JP2002540219A - Ethoxylated amino-functional polymers - Google Patents

Abstract

  (57) [Summary] Direct or indirect processing methods provide ethoxylated amino-functional polymers that exhibit reduced discoloration and malodor properties upon contact with acidic media as compared to untreated ethoxylated amino-functional polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to ethoxylated amino-functional polymers having low odor and good color properties, and to a process for their preparation.

[0002]

BACKGROUND OF THE INVENTION

Chemical manufacturers have addressed the fact that organic chemistry generally proceeds with the formation of undesirable by-products. These unwanted by-products, even in a small percentage of the total material present, can substantially affect the final product, for example by providing an undesirable color or odor. Therefore, removing these undesirable by-products has become an integral part of the manufacturing process.

In the field of laundry detergents, traders must consider not only the efficacy but also the aesthetics of the end product. For this reason and others, odorless starting materials are highly desirable. For example, fragrances are optionally added to detergent formulations to impart a desirable fragrance, but some consumers desire "no fragrance" substances. The presence of malodorous substances in laundry starting materials has limited the usefulness of these substances in fragrance sensitive formulations.

[0004] The removal of undesirable odors from laundry detergent components has been the focus of many years of research. Odorless surfactants are routinely produced and formulated in laundry products. Recently, a new class of materials, modified polyamines, also referred to herein as amino-functional polymers, has been increasingly used in laundry detergent compositions. The unique combination of properties imparted to these modified polyamines is attributed to a variety of properties, including granular and liquid detergent compositions, fabric softeners, stand-alone products for pre- or post-processing, and cleaning additives. They allow for the desired addition to laundry compositions.

[0005] These modified polyamines often have a polyalkyleneamine backbone as their starting material. Many forms of polyalkyleneamines are known to laundry products traders and are available in low odor forms. However, recent discoveries have revealed that these polyalkyleneamine modifications result in a class of materials with unique surface activity and fabric durability and novel metal chelation properties.
In addition, these modified polyamines provide care to the color of the fabric.

[0006] During the modification of these polyamine backbones, ethylene oxide is used in the presence of many chemical reagents, especially base catalysts, which are volatile or highly odorous, either themselves or offensive odor precursors. May produce reactive by-products. However, to date the true sources of odors have not been identified, and thus none of the various processes for removing odors from modified polyamines have been completely satisfactory.

Thus, there remains a need in the art for a method for removing aldehydes and other volatile components involved in malodor or malodor formation during ethoxylation of polyamines. There is also a need to provide a means to test for the presence of aldehyde-like substances and signal the removal of unwanted substances involved in malodor formation.

[0008]

[Summary of the Invention]

The main odor source was found to be the presence of aldehydes in the feed. Aldehydes are present in the process of making ethoxylated polyamines. In fact, the ethoxylation process usually causes overethoxylation, resulting in the formation of aldehyde by-products. Without being bound by theory, it is believed that the mechanism by which the aldehyde is produced is the result of the undesirable quaternization of the tertiary amine moiety by the alkylene oxide shown below:

Embedded image

[0009] These by-products can be "hidden" in the feedstock in the form of hemiacetals, acetals, enamines and the like, which are hydrolytically unstable in acidic media. Thus, if desired in the final product formulation, or if necessary to process the raw materials in the final product, acidification releases by-products and eliminates offensive odors and colors. The different possible forms of the "hidden" aldehyde are:

[0010] 1. The hemiacetal of hemiacetal acetaldehyde or higher unsaturated aldehyde is
It is one of the possible forms of "hidden" aldehydes. In the general case of hydroxyethylated amines, the hemiacetal of acetaldehyde itself is shown below:

Embedded image However, such hemiacetals are in equilibrium with alcohols and aldehydes under both basic and acidic conditions, so it is believed that they do not require acidification to release the aldehyde. However, release may be faster in strongly acidic systems.

[0011] 2. Michael Addition Products of Unsaturated Aldehydes Another possibility for "hidden" aldehydes is that unsaturated aldehydes, such as crotonaldehyde, undergo Michael addition of OH or NH to a double bond to produce the following species: Is to produce:

Embedded image These are considered to release unsaturated aldehydes under strongly acidic conditions by elimination reaction.

[0012] 3. Authentic Acetals Yet another possible form for "hidden" aldehydes is that of authentic acetal. The following scenario, based on the hemiacetal of acetaldehyde itself, illustrates a very plausible manner of producing an acetal under conditions where ethoxylation occurs:

Embedded image The hemiacetal hydroxyl is like the most acidic alcohol in the system,
Therefore, even under mild basic conditions, ethoxylation is easier than in the case of a larger number of hydroxyethyl groups. When this occurs, an acetal is formed that is trapped until it is acidified.

[0013] These ethoxylated amino-functional polymers can reduce or eliminate the content of malodorous compounds in several direct or indirect ways, so that all aldehydes designated as acetaldehyde in the feedstock Was unexpectedly found to be present at less than 100 ppm after contact with an acidic medium. In one method, the modified polyamine is contacted with sodium sulfite prior to acidification, such that the solution to be acidified contains about 0.5-1% w / w of added sodium sulfite. In another suitable method, the polyamine is contacted with the borohydride salt during or after ethoxylation, prior to acidification. Another suitable method is to use hydroxyethylation to less than 1 equivalent per reactive NH group and use the modified amine itself or add a strong basic catalyst to ethoxylate to the desired extent, underhydroxyethyl. (Underhy
droxyethylation).

It is an object of the present invention to provide an ethoxylated amino-functional polymer containing less than 100 ppm of all aldehyde compounds expressed as acetaldehyde after contact with an acidic medium. It is another object of the present invention to provide a method for reducing or eliminating the content of malodorous compounds from the following ethoxylated amino-functional polymers. In this method, the polyamine is contacted with sodium sulfite before acidification. Yet another object of the present invention is to provide a composition comprising the above compound. Another object of the present invention is that the modified polyamines described above are used to provide better color and odor materials. One aspect of the invention is an ethoxylated amino-functional polymer, characterized in that the polymer contains less than 100 ppm of total aldehyde compounds, expressed as acetaldehyde, after contact with an acidic medium. In another aspect of the invention, the ethoxylated polyamino-functional polymer is treated with sodium sulfite before acidification such that the acidified polymer contains 0.5-1% w / w of added sodium sulfite. A method is provided for obtaining a polymer as described above, including a step of processing. In yet another aspect of the present invention, there is provided a composition comprising a modified polyamine as described above. Yet another aspect of the present invention is the use of a modified amino-functional polymer as described above, which has reduced discoloration and malodor upon contact of the polymer with an acidic medium.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Ethoxylated amino-functional polymers The essential components of the present invention comprise, after contact with an acidic medium, less than 100 ppm, preferably less than 50 ppm, more preferably less than 25 ppm of all aldehyde compounds expressed as acetaldehyde. An ethoxylated amino-functional polymer. Of course, for the purposes of the present invention, the above-mentioned aldehydes are by-products of the amino-functional polymer as raw material and occur during the production of the polymer and under acidic conditions. It does not include the aldehyde of the fully formulated composition in which the polymer is used.

An “acidic medium” is an acidic pH, ie, less than 7, preferably less than 6, more preferably 2.0 to 5, most preferably 2.5 to 4.5, and most preferably 2.5 to 4.5. 3
. 5 means a particular medium. Typical examples of such acidic media include fabric softening compositions, as well as acidic treatment steps performed during the incorporation of the ethoxylated amino-functional polymer into the fully formulated composition, or fully formulated compositions containing the above polymers. Processing. Indeed, aldehyde by-products are formed upon contact with an acidic medium, whether the raw ethoxylated polymer is in raw form or incorporated into a fully formulated composition. However, the resulting fully formulated composition need not be acidic.

By “contacting” is meant that the ethoxylated polymer is present in the acidic medium for at least the time corresponding to the untreated ethoxylated polymer in forming the aldehyde by-product. The rate of by-product formation depends, of course, on the nature of the impurities, their amount and the pH value of the medium.

[0018] Typically, useful amino-functional polymers in the present invention, 200-10 ^6, preferably 600 to 20,000, and most preferably has a molecular weight of 1000 to 10,000. These polyamines have a linear or cyclic main chain. The polyamine backbone may also have more or less some polyamine branches. Preferably, in addition to the ethoxylation substitution, the polyamine backbone described herein may be substituted, quaternized, oxidized, or a combination thereof, of at least one, preferably each nitrogen, of the polyamine chain. Are modified as described below.

The linear or non-cyclic polyamine backbone making up the amino-functional polymer has the general formula:

Embedded image The cyclic polyamine backbone making up the amino-functional polymer has the general formula:

Embedded image Before the optional but preferred modifications, the backbone described above consists of primary, secondary and tertiary amine nitrogens connected by R "linking" units.

For the purposes of the present invention, the primary amine nitrogen making up the main or branched chain, when modified, is designated as a V or Z “terminal” unit. For example, when a primary amine moiety located at the end of a major polyamine backbone or branch, having the structure: H ₂ NR]-, is modified according to the present invention, it is a V "terminal" unit, or simply Displayed as V units. However, for the purposes of the present invention, some or all of the primary amine moiety may remain unmodified, subject to the restrictions further described below. These unmodified primary amine moieties remain "terminal" units due to their position in the backbone. Similarly, having the following structure, primary amine moiety, located at the end of the main polyamine backbone: When -NH ₂ is modified according to the present invention, it is displayed as Z "terminal" unit, or simply Z units, . This unit may be left unmodified according to the restrictions further described below.

Similarly, the secondary amine nitrogen making up the main or branched chain, when modified, becomes
It is designated as a "backbone" unit. For example, the main components of the main and branched chains of the present invention, having the following structure, a secondary amine moiety:

Embedded image When modified according to the present invention, it is designated as a W "backbone" unit, or simply as a W unit. However, for the purposes of the present invention, some or all of the secondary amine moiety may remain unmodified. These unmodified secondary amine moieties remain "backbone" units because of their position in the backbone.

Similarly, the tertiary amine nitrogen constituting the main chain or the branched chain, when modified,
It is referred to as a Y "branch" unit. For example, a tertiary amine moiety, which is a polyamine backbone or other branch or ring branch point, having the following structure:

Embedded image When modified according to the present invention, it is designated as a Y "branch" unit, or simply as a Y unit. However, for the purposes of the present invention, some or all of the tertiary amine moiety may be left unmodified. These unmodified tertiary amine moieties remain "branched" units because of their position in the backbone. The R units associated with the V, W, and Y unit nitrogens that serve to link the polyamine nitrogen are described below.

The final modified structure of the polyamine of the present invention therefore has the following general formula for a linear amino-functional polymer: V _{(n + 1)} W _m Y _n z For a cyclic amino-functional polymer, : can be represented by _{V (n-k + 1)} W m Y n Y 'k Z. In the case of a ring-containing polyamine, a Y ′ unit of the following formula:

Embedded image Serves as a branch point of a main chain or a branched ring. For each Y 'unit, there is a Y unit having the formula:

Embedded image This forms the point of attachment of the ring to the main polymer chain or branch. In the unique case where the backbone is a complete ring, the polyamine backbone has the formula:

Embedded image Thus free of Z terminal _{unit, V nk W m Y n Y} 'k above wherein k having the formula is the number of ring forming branching units. Preferably, the polyamine backbone of the present invention does not contain any rings.

In the case of acyclic polyamines, the ratio of index n to index m relates to the relative degree of branching. The fully unbranched linear modified polyamine according to the invention has the formula: VW _m Z, ie n is 0. The larger the value of n (the lower the ratio of m to n),
The degree of branching in the molecule increases. Typically, the value of m ranges from a minimum of 2 to 700,
It is preferably in the range of 4 to 400, but it is also preferable that the value of m is large, especially when the value of index n is very low or almost zero.

Each primary, secondary or tertiary polyamine nitrogen, when modified in accordance with the present invention, is further designated as belonging to one of three general classes of simple substitution, quaternization or oxidation. . Unmodified polyamine nitrogen units are classified as V, W, Y, Y 'or Z units, depending on whether they are primary, secondary or tertiary nitrogens. That is, for the purposes of the present invention, an unmodified primary amine nitrogen is a V or Z unit, an unmodified secondary amine nitrogen is a W or Y 'unit, and an unmodified tertiary amine nitrogen is a Y unit.

The modified primary amine moiety is designated as a V “terminal” unit having one of three forms: a) a simple substituted unit having the following structure:

Embedded image b) quaternized units having the following structure:

Embedded image (Where X is a suitable charge-balancing counterion); and c) an oxidized unit having the structure:

Embedded image

The modified secondary amine moiety is represented as a W “backbone” unit having one of three forms: a) a simple substituted unit having the following structure:

Embedded image b) quaternized units having the following structure:

Embedded image (Where X is a suitable charge-balancing counterion); and c) an oxidized unit having the structure:

Embedded image

Other modified secondary amine moieties are represented as Y ′ units having one of three forms: a) Simple substituted units having the following structure:

Embedded image b) quaternized units having the following structure:

Embedded image (Where X is a suitable charge-balancing counterion); and c) an oxidized unit having the structure:

Embedded image

The modified tertiary amine moiety is represented as a Y “branched” unit having one of three forms: a) an unmodified unit having the following structure:

Embedded image b) quaternized units having the following structure:

Embedded image (Where X is a suitable charge-balancing counterion); and c) an oxidized unit having the structure:

Embedded image

Certain modified primary amine moieties are designated as Z “terminal” units having one of three forms: a) Simple substituted units having the following structure:

Embedded image b) quaternized units having the following structure:

Embedded image (Where X is a suitable charge-balancing counterion); and c) an oxidized unit having the structure:

Embedded image

It is understood that when any nitrogen position is unsubstituted or unmodified, hydrogen is substituted for R '. For example, primary amine units having 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 end units, V and Z units.
Z "terminal" units are derived from terminal primary amino moiety of the structure -NH _2. The acyclic polyamine backbone according to the invention has only one Z unit and the cyclic polyamine has
No units. Unless the Z unit is modified to form an N-oxide,
The Z "terminal" unit can be replaced by any of the following R 'units. If the Z unit nitrogen is oxidized to the N-oxide, the nitrogen must be modified,
Therefore, R 'is not hydrogen.

The polyamine of the present invention has a main chain R “link” that serves to connect the nitrogen atoms of the main chain.
Includes units. R units include units referred to as "hydrocarbyl R" units and "oxy R" units for the purposes of the present invention. A “hydrocarbyl” R unit is
C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene (the hydroxyl moiety may be located at any position on the R unit chain except for the carbon atom directly connected to the polyamine main chain nitrogen. may be), C ₄ -C ₁₂ dihydroxy alkylene (hydroxyl moieties, with the exception of the directly linked carbon atoms in the polyamine backbone nitrogen, in any two of the carbon atoms on the R unit chain), C ₈ -C ₁₂ dialkylarylene (for the purposes of the present invention, an arylene moiety having two alkyl substituents as part of the connecting chain). For example, a dialkylarylene unit has the formula:

Embedded imageThe above units need not be 1,4-substituted and are 1,2 or 1,3-substituted C₂-C₁₂ Alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof
And more preferably ethylene. "Oxy" R units include-(R¹O
)_xR⁵(OR¹)_x-,-(CH₂CH (OR²) CH₂O)_z(R¹O)_y R¹(OCH₂CH (OR²) CH₂)_w-, -CH₂CH (OR²) CH₂-
,-(R¹O)_xR¹-And mixtures thereof. Preferred R units are C₂-
C₁₂Alkylene, C₃-C₁₂Hydroxyalkylene, C₄-C₁₂Dihydroxya
Lucylene, C₈-C₁₂Dialkylarylene,-(R¹O)_xR¹-, -CH₂ CH (OR²) CH₂-,-(CH₂CH (OH) CH₂O)_z(R¹O)_yR ¹ (OCH₂CH (OH) CH₂)_w-,-(R¹O)_xR⁵(OR¹)_x-Or
R units selected from the group consisting of₂-C₁₂Alkylene, C₃-C ₁₂ Hydroxyalkylene, C₄-C₁₂Dihydroxyalkylene,-(R¹O)_x R¹-,-(R¹O)_xR⁵(OR¹)_x-,-(CH₂CH (OH) CH₂O
)_z(R¹O)_yR¹(OCH₂CH (OH) CH₂)_w-And their mixtures
And even more preferred R units are C₂-C₁₂Alkylene, C₃Hydroxya
Alkylene and mixtures thereof, most preferred are C₂-C₆Archire
It is. The most preferred backbone of the invention comprises at least 50 ethylene R units.
Contains%.

Preferably, the amino-functional polymer of the present invention comprises: a) a linear or non-cyclic polyamine having a main chain of the formula:

Embedded image b) a cyclic polyamine having a main chain of the formula:

Embedded imageAnd mixtures thereof: wherein in at least one of the NR 'units of the polyamine backbone, R' is-(
CH₂CH₂O)_xH, others are hydrogen, C₁-C_{twenty two}Alkyl, C₃-C_{twenty two}Al
Kenil, C₇-C_{twenty two}Arylalkyl, C₂-C_{twenty two}Hydroxyalkyl,-(C
H₂)_pCO₂M,-(CH₂)_qSO₃M, -CH (CH₂CO₂M) CO₂ M,-(CH₂)_pPO₃M,-(R¹O)_mB, -C (O) R³Selected from
Wherein the main-chain linked R units are C₂-C₁₂Alkylene, C₄-C₁₂Alkenylene,
C₃-C₁₂Hydroxyalkylene, C₄-C₁₂Dihydroxyalkylene, C₈-
C₁₂Dialkylarylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵(OR ¹ )_x-,-(CH₂CH (OR²) CH₂O)_z(R¹O)_yR¹(OCH₂ CH (OR²) CH₂)_w-, -C (O) (R⁴)_rC (O)-, -CH₂CH
(OR²) CH₂-And mixtures thereof; wherein R is¹Is C₂-C₆Alkylene, C₃-C₆Alkyl-substituted alkylene
And mixtures thereof; R²Is hydrogen,-(R¹O)_xB
And mixtures thereof; R⁴Is C₁-C₁₂Alkylene
, C₄-C₁₂Alkenylene, C₈-C₁₂Arylalkylene, C₆-C_TenAlly
Selected from the group consisting of ren and mixtures thereof; R⁵Is C₁-C₁₂Archi
Ren, C₃-C₁₂Hydroxyalkylene, C₄-C₁₂Dihydroxyalkylene,
C₈-C₁₂Dialkylarylene, -C (O)-, -C (O) NHR⁶NHC (
O)-, -R¹(OR¹)-, -C (O) (R⁴)_rC (O)-, -CH₂CH
(OH) CH₂-, -CH₂CH (OH) CH₂O (R¹O)_yR¹OCH₂C
H (OH) CH₂-And mixtures thereof; R⁶Is C ₂ -C₁₂Alkylene or C₆-C₁₂Selected from the group consisting of arylene; R
'Unit is hydrogen, C₁-C_{twenty two}Alkyl, C₃-C_{twenty two}Alkenyl, C₇-C_{twenty two}Ally
Rualkyl, C₂-C_{twenty two}Hydroxyalkyl,-(CH₂)_pCO₂M,-(C
H₂)_qSO₃M, -CH (CH₂CO₂M) CO₂M,-(CH₂)_pPO₃ M,-(R¹O)_xB, -C (O) R³Selected from the group consisting of
B is hydrogen, C₁-C₆Alkyl,-(CH₂)_qSO₃M,-(CH ₂ )_pCO₂M,-(CH₂)_q(CHSO₃M) CH₂SO₃M,-(CH₂ )_q(CHSO₂M) CH₂SO₃M,-(CH₂)_pPO₃M, -PO₃M
And mixtures thereof; R³Is C₁-C₁₈Alkyl, C ₇ -C₁₂Arylalkyl, C₇-C₁₂Alkyl-substituted aryl, C₆-C₁₂Ants
M is hydrogen, or a charge barrier.
X is a water-soluble anion sufficient to fill the lance;
M has a value from 2 to about 700; n has a value from 0 to about 350;
Has a value of 6; q has a value of 0-6; r has a value of 0 or 1;
Has a value of 0 or 1; x has a value of 1-100; y has a value of 0-100
Has; z has a value of 0 or 1.

Preferably, x has a value in the range 1-20, preferably 1-10. Preferably, R is C₂-C₁₂Alkylene, C₃-C₁₂Hydroxyalkylene,
C₄-C₁₂Dihydroxyalkylene, C₈-C₁₂Dialkylarylene,-(R ¹ O)_xR¹-,-(R¹O)_xR⁵(OR¹)_x-,-(CH₂CH (OH)
CH₂O)_z(R¹O)_yR¹(OCH₂CH (OH) CH₂)_w-, -CH₂ CH (OR²) CH₂-And mixtures thereof.
Preferably R is C₂-C₁₂Alkylene, C₃-C₁₂Hydroxyalkylene, C₄-
C₁₂Dihydroxyalkylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵(O
R¹)_x-,-(CH₂CH (OH) CH₂O)_z(R¹O)_yR¹(OCH₂ CH (OH) CH₂)_w-Selected from the group consisting of
Preferably R is C₂-C₆Alkylene, C₃Hydroxyalkylenes and them
Are selected from the group consisting of: The most preferred R unit is C₂-C₆Archire
It is.

Preferably, R¹Is C₂-C₆Alkylene, C₃-C₆Alkyl-substituted alkylene
Selected from the group consisting of¹Is Echire
It is. Preferably, R²Is hydrogen. Preferably, R³Is C₁-C₁₂Alkyl, C₇-C₁₂Alkyl arylene and
And mixtures thereof, more preferably R³Is C₁-C₁₂A
Alkyl and mixtures thereof, most preferably R³Is C ₁ -C₆It is selected from the group consisting of alkyl and mixtures thereof. R³Nitori
The most preferred group is methyl. Preferably, R⁴Is C₁-C₁₂Alkylene, C₈-C₁₂Aryl alkylene
And mixtures thereof, more preferably R⁴Is C₂-C₆ Selected from the group consisting of⁴Is ethylene or butylene
. Preferably, R⁵Is ethylene, -C (O)-, -C (O) NHR⁶NHC (O
)-, -R¹(OR¹)_y-,-(CH₂CH (OH) CH₂O)_z(R¹O) _y R¹-(OCH₂CH (OH) CH₂)_w-, -CH₂CH (OH) CH₂-
And mixtures thereof, more preferably R⁵Is -CH₂ CH (OH) CH₂-.

Preferably, the R ′ units are hydrogen, C₃-C_{twenty two}Hydroxyalkyl, benzyl, C ₁ -C_{twenty two}Alkyl,-(R¹O)_xB, -C (O) R³,-(CH₂)_pCO₂ ⁻ M⁺,-(CH₂)_qSO₃ ⁻M⁺, -CH (CH₂CO₂M) CO₂M and
Or a mixture thereof, and more preferably, the R ′ unit is hydrogen, C ₁ -C_{twenty two}Alkyl,-(R¹O)_xB, -C (O) R³And their mixtures?
And most preferably, the R 'unit is-(R¹O)_xB.

Preferably, the B units are hydrogen, C₁-C₆Alkyl,-(CH₂)_qSO₃M,
-(CH₂)_q(CHSO₃M) CH₂SO₃M,-(CH₂)_q(CHSO₂ M) CH₂SO₃Selected from the group consisting of M and mixtures thereof, more preferably
Or B is hydrogen,-(CH₂)_qSO₃M,-(CH₂)_q(CHSO₃M) CH ₂ SO₃M,-(CH₂)_q(CHSO₂M) CH₂SO₃M and their mixtures
And B is most preferably selected from the group consisting of hydrogen.
, Where q has a value of 0-3.

M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance. For example, the sodium cation - _{(CH 2)} p CO ₂ M and - _{(CH 2)} satisfies equal _{q SO 3 M, - (CH} 2) p CO 2 Na , and - _{(CH 2)} q S
This results in an O ₃ Na moiety. 2 or more monovalent cations (sodium, potassium, etc.)
Can also be combined to satisfy the required chemical charge balance. However, two or more anionic groups may be charge balanced by divalent cations, or two or more monovalent cations may be required to meet the charge requirements of the polyanionic group. For example, it substituted with sodium atoms _{- (CH 2) p PO 3} M moiety of the formula _- with a _{(CH 2) p PO 3 Na} 3. Divalent cations such as calcium (Ca ²⁺ ) or magnesium (Mg ²⁺ ) may also be used in place of or in combination with other suitable monovalent water-soluble cations. Preferred cations are sodium and potassium, more preferably sodium. X is a water-soluble anion such as chlorine (Cl ⁻ ), bromine (Br ⁻ ) and iodine (I ⁻ ), or X is sulfuric acid (SO ₄ ²⁻ ) and methosulfate (CH ₃ SO ₃ ⁻ ). Such a negatively charged group. When no modification or substitution has been made at the nitrogen, a hydrogen atom remains as the moiety representing R '.

Preferred “oxy” R units are R¹, R²And R⁵It is further specified in units. Good
Preferred "oxy" R units are the preferred R¹, R²And R⁵Includes units. Book
A preferred agent of the invention is ethylene, R¹Contains at least 50% of units. Good
Good R¹, R²And R⁵The units are combined with “oxy” R units to form
Such preferred "oxy" R units are formed. i) More preferred R⁵To-(CH₂CH₂O)_xR⁵(OCH₂CH₂)_x-
If you replace it inside,-(CH₂CH₂O)_xCH₂CHOHCH₂(OCH₂C
H₂)_xIi) preferred R¹And R²To-(CH₂CH (OR²) CH₂O)_z-(R ¹ O)_yR¹O (CH₂CH (OR²) CH₂)_w-If replaced in-,-(C
H₂CH (OH) CH₂O)_z-(CH₂CH₂O)_yCH₂CH₂O (CH₂ CH (OH) CH₂)_wIii) preferred R²To -CH₂CH (OR²) CH₂-Replace in -C
H₂CH (OH) CH₂-Is formed.

When a V, W or Z unit is oxidized, ie when the nitrogen is an N-oxide, the R ′ unit is not a hydrogen atom. For example, the backbone or branch does not contain units of the following structure:

Embedded image In addition, when the V, W or Z unit is oxidized, ie when the nitrogen is an N-oxide, the R 'unit does not contain a carbonyl moiety directly attached to the nitrogen atom. According to the present invention, the R 'unit-C (O) R ³ moiety is not attached to the N-oxide modified nitrogen, ie, there is no N-oxide amide having the following structure, or combinations thereof:

Embedded image Further, it is mentioned that in the main chain formula described herein, NN bonds are not included.

The formula index has the following values: p has a value of 1 to 6; q has a value of 0 to 6
Has a value of 0 or 1; w has a value of 0 or 1; x has a value of 1
Y has a value of 0-100; z has a value of 0 or 1
M has a value of 2 to 700, preferably 4 to 400; n is 0 to 350,
Preferably it has a value of 0 to 200; m + n has a value of at least 5. Preferred
In particular, x has a value in the range 1-20, preferably 1-10. Preferably, the compounds of the present invention are polymers having an m: n ratio of at least 0.5: 1.
But not only in the high range of 10: 1, but also in linear polymers (where n is 0).
Equal), preferably the ratio is from 1: 1 to 2: 1. m: n
Is 2: 1, the ratio of primary: secondary: tertiary amine moieties, ie, -RNH ₂ , -RNH and -RN moieties are 1: 2: 1. The R units are preferably ethylene, 1,2-propylene, 1,3-propylene and
And mixtures thereof, and more preferably ethylene.
The R units serve to connect the amine nitrogens of the main chain.

Preferred polyamines of the invention have a backbone in which less than 50% of the R groups contain 4 or more carbon atoms. The use of 2 and 3 carbon spacers as R moieties between nitrogen atoms in the backbone is advantageous in controlling the fabric appearance enhancement of the molecule.
In a further preferred embodiment of the present invention, the portion having 4 or more carbon atoms is less than 25%. In an even more preferred backbone, moieties having 4 or more carbon atoms are 10
%. The most preferred backbone consists of 100% ethylene moieties.

The amino-functional polymers of the present invention have a homogeneous or heterogeneous polyamine backbone, preferably a uniform backbone. For the purposes of the present invention, the term "homogeneous polyamine backbone" is defined as a polyamine backbone having identical R units (ie, all ethylene). However, this same definition does not exclude polyamines with other heterogeneous units, including polymer backbones that are present due to the artificial nature of the chosen chemical synthesis method. For example, ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimine, and thus a sample of polyethyleneimine having one hydroxyethyl moiety due to the polymerization "initiator" is also uniform for the purposes of the present invention. It is known to those skilled in the art that it is believed to have a polyamine backbone. For purposes of the present invention, the term "heterogeneous polymer backbone" refers to one or more alkylene or substituted alkylene moieties taken together as R units,
For example, a polyamine backbone, which is a complex of ethylene and 1,2-propylene units.

The other polyamine constituting the main chain of the compound of the present invention is usually polyalkyleneimine (PAI), preferably polyethyleneimine (PEI). PEI constituting a preferable main chain of the polyamine of the present invention 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. . A specific method for manufacturing PEI is as follows.
U.S. Pat. No. 2,182,306; 1, issued to Ulrich et al. On Dec. 5, 939;
US Patent 3,033,746; 19 issued May 8, et al., Issued May 8, 962.
Esselmann et al., US Pat. No. 2,208,095, issued Jul. 16, 40;
US Patent No. 2,806,839 to Crowther issued September 17, 1957;
And Wilson US Pat. No. 2,553,69 issued May 21, 1951.
No. 6 (all incorporated herein by reference). In addition to linear and branched PEI, the present invention also includes cyclic amines typically formed as synthetic products. The presence of these substances may increase or decrease, depending on the conditions chosen by the trader. Commercially available alkoxylated amino functional polymers suitable for use in the present invention are MW20
Hydroxyethylated poly (ethylene imine) and Aldr from Polysciences
80% hydroxyethylated poly (ethylene imine) from ich.

Method for Removing Aldehydes from Ethoxylated Amino-Functional Polymer Raw Materials In order to obtain ethoxylated amino-functional polymers of good color and odor, typical methods for removing aldehydes are quaternary or aldehyde formation. By inhibition or removal of the formed aldehyde.

The following relates to ethoxylated polyamines and methods for inhibiting the formation of malodors or removing malodors therefrom. Controlling the level of primary ethoxylation: "Underhydroxyethylation" Typically, the first step in the process of ethoxylated polyamines is performed without the need for a base catalyst. This fact is mainly due to the high reactivity of primary and secondary amines compared to alcohols. However, when the more reactive primary amino moiety reacts with ethylene oxide and is converted to "hydroxyethylamine", the remainder is hindered and the less reactive secondary amine successfully undergoes hydroxyethylation. Takes more downtime above. During this important time when essentially 80-90% of the amino NH hydrogen is hydroxyethylated, the undesirable side reactions mentioned above often increase.

Thus, one means for limiting the amount of malodorous aldehydes and aldehyde precursors formed in the first or “hydroxyethylation” step is
The purpose is to limit the degree of hydroxyethylation of the polyamine before adding the base catalyst. Thus, one can minimize malodor-causing aldehydes by adding to the polyamine at least about 5% of the amount of ethylene oxide required to hydroxyethylate all or the polyamine backbone NH hydrogen. . Preferably, the amount of ethylene oxide added is less than about 75%, more preferably less than about 85%, and most preferably less than about 90%. Thus, the trader can effectively use less than a stoichiometric amount of ethylene oxide in the first abasic catalytic step of the process of the present invention to effectively trim the addition of ethylene oxide to the polyamine nitrogen. The formation of an ethoxylated polyamine having an average ethoxylation of at least about E _0.6 , preferably at least about E _0.75 , more preferably at least about E _0.85 , and most preferably at least about E _0.9 is a first step of the process of the present invention. As a step, it is a suitable method for controlling the formation of aldehydes which leads to malodor and color formation.

[0048] Typical methods of removal of the resulting aldehyde is as follows: 1. Post-treatment with sulfite or equivalent One method involves sulphating a solution of alkoxylated PEI prior to acidification so that the solution to be acidified contains about 0.5-1% w / w of added sodium sulfite. Treatment with a salt or equivalent, preferably the sodium salt. The specific method is useful at all pHs, especially at acidic pH. Typically, the solution of amino-functional polymer is made at a higher concentration than the desired final concentration and then at the end of the operation to the desired final concentration. A portion of the sodium sulfite stock solution is added to this solution of the polymer and the mixture is slowly added with concentrated HCl while controlling the heat release with a chill (a jacketed beaker stream or ice pillow) until the desired pH is obtained. Acidified. Of course, variations in which the solution is acidified and then treated with sodium sulfite are also suitable.

[0049] 2. Use of Borohydride and / or Borohydride-Like Reducing Agent Another method for improving aldehyde formation involves treating the crude reaction mixture with a borohydride reducing agent at any stage. The initial hydroxyethylation is typically performed without the aid of a catalyst, thanks to the nucleophilicity of the amino moiety, but the number of more reactive primary amino units is less than the less reactive secondary amino. As it decreases relative to units, the rate of hydroxyethylation decreases and the opportunity for aldehyde formation increases.

Contacting the reactants with a borohydride reducing agent during this first abasic catalyst first step can provide a means by which any aldehydes formed can be removed. For example, a trader may include an appropriate amount of a borohydride reagent in the reaction process mixture of step (a). Non-limiting examples of borohydride reagents include sodium borohydride, lithium borohydride, and the like. The borohydride reagent may be added as a work-up after the hydroxyethylation step or, if additional ethoxylation is performed, at the time of addition of the strong base catalyst. The addition of the borohydride may occur at any subsequent ethoxylation stage, including after completion of the strong base catalyzed ethoxylation step, or may occur before or after neutralization of the strong base catalysis. Multiple additions of borohydride at different points in the synthesis are also included in the present invention. The borohydride may be used in a continuous process or on a solid support or an inert, filterable solid support. Those skilled in the art may appropriately combine any of the above techniques using borohydride salts to improve malodor and color. In addition, methods not specifically mentioned above, wherein the borohydride salt is contacted with the ethoxylated polyamine during the formation or purification of the ethoxylated polyamine, are also considered to be included in the process.

[0051] 3. Steam Stripping and Evaporation of Malodorous Substances A) Water Evaporation : Another process for removing malodorous compounds from ethoxylated polyamines, as described above, uses up to one weight equivalent of liquid water that is converted to steam in situ. The process can be operated in a continuous, semi-continuous or batch manner. It has been found that when water is introduced in a particular manner and / or in a particular manner, the removal of undesirable volatile impurities in the ethoxylated polyamine is also improved.
However, the level of impurities formed in the process of ethoxylating the polyamine may set the operating conditions for the deodorization process. For example, some operating conditions may be necessary as impurity levels in hydroxyethylated polyamines increase, especially in the case of continuous or semi-continuous processes. The amount of water used in the process is typically less than 1 weight equivalent of the ethoxylated polyamine,
Preferably it is less than 0.5 weight equivalent. For example, 500 g of water is usually sufficient for deodorizing 1000 g of ethoxylated polyamine. However, the original polyamines, partially hydroxyethylated polyamines and fully hydroxyethylated polyamines are typically highly water-soluble substances, so that vendors do not exclude all deodorized water May be selected, so that more than the stoichiometric amount of water can be used in this type of process.

In the simplest case, the modified malodorous ethoxylated polyamine is a solid, gel,
It is placed in a container in the form of a viscous syrup or liquid. Alternatively, a vessel in which hydroxyethylation has been performed can also be used as a suitable reaction vessel. The vessel may be open to the atmosphere, but is typically a closed system suitable for gas sparge, vacuum, pressurization and other typical processing aids compatible with deodorization of ethoxylated polyamines. .
Although some agitation may be used in this water evaporation process, it may be advantageous for the trader to utilize external mechanical agitation. This is especially true for low temperature processes or processes that use highly water absorbing ethoxylated polyamines.

After the malodor containing substrate is placed in the deodorizing vessel, a heat source is used to raise the temperature of the ethoxylated polyamine above the boiling point of water. For the purposes of the present invention, the term "above the boiling point of water" means the temperature at which the injected liquid water is vaporized into steam. In addition, the vaporization of the injection water does not cool the surrounding heat transfer medium (typically the ethoxylated polyamine to be deodorized) enough to reduce the deodorization rate or change the rate of the injection water. As such, the temperature must be high enough. The boiling point of water observed under standard atmospheric pressure conditions appears to be 100 ° C. However, processes performed at elevated or reduced pressure will clearly have a regulated "boiling point of water".

Heating can be accomplished by jacketing the container, by applying steam or an electric heating coil, or by other means where the temperature is moderately controlled. To ensure that the material is maintained at a constant temperature, a uniform distribution of heat needs to occur. When the desired temperature is reached, the water is introduced at a rate such that the liquid water is completely vaporized by the surrounding medium into steam. This water, in turn in the form of steam, serves to extract volatile aldehyde malodorous compounds as it leaves the solution. The rate at which liquid water is introduced into the container must not cause the polyamine to cool to such an extent that liquid water accumulation occurs.

Alternatively, a predetermined amount of water may be added to the container containing the ethoxylated polyamine to be deodorized. The container may be at room temperature or at a temperature below the boiling point of water. The vessel is then heated to a temperature above the boiling point of water. The trader may choose to remove all of the water present, or the trader may choose to keep more water present than is necessary to deodorize the ethoxylated polyamine. For example, 0.
Five weight equivalents of water may be needed to remove malodorous substances from a sample of ethoxylated polyamine, but a trader may add a 0.5 weight equivalent excess of water. 0.
After removing 5 weight equivalents of water, the now deodorized ethoxylated polyamine is reduced to 0%.
. Contains 5 weight equivalents of water. This water may be desirable for subsequent formulation of the ethoxylated polyamine or may be required for another processing step. Therefore,
The process of the present invention does not require removal of any added water from the polyamine.

However, the amount of heat and the means of water introduction used are such that when the temperature is measured under standard atmospheric conditions, at least about 110 to about 200 ° C.
May be insignificant as long as it is exposed to a certain amount of water at a deodorizing temperature of preferably about 135 to about 175C, more preferably about 140 to about 160C.

The initial temperature at which the deodorization process is performed may be higher or lower than the final deodorization temperature. In one preferred embodiment of this malodor removal technique, the temperature of the ethoxylated polyamine is raised to a minimum temperature sufficient to effect deodorization, and the temperature is increased stepwise or constant during the process until a final deodorization temperature is obtained. I will increase it by the ratio. This constant increase in temperature or "temperature gradient" is from about 0.01 to about 10 ° C / min.
The reaction is preferably performed at a rate of about 0.1 to about 5 ° C / min, more preferably at a rate of about 0.1 to about 1 ° C / min. Typically, a temperature change of about 100 ° C is suitable for deodorizing the polyamine, preferably the temperature change is about 60 ° C during the deodorization process.

It has surprisingly been found that the residence time during which the introduced water is in the liquid state before evaporation is an important variable element under the conditions of the process. The liquid phase residence time should be adjusted to match the type of ethoxylated polyamine present or the degree of deodorization required.
It can be adjusted by the trader. This ability to adjust the evaporation rate allows for wide control over liquid water contact time. For example, one skilled in the art will recognize that longer liquid water / impurity contact times are preferred for removing certain malodors. This control can be performed by adjusting the water introduction speed and changing the temperature characteristics of the deodorizing container.

Unlike the deodorization processes known to edible fat processors, it is not important to limit the amount of water used in the removal of malodorous substances by the process. This is especially important when high temperatures are required to remove unwanted malodorous compounds. Unlike the deodorization of edible fats and oils having hydrolyzable triglyceride ester linkages, the process of the present invention takes advantage of the surprisingly stable properties and water compatibility of the ethoxylated polyamines described above.

The water may be introduced into the reaction vessel at any depth, especially if thorough stirring or mixing of the ethoxylated polyamine is performed. Traders may rely on agitation caused by evaporation of water and escape of generated steam to efficiently mix the contents of the deodorization vessel. The source of water is by a single water inlet at the bottom of the deodorizing vessel, along a removable vertical tube with multiple water inlets extending from the bottom of the vessel to a level just below the surface of the polyamine, or It may be introduced by a plurality of water inlets along the surface of the container itself. The form and means by which water is introduced into the container containing the ethoxylated polyamine does not affect the efficacy of the process. B) Gas Purge Process : This method also relates to a process for removing malodorous compounds from ethoxylated polyamines by using a certain amount of non-condensable gas which can be operated continuously, semi-continuously or batchwise. Examples of non-condensable gases suitable for use in the present process are helium, argon, carbon dioxide and nitrogen. However, this list is not an exhaustive list of all gases suitable for the present invention. It has been found that removal of undesirable volatile impurities in ethoxylated polyamines is also improved when non-condensable gases are introduced in certain ways and / or in certain ways. However, the level of impurities in the starting ethoxylated polyamine may determine the operating conditions of the deodorization process. For example, as the level of impurities in the starting material supplied to the deodorization vessel increases, some operating conditions may be required. The stripping gas is introduced by means such as sparging or dispensing means having a particular orifice size, preferably located in at least one of the upper, middle and lower sections of the vessel. However, both the amount of heat used and the means of introducing stripping gas require that the starting material in the deodorization vessel be at least about 11
0 to about 200 ° C, preferably about 135 to about 175 ° C, more preferably about 140 to
May be insignificant as long as it is exposed to a certain amount of stripping gas at a deodorization temperature of about 160 ° C. Typically, a temperature change of about 100 ° C is suitable for deodorizing the ethoxylated polyamine, preferably the temperature change is about 60 ° C during the deodorization process.

[0061] The amount of non-condensable gas entering the vessel should be at least the minimum required to produce a deodorized ethoxylated polyamine product having the desired characteristics described herein. The minimum amount of non-condensable gas will vary depending on the type of deodorizing vessel used, the type and degree of modification performed on the polyamine backbone, and the reaction conditions used to effect the modification. The invention does not limit not only the volume of gas introduced per unit time, but also the amount of gas introduced per unit mass of ethoxylated polyamine, and the volume of gas introduced per unit mass of water.

C) Water Evaporation and Gas Purge : The water evaporation process may be combined with a gas purge process. Typically, this combination is used because of deodorizing vessel geometry, the sensitivity of ethoxylated polyamines to decomposition by air, or to enhance the efficacy of low temperature deodorizing. Gas purging can begin before or after the introduction of water into the vessel, and can begin or end at any temperature point.

In addition, vacuum may be used to assist in the deodorization process. The vacuum is created by a pump, a steam injector or any other suitable means for creating a vacuum. The degree of vacuum may be varied or constant during the deodorization process. The degree of vacuum present during the deodorization process ranges from slightly vacuum to full vacuum. For the purposes of the present invention, the term "slight vacuum" is defined as a pressure reduction of the deodorization vessel of less than 10% below atmospheric pressure. For the purposes of the present invention, the term "complete vacuum" is defined as 0
. It is defined as the pressure inside the deodorizing vessel less than 1 mmHg. All other levels of vacuum are equally suitable for use in the process.

Method for Determining the Amount of Total Aldehydes Present in the Raw Material : When an ethoxylated amino-functional polymer is treated in accordance with the present invention, the total aldehyde is less than the maximum amount, expressed as the presence of acetaldehyde, 10
It is desirable to determine the exact amount of aldehyde present in the polymer so that it is certainly present at less than 0 ppm, preferably less than 50 ppm, more preferably less than 25 ppm.

Methods for determining the total amount of aldehydes present in a feed, including those hidden as hemiacetals, acetals or enamines, are well known in the art, as described in any of the following different ways: : Ann-Chim Rome, 1992,82 (5-6): 349-356, Chiavari G, Torsi G, Asmundsdottir AM
, "Different methods for HPLC analysis of aldehydes in aqueous solusions"
;Fresenius' journal of analytical chemistry, 1993, pp. 491-494, GOEBEL R, KRU
GA, KELLNER R, "Spectrophotometric flow injection analysis of formaldehyd
e in aqueous solutions using 3-methyl-2-benzthiazolinone hydrazone "; Nonwovens, Symposium Notes of the Technical Association of the pulp and
Paper Industry, 1988, Publ by TAPPI Press, Atlanta, GA, USA, p.29-33 from Lar
son, Gary; Staub, Reinhaultung der Luft. Zeitschriftenreihe Reinhaltung der Luft, Vo
lume 43, Issue 3, pp.95-101, Baumbach, G, "Messverfahren fuer Aldehyd-Emissio
nen in Verbrennungsabgasen "; GIT-Fachz-Lab. Jan 1996,40 (1): 49-50, Karst U," Determination of aldehydes a
nd ketones with 2,4-dinitrophenylhydrazine as derivatizing agent "

A typical titrant is 3-methyl-2-benzothiazolinone hydrazone hydrochloride (M
BTH). The concentration mol / L of total aldehyde obtained from the analysis of the polymer is converted to ppm (w / w) using the molecular weight of acetaldehyde as a control. The ethoxylated amino-functional polymer thus obtained can be used in various applications where care for the color of the fabric is desired. Typical examples of such compositions include stand-alone products, such as for use as pre and / or post cleaning additives. It is a laundry and cleaning composition as well as a rinse-added fabric softener composition and a dryer-added composition that exhibit softening and / or antistatic effects.
For example, it can be used in a completely formulated composition including a sheet). When used in such compositions of the present invention, the typical amount of amino-functional polymer used is at least 0.01%, preferably at least 1% by weight of the composition,
More preferably 1 to 50%, most preferably 1 to 10%, most preferably 1 to 5% by weight of the composition. The choice of components that are typical for use in such compositions will depend on their end use. For example, when formulated as a softening composition, it includes a fabric softening compound.

Typical compounding levels of the softening compound in the fabric softening compound softening composition are from 1 to 80 of the composition.
%, Preferably 5 to 75%, more preferably 15 to 70%, even more preferably 19 to 65%. The fabric softener compound is preferably selected from cationic, nonionic, amphoteric or anionic fabric softening components. A typical example of a cationic softening component is a quaternary ammonium compound or an amine precursor thereof as described below.

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

Embedded image Or the following formula:

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

Embedded image Each R unit is independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl and mixtures thereof, preferably methyl or hydroxyalkyl; each R ¹ unit is independently linear or branched C ₁₁ -C ₂₂ alkyl, linear or branched C ₁₁ -
C ₂₂ alkenyl, and mixtures thereof; ^{R 2} is _hydrogen, C 1 -C _{4 alkyl,} C 1 -C ₄ hydroxyalkyl, and mixtures thereof; X is compatible with fabric softener active and auxiliary ingredients anion Index m is 1-4, preferably 2, and index n is 1-4, preferably 2.

An example of a preferred fabric softener is a mixture of quaternized amines having the formula:

Embedded image Wherein R is preferably methyl; R ¹ is a straight or branched alkyl or alkenyl chain having at least 11 atoms, preferably at least 15 atoms. In the example fabric softener described above, the unit -O ₂ CR ¹ represents a fatty acyl unit typically 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, peanut oil, sunflower oil, corn oil, It is derived from soybean oil, tall oil, rice bran oil and the like, and mixtures of these oils.

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

Embedded image Wherein R, R ¹ , X and n are as described above for formulas (1) and (2); Q has the following formula:

Embedded image These preferred fabric softening activators are formed from the reaction of an amine with a fatty acyl unit to form an amine intermediate having the formula: R—N — [(CH ₂ ) _n —Z] ₂ (above formula medium R is preferably methyl, Z is -OH, is -NH ₂ or a mixture thereof), is quaternized then final softening active agents.

Non-limiting examples of preferred amines used to form the DEQA fabric softening activators according to the present invention include methyl bis (2-hydroxyethyl) amine having the formula:

Embedded image Methyl bis (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 Triethanolamine having the formula:

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

Embedded image There is.

The X ⁽⁻⁾ of the counterion is a softener-compatible anion, preferably a strong acid such as chloride, bromide, methyl sulfate, ethyl sulfate, sulfuric acid, nitric acid, and more preferably an anion of chloride or methyl sulfate. The anion is less preferred, but may be divalent, in which case X ^(-) represents half of the group.

Tallow and canola oil are convenient and inexpensive sources of fatty acyl units suitable for use in the present invention as R ¹ units. The following are non-limiting examples of quaternary ammonium compounds suitable for use in the compositions of the present invention. The term "tallowoil" as used below,
R ¹ units are derived from tallow triglyceride source, indicating that a mixture of fatty acyl units. Similarly, the use of the term canolyl relates to a mixture of fatty acyl units derived from canola oil.

TABLE I Fabric softener N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride N, N-di (canolyloxyethyl) -N, N-dimethylammonium chloride N, N -Di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride N, N-di (canolyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium chloride N , N-Di (2-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N, N-di (2-canolyloxy-2-oxoethyl) -N, N-dimethylammonium chloride N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N
-Dimethylammonium chloride N, N-di (2-canolyloxyethylcarbonyloxyethyl) -N, N-
Dimethyl ammonium chloride N- (2-tallowyloxy-2-ethyl) -N- (2-tallowyloxy-
2-oxoethyl) -N, N-dimethylammonium chloride N- (2-canolyloxy-2-ethyl) -N- (2-canolyloxy-2-
Oxoethyl) -N, N-dimethylammonium chloride N, N, N-tri (tallowyloxyethyl) -N-methylammonium chloride N, N, N-tri (canolyloxyethyl) -N-methylammonium chloride N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl) -N
, N-Dimethylammonium chloride N- (2-canolyloxy-2-oxoethyl) -N- (canolyl) -N, N
-Dimethylammonium chloride 1,2-ditaloyloxy-3-N, N, N-trimethylammoniopropane chloride 1,2-dicanolyloxy-3-N, N, N-trimethylammoniopropane chloride and the above active agent mixture

Another example of a quaternary ammonium flexible compound is methylbis (tallowamidoethyl) (
2-hydroxyethyl) ammonium methylsulfate and methyl bis (hydrogenated tallow amide ethyl) (a 2-hydroxyethyl) ammonium methylsulfate, these materials are available from Witco Chemical Company, respectively the trade name Varisoft ^R 222 and Varisoft ^R 110 ing. Particularly preferred is N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride, the tallow chain of which is at least partially unsaturated. The level of unsaturation contained in tallow, canola or other fatty acyl unit chains can be determined by the iodine value (IV) of the corresponding fatty acid, preferably 5 to 5 in the present invention.
It should be in the range of 100 and distinguishes between two categories of compounds having an IV below or above 25.

In practice, in compounds having an iodine value of 5 to 25, preferably 15 to 20, derived from tallow fatty acids and having the formula:

Embedded image It has been found that cis / trans isomer weight ratios greater than about 30/70, preferably greater than about 50/50, and more preferably greater than about 70/30 exhibit the best enrichment. For compounds of this type made from tallow fatty acids having an iodine value of greater than 25, the ratio of cis / trans isomers was found to be less important, unless very high concentrations were required.

Other suitable examples of fabric softening agents are the terms “cocoyl, palmyl, lauryl, oleyl,” in which the terms “tallowyl” and “canolyl” in the above example correspond to the triglyceride source from which the fatty acyl units are derived. Derived from fatty acyl groups such as "ricinoleyl, stearyl, palmityl". These alternative fatty acyl sources may be fully saturated or, preferably, have at least partially unsaturated chains. The R units as described above are preferably methyl, but suitable fabric softening activators include
The term "methyl" in the above example of Table II is described by replacing the units "ethyl, ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl". The counterion X in the examples of Table II can be suitably replaced by bromide, methylsulfate, formic acid, sulfuric acid, nitric acid and mixtures thereof. In fact, the anion X merely exists as a counterion of the positively charged quaternary ammonium compound. The scope of the present invention is not limited to any particular anion.

For the above ester fabric softeners, the pH of the composition is an important parameter of the present invention. In fact, it affects the stability of the quaternary ammonium or amine precursor compound, especially under long-term storage conditions. The pH as defined in this context is measured on the neat composition at 20 ° C. Although these compositions can be handled at a pH of less than about 6.0 for the best hydrolytic stability of these compositions, the neat pH measured under the above conditions is preferably in the range of about 2.0 to about 5, preferably Is 2.5 ~
4.5, preferably in the range of about 2.5 to about 3.5. The pH of these compositions can be adjusted by adding Bronsted acids.

Examples of suitable acids include inorganic mineral acids, carboxylic acids, especially low molecular weight (C₁-C₅) Cal
There are boric acid and alkyl sulfonic acids. HCl, H₂SO ₄ , HNO₃And H₃PO₄There is. Suitable organic acids include formic acid, acetic acid, citric acid
There are acids, methylsulfonic acid and ethylsulfonic acid. The preferred acid is citric acid
, Hydrochloric acid, phosphoric acid, formic acid, methylsulfonic acid and benzoic acid. The use of ethoxylated amino-functional polymers in this context is particularly beneficial
. Indeed, as noted above, the softening composition is preferably in the above pH range, i.e., acidic
Used under conditions. Under such acidic conditions, the aldehydes present in the raw materials
Ethoxylated amino-functional polymers that have not been treated to remove hide
These undesired by-products cause malodor and discoloration. Of the present invention
For amino-functional polymers, this is not the case and the polymer
It is stable, as are the odors and colors produced by them.

As used in the present invention, when a diester is specified, it contains the monoester normally present in the manufacture. For softening, under no / low detergent carryover laundering conditions, the percentage of monoester is as low as possible, preferably about 2%.
. Should be less than 5%. However, under high detergent carryover conditions, small amounts of monoester are preferred. The overall ratio of diester to monoester is about 10
0: 1 to about 2: 1, preferably about 50: 1 to about 5: 1, more preferably about 13:
1 to about 8: 1. Under high detergent carryover conditions, the di / monoester ratio is preferably about 11: 1. The level of monoester present can be controlled in making the softener compound. Mixtures of activators of formulas (1) and (2) may also be prepared. 2) Still other quaternary ammonium fabric softening compounds suitable for use in the present invention had a 2 or more long chain acyclic aliphatic C ₈ -C ₂₂ hydrocarbon group, or one of the groups and arylalkyl groups cation Nitrogenous salts, which can be used alone or as part of a mixture and are selected from the group consisting of: (i) acyclic quaternary ammonium salts having the formula:

Embedded image In the above formula, R ⁴ is a non-cyclic aliphatic C ₈ -C ₂₂ hydrocarbon group, R ⁵ is a C ₁ -C ₄ saturated alkyl or hydroxyalkyl group, and R ⁸ is a group consisting of R ⁴ and R ⁵ groups. 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 described above; (iii) mixtures thereof Examples of cationic nitrogen-containing salts of the above class are well-known. Dialkyl dimethyl ammonium salts such as ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated tallow) dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride. Di (hydrogenated tallow) dimethylammonium chloride and ditallowdimethylammonium chloride are preferred. Examples of commercially available dialkyldimethylammonium salts that can be used in the present invention include di (hydrogenated tallow) dimethylammonium chloride (trade name Adogen ^R 442), ditallow dimethyl ammonium chloride (trade name Adogen ^R 470, Praepagen ^R 3445), distearyl dimethyl an ammonium chloride (trade name Arosurf ^R TA-100), all Witco Chemic
Commercially available from al Company. Dibehenyl dimethyl ammonium chloride is
Kemamine trade name by Humko Chemical Division of Witco Chemical Corporation
Sold as Q-2802C. Dimethyl stearyl benzyl ammonium chloride, trade name by Witco Chemical Company Varisoft ^R SDC, and Onyx C
Sold as Ammonyx ^R 490 by the Chemical Company.

B) Amine Fabric Softening Active Compounds The amine fabric softening compounds suitable for use in the present invention in amine or cationic form are selected from: (i) hydroxyalkylalkylenediamines, dialkylenetriamines and the like. A reaction product of a polyamine and a higher fatty acid selected from the group consisting of: These reaction products are mixtures of several compounds in view of the polyfunctional structure of the polyamine. Preferred component (i) is a nitrogen-containing compound selected from the group consisting of reaction product mixtures or partially selected components of the mixture.

One preferred component (i) is a compound selected from the group consisting of substituted imidazoline compounds having the formula:

Embedded imageR in the above formula⁷Is acyclic aliphatic C_Fifteen-C_{twenty one}A hydrocarbon group;⁸Is divalent C₁-C ₃ It is an alkylene group. Ingredient (i) is a Mazamide from Mazer Chemicals^R6 or Sandoz Color
Ceranine for sale by s & Chemicals^RHC; trade name Alka from Alkaril Chemicals, Inc.
zine^RST or Schercozolone from Scher Chemicals, Inc.^RSteer sold at S
Rylhydroxyethylimidazoline; N, N ″ -ditalycoyldiethylene
Triamine; 1-tallowamidoethyl-2-tallowimidazoline (previous structure
And R¹Is aliphatic C_Fifteen-C₁₇A hydrocarbon group;⁸Is a divalent ethylene group
). Certain component (i) is most suitable for Bronsted acid dispersing aids having a pKa value of about 4 or less.
Although initially dispersed, the pH of the final composition should be less than about 6. Part of
Preferred dispersing aids are hydrochloric acid, phosphoric acid or methyl sulfonic acid.

N, N ″ -Ditallowalcoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are both reaction products of tallow fatty acids and diethylenetriamine and are cationic fabric softeners methyl-1-tallowamide It is a precursor of ethyl-2-tallowimidazolinium methyl sulfate ("Cat
ionic Surface Active Agents as Fabric Softeners ", RREgan, Journal of the
American Oil Chemical's Society, January 1978, pages 118-121). N,
N "-Ditalowalcoyldiethylenetriamine and 1-tallow (amidoethyl) -2-tallowimidazoline are obtained from Witco Chemical Company as experimental compounds. Methyl-1-tallowamidoethyl-2-tallowimidazolinium methyl sulfate is sold by Witco Chemical Company under the trade name Varisoft ^R 475.

(Ii) softener having the formula:

Embedded image Wherein each R ² is a C _1-6 alkylene group, preferably an ethylene group; G is an oxygen atom or a —NR— group; each R, R ¹ , R ² and R ⁵ is as defined above. having; a ^- the X ^- has the been defined for. An example of compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride, R ¹ is an acyclic aliphatic C ₁₅ -C ₁₇ hydrocarbon group, R ² is an ethylene group, G Is an NH group, R ⁵ is a methyl group, and A ⁻ is a chloride anion.

(Iii) softener having the formula:

Embedded image In the above formula, R, R ¹ , R ² and A ⁻ are as described above. Examples of compound (iii) are compounds having the formula:

Embedded image In the above formula, R ¹ is derived from oleic acid.

Additional fabric softeners useful in the present invention are US Pat. No. 4,661,269, US Pat.
335, and US 3,861,870, 4,308,151, 3,886.
075, 4,233,164, 4,401,578, 3,974,076, 4,
237,016, and EP 472,178, all of which are incorporated herein by reference. Of course, the term "soft active" can also include mixed soft actives. Preferred among the above classes of softening compounds are diester or diamide quaternary ammonium fabric softening active compounds (DEQA). The composition of the present invention may contain one or more of the following components in addition to or instead of the above components.

Optional Component (A) Liquid Carrier An optional but preferred component is a liquid carrier. The liquid carrier used in the present composition is preferably at least predominantly water, due to its low cost, relatively easy availability, safety and environmental compatibility. The level of water in the liquid carrier is
Preferably it is at least 50% by weight of the carrier, most preferably at least 60%. Mixtures of water and low molecular weight, for example, <200 organic solvents, for example, lower alcohols such as ethanol, propanol, isopropanol or butanol, are also useful as carrier liquids. Low molecular weight alcohols include monohydric, dihydric (such as glycol), trihydric (such as glycerol) and higher polyhydric (polyol) alcohols.

(B) Additional Solvents The compositions of the present invention may include one or more solvents that increase the ease of formulation. All of these formulation facilitating solvents are disclosed in WO 97/03169. This is especially the case when formulating liquid transparent fabric softening compositions. When used, the formulation facilitating solvent system preferably comprises less than about 40% by weight of the composition, preferably about 10 to about 35%, more preferably about 12 to about 25%, and even more preferably about 14 to about 25%. 20
%. The formulation facilitating solvent is selected to impart a low viscosity to the final composition with minimal solvent odor impact in the composition. For example, isopropyl alcohol is not very effective and has a strong odor. n-Propyl alcohol is more effective, but also has a unique odor. Some butyl alcohols also have an odor, but can be used for effective clarity / stability, especially when used as part of a formulation facilitating solvent system to minimize their odor. The alcohols were also selected for best low temperature stability, i.e., they were about 40 ° F (about 4.4F).
C.) to form a composition that is acceptable, low in viscosity, translucent, and preferably a clear liquid, which can be recovered after storage to about 20.degree. F. (about 6.7.degree. C.). it can.

The suitability of a formulation facilitating solvent for the formulation of a liquid, concentrated, preferably transparent fabric softener composition with essential stability is surprisingly selective. Suitable solvents may be selected based on their octanol / water partition coefficient (P) as defined in WO 97/03169. The formulation facilitating solvent is from about 0.15 to about 0.64, preferably from about 0.25 to about 0.1.
62, and more preferably selected from those having a ClogP of about 0.40 to about 0.60, wherein the formulation facilitating solvent is preferably at least somewhat asymmetric, and preferably forms a liquid at or near room temperature. Melting point or freezing point. Solvents having a low molecular weight and being biodegradable are also desirable for some purposes. Asymmetric solvents seem to be highly desirable, while highly symmetric solvents such as 1,7-heptanediol or 1,4-bis (hydroxymethyl) cyclohexane with a center of symmetry are When used alone, it does not seem to provide an essentially transparent composition, even though their ClogP values fall within the preferred range.

The most preferred formulation facilitating solvent can be identified by the appearance of the softener vesicles, as seen from cryogenic electron microscopy of the composition diluted to the concentration used for rinsing. These dilute compositions appear to have a dispersibility of fabric softener that exhibits a single lamellar appearance than conventional fabric softener compositions. The closer the appearance is to a single lamella, the better the composition will perform. These compositions exhibit surprisingly good fabric softness as compared to similar compositions made in a conventional manner with similar fabric softening activators.

Useful formulation facilitating solvents having ClogP values that fall within the required range are disclosed and listed below. These include monool, 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 ethers, di (hydroxyalkyl) ethers, aryl glyceryl ethers, aromatic glyceryl ethers, alicyclic diols and derivatives,
C ₃ C ₇ diol alkoxylated derivatives, aromatic diols, and unsaturated diols. Particularly preferred formulation facilitating solvents are 1,2-hexanediol and 2
Hexanediols such as -ethyl-1,3-hexanediol, 2,2,4
Pentanediols such as -trimethyl-1,3-pentanediol.

(C) Dispersing Aid A relatively concentrated composition containing both saturated and unsaturated diester quaternary ammonium compounds that is stable without the addition of a concentration aid can be produced. However, the compositions of the present invention may require organic and / or inorganic thickening auxiliaries for higher concentrations and / or to meet higher stability standards, depending on the other ingredients. There is. These thickening aids, which are typical viscosity modifiers, are required or preferred to ensure stability under extreme conditions where special soft activator levels are used. Surfactant concentration aids typically include (1) single long chain alkyl cationic surfactants, (2) nonionic surfactants, (3) amine oxides, (4) fatty acids and (5) Are selected from the group consisting of: These auxiliaries are described in WO 94/20597, in particular from page 14, line 12 to page 20, 12
Line, which is incorporated herein by reference. When the above dispersing aids are present, their total level is from 2 to 25% by weight of the composition, preferably 3 to 17%, more preferably 4 to 15%, even more preferably 5 to 13%.
%. These materials, such as mono-long chain alkyl cationic surfactants and / or fatty acids, which are the reactants used to form the biodegradable fabric softeners as described above, are used in the active softener raw material (I). Added as part or as a separate component. The total level of dispersing aid also includes the amount present as part of component (I).

Inorganic viscosity / dispersibility control agents that act like or enhance the effect of surfactant concentration aids are water soluble and ionizable, optionally incorporated into the compositions of the present invention. There is salt. Various ionizable salts can be used. Examples of suitable salts are halides of metals of 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 the process of mixing the ingredients to achieve the desired viscosity after making the composition. The amount of ionizable salt used will depend on the amount of active ingredient used in the composition and can be adjusted as desired by the skilled artisan. Typical levels of salts used to control the viscosity of the composition are:
About 20 to about 20,000 parts by weight / million (ppm) of the composition, preferably about 20 to
It is about 11,000 ppm.

[0094] In addition to the ionizable water-soluble salts described above, alkylene polyammonium salts
Alternatively, it can be incorporated into the composition for viscosity control. In addition, these agents may act as scavengers and form ion pairs with the rinse solution and anionic detergent carried over on the fabric from the main wash liquor to improve softness performance. These agents can also stabilize viscosity over a wide range of temperatures, especially at low temperatures, compared to inorganic electrolytes. Specific examples of alkylene polyammonium salts include l-lysine monohydrochloride and 1,1
There is 5-diammonium 2-methylpentane dihydrochloride.

(D) Dye Fixing Agent The composition of the present invention may optionally contain a dye fixing agent. Dye fixatives or "fixatives" are well-known commercial materials and are designed to improve the appearance of colored fabrics by minimizing the release of dye from the fabric upon washing. Components that are fabric softeners, or those described above as amino-functional polymers, are not included within this definition.

Many dye fixatives are cationic and are based on various quaternized or otherwise positively charged organic nitrogen compounds. Cationic fixatives are commercially available from several vendors under various trade names. Representative examples include Crosfield to CROSC
OLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8444); INDOSOL E-50 from Sandoz (Feb. 27, 1984, Ref.
No. 6008.35.84; polyethylene amine base); also commercially available from Sandoz,
SANDOFIX TPS, which is a preferable polycationic fixing agent for use in the present invention, and SAND
OFIX SWE (cationic resin compound); CHT-Beitlich GMBH to REWIN SRF, REWIN
SRF-O and REWIN DWR; commercially available from Ciba-Geigy Tinofix ^R ECO, Tino
There are fix ^R FRD and Solfin ^R. Another cationic dye fixative is "Aftertreatments for improving the fastness
of dyes on textile fibres ", Christopher C. Cook (REV.PROG.COLORATION, Vol.12
, 1982). Dye fixatives suitable for use in the present invention include ammonium compounds such as fatty acid-diamine condensates, such as hydrochloric acid, acetic acid, methosulfuric acid and benzyl hydrochloride of oleyldiethylaminoethylamide, oleylmethyldiethylenediaminemethosulfate, monostearyl- Oxidation products of ethylenediaminotrimethylammonium methosulfate and tertiary amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrin.

The typical amount of dye fixative used in the composition of the present invention is preferably 90% of the composition.
% By weight, preferably within 50% by weight, more preferably 0.001 to 10% by weight, and most preferably 0.5 to 5% by weight.

(E) Stabilizers Stabilizers can also be present in the compositions of the present invention. As used herein, the term "stabilizer" includes antioxidants and reducing agents. These agents range from 0 to about 2%, preferably from about 0.01 to about 0.2%, more preferably about 0.03% in the case of antioxidants.
5 to about 0.1%, more preferably about 0.01 to about 0.2% in the case of a reducing agent. These ensure good aroma stability under long-term storage conditions for the compositions and compounds stored in the molten form. The use of stabilizers, which are antioxidants and reducing agents, is particularly important in the case of low fragrance products (low fragrance).

Examples of antioxidants that can be added to the compositions of the present invention include the trade names Tenox^RPG and
Asco commercially available from Eastman Chemical Products, Inc. as Tenox S-1
Mixture of rubic acid, ascorbic acid palmitate, propyl gallate; trade name T
BHT commercially available from Eastman Chemical Products, Inc. as enox-6
Tylated hydroxytoluene), BHA (butylated hydroxyanisole), gallic
Mixture of propyl citrate and citric acid; trade name Sustane^RUOP Proc as BHT
Butylated hydroxytoluene commercially available from ess Division; Tenox TBHQ
Tertiary butyl hydroquinone from Eastman Chemical Products, Inc .; Tenox GT-1 / G
Natural tocopherols of Eastman Chemical Products, Inc. as T-2; BHA
Butylated hydroxyanisole from Eastman Chemical Products, Inc .; Gallic
Long-chain esters of acids (C₈-C_{twenty two}), Eg dodecyl gallate; Irganox^R1010, I
rganox^R1035, Irganox^RB 1171, Irganox^R1425, Irganox^R3114, Irganox^R31
25 and mixtures thereof; preferably Irganox^R3125, Irganox^R1425, Irganox
^R3114 and mixtures thereof; more preferably citric acid and / or citric acid
Irganox mixed with other chelators, such as isopropyl acid, or alone^RThree
125; Chemical name 1-hydroxyethylidene-1, 1-, commercially available from Monsanto
Dequest of diphosphonic acid (etidronic acid)^R2010; commercially available from Kodak
Chemical name 4,5-dihydroxy-m-benzenesulfonic acid / sodium salt Tiron
^REDDS; chemical name diethylenetriaminepentaacetic acid, commercially available from Aldrich
DTPA^RThere is. Some chemical names and CAS numbers of the above stabilizers are
It is listed in Table II.

TABLE II Antioxidants CAS No. Chemical name Irganox ^R 1010 6683-19-8 Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnaname ) used in the regulations of the Federal Regulations . G) Methane Irganox ^R 1035 41484-35-9 Thiodiethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) Irganox ^R 1098 23128-74-7 N, N'-hexamethylenebis (3,5-di -tert- butyl-4-hydroxy hydro-cinnamamide) Irganox ^R B 1171 31570-04-4 23128-74-7 of Irganox ^R 1098 and Irgafos ^R 168 1: 1 blend Irganox ^R 1425 65140-91- 2 bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium Irganox ^R 3114 65140-91-2 bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) Phosphone DOO] Calcium Irganox ^R 3125 34137-09-2 1,3,5- tris (2-hydroxyethyl) -S- triazine -2,4,6- (1H, 3H, 5H) trione and 3,5-di -Tert-butyl-4-hydroxyhydrocinnamic acid triester Irgafos ^R 168 31570-04-4 Tris (2,4-di-tert-butylphenyl) phosphite Examples of reducing agents include sodium borohydride and There are phosphorous acid, Irgafos ^R 168 and mixtures thereof.

(F) Soil Release Agents Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions of the present invention. The polymer soil release agent is a hydrophilic segment that renders the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and continues to adhere to the hydrophobic fibers on the hydrophobic fibers until the end of the wash and rinse cycle, thus removing the hydrophilic segments. It is characterized by having both a hydrophobic segment that acts as an anchor. In this way, the soil generated after treatment with the soil release agent can be more easily removed in a subsequent washing operation. If utilized, the soil release agent will typically comprise from about 0.01 to about 10.0 of the present detergent composition.
%, Typically from about 0.1 to about 5%, preferably from about 0.2 to about 3.0%.

The following are all incorporated herein by reference and describe soil release polymers suitable for use in the present invention. Hays US issued May 25, 1976
3,959,230; Basadur US 3,8 issued on July 8, 1975.
93,929; Nicol et al., US 4,004, issued December 28, 1976.
Gosselink U.S. Pat. No. 4,009,093; issued Oct. 27, 1987;
Scheibel et al., US Pat. No. 4,968,45, issued Nov. 6, 702,857;
1: US 4,702,85 of Gosselink issued October 27, 1987
7; Gosselink et al., US Pat. No. 4,711,73, issued Dec. 8, 1987.
0; Gosselink US Pat. No. 4,721,580 issued Jan. 26, 1988.
Maldonado et al., US Pat. No. 4,877,89, issued Oct. 31, 1989;
6; Gosselink et al., US Pat. No. 4,956,44, issued Sep. 11, 1990.
7; Gosselink et al., US Pat. No. 5,415,80, issued May 16, 1995.
7; European Patent Application 0,219, published April 22, 1987 by Kud et al.
, 048. Other suitable soil release agents are US Pat. No. 4,201,824 to Violland et al .; US Pat. No. 4,240,918 to Lagasse et al .; US Pat. No. 4,525,524 to Tung et al.
S4,579,681; US4,240,918; US4,787,989; U
S4,525,524; 1988, Rhone-Poulenc Chemie, EP 279,134.
A; EP457, 205A of BASF (1991); and Unilever 1974
It is described in NV DE 2,335,044, all of which are incorporated herein by reference. Commercially available soil release agents include METOLOSE SM100 and METOLOSE SM2 manufactured by Shin-Etsu Chemical KK
00, a substance of the SOKALAN type commercially available from BASF (Germany), such as SOKALAN HP-22, ZE
There are LCON 5126 (Dupont) and MILEASE T (ICI).

(G) Disinfectant Examples of disinfectants used in the composition of the present invention include glutaraldehyde, formaldehyde, Philadelph as trade name Bronopol ^R , with an agent of 1 to 1000 ppm by weight.
2-bromo-2-nitropropane-1,3-diol, sold by Inolex Chemicals, Pennsylvania, Rohm and Haas Company under the trade name Kathon
There is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one sold by the company.

(H) Fragrance The present invention can contain a fragrance. A suitable fragrance is US Patent 5,500,1
38, which patent is incorporated herein by reference. Flavors used in the present invention include natural (ie, obtained by extraction of flowers, herbs, leaves, roots, bark, trees, flowers or plants), artificial (ie, a mixture of different natural oils or oil components) and synthetic There are fragrances, including fragrances (ie, made synthetically) or mixtures thereof. Such substances are often accompanied by auxiliary substances such as fixatives, extenders, stabilizers and solvents. These adjuvants are also used in the present invention as "fragrances"
Is included in the meaning of. Typically, a fragrance is a complex mixture of a plurality of organic compounds.

The range of natural raw materials includes not only volatile components but also moderately volatile components and slightly volatile components. In the case of synthetic compounds, as is clear from the following examples, practically all classes are used. Representative examples of aromatic substances: natural products such as Tree Moss Absolut (
tree moss absolute), basil oil, citrus fruit oil (eg bergamot oil, mandarin oil, etc.), mastic oil (mastix absolute), myrte oil, palmarosa oil, patchouli oil, petitgren oil Paraguay, bittersweet oil, alcohols such as farnesol Geraniol, linalool, nerol, phenylethyl alcohol, rosinol, cinnamyl alcohol, aldehydes such as citral, Helional ^™ , α-hexylcinnamaldehyde, hydroxycitronellal, Lilial ^™ (p-tert-butyl-α-methyldihydro Cinnamaldehyde), methylnonylacetaldehyde, ketones such as allylyonone, α-yonone, β-yonone, isorardine (isomethyl-α-yonone), methylyonone, esters such as phenoxy Allyl acid, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxylate, decyl acetate, dimethyl benzyl carbyl acetate, dimethyl benzyl carbyl butyrate, ethyl acetoacetate, ethyl acetyl acetate, hexenyl isobutyrate, linalyl acetate, methyl Lactones such as dihydrojasmonate, styralyl acetate, vetiveryl acetate, etc., for example γ-undecalactone, various components commonly used in perfumery, for example, musk ketone, indole, p-menthan-8-thiol-3-one and methyleugenol including. Similarly, any conventional fragrance acetal or ketal known in the art may be added to the composition as an optional ingredient of the conventionally formulated perfume (c). Such conventional aromatic acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetal or ketals based on benzaldehyde, those containing a phenylethyl moiety, or "Acetals and Ketals of Oxo-Tetralins and Oxo. -Indanes "(see US Pat. No. 5,084,440, issued Jan. 28, 1992 and assigned to Givaudan Corp.). There are special products. Of course, other recent synthetic specialties can also be included in perfume compositions for fully formulated fabric softening compositions. These include US Patents 5,3
There are alkyl-substituted oxotetralins and enol ethers of oxoindane as described in US Pat. No. 32,725, or Schiff bases as described in US Pat. No. 5,264,615.

The perfumes useful in the compositions of the present invention are substantially free of halogenated substances and nitromsk. The perfume may be present at a level of 0-10%, preferably 0.1-5%, more preferably 0.2-3% by weight of the final composition. The fabric softener composition of the present invention exhibits improved fabric perfume adhesion.

(I) Chelating Agents In the present compositions and methods, one or more copper and / or nickel chelators (“chelators”) may optionally be used. Such water-soluble chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators, and mixtures thereof, all as described below. The whiteness and / or vividness of the fabric is substantially improved or restored with such chelating agents, and the stability of the material in the composition is improved.

The aminocarboxylates useful as chelating agents in the present invention include ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetrapropionic acid, ethylenediamine-N, N '-Diglutamic acid, 2-hydroxypropylenediamine-N, N'-
Disuccinic acid, triethylenetetraamine hexaacetic acid, diethylenetriaminepentaacetic acid (
DETPA) and ethanol diglycine, their alkali metal, their water-soluble salts such as ammonium and substituted ammonium salts, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are found in detergent compositions, including ethylenediaminetetrakis (methylenephosphonate) and diethylenetriamine. -N, N, N ', N ", N" -pentakis (methanephosphonate) (DETMP
). Preferably, these aminophosphonates do not have alkyl or alkenyl groups having about 7 or more carbon atoms.

[0110] Chelating agents are typically used in the present rinsing process at a level of 2-25 ppm during soaking for one minute to several hours. Preferred EDDS chelators used in the present invention (ethylenediamine-N, N
'-Disuccinic acid) is also known from US Pat.
No. 4,233. EDDS as disclosed in that patent
Can be prepared using maleic anhydride and ethylenediamine. Preferred biodegradable [S, S] isomers of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane. EDDS is advantageous over other chelators in that it is effective in chelating both copper and nickel cations, is available in a biodegradable form, and does not contain phosphorus. The EDDS used in the present invention as a chelator is typically in its salt form, ie, one or more of the four acidic hydrogens are replaced by a water-soluble cation M such as sodium, potassium, ammonium, triethanolammonium and the like. I have. At some pH, EDDS is preferably used in combination with a zinc cation.

As can be seen from the foregoing, various chelators can be used in the present invention. In fact, simple polycarboxylates such as citrate, oxydisuccinate, etc. can be used, but such chelators are not as effective as aminocarboxylates and phosphonates on a weight basis. Thus, usage levels may be adjusted to take into account different degrees of chelation effectiveness. The chelators preferably have a stability constant (of a fully ionized chelator) of at least 5, preferably at least 7, in the case of copper ions. Typically, the chelator will comprise 0.5 to 10% by weight of the composition, more preferably 0.75 to 5%. Preferred chelators include DETMP, DET
There are PA, NTA, EDDS and mixtures thereof.

[0112] The (J) enzyme present compositions can optionally be used lipase, protease, cellulase, one or more enzymes such as amylases and peroxidases. A preferred enzyme for use in the present invention is a cellulase enzyme. In fact, this type of enzyme further imparts a color care effect to the treated fabric. Cellulases that can be used in the present invention include both bacterial and fungal types, preferably having an optimal pH of 5 to 9.5. In US 4,435,307, Humicola insolens or Humicola
Suitable fungal cellulases from strain DSM1800, or cellulase 212 producing fungi belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander are disclosed. A suitable cellulase is G
BA-2,075,028, GB-A-2,095,275 and DE-OS
-2,247,832. CAREZYME ^R and CELLUZYME ^R (Nov
o) is particularly useful. Other suitable cellulases are described in Novo WO 91/17243.
WO 96/34092, WO 96/34945 and EP-A-0,739,
982. In terms of current commercial formulations, a typical amount is the detergent composition g
Within 5 mg, more typically 0.01 to 3 mg, of active enzyme per weight. In other words, the composition is typically present at 0.001 to 5% by weight, preferably 0.01 to 5% by weight.
Contains 1% commercial enzyme preparation. In certain cases where the activity of the enzyme preparation is defined, for example, by cellulase, the corresponding activity unit (eg, CEVU or cellulase equivalent viscosity unit) is preferred. For example, the composition of the present invention may have a concentration of about
The cellulase enzyme can be contained at a level corresponding to the activity of composition g. Cellulase enzyme preparations used to formulate compositions of the present invention typically include:
It has an activity of 1000 to 10,000 CEVU / g in liquid form and about 1000 CEVU / g in solid form.

(H) Other Optional Ingredients The compositions of the present invention are optional ingredients commonly used in fully formulated laundry detergent compositions as described in WO 97/05226, such as builders, bleach, brighteners, colorants ,
Surfactants, anti-shrink agents, fabric crisping agents, stain removers, bactericides, fungicides, antioxidants such as butylated hydroxytoluene, corrosion inhibitors, defoamers and the like can be included. . In the present invention, WO96 / 02625, WO9
Including those disclosed in US Pat. No. 6,217,714 and WO 96/21715,
Other compatible components can also be included.

Method In another aspect of the present invention, there is provided the use of the above ethoxylated amino-functional polymer, wherein the discoloration and malodor resulting from the contact of the polymer with an acidic medium are reduced. Preferably, the acidic medium is provided by a fabric softening composition as described above in which the polymer is used. The aldehyde malodor reduction effect is evaluated in comparison to a composition containing no polymer, and an acceptable product is when a trained perfume cannot distinguish the difference in scent between the two compositions. Color effect is control (composition containing the same polymer, but not subjected to acidic conditions)
Is evaluated visually by comparison with a polymer-containing composition subjected to acidic conditions. Compositions containing the polymers according to the invention show less color difference from the respective control compared to the polymer having 100 ppm or more after the acidic treatment.

Applications The compositions of the present invention may be suitable for use in any of the steps of household treatment, ie, pre- or post-treatment compositions, wash additives, laundry compositions, rinse cycles of the wash cycle or dryer sheets. Suitable for use as the composition applied above. Obviously, for the purposes of the present invention, such as treating a fabric with the pre-treatment composition of the present invention and further with the composition of the present invention suitable for use in a rinse cycle and / or suitable for use as a dryer sheet, Many applications can be made. The composition of the invention may take the form of a spray, foam or aerosol, for example, which is suitable for use in ironing or applied to the surface of a tumble dryer.

The present invention is illustrated by the following non-limiting examples, in which all percentages are on an active weight basis unless otherwise indicated. In the examples, the abbreviated component designations have the following meanings: DEQA: di (tallowyloxyethyl) dimethylammonium chloride DOEQA: di (oleyloxyethyl) dimethylammonium methylsulfate DTDMAC: ditallowdimethylammonium chloride DHEQA : Di (soft tallowyloxyethyl) hydroxyethyl methyl ammonium methyl sulfate fatty acid: tallow fatty acid with IV = 18 Electrolyte: calcium chloride DTDMAMS: ditallow dimethyl ammonium methyl sulfate SDASA 1: stearyl dimethylamine in a 3: 2 ratio: triple pressed ( Glycosperse stearic acid S-20: Lonza Commercially available polyethoxylated sorbitan monostearate Clay: Calcium sold by Southern Clay Products Bentonite L TAE25: Tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol PEG: Polyethylene glycol 4000 PEI1800E4: Ethoxylated polyethyleneimine as synthesized and treated in Synthesis Example 1 (MW 1800 with 50% activity) PEI1800E7: Ethoxylated polyethyleneimine as synthesized and treated in Synthesis Example 1 (MW1800 with 50% activity) PEI1200E1: Ethoxylated polyethyleneimine as synthesized and treated in Synthesis Example 2 (MW1200 with 50% activity in water) Dye fixative 1: Cationic dye fixative (50% active) sold by Ciba-Geigy under the trade name Tinofix Eco Dye fixative 2: emulsified dye sold by CHT-Beitlich under the trade name Rewin SRF-O On dye fixing agent (30% active) LAS: Sodium linear C ₁₂ alkyl benzene sulphonate TAS: Sodium tallow alcohol sulfate C25AS: Sodium C ₁₂ -C ₁₅ linear alkyl sulfate CxyEzS: z moles of ethylene oxide condensed with sodium C _1X -C _1Y branched alkyl sulfates C45E7: average 7 moles of predominantly straight chain primary alcohols of C ₁₄ -C ₁₅ which is engaged ethylene oxide condensed C25E3: average of 3 moles of ethylene oxide condensed with C _12-15 branched primary alcohol cationic ester mixture soap C ₁₂ / C ₁₄ choline ester: tallow and coconut oil 80/20 mixture derived sodium linear alkyl from carboxylate TFAA: C ₁₆ -C ₁₈ alkyl N- methyl glucamide TPKF : C ₁₂ -C ₁₄ Toppudo Ho - Le Cut (topped whole cut) fatty Zeolite A: formula Na _{12 (AlO} 2 _SiO 2) having a primary particle size of 0.1~10μm range ₁₂ - ₂₇ H ₂ O of Hydrated sodium aluminosilicate Citric acid: Citric anhydride Carbonate: Anhydrous sodium carbonate silicate having a particle size of 200 to 900 μm: Amorphous sodium silicate (SiO ₂ : Na ₂ O; 2.0 ratio) Sulfate: Anhydrous sodium sulfate citrate: 86.4% active trisodium citrate dihydrate MA / AA 1: 4 maleic / acrylic acid copolymer with a particle size distribution of 425-850 μm, average molecular weight about 70,000 CMC: sodium carboxymethylcellulose Savinase: 4KNPU / g activity protease: Carezyme: 1000 CEVU / g activity cellulo Terminyl: 60 KNU / g active amylolytic enzyme Lipolase: 100 kLU / g active lipolytic enzyme All are sold by NOVO Industries A / S and have the above activities unless otherwise specified. : empirical formula _{NaBO 2 · 3H 2 O · H} 2 O 2 of sodium perborate tetrahydrate PB1: empirical formula NaBO ₂ · _{H 2 O 2} in anhydrous sodium perborate bleach TAED: tetraacetylethylenediamine DTPMP: from Monsanto Diethylenetriaminepenta (methylenephosphonate) sold under the trade name Dequest 2060 Photoactivated bleach: sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer Brightener: 4,4'-bis (4-anilino-6-morpholino) -1,3,5-Triazin-2-yl) amino) stilbene-2 2'-disulfonic acid disodium Silicone antifoam: 10: 1 to 100: 1 foam control agent to dispersant ratio was with siloxane oxyalkylene copolymer as dispersing agent, polydimethylsiloxane suds suppressors

Synthesis Example 1-Preparation of PEI 1800E ₁ A) Ethoxylation equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purge, sampling, and introduction of ethylene oxide as liquid. Performed in a 2 gallon (about 8 L) stirred stainless steel autoclave. Ethylene oxide net ２０20 lb (〜9 kg) cylinder (ARC) is set up to pump ethylene oxide as a liquid to the autoclave and the cylinder is placed on a scale so that the weight change of the cylinder is monitored. Polyethyleneimine (PEI) (0.417 mol of polymer and nitrogen group 17.
(Epomin SP-018, Nippon Shokubai having a listed average molecular weight of 1800 corresponding to 4 moles)
Add 750 g to the autoclave. The autoclave is then sealed and purged with air (evacuated to -28 "Hg, then 250 psia with nitrogen (about 17.6).
kg / cm ² ) and then exhaust to atmospheric pressure). 13 autoclave contents
Apply vacuum while heating to 0 ° C. After about one hour, the autoclave is filled with about 25 nitrogen.
The autoclave is cooled to about 105 ° C. while charging to 0 psia. The autoclave pressure, temperature and ethylene oxide flow rate are closely monitored as ethylene oxide is then slowly added to the autoclave over time. Turn off the ethylene oxide pump and provide cooling to limit temperature rise due to reaction exotherm. While maintaining the temperature at 100-110 ° C, the total pressure is gradually increased during the reaction. After a total of 750 g of ethylene oxide (approximately one mole of ethylene oxide per PEI nitrogen radical) has been added to the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for a further hour. At this point, vacuum is applied to remove residual unreacted ethylene oxide.

Step B) The reaction mixture is then reacted with about 100 cu.ft. (about 2.8) of inert gas (argon or nitrogen) from the gas dispersion frit while stirring and heating the mixture to 130 ° C. Deodorize by passing through the mixture. The final reaction product is cooled slightly and collected in a glass container purged with nitrogen. In other productions, neutralization and deodorization are performed in a reactor before removing the product. The resulting polymer contains 476 ppm on a 100% acetaldehyde basis. After treatment with 1% Na ₂ SO ₃ , the polymer contained 6.8 ppm on a 100% acetaldehyde basis. If PEI1800E ₇ is desired, step A the catalyst addition the following steps
And between B. While continuously applying vacuum, the autoclave was cooled to about 50 ° C and 376 g of 25% sodium methoxide in methanol solution (10%
(1.74 mol of the catalyst). The methoxide solution was sucked into the autoclave under vacuum, and then the autoclave temperature controller was set to 130 ° C.
Enhance. The device is used to monitor the power consumed by the stirrer. Monitor stirrer power along with temperature and pressure. The stirrer power and temperature values increased gradually as the methanol was removed from the autoclave, increasing the viscosity of the mixture and stabilizing in about 1 hour, indicating that most of the methanol was removed. The mixture is heated and stirred under vacuum for a further 30 minutes. The vacuum is turned off and the autoclave is cooled to 105 ° C while nitrogen is added to it.
Pump to psia and then evacuate to atmospheric pressure. 200 psia nitrogen in autoclave
(About 14.1 kg / cm ² ). While ethylene oxide is being added to the autoclave little by little again as described above, the autoclave pressure, temperature and ethylene oxide flow rate are closely monitored and the temperature is maintained at 100-110 ° C. to limit the temperature rise due to the reaction exotherm. After the addition of 4500 g of ethylene oxide (corresponding to a total of 7 moles of ethylene oxide per mole of PEI nitrogen radicals) over several hours, 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 purge vessel and finally transferred into a 22 L three-necked round bottom flask equipped with heating and stirring. Strong alkali catalyst is methanesulfonic acid 16
Neutralize by adding 7 g (1.74 mol). The resulting polymer contains 980 ppm on a 100% acetaldehyde basis. After treatment with 1% Na ₂ SO ₃ , the polymer contained 5.6 ppm on a 100% acetaldehyde basis. PEI1800E2, PEI1800E4, PEI1800E15 and PE
Other preferred examples, such as I1800E20, can be prepared by the above methods, adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

[0119] Production Step A Synthesis Example 2-PEI1200E ₁₎ ethoxylated, temperature measurement and control, pressure measurement, vacuum and inert gas purging, for sampling, and subjected to equipment for introduction of ethylene oxide as a liquid Performed in a 2 gallon stirred stainless steel autoclave. Ethylene oxide net ~ 20 lb cylinder (ARC) is set up so that the pump can deliver ethylene oxide as a liquid to the autoclave and place the cylinder on the scale so that the weight change of the cylinder is monitored. Polyethyleneimine (PEI) (about 0.625 mol of polymer and 17
. 750 g (having a listed average molecular weight of 1200 corresponding to 4 mol) are added to the autoclave. The autoclave is then sealed and purged with air (-28 "H
g, then pressurize to 250 psia with nitrogen and then evacuate to atmospheric pressure). Apply vacuum while heating the autoclave contents to 130 ° C. After about one hour, the autoclave is cooled to about 105 ° C. while the autoclave is filled with nitrogen to about 250 psia. The autoclave pressure, temperature and ethylene oxide flow rate are closely monitored as ethylene oxide is then slowly added to the autoclave over time. Turn off the ethylene oxide pump and provide cooling to limit temperature rise due to reaction exotherm. While maintaining the temperature at 100-110 ° C, the total pressure is gradually increased during the reaction. After a total of 750 g of ethylene oxide (approximately one mole of ethylene oxide per PEI nitrogen radical) has been added to the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for a further hour. At this point, vacuum is applied to remove residual unreacted ethylene oxide.

Step B) The reaction mixture is then passed by passing about 100 cu.ft. of inert gas (argon or nitrogen) from the gas dispersion frit into the reaction mixture while stirring and heating the mixture to 130 ° C. Deodorize. The final reaction product is cooled slightly and collected in a glass container purged with nitrogen. In other productions, neutralization and deodorization are performed in a reactor before removing the product. The resulting polymer contains 4894 ppm acetaldehyde on a 100% basis. After treatment with 1% Na ₂ SO ₃ , the polymer contained 28.5 ppm on a 100% acetaldehyde basis. If PEI1200E ₇ is desired, step A the catalyst addition the following steps
And between B. While continuously applying vacuum, the autoclave was cooled to about 50 ° C and 376 g of 25% sodium methoxide in methanol solution (10%
(1.74 mol of the catalyst). The methoxide solution is aspirated under vacuum into the autoclave, after which the autoclave temperature controller setting is increased to 130 ° C. The device is used to monitor the power consumed by the stirrer. Monitor stirrer power along with temperature and pressure. The stirrer power and temperature values gradually increased as the methanol was removed from the autoclave, indicating that the viscosity of the mixture had increased and stabilized in about 1 hour, indicating that most of the methanol had been removed. The mixture is heated and stirred under vacuum for a further 30 minutes. The vacuum is turned off and the autoclave is cooled to 105 ° C while nitrogen is added to it.
Pump to psia and then evacuate to atmospheric pressure. 200 psia nitrogen in autoclave
Insert up to While ethylene oxide is being added to the autoclave little by little again as described above, the autoclave pressure, temperature and ethylene oxide flow rate are closely monitored and the temperature is maintained at 100-110 ° C. to limit the temperature rise due to the reaction exotherm. After several hours of addition of 4500 g of ethylene oxide (corresponding to a total of 7 moles of ethylene oxide per mole of PEI nitrogen radicals), the temperature was raised to 110 ° C.
And the mixture is stirred for another hour. The reaction mixture is then collected in a nitrogen purge vessel and finally transferred into a 22 L three-necked round bottom flask equipped with heating and stirring. Strong alkali catalyst is methanesulfonic acid 16
Neutralize by adding 7 g (1.74 mol). The resulting polymer contains 388 ppm acetaldehyde on a 100% basis. After treatment with 1% Na ₂ SO ₃ , the polymer contained 5.8 ppm on a 100% acetaldehyde basis. PEI1200E2, PEI1200E3, PEI1200E15 and PE
Other preferred examples, such as I1200E20, can be prepared by the above methods, adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

[0121] Production ethoxylation of Synthesis Example 3-PEI1800E _7, the temperature measurement and control, pressure measurement, vacuum and inert gas purging, for sampling, and 2 gallons stirred subjected to equipment for introduction of ethylene oxide as a liquid Performed in a stainless steel autoclave.
Ethylene oxide net ~ 20 lb cylinder (ARC) is set up so that the pump can deliver ethylene oxide as a liquid to the autoclave and place the cylinder on the scale so that the weight change of the cylinder is monitored. Polyethyleneimine (PEI) (0.417 mol of polymer and nitrogen group 17.
(Epomin SP-018, Nippon Shokubai having a listed average molecular weight of 1800 corresponding to 4 moles)
Add 750 g to the autoclave. The autoclave is then sealed and purged with air (evacuated to -28 "Hg, then pressurized with nitrogen to 250 psia and then evacuated to atmospheric pressure). While heating the autoclave contents to 130 ° C,
Apply vacuum. After about one hour, the autoclave is cooled to about 105 ° C. while the autoclave is filled with nitrogen to about 250 psia. The autoclave pressure, temperature and ethylene oxide flow rate are closely monitored as ethylene oxide is then slowly added to the autoclave over time. Turn off the ethylene oxide pump and provide cooling to limit temperature rise due to reaction exotherm. Temperature between 100 and 110 ° C
While gradually increasing the total pressure during the course of the reaction. After a total of 750 g of ethylene oxide (approximately one mole of ethylene oxide per PEI nitrogen radical) has been added to the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for a further hour. At this point, vacuum is applied to remove residual unreacted ethylene oxide.

The autoclave was then cooled to about 50 ° C. while continuously applying vacuum,
376 g of 25% sodium methoxide in methanol solution (1.74 mol of a 10% catalytic amount with respect to the PEI nitrogen radicals) are introduced. The methoxide solution was sucked into the autoclave under vacuum, and then the autoclave temperature controller was set to 1
Increase to 30 ° C. The device is used to monitor the power consumed by the stirrer.
Monitor stirrer power along with temperature and pressure. The stirrer power and temperature values increased gradually as the methanol was removed from the autoclave, increasing the viscosity of the mixture and stabilizing in about 1 hour, indicating that most of the methanol was removed. The mixture is heated and stirred under vacuum for a further 30 minutes. The vacuum is turned off and the autoclave is cooled to 105 ° C while nitrogen is added to it.
Pump to psia and then evacuate to atmospheric pressure. 200 psia nitrogen in autoclave
Insert up to While ethylene oxide is being added to the autoclave little by little again as described above, the autoclave pressure, temperature and ethylene oxide flow rate are closely monitored and the temperature is maintained at 100-110 ° C. to limit the temperature rise due to the reaction exotherm. After several hours of addition of 4500 g of ethylene oxide (corresponding to a total of 7 moles of ethylene oxide per mole of PEI nitrogen radicals), the temperature was raised to 110 ° C.
And the mixture is stirred for another hour. The reaction mixture is then collected in a nitrogen purge vessel and finally transferred into a 22 L three-necked round bottom flask equipped with heating and stirring. Strong alkali catalyst is methanesulfonic acid 16
Neutralize by adding 7 g (1.74 mol). The reaction mixture is then deodorized by passing about 100 cu.ft. of inert gas (argon or nitrogen) from the gas dispersion frit into the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled slightly and collected in a glass container purged with nitrogen. In other productions, neutralization and deodorization are performed in a reactor before removing the product.

[0123] Synthesis Example 4-PEI1800E _0.9 in the manufacture ethoxylation PEI1800E ₇ added catalyst, equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, for sampling, and introduction of ethylene oxide as a liquid In a 2 gallon stirred stainless steel autoclave.
Ethylene oxide net ~ 20 lb cylinder (ARC) is set up so that the pump can deliver ethylene oxide as a liquid to the autoclave and place the cylinder on the scale so that the weight change of the cylinder is monitored. Polyethyleneimine (PEI) (about 0.216 moles of polymer and nitrogen groups 9.
388 g of Epomin SP-018 (Nippon Shokubai) having a listed average molecular weight of 1800, corresponding to 16 mol, are added to the autoclave. The autoclave is then sealed, purged with air (evacuated to -28 "Hg, then pressurized to 250 psia with nitrogen,
Then exhaust to atmospheric pressure). Apply vacuum while heating the autoclave contents to 130 ° C. After about one hour, the autoclave is cooled to about 105 ° C. while the autoclave is filled with nitrogen to about 250 psia. The autoclave pressure, temperature and ethylene oxide flow rate are closely monitored as ethylene oxide is then slowly added to the autoclave over time. Stop the ethylene oxide pump,
Cooling is performed to limit temperature rise due to reaction exotherm. Temperature between 100 and 110
While maintaining at 0 ° C, the total pressure is gradually increased during the course of the reaction. After a total of 363 g of ethylene oxide (approximately 0.9 moles of ethylene oxide per PEI nitrogen radical) have been added to the autoclave, the temperature is increased to 110 ° C. and the autoclave is stirred for a further hour. At this point, vacuum is applied to remove residual unreacted ethylene oxide.

The autoclave was then cooled to about 50 ° C. while continuously applying vacuum,
195 g of 25% sodium methoxide in methanol solution (0.9 mol of a 10% catalytic amount based on PEI nitrogen groups) are introduced. The methoxide solution was aspirated into the autoclave under vacuum and then the autoclave temperature controller set to 13
Increase to 0 ° C. The device is used to monitor the power consumed by the stirrer. Monitor stirrer power along with temperature and pressure. Stirrer power consumption and temperature values gradually increase as methanol is removed from the autoclave, increasing the viscosity of the mixture and stabilizing in about 1 hour, indicating that essentially all of the methanol has been removed. The mixture is heated and stirred under vacuum for a further 30 minutes. The vacuum is turned off and the autoclave is cooled to 105 ° C while nitrogen is added to it.
Pump to psia and then evacuate to atmospheric pressure. 200 psia nitrogen in autoclave
Insert up to While ethylene oxide is being added to the autoclave little by little again as described above, the autoclave pressure, temperature and ethylene oxide flow rate are closely monitored and the temperature is maintained at 100-110 ° C. to limit the temperature rise due to the reaction exotherm. After several hours of addition of 2178 g of ethylene oxide (corresponding to a total of 7 moles of ethylene oxide per mole of PEI nitrogen radicals), the temperature was raised to 110 ° C.
And the mixture is stirred for another hour. The reaction mixture is then collected in a nitrogen purge vessel and finally transferred into a 22 L three-necked round bottom flask equipped with heating and stirring. Strong alkali catalyst is methanesulfonic acid 86
. Neutralize by adding 5 g (0.9 mol). The reaction mixture is then deodorized by passing about 100 cu.ft. of inert gas (argon or nitrogen) from the gas dispersion frit into the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled slightly and collected in a glass container purged with nitrogen. For comparative purposes, the synthesis is repeated, adding the catalyst after hydroxyethylation to the E1 level. The color of the sample is brighter than in the preparation example where the catalyst was added after hydroxyethylation to the E0.9 level. After the hydroxyethylation to the E0.1 level, the base catalyst is added and the synthesis is repeated. The color of the final ethoxylated sample is brighter than the control with the catalyst added after hydroxyethylation to the E1 level.

[0125] Production ethoxylation of Synthesis Example 5 Synthesis of PEI1800E ₁ adding sodium borohydride, the temperature measurement and control, pressure measurement, vacuum and inert gas purging, for sampling, and introduction of ethylene oxide as a liquid Performed in a 2 gallon stirred stainless steel autoclave equipped for
Ethylene oxide net ~ 20 lb cylinder (ARC) is set up so that the pump can deliver ethylene oxide as a liquid to the autoclave and place the cylinder on the scale so that the weight change of the cylinder is monitored. 13. Polyethyleneimine (PEI) (about 0.35 mol of polymer and nitrogen groups
633 g of Epomin SP-018 (Nippon Shokubai) having a listed average molecular weight of 1800 corresponding to 95 mol and 600 mg of sodium borohydride are added to the autoclave. The autoclave is then sealed and purged with air (evacuated to -28 "Hg, then pressurized to 250 psia with nitrogen and then evacuated to atmospheric pressure). After about one hour, the autoclave is cooled to about 105 ° C., while introducing nitrogen to the autoclave to about 250 psia, and then the autoclave pressure, temperature, and ethylene oxide flow rate are closely monitored while ethylene oxide is gradually added to the autoclave over time. Turn off the ethylene oxide pump and perform cooling to limit the temperature rise due to the reaction exotherm, gradually increasing the total pressure during the reaction while maintaining the temperature at 100-110 ° C. (To 1 mole of ethylene oxide per PEI nitrogen group) After adding URN corresponding) to the autoclave, the temperature 1
Increase to 10 ° C. and stir the autoclave for another hour. At this point, vacuum
The residual unreacted ethylene oxide is removed.

The reaction mixture is then collected in a nitrogen purge vessel and finally transferred into a 2 L three-necked round bottom flask equipped with heating and stirring. The reaction mixture is then deodorized by passing about 100 cu.ft. of inert gas (argon or nitrogen) from the gas dispersion frit into the reaction mixture while stirring and heating the mixture to 130 ° C. The final reaction product is cooled slightly and collected in a glass container purged with nitrogen. For comparative purposes, the synthesis is repeated without adding sodium borohydride. The color of the product obtained in the presence of sodium borohydride is quite light. However, adding sodium borohydride to samples made without borohydride improves the odor. The synthesis is repeated at the beginning with the addition of sodium borohydride, except that after hydroxyethylation to the E1 level, a strong base catalyst is added and ethoxylation is resumed until the E7 level is reached. The color is brighter than in a control experiment performed similarly, except that the borohydride was omitted. After hydroxyethylation to the E1 level, sodium borohydride is added and a strong base catalyst is added, and the synthesis is repeated. Furthermore, ethoxylation up to the E7 level gives a lighter color than the control without added borohydride.

[0127] Example 1 The following compositions according to the invention: Ingredients A B C D E F G H DEQA 2.6 2.9 18.0 19.0 19.0 - - - TAE25 - - 1.0 - - - - - fatty acid 0.3 - 1.0 - - - - - Hydrochloric acid 0.02 0.02 0.02 0.02 0.02---PEG--0.6 0.6 0.6----Fragrance 1.0 1.0 1.0 1.0 1.0 0.1 0.1 0.1 Silicone defoamer 0.01 0.01 0.01 0.01 0.01----PEI1800E7 0.5-32----5 PEI1200E1- 3 3--15--PEI1800E4-3 10 5 Dye fixing agent 1-11 1--10-Dye fixing agent 2-2 2----Electrolyte (ppm)--600 600 1200----Dye ( ppm) 10 10 50 50 50 - - - Ingredient to water and other balance 100 I J K L M N O P Q DTDMAC - - - - - - - 4.5 15 DEQA 2.6 2.9 18.0 19.0 19.0 - - - - TAE25 0.3 - 1.0-0.1 ---Fatty acids 0.3-1.0-------Hydrochloric acid 0.02 0.02 0.02 0.02 0.02--0.02 0.02 PEG--0.6 0.6 0.6---0.6 Fragrance 1.0 1.0 1.0 1.0 1.0 0.1 0.1 1.0 1.0 Silicone defoamer 0.01 0.01 0.01 0.01 0.01--0.01 0.01 PEI1800E4 3--3-5----PEI1800E7----3-5---3 PEI1200E1-3 3-3-15-3-Dye Fixing agent 11-1 1 1 3 10 5 1 1 Dye Fixing agent 22-22----22 Electrolyte (ppm)--600 600 1200---600 Dye (ppm) 10 10 50 50 50--10 50 Water and others Up to 100

[0128] Example 2 The following compositions used as dryer added sheets according to the present invention: R S T U V W DOEQA 40 25 - - - - DHEQA - - 20 - - - DTDMAMS - - - 20 12 60 SDASA 30 30 20 30 20-Glycosperse S-20------Glycerol monostearate----20 10-Clay 4 4 3 4 4-Fragrance 0.7 1.1 0.7 1.6 2.6 1.4 PEI1800E4-5-----PEI1200E1--4 2.2 --PEI1800E72----5 7.0 Dye fixing agent 1 25 4 2.2-3 Stearic acid balance

[0129] EXAMPLE 3 Detergent Formulations X and Y below according to the present invention: X Y Zeolite A 24.0 23.0 Sulfate 9.0 - MA / AA 4.0 4.0 LAS 8.0 8.0 TAS -2.0 silicate 3.0 3.0 CMC 1.0 0.4 Brightener 0.2-Soap 1.0-DTPMP 0.4 0.4 C45E7 2.5 2.0 C25E3 2.5 2. 0 Silicone defoamer 0.3 5.0 Fragrance 0.3 0.3 Carbonate 13.0 16.0 Citrate-5.0 PB4 18.0-PB1 4.0 14.0 TAED 3.0 6.0 Light Activation bleach 0.02%-Savinase 1.0 1.0 Lopolase 0.4 0.4 Termamyl 0.30 0.6 Carezyme-0.6 PEI1800E7 1.0-PEI1200E1-1.0 Remainder (moisture and other) Up to 100

Example 4 The following liquid detergent formulation according to the present invention was prepared: Z C25AS 13 C25E3S 2 TFAA 6 C12-14 alkyldimethylhydroxyethylammonium chloride 1 Cationic ester 1.5 TPKFA 15 Citric acid 1 Ethanol 21 2-propanediol 8 NaOH (to the right pH) 7.5 DTPMP 1.2 Savinase 0.5 Termamyl (300 KNU / g) 0.15 Boric acid 1.5 Bentonite type softening clay 4 Suspended clay SD30 0.3 PEI1200E1 1 balance (moisture and other) 100

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventors Serge, Gabriel, Koberg Be-9100, Belgium, Nieukerken, Thunder, Vinantslane, 9 (72) Inventor Jeffrey, Scott, Dupont United States Ohio, Fairfield, Southgate, Bluebird, 5233 Gee (72) Inventor Eugene, Paul, Gosselink United States of America Ohio, Cincinnati, Susanna, Drive, 3754 (72) Inventor Janet, Sue, Litig United States Ohio, Fairfield, Hidden, Hills, Drive, 159 (72) Inventor Axel, Ma Schelen, Belgium-1050, Brussels, Rue, Fayder, 47 (72) Inventor Timothy, Schroeder United States of America, Ohio, Mason, Joseph, Rein, 5249 (72) Inventors Christian, Arthur, Jack, Toen United States Ohio, West, Chester, Lap, Farm, Drive, 8485 F-term (reference) 4J005 AA09 4J043 PA02 PA05 PA09 PA13 PB13 PC066 QA04 UB141 UB211 ZA60 ZB06

Claims (11)

[Claims] 1. An ethoxylated amino-functional polymer, characterized in that the polymer contains less than 100 ppm of total aldehydes, expressed as acetaldehyde, after contact with an acidic medium. 2. An amino-functional polymer comprising: a) a linear or non-cyclic polyamine having a main chain of the formula:b) a cyclic polyamine having a main chain of the following formula:And mixtures thereof, wherein in at least one of the NR 'units of the polyamine backbone, R' is-(
CH₂CH₂O)_xH, others are hydrogen, C₁-C_{twenty two}Alkyl, C₃-C_{twenty two}Al
Kenil, C₇-C_{twenty two}Arylalkyl, C₂-C_{twenty two}Hydroxyalkyl,-(C
H₂)_pCO₂M,-(CH₂)_qSO₃M, -CH (CH₂CO₂M) CO₂ M,-(CH₂)_pPO₃M,-(R¹O)_mB, -C (O) R³Selected from
Wherein the main-chain linked R units are C₂-C₁₂Alkylene, C₄-C₁₂Alkenylene,
C₃-C₁₂Hydroxyalkylene, C₄-C₁₂Dihydroxyalkylene, C₈-
C₁₂Dialkylarylene,-(R¹O)_xR¹-,-(R¹O)_xR⁵(OR ¹ )_x-,-(CH₂CH (OR²) CH₂O)_z(R¹O)_yR¹(OCH₂ CH (OR²) CH₂)_w-, -C (O) (R⁴)_rC (O)-, -CH₂CH
(OR²) CH₂-And mixtures thereof; wherein R is¹Is C₂-C₆Selected from the group consisting of alkylene and mixtures thereof
Selected; R²Is hydrogen,-(R¹O)_xFrom the group consisting of B and their mixtures
Selected; R⁴Is C₁-C₁₂Alkylene, C₄-C₁₂Alkenylene, C₈-C ₁₂ Arylalkylene, C₆-C_TenGroup consisting of arylenes and their mixtures
Selected from; R⁵Is C₁-C₁₂Alkylene, C₃-C₁₂Hydroxyalkyl
N, C₄-C₁₂Dihydroxyalkylene, C₈-C₁₂Dialkylarylene,-
C (O)-, -C (O) NHR⁶NHC (O)-, -R¹(OR¹)-, -C (
O) (R⁴)_rC (O)-, -CH₂CH (OH) CH₂-, -CH₂CH (O
H) CH₂O (R¹O)_yR¹OCH₂CH (OH) CH₂-And their mixtures
Selected from the group consisting of compounds; R⁶Is C₂-C₁₂Alkylene or C₆-C₁₂ R 'units are selected from the group consisting of arylene;₁-C_{twenty two}Alkyl,
C₃-C_{twenty two}Alkenyl, C₇-C_{twenty two}Arylalkyl, C₂-C_{twenty two}Hydroxya
Lucil,-(CH₂)_pCO₂M,-(CH₂)_qSO₃M, -CH (CH₂C
O₂M) CO₂M,-(CH₂)_pPO₃M,-(R¹O)_xB, -C (O) R ³ And B is hydrogen, C is selected from the group consisting of₁-C₆Al
Kill,-(CH₂)_qSO₃M,-(CH₂)_pCO₂M,-(CH₂)_q(C
HSO₃M) CH₂SO₃M,-(CH₂)_q(CHSO₂M) CH₂SO₃M
,-(CH₂)_pPO₃M, -PO₃Selected from the group consisting of M and mixtures thereof
Selected; R³Is C₁-C₁₈Alkyl, C₇-C₁₂Arylalkyl, C₇-C ₁₂ Alkyl-substituted aryl, C₆-C₁₂Group consisting of aryls and mixtures thereof
M is hydrogen or a water-soluble amount sufficient to satisfy the charge balance
X is a water-soluble anion; m has a value from 2 to about 700;
n has a value of 0 to about 350; 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 has a value of 0 or 1;
Has a value of 00; y has a value of 0-100; z has a value of 0 or 1
The polymer of claim 1. 3. The polymer according to claim 1, wherein x has a value in the range of 1-20, preferably 1-10. 4. A method for treating an ethoxylated polyamino-functional polymer with sodium sulfite prior to acidification such that the acidified polymer contains 0.5-1% w / w of added sodium sulfite. A method for obtaining the polymer according to any one of claims 1 to 3. 5. The step of hydroxyethoxylating the polyamine, the step of further ethoxylating the polyamine in the presence of a base catalyst, after the further ethoxylation step is completed, after the base catalyst is neutralized, and 4. A process for obtaining a polymer as claimed in any one of the preceding claims, comprising contacting the polyamine with borohydride or borohydride equivalent upon the combination of. 6. A method for obtaining a polymer as claimed in claim 1, comprising the step of underhydroxylating the polyamine before adding the base catalyst. 7. A polymer as claimed in claim 1, comprising at least 0.01% by weight.
A fabric care composition comprising: 8. The composition, preferably selected from cationic fabric softener compounds, more preferably the following formula: Or the following formula: A fabric softener compound selected from the quaternary ammonium fabric softeners of Formula I wherein Q is a carbonyl unit having the formula: Each R unit is independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl and mixtures thereof, preferably methyl or hydroxyalkyl; each R ¹ unit is independently linear or branched C ₁₁ -C ₂₂ alkyl, linear or branched C ₁₁ -
C ₂₂ alkenyl, and mixtures thereof; ^{R 2} is _hydrogen, C 1 -C _{4 alkyl,} C 1 -C ₄ hydroxyalkyl, and mixtures thereof; X is compatible with fabric softener active and auxiliary ingredients anion The composition according to claim 7, further comprising: index m is 1 to 4, preferably 2; index n is 1 to 4, preferably 2. 9. The composition according to claim 1, wherein the composition has a pH of less than 6, preferably 2.0 to 5, more preferably 2.5 to 4.5, most preferably 2.5 to 3.5. 9. The composition according to 7 or 8. 10. The composition according to claim 7, wherein the composition is in a liquid form. 11. The method according to claim 1, wherein discoloration and malodor are reduced by contacting the polymer with an acidic medium.
Use of an ethoxylated amino-functional polymer according to any one of the preceding claims.