JP2001524618A - Stabilized fabric softener composition - Google Patents

Abstract

  (57) [Summary] The present invention is a composition comprising a polyamino-functional polymer, wherein the composition is stabilized by the use of a crystal growth inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION [0001] The present invention relates to a fabric protection composition comprising a polyamino-functional polymer, thereby effectively stabilizing the composition.

BACKGROUND OF THE INVENTION The appearance of colored fabrics, such as clothing, bedding, household fabrics, such as table linen, is an important area for consumers. Indeed, the typical use of the fabric by consumers, such as wearing, washing, rinsing and / or tumble drying the fabric, may result in a poor appearance of the fabric, which is at least partially due to color fidelity and This is because color clarity is lost. The problem of such poor color quality becomes more acute after many washing cycles.

[0003] It is therefore an object of the present invention to provide a composition that more effectively protects the color of washed fabrics, especially after many washing cycles.

[0004] Recently, a new class of materials, namely amino-functional polymers, has been increasingly used in fabric treatments to protect the color of the fabric.

However, it has been found that compositions comprising these amino-functional polymers tend to cause storage stability problems. Characteristic of this problem is the yellowing of the composition as well as offensive odor on the treated fabric. This problem is more acute when formulating the product as a stand-alone product. In fact, when well formulated, as in softening compositions, the perfume present therein masks the odor to some extent and the resulting odor becomes less noticeable. In contrast, in the stand-alone product, the fragrance does not mask the odor well unless it is present at very high levels. However, high levels of perfume increase prescription costs. In addition, the use of high levels of perfume to mask odors does not provide long-term concealment of odors. In fact, fragrances mask odors momentarily, but during storage, fragrances, including volatile top notes, evaporate, reducing the odor masking properties.

[0006] Accordingly, formulators of fabric protection compositions face the dual problem of formulating compositions that protect the fabric without adversely affecting the stability of the composition.

[0007] The applicant has now surprisingly discovered that adding a crystal growth inhibitor to a composition comprising a modified amino-functional polymer solves this problem.

[0008] One detailed description essential component of the amino functional polymer This invention is an amino-functional polymer. The amino-functional polymer effectively protects the color of the fabric.

[0009] The amino-functional polymer of the present invention is a water-soluble or dispersible polyamine. Typically, the amino functional polymers for use herein have a molecular weight from 200 to 10 ^6, preferably from 600 to 20,000, most preferably 1000 to 10,000.
The skeleton contained in these polyamines 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” refers to the chemical structure of a polyamine and refers to the skeleton —N
It is defined as replacing the hydrogen atom of H with an R 'unit (substitution), quaternizing the skeletal nitrogen (quaternization), or oxidizing the skeletal nitrogen to N-oxide (oxidation). 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.

[0011] The linear or acyclic polyamine skeleton constituting the amino-functional polymer is one of the following.
R ′ || [R ′ having the general formula₂NR]_{n + 1}-[NR]_m-[NR]_n-NR '₂ The cyclic polyamine skeleton constituting the amino-functional polymer has a general formula: | R'R ||| [R '₂NR]_{nk + 1}-[NR]_m-[NR]_n-[NR]_k-NR ' ₂ Having.

[0012] The backbone described above, prior to subsequent denaturation (optionally preferred, but preferred), comprises 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 modification. 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 denaturation,
It is 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.

[0015] Further 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. R, which serves to connect the polyamine nitrogen, attached to the nitrogen in the V, W and Y units is described below.

[0016] 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. If skeleton is a special complete ring, the polyamine backbone has the formula _{R '| | [R' 2} N-R] n - [N-R] m - [N-R] n - has, therefore Z terminal not contain units having 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, ie, n is 0. The larger the number of n (the smaller the ratio of m and n)
, The degree of branching in the molecule is large. Typically, the value of m is a minimum of 2 to 700, preferably 4 to 400, but larger values of m are also preferred, especially if the value of the index n is very small or close to zero.

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 the following three forms: a) a simply substituted unit having the structure: R'-NR- | 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 types of forms: a) a simply substituted unit having the structure: —N—R— | R ′ b) a group 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 '.

The other modified secondary amine moieties have the following three forms: a) a simply substituted unit having the structure: -NR- | 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 structure: -NR- | b) a quaternized 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) a structure having 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 backbone R “bond” that serves to connect the nitrogen atoms of the backbone.
Comprising units. An R unit is a “hydrocarbyl R” unit for the purposes of the present invention and
It comprises units called "oxy R" units. "Hydrocarbyl R" unit is C₂~ C₁₂Alkylene, C₄~ C₁₂Alkenylene, C₃~ C₁₂Hydroxy
Alkylene (the hydroxy moiety is a carbon atom directly attached to the polyamine backbone nitrogen
Can be taken at any position on the R unit chain except)₄~ C₁₂Jihid
Roxyalkylene (the hydroxy moiety is a carbon directly attached to the polyamine backbone nitrogen
Can be occupied by any two of the carbon atoms in the R unit chain except for the atom), C ₈ ~ C₁₂Dialkylarylene (which, for the purposes of the present invention,
And is an arylene moiety having two alkyl substituents). For example,
The alkylarylene unit has the formula

Embedded imageBut the 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.

[0029] 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.

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.

OO O OO ↑ ‖ ↑ ↑ ‖ -NR or R³-C-N-R or -N-C-R³ ||| C = O R'R '| R³ 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 has a value of 1 to 20, preferably 1 to 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 comprise no more than 3 carbon atoms and are preferred "hydrocarbyl" R units. That is, when R units of the backbone is a _C 2 _{-C 12 alkylene,} C 2 -C ₃ alkylene is preferred, ethylene being most preferred.

The amino-functional polymers of the present invention comprise a modified homogeneous and heterogeneous polyamine backbone, wherein up to 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 of various R unit lengths 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.

Preferred amino-functional polymers of the present invention include a homogeneous polyamine backbone 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 backbone 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 that are C ₂ alkylene (ethylene) units, also called polyethylene imine (PEI). Preferred PEIs have at least moderate branching, ie, the ratio of m to n is less than 4: 1,
PEI having a ratio of m to n of 2: 1 is most preferred. Preferred backbones have the following formula before modification:

R '|| [R'₂NCH₂CH₂]_n-[NCH₂CH₂]_m-[NCH₂CH₂]_n-NR ’ ₂ Wherein R ', m and n are as defined above. Preferred PEIs have a molecular weight
Exceeds 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 ethyleneimine 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. The amino-functional polymers of the present invention comprising PEI are shown in Formulas I-IV.

Formula I shows a PEI skeleton having the following formula, wherein all substitutable nitrogens have been modified by replacing hydrogen with a polyoxyalkyleneoxy unit — (CH ₂ CH ₂ O) H. Figure 4 shows an amino-functional polymer comprising.

[0053]

Embedded image Formula I This is an example of an amino-functional polymer that is completely modified in one type of moiety.

Formula II shows that all substitutable primary amine nitrogens can be modified by replacing hydrogen with a polyoxyalkyleneoxy unit — (CH ₂ CH ₂ O) ₂ H, followed by all oxidations 1 shows an amino-functional polymer comprising a PEI backbone, the molecule of which has been modified by oxidizing primary and secondary nitrogen to N-oxide. The polymer has the following formula:

[0055]

Embedded image Formula II Formula III shows an amino-functional polymer comprising a PEI backbone, wherein all backbone hydrogen atoms have been replaced and some backbone amine units have been quaternized. The substituent is a polyoxyalkyleneoxy unit — (CH ₂ CH ₂ O) ₇ H or a methyl group. This modified PEI has the following formula:

[0056]

Embedded image Formula III Formula IV, substituted skeletal nitrogen (i.e. _- by _{(CH 2 CH 2 O) 3} H or methyl), quaternized, oxidized to N- oxides, or modified by a combination thereof, include PEI backbone 1 shows an amino-functional polymer consisting of The resulting polymer has the following formula:

[0057]

Embedded image Formula IV In the above example, not all nitrogens in one unit section contain the same modification. The present invention allows the formulator to ethoxylate some of the secondary amine nitrogens and oxidize other secondary amine nitrogens 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. Except for the limitations described above, any possible combination of R 'groups can be substituted on the primary and secondary amine nitrogen.

Commercially available aminofunctional 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 from Polysciences, and commercially available from Aldrich. 80% hydroxyethylated poly (ethylene imine).

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, more preferably 0.1% by weight. -20% by weight, most preferably 0.5-15% by weight.

Crystal Growth Inhibitor Crystal growth inhibitor (CGI) is an essential component of the present invention. `` Crystal growth inhibitor ''
By is meant a compound that reduces the rate of formation of inorganic crystallites, thereby reducing the size and / or amount of such crystallites on the fabric surface.

The CGI suitable for use here can be confirmed by the following procedure, so-called crystal growth suppression test measurement.

Crystal Growth Inhibition Test Measurement The ability of a compound to inhibit crystal growth can be assessed by in vitro evaluating the effect on the growth rate of inorganic microcrystals. For this purpose, 19
Nancollas, GH and Koutsoukos, developed by GH Nancollas in 1964,
The method described in PG "Calcium Phosphate Nucleation and Growth in solution." Prog. Crystal Growth Charact. 3, 77-102 (1980) can be used. This method consists in measuring the growth rate of calcium phosphate seeded with hydroxyapatite ([Ca ₅ (PO ₄ ) ₃ OH] or HAP) in the presence of CaCl ₂ and NaH ₂ PO ₄ . Protons released by the growth of calcium phosphate can be titrated with a strong base. The amount of base required to maintain a constant pH throughout the crystal growth allows one skilled in the art to directly measure the crystal growth rate and to identify the effects of potential crystal growth rate inhibitors. A typical plot of such an experiment is shown below.

(Equation 1)

The observed t-lag value defines the efficiency of a compound in inhibiting the growth of calcium phosphate crystals; the higher the t-lag, the better the CGI.

The following procedure can be used to experimentally generate the above plot.

[0065] 350 mL of distilled water (double distilled), 35 mL of 2.1 M KCl, 50 mL of 0.01
75 M CaCl ₂ and 50 ml of 0.01 M KH ₂ PO ₄ are placed in a reaction vessel. Insert a glass pH electrode and a standard calomel reference electrode connected to an automatic titrator. Bubble with nitrogen gas to stabilize the temperature of the reaction mixture at 37 ° C. Once the temperature and pH are stabilized, add test CGI concentrations tested (e.g. 1.10 ⁶ M). Titrate to pH 7.4 with 0.05M KOH. The reaction mixture is then seeded with ₅ mL of a hydroxyapatite slurry [Ca ₅ (PO ₄ ) ₃ OH].

The hydroxyapatite slurry is produced as follows.

100 g of Bio-Gel (trade name) HTP hydroxyapatite powder is dispersed in 1 L of distilled water. The pH of the resulting slurry is lowered to 2.5 by adding 6N HCl dropwise. This is then heated to boiling in a 2 L round bottom flask equipped with a condenser and refluxed with stirring for 7 days. 50% after cooling to room temperature
The pH is adjusted to 12.0 by dropwise addition of NaOH and the slurry is refluxed for a further 7 days as before. The slurry is allowed to settle for 2 days and the supernatant is aspirated. The flask is again filled with 1.5 L of distilled water, stirred vigorously and allowed to settle again for 2 days. Rinse a total of 7 times as described above. With vigorous stirring, 2N HCl
Is added dropwise to adjust the pH to 7.0. The resulting slurry is stored at 37 ° C. for 11 months.

The above plot is obtained by recording the amount of base added over time to maintain the pH of the reaction medium. The T-lag for a particular crystal growth inhibitor is determined from the graph as shown in the figure above.

The crystal growth inhibitors used for the purposes of the present invention have a t-lag at a concentration of 1.10 ⁶ M for at least 10 minutes, preferably for at least 20 minutes, most preferably for at least 50 minutes.

Yet another T-lag compatible method suitable for determining the crystal growth inhibition properties of a particular component is visual grading. This method is as follows. A multi-cycle wash test is performed with several cycles (eg, 10) of repeated washing and tumble drying. Use conditions that are representative of the desired geographical area (eg, household washing machine used, detergent used, rinsing product used, water hardness, fabric product to be washed, etc.). At least two test steps, a step involving the composition of the invention and another reference step, are performed in parallel. After performing the required number of washing cycles, an expert judge compares the test garments (fabric products) under adjusted lighting conditions.
Visual grading is a better / worse comparison of the visible crystalline residue on the test garment surface, comparing the test run to a reference run. Dark colored, knitted cotton products are best suited for this comparison.

Furthermore, crystal growth inhibitors are distinguished from chelators by their low affinity for copper as defined by Log K, ie, ML / ML of CGI at 25 ° C., 0.1 ionic strength. Log K is less than 15, preferably less than 12.

Preferably, the CGI used in the present invention is selected from carboxylic compounds, organic monophosphonic acids, organic diphosphonic acids, and mixtures thereof.

Carboxyl Compounds Typical carboxyl compounds used herein include glycolic acid, phytic acid,
A carboxyl compound selected from monomeric polycarboxylic acids, homo- or copolymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acids are at least two carbon atoms separated from each other by no more than two carbon atoms. One carboxyl group.

When used in the form of a salt, the salts of the alkali metals, such as sodium, potassium and lithium, or alkanolammonium are preferred.

Suitable organic detergents CGI for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, “polycarboxylate” refers to a compound having multiple carboxylate groups, preferably at least three carboxylate groups. The polycarboxylate CGI can generally be added to the composition in the form of an acid, but can also be added in the form of a neutralized salt. When used in a salt form, an alkali metal such as sodium,
Potassium and lithium or alkanol ammonium salts are preferred.

[0076] The polycarboxylate CGI includes a variety of useful materials. An important class of polycarboxylate CGIs are ethers, including oxydisuccinates as described in U.S. Pat. Nos. 3,128,287 and 3,635,830. And polycarboxylates. See also "TMS / TDS" CGI in U.S. Pat. No. 4,663,071. Suitable ether polycarboxylates are cyclic compounds, especially cycloaliphatic compounds, such as US Pat. Nos. 3,923,679, 3,835,163, 4,1.
58,635, 4,120,874 and 4,102,9
No. 03, also included.

Other useful CGIs include ether hydroxy polycarboxylates, polyacrylate polymers, copolymers of maleic anhydride and ethylene or vinyl methyl ether, or acrylic acid, 1,3,5-trihydroxybenzene- 2,4,6-
Various alkali metal, ammonium and substituted ammonium salts of trisulfonic acid, and carboxymethyloxysuccinic acid, polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, and polymaleic acid. Benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

The molecular weight of these polymers and copolymers is preferably less than 100,000,
Most preferably, it is 500 to 50,000.

Polymers suitable for use herein that are commercially available and that inhibit the precipitation of salts of buffer components when the composition is diluted with water are Good-Rite, Rohm & Haas from BF Goodrich.
Acrysol from BASF, Sokalan from BASF, and Norasol from Norso Haas. Preferred commercially available polymers are polyacrylate polymers, especially the Norasol® polyacrylate polymer available from Norso Haas, more preferably the polyacrylate polymer Norasol® 410N (molecular weight 10,000) and amino. Nora, a polyacrylate polymer modified with phosphonic groups
sol (trade name) 440N (molecular weight 4000) and its corresponding acid form Norasol (trade name) QR784 (molecular weight 4000).

Citrate salts, such as citric acid and its soluble salts, especially the sodium salt, are suitable polycarboxylate CGIs for use herein.

The 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in US Pat. No. 4,566,984 are also suitable for the compositions of the present invention. is there. Useful succinic acid CGI _include the C 5 _{-C 20} alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of the succinate CGI include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinate is a preferred CGI of this group and is described in European Patent No. 0.
, 200,263. Other suitable polycarboxylates are described in U.S. Pat. Nos. 4,144,226 and 3,308,067.
It is described in the specification. See also U.S. Pat. No. 3,723,322.

Organic Monophosphonic Acids Organomonophosphonic acids or salts or complexes thereof 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 component is 2-phosphonobutane-1,2,4-tricarboxylic acid, commercially available from Bayer under the trade name Bayhibit.

Organodiphosphonic Acids Organodiphosphonic acids or salts or complexes thereof are also suitable here for use as CGI.

The term “organodiphosphonic acid” as used herein means 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 component can be present in its acid form or in its salt or complex form with a suitable counter cation. Preferably, all salts / complexes are water-soluble, alkali metal and alkaline earth metal salts / complexes being particularly preferred.

The organodiphosphonic acid is preferably a C ₁ -C ₄ diphosphonic acid, more preferably ethylene diphosphonic acid, α-hydroxy-2-phenylethyl diphosphonic acid, methylene diphosphonic acid, vinylidene 1,1 diphosphonic acid, a C ₂ diphosphonic acid selected from 1,2-dihydroxy ethane 1,1 diphosphonic acid and hydroxy ethane 1,1 diphosphonic acid and salts thereof and mixtures thereof.

The most preferred organodiphosphonic acids are hydroxyethane 1,1 diphosphonic acid (
HEDP).

Of the above group of CGIs, a preferred group for use herein is the group of organic monophosphonic acids and / or organic diphosphonic acids.

For the purposes of the present invention, when the CGI is selected from carboxylic acids, organic diphosphonic acids, and mixtures thereof, the CGI is less than 1% by weight of the composition, preferably less than 0.0%.
It is present in an amount of from 0.5 to 0.5% by weight, more preferably from 0.05 to 0.50% by weight, most preferably from 0.1 to 0.2% by weight.

Typical amounts of CGI other than carboxylic acids, organic diphosphonic acids, and mixtures thereof, such as organomonophosphonic acids, are less than 10% by weight of the composition, more preferably 0.005 to 0.50% by weight. %, Most preferably 0.1-0.2% by weight.

Preferably, for the purposes of the present invention, a composition comprising a polyamino-functional polymer comprises the CG
The weight ratio of I to the polymer is from 0.005: 1 to 0.5: 1, preferably 0.01: 1.
It is most effectively stabilized when 0.1: 1.

The compositions of the present invention can be used in stand-alone products, including pre-wash or post-wash additives. The compositions of the present invention may also include laundry compositions, and fabric softener compositions added during rinsing and dryer applied compositions (eg, sheets) that provide softness and / or antistatic properties, and It can also be used in well-formulated compositions, including compositions added during rinsing.

The composition can comprise optional ingredients such as dye fixatives, fabric softener compounds, and other optional ingredients.

Dye Fixing Agent The composition of the present invention can optionally contain a dye fixing agent. Dye fixatives, or "fixers", are well-known, commercially available materials designed to improve the appearance of dyed fabrics by minimizing the loss of dye from the fabric upon washing. is there. Materials described above as fabric softeners or amino-functional polymers are not included in this definition.

[0098] 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).

[0099] Other cationic dye fixatives are described in "Aftertreatments by Christopher C. Cook.
for improving the fastness of dyes on textile fibres '' (REV.PROG.COLORAT
ION Vol. 12, 1982). Dye fixatives suitable for use in the present invention are ammonium compounds, such as fatty acid diamine condensates, such as hydrochloride, acetate, methosulfate and benzyl hydrochloride of oleyldiethylaminoethylamide, oleylmethyldiethylenediaminemethosulfate. Oxidized products of monostearyl-ethylenediaminotrimethylammonium methosulfate and tertiary amines, derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrin.

Typical amounts of dye fixatives used in the compositions of the present invention are up to 90%, preferably up to 50%, more preferably 0.001-10%, most preferably up to 90% by weight of the composition. 5 to 5% by weight.

The compositions of the present invention can also be formulated as a fabric softening composition. Thus, when formulated as a softening composition, the composition also comprises a fabric softening compound.

Typical amounts of softening compound in the fabric softening compound are from 1 to 80% by weight of the composition.
, Preferably 5 to 75% by weight, more preferably 15 to 70% by weight, still more preferably 19 to 65% by weight.

The fabric softening compound is preferably selected from cationic, nonionic, amphoteric or anionic fabric softening components. Typical cationic softening components are quaternary ammonium compounds or their amine precursors as defined below.

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

[0105]

Embedded image Or

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

[0106]

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 a mixture thereof, X is an anion is fabric softening agent active ingredient and auxiliary ingredients compatible, the index m is from 1 to 4, preferably 2, the index n Is 1
-4, preferably 2.

Examples of preferred fabric softener active ingredients are mixtures of quaternary amines having the formula:

[0108]

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.

The fabric softening active of the present invention is a diester and / or diamide quaternary ammonium (DEQA) compound, wherein the diester and diamide have the formula:

[0110]

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

[0111]

Embedded image These preferred fabric softening actives are prepared by reacting an amine with a fatty acyl unit to form

Embedded image Wherein R is preferably methyl and Q and R ¹ are as previously defined, followed by quaternization to provide the final softener active ingredient. It is manufactured by forming.

Examples of preferred amines used in forming the DEQA fabric softening active of the present invention include, but are not limited to, materials having the formula:

[0113]

Embedded image The counter ion, X ^(-) above, is any anion compatible with the softener, preferably a strong acid anion, such as chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, nitrate, and the like. , More preferably chloride or methyl sulfate. The anion can also have twice the 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 R ¹ units in the present invention. The quaternary ammonium compounds suitable for use in the compositions of the present invention are exemplified below, but not limited thereto. The term "tallowyl" used below indicates that the R ¹ units are derived from a tallow triglyceride source and are a mixture of fatty acyl units. Similarly, the term canolyl means a mixture of fatty acyl units derived from canola oil.

TABLE II Fabric Softener Active Ingredients N, N-Di (tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride, N, N-Di (canolyl-oxy-ethyl) -N, N-dimethyl Ammonium chloride, N, N-di (tallowyl-oxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride, N, N-di (canolyl-oxy-ethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride, N, N-di (2-tallowyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride, N, N-di (2-canolyloxy- 2-oxo-ethyl) -N, N-dimethylammonium chloride, N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N-
Dimethylammonium chloride, N, N-di (2-canolyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride, N- (2-tallowyloxy-2-ethyl) -N- (2- Taroyloxy-2
-Oxo-ethyl) -N, N-dimethylammonium chloride; N- (2-canolyloxy-2-ethyl) -N- (2-canolyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride, N, N, N-tricanolyl-oxy-ethyl) -N-methylammonium chloride, N- (2-tallowyloxy) -2-oxoethyl) -N- (tallowyl) -N
, N-dimethylammonium chloride, N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-
Dimethylammonium chloride, 1,2-ditallowyloxy-3-N, N, N-trimethylammoniopropane chloride, and 1,2-dicanolyloxy-3-N, N, N-trimethylammoniopropane chloride And mixtures of the above active ingredients. Other examples of quaternary ammonium softening compounds are methyl bis (tallowamidoethyl) (2-hydroxyethyl) ammonium methyl sulphate and methylbis (hydrogenated tallowamidoethyl) (2-hydroxyethyl) Ammonium methyl sulphate, these materials are from Vaitco Chemical Company
Commercially available under the trade names risoft 222 and Varisoft 110.

N, N-di (tallowoil-oxy-ethyl) -N, N-dimethylammonium chloride in which 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:
Preferably, I is in the range of 5-100, but less than 25 or greater than 25.
A distinction is made between two compounds having V.

In fact, the following equation

Embedded image For compounds derived from tallow fatty acids having an iodine value of 5 to 25, preferably 15 to 20, the weight ratio of cis / trans isomers is greater than about 30/70, preferably about 50/50. It has been found that above this, more preferably above about 70/30, results in optimal concentration. 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 the term `` cocoyl, palmyl, lauryl, '' in which `` tallowyl '' and `` canolyl '' in the above examples correspond to the triglyceride source from which the fatty acyl units are derived. Oleyl, ricinoleyl, stearyl, palmityl "derived from fatty acyl groups. 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 are identified by the term “methyl” in the examples of Table II above in the units “ethyl, ethoxy, propyl, propoxy”. , Isopropyl, butyl, isobutyl and t-butyl.

The counter ion X in the example of Table II is bromide, methyl sulfate, formate,
Sulfate, nitrate, and mixtures thereof can be replaced 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.

With respect to the ester fabric softeners described above, the pH of the composition is an important parameter of the invention.
Meter. Indeed, the pH is the pH of the quaternary ammonium or amine precursor compound.
Affects qualitative, especially under long-term storage conditions. The pH specified here should be diluted
Measured at 20 ° C. on the uncomposed composition. These compositions have a pH of less than about 6.0.
Can also function, but to obtain optimal hydrolytic stability of these compositions,
The undiluted pH, measured below, is preferably from about 2.0 to about 5,
Preferably it should be in the range of 2.5 to 4.5, preferably about 2.5 to about 3.5.
No. The pH of these compositions should be adjusted by adding Bronsted acid
Can be. Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially low molecular weight (C₁~ C ₅ ) Carboxylic acids, and alkylsulfonic acids. Suitable inorganic acids include
HCl, H₂SO₄, HNO₃And H₃PO₄Is mentioned. Suitable organic acids
Include formic acid, acetic acid, citric acid, methyl sulfonic acid and ethyl sulfone
You. Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic, and
It is benzoic acid.

As used herein, reference to a diester includes monoesters commonly present in the manufacture. For softening under laundry conditions with no carryover / low detergent, the percentage of monoester should be as low as possible, preferably no more than about 2.5%. 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 about 13: 1 to about 8: 1. Under conditions of high detergent carryover, the di / monoester ratio is preferably about 11: 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) - where suitable for use, yet other quaternary ammonium fabric softening compound, two or more long chain acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group or said, A cationic nitrogen-containing salt having one group and one arylalkyl group,
(I) an acyclic quaternary ammonium salt having the 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 dialkyl dimethyl ammonium salts that can be used in the present invention include di (hydrogenated tallow) dimethyl ammonium chloride (trade name Adog), all commercially available from Witco Chemical Company.
en 442), ditallow dimethyl ammonium chloride (trade name Adogen 470, Praepage
n 3445), distearyl dimethyl ammonium chloride (trade name: Arosurf TA-100)
Is mentioned. Dibehenyl dimethyl ammonium chloride is available from Witco Chemical Cor
It is sold under the trade name Kemamine Q-2802C by Humko Chemical Division of poration. Dimethyl stearyl benzyl ammonium chloride is available from Witco Chemical C
Sold by Varisoft SDC by ompany and Ammonyx 490 by Onyx Chemical Company.

B) -Amine Fabric Softening Active Compound Suitable amine fabric softening compounds, which may be in amine or cationic form, for use herein 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.
oline S Product name commercial stearic hydroxyethyl imidazoline, N, N "- ditallow alkoyl diethylenetriamine, in the structure of 1-tallow amido ethyl-2-tallow imidazoline (above, ^{R 1} is aliphatic _C 15 _{-C 17} A hydrocarbon group, and R ⁸ is a divalent ethylene group).

Certain components (i) can be first dispersed in a Bronsted acid dispersing aid having a pKa value of about 4 or less, except that the pH of the final composition is about 6 or less.
Certain preferred dispersing aids are hydrochloric, phosphoric, or methyl sulfonic acids. Both N, N "-ditallowalcoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are the reaction products of tallow fatty acids and diethylenetriamine, and the cationic fabric softener methyl-1-tallowamide Ethyl-2-tallow imidazolinium methyl sulfate precursor (
`` Cationic Surface Active Agents as Fabric Softners '', RR Egan, Journal
of the American Oil Chemicals' Society, January 1978, pp. 118-121). N, N "-Ditallowalcoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline are available as test chemicals from Witco Chemical Company. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl Sulfate is commercially available from Witco Chemical Company under the trade name Varisoft 475.

(Ii) Softener having the 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,
R ² is an ethylene group, G is an NH group, R ⁵ is a methyl group, and A ⁻ is a chloride anion.

(Iii) softener having the formula:

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

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

[0135]

Embedded image Wherein R ¹ is derived from oleic acid.

Other fabric softeners useful herein are described in Toan Trinh, Errol H. Wahl, Donald M.
U.S. Pat. No. 4,661,264 to Swartley and Ronald L. Hemingway.
No. 69, issued April 28, 1987, U.S. Pat. No. 4,439,335, Burns, issued Mar. 27, 1984, and U.S. Pat. No. 3,861,87.
No. 0, Edwards and Diehl, 4,308,151, Cambre,
No. 3,886,075, Bernardino, No. 4,233,164,
Davis, 4,401,578, Verbruggen, 3,974,076, Wiersema and Rieke, 4,237,016, Rudkin, Clin.
Published European Patent Application No. 47 by T. Young and Yamamura et al.
No. 2,178, which is incorporated herein by reference in its entirety.

Of course, the term “softening active” also encompasses mixed softening actives.

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 clear fabric softening compositions. When used, the solvent system which facilitates the formulation is preferably 4% of the composition.
0% by weight, preferably about 10 to about 35% by weight, more preferably about 12 to about 2%.
5% by weight, more preferably about 14% to about 20% by weight. Solvents that facilitate formulation are selected to minimize the effect 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 but has a pronounced odor. Certain butyl alcohols also have an odor, but transparency / stability can be effectively obtained, especially when used as part of a solvent system to facilitate formulation and to minimize their odor. The alcohol is also selected for optimal low temperature stability, ie, the alcohol is a liquid having a reasonably low viscosity up to low temperatures of about 40 ° F. (about 4.4 ° C.), and is translucent, preferably Can form a composition that is transparent and can be recovered after storage at low temperatures, up to about 20 ° F. (about −6.7 ° C.).

The suitability of all major solvents for the formulation of the liquid, concentrated, preferably transparent, fabric softener composition of the invention with the required stability is surprisingly 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 softening vesicles when the composition diluted to the concentration used for rinsing is observed by cryo-electron microscopy. These diluted compositions appear to have a dispersion of the 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 provide surprisingly good fabric softening properties when compared to similar compositions made in the conventional manner using the same fabric softener active ingredient.

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 the addition of 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 aids to achieve higher concentrations and / or to meet higher stability standards depending on other ingredients. . These thickening aids (which may typically be viscosity improvers) are required to ensure stability under extreme conditions when using particular softener active ingredient amounts, Or it may be preferred. Surfactant concentrating 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 include a single long chain alkyl cationic surfactant and / or a reactant used to form the active softener raw material (I), for example, the biodegradable fabric softener active ingredient previously described. Fatty acids can be added as part of or as a separate component. The total amount of dispersing aid includes all that may be present as part of component (I).

Acts like a surfactant concentration aid, including water-soluble and ionizable salts;
Alternatively, an inorganic viscosity / dispersibility modifier capable of increasing its effect can also be incorporated into the composition of the present invention, if desired. 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 also act as scavengers and can form ion pairs in the rinse water and on the fabric with anionic surfactants carried over from the main wash liquor, improving softening performance. These substances can stabilize the viscosity over a wide temperature range, especially at low temperatures, as compared to inorganic electrolytes. Specific examples of alkylene polyammonium salts include l-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 agents 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, and propyl gallate, commercially available from ducts, Inc. under the trade names Tenox PG and Tenox S-1, Eastman Ch.
A mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, commercially available from Emical Products, Inc. under the trade name Tenox-6, Sustane BHT from UOP Process Division
Butylated hydroxytoluene commercially available under the trade name Eastman Chemical Pro
Eastman, a tertiary butyl hydroquinone commercially available as Tenox TBHQ from ducts, Inc.
Chemical Products, commercial natural tocopherols as Tenox GT-1 / GT-2 from Inc., and Eastman Chemical Products, commercially available butylated hydroxy anisole as BHA from Inc., long chain esters of gallic acid (C ₈ ~C ₂₂₎ For example, dodecyl gallate, Irganox (trade name) 1010, Irganox (trade name) 1035, Irganox (trade name) B 1171, Irganox (trade name) 1425, Irganox (trade name) 3114, Irganox (trade name)
Trade name) 3125, and mixtures thereof, preferably Irganox (trade name) 3125, Ir
ganox (trade name) 1425, Irganox (trade name) 3114, and a mixture thereof, 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.

[0152]

[Table 1] Examples of reducing agents include sodium borohydride, hypophosphorous acid, Irgafos® 168, and mixtures thereof.

(E)-Soil Release Agent Preferably, a soil release agent is used in the fabric softening composition 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. Patent No. 3,893,929, Basadur, promulgated July 8, 1975, U.S. Patent 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.

In addition, 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. 4,787,969, 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.

[0157] 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.

(F) -Fungicides Examples of fungicides optionally used in the compositions of the present invention include glutaraldehyde,
Formaldehyde, from Inolex Chemicals of Philadelphia, PA
2-Bromo-2-nitropropane-1,3-sold under the trade name Bronopol
Diols, and about 1 to about 1,000 ppm by weight of the drug, 5-chloro-2-methyl-4-isothiazolin-3-one and 2- diol, sold under the trade name Kathon by the Rohm and Haas Company A mixture of methyl-4-isothiazolin-3-one is mentioned.

(G) -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, 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 often involve auxiliary materials, such as fixatives, spreaders, stabilizers and solvents. These auxiliary ingredients also fall under the meaning of "perfume" as used herein. Typically, a fragrance is a complex mixture of multiple organic compounds.

The range of natural raw materials extends not only to readily volatilizable substances, but also to moderately volatile and slightly volatile components, and the range of synthetics, as apparent from the list below,
Represented by virtually all types of aromatic substances. Natural substances, such as tree moss anhydride, basil oil, citrus oil (eg, bergamot oil, poncan oil, etc.), mastic anhydride, myrtle oil, palmarosa oil, patchouli oil, petitgren oil Paraguay, mugwort oil, alcohol such as farnesol Geraniol, linalool, nerol, phenylethyl alcohol, rosinol, cinnamon alcohol, aldehydes such as citral, Helional (trade name), alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial (trade name) (p-tert.
Butyl-alpha-methyldihydrocinnamaldehyde), methylnonylacetaldehyde, ketones such as allylionone, alpha-ionone, beta-ionone, isoraldein (isomethyl-alpha-ionone), methylionone, esters such as allyl phenoxyacetate, benzyl salicylate, propionic acid Cinnamyl, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethylbenzylcarbyl acetate, dimethylbenzylcarbylbutyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyldihydrojasmonate, styralyl acetate, acetic acid Lactones such as betiberyl, etc., for example gamma-undecalactone, various components often used in perfumes, for example, mask ketone, indole, p- Mentan-8-thiol-3-one, and methyl eugenol. Similarly, any of the customary fragrant acetals or ketals known in the art can be added to the compositions of the present invention as an optional ingredient in the conventionally formulated perfume (c). Such conventional aromatic acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as substances comprising the benzaldehyde-based acetal or ketal, phenylethyl moieties, or more recently developed. Special products such as "Oxo-
U.S. Pat. No. 5,084,440 entitled "Acetals and Ketals of Tetralin and Oxo-Indane", issued on Jan. 28, 1992, Givaudan Cor.
There are substances listed in Assigned to, p. Of course, the perfume composition for the fabric protection composition of the present invention can also include other recent synthetic specialty products. These materials include alkyl-substituted oxo-tetralin and oxo-indane enols as described in U.S. Pat. No. 5,332,725 to Givaudan, Jul. 26, 1994. Ethers, or Schiff bases as described in US Pat. No. 5,264,615, assigned to Givaudan, December 9, 1991.

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

The perfume 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.

(H) -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 types of cellulases, and preferably have an optimal pH of 5-9.5. U.S. Pat. No. 4,435,307 describes:
Disclosed are suitable fungal cellulases obtained from cellulase 212 producing fungi belonging to the genus Humicola insolens or Humicola strain DSM 1800 or Aeromonas, and cellulases extracted from the hepatopancreas of the marine mollusc, Dolabella Auricula Solander. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2.
, 247, 832. CAREZYME (brand name) and CELL
UZYME (brand name) (Novo) is particularly useful. Other suitable cellulases are described in WO 91/17243, WO 96/34092 and WO 96/3 to Novo.
It is also described in the specification of 4945 and EP-A-0,739,982. Typical amounts actually used in current commercial formulations are up to 5 mg, more typically 0.01 mg to 3 mg, of active enzyme per gram of detergent composition by weight.
That is, the composition is typically present in an amount of 0.001 to 5% by weight, preferably 0.01 to 5% by weight.
1% by weight of a commercial enzyme preparation. In the special case where the activity of the enzyme preparation can be defined in other ways, for example as in cellulase, the corresponding activity unit is preferred (for example,
CEVU or cellulase equivalent viscosity unit). For example, the compositions of the present invention can include the cellulase enzyme in an amount equivalent to an activity of 0.5 to 1000 CEVU / gram composition. Cellulase enzyme preparations used for formulating the compositions of the present invention have an activity of 1,000 to 10,000 CEVU / gram in liquid form and about 1,000 CEV in solid form.
VU / gram.

Other Optional Components The present invention relates to other optional components commonly used in textile treatment compositions, such as brighteners, colorants, preservatives, surfactants, shrinkage inhibitors. Fabric crisping agents, dyeing agents, disinfectants, fungicides, antioxidants such as butylated hydroxytoluene, corrosion inhibitors, defoamers, and the like.

The present invention relates to International Patent No. WO 96/02625, WO 96/2171.
4, and other compatible components, including those disclosed in WO 96/21715, and the pending application PCT / US97 / 016.
There is a dispersible polyolefin described in Japanese Patent No. 44, such as Velustrol (trade name). The present invention can also include an optional chelating agent.

An advantage obtained by using the present invention is that the composition comprising the polyamino-functional polymer is stabilized by CGI. Thus, one aspect of the present invention provides a method for stabilizing a composition comprising an amino-functional polymer using a crystal growth inhibitor.

As a result, the compositions of the present invention protect fabrics more effectively as compared to compositions without such stabilizing means. Thus, in another aspect of the present invention, there is provided a method of protecting a colored fabric, comprising the step of contacting the fabric with the composition of the present invention.

The protection of the color can be assessed visually or by measuring the so-called Delta E value.

When using visual evaluation, a skilled grader will visually compare fabrics treated and untreated with the compositions of the present invention according to established panel score units (PSU). Positive PSU values indicate excellent performance (PSU scale: 0 = no difference, 1 = likely, 2 = have difference, 3 = have significant difference, 4 = have significant difference) .

Another method of evaluating the color protection properties for fabrics is the measurement of the so-called Delta E value. Delta E is specified, for example, in ASTM D2244. Delta E is the color difference calculated as specified in ASTM D2244, ie, CIE 1976 CIELAB Competitive Color Space, Hunter Competitive Color Space, Friele-Mac Adam-Chic
Two spirits defined by tristimulus values or by chromaticity coordinates and nominal reflectance, calculated using a specific set of color difference equations defined in the kering color space or any equivalent color space The magnitude and direction of the difference between physical color stimuli.

Uses The compositions of the present invention can be used in all stages of household treatment, ie, as pretreatment compositions, as cleaning additives, as compositions for use in the rinsing cycle of a wash cycle, or in a dry state. Suitable for application to machine sheets. Of course, for the purposes of the present invention, a composition of the present invention wherein the fabric is treated with the pre-treatment composition of the present invention and then suitable for use in a rinsing cycle and / or suitable for use as a dry sheet It can also be used multiple times, such as by treating with an object. The composition of the invention may be sprayed, suitable for ironing or applied to the surface of a tumble dryer.
It may be in the form of a foamed material or an aerosol.

The invention is illustrated by the following non-limiting examples, in which all percentages are given by weight of active ingredient, 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 Fatty acid: Tallow fatty acid IV = 18 Electrolyte: Calcium chloride DTDMAMS: Ditallow dimethyl ammonium methyl sulfate SDASA: Stearyl dimethylamine in a 1: 2 ratio: Triple press stearic acid Glycosperse S-20: Monostearic acid Polyethoxylated sorbitan, commercially available from Lonza Clays: Calcium Bentonite Clay, Bentonite L, Southern Clay Produc
TAE25: Tallow alcohol, ethoxylated with 25 moles of ethylene oxide per mole of alcohol PEG: polyethylene glycol 4000 PEI 1800 E1: ethoxylated polyethyleneimine (molecular weight 1800, 50% active) synthesized in Synthesis Example 1 PEI 1800 E3: ethoxyl PEI 1800 E7 AO: Amine oxide of ethoxylated polyethyleneimine (molecular weight 1)
PEI 1200 E1: Ethoxylated polyethyleneimine (molecular weight 1200, 50% in water)
Activity) synthesized in Synthesis Example 5 PEI 1200 E2: ethoxylated polyethyleneimine (molecular weight 1200, 50% in water
Activity) synthesized in Synthesis Example 5 PEI 1200 E4: ethoxylated polyethyleneimine (molecular weight 1200, 50% in water
Activity) Synthesized in Synthesis Example 5 PEI 1200 E7: Ethoxylated polyethyleneimine (molecular weight 1200, 50% in water
Activity) Synthesized in Synthesis Example 5 PEI 1200 E7 AO: Amine oxide of ethoxylated polyethyleneimine (molecular weight 1)
Dye fixative 1: Cationic dye fixative (50% active), Tinofix from Ciba-Geigy
Dye fixative 2: marketed under the trade name Eco Dye fixative 2: emulsified cationic dye fixative (30% active), marketed under the trade name Rewin SRF-O from CHT-Beitlich NH4Cl: ammonium chloride LAS: sodium linear C ₁₂ alkyl benzene sulfonate TAS : Sodium tallow alcohol sulfate C25AS: sodium C ₁₂ -C ₁₅ linear alkyl sulfate CxyEzS: sodium C _1x -C _1y branched alkyl sulfate, condensed with z mole of ethylene oxide C45E7: mainly linear primary alcohol of C _14-15 , average 7 moles of ethylene oxide condensed _{C25E3: C 12-15} branched primary alcohol, average of 3 moles of ethylene oxide and condensation cationic _ester: mixture of C 12 _{/ C 14} choline ester soap: tallow and coconut oil 80/20 from the mixture, sodium linear alkyl carboxylate _{TFAA: C} 16 ~C ₁₈ alkyl N- methyl glucamide _{TPKFA: C 12 ~C 14 topped whole} cut fatty acids Zeolite A: formula _Na 12 _(AlO 2 _SiO 2) ₁₂ . 27H ₂ O hydrated sodium aluminosilicate, primary particle size 0.1 to 10 μm Citric acid: anhydrous citric acid carbonate: anhydrous sodium carbonate, particle size 200 μm to 900 μm Silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O, 2.0 ratio) Sulfate: anhydrous sodium sulfate citrate: trisodium citrate dihydrate, activity 86.4%, particle size distribution 42
5 μm to 850 μm MA / AA: maleic acid / acrylic acid 1: 4 copolymer, average molecular weight about 70,0
00 CMC: Sodium carboxymethylcellulose Savinase: Proteolytic enzyme, activity 4 KNPU / g Carezyme :: Cellulolytic enzyme, activity 1000 CEVU / g Termamyl: Starch degrading enzyme, activity 60 KNU / g Lipolase: Lipolytic enzyme, activity 100 kLU / g All sold by NOVO Industries A / S with the above activity unless otherwise indicated. PB4: Sodium perborate tetrahydrate, nominal formula NaBO ₂ . 3H ₂ O. H ₂ O ₂ PB1: Anhydrous sodium perborate bleach, nominal NaBO ₂ . H ₂ O ₂ TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta (methylene phosphonate), Monsanto
Light activated bleach: sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer Brightener: disodium 4,4'-bis (4-anilino-6-morpholino-
1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate Silicone antifoaming agent: polydimethylsiloxane foam regulator containing siloxane-oxyalkylene copolymer as dispersant, foam regulation Ratio of the dispersant to the dispersant 10: 1 to 1
100: 1 HEDP: 1,1-hydroxyethanediphosphonic acid PBT: 2-phosphonobutane-1,2,4-tricarboxylic acid polycarboxylic: a polycarboxyl compound commercially available under the trade name Sokalan CP 10 from BASF Glycolic: glycol Acid Synthesis Example 1-Preparation of PEI 1800E ₁ A) -Ethoxylation is equipped for temperature measurement and control, pressure measurement, vacuum and inert gas scavenging, sampling, and introduction of ethylene oxide as liquid. In a stirred 2 gallon 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) (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 functionality) is added to the autoclave. The autoclave is then sealed and purged of air (applying a vacuum of -28 "Hg, followed by pressurizing to 250 psia with nitrogen, 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.

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 (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, for example 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.

Synthesis Example 2 Poly (ethylene imine), molecular weight 1800, ethoxylation degree 7 (224 g, 0.637 mol nitrogen) were placed in a 500 ml Erlenmeyer flask equipped with a 4.7% quaternized magnetic stirring bar of PEI 1800E7. , Prepared as in Synthesis Example 1) and acetonitrile (Baker, 150 g, 3.65 mol). To the rapidly stirring solution was added dimethyl sulfate (Aldrich, 3.8 g, 0.030 g).
Mol) in one portion, stopper and stir at room temperature overnight. The acetonitrile is evaporated on a rotary evaporator at about 60 ° C. followed by a Kugelrohr apparatus (Aldrich) at about 80 ° C. to give about 220 g of the desired product as a dark brown viscous liquid. ¹³ C-NMR (D ₂ O
) The spectrum shows that there is no peak at about 58 ppm corresponding to dimethyl sulfate. ^{The 1} H-NMR (D ₂ O) spectrum shows that the peak at 2.5 ppm (methylene added to non-quaternized nitrogen) is about 3.0 ppm.
Is partially migrated.

Synthesis Example 3-4.7% quaternized PEI 1800E7 oxidized in a 500 ml Erlenmeyer flask equipped with a magnetic stir bar and ethoxylated seven times and quaternized with dimethyl sulfate about 4.7%. Poly (ethylene imine), molecular weight 1800,
(121.7 g, about 0.32 mol of oxidizable nitrogen, prepared in Synthesis Example 2), hydrogen peroxide (Aldrich, 40 g of a 50% by weight aqueous solution, 0.588 mol), and water (109
. 4 g) is added. The flask is stoppered and after the first exotherm the solution is stirred at room temperature overnight. _{^{1 H-NMR (D 2 O}} ) spectrum shows that the methylene peak at 2.5 to 3.0 ppm is completely migrated to approximately 3.5 ppm. About 5 g of 0.5% Pd on alumina pellets is added to this solution, and the solution is left at room temperature for 3 days. The peroxide indicator paper indicates that no peroxide remains in the system. Store this material as a 46.5% aqueous solution.

Synthesis Example 4 Formation of Amine Oxide of PEI 1800E _{7 In} a 500 ml Erlenmeyer flask equipped with a magnetic stirring bar, polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI) was prepared.
1800, E ₇ ) (209 g, 0.595 mol nitrogen, prepared in Synthesis Example 1) and hydrogen peroxide (120 g of a 30% by weight aqueous solution, 1.06 mol). The flask is stoppered and after the first exotherm the solution is stirred at room temperature overnight. A ¹ H-NMR (D ₂ O) spectrum obtained on a sample of the reaction mixture indicates complete conversion. The resonance, thought to be due to the methylene protons adjacent to the nitric oxide, was about 2.5
It has shifted from its original position in ppm to about 3.5 ppm. About 5 g of 0.5% Pd on alumina pellets is added to the reaction solution, and the solution is left at room temperature for 3 days. This solution is tested on indicator paper and found to be negative for peroxide. This material is suitable for storage as a 51.1% active aqueous solution.

Synthesis Example 5-Preparation of PEI 1200E ₁ A) -Ethoxylation is equipped for temperature measurement and control, pressure measurement, vacuum and inert gas scavenging, sampling, and introduction of ethylene oxide as liquid. 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 parts 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, followed by pressurizing to 250 psia with nitrogen, and then evacuating to atmospheric pressure).
Heat to 0 ° C. After about one 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 ethylene oxide flow rate. The ethylene oxide pump is stopped and cooled to limit the 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 container 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, the autoclave was cooled 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 was removed and the autoclave was cooled to 105 ° C. while 250 psi of nitrogen was 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 1200E3, 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.

The corresponding amine oxide of the ethoxylated PEI described above can also be prepared according to Synthesis Example 4.

Synthesis Example 6 Poly (ethylene imine), molecular weight 1200, ethoxylation degree 7 (248.4 g, 0.707) were placed in a 500 ml Erlenmeyer flask equipped with a 9.7% quaternized magnetic stirring bar of PEI 1200E7. Molar nitrogen, Synthesis Example 5
) And acetonitrile (Baker, 200 ml). To the rapidly stirring solution, add dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) in one portion, stopper and stir at room temperature overnight. Acetonitrile in a rotary evaporator at about 60 ° C
Followed by evaporation in a Kugelrohr apparatus (Aldrich) at about 80 ° C. to give about 2% of the desired product.
20 g are obtained as a dark brown viscous liquid. ^{The 13} C-NMR (D ₂ O) spectrum shows that there is no peak at about 58 ppm corresponding to dimethyl sulfate. ^{The 1} H-NMR (D ₂ O) spectrum has a peak at 2.5 ppm (the fourth peak).
(Methylene added to ungraded nitrogen) is partially migrated to about 3.0 ppm.

Synthesis Example 7-9.5% Quaternized PEI 1200E7 4.7% Oxidation A 500 % Erlenmeyer flask equipped with a magnetic stir bar was ethoxylated seven times, and about 9.5% with dimethyl sulfate. Quaternized poly (ethylene imine), molecular weight 1200,
(144 g, about 0.37 mol of oxidizable nitrogen, prepared in Example 6), hydrogen peroxide (Aldr
ich, 35.4 g of a 50% by weight aqueous solution, 0.52 mol) and water (100 g). The flask is stoppered and after the first exotherm the solution is stirred at room temperature overnight. ¹ H-
NMR _(D 2 O) spectrum shows that the methylene peak at 2.5 to 3.0 ppm is completely migrated to approximately 3.5 ppm. This solution contains just enough sodium bisulfite at 40% to reduce residual peroxide levels to 1-5 ppm.
Add as an aqueous solution. The resulting sodium sulphate separates the aqueous phase, containing salts but little or no organic matter. The aqueous salt phase is removed and the desired oxidized polyethyleneimine derivative is removed and stored as a 52% aqueous solution.

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

[0200]

[Table 2]

[Table 3]

[Table 4] Example 2 The following composition for use as a sheet to be added to a dryer is in accordance with the invention.

[0201]

[Table 5] Example 3

[Table 6] Example 4 The following liquid detergent composition according to the present invention was prepared.

[0202]

[Table 7]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), BR, CA, CN, CZ, JP, MX, NO, US (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Christian, Arthur, Jack, Ka Miel, Toen Ohio, U.S.A., West, Chester, Loop, Farm, Drive, 8485 (72) Inventor Rafael, Angeline, Alphonse, Surmans Bé-3210, Belgium Over click, Colt Likes Trad, 34 F-term (Reference) 4H003 AB03 AB19 AB31 AC13 AE05 AE06 BA12 DA01 EA02 EA21 EA27 EB04 EB08 EB24 EB38 EC01 EC02 ED02 ED28 FA22 FA28 4L033 AB04 AC02 BA17 BA37 BA87 CA57

Claims (15)

[Claims] 1. A fabric protection composition comprising a polyamine-functional polymer and a crystal growth inhibitor, wherein the crystal growth inhibitor is selected from carboxylic acids, organic diphosphonic acids, and mixtures thereof. Wherein the crystal growth inhibitor is present in an amount less than 1% by weight of the composition. 2. The polymer comprises a polyamine skeleton corresponding to the following formula:Formula V of polyamine_{(N + 1)}W_mY_nHaving Z or corresponding to the following formula:
Comprising a lamine skeleton,Formula V of polyamine_{(Nk + 1)}W_mY_nY '_kWherein k is n or less and the polyamine skeleton is greater than 200 daltons.
I) the V unit is a terminal unit having the following formula:ii) The W unit is a skeletal unit having the following formula:iii) the Y unit is a branch unit having the following formula:iv) the Y 'unit is a branch point for a skeleton or branched ring having the formula:v) The Z unit is a terminal unit having the following formula: The backbone R unit is C₂~ C₁₂Alkylene, C₄~ C₁₂Alkenylene, C ₃ ~ C₁₂Hydroxyalkylene, C₄~ C₁₂Dihydroxy-alkylene, C ₈ ~ C₁₂Dialkylarylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵ (OR¹)_x-,-(CH₂CH (OR²) -CH₂O)_z− (R¹O)_yR¹ (OCH₂CH (OR²) CH₂)_w-, -C (O) (R⁴)_rC (O)-,-
CH₂CH (OR²) CH₂Selected from the group consisting of-and mixtures thereof.
R¹Is C₂~ C₆Selected from the group consisting of alkylenes and mixtures thereof
R²Is hydrogen,-(R¹O)_xB, and mixtures thereof.
R⁴Is C₁~ C₁₂Alkylene, C₄~ C₁₂Alkenylene, C₈~ C_{1 2} Arylalkylene, C₆~ C₁₀From arylenes and their mixtures
R is selected from the group⁵Is C₁~ C₁₂Alkylene, C₃~ C₁₂Hydroxyalkylene, C ₄ ~ C₁₂Dihydroxy-alkylene, C₈~ C₁₂Dialkylarylene,-
C (O)-, -C (O) NHR⁶NHC (O)-, -R¹(OR¹)-, -C (
O) (R⁴)_rC (O)-, -CH₂CH (OH) CH₂-, -CH₂CH (O
H) CH₂O (R¹O)_yR¹OCH₂CH (OH) CH₂− And their
R is selected from the group consisting of mixtures⁶Is C₂~ C₁₂Alkylene or C₆~ C₁₂Group consisting of arylenes
R ′ units are hydrogen, C₁~ C₂₂Alkyl, C₃~ C₂₂Alkenyl, C₇~
C₂₂Arylalkyl, C₂~ C₂₂Hydroxyalkyl,-(CH₂)_pC
O₂M, (CH₂)_qSO₃M, -CH (CH₂CO₂M) -CO₂M,-(C
H₂)_pPO₃M,-(R¹O)_xB, -C (O) R³, And their mixtures
B is hydrogen, C₁~ C₆Alkyl,-(CH₂)_qSO₃M,-(CH₂)_p -CO₂M,-(CH₂)_q(CHSO₃M) CH₂SO₃M,-(CH₂)_q − (CHSO₂M) CH₂SO₃M,-(CH₂)_pPO₃M, -PO₃M, you
And a mixture thereof.³Is C₁~ C₁₈Alkyl, C₇~ C₁₂Arylalkyl, C₇~ C ₁₂ Alkyl-substituted aryl, C₆~ C₁₂Aryl and their mixtures
M is hydrogen or a water-soluble cation sufficient to satisfy the charge balance.
X is a water-soluble anion; m has a value of 2 to 700; n has a value of 0 to 350; p has a value of 1 to 6; R has a value of 0 or 1; w has a value of 0 or 1; x has a value of 1 to 100; y has a value of 0 to 100; The composition according to claim 1, wherein z has a value of 0 or 1. 3. The amino-functional polymer of claim 1, wherein the R ′ units are hydrogen, C ₃ -C ₂₂ hydroxyalkyl,
_Benzyl, C 1 _{-C 22 ^{alkyl, - (R 1 O) x}} B, -C (O) R 3, - (C
^{_{H 2) p CO 2 - M}} +, (CH 2) q SO 3 - M +, -CH (CH 2 CO 2 M)
-CO ₂ M, and is one selected from the group consisting of a mixture thereof, preferably R 'units, _hydrogen, C 1 _{-C 22 ^{alkyl, - (R 1 O) x}} B, -
C (O) R ^3, and is one selected from the group consisting of mixtures thereof, more preferably R 'units - a (R 1 ^O) x _B, A composition according to claim 2. 4. The composition according to claim 2, wherein x has a value of 1-20, preferably 1-10. 5. The method according to claim 1, wherein said polymer is active up to 90% by weight of the composition, preferably 0.01 to 50%, more preferably 0.1 to 20%, most preferably 0.5 to 15%. A composition according to any one of claims 1 to 4, wherein the composition is present in an amount of 6. The method according to claim 1, wherein the crystal growth inhibitor is selected from a carboxyl compound, an organic monophosphonic acid, an organic diphosphonic acid, and a mixture thereof, and is preferably an organic diphosphonic acid. A composition according to claim 1. 7. The composition according to claim 6, wherein said organic monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid. 8. The composition of claim 6, wherein said organic diphosphonic acid compound is hydroxy-ethane 1,1 diphosphonic acid. 9. The composition of claim 1, wherein the crystal growth inhibitor is present in an amount of 0.005 to 0.50% by weight of the composition, preferably in an amount of 0.1 to 0.2% by weight. A composition according to any one of the preceding claims. 10. The composition according to claim 1, wherein the composition further comprises a fabric softener. 11. The softening agent is a cationic fabric softening agent, preferably represented by the following formula: 11. The composition according to claim 10, wherein the composition is selected from those represented by the following formula. Embedded image [Wherein Q is a carbonyl unit having the following formula: 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 Linear or branched C ₁₁ -C ₂₂ alkyl, 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 hydroxyalkyl X is an anion compatible with the fabric softener, the index m is 1-4, preferably 2, and the index n is 1-4, preferably 2. ] 12. The composition according to claim 1, wherein the composition further comprises a dye fixing agent. 13. The composition according to claim 1, wherein the composition is in a liquid form. 14. Use of a crystal growth inhibitor for stabilizing a composition comprising an amino-functional polymer. 15. A method for protecting a colored fabric, comprising contacting the fabric with the composition according to any one of claims 1 to 13.