organodiphosphonic acid that does not contain nitrogen as part of its chemical structure. Thus, although this definition excludes organoaminophosphonates, this material can be included in the compositions of the present invention as a heavy metal sequestrant.

The organodiphosphonic acid is preferably a C ₁ -C ₄ diphosphonic acid, more preferably a C ₂ diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid ( HEDP) and can exist in partially or fully ionized form, especially as salts or complexes.

Here, organic monophosphonic acids are also useful as crystal growth inhibitors. Organomonophosphonic acids or one of its salts or complexes are also suitable here for use as CGI.

The term “organomonophosphonic acid” as used herein means an organomonophosphonic acid that does not contain nitrogen as part of its chemical structure. Thus, although this definition excludes organoaminophosphonates, this material can be included in the compositions of the present invention as a heavy metal sequestrant.

The organomonophosphonic acid component can be present in its acid form or in its salt or complex form with a suitable counter cation. Preferably, all salts /
The complexes are water-soluble, and alkali metal and alkaline earth metal salts / complexes are particularly preferred.

A preferred organomonophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the trade name Bayhibit.

Further components suitable for use in the present invention are described below.

Soil Release Agents Soil release agents are preferably used in the fabric protection compositions of the present invention. All polymeric soil release agents known to those skilled in the art can be used in the compositions of the present invention, if desired. The characteristics of the polymeric soil release agent are the hydrophobic parts, such as polyester and nylon, which impart hydrophilicity to the surface, and which adhere to the hydrophobic fibers and remain there until the washing and rinsing cycle is completed. To stop and have both a hydrophobic part that acts as an anchor for the hydrophilic part. This makes it possible to more easily wash the stain generated after the treatment with the soil release agent in a later washing procedure.

When used, soil release agents generally comprise from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, preferably from about 0.2% by weight of the detergent composition. ~ About 3.0% by weight
Is configured.

The following documents, which are incorporated herein by reference, all describe soil release polymers suitable for the present invention. U.S. Pat. No. 3,959,230, Hays, May 1976
May 25, U.S. Pat. No. 3,893,929, Basadur, promulgated July 8, 1975, U.S. Pat. No. 4,000,093, Nicol et al., 197.
U.S. Pat. No. 4,702,857 issued Dec. 28, 6; Gosselink,
U.S. Pat. No. 4,968,451 issued Oct. 27, 1987, Scheib
el et al., promulgated Nov. 6, U.S. Pat. No. 4,702,857, Gossel
ink, promulgated October 27, 1987, U.S. Pat. No. 4,711,730,
Gosselink et al., Promulgated December 8, 1987, U.S. Pat. No. 4,721,580.
No. 4,877,8, issued Jan. 26, 1988, to Gosselink.
No. 96, Maldonado et al., Issued Oct. 31, 1989, U.S. Pat.
U.S. Pat. No. 5,415,807, Gosselink et al., May 16, 1995. Gosselink et al., Issued on Sep. 11, 1990.
Published by Kud, et al., European Patent Application No. 0219048, Apr. 22, 1987.

Further, suitable soil release agents are described in US Pat.
201,824, Violland et al., U.S. Pat. No. 4,240,918, Lagasse et al., U.S. Pat. No. 4,525,524, Tung et al.
U.S. Pat. No. 4,579,681; Ruppert et al., U.S. Pat.
240,918, U.S. Pat. No. 4,787,989, U.S. Pat. No. 4,525,524, European Patent 279,134A, 1
988 Rhone-Poulenc Chemie, EP 457,205A,
BASF (1991), and German Patent 2,335,044, Unilever N
V. 1974.

Commercially available soil release agents include ME manufactured by Shin-Etsu Chemical Co., Ltd.
TOLOSE SM100, METOLOSE SM200, SOKALAN type materials available from BASF (Germany), such as SOKALAN HP-22, ZELCON 5126 (from Dupont) and MILEASE T (from ICI)
There is.

[0098] When the composition is formulated as a softening composition, the composition also comprises a fabric softening compound.

Typical loadings of the softening compound in the fabric softening compound composition are 1-80% by weight of the composition,
It is preferably from 5 to 75% by weight, more preferably from 15 to 70% by weight, even more preferably from 19 to 65% by weight.

A typical cationic softening component is a quaternary ammonium compound or an amine precursor thereof as defined below.

A) -Quaternary ammonium fabric softening active compound (1) Preferred quaternary ammonium fabric softening active compounds have the formula:

[0102]

Embedded image Or

Embedded image Wherein Q is a carbonyl unit having the formula:

[0103]

Embedded image Wherein each R unit is independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxyalkyl, and each R ¹ unit is Independently a linear or branched C ₁₁ -C ₂₂ alkyl, a linear or branched C ₁₁ -C ₂₂ alkenyl, and mixtures thereof, wherein R ² is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C _{4 4} hydroxyalkyl, and mixtures thereof, where X is an anion that is compatible with the fabric softener active and adjunct ingredients, has an index m of 1-4, preferably 2, and an index n of 1 to
4, preferably 2.

An example of a preferred fabric softener active ingredient is a mixture of quaternary amines having the formula:

[0105]

Embedded image Wherein R is preferably methyl and R ¹ is a linear or branched alkyl or alkenyl chain having at least 11, preferably at least 15, carbon atoms. In the above example of fabric softening agents, the unit -O ₂ CR ¹ typically represents a fatty acyl unit derived from a triglyceride source. The triglyceride source is preferably tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oil and / or partially hydrogenated vegetable oil, such as canola oil, safflower oil, Derived from peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc., and mixtures of these oils.

Preferred fabric softening actives of the present invention are diesters and / or diamides quaternary ammonium (DEQA) compounds, wherein the diesters and diamides have the formula:

[0107]

Embedded image In the formula, R, R ¹ , X and n are the same as defined in the above formulas (1) and (2), and Q has the following formula.

O H O ‖ | ‖ -OC- or -NC- These preferred fabric softening actives are prepared by reacting an amine with a fatty acyl unit to form a compound of the formula

Embedded image Wherein R is preferably methyl, and Q and R ¹ are as defined above, followed by the addition of quaternary to the final softener active ingredient.
It is manufactured by grading.

Examples of preferred amines used in forming the DEQA fabric softening actives of the present invention include methyl bis (2-hydroxyethyl) amine having the formula:

Embedded image Methylbis (2-hydroxypropyl) amine having the formula:

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

Embedded image Methyl bis (2-aminoethyl) amine having the formula:

Embedded image A triethanolamine having the formula:

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

Embedded image However, the present invention is not limited to these.

The counter ion X ⁽⁻⁾ is any anion compatible with the softener, preferably a strong acid anion, such as chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, nitrate, And more preferably chloride or methyl sulfate. The anion can also have a double charge (where X ^(-) represents half the group), but this is less preferred.

Tallow and canola oil are advantageous and inexpensive sources of fatty acyl units suitable for use as the R ¹ unit in the present invention. The quaternary ammonium compounds suitable for use in the composition of the present invention are exemplified below, but not limited thereto. The term "tallowyl" as used below indicates that the R ¹ units are derived from a tallow triglyceride source and are a mixture of fatty alkyl or alkenyl units. Similarly, the term canolyl means a mixture of fatty alkyl or alkenyl units derived from canola oil.

The following table sets forth examples of suitable fabric softeners according to the above formula, but is not limited to these examples. In this list, "oxy" defines an O-C-unit, while the term "oxo" defines an -O- unit.

TABLE II Fabric Softener Active Ingredient N, N-Di (tallowyl-oxy-2-oxo-ethyl) -N-methyl, N- (
2-hydroxyethyl) ammonium chloride, N, N-di (canolyl-oxy-2-oxo-ethyl) -N-methyl, N- (2
-Hydroxyethyl) ammonium chloride, N, N-di (tallowyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride, N, N-di (canolyloxy-2-oxo-ethyl) -N, N -Dimethylammonium chloride, N, N, N-tri (tallowyl-oxy-2-oxo-ethyl) -N-methylammonium chloride, N, N, N-tri (canolyl-oxy-2-oxo-ethyl) -N -Methylammonium chloride, N- (tallowyloxy-2-oxo-ethyl) -N- (tallowyl) -N, N
-Dimethylammonium chloride, N- (canolyloxy-2-oxo-ethyl) -N- (canolyl) -N, N-dimethylammonium chloride, 1,2-di (tallowyloxy-oxo) -3-N, N, N-trimethylammoniopropane chloride, and 1,2-di (canolyloxy-oxo) -3-N, N, N, N-trimethylammoniopropane chloride, and mixtures of the above active ingredients.

Other examples of quaternary ammonium softening compounds include methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate and methyl bis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulfate These materials are commercially available from Witco Chemical Company under the trade names Varisoft 222 and Varisoft 110, respectively.

N, N-di (tallowyl-oxy-2-oxo-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride wherein the tallow chain is at least partially unsaturated is particularly preferred.

The level of unsaturation contained in a tallow, canola, or other fatty acyl unit chain can be measured by the iodine value (IV) of the corresponding fatty acid, which in the present invention is:
IV, preferably in the range of 5-100, but less than or greater than 25
Are distinguished into two types of compounds having:

In fact, the following equation

Embedded image For compounds derived from tallow fatty acids having the iodine value of 5 to 25, preferably 15 to 20, the weight ratio of cis / trans isomers exceeds about 30/70, preferably about 50/50. It has been found that above this, more preferably above about 70/30, results in optimal concentrating properties. For such compounds made from tallow fatty acids having an iodine value of more than 25, the ratio of the cis to trans isomer has proven to be less important, unless very high concentrations are required.

Another suitable example of a fabric softener active ingredient is that “tallowyl” and “canolyl” in the above examples are replaced by the term “cocoyl, palmyl, lauryl, oleyl, ricinoleyl, stearyl, palmityl” , Derived from fatty acyl groups, but these terms correspond to the triglyceride source from which the fatty acyl units are derived. These alternative fatty acyl sources can comprise fully saturated or, preferably, partially unsaturated chains.

As noted above, the R unit is preferably methyl, but suitable fabric softener active ingredients include the term “methyl” in the examples of Table II above in units “ethyl, ethoxy, propyl, Illustrated by replacing with propoxy, isopropyl, butyl, isobutyl and t-butyl.

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

For the above ester fabric softeners, the pH of the composition is an important parameter of the present invention. In fact, pH affects the stability of the quaternary ammonium or amine precursor compound, especially under prolonged storage conditions. The pH specified here is measured at 20 ° C. for the undiluted composition. These compositions have a p of less than about 6.0.
H may work, but in order to obtain optimal hydrolytic stability of these compositions, the pH in the undiluted state, measured under the above conditions, is preferably 2.0-5, preferably Must be in the range 2.5-4.5, preferably 2.5-3.5. The pH of these compositions can be adjusted by adding a Bronsted acid. Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially low molecular weight _(C 1 _~C 5)
Carboxylic acids, and alkyl sulfonic acids. Suitable inorganic acids include HC
_{l, H 2 SO 4, HNO} 3 and _H 3 PO ₄ and the like. Suitable organic acids include
Formic acid, acetic acid, citric acid, methyl sulfonic acid and ethyl sulfone.
Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic, and benzoic acids.

As used herein, reference to a diester includes monoesters commonly present in the manufacture. To provide flexibility under laundry conditions with no / low detergent carryover, the monoester percentage should be as low as possible, preferably about 2.5%.
You should: However, under conditions where detergent carryover is high, some monoester is preferred. The overall ratio of diester to monoester is about 100: 1 to
About 2: 1, preferably about 50: 1 to about 5: 1, more preferably 13: 1 to 8: 1.
It is. Under conditions of high detergent carryover, the di / monoester ratio is preferably about 1
1: 1. The amount of monoester present can be adjusted in making the softener compound.

A mixture of the active ingredients of the formulas (1) and (2) can also be prepared.

[0124] 2) - suitable, yet another quaternary ammonium fabric softening compounds for use herein, two or more long chain acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group or, A cationic nitrogen-containing salt having one such group and one arylalkyl group, which can be used alone or as a part of a mixture, and (i) an acyclic quaternary ammonium salt having the following formula:

Embedded image Wherein R ⁴ is an acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group, R ⁵ is a C ₁ -C ₄ saturated alkyl or hydroxyalkyl group, and R ⁸ is R ⁴ and R ⁵ Wherein A- is an anion as defined above), (ii) a diaminoalkoxylated quaternary ammonium salt having the formula:

Embedded image Wherein n is 1 to about 5 and R ¹ , R ² , R ⁵ and A ⁻ are as defined above, and (iii) mixtures thereof.

Examples of cationic nitrogen-containing salts of the type described above are the well-known dialkyldimethylammonium salts such as ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride , Distearyl dimethyl ammonium chloride and dibehenyl dimethyl ammonium chloride. Di (hydrogenated tallow) dimethylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of commercially available dialkyldimethyl ammonium salts that can be used in the present invention are all Wi
Di (hydrogenated tallow) dimethyl ammonium chloride (trade name Adogen 442), ditallow dimethyl ammonium chloride (trade name Adogen 470, Praepagen 3445), distearyl dimethyl ammonium chloride (trade name Arosurf TA-) commercially available from tco Chemical Company. 100). Dibehenyl dimethyl ammonium chloride is available from Witco Chemical Corporation's Humko Chemical Division.
Sold under the trade name Kemamine Q-2802C. Dimethylstearylbenzylammonium chloride is sold by Witco Chemical Company under the trade name Varisoft SDC and by Onyx Chemical Company under the trade name Ammonyx 490.

B)-Amine Fabric Softening Active Compounds The amine fabric softening compounds suitable for use herein, which may be in amine or cationic form, are selected from the following materials.

(I) A reaction product of a higher fatty acid with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines, dialkylenetriamines and mixtures thereof. These reaction products are mixtures of several compounds with respect to the polyfunctional structure of the polyamine. Preferred components (i) are nitrogen-containing compounds selected from the group consisting of a mixture of reaction products or some selected component of the mixture. One of the preferred components (i) is a compound selected from the group consisting of substituted imidazoline compounds having the formula:

[0128]

Embedded image Wherein R ⁷ is an acyclic aliphatic C _{15 to} C ₂₁ hydrocarbon group, and R ⁸ is a divalent C ₁ to
It is a C ₃ alkylene group.

The ingredients for component (i) are commercially available from Mazer Chemicals, Mazamide ™, Sand
oz Colors & Chemicals commercially available Ceranine (trade name) HC, Alkaril Chemicals
Inc. under the trade name Alkazine ST or Schercoz from Scher Chemicals, Inc.
Stearic hydroxyethyl imidazoline commercially available under the trade name oline S, N, N
"-Ditalowalcoyldiethylenetriamine, 1-tallowamidoethyl-2-
It is commercially available as tallow imidazoline (in the above structure, R ¹ is an aliphatic C ₁₅ -C ₁₇ hydrocarbon group and R ⁸ is a divalent ethylene group).

Certain components (i) may be first dispersed in a Bronsted acid dispersing aid having a pKa value of about 4 or less, provided that the pH of the final composition is about 6 or less. There is. Preferred dispersing aids include hydrochloric, phosphoric, or methyl sulfonic acid.

N, N ″ -Ditallowalcoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are both reaction products of tallow fatty acids and diethylenetriamine, and the cationic fabric softener methyl- It is a precursor of 1-tallowamidoethyl-2-tallowimidazolinium methyl sulfate ("Cationic Surface Active Agents as Fabric Softners", RR Egan, Jou
rnal of the American Oil Chemicals' Society, January 1978, 118-121
Page). N, N "-Ditalowalcoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline are available as test chemicals from Witco Chemical Company. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl Sulfate is available from Witco Chemical Company as Varisoft 4
It is marketed under 75 trade names.

(Ii) A softener having the following formula:

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

An example of compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride, wherein R ¹ is an acyclic aliphatic C ₁₅ -C ₁₇ hydrocarbon group and R ² Is an ethylene group, G is an NH group, R ⁵ is a methyl group, and A ⁻ is a chloride anion.

(Iii) A softener having the following formula:

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

Examples of compound (iii) are those having the formula:

[0136]

Embedded image Wherein R ¹ is derived from oleic acid.

Other fabric softeners useful herein are described in Toan Trinh, Errol H. Wahl, Donald
U.S. Patent No. 4,661, M. Swartley and Ronald L. Hemingway
, 269, promulgated on April 28, 1987, U.S. Patent No. 4,439,335, Bu
rns, promulgated March 27, 1984, and U.S. Pat. No. 3,861,870, Ed.
wards and Diehl, 4,308,151, Cambre, 3,886,075
No. Bernardino, No. 4,233,164, Davis, No. 4,401,578,
Verbruggen, 3,974,076, Wiersema and Rieke, 4,237,
016, published in European Patent Application No. 472,178 by Rudkin, Clint and Young, and Yamamura et al., The entirety of which is incorporated herein by reference.

Of course, the term “softening active ingredient” also includes mixed softening active agents.

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

A well-formulated fabric softening composition can include, in addition to the above components, one or more of the following components.

Optional Component (A) Liquid Carrier Another optional but preferred component is a liquid carrier. The liquid carrier used in the composition has low cost, relative availability, safety,
Water is preferably at least uniquely defined from the viewpoint of compatibility with the environment. The amount of water in the liquid carrier is preferably at least about 50%, most preferably at least about 60%, by weight of the carrier. Mixtures of water and organic solvents of low molecular weight, such as <about 200, such as lower alcohols, such as ethanol, propanol, isopropanol or butanol, are useful as liquid carriers. Low molecular weight alcohols include monohydric, dihydric (glycols, etc.), trivalent (glycerol, etc.), and higher polyhydric (polyol) alcohols.

(B) -Other Solvents The compositions of the present invention can comprise one or more solvents that facilitate formulation. Solvents which facilitate these formulations are described in WO 97/03169. This is especially true when formulating liquid transparent fabric softening compositions. When used, the solvent system that facilitates formulation is preferably less than 40% by weight of the composition, preferably about 10% to about 35%, more preferably about 12% to about 35%.
It comprises about 25% by weight, more preferably about 14 to about 20% by weight. Solvents that facilitate formulation are selected to minimize the effects of solvent odor in the composition and to provide low viscosity to the final composition. For example, isopropyl alcohol is not very effective and has a strong odor. n-Propyl alcohol is more effective,
Has a pronounced odor. Certain butyl alcohols also have odors, especially when used as part of a solvent system to facilitate formulation and minimize those odors.
Transparency / stability can be obtained effectively. Alcohol is also selected for optimal low temperature stability, i.e., alcohol is about 40 ° F (about 4.4 ° C).
A) a liquid having a reasonably low viscosity up to low temperatures, forming a composition that is translucent, preferably transparent and that can be recovered after storage at low temperatures up to about 20 ° F. (about 6.7 ° C.) Can be.

The suitability of all formulation-facilitating solvents for use in formulating liquid, concentrated, preferably transparent, fabric softener compositions of the present invention having the required stability is surprising. More selective. Suitable solvents can be selected according to their octanol / water partition coefficient (P), as defined in WO 97/03169.

Solvents that facilitate the formulation of the present invention include those having a ClogP of about 0.15 to about 0.64, preferably about 0.25 to about 0.62, more preferably about 0.40 to about 0.60. The solvent that facilitates the formulation is preferably somewhat asymmetric, and preferably has a melting or freezing point such that it becomes a liquid at or near room temperature. For certain purposes, solvents having low molecular weight and biodegradability are also desirable.
Higher asymmetry solvents appear to be highly preferred, while more symmetric solvents having a center of symmetry, such as 1,7-heptanediol or 1,4-bis (
(Hydroxymethyl) cyclohexanes, although their ClogP values fall within the preferred range, appear to be unable to provide a substantially clear composition when used alone.

The most preferred formulation facilitating solvent can be identified by the appearance of the softener vesicles when the composition diluted to the concentration used for rinsing is observed by cryo-electron microscopy. These dilute compositions appear to have a dispersion of fabric softener that exhibits a more uniform laminar appearance than conventional fabric softener compositions. The closer the appearance is to a single thin layer, the better the performance of the composition appears. These compositions are:
The use of the same fabric softener active ingredient gives surprisingly good fabric softness compared to similar compositions made in a conventional manner.

Solvents that can be used and that facilitate the formulation with ClogP falling within the required range are listed below. These solvents include mono-ol, C6 diol, C7 diol, octanediol isomer, butanediol derivative, trimethylpentanediol isomer, ethylmethylpentanediol isomer, propylpentanediol isomer,
Dimethylhexanediol isomer, ethylhexanediol isomer, methylheptanediol isomer, octanediol isomer, nonanediol isomer, alkyl glyceryl ether, di (hydroxyalkyl) ether, and aryl glyceryl ether, aromatic glyceryl ether, oil Cyclic diols and derivatives,
C ₃ C ₇ diol alkoxylated derivatives, aromatic diols, and unsaturated diols. Particularly preferred solvents which facilitate formulation are hexanediols such as 1,2-hexanediol and 2-ethyl-1,3-hexanediol and pentanediol such as 2,2,4-trimethyl-1,3. -Pentanediol.

(C) -Dispersing Aids Producing relatively concentrated, stable compositions without added concentration aids, comprising both saturated and unsaturated diester quaternary ammonium compounds. Can be. However, the compositions of the present invention may require organic and / or inorganic thickening auxiliaries to achieve higher concentrations and / or to meet higher stability standards depending on other ingredients. . Are these thickening aids (which can typically be viscosity improvers) required to ensure stability under extreme conditions when using particular softener active ingredient amounts? Or may be preferred. Surfactant concentration aids generally include (1) single long chain alkyl cationic surfactants, (2) nonionic surfactants, (3) amine oxides, (4) fatty acids, and (5) Select from the group consisting of mixtures thereof. These auxiliaries are described in particular in WO 94/20597, page 14, line 12 to page 20, line 12, incorporated herein by reference.

When the dispersing aid is present, its total amount is 2 to 25% by weight of the composition, preferably 3 to 17% by weight, more preferably 4 to 15% by weight, even more preferably 5 to 13% by weight.
% By weight. These materials may be added as part of the active softener raw material (I), for example, the fatty acids that are the reactants used to form the biodegradable fabric softener active ingredients described above, or may be added separately. Can be added as a component. The total amount of dispersing aid includes all that may be present as part of component (I).

Inorganic viscosity / dispersibility modifiers which act like surfactant concentration aids or can increase their effects can be incorporated into the compositions of the present invention if desired. And salts that can be ionized with A wide variety of ionizable salts can be used. Examples of suitable salts are halides of metals from Groups IA and IIA of the Periodic Table of the Elements, such as calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride. Ionizable salts are particularly useful in mixing the components to produce the compositions of the present invention and then obtaining the desired viscosity. The amount of ionizable salt used depends on the amount of active ingredient used in the composition and can be adjusted as desired by the formulator. Typical amounts of salts used to adjust the viscosity of the composition are from about 20 to about 20,000 ppm, preferably from about 20 to about 11,000 ppm by weight of the composition.

In addition to or instead of the water-soluble, ionizable salts described above, alkylene polyammonium salts can be incorporated into the composition to control the viscosity. further,
These substances can also act as scavengers, form ion pairs in the rinse water and on the fabric with anionic detergents carried over from the main wash liquor, and improve flexibility. These substances can stabilize the viscosity over a wide temperature range, especially at low temperatures, as compared to inorganic electrolytes. Specific examples of the alkylene polyammonium salt include l-
Includes lysine monohydrochloride and 1,5-diammonium 2-methylpentane dihydrochloride.

(D) -Stabilizer A stabilizer can be present in the composition of the present invention. The term "stabilizer" as used herein includes antioxidants and reducing agents. These materials are from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably about 0.035% with respect to antioxidants.
% To about 0.1%, more preferably about 0.01% to about 0.2% with respect to the reducing agent. These substances ensure that the compositions and compounds stored in the molten state have good odor stability under long-term storage conditions. The use of antioxidants and reducing stabilizers is particularly important for low fragrance (low perfume) products.

Examples of antioxidants that can be added to the compositions of the present invention include Eastman Chemical Pro
A mixture of ascorbic acid, ascorbic palmitate, propyl gallate, commercially available under the trade names Tenox PG and Tenox S-1 from ducts, Inc., Eastman
A mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, commercially available from Chemical Products, Inc. under the trade name Tenox-6, Sustane BH from UOP Process Division
Butylated hydroxytoluene, commercially available under the trade name T, Eastman Chemical P
Eastma, a tertiary butyl hydroquinone commercially available as Tenox TBHQ from roducts, Inc.
n Natural tocopherol commercially available from Chemical Products, Inc. as Tenox GT-1 / GT-2, and butylated hydroxyanisole commercially available as BHA from Eastman Chemical Products, Inc., long chain esters of gallic acid (C ₈ -C ₂₂ ), For example, dodecyl gallate, Irganox (trade name) 1010, Irganox (trade name) 1035, Irganox (
(Brand name) B 1171, Irganox (Brand name) 1425, Irganox (Brand name) 3114, Irganox
(Trade name) 3125, and mixtures thereof, preferably Irganox (trade name) 3125,
Irganox (trade name) 1425, Irganox (trade name) 3114, and a mixture thereof, and more preferably, Irganox (trade name) 3125 alone. The chemical names and CAS numbers of some of the above stabilizers are shown in Table II below.

TABLE II Antioxidants CAS Number Chemical Name Irganox 1010 6683-19-8 Tetrakis [methylene (3,5-di-tert-butyl-4- (trade name) Hydroxyhydrocinnamate Used in Federal Regulations )] Methane Irganox 1035 41484-35-9 Thiodiethylenebis (3,5-di-tert-butyl-4- (trade name) hydroxyhydrocinnamate Irganox 1098 23128-74-7 N, N'-hexamethylenebis ( 3,5-di-tert-butyl (trade name) -4-hydroxyhydrocinnamamide Irganox B 1171 31570-04-4 (trade name) 23128-74-7 Irganox (trade name) 1098 and Irgafos (trade name) 1: 1 mixture of 168 Irganox 1425 65140-91-2 Calcium bis [monoethyl (3,5-di-tert-buty (trade name) ru-4-hydroxybenzyl) phosphonate] Irganox 3114 65140-91-2 Calcium bis [ Monoethyl (3,5-di-tert-buty (trade name) ru-4-hydroxybenzyl) phosphonate] Irganox 3125 34137-09-2 3,5- Di-tert-butyl-4-hydroxy-hydro (trade name) 1,3,5-tris (2-hydroxyethyl) -s-triazine-2,4,6- (1H, 3H, Triester with 5H) -trione Irgafos 168 31570-04-4 Tris (2,4-di-tert-butyl-phenyl) phosphite (trade name) Examples of reducing agents include sodium borohydride and phosphorus hypophosphite. There are acids, Irgafos (trade name) 168, and mixtures thereof.

(E) -Fungicides Examples of fungicides used in the compositions of the present invention include glutaraldehyde, formaldehyde, Philadelphia, 2-bromo- sold by Inolex Chemicals of Pennsylvania under the trade name Bronopol. 2-nitropropane-1,3-diol,
And about 1 to about 1,000 ppm of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-, sold by the Rohm and Haas Company under the trade name Kathon. A mixture of 4-isothiazolin-3-one is exemplified.

(F) -Fragrance The present invention can include a fragrance. Suitable perfumes are described in U.S. Patent No. 5,500,138, which is incorporated herein by reference.

As used herein, perfumes include natural (ie, obtained by extraction of flowers or herbs, leaves, roots, bark, wood, fruit flowers or grasses), artificial (ie, various natural oils or Scented substances or mixtures of substances, including oily components) and synthetic (ie, synthetically produced) fragrances. Such materials are often accompanied by auxiliary materials, such as fixatives, spreaders, stabilizers and solvents. These auxiliary ingredients also fall under the meaning of "perfume" as used herein. Typically, perfumes are complex mixtures of multiple organic compounds.

Examples of useful perfume ingredients for the perfume of the composition of the present invention include hexylcinnamaldehyde, amylcinnamaldehyde, amyl salicylate, hexyl salicylate, terpineol, 3,7-dimethyl-cis-2,6-octadiene-. 1-ol, 2
2,6-dimethyl-2-octanol, 2,6-dimethyl-7-octen-2-ol, 3,7-dimethyl-3-octanol, 3,7-dimethyl-trans-2
, 6-octadien-1-ol, 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-1-octanol, 2-methyl-3- (para-tert
-Butylphenyl) -propionaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, tricyclodecenyl propionate, tricyclodecenyl acetate, anisaldehyde, 2- Methyl-2- (para-iso-propylphenyl) -propionaldehyde, ethyl-3
-Methyl-3-phenylglycidate, 4- (para-hydroxyphenyl) -butan-2-one, 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -2-butene-1- Examples include, but are not limited to, on, para-methoxyacetophenone, para-methoxy-alpha-phenylpropene, methyl-2-n-hexyl-3-oxo-cyclopentanecarboxylate, undecalactone gamma.

Other examples of fragrance materials include orange oil, lemon oil, grapefruit oil, bergamot oil, chopped oil, dodecalactone gamma, methyl-2- (2-pentyl-
3-oxo-cyclopentyl) acetate, beta-naphthol methyl ether, methyl-beta-naphthyl ketone, coumarin, decylaldehyde, benzaldehyde, 4-tert-butylcyclohexyl acetate, alpha, alpha-dimethylphenethyl acetate, methylphenylcarbinyl acetate, 4-
Schiff base of (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde and methyl anthranilate, cyclic ethylene glycol diester of tridecanedioic acid, 3,7-dimethyl-2,6-octadiene-1 -Nitrile, ionone gamma methyl, ionone alpha, ionone beta,
Petitglen, methyl sedron, 7-acetyl-1,2,3,4,5,6,7,
8-octahydro-1,1,6,7-tetramethylnaphthalene, iononemethyl, methyl-1,6,10-trimethyl-2,5,9-cyclododecatriene-1
-Yl ketone, 7-acetyl-1,1,3,4,4,6-hexamethyltetralin, 4-acetyl-6-tert-butyl-1,1-dimethylindane, benzophenone, 6-acetyl-1,1,1 2,3,3,5-hexamethylindane, 5
-Acetyl-3-isopropyl-1,1,2,6-tetramethylindane, 1-
Dodecanal, 7-hydroxy-3,7-dimethyloctanal, 10-undecen-1-al, iso-hexenylcyclohexylcarboxaldehyde, formyltricyclodecane, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, 1,3,4,6,7,8-hexahydro-4,6,6
7,8,8-Hexamethylcyclopenta-gamma-2-benzo-pyran, ambroxane, dodecahydro-3a, 6,6,9a-tetramethyl-naphtho [2,1b] furan, cedrol, 5- (2,2,3-trimethylcyclopenta-3-enyl) -3-methylpentan-2-ol, 2-ethyl-4- (2
, 2,3-Trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, caryophyllene alcohol, ceryl acetate, para-tert-butylcyclohexyl acetate, patchouli, oribanum resinoid, labdanam, vetiver
(vetivert), copaiba balsam, fir balsam, and condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indole, condensation products of phenylacetaldehyde and indole, 4
-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde and the condensation product of methyl anthranilate, but are not limited thereto.

Other examples of perfume ingredients include geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol acetate, terpinyl acetate, nopol, Nopyr acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styralyl acetate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl, methylphenylcarbinyl acetate, isononyl acetate, Vetiveryl acetate, vetiverol, 2-methyl-3- (p-te
rt-butylphenyl) -propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (p-tert-butylphenyl) -propanal, 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbaldehyde, 4-acetoxy-3-pentyltetrahydropyran, methyldihydrojasmonate, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-
Cyclopentanone, n-decanal, n-dodecanal, 9-decenol-1,
Phenoxyethyl isobutyrate, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, geranonitrile, citronellonitrile, ceryl acetal, 3-isocamphyl cyclohexanol, ceryl methyl ether, isolongifolanone, ovepinnitrile, ovepin, helio Tropine, eugenol, vanillin, diphenyl oxide, hydroxycitronellal ionone, methyl ionone, isomethyl ionone, iron, cis-3-hexenol and its ester, indan mask flavor, tetralin mask flavor,
Isochroman mask fragrance, macrocyclic ketone, macrolactone mask fragrance, ethylene brasilate.

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

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

The fragrance may comprise from 0 to 10%, preferably from about 0.1 to 5% by weight of the finished composition,
More preferably it can be present in an amount of 0.2-3% by weight. The fabric softener composition of the present invention has excellent perfume adhesion to fabric.

The perfume ingredients are described as releasable odors, for example, US Pat. No. 5,652,205, Hartman et al., Issued Jul. 29, 1997, which is hereby incorporated by reference.
International Patent Nos. WO95 / 04809, WO96 / 02625,
PCT filed August 19, 1997 and claiming priority on August 19, 1996
/ US 97/14610 and European Patent EP-A-0,75.
It can also be added as a pro-perfume or pro-fragrance as described in 2,465.

(G) -Enzymes The compositions and methods of the present invention may optionally include one or more enzymes, such as a lipase,
Proteases, cellulases, amylases and peroxidases can be used. A preferred enzyme for use herein is a cellulase enzyme. In fact,
Such enzymes have the further advantage of protecting the color of the treated fabric. Cellulases that can be used herein include both bacterial and fungal cellulases, preferably with an optimum pH between 5 and 9.5. U.S. Pat. No. 4,435,307 describes Hu.
Suitable fungal cellulases obtained from cellulase 212 producing fungi belonging to the genus micola insolens or Humicola strain DSM 1800 or Aeromonas and cellulases extracted from the hepatopancreas of the marine mollusc, Dolabella Auricula Solander, are disclosed. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,275 and German patent DE-OS-2,
No. 247,832. CAREZYME (brand name) and CELLUZ
YME (brand name) (Novo) is particularly useful. Other suitable cellulases are described in WO 91/17243, WO 96/34092, WO 96/34945 to Novo and EP-A-0,739, EP.
No. 982. Typical amounts actually used in current commercial formulations are up to 5 mg per gram of detergent composition by weight, more typically
1 mg to 3 mg of active enzyme. That is, the composition is typically comprised between 0.001 and 5
% By weight, preferably 0.01-1% by weight of a commercially available enzyme preparation. In the special case where the activity of the enzyme preparation can be defined in other ways, such as for example cellulase, the corresponding activity unit is preferred (eg CEVU or cellulase equivalent viscosity unit). For example,
The compositions of the present invention may include the cellulase enzyme in an amount equal to the activity of 0.5-1000 CEVU / gram composition. Cellulase enzyme preparations used to formulate the compositions of the invention have an activity of 1,000 to 10,000 CEVU / gram in liquid form and about 1,000 CEVU / gram in solid form.

Other Optional Ingredients The present invention relates to other optional ingredients commonly used in textile treatment compositions, such as brighteners, chlorine scavengers, such as European Patent EP-A-A. 0,
Non-polymeric chlorine scavengers, colorants, surfactants, anti-shrink agents, fabric crisping agents, dyeing agents, disinfectants, as disclosed in US Pat. Fungicides, antioxidants such as butylated hydroxytoluene, corrosion inhibitors,
Antifoaming agents, sun protection agents, such as, for example, substances as disclosed in EP-A-0,773,987, and the like, can be included.

The present invention relates to International Patent No. WO 96/02625, WO 96/2171.
No. 4, and WO 96/21715,
And Ve disclosed in pending application PCT / US97 / 01644.
Other compatible components, including dispersible polyolefins such as lustrol, may also be included. The present invention can also include an optional chelating agent, for example, the (S, S) isomer in the form of ethylenediamine-N, N'-disuccinic acid, sodium salt (EDDS).

Various other, optionally used, auxiliary ingredients can be used to form well-formulated detergent compositions. Such conventional detergent ingredients include detergent surfactants, builders, bleaching compounds, and mixtures thereof, such as those described in International Patent
98/20098.

Composition Forms The present color protection compositions are liquid, for example aqueous or non-aqueous compositions, and solid forms,
It can take a variety of physical forms, including, for example, solid particulate forms. Such compositions can be applied to a substrate, such as a dryer sheet product, or used as a product added during rinsing, or as a spray or foam product.

Method of Use In another aspect of the present invention, there is provided a method of inhibiting or inhibiting fabric fade, comprising the step of contacting the fabric with a divalent salt or composition of the present invention. Also provided is the use of the divalent salt for inhibiting or inhibiting the fading of fabrics.

Surprisingly, the fabrics treated according to the present method and use have a better appearance of the fabrics compared to fabrics treated with the composition without divalent salts, especially with regard to their color protection. I understood that.

Preferably, the method is used for domestic processing. By "home treatment" is meant all the steps common to home laundering, such as dipping, washing, rinsing, and / or spraying, and the use of dryer sheets to which the composition has been adsorbed.

Preferably, the contacting is carried out in a washing process, preferably in the rinsing step of the washing process, more preferably at a temperature below 30 ° C, preferably at 5 to 25 ° C.

The present invention is illustrated by the following examples, but is not limited to these examples. All percentages are by weight unless otherwise indicated.

In these examples, the abbreviated components have the following meanings.

DEQA: di- (tallowyl-oxy-ethyl) dimethylammonium chloride DOEQA: di- (oleyloxyethyl) dimethylammonium methyl sulfate DTDMAC: ditallow dimethylammonium chloride DHEQA: di- (soft-tallowyl-oxy-ethyl) Hydroxyethyl methyl ammonium methyl sulfate DTDMAMS: ditallow dimethyl ammonium methyl sulfate SDASA: Stearyl dimethylamine in a 1: 2 ratio: triple compressed stearic acid Glycosperse S-20: polyethoxylated sorbitan monostearate, commercially available from Lonza Clay: calcium bentonite clay , Bentonite L, Southern Clay Product
PEG: polyethylene glycol 4000 PEI 1800 E1: ethoxylated polyethyleneimine (molecular weight 1800, 50% active) synthesized in Synthesis Example 1 PEI 1800 E3: ethoxylated polyethyleneimine (molecular weight 1800, 50% active) synthesized in Synthesis Example 1 PEI 1200 E1: Ethoxylated polyethyleneimine (molecular weight 1200, 50% in water
Activity) Synthesized in Synthesis Example 2. PEI 1200 E4: Ethoxylated polyethyleneimine (molecular weight 1200, 50% in water
Activity) Synthesized in Synthesis Example 2. Dye fixative 1: Cellulose-reactive dye fixative, commercially available from Clariant under the trade name Indosol CR Dye fixative 2: Cellulose-reactive dye fixative, trade name Rewin from CHT R. Beitlich
Commercially available on WBS Divalent salt 1 Magnesium sulfate Divalent salt 2 Magnesium chloride Divalent salt 3 Calcium chloride LAS: Sodium linear C _11-13 alkyl benzene sulfonate CxyAS: Sodium C _{1x to} C _1y alkyl sulfate CxyEzS: Sodium C _{1x to} C _1y Alkyl sulfate, condensed with z moles of ethylene oxide CxyEz: Mainly linear primary alcohol of C _{1x to} C _1y , condensed with z moles of ethylene oxide APA: C _{8 to} C ₁₀ amidopropyldimethylamine CFAA: C _{12 to} C ₁₄ (coco ) alkyl N- methyl glucamide _TFAA: C 16 _{-C 18} alkyl N- methyl glucamide _{TPKFA: C 12 ~C 14 topped whole} cut fatty acids citric acid: anhydrous citric acid borate: sodium borate protease : A proteolytic enzyme, the active enzyme 3.3 wt%, Savinase
Alcalase: Proteolytic enzyme, NOVO Industrie with 5.3% by weight of active enzyme
Cellulase: Cellulolytic enzyme, NOVO Ind with 0.23% by weight of active enzyme
Amylase: amylolytic enzyme, NOVO Industr with 1.6% by weight active enzyme from ustries A / S
Available from ies A / S under the trade name Termamyl 120T Lipase: lipolytic enzyme, NOVO Industries A / with 2.0% by weight active enzyme
Endolase: Endoglucanase enzyme, NOVO Ind with 1.5% by weight of active enzyme, sold under the trade name Lipolase from S
ustries Sold by A / S DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta (methylene phosphonate), Monsanto
Brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl Brightener 2: disodium 4,4'-bis (4-anilino-6-morpholino-1, 3,5-triazin-2-yl) amino) stilbene-2: 2′-disulfonate HEDP: 1,1-hydroxyethanediphosphonic acid TEMPAE: tetraethylenepentamine ethoxylate PVNO: polyvinylpyridine N-oxide polymer, Average molecular weight 50,000 SRP1: Anionic end-capped polyester SRP2: Diethoxylated poly (1,2-propylene terephthalate) short block polymer Silicone defoamer: Polydimethylsiloxane containing siloxane-oxyalkylene copolymer as dispersant Cell adjusting agent, the cell adjusting agent The dispersant of the ratio of 10: 1
100: 1 opacifier: water-based monostyrene latex mixture, commercially available from BASF under the trade name Lytron 621 Polycarboxylic: polycarboxylic acid compound, commercially available under the trade name Sokalan CP 10 from BASF Glycolic: glycolic acid Polymer I: polyvinylpyrrolidone K90, marketed under the trade name Luviskol K90 from BASF
Bayhibit AM: 2-phosphonobutane-1,2,4-tricarboxylic acid, commercially available from Bayer pH: Measured in a 1% distilled aqueous solution at 20 ° C. Synthesis Example 1 Preparation of PEI 1800E ₁ A) -Ethoxylation is carried out by temperature measurement and It is carried out in a 2 gallon stirred stainless steel autoclave equipped for control, pressure measurement, vacuum and inert gas scavenging, sampling, and introduction of ethylene oxide as liquid. An approximately 20 lb. net ethylene oxide cylinder (ARC) is placed on a balance so that the weight change of the cylinder can be monitored, and the pump is arranged to supply ethylene oxide as a liquid to the autoclave.

750 g part of polyethyleneimine (PEI) (Nippon Shokubai, Epomin SP-
018, indicated, having an average molecular weight of 1800, equal to 0.417 mole of polymer and 17.4 moles of nitrogen functional groups). The autoclave is then sealed and purged of air (applying a vacuum of -28 "Hg, followed by pressurizing with nitrogen to 250 psia and then evacuating to atmospheric pressure). After about 1 hour, load the autoclave with nitrogen at about 250 psia while cooling the autoclave to about 105 ° C. Then, while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate, Ethylene oxide is gradually added to the autoclave over time, the ethylene oxide pump is stopped and cooled to limit the temperature increase due to the exothermic reaction, and the total pressure is gradually increased while maintaining the temperature at 100 to 110 ° C during the reaction. A total of 750 grams of ethylene oxide (1 mole of ethylene per PEI nitrogen functional group) After loading approximately equal) to the autoclave N'okishido, the temperature 11
Raise to 0 ° C. and stir autoclave for another hour. At this point, vacuum is applied to remove any remaining unreacted ethylene oxide.

Step B) —The reaction mixture is then heated to 130 ° C. and, while stirring, about 100 cu. Ft. Of inert gas (argon or nitrogen) is passed through the gas dispersion frit and the reaction mixture, and the reaction mixture is Deodorizes.

The final reaction product is cooled slightly and collected in a glass container purged with nitrogen.

In another production, neutralization and deodorization are carried out in the reactor before discharging the product.

If PEI 1800E ₇ is desired, the following catalyst addition step between steps A and B is included.

While continuously applying vacuum, cool the autoclave to about 50 ° C.
376 g of a methanol solution of sodium methoxide are introduced (1.74 mol, P
Achieve 10% catalyst loading on the EI nitrogen function). The methoxide solution is sucked into the autoclave under vacuum, then the set point of the autoclave temperature controller is increased to 130 ° C. Use a device to monitor the power consumed by the stirrer. The power of the stirrer is monitored along with the temperature and pressure. As methanol was removed from the autoclave and the viscosity of the mixture increased, the power and temperature values of the stirrer gradually increased and stabilized in about 1 hour, indicating that most of the methanol had been removed. The mixture is further heated and stirred under vacuum for another 30 minutes.

Remove the vacuum and cool the autoclave to 105 ° C. while
a and then vented to atmospheric pressure. The autoclave is filled to 200 psia with nitrogen. Again, the pressure, temperature, and ethylene oxide flow rate of the autoclave are closely monitored, and ethylene oxide is gradually added to the autoclave as before while maintaining the temperature at 100 to 110 ° C. and limiting the temperature increase due to the exothermic reaction.
After the addition of 4500 g of ethylene oxide over a period of several hours (to a total of 7 mol of ethylene oxide per mol of PEI nitrogen function), the temperature is increased to 110 ° C. and the mixture is stirred for a further hour.

The reaction mixture is then collected in a nitrogen purged vessel and finally transferred into a 22 L 3-neck round bottom flask equipped with heating and stirring equipment. 167 g of methanesulfonic acid (1
. (74 mol) to neutralize the strong alkali catalyst.

Other preferred examples, such as PEI 1800E2, PEI 1800E3, PE
I 1800E15 and PEI 1800E20 can be produced by the methods described above by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

[0185] Production Step A Synthesis Example 2-PEI 1200E ₁₎ - ethoxylation temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and introduction of ethylene oxide as a liquid, equipment for performing In a 2 gallon stirred stainless steel autoclave. An approximately 20 lb. net ethylene oxide cylinder (ARC) is placed on a balance so that the weight change of the cylinder can be monitored, and the pump is arranged to supply ethylene oxide as a liquid to the autoclave.

750 g part of polyethyleneimine (PEI) (labeled polymer about 0.62
5 moles and an average molecular weight of 1200 equal to 17.4 moles of nitrogen functionality) are added to the autoclave. The autoclave is then sealed and purged of air (applying a vacuum of -28 "Hg, then pressurizing to 250 psia with nitrogen and then evacuating to atmospheric pressure).
Heat to 0 ° C. After about 1 hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ° C. Ethylene oxide is then slowly added to the autoclave over time, while closely monitoring the autoclave pressure, temperature, and flow rate of ethylene oxide. The ethylene oxide pump is stopped and cooled to limit temperature increase due to the exothermic reaction. During the reaction, the temperature is 100 ~
While maintaining at 110 ° C., gradually increase the total pressure. Total 750 grams of ethylene oxide (approximately one mole of ethylene oxide per PEI nitrogen functional group)
After loading into the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for another hour. At this point, vacuum is applied to remove any remaining unreacted ethylene oxide.

Step B) —The reaction mixture is then heated to 130 ° C. and, while stirring, about 100 cu. Ft. Of inert gas (argon or nitrogen) is passed through the gas dispersion frit and the reaction mixture, and the reaction mixture is Deodorizes.

The final reaction product is cooled slightly and collected in a glass vessel purged with nitrogen.

In another production, neutralization and deodorization are carried out in the reactor before discharging the product.

If PEI 1200E ₇ is desired, the following catalyst addition step between steps A and B is included.

While continuously applying vacuum, cool the autoclave to about 50 ° C.
376 g of a methanol solution of sodium methoxide are introduced (1.74 mol, P
Achieve 10% catalyst loading on the EI nitrogen function). The methoxide solution is sucked into the autoclave under vacuum, then the set point of the autoclave temperature controller is increased to 130 ° C. Use a device to monitor the power consumed by the stirrer. The power of the stirrer is monitored along with the temperature and pressure. As methanol was removed from the autoclave and the viscosity of the mixture increased, the power and temperature values of the stirrer gradually increased and stabilized in about 1 hour, indicating that most of the methanol had been removed. The mixture is further heated and stirred under vacuum for another 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C. while 250 psi of nitrogen is applied.
a and then vented to atmospheric pressure. The autoclave is filled to 200 psia with nitrogen. Again, the pressure, temperature, and ethylene oxide flow rate of the autoclave are closely monitored, and ethylene oxide is gradually added to the autoclave as before while maintaining the temperature at 100 to 110 ° C. and limiting the temperature increase due to the exothermic reaction.
After the addition of 4500 g of ethylene oxide over a period of several hours (totaling 7 mol of ethylene oxide per mole of PEI nitrogen function), the temperature is increased to 110 ° C. and the mixture is stirred for a further hour.

The reaction mixture is then collected in a nitrogen purged vessel and finally transferred into a 22 L 3-neck round bottom flask equipped with heating and stirring equipment. 167 g of methanesulfonic acid (1
. (74 mol) to neutralize the strong alkali catalyst.

Other preferred examples, for example PEI 1200E2, PEI 1200E4, PE
I 1200E15 and PEI 1200E20 can be produced by the methods described above by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

Example 1 The following fabric protection composition is in accordance with the invention.

[0196]

[Table 1]

[Table 2]

[Table 3] Example 2 The following composition for use as a dryer-added sheet is in accordance with the invention.

[0197]

[Table 4] Example 3 The following liquid detergent formulation was prepared according to the present invention (amounts are given in parts by weight).

[0198]

[Table 5] Example 4 The following liquid detergent formulation was prepared according to the present invention (amounts are given in parts by weight).

[0199]

[Table 6] Example 5 The following liquid detergent formulation was prepared according to the invention (amounts are given in parts by weight).

[0200]

[Table 7]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // D06M 11/56 D06M 13/463 13/463 11/04 Z (81) Designated country EP (AT, BE) , CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA , GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY) , KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT , LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA F term (Reference) BA17 BA35 DA09 4L033 BA08 BA34 BA58 BA79 BA86

Claims (12)

[Claims] 1. A color protective composition comprising: i) a dye fixing agent; and ii) a divalent salt. 2. The composition according to claim 1, wherein the dye fixing agent is a cationic dye fixing agent. 3. The dye-fixing agent is a cellulose-reactive dye-fixing agent. Preferably, the cellulose-reactive dye-fixing agent is a halogeno-triazine compound, a vinylsulfone compound, an epichlorohydrin derivative, a hydroxyethylene urea derivative, or formaldehyde. 2. The composition according to claim 1, wherein the composition is a compound comprising a reactive group of a reactive dye segment selected from condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives and mixtures thereof. 4. The method according to claim 1, wherein the cellulose-reactive dye fixing agent is formed from a condensation product derived from formaldehyde and a group selected from an amino group, an imino group, a phenol group, a urea group, a cyanamide group, and an aromatic group. A formaldehyde condensation product selected,
A composition according to claim 3. 5. The method according to claim 1, wherein the dye fixing agent comprises 0.01 to 50% by weight, preferably 0.01 to 2% by weight of the composition.
A composition according to any of the preceding claims, being present in an amount of 5% by weight. 6. The composition according to claim 1, wherein the divalent salt is formed from an alkaline earth metal salt, preferably selected from magnesium, calcium and mixtures thereof. 7. The method according to claim 1, wherein the divalent salt is magnesium sulfate, magnesium bicarbonate, magnesium chloride,
The composition according to any one of claims 1 to 6, wherein the composition is selected from magnesium borate, magnesium citrate and mixtures thereof, more preferably selected from magnesium sulfate, magnesium chloride and mixtures thereof. 8. The divalent salt comprises from 0.01 to 90%, preferably from 0.5 to 90%, more preferably from 1 to 20%, most preferably from 3 to 10% by weight of the composition. The composition according to any one of claims 1 to 6, which is present in an amount. 9. The use of a divalent salt for inhibiting or inhibiting the fading of fabrics. 10. A method for inhibiting or suppressing the fading of a fabric, comprising the step of contacting the fabric with a divalent salt or a composition according to any one of claims 1 to 9. . 11. The method of claim 10, wherein the method is performed in a home process. 12. The method according to claim 11, wherein said method is performed in a rinsing step.