JP2002521583A - Fabric protection composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to nitrogen-containing compounds selected from polyamino-functional polymers, dye fixatives, and mixtures thereof, and water-soluble cationic surfactants, polyoxyalkylene alkylamine surfactants, and mixtures thereof. For compositions comprising the selected dregs inhibitor, the composition inhibits or reduces formation of dregs on the fabric and / or washing machine parts as compared to compositions without the dregs inhibitor. Block.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a fabric protection composition, and more particularly to a fabric treated with the composition that forms little or no scum on the fabric and / or parts of the washing machine. And a method for protecting the color of the composition.

[0002] background colored fabric of the invention, for example clothing, bedding, household fabrics, for example, table linens, the appearance is an important area for the consumer. Indeed, the typical use of the fabric by consumers, such as the wearing, washing, rinsing and / or tumble drying of the fabric, results in a poor appearance of the fabric, which is at least partially due to color fidelity and 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] Dye fixing components such as those described in EP 462806 are suitable components for this purpose. In fact, these components protect the color of the fabric by enhancing the binding of loosely held dyes to the fabric.

In addition, a new class of materials can be used, namely amino-functional polymers. In fact, these materials have recently been increasingly used in fabric treatments to protect the color of the fabric.

[0006] However, a problem encountered when treating with compositions comprising such dye fixatives and / or amino-functional polymers is that debris may form on the treated fabric and / or washing machine parts. Is to be formed.

[0007] Without theoretical support, such nitrogen-containing compounds, ie, amino-functional polymers and / or dye fixatives, and anionic substances, such as detergents, are carried over, especially over many washing cycles, from anions. It is believed that dregs are formed from the interaction with the ionic surfactant. This interaction results in an insoluble sticky precipitate on the fabric and / or washing machine parts.

[0008] As such, formulators of fabric protection compositions have addressed the dual problem of formulating compositions that do not impair the color of the treated fabric and that form little or no scum.

[0009] The applicant has now surprisingly found that a debris inhibitor selected from water-soluble cationic surfactants, polyoxyalkylene alkylamine surfactants, and mixtures thereof, may be substituted with amino-functional surfactants. It has been found that this problem is solved by adding it to a composition comprising a nitrogen-containing compound selected from polymers, dye fixatives, and mixtures thereof.

SUMMARY OF THE INVENTION [0010] The present invention comprises: i) a nitrogen-containing compound selected from a polyamino-functional polymer, a dye fixative, and mixtures thereof; and ii) a water-soluble cationic surfactant, a polyoxyalkylene alkyl. An amine surfactant, and a dross inhibitor selected from mixtures thereof, provided that the only nitrogen-containing compound is a polyamino-functional polymer, the polymer being present in an amount greater than 1% by weight. And a fabric protection composition. In another aspect of the present invention, a composition comprising a nitrogen-containing compound selected from a polyamino-functional polymer, a dye fixative, and mixtures thereof, wherein the composition comprises a surfactant and the fabric is contacted with the composition. Alternatively, a method for suppressing or preventing the formation of scum on a washing machine component is provided.

[0011] In accordance with one aspect of the Detailed Description of the Invention The present invention provides a fabric protection composition having a color protective properties with effective and durable.

One of the essential components of the present invention is a nitrogen-containing compound selected from amino-functional polymers, dye fixatives, and mixtures thereof.

Amino-functional polymers Amino-functional polymers effectively protect the color of the fabric.

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.
These polyamines comprise a skeleton that may be linear or cyclic. The polyamine backbone can also comprise more or less polyamine branches. Preferably, the polyamine backbone described herein will be described below with respect to units in which at least one, preferably each nitrogen, of the polyamine chain is substituted, quaternized, oxidized, or a combination thereof. Modified as described.

For the purposes of the present invention, the term “modified” relates to the chemical structure of a polyamine and refers to the 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.

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

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

Embedded image Having.

[0017] The above skeleton may (optionally, but preferably) be treated with R "
Comprising primary, secondary and tertiary amine nitrogens connected by a "bond" unit.

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

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

[0020] 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 due to their position in the backbone. The R units associated with the nitrogens of the V, W and Y units and serving to connect the polyamine nitrogen are described below.

[0021] Thus, the final modified structure of the polyamines of the present invention, with respect to the linear amino-functional polymer of the general formula V _{(n + 1)} expressed in W _m Y _n Z, with respect to the cyclic amino-functional polymer, formula V _(n-k + ₁₎ can be represented by _{W m Y n Y 'k Z} . In the case of a polyamine comprising a ring, the Y 'unit of the formula | R |-[NR]-serves as a skeleton or branch point of a branched ring. For each Y 'unit, there is a Y unit having the formula |-[NR]-, which forms the point connecting the ring to the polymer backbone or branch. In the special case where the backbone is a complete ring, the polyamine backbone has the formula

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

In the case of acyclic polyamines, the ratio of the index n to the index m is related to the relative degree of branching.
The completely unbranched linear modified polyamines of the present invention have the formula VW _m Z, 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, a hydrogen atom will of course replace R '. 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, so that R 'cannot be a hydrogen atom.

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

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

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

[0034] 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 a hydrogen atom, C₁~ C₂₂Alkyl, C₃~ C₂₂Alkenyl, C ₇ ~ C₂₂Arylalkyl, C₂~ C₂₂Hydroxyalkyl,-(CH₂) _p CO₂M, (CH₂)_qSO₃M, -CH (CH₂CO₂M) CO₂M,-(
CH₂)_pPO₃M,-(R¹O)_mB, -C (O) R³, Preferably a hydrogen atom
, C₂~ C₂₂Hydroxyalkylene, benzyl, C₁~ C₂₂Alkylene,-
(R¹O)_mB, -C (O) R³,-(CH₂)_pCO₂M,-(CH₂)_qS
O₃M, -CH (CH₂CO₂M) CO₂M, more preferably C₁~ C₂₂Al
Kiren,-(R¹O)_xB, -C (O) R³,-(CH₂)_pCO₂M,-(C
H₂)_qSO₃M, -CH (CH₂CO₂M) CO₂M, most preferably C₁~
C₂₂Alkylene,-(R¹O)_xB and -C (O) R³Choose from the group consisting of
I do. If no modification or substitution is made on the nitrogen, the hydrogen atom represents R '
Remains as a part. The most preferred R 'units are (R¹O)_xB. V, W and
Is an R 'unit when the Z unit is oxidized, i.e., when the nitrogen is an N-oxide.
Does not contain a hydrogen atom. For example, a skeleton chain or a branched chain is a unit having the following structure:
Not included.

In addition, the V, W or Z units are oxidized, ie, the nitrogen is an N-oxide. OO O ↑ ↑ ↑ —N—R or H—N—R or —N−H ||| HHH 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 combination of the following are not present.

[0043]

Embedded image B is a hydrogen atom, C₁~ C₆Alkyl,-(CH₂)_qSO₃M,-(CH₂) _p -CO₂M,-(CH₂)_q(CHSO₃M) CH₂SO₃M,-(CH₂) _q − (CHSO₂M) CH₂SO₃M,-(CH₂)_pPO₃M, -PO₃M,
Preferably a hydrogen atom,-(CH₂)_qSO₃M,-(CH₂)_q(CHSO₃M
) CH₂SO₃M,-(CH₂)_q− (CHSO₂M) CH₂SO₃M, better
Preferably, a hydrogen atom or-(CH₂)_qSO₃M. M is the balun of charge
A sufficient amount of hydrogen atoms or water-soluble cations to fill the solution. For example, Nato
The lithium cation is-(CH₂)_pCO₂M, and-(CH₂)_qSO₃M etc.
So that-(CH₂)_pCO₂Na, and-(CH₂)_qS
O₃Form a Na portion. Two or more monovalent cations (sodium, potassium, etc.)
) Can be used to satisfy the required chemical charge balance. However,
To meet the charge requirements of the anionic groups, two or more anionic groups must be
Either balance the charges with divalent cations, or have at least two monovalent cations.
It will be important. For example,-(CH substituted with a sodium atom₂)_pPO₃M part
Is of the formula-(CH₂)_pPO₃Na₃Having. Divalent cations such as calcium
(Ca²⁺) Or magnesium (Mg²⁺) Is other suitable monovalent water-soluble cation
It can replace or be combined with ions. Preferred yang
The ions are sodium and potassium, with sodium being more preferred.

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

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

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

The most preferred amino-functional polymer that does not contain an “oxy” R unit has a 50
% Comprises a polyamine skeleton having 4 or more carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene 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 according to the invention comprise modified homogeneous and heterogeneous polyamine backbones, wherein not more than 100% of the —NH units are modified. For the purposes of the present invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having the same R units (ie all ethylene). However, this definition of identity does not exclude other polyamines that contain extraneous units that make up the polyamine backbone that are present because they are artifacts of the chosen chemical synthesis method. For example, as will be apparent to those skilled in the art, ethanolamine can be used as an "initiator" for the synthesis of polyethyleneimine, and thus the resulting 1
A sample of polyethyleneimine comprising a single hydroxyethyl moiety is considered, for the purposes of the present invention, to comprise a homogeneous polyamine backbone. A polyamine skeleton comprising all ethylene R units and no branching Y units is a homogeneous skeleton. The polyamine skeleton comprising all ethylene R units is a homogeneous skeleton, regardless of the degree of branching or the number of cyclic branches present.

For the purposes of the present invention, the term “heterogeneous polymer backbone” means a polyamine backbone that is a composite material 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 partially oxidized nitrogen 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, which are C ₂ alkylene (ethylene) units, and is 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:

[0053]

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

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

These polyamines can be produced, for example, by polymerizing 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.

Examples of amino-functional polymers comprising PEI are shown in Formulas I-IV.

Formula I shows that a hydrogen atom is a polyoxyalkyleneoxy unit — (CH ₂ CH ₂ O) H
Wherein the amino-functional polymer comprising a PEI backbone, having the following formula, wherein all substitutable nitrogens have been modified by substitution:

[0058]

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

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

[0060]

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:

[0061]

Embedded image Formula III Formula IV, the backbone nitrogen substitution (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:

[0062]

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 amino-functional polymers suitable for use herein include poly (ethylene imine) having a molecular weight of 1200, hydroxyethylated poly (ethylene imine) having a molecular weight of 2,000 available from Polysciences, and commercially available from Aldrich. 80% hydroxyethylated poly (ethylene imine).

The typical amount of amino-functional polymer used in the composition of the present invention, when used as the only nitrogen-containing compound, is more than 1% by weight of the composition, preferably 50%
, More preferably more than 1 wt%, up to 25 wt%, most preferably more than 1 wt% and up to 10 wt% activity.

Dye fixatives Dye fixatives, or "fixers", are well known, designed to improve the appearance of dyed fabrics by minimizing dye loss from the fabric upon washing. It is a commercially available material. Materials described below as fabric softeners or amino-functional polymers are not included in this definition.

Many dye fixatives are cationic and are based on various quaternized or cationically charged organic nitrogen compounds. Cationic fixatives are commercially available from several suppliers under various trade names. Representative examples include Clariant to Ca
rtafix, CROSCOLOR PMF from Crosfield (July 1981, code number 7894)
And CROSCOLOR NOFF (January 1988, code number 8544), IN from Sandoz
DOSOL E-50 (February 27, 1984, Reference No. 6008.35.84, polyethyleneamine based), also commercially available from Sandoz, the preferred polycationic fixatives SANDOFIX TPS and SANDOFIX. SWE (cationic resinous compound), REWIN SRF, REWIN SRF-O and REWIN DWR commercially available from CHT-Beitlich GMBH
Tinofix (trade name) ECO, Tinofix (trade name) ERD and So available from Ciba-Geigy
lfin (trade name).

Other cationic dye fixatives are described by Christopher C. Cook in “Aftertreatments
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 hydrochlorides of fatty acid diamine condensates such as oleyldiethylaminoethylamide, acetate, methosulfate and benzylhydrochloride, oleylmethyldiethylenediaminemethosulfate, monostearyl. Oxidation products of ethylenediaminotrimethylammonium methosulphate and tertiary amines, derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrin.

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

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

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

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

A control 2 piece of cloth, which was not soaked and not ironed, is also used for this measurement.

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

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

The lower the Delta E value for a new product, the better the washing fastness is improved.

Ironing—If the wash fastness of the dipped piece of cloth is better than that of the non-ironed piece of dipped cloth and better than each of the two comparisons 1 and 2, The test agent is a cellulose-reactive dye fixing agent that can be used for the purpose of the present invention.

Typical cellulose-reactive dye fixatives include halogeno-triazine products, vinyl sulfone compounds, epichlorohydrin derivatives, hydroxyethylene urea derivatives, formaldehyde condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives and A product containing reactive groups of the reactive dye category selected from these mixtures.

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

[0079] Preferred hydroxyethylene urea derivatives include dimethylol dihydroxyethylene, urea, and dimethyl urea glyoxal.

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

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

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

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

Typical amounts of dye fixative used in the compositions of the present invention are preferably one part of the composition.
５０50% by weight, more preferably 1-25% by weight, most preferably 1.5-10% by weight of active ingredient.

When using both a dye fixative and a polyamino-functional polymer, the total amount of these components is typically up to 90%, preferably up to 50%, more preferably from 1 to 25% by weight of the composition. %, Most preferably 1 to 10% by weight active ingredient. A water-soluble cationic surfactant, a "water-soluble wetting agent", forms a substantially transparent, isotropic solution when the wetting agent is dissolved in water at 25 ° C at 0.2% by weight. Means to do.

[0086] All types of water-soluble cationic surfactants can be used to impart the scum-inhibiting properties. However, certain water-soluble cationic surfactants and mixtures thereof are more preferred. Therefore, the cationic surfactant is preferably a surface-active molecule having a linear or branched hydrophobic tail and a positively charged hydrophilic head group, and more preferably the cationic surfactant used in the present invention. The system surfactant is a quaternary ammonium salt having the following formula.

[0087] ^{[R 1 N + R3] X} - In the formula, ^{R 1} groups is interrupted _C 10 _{-C 22} hydrocarbon group, preferably either a _C 12 _{-C 18} alkyl group, or a corresponding ester linkage a group comprising a short alkylene _(C 1 ~C ₄₎ group between the ester linkage and N, have a similar hydrocarbon group,
For example, fatty acid esters of choline, preferably C ₁₂ -C ₁₄ (coco) choline esters and / or C ₁₆ -C ₁₈ tallow choline esters. The hydrocarbon groups may be interrupted by other groups such as COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO. Each R is C ₁ -C ₄ alkyl or substituted (eg, hydroxy) alkyl, or a hydrogen atom, preferably methyl, and the counterion X ⁻ is an anion that is compatible with the softener, such as chloride. , Bromide, methyl sulfate, and the like.

The long-chain group R 1 of a single long-chain alkyl surfactant typically has 10 to 22 carbon atoms,
Preferably, it contains an alkylene group having 12 to about 16 carbon atoms, more preferably 12 to 18 carbon atoms. The R1 group can be attached to the cationic nitrogen atom through a group containing one or more ester, amide, ether, amine, etc., preferably ester, linking groups which are preferred to increase hydrophilicity, biodegradability, etc. Can be added.
Preferably, such a linking group is within about 3 carbon atoms of the nitrogen atom. A preferred cationic surfactant of this type is N, N dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecyl ammonium bromide.

When using the corresponding non-quaternary amine, any acid added to keep the ester group stable (preferably a mineral acid or polycarboxylic acid) also maintains the amine protonation in the composition. I do.

A typical disclosure of these cationic surfactants suitable for use in the present invention is a choline ester surfactant having the formula:

[0091]

Embedded image Wherein R ₁ is a C ₁₀ -C ₂₂ linear or branched alkyl, alkenyl or alkaryl chain or M ⁻ . N ⁺ (R ₆ R ₇ R ₈ ) (CH ₂ ) _s , wherein X and Y are independently COO, OCO, O, CO, OCOO, CONH, NHCO,
Selected from the group consisting of OCONH and NHCOO, wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group;
R ₂ , R ₃ , R ₄ , R ₆ , R ₇ , and R ₈ independently comprise an alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl group having 1-4 carbon atoms and an alkaryl group. R ₅ is independently H or a C ₁ -C ₃ alkyl group, the values of m, n, s and t are independently in the range of 0-8, and the value of b is 0. -20, and the values of a, u and v are independently 0 or 1, provided that at least one of u or v must be 1 and M
Is a counter anion. Preferably, M is selected from the group consisting of halides, methyl sulfate, sulfate, and nitrate, more preferably, methyl sulfate, chloride, bromide or iodide. Highly preferred water-dispersible choline ester surfactants are esters having the formula:

[0092]

Embedded image Wherein m is 1-4, preferably 2 or 3, and R ₁ is C ₁₁ -C ₁₉ linear or branched alkyl.

Particularly preferred choline esters of this type include stearoyl choline esters quaternary.
Quaternary methyl ammonium halide (R ¹ C ₁₇ alkyl), palmitoylcholine ester quaternary methyl ammonium halide (R ¹ ＣC ₁₅ alkyl)
, Myristoylcholine ester quaternary methylammonium halide (R ¹ =
C ₁₃ alkyl), lauroyl choline ester methylammonium halides ^(R 1 _{= C 11} alkyl), cocoyl choline ester quaternary methylammonium halides ^(R ₁ = _C 11 ^~C ₁₃ alkyl), tallow yl choline ester quaternary methylammonium halides ^(R ₁ = _C 15 ^~C ₁₇ alkyl), and mixtures thereof.

Particularly preferred choline esters of this type are selected from myristoylcholine ester quaternary methylammonium halides, lauroylcholineester methylammonium halides, cocoylcholineester quaternary methylammonium halides, and mixtures thereof. .

The above particularly preferred choline esters can be produced by directly esterifying a fatty acid having a desired chain length with dimethylaminoethanol in the presence of an acid catalyst. Then, preferably solvents, such as ethanol, water, propylene glycol or preferably a fatty alcohol ethoxylate such as ethoxylated degree of 3 to 50 ethoxy groups per mole of C ₁₀ -C ₁₈ fatty alcohol ethoxylates, in the presence of The reaction product is quaternized with methyl halide to form the desired cationic material. These choline esters can also be produced by directly esterifying a long-chain fatty acid having a desired chain length with 2-haloethanol in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine,
Form the desired cationic material.

Polyoxyalkylene alkylamine surfactant A polyoxyalkylene alkylamine surfactant is another essential component of the present invention. In fact, the use of this component suppresses or prevents the formation of scum.

Preferably, polyoxyalkylene alkylamine nonionic surfactants suitable for use in the present invention have the formula:

[0098]

Embedded imageWhere R is C₇~ C₂₁Linear alkyl, C₇~ C₂₁Branched alkyl, C₇~ C ₂₁ Linear alkenyl, C₇~ C₂₁Branched alkenyl, and mixtures thereof
Selected from The nonionic surfactant of the present invention may be a synthetic or natural raw material,
Alternatively, the nonionic surfactant is derived from a natural source, and the nonionic surfactant has the following formula:
Comprising an acyl unit.

O ‖ R—C— The acyl unit comprises tallow, partially hydrogenated tallow, lard, coconut oil, partially hydrogenated coconut oil, palm kernel oil, hydrogenated palm kernel oil, Canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated Sunflower oil, corn oil, hydrogenated corn oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated It is derived from a triglyceride source selected from the group consisting of rice bran oil, and mixtures thereof. Other preferred sources of triglycerides for the acyl units are not derived from natural sources, but are synthetic triglyceride raw materials such as those produced by chemical reactions or other processes.
More preferred sources of the acyl units are tallow, partially hydrogenated tallow, coconut oil, partially hydrogenated coconut oil, canola oil, hydrogenated canola oil, synthetic triglycerides, and mixtures thereof. One preferred triglyceride source is tri-oleyl triglyceride.

R ¹ is ethylene and R ² is selected from C ₃ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl, and mixtures thereof, preferably R ² is 1,2-propylene . R ¹ and comprising a mixture of R ² units nonionic surfactant, preferably from about 4 to about 12 ethylene units, contain in combination with from about 1 to about 4 1,2-propylene units It becomes. These units may be alternating or in groups of combinations that are suitable for the prescriber. Preferably, the ratio of ^{R 1} units to ^{R 2} units is from about 4: 1: 1 to about 8. Preferably, ^{R 2} unit (i.e. 1,2-propylene) is added to the nitrogen atom, the remainder of the chain followed by 4-8
Of ethylene units.

R ³ is selected from a hydrogen atom, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl, and mixtures thereof, and is preferably a hydrogen atom or methyl, more preferably a hydrogen atom.

R ⁴ is selected from a hydrogen atom, C ₁ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl, and mixtures thereof, and is preferably a hydrogen atom. If the exponent m is 2, the index n must be 0, ^{R 4} unit is absent and is replaced by _{^{[(R 1 O) x (}} R 2 O) y R 3] unit instead.

A is

Embedded image It is.

R ⁵ is [(R ¹ O) _x (R ² O) _y ] unit, C ₁ -C ₁₆ linear alkyl,
Selected from C ₁ -C ₁₆ branched alkyl, C ₁ -C ₁₆ linear alkenyl, C ₁ -C ₁₆ branched alkenyl, and mixtures thereof, preferably C ₃ linear alkyl, C ₃ branched alkyl, C ₃ linear. alkenyl, C ₃ branched alkenyl, and mixtures thereof.

The index m is 1 or 2, and the index n is 0 or 1, provided that when m is 1, n is 1 and when m is 2, n is 0; Preferably m is 2
And n is 0, and there are two [(R ¹ O) _x (R ² O) _y (R ³ ) units and no R ^{4. The} index x ranges from 0 to about 50, preferably It is about 1 to about 25, more preferably about 3 to about 10. The index y is 0 to about 10, preferably 0, but when the index y is not 0, y is 1 to about 4. Where all of the alkyleneoxy units are ethyleneoxy units. As will be apparent to those skilled in the art of ethoxylated polyoxyalkylenealkylamine surfactants, the indices x and y
Are mean values, and the true values range over several values, depending on the recipe used for the alkoxylation of the amine.

The index q is 0 or 1.

[0107] Polyoxyalkylene alkylamines are commercially available from several suppliers under various trade names. Representative examples include Ethomeen, Ethoduomeen, commercially available from Akzo Chemicals.
And / or Secomine commercially available from Stepan.

A polyoxyalkylene alkylamine surfactant is typically included in the composition at 0.1.
It is present in an amount of 001-20% by weight, preferably 0.5-12% by weight, more preferably 1-8% by weight.

[0109] Among the materials described herein, water-soluble cationic surfactants are preferred.

In order to further improve the debris control performance of the composition, if the polyamino-functional polymer is the only nitrogen-containing compound, the debris depressant and the polymer may be reduced to 0.1%.
02: 1 to 2: 1, preferably 0.05: 1 to 1.5: 1, most preferably 0.1: 1.
It has been found preferable to be present in a weight ratio of 1: 1 to 0.8: 1.

When the dye fixative is the only nitrogen-containing compound, for optimum dross control, the weight ratio of the dregs inhibitor to the dye fixative is 0.05: 1 to 5: 1, more preferably 0%. .1
: 1 to 2.5: 1, most preferably 0.5: 1 to 1: 1.

When using a mixture of a polyamino-functional polymer and a dye-fixing agent, to improve the dregs control, the weight ratio of the dregs-suppressing agent, the polyamino-functional polymer and the dye-fixing agent is preferably 0%. 0.05: 1 to 2: 1, preferably 0.1: 1 to 1: 1.

It is found that the use of a water-soluble cationic surfactant, which is generally called a fabric softening compound, in addition to the above-mentioned dregs inhibitor effectively reduces the dregs suppression performance. Was.

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

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

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

[0117]

Embedded image Or

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

[0118]

Embedded image Wherein each R unit is independently a hydrogen atom, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, and mixtures thereof, preferably methyl or hydroxyalkyl, and each R ¹ unit are independently linear or branched _C 11 _{-C 2 2} alkyl, straight or branched _C 11 _{-C 22} alkenyl, and mixtures thereof, ^{R 2} is a hydrogen _atom, C 1 -C ₄ alkyl, C _{1 to} C ₄ hydroxyalkyl, and mixtures thereof, wherein X is an anion that is compatible with the fabric softener active and auxiliary components, and has an index m of 1-4, preferably 2 The index n is between 1 and 4, preferably 2.

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

[0120]

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

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

[0122]

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

[0123]

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

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

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

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

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

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

Embedded image A triethanolamine having the formula:

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

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

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

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

TABLE II Fabric softener active ingredient N, N-di (tallowyl-oxy-ethyl) -N, N-dimethylammonium chloride, N, N-di (canolyl-oxy-ethyl) -N, N- Dimethylammonium chloride, N, N-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-tallowyl Oxy-2
-Oxo-ethyl) -N, N-dimethylammonium chloride; N- (2-canolyloxy-2-ethyl) -N- (2-canolyloxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride, N, N, N-tricanolyl-oxy-ethyl) -N-methylammonium chloride, N- (2-tallowyloxy-2-oxoethyl) ) -N- (Taroyl) -N,
N-dimethylammonium chloride, N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N-
Dimethylammonium chloride, 1,2-ditayloxy-3-N, N, N-trimethylammoniopropane chloride, and 1,2-dicanolyloxy-3-N, N, N-trimethylammoniopropane chloride, and the above Mixture of active ingredients.

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

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

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

In fact, the following equation

Embedded image For compounds derived from tallow fatty acids having the iodine value of 5 to 25, preferably 15 to 20, the weight ratio of cis / trans isomers exceeds about 30/70, preferably about 50/50. It has been found that above this, more preferably above about 70/30, results in optimal concentrating properties. For such compounds made from tallow fatty acids having an iodine value of more than 25, the ratio of the cis to trans isomer has proven to be less important, unless very high concentrations are required. Another suitable example of a fabric softener active ingredient is a fatty acyl, wherein the "tallowyl" and "canolyl" in the above examples are replaced by the term "cocoyl, palmyl, lauryl, oleyl, ricinoleyl, stearyl, palmityl". Derived from the group, these terms correspond to the triglyceride source from which the fatty acyl unit is derived. These alternative fatty acyl sources can comprise fully saturated or, preferably, partially unsaturated chains.

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

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

With respect to the above ester fabric softeners, the pH of the composition is an important parameter of the present invention. In fact, pH affects the stability of the quaternary ammonium or amine precursor compound, especially under prolonged storage conditions.

The pH specified here is measured at 20 ° C. for the undiluted composition. Although these compositions may work at a pH of less than about 6.0, optimum pH stability of these compositions may be achieved by adjusting the undiluted pH, as measured under the conditions described above. , Preferably 2.0-5, preferably 2.5-4.5, preferably 2.5-3.
Must be in the range of 5. The pH of these compositions can be adjusted by adding a Bronsted acid.

Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially low molecular weight (C ₁ -C ₅ ) carboxylic acids, and alkyl sulfonic acids. Suitable inorganic acids include HCl,
H ₂ SO _4, HNO ₃ and _H 3 PO ₄ and the like. Suitable organic acids include formic acid, acetic acid, citric acid, methyl sulfonic acid and ethyl sulfone. Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic, and benzoic acids.

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

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

[0139] 2) - suitable, yet another quaternary ammonium fabric softening compounds for use herein, two or more long chain acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group or, A cationic nitrogen-containing salt having one such group and one arylalkyl group, which can be used alone or as a part of a mixture, and (i) an acyclic quaternary ammonium salt having the following formula:

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

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

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

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

(I) A reaction product of a higher fatty acid and 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:

[0143]

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

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

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

[0146] Both N, N "-ditallowalcohol diethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are the reaction products of tallow fatty acids and diethylenetriamine, and the cationic fabric softener methyl- It is a precursor of 1-tallowamidoethyl-2-tallowimidazolinium methyl sulfate ("Cationic Surface Active Agents as Fabric Softners", RR Egan, Jou
rnal of the American Oil Chemicals' Society, January 1978, 118-121
Page). N, N "-Ditalowalcoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline are available as test chemicals from Witco Chemical Company. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl Sulfate is available from Witco Chemical Company as Varisoft 4
It is marketed under 75 trade names.

(Ii) A softener having the following formula:

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

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

(Iii) A softener having the following formula:

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

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

[0151]

Embedded image Wherein R ¹ is derived from oleic acid.

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

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

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

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

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

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

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

Solvents which 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) cyclohexane, although these ClogP values fall within the preferred range, does not appear to be able to give a substantially clear composition when used alone.

[0160] Solvents that facilitate the most preferred formulation can be identified by the appearance of the softener vesicles when cryo-electron microscopy of the composition diluted to the concentration used for rinsing. These dilute compositions appear to have a dispersion of fabric softener that exhibits a more uniform laminar appearance than conventional fabric softener compositions. The closer the appearance is to a single thin layer, the better the performance of the composition appears. These compositions are:
The use of the same fabric softener active ingredient gives surprisingly good fabric softness compared to similar compositions made in a conventional manner.

Solvents which can be used and which 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 auxiliaries to achieve higher concentrations and / or to meet higher stability standards depending on other ingredients. . Are these thickening aids (which can typically be viscosity improvers) required to ensure stability under extreme conditions when using particular softener active ingredient amounts? Or may be preferred. Surfactant concentration aids generally include (1) single long chain alkyl cationic surfactants, (2) nonionic surfactants, (3) amine oxides, (4) fatty acids, and (5) It is selected from the group consisting of these mixtures. These auxiliaries are described in particular in WO 94/20597, page 14, line 12 to page 20, line 12, incorporated herein by reference.

If present, the total amount of the dispersing aids is 2 to 25% by weight of the composition, preferably 3 to 17% by weight, more preferably 4 to 15% by weight, even more preferably 5 to 13% by weight.
% By weight. These materials may be added as part of the active softener raw material (I), such as a fatty acid which is a reactant used to form the biodegradable fabric softener active ingredient described above, or may be added separately. Can be added as a component. The total amount of dispersing aid includes all that may be present as part of component (I).

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

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

Specific examples of the alkylene polyammonium salt include l-lysine monohydrochloride and 1,5-
And diammonium 2-methylpentane dihydrochloride.

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

Examples of antioxidants that can be added to the compositions of the present invention include Eastman Chemical Pro
A mixture of ascorbic acid, ascorbic palmitate, propyl gallate, commercially available under the trade names Tenox PG and Tenox S-1 from ducts, Inc., Eastman
A mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, commercially available from Chemical Products, Inc. under the trade name Tenox-6, Sustane BH from UOP Process Division
Butylated hydroxytoluene, commercially available under the trade name T, Eastman Chemical P
Eastma, a tertiary butyl hydroquinone commercially available as Tenox TBHQ from roducts, Inc.
n Natural tocopherol commercially available from Chemical Products, Inc. as Tenox GT-1 / GT-2, and butylated hydroxyanisole commercially available as BHA from Eastman Chemical Products, Inc., long chain esters of gallic acid (C ₈ -C ₂₂ ), For example, dodecyl gallate, Irganox (trade name) 1010, Irganox (trade name) 1035, Irganox (
(Brand name) B 1171, Irganox (Brand name) 1425, Irganox (Brand name) 3114, Irganox
(Trade name) 3125, and mixtures thereof, preferably Irganox (trade name) 3125,
Irganox® 1425, Irganox® 3114, and mixtures thereof, more preferably Irganox® 3125 (alone or with citric acid and / or other chelating agents such as isopropyl citrate) Mixed), Dequest 2010 (trade name) commercially available under the chemical name 1-hydroxyethylidene-1,1-diphosphonic acid (etidronic acid) from Monsanto, and 4,5-dihydroxy-m-benzene-sulfonic acid from Kodak Tiron (trade name), commercially available under the chemical name of / sodium salt, and
DTPA (trade name) commercially available from Aldrich under the chemical name of diethylenetriaminepentaacetic acid
Is mentioned. The chemical names and CAS numbers of some of the above stabilizers are shown in Table II below.

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

(E)-Soil Release Agent The fabric softening composition of the present invention preferably uses a soil release agent. 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.

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

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

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

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

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

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

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

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

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

The perfume ingredients are described as releasable odors, for example, US Pat. No. 5,652,205, Hartman et al., Issued Jul. 29, 1997, which is hereby incorporated by reference.
It can also be added as a pro-perfume or pro-flavour as described in

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

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

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

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

By organomonophosphonic acid is meant here organomonophosphonic acid which does not contain nitrogen as part of its chemical structure. Thus, although this definition excludes organoaminophosphonates, this material can be included in the compositions of the present invention as a heavy metal sequestrant.

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

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

Other Optional Ingredients The present invention relates to other optional ingredients commonly used in textile treatment compositions, such as brighteners, colorants, surfactants, anti-shrink agents, fabric shrinkage. Treatment agent (c
risping agents, disinfectants, fungicides, fungicides, antioxidants such as butylated hydroxytoluene, corrosion inhibitors, defoamers, and the like.

The present invention relates to International Patent Nos. WO 96/02625, WO 96/2171.
No. 4, and WO 96/21715,
And Ve disclosed in pending application PCT / US97 / 01644.
Other compatible components, including dispersible polyolefins such as lustrol, may also be included. The present invention provides for the use of optional chelating agents such as ethylenediamine-N, N'-disuccinic acid, the (S, S) isomer in the form of sodium salt (EDDS), and crystal growth inhibitors such as glycolic acid and And / or 1,1-hydroxyethanediphosphonic acid (HEDP). Form of the composition The fabric protection composition comprises a liquid, e.
It can take various physical forms, including, for example, solid particulate forms. Such compositions can be applied to a substrate, such as a dryer sheet product, or used as a product added during rinsing, or as a spray or foam product.

Thus, in another aspect of the present invention, a surfactant, preferably a debris suppressant as described above, may be used with a nitrogen-containing compound selected from polyamino-functional polymers, dye fixatives, and mixtures thereof. Also provided is a method for use in a composition comprising the same, wherein the method inhibits or prevents the formation of scum on fabric or washing machine parts in contact with the composition. In other words, a composition containing the nitrogen-containing compound as defined herein, but not containing the dregs inhibitor,
A large amount of scum is formed compared to the composition of the present invention.

Process The fabric softening composition can be conveniently prepared by processes well known to those skilled in the art. A representative example is European Patent EP-A-0,668,9.
No. 02.

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

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

DEQA: di- (tallowyl-oxy-ethyl) dimethylammonium chloride DOEQA: di- (oleyloxyethyl) dimethylammonium methyl sulfate DTDMAC: ditallow dimethylammonium chloride DHEQA: di- (soft-tallowyl-oxy-ethyl) Hydroxyethyl methyl ammonium methyl sulfate 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 compressed stearic acid Glycosperse S-20: Polyethoxylated sorbitan Monostearate, commercially available from Lonza Clay: Calcium Bentonite Clay, Bentonite L, Southern Clay Product
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: PEI 1800 E7 AO: Amine oxide of ethoxylated polyethyleneimine (molecular weight 1) synthesized with ethoxylated polyethyleneimine (molecular weight 1800, 50% activity) Synthesis Example 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 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: cellulose-reactive dye fixative, commercially available from Ciba-Geigy under the trade name Tinofix FRD Dye fixative 2: cellulose-reactive dye fixative, CHT R Reit from Beitlich
Commercially available in DWR Dust inhibitor 1: N, N-dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecyl ammonium bromide Dust inhibitor 2: C12 / C14 choline ester Dust inhibitor 3: Poly Oxyalkylenealkylamines from Akzo to Ethomeen T / 1
Commercially available under the trade name 5 Dust Suppressor 4: Polyoxyalkylenealkylamine, Secomine T from Stepan
Commercially available under the trade name A15 Dust Inhibitor 5: Polyoxyalkylenealkylamine, from Akzo to Ethoduomeen
LAS: sodium linear C ₁₂ alkylbenzene sulfonate TAS: sodium tallow alcohol sulfate C25AS: sodium C ₁₂ -C ₁₅ linear alkyl sulfate CxyEzS: sodium C _1x -C _1y branched alkyl sulfate, ethylene oxide zmol condensation _C45E7: predominantly linear primary alcohol of _{C 14-15} and an average 7 moles of ethylene oxide condensed _{C25E3: C 12-15} branched primary alcohol, average of 3 moles of ethylene oxide and condensation soap: tallow and coconut oil from 80/20 mixture, sodium linear alkyl carboxylate _{TFAA: C} 16 ~C ₁₈ alkyl N- methyl glucamide _{TPKFA: C 12 ~C 14 topped whole} cut fatty acids zeo Light 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 dextrin, encapsulated in 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 controlling agent, said foam containing siloxane-oxyalkylene copolymer as dispersant The ratio of modifier to dispersant 10: 1 to 1
100: 1 HEDP: 1,1-hydroxyethanediphosphonic acid Bayhibit AM: 2-phosphonobutane-1,2,4-tricarboxylic acid, commercially available from Bayer TPTA: N, N'-bis (3-aminopropyl) 1,3 -Propanediamine,
Synthetic Example 1 Commercially Available from Aldrich Step 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 2 gallon stirred stainless steel autoclave. An approximately 20 lb. net ethylene oxide cylinder (ARC) is placed on a balance so that the weight change of the cylinder can be monitored, and the pump is arranged to supply ethylene oxide as a liquid to the autoclave.

750 g part of polyethylene imine (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 slightly cooled and collected in a nitrogen purged glass container.

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 three neck round bottom flask equipped with heating and stirring equipment. 167 g of methanesulfonic acid (1
. (74 mol) to neutralize the strong alkali catalyst.

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

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 at 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, which is thought to be due to the methylene protons adjacent to the unoxidized nitric oxide, is about 2.5 p.
It has shifted from its original position at pm 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 substance
Suitable for storage as a 51.1% active aqueous solution.

[0211] Production Step A of Synthesis Example 5-PEI 1200E ₁₎ - ethoxylation temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and introduction of ethylene oxide as a liquid, equipment for performing In a 2 gallon stirred stainless steel autoclave. An approximately 20 lb. net ethylene oxide cylinder (ARC) is placed on a balance so that the weight change of the cylinder can be monitored, and the pump is arranged to supply ethylene oxide as a liquid to the autoclave.

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

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

[0224]

[Table 1] Example 2 The following composition is in accordance with the invention.

[0225]

[Table 2]

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

[0226]

[Table 4] Example 4 The following detergent formulations S and T are in accordance with the invention.

[0227]

[Table 5] Example 5 The following liquid detergent formulation according to the present invention was prepared.

[0228]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/02 C08L 101/02 C11D 1/44 C11D 1/44 1/62 1/62 3/37 3 / 37 10/02 10/02 D06M 13/463 D06M 13/463 15/61 15/61 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW. ) Inventor Axel, Marslan Be-1050, Belgium, Brussels, Rue, Feder, 47 (72) Inventor Roberta, Longhui, Wu La, Ohio, United States of America Land, Waterford, Place, Number 207, 9672 F-term (reference) 4H003 AB03 AB19 AB27 AC08 AE02 AE05 AE06 DA01 EA15 EA16 EA20 EA28 EB08 EB12 EB22 EB24 EB26 EB28 EB32 EB37 EB42 EC01 EC02 EC03 ED02 EA05 CM14 EN137 EP016 EU196 EV246 FD096 FD31X FD317 GK02 HA04 4L033 AB05 AB06 AB07 AC15 BA86 CA57

Claims (11)

[Claims] 1. A nitrogen-containing compound selected from: i) a polyamino-functional polymer, a dye fixing agent, and a mixture thereof; ii) a water-soluble cationic surfactant, a polyoxyalkylene alkylamine surfactant, And a dross inhibitor selected from mixtures thereof, wherein when the only nitrogen-containing compound is a polyamino-functional polymer, the polymer is present in an amount greater than 1% by weight. A fabric protection composition, provided that: 2. The water-soluble cationic surfactant is represented by the following formula:
A composition according to claim 1. [R ¹ N ⁺ R 3] X ⁻ [wherein R ¹ is interrupted by a C ₁₀ -C ₂₂ hydrocarbon group or a corresponding ester bond having a C ₁ -C ₄ alkylene group between N and an ester bond. Wherein each R is a C ₁ -C ₄ alkyl or substituted alkyl, or a hydrogen atom, and the counterion X ⁻ is an anion compatible with the softener. 3. The water-soluble cationic surfactant comprises N, N-dimethyl-N- (2-hydroxyethyl) -N-dodecyl / tetradecylammonium bromide, myristoylcholine ester quaternary methylammonium halide, The composition of claim 2, wherein the composition is selected from lauroylcholine ester methylammonium halide, cocoylcholine ester quaternary methylammonium halide, and mixtures thereof. 4. The composition according to claim 1, wherein the polyoxyalkylene alkylamine surfactant has the following formula: Embedded image Wherein R is selected from C ₇ -C ₂₁ linear alkyl, C ₇ -C ₂₁ branched alkyl, C ₇ -C ₂₁ linear alkenyl, C ₇ -C ₂₁ branched alkenyl, and mixtures thereof R ¹ is ethylene; R ² is selected from C ₃ -C ₄ linear alkyl, C ₃ -C ₄ branched alkyl, and mixtures thereof; R ³ is a hydrogen atom, C ₁ -C ₄ linear _alkyl, C 3 -C ₄ branched alkyl, and mixtures thereof, ^{R 4} is a hydrogen _atom, C 1 -C ₄ linear alkyl,
Selected from C ₃ -C ₄ branched alkyls and mixtures thereof, wherein A is represented by the following formula: —N— (R ⁵ ) | [(R ¹ O) _x (R ² O) _y R ³ ] R ⁵ is a [(R ¹ O) _x (R ² O) _y ] unit, a C ₁ -C ₁₆ linear alkyl,
Selected from C ₁ -C ₁₆ branched alkyl, C ₁ -C ₁₆ linear alkenyl, C ₁ -C ₁₆ branched alkenyl, and mixtures thereof, wherein the index m is 1 or 2 and the index n is 0 Or 1 wherein n is 1 when m is 1 and n is 0 when m is 2; the index x is 0 to about 50, preferably 1 to 25; The index y is 0 to about 10, and the index q is 0 or 1.] 5. The composition according to claim 4, wherein said index x is from 1 to 25. 6. The composition according to claim 4, wherein the index m is 2 and n is 0. 7. The polymer of formula V_{(N + 1)}W_mY_nCorresponds to the following formula having a polyamine of Z
Comprising a polyamine skeleton, or Equation V_{(Nk + 1)}W_mY_nY '_kCorresponding to the following formula having a polyamine of Z
The composition according to any one of claims 1 to 6, comprising a polyamine skeleton. Embedded imageWherein k is n or less, the polyamine skeleton has a molecular weight of more than about 200 daltons, and i) V units are terminal units having the following formula: ii) The W unit is a skeleton unit having the following formula: iii) Y unit is a branch unit having the following formula: iv) The Y 'unit is a skeleton or a branch point of a branched ring having the following formula: v) Z units are terminal units having the formula: The backbone R unit is C₂~ C₁₂Alkylene, C₄~ C₁₂Alkenylene, C ₃ ~ C₁₂Hydroxyalkylene, C₄~ C₁₂Dihydroxyalkylene, C₈  ~ C₁₂Dialkylarylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵ − (OR¹)_x-,-(CH₂CH (OR²) CH₂O)_z− (R¹O)_yR¹ (OCH₂CH (OR²) CH₂)_w-, -C (O) (R⁴)_rC (O)-,-
(CH₂CH (OR²) CH₂-, And mixtures thereof.
R¹Is C₂~ C₆Selected from the group consisting of alkylenes and mixtures thereof
And R²Is a hydrogen atom,-(R¹O)_xB, and mixtures thereof.
R⁴Is C₁~ C₁₂Alkylene, C₄~ C₁₂Alkenylene, C₈~ C₁₂A
Reel alkylene, C₆~ C₁₀Group consisting of arylenes and mixtures thereof
R is selected from⁵Is C₁~ C₁₂Alkylene, C₃~ C₁₂Hydroxyalkylene, C₄~
C₁₂Dihydroxyalkylene, C₈~ C₁₂Dialkylarylene, -C (O
)-, -C (O) NHR⁶NHC (O)-, R¹(OR¹)-, -C (O) (R ⁴ )_rC (O)-, -CH₂CH (OH) CH₂-, -CH₂CH (OH) CH ₂ O (R¹O)_yR¹-OCH₂CH (OH) CH₂-, And mixtures thereof
R is selected from the group consisting of⁶Is C₂~ C₁₂Alkylene or C₆~ C₁₂From the group consisting of arylenes
R ′ unit is a hydrogen atom, C₁~ C₂₂Alkyl, C₃~ C₂₂Alkenyl, C₇ ~ C₂₂Arylalkyl, C₂~ C₂₂Hydroxyalkyl,-(CH₂)_p CO₂M,-(CH₂)_qSO₃M, -CH (CH₂CO₂M) -CO₂M,-
(CH₂)_pPO₃M,-(R¹O)_xB, -C (O) R³, And mixtures of these
B is a hydrogen atom, C₁~ C₆Alkyl,-(CH₂ )_q-SO₃M,-(CH₂)_pCO₂M,-(CH₂)_q(CHSO₃M) C
H₂SO₃M,-(CH₂)_q− (CHSO₂M) CH₂SO₃M,-(CH₂ )_pPO₃M, -PO₃M, and mixtures thereof.
And R³Is C₁~ C₁₈Alkyl, C₇~ C₁₂Arylalkyl, C₇~ C₁₂ Alkyl-substituted aryl, C₆~ C₁₂Consisting of aryl, and mixtures thereof
M is a hydrogen atom or a water-soluble cation in an amount sufficient to satisfy the charge balance.
X is a water-soluble anion, m has a value of 2 to 700, and n has a value of 0 to 350
And p has a value of 1 to 6, q has a value of 0 to 6, and r has a value of 0 or 1.
Has, w has a value of 0 or 1, x has a value of 1-100, y has a value of 0-100
And z has a value of 0 or 1.] 8. The composition according to claim 1, wherein the dye fixing agent is a cellulose-reactive dye fixing agent. 9. The composition of claim 1 wherein said nitrogen-containing compound is 1 to 25% by weight, most preferably 1 to 1% by weight of the composition.
A composition according to any one of the preceding claims, wherein the composition is present at 0% by weight of the active ingredient. 10. The composition comprising a nitrogen-containing compound selected from a polyamino-functional polymer, a dye fixative, and mixtures thereof, wherein the composition comprises a fabric or washing machine part that contacts the composition. Use of the composition as a surfactant for suppressing or preventing the formation of scum. 11. The surfactant is selected from a water-soluble cationic surfactant, a polyoxyalkylene alkylamine surfactant, a water-insoluble flexibility-imparting compound, and a mixture thereof. Item 9. Use according to item 9.