KR920001796B1 - Detergent compositions containing cationic compounds - Google Patents

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Description

[Name of invention]

Detergent composition containing cationic compound

Detailed description of the invention

The present invention relates to cationic compounds having the property of removing clay contamination and preventing redeposition in detergent compositions.

A particularly important property of detergent compositions is the ability to remove particulate contamination from various types of fabrics during washing. Perhaps the most important particulate contamination is clay type pollution. Clay contaminated particles generally consist of positively charged cations (eg calcium) that connect them together between the negatively charged layer of aluminosilicate and the negatively charged layer.

Various models of compounds can be proposed that have the property of removing clay contamination. One model requires that the compound have two distinct characteristics. The first is that the compound can be adsorbed onto the negatively charged layer of clay particles, and the second is that once adsorbed compound separates (expands) the negatively charged layers from one another, the clay particles lose cohesion and can be removed into the wash water. Should be.

One class of clay decontamination compounds that have been shown to work in accordance with this model is the pleethoxy zwitterionic surfactants known from US Pat. No. 4,301,044 (Wentler et al., November 17, 1981). Representative of these compounds are those of the general formula:

Wherein R ¹ is a C ₁₄ -C ₂₀ alkyl group; X is 1 or an integer from 3 to 5; y is 6 to 12.

Other reference patents are described in US Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975, detergent compositions containing polyethoxy zwitterionic surfactants and other detergent surfactants), US Pat. No. 3,925,262 (Laughlin et al., December 1975). .9, detergent compositions containing polyethoxy zwitterionic surfactants and detergent builders, US Pat. No. 4,157,277 (Gosselink et al., June 6, 1979, C ₄ polyoxyalkylene zwitter ion surfactants useful in detergent compositions). U.S. Patent 4,165,334 (Gosselink et al., Aug. 21, 1979, sulfonium type polyethoxy zwitter ion surfactants).

Such polyethoxy zwitterionic surfactants are generally compatible with other detergent surfactants such as nonionic, zwitterionic and amphoteric. However, as pointed out in Wembley et al., Most anionic surfactants interfere with the particulate removal performance of these compounds and also interfere with anionic contamination such as fatty acids. Since anionic detergent surfactants form the most important class of these materials used in detergent compositions, the lack of miscibility between these polyethoxy zwitterionic surfactants and anionic surfactants is responsible for removing particulate (clay) contamination. It is a great obstacle where it is required.

In addition to the clay decontamination, one of the other properties mentioned in the Moglin et al. Patent for this polyethoxy zwitterionic surfactant is that the contaminants removed during washing remain in the suspension. Contaminants removed from the material and suspended in the wash water may be redeposited on the fabric surface. This redeposited contamination causes noticeable clouding or "greying", especially with white fabrics. Since staining is generally hydrophobic, this graying phenomenon is a particularly important problem for fabrics in which all or part of the hydrophobic fibers (such as polyester) are made.

To minimize this problem, the detergent composition may contain a re-deposition inhibitor or a white oil retainer. In addition to the aforementioned polyethoxy zwitterionic surfactants, there are a variety of other compounds that can be used as antideposition agents. One such class of reagents is water-soluble copolymers of acrylic or methacrylic acid with acrylic or methacrylic acid-ethylene oxide condensates known from US Pat. No. 3,719,647 (Hardy et al., 1973.3.6). Another class of re-deposition inhibitors is U.S. Patent No. 3,597,416 (Diehl, Aug. 3, 1971, ionic bonding of dodecyltrimethyl phosphonium chloride and sodium carboxymethylcellulose) and U.S. Patent No. 3,523,088 (Dean et al., 1970.8.4). Cellulose and carboxy methine cellulose derivatives known in the " Anti-deposition agent comprising alkali metal carboxymethine cellulose and hydroxy propyl cellulose ". Mixtures of these compounds are also used to exhibit re-deposition prevention and clay decontamination. US Patent No. 4,228,044 (Carnbre, Oct. 14, 1980) discloses a re-deposition preventive and clay decontamination detergent comprising a nonionic alkyl polyethoxy surfactant, a polyethoxyalkyl quaternary cationic surfactant and a fatty amide surfactant. Compositions are known.

Such anti-deposition agents have several drawbacks. While there is an effect of keeping contamination suspended, these compounds may lack clay decontamination. A mixture of compounds may also be required to achieve the effect of preventing redeposition as is known in the patents of diyl and diyne. There is a need for a mixture of compounds that can simultaneously achieve re-deposition prevention / clay decontamination effects, as known in the Cambre patent.

It is therefore an object of the present invention to provide a composition useful as a detergent which exhibits particulate contamination, in particular clay decontamination effect.

It is another object of the present invention to provide compounds useful in detergent compositions which have the advantage of clay decontamination and are compatible with anionic detergent surfactants.

Another object of the present invention is to provide a compound useful in detergent compositions having anti-deposition properties.

Another object of the present invention is to provide a compound useful in detergent compositions having both clay decontamination and anti-deposition properties.

These and other objects of the present invention are described below. United States Patent No. 3,838,057 (Barnes et al., September 24, 1974) introduces a cosmetic soap containing an ethoxylated quaternary ammonium compound, including ethoxylated quaternary PEI, which has been shown to be useful as an antistatic and softener in the detergent, textile and polymer industries. And the general formula of these ethoxylated quaternary is as follows.

Wherein R ₁ is a miscible quaternary nitrogen substituent; n is at least 2 and X is 3 to 40; X ⁻ is a miscible anion.

Preferred compounds are those in which R ₁ is a C ₈ -C ₂₂ alkyl group or R'COO (EO) _y -CH ₂ CHOHCH ₂ -group wherein R 'is a C ₈ -C ₂₂ alkyl group, y is 3 to 40 ) Compound. See also U.S. Patent No. 4,179,382 (Rudkin et al., December 18, 1979), U.S. Patent No. 4,152,272 (young, 1979.5.1), and European Patent Application No. 2,085 (Rudkin et al., May 30, 1979). Ethoxylated quaternary polyamines are known in which C ₁₀ -C ₂₄ alkyl or alkylene groups are bonded to one of the atoms. U.S. Patent No. 3,671,305 (Brown et al., 1972.6.20) discloses zwitterionic monomers that produce polymers for use in treating films, sheets and filament materials, which treatments are durable, hydrophilic and antistatic. , Anti-contamination, decontamination and polishing. The general formula of these monomers is as follows:

Wherein n is 0 to 10; R ⁰ is hydrogen or methyl; Z is oxygen or -NH-; when n is 1 to 10, A can be a C ₂ -C ₃ alkylene group (eg ethylene); R ₁ and R ₂ may be C ₁ -C ₄ alkyl; A 'may be C ₁ -C ₄ alkylene; R may be SO ₂ .

U.S. Patent No. 3,671,502 (Samour et al., 1972.6.20) discloses copolymers useful as binders in the production of nonwovens. These copolymers are essentially the following general formula,

의 단량체 약 5 내지 90%와

With about 5 to 90% of monomers

The following general formula,

Hydroxy acrylate such as polyglycerol acrylate / methacrylate of about 10 to 95% by weight (wherein R ₁ is hydrogen or methyl; A is oxygen or —NH—, R ₂ is ethylene, propylene, 2-hydroxy propylene or 2-acetoxypropylene; R ₃ and R ₄ are alkyl; n ₁ is 1-4; X- is SO ₃ ^- or CO ₂ ^- and R 'is hydrogen or methyl; R 'is hydrogen, methyl or hydroxy; n ₂ is 0 when R' is hydrogen or methyl (eg ethylene group); n ₃ is 2-4).

U.S. Patent No. 3,301,783 (Dickson et al., 1967.1.31) discloses oxyalkylation, acylation, alkylation, carbonylation and olefination derivatives of polyalkyleneimines, in particular polyethyleneimine (PEI). In the case of oxyalkylated derivatives, alkylene oxides (eg ethylene oxide) react with polyalkyleneimines in a molar ratio of from 1: 1 to 1000: 1, preferably from 1: 1 to 200: 1. Known epoxy PEIs include Examples 1-0 ₇ and 1-0 ₈ produced by condensation of ethylene oxide 105 and 200 moles with 900 M W. PEI, respectively. The ethoxylation degree was calculated to be about 4. 5 and 8 ethoxy groups per reactive site, respectively. Ethoxylated polypropyleneimines (molecular weight 500) having about 4 and 8 ethoxy units per reactive site, respectively, are shown in Examples 27-0 ₅ and 27-0 ₆ . Among the various known uses of these polyalkyleneimine derivatives, it is shown that they are useful as detergent softeners and antistatic agents. Preferred uses known in this patent are as chelating agents, lubricant additives, emulsifiers and cutting oils.

United States Patent No. 2,792,371 (Dickson, 1957.5.14) describes a process for breaking mineral oil emulsions with oxyalkylated tetraethylenepentaamine (TEPA). Certain known ethoxylated TEPAs contain about 5 (Example 3aa), about 7 (Example 4aa), about 8. 5 (Example 5a), and about 15. 5 ethoxy units per reactive site ( Example Bc) Contains. Similarly, U.S. Pat.Nos. 2,792,370 (Dickson, 1957.5.14) show ethoxy units per reactive site at about 5. 5 (Example 3aa), 7. 5 (Example 4aa), 9 (Example 5a), and 16 It is known to destroy mineral oil emulsions with oxyalkylated triethylene tetramin (TETA), including those containing Example 5 (Example Bc). Other reference patents include U.S. Patent No. 2,792,372 (Dickson, 1957.5.14, oxyalkylated PEA used to destroy mineral oil emulsions) and U.S. Patent No. 2,792,369 (Dickson, 1957.5.14. Oxygen used to destroy mineral oil emulsions. Alkylated diethyltetraamine).

U.S. Patent No. 4,171,278 (Andree et al., October 16, 1979) discloses cold water detergent compositions containing detergent surfactants (eg anionic) and hydroxyalkylamines in a weight ratio of 100: 1 to 1: 1. An amine is a compound of the following general formula.

Wherein R ₁ is C ₁ -C ₁₆ alkyl; R ₂ is H or C ₁ -C ₁₆ alkyl; R ₁ + R ₂ has 6 to 20 carbon atoms; R ₄ is H or methyl; m, n and o are each 0 to 3; A is

(Wherein R ₃ is H or methyl, X is 2 to 6; y is 1 to 3; P is 0 to 3; the sum of mP is 1 to 5. 5, preferably 1 to 2) Of crosslinked groups.

In addition, Federal Republic of Germany Patent No. 2,165,900 (Henkel, July 7, 1973) describes gray formed by the reaction product of PEI with alkylglycidyl ether and ethylene oxide (2-hydroxyethyl powder at each reactive site when ethoxylated). Antioxidant cleaners are known. There are several patents known such as detergent compositions shampoo compositions containing slightly ethoxylated PEI (ethylene oxide: PEI weight ratio is 4: 1 or less). See, for example, US Pat. No. 3,489,686 (Parran, 1970.1.13); US Patent No. 3,580,853 (Parran, 1971 5.25); United Kingdom Patent Publication No. 1,111,708 (Procter Gamble, January 1, 1968), United States Patent No. 3,549,546 (Moore, December 22, 1970) and United States Patent No. 3,549,542 (Holderby, December 22, 1970).

The present invention relates to detergent compositions containing from about 0.05% to about 95% by weight of a water soluble cationic compound having clay decontamination / predeposition resistance. These compounds are selected from the group consisting of:

(1) an ethoxylated cationic monoamine of the following general formula;

(2) an ethoxylated cationic diamine of the following general formula;

(Wherein M ¹ is an N ⁺ or N group; M ² is each an N ⁺ or N group and at least one M ² is an N ⁺ group)

(3) an ethoxylated cationic polyamine of the following general formula;

(4) an ethoxylated cationic polymer composed of a polymer backbone, two or more M groups and one or more LX groups, wherein M is a cationic group attached to or integrated with the backbone and contains an N ⁺ positive charge center; L connects groups M and X, or groups X to the polymer backbone);

(5) mixtures thereof

Or -0-, R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is a C ₂ -C ₁₂ alkylene, hydroxy alkylene, alkenylene, arylene or alxarylene, or a C ₂ -C ₃ oxyalkylene residue containing 2 to about 20 oxyalkylene units, Provided that no 0-N bond is formed and R ² is each C ₁ -C ₄ alkyl or hydroxyalkyl, the remainder -LX or two R ² together are-(CH ₂ ) rA ^2- (CH ₂ ) s Forms-wherein A ² is -O- or -CH _2- , r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; R ³ is each C ₁ -C ₈ alkyl or hydroxyalkyl, benzyl, LX or two R ³ groups or one R ² and one R ³ together are-(CH ₂ ) _r -A ^2- (CH ₂ ) _s- ; R ⁴ is an alkaryl group having substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or P-substituted sites; R ⁵ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene, or a C ₂ -C ₃ oxyalkylene residue containing about 2 to 20 oxyalkylene units Provided no 0-0 or 0-N bonds are formed; X is a nonionic group selected from the group consisting of H, C ₁ -C ₄ alkyl, or hydroxyalkylesters or ether groups or mixtures thereof; L is a hydrophilic chain containing a polyoxyalkylene moiety-[(R ⁶ 0) _m (CH ₂ CH ₂ O) _n ]-, where R ⁶ is C ₃ -C ₄ alkylene or hydroxyalkylene, m and n are numbers such that-(H ₂ CH ₂ O) _n -constitutes at least about 50% by weight of the polyoxyalkylene moiety); d is 1 when M ² is N ⁺ and 0 when M ² is N; n is at least about 12 for the cationic monoamine, at least about 6 for the cationic diamine, and at least about 3 for the cationic polyamine and dicatalytic polymer; p is 3 to 8; q is 1 or 0; t is 1 or 0; However, when q is 1, t is 1.

In addition to the cationic compound, the detergent composition also consists of about 1 to 75% by weight of nonionic, anionic, amphoteric, zwitter or cationic surfactants or mixtures thereof. In addition to these detergent surfactants, the detergent composition may optionally contain 0 to about 30 weight percent detergent builders.

Cationic compounds of the present invention can be miscible with anionic detergent surfactants while having clay decontamination benefits. It is believed that this is because the positively charged cationic group causes the compound to adsorb in the clay particles negatively. It is also believed that the hydrophilic ethoxy unit attached to the compound expands the clay particles, causing the clay particles to lose coagulation and to be washed off in the wash water.

The anti-redeposition benefits obtained by these cationic compounds are believed to be due to the positively charged cationic groups allowing the compounds to adsorb to the contamination suspended in the wash water. The more these compounds are adsorbed to suspended contamination, the more they accumulate in the hydrophilic layer created by the attached ethoxy units. This contamination surrounded by hydrophilic groups prevents redeposition of the fabric during washing, especially hydrophobic fabrics such as polyester.

Water-soluble cationic amines useful in the detergent compositions of the present invention include the above-mentioned ethoxylated cationic monoamines, ethoxylated cationic diamines, ethoxylated cationic polyamines.

환상(예,

) 또는 가장 바람직하게는 직쇄(예 : -CH₂-CH₂, CH₂-CH₂-CH₂-, -CH₂-CH)) 알킬렌, 하이드록시알킬렌, 알케닐렌, 알크아릴렌 또는 옥시 알킬렌일 수 있다.R in the general formula of the above cationic amine^OneSilver side chains (e.g. -CH²

Fantasy (e.g.,

) Or most preferably straight chain (e.g. -CH₂-CH₂, CH₂-CH₂-CH₂-, -CH₂-CH)) alkylene, hydroxyalkylene, alkenylene, alxarylene or oxy alkylene.

R ¹ is preferably C ₂ -C ₆ alkylene when it is an ethoxylated cationic diamine. R 2 is preferably each methyl or —LX, and R ³ is preferably each C ₁ -C ₄ alkyl or hydroxyalkyl, most preferably methyl.

, SO

, PO

, MeOSO₃-와 같은 것이 포함된다. 특히 바람직한 반대 음이온은 Cl- 및 Br-이다.The positive charge of the N ⁺ group is canceled by a suitable number of counter anions. Suitable counter anion groups include Cl-, Br-, SO

, SO

, PO

, MeOSO ₃ -and the like. Particularly preferred counter anions are Cl- and Br-.

X may be a nonionic group selected from hydrogen (H), C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups or mixtures thereof. Preferred esters or ethers are acetate esters and methyl ethers, respectively. Particularly preferred non-ionic groups are H and methyl ether.

In the above general formula, the hydrophilic chain L is usually composed entirely of polyoxyalkylene moieties-[(R ⁴ O) _m (CH ₂ CH ₂ O) _n ]-. The-(R ⁴ O) _m -and-(CH ₂ CH ₂ O) _n -moieties in the polyoxyalkylene moiety can be mixed together or preferably-(R ⁴ O) _m -and-(CH ₂ CH ₂ O) _n -form a block of parts. R ⁶ is preferably C ₃ H ₆ (propylene). m is preferably 0 to 5, most preferably m is 0, that is, it is preferred that the polyoxyalkylene moiety consists entirely of-(CH ₂ CH ₂ O) _n- . The-(CH ₂ CH ₂ O) _n -moiety preferably consists of at least 85% by weight of polyoxyalkylene, most preferably 100% by weight (m = 0).

In the above structures, M ¹ and M ² are each preferably N ⁺ groups for cationic diamines and polyamines.

The general formula of the preferred ethoxylated cationic mono- and diamines is as follows.

Wherein X and n are as defined above and a is 0 or 4 (eg ethylene, propylene and hexamethylene); b is 1 or 0.

For preferred cationic monoamines (a = 0) n is preferably at least about 12, typically in the range of 15-25. For preferred cationic diamines (b = 1), n is at least about 12, typically from about 12 to 42.

이고; n은 바람직하게는 약 12이상이며 통상적으로 약 12 내지 42범위이며; p는 바람직하게는 3 내지 6이다. R⁴가 치환된 아릴 또는 알크 아릴 그룹인 경우, q는 바람직하게는 1 이며 R⁵는 바람직하게는 C₂-C₃알킬렌이다. R⁴가 알킬, 하이드록시알킬, 또는 알케닐 그룹인 경우와 q가 0인 경우 R⁵는 바람직하게는 C₂-C₃옥시알킬렌이며; q가 1인 경우 R⁵는 바람직하게는 C₂-C₃알킬렌이다.R ⁴ (straight chain, branched or cyclic) in the structure of the above ethoxylated cationic polyamine is preferably a substituted C ₃ -C ₆ alkyl, hydroxyalkyl or aryl group; A ¹ is preferably

ego; n is preferably at least about 12 and typically ranges from about 12 to 42; p is preferably 3 to 6. When R ⁴ is a substituted aryl or alk aryl group, q is preferably 1 and R ⁵ is preferably C ₂ -C ₃ alkylene. When R ⁴ is an alkyl, hydroxyalkyl, or alkenyl group and q is 0 R ⁵ is preferably C ₂ -C ₃ oxyalkylene; When q is 1 R ⁵ is preferably C ₂ -C ₃ alkylene.

Such ethoxylated cationic polyamines can be derived from polyaminoamides as follows.

Such ethoxylated cationic polyamines can also be derived from polyamino propyleneoxide derivatives as follows.

Wherein C is a number from 2 to about 20, respectively.

[Production method of cationic amine]

[Method 1]

Cationic amines of the invention can be prepared according to the following scheme:

The method for synthesizing such cationic amines is described below.

Example 1

Step 1: Ethoxylation Method.

N-2-hydroxyethyl morpholine (0.8 mole) is placed in a flask equipped with a magnetic stirrer, a cooler, an argon introduction tube, an ethylene oxide sparger and an internal thermometer. After clarification with argon NaH (0.2 mol) is added to the flask. The reaction mixture is stirred until NaH is reacted. Ethylene oxide is added with vigorous stirring and the temperature is maintained at about 80-120 ° C. The reaction is stopped when the ethoxylated compound has a degree of ethoxylation of about 11.

Step 2: Level 4

Mix the ethoxylated compound (0.03 mol) from step 1 with 1,6-dibromohexane (0.015 mol) and mix the reaction mixture, then put it into a jar and seal it and heat it to 80 ° C. for 10 days Crude quaternary 1,6-bis [(N-morpholidioethoxylate (11)]-hexanedibromide is obtained.

[Method 2]

The ethoxylated cationic amines of the present invention can also be prepared by standard methods of ethoxylating and quaternizing amines. It is preferred that there is an initial step of condensing a sufficient amount of ethylene oxide to introduce 2-hydroxyethyl groups at each reactive site (hydroxyethylation). This initial step can be omitted by using 2-hydroxyethylamine as starting material. Subsequently, an appropriate amount of ethylene oxide is used as the catalyst using an alkali metal (e.g., sodium or potassium) or its hydride or hydroxide as a catalyst to obtain ethoxylated amines, respectively. The degree (n) of ethoxylated amines per reactive site can be determined according to the following formula;

Ethoxylation degree = E / (AXR)

[Where E is the total number of moles of condensed ethylene oxide (including hydroxyethylation), A is the number of moles of starting amine, R is the number of reactive sites of the starting amine (3 for normal monoamines, diamine 4, polyamine is 2xP)

The ethoxylated amine can then be quaternized with an alkyl halide gun such as methyl bromide to produce an ethoxylated cationic amine.

Representative synthesis methods of the ethoxylated cationic amines of the present invention by this method are as follows;

Example 2a

Step 1: ethoxylation method

1,6-hexamethylenediamine (100 g, 0.86 mole) is placed in a flask and heated to 85 ° C. under argon. Ethylene oxide (EO) is blown into the flask. The temperature of the reaction was slowly increased to 120 ° C. over about 5 hours, and then briefly raised to 158 ° C. and cooled to 100 ° C. H-NMR showed about 4 moles of EO bound at this point.

Sodium spheres (1.24 g, 0.05 mole) are added and the reaction is stirred overnight after sodium is consumed. Further EO is added and the reaction temperature is increased to 120 ° C. After 3 hours, H-NMR showed about 10 moles of EO bound per mole of diamine. Additional sodium spheres are added (3. 6 g, 0 15 moles) and ethoxylation is continued. The temperature is increased to 125-130 ° C. Continue ethoxylation for about 22 hours. The reaction is terminated when about 96 moles of EO are consumed per mole of diamine, resulting in an ethoxylation degree of about 24 degrees.

Step 2: Level 4 Course

Part of the ethoxylated diamine (25 g, 0.0057) from step 1 is first quaternized by dissolving the diamine in methanol (100 ml) containing a small amount of NaOH. Excess methyl bromide is added using a dry ice cooler. The reaction mixture is allowed to stand overnight after the pH is reduced to about 4. NaOH in methanol is added to increase the pH to about 9. The quaternary compound is isolated by stripping off methanol and remaining methyl bromide. The resulting wet substance is washed several times with dichloromethane. The dichloromethane washes were collected and filtered to remove solids and stripped to give 27. 5 g of yellow oil which solidified at room temperature. This oil contains an ethoxylated quaternary amine.

Example 2b

Step 1: ethoxylation method

Dry triethanolamine (TEA) (16.O1 g, 0.107 mol) was catalyzed with 0.5 g (0.0125 mol) of 60% NaOH in mineral oil. Subsequently, ethylene oxide (EO) is added while stirring at 150-170 degreeC and atmospheric pressure. After 23 hours, 36.86 g (8.38 moles) of EO were added to give a calculated total ethoxylation degree of 26.1. TEA (PEI 17) under ethoxy is a light brown waxy solid.

Step 2: Level 4

A portion of the ethoxylated TEA from step 1 (31.68 g, 0.0088 moles) is dissolved in H ₂ O to give a about 50% solution. The solution is heated to 60-70 ° C. with magnetic stirring. Sodium bicarbonate is added as needed to introduce methyl bromide gas through the reactor for 8 hours while maintaining the pH above about 7. After quaternization, the solution is dialyzed for 3 hours to remove salt. Dilute the solution to obtain a 10% slightly pale golden aqueous solution containing ethoxylated quaternary TEA.

Cationic Polymer

The water soluble cationic polymer of the present invention is composed of one polymer backbone, two or more M groups and one or more LX groups (wherein M is a cation attached to or incorporated into the backbone; X is H, Or a C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether group or a mixture thereof; L is a hydrophilic chain which connects groups M and X or X to the polymer backbone.

As used herein, “polymer backbone” means a polymerized moiety to which groups M and L-X are attached or integrated into one. The term includes oligomeric backbones (2-4 units) and electron polymerization backbones (5 or more units).

The term “attached” as used herein may be represented by the following general formulas (A) and (B) as the group is suspended in the polymer backbone.

As used herein, the term "unified" means that the group constitutes part of the polymer backbone and may be represented, for example, by the following general formulas (C) and (D).

Any polymer backbone can be used as long as the resulting cationic polymer is water soluble and has antidecontamination / antideposition properties. Suitable polymer backbones include polyurethanes, polyesters, polyethers, polyamides, such as polyimides and polyacrylates, polyacrylamides, polyvinylethers, polyethylene, polypropylene and other polyalkylenes, polystyrenes and other polyalkylenes Polyalkyleneamines, polyalkyleneimines, polyvinylamines, polyallylamines, polydiallylamines, polyvinylpyridine, polyaminotriazoles, polyvinylalcohols, aminopolyureylenes and mixtures thereof.

M can be any miscible cation group composed of N ⁺ (grade), positively charged centers. The quaternary positive charge center can be represented by the following general structures (E) and (F).

Particularly preferred M groups are those containing a quaternary center represented by the general structure (E). The cationic group is preferably located close to or integrated with the polymer backbone.

The positive charge at the N ⁺ center is canceled by an appropriate number of counter anions. Suitable anions include Cl opposite _{^{-, Br - SO 3 -2,}} SO 4 -2, PO 4 -2, 3 MeOSO - include those as. Particularly preferred counter anions are Cl ⁻ and Br ⁻ .

X may be an anionic group selected from hydrogen (H), C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups and mixtures thereof. Preferred ester or ether groups are acetate esters and methyl ethers, respectively. Particularly preferred anionic groups are H and methyl ether.

Cationic polymers of the present invention typically have a ratio of cationic group M to nonionic group X of about 1: 1 to 1: 2. However, the ratio of cationic group M to nonionic group X can be varied, for example, by suitable copolymerization of cationic, anionic (such as containing L-X groups) and mixed cationic / anionic monomers. The ratio of group M to group X is typically in the range of about 2: 1 to 1:10. In preferred cationic polymers the ratio is about 1: 1 to 1: 5. Polymers resulting from such copolymerization are usually randomly copolymerized in non-repeating sequences, ie cationic, anionic and mixed cationic / anionic monomers are copolymerized.

Units containing group M and group LX may constitute 100% of the cationic polymer of the present invention. However, other units (preferably anionic) may also be included in the polymer. Other units include units containing, for example, acrylamide, vinyl ether and non-quaternized tertiary amine groups (M ¹ ) with N centers. These other units may constitute about 0 to 90% of the polymer (about 10 to 100% of the polymer includes M ¹ -LX groups as units containing M and LM groups). Typically, these other units make up about 0-50% of the polymer (about 50-100% of the polymer is the unit containing M and LX groups).

The number of groups M and L-M usually ranges from about 2 to 200. The number of groups M and L-X is typically about 3 to 100. The number of groups M and LX is preferably about 3 to 40.

In addition to the linking groups M and X or the attachment to the polymer backbone, the hydrophilic chain L generally consists entirely of the polyalkylene moiety-[(R'0) _m (CH ₂ CH ₂ 0) _n ]-. . The-(R'0) _m -and-(CH ₂ CH ₂ O) _n -portions of the polyoxyalkylene moiety can be mixed together and preferably-(R'0) _m -and-(CH ₂ CH ₂ 0 ) _n -form a block of parts R 'is preferably C ₃ H ₆ (propylene) and m is preferably from 0 to about 5, wherein 0 is that the polyoxyalkylene moiety consists entirely of-(CH ₂ CH ₂ 0) _n-. Most preferred. -(CH ₂ CH ₂ 0) _n -is preferably composed of at least about 85% by weight polyoxyalkylene moiety, most preferably 100% (ie m = 0). It is preferable that n is about 12-42.

Multiple (2 or more) -L-X moieties are linked to each other or attached to a group M or polymer backbone, for example this can be represented by the general formulas (G) and (H) below.

Structures such as (G) and (H) can be produced, for example, by reacting glycidol with group M or the polymer backbone and subsequently ethoxylating the formed hydroxy group.

Representative types of the cationic polymer of the present invention are as follows.

A. Polyurethanes, Polyesters, Polyethers, Polyamides, and Similar Polymers

One class of suitable cationic polymers is derived from such as polyurethanes, polyesters, polyethers, polyamides. These polymers consist of units selected from compounds of the general formulas (I), (II) and (III):

또는

이며; X는 0 또는 1이고; R은 H 또는 C₁-C₄알킬 또는 하이드록시알킬이며; R¹은 C₂-C₁₂알킬렌, 하이드록시 알킬렌, 알케닐렌, 사이클로알킬렌, 아릴렌, 또는 알크아릴렌이거나 또는 2 내지 20개의 옥시알킬렌 단위를 갖고 있는 C₂-C₃옥시알킬렌 부분으로 단 이때 A¹과 어떤 0-0 또는 0-N 결합도 형성되어 있지 않고; X가 1일때 R²는 A가

인 경우를 제외한 -R⁵-이거나 또는 -(OR₈)y- 또는 -OR⁵-이며, 단 이들은 A¹가 어떤 O-O 또는 N-O 결합도 형성하지 않고; R³는 A¹이

인 경우를 제외한 -R⁵- 또는 -(R⁸O)- 또는 -R⁵-이며 단 이들은 A¹과 어떤 O-O 또는 O-N 결합도 형성하지 않고; X가 0인 경우 R²는 -(OR⁸)_y-, -OR⁵-,

,

,

,

,

,

또는

R⁵-이며 R³은 -R⁵-이고; R⁴는 C₁-C₄알킬 또는 하이드록시알킬 또는 -(R⁵)k-[(C₃H₆O)m(CH₂CH₂0)_n]-X이며, R⁵는 알킬렌, 하이드록시알킬렌, 알케닐렌, 아릴렌 또는 알크아릴렌이고; R⁶는 각각 C₁-C₄알킬 또는 하이드록시알킬 또는 -(CH₂)r -A²- (CH₂)_s-이며 (여기서, A²는 -0- 또는 -CH₂-이다). R⁷은 H 또는 R⁴이고, R⁸은 C₂-C₃알킬렌 또는 하이드록시알킬렌이며; X는 H -

R⁹, -R⁹또는 이의 혼합물이고(여기서 R⁹는 C₁-C₄알킬 또는 하이드록시알킬이다); k는 0 또는 1이며; m과 n은 - (CH₂CH₂0)_n- 부분이 -(C₃H₆)_m(CH₂CH₂0)_n- 부분의 85% 이상을 구성하는 수이고; m은 0 내지 약 5이며, n은 약 3이고, r은 1 또는 2이며; s는 1 또는 2이고, r+s는 3 또는 4이며, y는 약 2 내지 20이고, u, v, w는 2개 이상의 N⁺중심과 2개 이상의 X그룹이 존재하는 수이다.Wherein A ¹ is

or

Is; X is 0 or 1; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxy alkylene, alkenylene, cycloalkylene, arylene, or alkarylene or C ₂ -C ₃ oxyalkyl having 2 to 20 oxyalkylene units No 0-0 or 0-N bond is formed with A ^{1 at} this time; When X is 1, R ² is A

-R ⁵ -or-(OR ₈ ) y- or -OR ⁵ -except when: A ¹ does not form any OO or NO bonds; R ³ is A ¹

-R ⁵ -or-(R ⁸ O)-or -R ⁵ -except when they do not form any OO or ON bond with A ¹ ; If X is 0 then R ² is-(OR ⁸ ) _y- , -OR ^5- ,

,

,

,

,

,

or

R ⁵ -and R ³ are -R ^5- ; R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl or-(R ⁵ ) k-[(C ₃ H ₆ O) m (CH ₂ CH ₂ 0) _n ] -X, R ⁵ is alkylene, hydroxy Oxyalkylene, alkenylene, arylene or alxarylene; R ⁶ is C ₁ -C ₄ alkyl or hydroxyalkyl or — (CH ₂ ) r —A ² — (CH ₂ ) _s —, where A ² is —0- or —CH ₂ —. R ⁷ is H or R ⁴ and R ⁸ is C ₂ -C ₃ alkylene or hydroxyalkylene; X is H-

R ⁹ , -R ⁹ or a mixture thereof, wherein R ⁹ is C ₁ -C ₄ alkyl or hydroxyalkyl; k is 0 or 1; m and n are _{- (CH 2 CH 2 0)} n - part is _{- (C 3 H 6) m} (CH 2 CH 2 0) n - number of constituting at least 85% of the portion, and; m is 0 to about 5, n is about 3 and r is 1 or 2; s is 1 or 2, r + s is 3 or 4, y is about 2 to 20, u, v, w is the number of two or more N ⁺ centers and two or more X groups present.

또는

인 것이 바람직하며, A²는 -O-인 것이 바람직하고, -X-는 1인 것이 바람직하며; R은 H인 것이 바람직하다. R¹은 직쇄(예, -CH₂-CH₂-CH₂,

) 또는 측쇄(예, -CH₂-

, -

,

)알킬렌, 하이드록시알킬렌, 알케닐렌, 사이클로알킬렌, 알크아릴렌, 또는 옥시알킬렌이며; R¹이 C₂-C₃옥시알킬렌 부분인 경우 옥시알킬렌 단위들의 수는 약 2 내지 12인 것이 바람직하고, R¹은 C₂-C₆알킬렌 또는 페닐렌인 것이 바람직하며; C₂-C₆알킬렌(예, 에틸렌, 프로필렌, 헥사메틸렌)인 것이 가장 바람직하다. R²는 -OR⁵- 또는 - (OR⁸)_y인 것이 바람직하며, R³는 -R⁵-0- 또는 -(R⁸O)_y-인 것이 바람직하고, R⁴와 R⁶는 메틸인 것이 바람직하다. R¹과 같이 R³는 직쇄 또는 측쇄일 수 있으며 바람직하게는 C₂-C₃알킬렌이며; R⁷은 바람직하게는 수소 또는 C₁-C₃알킬이고; R⁸은 바람직하게는 에틸렌이며; R⁹은 바람직하게는 메틸이고; X는 바람직하게는 H 또는 메틸이며; k는 바람직하게는 0이고, m은 바람직하게는 0이며, r 및 s는 바람직하게는 각각 2이고; y는 2 내지 12인 것이 바람직하다.In the general formula, A ¹ is

or

Is preferably, A ² is -O-, and -X- is preferably 1; R is preferably H. R ¹ is linear (eg, —CH ₂ —CH ₂ —CH ₂ ,

) Or side chains (eg -CH _2-

,-

,

) Alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene, or oxyalkylene; When R ¹ is a C ₂ -C ₃ oxyalkylene moiety, the number of oxyalkylene units is preferably about 2 to 12, and R ¹ is preferably C ₂ -C ₆ alkylene or phenylene; Most preferred is C ₂ -C ₆ alkylene (eg ethylene, propylene, hexamethylene). R ² is preferably -OR ⁵ -or-(OR ⁸ ) _y , R ³ is preferably -R ⁵ -0- or-(R ⁸ O) _y- , and R ⁴ and R ⁶ are methyl It is preferable. As R ¹ R ³ may be linear or branched and preferably C ₂ -C ₃ alkylene, and; R ⁷ is preferably hydrogen or C ₁ -C ₃ alkyl; R ⁸ is preferably ethylene; R ⁹ is preferably methyl; X is preferably H or methyl; k is preferably 0, m is preferably 0 and r and s are each preferably 2; It is preferable that y is 2-12.

In the general formula, n is preferably about 6 or more when the number of N ⁺ centers and X groups is 2 or 3, most preferably 12 or more, and usually u + v + w is in the range of about 12 to 42. In the case of a single polymerizer (V and W are zero), u is preferably from about 3 to 40, preferably from about 3 to 20. For random copolymers (u is at least 1 or preferably 0) it is preferred that v and w are each from about 3 to 40.

B. Methods of Making Polyacrylates, Polyacrylamides, Polyvinyl Ethers or Similar Polymers

Another class of suitable cationic polymers is derived from such as polyacrylates, polyacrylamides, polyvinylethers. These polymers consist of units selected from compounds of the general formulas (IV), (V) and (Vl):

,

,

,

,

,

,

,

, 또는

이며; R은 H 또는 C₁- C₄알킬 또는 하이드록시알킬이고; R¹은 치환 C₂-C₁₂알킬렌 하이드록시알킬렌, 알케닐렌, 아릴렌 또는 알크아릴렌 또는 C₂-C₃옥시알킬렌이며; R²는 각각 C₁-C₁₂알킬렌, 하이드록시알킬렌, 알케닐렌, 아릴렌 또는 알크아릴렌이고, R³는 각가 C₁-C₄알킬 또는 하이드록시알킬, 또는 -(R²)_k-[(C₃H₀O)_m(CH₂CH₂O)_n]-X이거나 또는 이들은 함께 -(CH₂)r-A²-(CH₂)s-를 형성하며(여기서 A²는 -0- 또는 -CH₂-이다); R⁴는 각각 C₁-C₄알킬 또는 하이드록시알킬이거나 두개의 R⁴가 함께 -(CH₂)r -A²-(CH₂)s-를 형성하고; X는 H, -

R⁵, -R⁵또는 이의 혼합물이며(여기서 R⁵는 C₁-C₄알킬 또는 하이드록시알킬이다); j는 1 또는 0이고, k는 1 또는 0이며; m과 n은 각 각 -(CH₂CH₂O)_n- 부분이 -(C₃H₆O)_m-(CH₂CH₂O)_n- 부분의 약 85중량% 이상을 구성하게하는 수이고; m은 0 내지 5이며; n은 약 3이상이고, r은 1 또는 2이며; s는 1 또는 2이고, r+s는 3 또는 4이며; u, v, w는 각각 2개 이상의 N⁺중심과 2개 이상의 2X 그룹이 존재하게하는 수이다.Wherein A ¹ is -O-,

,

,

,

,

,

,

,

, or

Is; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is substituted C ₂ -C ₁₂ alkylene hydroxyalkylene, alkenylene, arylene or alxarylene or C ₂ -C ₃ oxyalkylene; R ² is each C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, and R ³ is each C ₁ -C ₄ alkyl or hydroxyalkyl, or-(R ² ) _k — [(C ₃ H ₀ O) _m (CH ₂ CH ₂ O) _n ] -X or they together form-(CH ₂ ) rA ^2- (CH ₂ ) s- where A ² is -0- Or -CH _2- ; R ⁴ is each C ₁ -C ₄ alkyl or hydroxyalkyl or two R ⁴ together form — (CH ₂ ) r —A ² — (CH ₂ ) s—; X is H,-

R ⁵ , -R ^5, or mixtures thereof, wherein R ⁵ is C ₁ -C ₄ alkyl or hydroxyalkyl; j is 1 or 0 and k is 1 or 0; m and n are each _{- (CH 2 CH 2 O)} n - part is _{- (C 3 H 6 O)} m - (CH 2 CH 2 O) n - number of which make up the 85% by weight or more of the part and ; m is 0 to 5; n is at least about 3 and r is 1 or 2; s is 1 or 2 and r + s is 3 or 4; u, v, w are each a number such that at least two N ⁺ centers and at least two 2X groups exist.

, -

또는 -O-이며; A²는 바람직하게는 -O-이고; R은 바람직하게는 H이다. R¹은 직쇄(예, -CH₂-CH₂-CH₂-, -CH₂

) 또는 측쇄 (예, -CH₂-

,

) 치환 알킬렌, 하이드록시알킬렌, 알케닐렌, 알크아릴렌 또는 옥시알킬렌일 수 있으며; R¹은 바람직하게는 치환 C₂-C₆알킬렌 또는 치환 C₂-C₃옥시알킬렌이고 가장 바람직하게는 -CH₂

H - 또는 -CH

이다. R²는 각각 C₂-C₃알킬렌인 것이 바람직하며; R³와 R⁴는 각각 메틸인 것이 바람직하고; R⁵는 메틸인 것이 바람직하며; X는 H 또는 메틸인 것이 바람직하고, j는 1인 것이 바람직하며; k는 0인 것이 바람직하고; m은 0인 것이 바람직하며; r과 s는 각각 2인 것이 바람직하다.In the above formula, A^OneIs preferably

,-

Or -O-; A²Is preferably -O-; R is preferably H. R^OneSilver chain (e.g. -CH₂-CH₂-CH₂-, -CH₂

) Or side chains (eg -CH₂-

,

) Substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R^OneIs preferably substituted C₂-C₆Alkylene or substituted C₂-C₃Oxyalkylene and most preferably -CH₂

H-or -CH

to be. R²Are each C₂-C₃Preferably alkylene; R³And R⁴Are each methyl; R⁵Is preferably methyl; X is preferably H or methyl, and j is preferably 1; k is preferably 0; m is preferably 0; It is preferable that r and s are 2, respectively.

In the general formula, n, u, v and W may vary depending on n, u, v and w of the polyurethane and similar polymers.

C. Methods of Making Polyalkyleneamines, Polyalkyleneimines or Similar Polymers

Another class of suitable cationic polymers are those derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers consist of units selected from compounds of the general formulas (VII), (IX) and (IX) below.

, -R⁴또는 이의 혼합물이며(여기서 R⁴는 C₁-C₄알킬 또는 하이드록시알킬이다); d는 M'가 N⁺일때 1이고, M'가 N일때 0이며; e는 M'가 N⁺일때 2이고; M'가 N일때 O이며; k는 1 또는 0이고; m과 n은 -(CH₂CH₂0)_n- 부분이 -[(C₃H₆O)_m(CH₂CH₂0)_n]- 부분의 약 85중량% 이상을 구성하게하는 수이며, m은 0 내지 약 5이고; n은 약 3이상이며; x, y 및 z는 각각 2M' 그룹, 2N⁺중심 및 2x 그룹이 존재하게하는 수이다.Wherein R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alxarylene or C ₂ -C ₃ containing about 2 to 20 oxyalkylene units No 0-N bond is formed from the oxyalkylene moiety; R ² is C ₁ -C ₄ alkyl or hydroxyalkyl, or — (R ³ ) _k -[(C ₃ H ₆ C) _m (CH ₂ CH ₂ ) _n ] -X; R ³ is C ₁ -C ₁₂ alkylene, hydroxyalkylene alkenylene, arylene or alxarylene; M ¹ is N ⁺ or N center; X is H,

, -R ⁴ or a mixture thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl; d is 1 when M 'is N ⁺ and 0 when M' is N; e is 2 when M 'is N ⁺ ; O when M 'is N; k is 1 or 0; m and n are numbers such that the-(CH ₂ CH ₂ 0) _n -moiety constitutes at least about 85% by weight of the-[(C ₃ H ₆ O) _m (CH ₂ CH ₂ 0) _n ]-moiety, m is 0 to about 5; n is about 3 or greater; x, y and z are the numbers that allow 2M 'groups, 2N ⁺ centers and 2x groups, respectively.

In the above general formula, R ¹ may be varied as in R ¹ of polyurethane and homopolymer; R ² is methyl or — (R ³ ) _k -[(C ₃ H ₆ 0) _m (CH ₂ CH ₂ 0) _n ] -X, respectively; R ³ is preferably C ₂ -C ₃ alkylene and R ⁴ is preferably methyl; X is preferably H; K is preferably 0; m is preferably 0.

N is preferably about 6 or more when the number of M 'and X groups is 2 or 3; Most preferably, n is about 12 or more, and x + y + z is typically about 12 to 42. x + y + z is usually from 2 to about 40 and preferably from 2 to about 20. For short chain polymers x + y + z can range from 2 to 9 with 2 to 9 N ⁺ centers and 2 to 11 X groups. For long chain polymers x + y + z is at least 10 and preferably from about 10 to 42. In the case of short and long chain polymers the M ⁺ group is usually a mixture of about 50 to 100% N ⁺ centers and about 0 to 50% N centers.

Preferred cationic polymers of this class are C ₂ -C ₃ polyalkyleneamines (y + x + z is 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably 10 To about 42). Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are cationic polyethyleneamines (PRAs) and polyethyleneimines (PEIs). These preferred cationic polymers consist of units of the following general formula.

Wherein R ² (preferably methyl) M ′, X, D, x, y, z and n are as defined above; a is 1 or 0; Prior to ethoxylation, the PEA used to prepare the cationic polymer of the present invention has the following general formula:

Wherein x + y + z is 2 to 9 and a is 0 or 1 (molecular weight about 100 to 400). Each hydrogen atom attached to each nitrogen atom represents the active site of subsequent epoxidation. In preferred PEAs x + y + z ranges from about 3 to 7.

(Molecular weight about 110 to 310). These PEAs can be obtained by reaction with ammonia and ethylene dichloride and subsequent fractional distillation. Common PEAs thus obtained are triethylenetetraamine (TETA) and tetraethylenepentamine (TEPA). Amines above pentaamine, ie hexaamines, heptaamines, octaamines and possibly mixtures derived simultaneously from nonamines, do not appear to be separated by distillation and may include other substances such as cyclicamines and especially piperazine. There may also be cyclicamines having side chains with nitrogen atoms. The preparation of the PEA is described in US Pat. No. 2,792,372 (Dickson, May 14, 1957) by reference.

The minimum degree of ethoxylation needed to exhibit the desired clay decontamination / anti-deposition performance depends on the number of units in the PEA. When y + z is 2 or 3, n is preferably about 6 or more. Suitable advantages are obtained when n is 3 or more when y + z is 4 to 9. In most preferred ethoxylated PEAs n is at least about 12 and typically ranges from about 12 to 42.

The PEI used to prepare the compounds of the present invention has a molecular weight of at least about 440 prior to ethoxylation and represents at least about 10 units. Preferred compounds for the PEI used to prepare such compounds are those having a molecular weight of about 600 to 1800. The polymer backbone of these PEIs can be represented by the following general formula:

Wherein the sum of x, y and z represents a number large enough to yield a polymer having the molecular weight defined above. Although it may be a straight chain polymer backbone, side chains may also occur. The relative proportions of primary, secondary and tertiary amines present in the polymer depend on the method of preparation. The partition ratio of amine groups is typically as follows:

The hydrogen atom attached to each nitrogen atom of PEI represents the active site of subsequent ethoxylation. These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as sodium sulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like in carbon dioxide. See, for example, United States Patent No. 2,182,306 (Ulrich et al., December 5, 1939), US Pat. US Pat. No. 2,208,095 (Esselmann et al., July 16, 1940), US Pat. No. 2,806,839 (Crowther 1957. 17. 17), and US Pat. No. 2,553,696 (Wilson, 1951.5.21).

As defined in the general formula above, n is at least about 3 in cationic PEI. However, the minimum degree of ethoxylation needed for proper clay decontamination / redeposition prevention performance can be increased, especially if the PEI molecular weight is increased, even greater than about 1800. In addition, the degree of ethoxylation of the preferred compounds increases with increasing PEI molecular weight. In PEIs having a molecular weight of at least about 600, n is preferably at least about 12 and usually ranges from 12 to 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24 and usually in the range from 24 to 42.

D. Process for preparing diallylamine polymer

Another class of suitable cationic polymers are polymers derived from diallylamine. These polymers consist of units selected from compounds of the general formulas (X) to (VI).

⁴-R⁴또는 이의 혼합물이고(여기서, R⁴는 C₁-C₄알킬 또는 하이드록시 알킬이다); k는 1 또는 0이며, m과 n은 -(CH₂CH₂O)_n-부분이 [(C₃H₆O)_m(CH₂CH₂O)_n-]-의 약 85% 이상을 구성하게 하는 수이고; m은 0 내지 약 5이며; n은 약 3 이상이고, r은 1 또는 2이며, s는 1 또는 2이고, r+s는 3 또는 4이며; x는 1 또는 0이고; y는 x가 0일 때는 1이며, x가 1일 때는 0이고; u와 v는 각각 2개 이상의 N⁺중심과 2개 이상의 X 그룹이 존재하게 하는 수이다.Wherein R ¹ is C ₁ -C ₄ alkyl or hydroxyalkyl, or (R ² ) _k -[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] -X; R ² is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkylene, arylene or alxarylene; R ³ is each C ₁ -C ₄ alkyl or hydroxyalkyl, or together forms — (CH ₂ ) rA— (CH ₂ ) _s — where A is —O— or —CH ₂ — ; X is H, -C

⁴ -R ⁴ or a mixture thereof, wherein R ⁴ is C ₁ -C ₄ alkyl or hydroxy alkyl; k is 1 or 0, and m and n are-(CH ₂ CH ₂ O) _n -moieties constitute at least about 85% of [(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n -]- It is a letting number; m is 0 to about 5; n is at least about 3, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1; u and v are each a number such that at least two N ⁺ centers and at least two X groups exist.

In the above formula, A is preferably -0-; R ¹ is preferably methyl; Each of R ² is preferably C ₂ -C ₃ alkylene; Each of R ³ is preferably methyl; R ⁴ is preferably methyl; X is preferably N, k is preferably 0 and m is preferably 0; It is preferable that r and s are 2, respectively.

In the general formula, n is preferably about 6 or more when the number of N + centers and X groups is 2 or 3, respectively, n is preferably 12 or more, and typically U + V ranges from 12 to 42. Typically V is 0 and U is 2 to about 40, preferably 2 to about 20.

[Manufacturing Method of Cationic Polymer]

A. Manufacturing Method of Polyurethane

The polyurethane of the present invention may be prepared according to the following general scheme:

Example 3

Step 1: ethoxylation method

Monotetrahydropyranyl ether of diethylene glycol (1.77 moles) [Compt, Rend 260, 1399-1401 (1965)] is ethoxylated with 5 mole% NaH to produce the corresponding alkoxide catalytic amount. Ethoxylation is carried out at 90 to 120 ° C. until about 22 moles (n = 22) of ethylene oxide is absorbed per mole of starting alcohol to produce an ethoxylated compound.

Step 2: tosilization method

The ethoxylated compound from step 1 is dissolved in 1000 ml of acetonitrile and then cooled to about 10 ° C. 2. 67 moles of tosyl chloride dissolved in 500 ml of acetonitrile are added to this solution, cooled to 10 ° C. and then 2. 9 moles of triethylamine are added. After the reaction is completed, H ₂ O is added to decompose the remaining tosylchloride.

Step 3: Amination Method

To the reaction mixture from step 2 3. mole of diethanolamine is added and heated at 80 ° C. for 18 hours, after which the reaction mixture is cooled and acidified to pH slightly above 7 with HC1 and extracted with ether. The aqueous phase is then washed twice with a mixture of ether acetonitrile (about 5: 2 ratio). The aqueous phase is separated and basified with 50% NaOH. This aqueous phase is extracted with dichloromethane (2000m1). After separating the lower layer, 50% NaOH was added sufficiently and the aqueous phase was extracted three times with 2000 ml of 1/4 saturated NaOH solution while maintaining the strong basicity (pH of about 11).

The lower organic layer is removed to give the desired amination compound. Toluene (200 ml) is added and the mixture is stripped again to give the desired amination monomer.

Step 4: Polymerization Method

The monomer from step 3 is dissolved in chloroform without ethanol stabilizer and the monomer is pretreated at 80-90 ° C. under vacuum (1 ml pressure), Kuror apparatus for at least 18 hours. The monomer in chloroform is dried overnight between 3 A molecules and then transferred to an argon dry flask (with magnetic stirrer). To the monomer is added a dibutyltin dilaurate catalyst (0.058 molar equivalents) in chloroform under argon. To the stirred reaction mixture is added 0.7 moles of hexamethylene diisocyanate per mole of aminated monomer over 5 minutes. The reaction mixture is stirred at rt for 18 h. Chloroform is removed at about 60 ° C. under vacuum to afford a polymer.

Step 5: How to Level 4 and Remove the Protector

The polymer from step 4 is dissolved in methanol and excess ethyl bromide is added. After about 5 hours, the pH is adjusted to about 4 with aqueous HC1 and left overnight to solubilize the tetrahydropyranyl protecting group.

The solution is then neutralized with NaOH and stripped to give the crude polyurethane. The crude polyurethane is dissolved in chloroform and then filtered to remove the salt. This chloroform is stripped to give a polymer free of the desired salt.

B. Process for preparing random copolymers of ethoxylated acrylate and cationic methacrylamide

The random copolymer of the present invention may be prepared according to the following general scheme:

The method for synthesizing such random copolymers is described below.

Example 4

Decaethylene glycol monomethacrylate monomer (0.008 mol) and N- (3-dimethylaminopropyl) -methacrylamide monomer (0.011 mol) are dissolved in 40 ml of acetonitrile. Argon is introduced into the reaction mixture to remove oxygen.

0.23 g of benzoyl peroxide is dissolved in 10 ml of acetonitrile to similarly remove oxygen. The reaction mixture is heated to reflux and then benzoyl peroxide solution is added over 0.5 hours. Then, a solution in 5 ml of acetonitrile of 0.28 g of azobisisobutyronitrile is added to the reaction mixture and the overnight heating is continued. The methyl bromide stream is then passed through the reaction mixture and warmed slightly eK for 1 hour. The desired random copolymer is separated by stripping off the solvent.

C: Method for producing quaternary polyethyleneamines and polyethyleneimines.

Quaternary polyethylene amines and polyethyleneimines can be prepared using standard methods for ethoxylating amines followed by quaternization. Representative synthetic methods of such polyethyleneamine and polyethyleneimine are as follows.

Example 5a

Step 1: ethoxylation method

Tetraethylene pentamine (TEPA) (molecular weight 189, 13.5 g, 0.071 mol) is placed in a drying flask and dried under vacuum at 110 to 120 ° C. (pressure of 1 mmHg or less) for 0.5 hour while stirring. Vacuum is released by ethylene oxide (EO) discharged from the prepurged trap connected to the feed bank. Once the flask is filled with EO, carefully open the discharge stop cock to the trap connected to the discharge bubbler. Stirring at 115-125 ° C. for 3 hours followed by analysis of H-NMR yielded 1 degree of ethoxylation per reaction site. The reaction mixture is cooled through argon and 0.5 g (0.0125 mol) of 60% sodium hydride in mineral oil is added. Argon is passed through the stirred reaction mixture until the end of labor stops. Subsequently, EO is added to the mixture under atmospheric pressure with moderately stirring at 117 to 135 ° C. After 31 hours, 459 g (10.48 moles) of EO is added to give a calculated total epoxidation degree 21.

Step 2: Level 4

34.8 g (0.0052 mol) of ethoxylated TEPA, a brown waxy solid obtained from step 1, was dissolved in D ₂ O to give a 50% solution. The pH of the solution is about 8. The solution is heated to 60 ° C. and methyl bromide gas is passed through a reaction vessel whose outlet is connected to a bubbler. During the reaction for several minutes the pH becomes acidic and NaHCO ₃ is added to maintain the reaction at about pH 8. After about 20 hours the sweep bubbler is placed under the reaction mixture surface to allow methyl bromide to be introduced through the mixture, increasing the stirring speed. After a total of 22 hours the reaction mixture is dialyzed to 25% and dialyzed to remove salt. The reaction mixture is then lyophilized to yield quaternary ethoxylated TEPA which is a pale brown crystalline solid.

Example 5b

Step 1: ethoxylation method

In a similar manner to Example 3a, PEI (21.5 g molecular weight 600, 0.5 mole) was dried under vacuum at 120 ° C. and EO was introduced until hydroxy ethylation was complete. After 3 hours, the hydroxyethylated compound is cooled under argon and 50% NaH 0.1g (0.0022 mol) in mineral oil is added. The reaction mixture is heated to about 70 ° C. and then 88.5 g of EO is added to inject EO for 13 hours until ethoxylation degree 3.4 is obtained.

53 g (0.0173 mol) of this compound are placed in a similar apparatus, heated to 120 ° C., vacuumed for 0.5 hours, cooled under argon, and additionally 0.5 g (0.010 mol) of 50% NaH is added. Add EO for 11 hours until 103 g of EO is added. This increases the total ethoxylation to 11.6.

74 g (0.0082 mole) of PEI having an ethoxylation degree of 11.6 are added to a similar apparatus, and 70 g of EO is added at 170 ° C. and EO is injected over 6 hours until the total ethoxylation degree is 23.4.

Step 2: Level 4

In a similar manner to Example 3a, 20 g (0.00114 mol) of PEI having a degree of ethoxylation of 23.4 obtained in step 1 was dissolved in D ₂ O, heated to 50 to 60 ° C., and passed through methyl bromide for a total of 9 hours to give a quaternary ethoxy Obtained PEI is obtained.

D. Process for preparing diallylamine polymer

The diallylamine polymer of the present invention may be prepared according to the following general scheme.

The synthesis of these polymers is described below:

Example 6

Step 1: ethoxylation method

Diallylamine (1.7 mol) is dissolved in methanol (160 ml) under argon and then heated to 45 ° C. The reaction mixture is heated to 100 ° C. under vacuum to remove methanol. While stirring the residue, sodium hydride (6.6 g, 0.165 mol) in mineral oil is added until hydrogen evolution stops. Subsequently, ethylene oxide is added until the ethoxylation degree (n) reaches 7.

Step 2: Level 4

The crude ethoxylated diallylamine obtained from step 1 is dissolved in the same volume of 1N methanolic NaOH and methyl bromide is added. This methyl bromide addition continued until the H-NMR analysis showed that the methylene hydrogen adjacent to the tertiary nitrogen disappeared completely. Add 1N methanolic NaOH as needed to maintain the pH of the reaction mixture at about 9.

Methanol is removed to give a wet mass. This is washed several times with dichloromethane. The tax solution is collected and concentrated to give the desired quaternary compound.

Step 3: Polymerization Method

The quaternary monomer from step 2 is mixed with D ₂ O (20 ml) and heated at 95 ° C. for 1 h under argon. Tertiary butyl hydroperoxide (25 drops) was then added and reacted at 90 ° C for 18 hours. Then add 20 drops of hydroperoxide. After heating for 3 more days, the water was removed under vacuum (50-60 ° C., 0 1 mm pressure) to obtain a prepared polymer.

The amount that the cationic compound (s) may be present in the detergent composition of the present invention may vary depending on the compound used, the particular detergent form (liquid, granules) and the desired effect. These compositions can be used as detergents, laundry additives, laundry pretreatments. Generally cationic compounds contain from about 0.05 to 95 weight percent of the composition and usually range from 0.1 to 10 weight percent of laundry detergents. In view of the desired effect, preferred detergent compositions may contain from about 0.5 to 5% by weight of the cationic compound of the present invention. Typically, the composition preferably contains about 1 to 3 weight percent of these compounds. These compounds are present in the wash liquor at a concentration of about 2 to 200 ppm, preferably about 10 to 100 ppm, of US recommended amounts or about 30 to 1000 ppm, preferably about 50 to 500 ppm, of European recommended amounts. It is common to do

[Detergent detergent]

The amount of detergent surfactant contained in the detergent compositions of the present invention depends on the type of detergent surfactant formulated composition used (e.g. granules, liquids) and the desired effect. It is preferably made up by weight%. Detergent surfactants may be nonionic, anionic, amphoteric, zwitterionic, cationic or mixtures thereof.

A. Nonionic Surfactants

Nonionic surfactants suitable for use in the detergent compositions of the present invention are generally known from US Pat. No. 3,929,678 (see Laughlin et al., Dec. 30, 1975, column 13, line 14 to column 16, line 6). Included in the nonionic surfactants are:

1. Polyethylene oxide condensates of alkyl phenols, such compounds include condensation products of alkyl phenols with ethylene oxide with straight or branched chain alkyl groups containing 6 to 12 carbon atoms, wherein ethylene oxide is 5 to per mole alkylphenol Present in an amount corresponding to 25 moles of ethylene oxide. Alkyl substitutions in these compounds can be derived from, for example, polymerized propylene, diisobutylene. Compounds of this type include nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol; Dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol: dinonylphenol condensed with about 15 moles of ethylene oxide per mole of phenol: diisooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (Igepa1 CO-630, manufactured by GAF) Triton X-45, X-114, X-110 and X-1O2 (Rom & Haas). This includes.

2. Condensation products of aliphatic alcohols with about 1-25 moles of ethylene oxide The alkyl chains of aliphatic alcohols are typically straight or branched chains having 8 to 22 carbon atoms or may be primary or secondary. Condensation products of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of ethoxylated alcohol and condensation products with about 9 moles of ethylene oxide of fatty alcohols having a Cocoal alcohol alkyl chain of C ₁₀ -C ₁₄ . Commercially available nonionic surfactants of this type include Tergitol 15-5-9 (Tergitol, Union Carbide), Neodol 45-9, Neodol 23-6.5 Neodol 45-7 and Neodol 45-4 (Shell Kaycal) and EOB (Procter & Gamble) as key.

3. Condensation products of hydrophobic bases and ethylene oxide produced by condensation of propylene oxide and propylene glycol, the hydrophobic portion of these compounds having a molecular weight of about 1500 to 1800 and exhibit water insolubility. The addition of polyoxyethylene to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid properties of the product are at the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, up to about 40 mol of ethylene oxide It is maintained to the point corresponding to condensation. Examples of this type of compound include commercially available Pluronic Surfactants (manufactured by Wyandotte Chemical Corporation).

4. Condensation product of ethylene oxide with ethylene oxide produced by the reaction of propylene oxide with ethylenediamine, the hydrophobic portion of these products consisting of the reaction product of ethylenediamine with excess propylene oxide, of about 2500 to 3000 Has a molecular weight. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains about 40 to 80 weight percent polyoxyethylene and has a molecular weight of about 5000 to 11000. Examples of nonionic surfactants of this type include several tetronic compounds sold by Yandodot Chemical Corporation.

5. Water-soluble amine oxides containing two moieties selected from the group consisting of one alkyl moiety containing 10 to 18 carbon atoms and an alkyl group and hydroxyalkyl group containing 1 to 3 carbon atoms: about 10 to about carbon atoms A water-soluble phosphine oxide containing two moieties selected from a group consisting of one alkyl moiety of 18, an alkyl group containing 1 to 3 carbon atoms and a hydroxyalkyl group, and one alkyl moiety having about 10 to 18 carbon atoms; A semipolar nonionic detergent surfactant comprising a water-soluble sulfoxide containing one moiety selected from the group consisting of alkyl and hydroxyl alkyl groups containing 1 to 3 carbon atoms. Preferred semipolar nonionic surfactants are amine oxide detergent surfactants of the general formula:

Wherein R ³ is C ₈ -C ₂₂ alkyl, hydroxyalkyl, alkylphenyl or a mixture thereof, R ⁴ is a C _2-3 alkylene or hydroxy alkylene group, or a mixture thereof; X is 0 to 3; R ⁵ are each C ₁ - is an alkyl or hydroxyalkyl group of _{3, the} replicon ethylene oxide group containing from 1 to 3 ethylene oxide groups.

The R ⁵ groups may be linked to one another via oxygen or nitrogen atoms such as to form a ring structure. Preferred amineoxide detergent surfactants are C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxy ethyldihydroxyethylamine oxides.

6. Hydrophobic groups containing about 6 to 30, preferably 10 to 16, carbon atoms and about 1 1/2 to 10, preferably about 1 1/2 to 3, most preferably about 1.6 to 2 Polysaccharides containing a sugar unit of 7 (e.g. polyglycosides), 5 to 6 alkyl polysaccharide carbon atoms known from U.S. Patent Application No. 371,747 (Ramon A, Llenado Apr. 26, 1982) containing a hydrophilic group. Any reducing sugars containing (e.g. glucose, galactose) may be used, and the galactosyl moiety may be substituted with a glucosyl moiety (optionally hydrophobic groups are bonded at positions 2, 3, 4, etc. to form glucose or galactose). Glucoside or galactoside) There may be a linkage between sugars between the 2-, 3-, 4- and / or 6-position on the preceding sugar unit and one position of another sugar unit.

Optionally, there may be less preferred but polyalkyleneoxide chains connecting the hydrophobic and polysaccharide moieties. Preferred alkylene oxides are ethylene oxide. Typical hydrophobic groups include saturated or unsaturated straight or branched C _8-18 , preferably C _10-16 alkyl groups. Preferred alkyl groups are straight chain saturated alkyl groups. The alkyl group may contain up to three hydroxy groups and / or the polyalkylene oxide may contain about 10, preferably 5, most preferably 0 alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucoside, galacto Side, lactoside, glucose, furacttoside, furactose and / or galactose. Suitable mixtures include cocoal alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred alkyl polyglycosides are compounds of the general formula:

R ² O (C _n H _2n O) _t (glycosyl) _x

Wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains about 10 to 18, preferably about 12 to 14 carbon atoms To; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; X is 1 1/2 to 10, preferably about 1 1/2 to 3, most preferably about 1.6 to 2. 7. Glycosyl is preferably derived from glucose. Alcohols or alkyl polyethoxy alcohols are first produced to prepare such compounds, and then reacted with glucose or glucose sources to produce glucosides (linked to the 1-position). Another glycosyl unit can be linked between these 1-positions and the aforementioned glycosyl units 2-, 3-, 4- and / or 6-positions, preferably 2-positions.

7. Fatty acid amide detergent surfactants of the general formula:

Wherein, R ⁶ is a C _7-21 alkyl group (preferably C _9-17), R ⁷ are each hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and - (C ₂ H ₄ 0) _x H (where x is 1 to 3).

Preferred amides are C ₈ -C ₂₀ ammoniaamide, monoethanolamide, diethanolamide and isopropanolamide.

B. Anionic Surfactants

Suitable anionic surfactants for the detergent compositions of the present invention are generally known from US Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975, column 23. 58 to column 29. 23).

Included in the class of anionic surfactants are as follows.

1. Alkali metal soaps, such as C ₈ -C _24, preferably C ₁₀ -C ₂₀ higher fatty acid sodium, potassium, ammonium and alkylol ammonium salts.

2. Water-soluble salts of organic sulfuric acid reaction products having C ₁₀ -C ₂₀ alkyl groups and sulfonic acid or sulfuric acid ester groups in their molecular structure, preferably alkali metals, ammonium and alkyl are ammonium salts. Alkyl moieties of acyl groups are also included).

Such anionic surfactants include, for example, compounds obtained by sulfated higher alcohols (C ₈ -C ₁₈ carbon atoms), such as those obtained by reduction of sodium and potassium alkyl sulfates, in particular resin oils or glycerides of coconut oil. And sodium and potassium alkylbenzene sulfonates (alkyl groups contain about 9 to 15 carbon atoms as straight or branched chain). For example, those of the type mentioned in US Pat. Nos. 2,220,099 and 2,477,383 are included.

Particularly useful are linear linear alkyl benzene sulfonates having an average of about 11 to 13 carbon atoms in the alkyl group, abbreviated C ₁₁ -C ₁₃ LAS.

Preferred anionic surfactants of this type are alkyl poly ethoxylate sulfates, in particular alkyl groups containing from about 10 to 22, preferably from about 12 to 18 carbon atoms, wherein the polyethoxylate chains are from about 1 to 15, preferably about 1 to 3 ethoxylate moieties. These anionic detergent surfactants are particularly preferred when making heavy liquid laundry detergent compositions.

Other such anionic surfactants include sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from resin and coco oils: sodium coco oil fatty acid monoglyceride sulfonates and sulfates: about 1 per molecule. Sodium or potassium salts of alkylphenolethylene oxide ether sulfates containing from 10 to 10 units of ethylene oxide, wherein the alkyl group has about 8 to 12 carbon atoms: alkyl containing about 1 to 10 units of ethylene oxide per molecule Sodium or potassium salt of ethylene oxide ether sulfate, wherein the alkyl group has about 10 to 20 carbon atoms

Other water-soluble salts of alpha-sulfone fatty acid esters containing fatty acid groups of 6 to 20 carbon atoms and esters of 1 to 10 carbon atoms: 2-acyloxy- containing acyl groups of 2 to 9 carbon atoms and alkanes of 9 to 23 carbon atoms Water-soluble salts of alkan-1-sulfonic acids: Alkyl ether sulfates containing about 1-30 moles of ethylene oxide alkyl groups having 10 to 20 carbon atoms: Water-soluble salts of olefin sulfonates having about 12 to 24 carbon atoms and 1 to 3 carbon atoms Also included are beta-alkyloxy alkanesulfonates containing an alkyl group of and containing an alkane group of about 8 to 20 carbon atoms.

3. Nonionic Phosphate Surfactant

4. N-alkyl Substituted Succinamate

C. Amphoteric Surfactants

Amphoteric surfactants are aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocycle secondary and tertiary amines, wherein the aliphatic radicals can be straight or branched, and one of the aliphatic substituents has about 8 carbon atoms. To 18 and at least one contains anionic water soluble groups such as carboxy, sulfonate, sulfate. An example of an amphoteric surfactant is referred to in US Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975, column 19, lines 18 to 35).

D. Zwitter Ion Surfactants

Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocycle secondary and tertiary amines, quaternary ammonium salts, quaternary phosphonium or tertiary sulfonium compounds. . Examples of zwitterionic surfactants are mentioned by reference in US Pat. No. 3,929,673 (Laughlin et al., Dec. 30, 1975, column 19,38, column 22,48).

E. Cationic Surfactants

Cationic surfactants may also be included in the compositions of the present invention. Suitable cationic surfactants include quaternary ammonium surfactants of the general formula:

[R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X-

Wherein R ² contains an alkyl or alkyl benzine group of about 8 to 18 carbon atoms in the alkyl chain; R ³ is each selected from the group consisting of —CH ₂ CH ₂ , —CH ₂ CH (CH ₃ ) —— CH ₂ CH (CH ₂ OH) —, —CH ₂ CH ₂ CH ₂ — and mixtures thereof; ⁴ is C ₁ -C ₄ alkyl C ₁ -C ₄ hydroxy alkyl, benzyl and ring structure formed by combining two R ⁴ groups, -CH ₂ CHOHCHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is hexasaccharide or molecular weight Less than 1000 hexavalent sugar polymer), and when y is non-zero, hydrogen is selected from the group consisting of; R ⁵ is the same as R ⁴ or is an alkyl chain, and the sum of the carbon number of R ² and R ⁵ is 18 or less; y is 0 to 10, respectively, and the sum of y is about 0 to 15: x is any compatible anion.

Preferred of the foregoing are single long-chain alkyl surfactants represented by the above structure when alkyl quaternary ammonium surfactants, in particular R ^5, are selected from the same group as R ⁴ . Most preferred quaternary ammonium surfactants are chloride, bromide and methylsulfate C ₈ -C ₁₆ alkyltrimethyl ammonium salts, C ₈ -C ₁₆ alkyl di (hydroxyethyl) methylammonium salts, C ₈ -C ₁₆ alkylhydroxy methyldimethyl ammonium salts and C ₈ -C ₁₆ alkyloxy propyl trimethylammonium salt.

Among the above-mentioned compounds, decyl trimethyl ammonium methyl sulfate, lauryl trimethyl ammonium chloride, myristyl trimethylammonium bromide and cocosam trimethyl ammonium chloride and methyl sulfate are particularly preferred.

Detergent Builder

Detergent compositions of the present invention may contain detergent builders, ie, inorganic or organic detergent builders that optionally help control the mineral hardness. These builders may make up about 0-80% by weight of the composition. When these builders are contained they can usually contain up to about 60% by weight of the detergent composition. The built-in liquid composition containing the builder preferably contains about 10-25% detergent builders, while the built-in granule composition preferably contains about 10-50% by weight.

Suitable detergent builders include crystalline aluminosilicate ion exchange materials of the general formula:

_{Na z [(AlO 2) z} · (SiO 2) y · XH 2 O]

Wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to 0.5 and X is from about 10 to 264. Amorphous hydrated aluminosilicate materials useful herein have the following empirical formula:

M _z ( _z A1O _{2 y} SiO ₂ )

In which M is sodium, potassium, ammonium or substituted ammonium; Z is about 0.5 to 2; y is 1 and the substance has magnesium ion exchange capacity equivalent to about 50 mg or more of CaCO ₃ per gram of anhydrous aluminosilicate.

The aluminosilicate ion exchange builder material is in hydrated form and contains about 10 to 28% by weight of water when crystalline and more in water when amorphous. Very preferred crystalline aluminosilicate ion exchange materials contain about 13-22% water in their crystal matrix. Preferred crystalline aluminosilicate ion exchange materials are also characterized as having a particle size diameter of about 0.1 to 10 microns.

Amorphous materials are often smaller, for example up to about 0.01 micron or less. More preferred ion exchange materials are those having a particle size diameter of about 0.2 to 4 microns. The term “particle size diameter” here refers to the average particle size diameter of the ion exchange material obtained when measured by conventional analytical methods such as microscopy using scanning electron microscopy. The crystalline aluminosilicate ion exchange material is characterized by having a calcium ion exchange capacity of water hardness equivalent to at least 200 mg of CaCO ₃ per gram of aluminosilicate (anhydride), usually 300 mg eq / g352-mg eq g. The aluminosilicate ion exchange material is also characterized by having a calcium ion exchange rate of greater than about 2 degrees Ca / gallon / min / g / gallon [of aluminosilicate (based on anhydride)], which is usually based on calcium ion hardness. When in the range of about 2 degrees / gallon / minute / g / gallon to 6 degrees / gallon / minute / g / gallon. Suitable aluminosilicates for builder purposes are those having a calcium ion exchange rate of about 4 degrees / gallon / min / g / gallon or higher.

Amorphous aluminosilicate ion exchange materials typically have a Mg ⁺⁺ ion exchange capacity of at least about 50 mg eq Cac0 ₃ / g (12 mg Mg ⁺⁺ / g) and a Mg ⁺⁺ ion exchange rate of at least about 1 degree gallon / min / g / gallon It is common to have It was found that the amorphous material exhibited diffraction that could be observed upon examination by Cu irradiation method (1.54 kV unit).

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be structurally crystalline or amorphous and may be naturally occurring aluminosilicates or composites. The preparation of aluminosilicate ion exchange materials is known from US Pat. No. 3,935,669 (Krummel et al. 12 October 1976). Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are used under the names Zeolite A, Zeolite P (B) and Zeolite X. A particularly preferred example is the crystalline aluminosilicate ion exchange material having the general formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] XH ₂ O

Wherein X is about 20 to 30, in particular about 27.

Examples of detergent builders include various water soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxyls Rate is included. The alkali metals mentioned above, in particular sodium salts, are preferred.

Special examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates, polymeric methacrylates having a degree of polymerization of about 6 to 21 and orthophosphates. Polyphosphonate builders include, for example, sodium and potassium salts of ethylene-1,1-diphosphonic acid, sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid, ethane 1,1,2-triphosphonic acid Sodium and potassium salts. Other phosphorus-containing builder compounds are known by reference in US Pat. Nos. 3,159,581: 3,213,030: 3,422,021: 3,422,137: 3,400,176 and 3,400,143.

Inorganic builders that do not contain phosphorus include, for example, a molar ratio of SiO ₂ to sodium and potassium, carbonates, bicarbonates, seski carbonates, tetraborates · hydrates, and alkali metal oxides of about 0.5 to 4.0, preferably about There are silicates that are 1.0 to 2.4.

Useful as organic builders that do not contain water-soluble phosphorus include various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Polyacetate and polycarboxylate builders include, for example, sodium potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitric acid, benzene polycarboxylic acid and citric acid.

Very preferred polycarboxylate builders are known from US Pat. No. 3,305,067 (Diehl, March 7, 1967). These substances include maleic acid. Water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as itaconic acid, mesaconic acid, fumaric acid, aconic acid, citraconic acid and methylenemalonic acid.

Other builders include carboxylated hydrocarbons known from US Pat. No. 3,723,322 (Diehl, March 28, 1973).

Other useful builders include sodium and potassium carboxymethyloxy malonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane tetracarboxylate prologlucinol trisulfonate, water soluble polyacrylate (molecular weight: about 2000 to 200,000) and a copolymer of vinyl methyl ether or ethylene and maleic anhydride.

Other suitable polycarboxylates are the polyacetal carboxylates known from US Pat. No. 4,144,226 (Crutchfield et al., March 13, 1979) and US Pat. No. 4,246,495 (crutchfield et al., March 27, 1979. Such polyacetal carboxylate can be prepared by combining an ester of glyoxylic acid and a polymerization initiator under polymerization conditions. The resulting polyacetalcarboxylate ester is then attached to chemically adjacent end groups and then converted to the corresponding salts to the surfactant to stabilize it against rapid deweighting in alkaline solution.

Another useful detergent builder material is the Seeded builder known from Belgian Patent 798,856 (October 29, 1973). Representative examples of such inoculation builder mixtures include a 1: 3 wt mixture of calcium carbonate and sodium carbonate having a particle diameter of 5 microns and a 1: 2.7 wt mixture of calcium carbonate and a cesium carbonate having a particle size of 0.5 microns with a particle diameter of 0.01 micron. 1: 20 wt mixture of calcium hydroxide and sodium sesquicarbonate; And calcium hydroxide having a particle diameter of 5 microns; Sodium aluminate. 1: 3: 3wt mixture of sodium carbonate.

[Other detergent ingredients]

In addition, any component that may be mixed in the detergent composition of the present invention includes a solvent, a bleach, a bleach activator, a suspending agent, a corrosion inhibitor, a dye, a weight agent, an optical varnish, a bactericide, a pH adjusting agent (monoethanolamine, sodium carbonate, hydroxide). Sodium, etc.), enzymes, enzyme stabilizers, fragrances, fabric softeners, antistatic agents and the like, which are typically used in a set amount of use (ie, 0 to 20%).

[Detergent Formulation]

The granular detergent composition of the present invention can be prepared by conventional methods, for example, by slurrying individual components in water and then spray drying the resulting mixture or by pan or drum granulating the components. Granules are generally preferably composed of about 10-30% of the negative silver surfactant.

Detergent compositions in liquid form may or may not contain builders. If not present, these compositions usually contain about 1-50% surfactant and about 0-10% mono-. Organic bases such as di- or tri-alkanolamines, neutralization systems such as alkali metal hydroxides and lower primary alcohols such as ethanol or isopropanol and about 20 to 80% water. Such compositions are typically homogeneous single phase liquids with low viscosity (about 100 to 150 centipoas at 29 ° C.).

The builder-containing detergent composition may be in a single phase liquid state when the builder is dissolved in the mixture at the dosage. Such liquids usually contain 10 to 25% surfactant and 10 to 25% builder and the builder may consist of 3 to 10% suspending agent and 40 to 77% water as organic or inorganic. Liquids of this type also have low viscosity. A builder-containing liquid detergent in which the (100-150 centipoas) components are mixed at 29 ° C. to form a heterogeneous mixture (or the builder amount is not completely dissolved) also constitutes the detergent composition of the present invention. These solutions usually use a viscosity modifier to create a system with plastic shear properties to maintain stable dispersion and to prevent phase separation or solid settling.

Almost Neutral Washing pH Detergent Formulation

The detergent composition of the present invention operates over a wide pH range (i.e. about 5 to 12) but when formulated such that the initial pH is about 8.0 to 8.5 at a solution concentration of about 20 [deg.] C., 0.1 to 2 wt% These are particularly suitable. In such compositions the washing pH is preferably between about 7.0 and 8.5 and more preferably between about 7.5 and 8.0.

Preferred as almost neutral laundry pH detergent compositions are known from US Pat. No. 380,988 (J. H. M. Wertz and P. C. E Goffinet, May 24, 1982). These preferred formulations are (a) about 2 to 60% by weight (preferably about 10 to 25%) of the aforementioned anionic synthetic surfactant. (b) about 0.25-12% (preferably about 1-4%) of an auxiliary surfactant selected from the group consisting of (i)-(vi) below. (i) Quaternary ammonium surfactants of the general formula:

[R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X-

Wherein R ² , R ³ , R ⁴ , R ⁵ , X and y are as defined above and y is 0 to 10, the sum of y is 0 to 15; X is an anion that can be miscible); (ii) diquaternary ammonium surfactants of the general formula;

_{^{[R 2 (OR 3) y}} ] [R 4 (OR 3) y] 2 N + R 3 N + R 5 [R 4 (OR 3) y] 2 (X -) 2

Wherein R ² , R ³ , R ⁴ , y and X are as defined above and particularly preferred are C ₈ -C ₁₆ alkylpentamethylethylene diaminechloride, bromide and methylsulfate salts; (iii) amine surfactants of the general formula

[R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] R ⁵ N

Wherein R ² , R ³ , R ⁴ , R ⁵ and y are as defined above and particularly preferred is C ₁₂ -C ₁₆ alkyldimethyldamine; (iv) diamine surfactants of the general formula

[R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] NR ³ NR ⁵ [R ⁴ (OR ³ ) _y ]

Wherein R ² , R ³ , R ⁴ , R ⁵ , y are as defined above and particularly preferred are C ₁₂ -C ₁₆ alkyldimethyldiamines; (v) Amine oxide surfactants of the general formula

[R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] R ⁵ N ‥‥‥‥‥‥ → O

Wherein R ² , R ³ , R ⁴ , R ⁵ and y are as defined above and particularly preferred is C ₁₂ -C ₁₆ alkyldimethylamine oxide; And (vi) di (amine oxide) surfactants of the general formula

[R⁴(OR³)_y][R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ]

[R ⁴ (OR ³ ) _y ]

Wherein R ² , R ³ , R ⁴ , R ⁵ and y are as defined above and preferred is C ₁₂ -C ₁₆ alkyl trimethylethylenedi (amine oxide).

(c) about 5 to 40% by weight of fatty acids containing about 10 to 22 carbon atoms (preferably C ₁₀ -C ₁₄ saturated fatty acids or mixtures thereof, preferably 7 to 30% by weight, most preferably about 10 Wherein the molar ratio of the anionic surfactant to the cosurfactant is at least, preferably about 2: 1 to 20: 1.

Such compositions also preferably contain about 3 to 15 weight percent of ethoxyalkylphenols or ethoxyalcohols (nonionic surfactants) as defined above. Very preferred compositions of this type also contain about 2 to 10 weight percent citric acid and small amounts of neutralizing agents such as those mentioned in US Pat. No. 4,285,841 (Barrat et al., Aug. 25, 1981. 8/25/1981). , Buffers, phase-controlling agents, suspending agents, enzymes, enzyme stabilizers, polyacids, foam control agents, milking agents, sulfates, fungicides, dyes, flavorings and brightening agents.

[Specific embodiments of detergent composition according to the present invention]

The following embodiments illustrate but are not limited to the detergent compositions of the present invention.

Granular detergent composition is as follows.

The components are added together with continuous mixing to form an aqueous slurry which is then spray dried to obtain a composition. Instead of polyurethane, the compound of Example 1 or 2, the random copolymer of Example 4, the PEA of Example 5a, the PEI of Example 5b or the diallylamine polymer of Example 6 may be substituted.

Embodiment II

The liquid detergent composition is as follows.

The components are added together with continuous mixing to obtain a composition. Instead of the random copolymer, the polyurethane of Example 3, PEA of Example 5a, PEI of Example 5b or the diallyl polymer of Example 6 may be substituted.

Embodiments III and IV

The liquid detergent composition is as follows.

Embodiment IV adds the components together in successive mixing in the following order to obtain a clear liquid; Paste premixes of alkylbenzenesulfonic acid, 0.9 parts sodium hydroxide, propylene glycol, 2.3 parts ethanol; Paste premix with alkylpolyethoxysulfuric acid, 1.1 parts sodium hydroxide and 3.1 parts ethanol; A premix of monoethanolamine, triethanolamine and 1.5 parts of sodium hydroxide with brightener, remaining ethanol, citric acid, formate; 1.4 parts potassium hydroxide; fatty acid; Adjust the pH to about 8. 4 with pentaacetic acid, alkyltrimethylammonium chloride, potassium hydroxide, water or citric acid; enzyme; Quaternary HMDA (50% aqueous solution); And spices.

Embodiment III can be prepared by a similar method. Instead of PEA, the polyurethane of Example 3, the random copolymer other than Example 4, the PEI of Example 5b or the diallylamine polymer of Example 6 may be substituted and used.

Embodiment V

The liquid detergent composition is as follows.

The components are added together with continuous mixing to obtain a composition. Instead of PEA, the compound of Example 1 or 2, the polyurethane of Example 3, the random copolymer of Example 4, PE1 of Example 5b or the diallylamine polymer of Example 6 may be substituted.

Clay Decontamination / Redeposition Prevention of Various Ethoxylated Quaternary Amines

A. Experimental Method

1. Clay decontamination

A comparative test of clay decontamination is carried out in 1 L tergotometer using a water of 7 ° C (Ca ⁺⁺ : Mg ⁺⁺ 3: 1) temperature 43 ℃. Contaminated swatches are washed for 10 minutes in a tachometer and then for 2 minutes in 21 ° C. water (hardness 7 degrees).

65% polyester / 35% cotton blend fabric is used as swatch. The swatch is 13cmx13cm in size, which is immersed in an aqueous slurry of clay, partially contaminated and salted to remove water. Repeat the impregnation and salt treatment five times.

2000 ppm of the control liquid detergent composition containing the following surfactant was used for the first washing.

The same detergent composition as above was used except that 20 ppm of ethoxylated quaternary amine was used for the second washing.

None of the compositions contain optical brighteners.

The washing of this product is almost the same as that of household washing. After washing, the swatch is dried in a drier in advance.

The whiteness of the swatches is graded by reading L, a and b coordinates on a Gardner whiteness meter before and after washing.

Whiteness degree w is calculated as follows.

W =

The clay decontamination performance of each detergent composition is determined by looking at the difference in whiteness (w) before and after washing.

△ W = after washing-before washing

The enhancement of clay decontamination performance of a composition containing an ethoxylated quaternary amine is determined by the difference in w values (Δ ² w) for the control composition.

2. Re-deposition Prevention

The re-deposition prevention comparative test is carried out using a water of 35 ° C and 7 ° C in a 5-pot automatic mini washer (AMW). The test swatches are washed for 10 minutes and then rinsed twice with 21 ° C water.

Fill each AMW pot with 6 liters of water, add the detergent composition to be tested (containing the control or 20 ppm ethoxylated amine as in the Clair decontamination test) and stir for 2 minutes. Background contaminant mixtures (200 ppm for artificial humans, 100 ppm for vacuum cleaner contamination, 200 ppm for clay contamination) are added and then further stirred for 3 minutes. Add three 131 cmx13 cm test swatches (50% polyester / 50% cotton T-sheath), followed by two 80% cotton / 2o% polyester dissociation fabrics and two 28 cmx28 cm swatches of 100% polyester knit fabric. Wash for 10 minutes at this point.

Rinse and dry the test swatches in a mini dryer. The Gardner white dome is measured (L, a and b) and the whiteness for the three test swatches is measured. Then calculate the redeposition prevention performance (ARD) by the following formula.

ARD =

Subsequently, the ARD values of the three test swatches are averaged. Enhancement of the anti-redeposition performance of compositions containing ethoxylated quaternary amines is determined by the difference in ARD values (ΔARD) relative to the control composition.

B. Test result

The results of clay decontamination and re-deposition prevention of various ethoxylated quaternary amines are shown in the following table.

EDA = ethylenediamine, PPA = propylenediamine, HMDA = hexamethylenediamine, PMDA = 1,3-bis- (N-morpholino) -propane, PEA = polyethyleneamine.

* C ₁ = methyl, C ₄ = butyl, B ₂ = benzyl

PEG 6000 (polyethylene glycol, molecular weight 6000) is used as a control is a △ ² W value of 4.9 and △ ARD value is 8.9.

Claims (31)

About 1 to 75% by weight of nonionic, anionic, amphoteric, zwitterionic, or cationic detergent surfactants or mixtures thereof, and ethoxylated cationic monoamines of formula (1), ), (3) or (4) ethoxylated cationic diamine; Ethoxylated cationic polyamines of the general formula (5); A water soluble cationic having the property of removing clay contamination and preventing redeposition, selected from the group consisting of a polymer backbone, an ethoxylated cationic polymer containing at least two M groups and at least one LX group, and mixtures thereof And about 0.05 to about 95 weight percent of the compound.

Wherein M ¹ is an N ⁺ or N group, M ² is each an N ⁺ or N group, at least one M ² is an N ⁺ group, and M is a cationic group bonded to or integrated with the main chain, N ⁺ Has a positive charge center, L connects groups M and X or groups X to the polymer backbone,

Or -0-, R is H or C ₁ -C ₄ alkyl or hydroxyalkyl, R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, or A C ₂ -C ₃ oxyalkylene moiety containing from about 20 oxyalkylene units, provided that no 0-N bond is formed, and R ² is C ₁ -C ₄ alkyl or hapidoxyalkyl or a moiety, respectively -LX, or two R ² together form a residue-(CH ₂ ) rA ^2- (CH ₂ ) s-, and R ³ is each C ₁ -C ₈ alkyl or hydroxyalkyl, benzyl or residues -LX Or two R ³ or one R ² and R ³ together form the residue-(CH ₂ ) rA ^2- (CH ₂ ) s-, A ² is -0- or -CH _2- , r Is 1 or 2, s is 1 or 2, r + s is 3 or 4, and R ⁴ is an alkyl having a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or P-substituted moiety Is a karyl group, R ⁵ is C ₁ -C ₁₂ alkylene, hydroxyalkylene , An alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene moiety containing from 2 to about 20 oxyalkylene units, provided that no OO or ON bond is formed and X is H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or nonionic group selected from the group consisting of ether groups and mixtures thereof, L is a polyoxyalkylene moiety-[(R ⁶ O) m (CH ₂ CH ₂ O) n ]-Containing a hydrophilic chain, R ⁶ is C ₃ -C ₄ alkylene or hydroxyalkylene, m and n are residues-(CH ₂ CH ₂ O) n- is about the polyoxyalkylene residue Is at least 50% by weight, d is 1 when M ² is N ⁺ , 0 when M ² is N, and N is at least about 12 in the case of the cationic monoamine, and At least about 6 for cationic diamine, at least about 3 for cationic polyamines and cationic polymers, and p is 3 Five, and q is 1 or 0, t is 1 when t is 1 or 0, and stage, q is 1. The composition of claim 1, wherein the cationic compound is an ethoxylated cationic monoamine, wherein one R ² is methyl and two R ² are residues LX. The composition of claim 2, wherein m is 0 and n is at least about 15. 4. The composition of claim 1 wherein the cationic compound is an ethoxylated cationic diamine and R ¹ is C ₂ -C ₆ alkylene. The composition of claim 4 wherein R ¹ is hexamethylene. The compound of claim 1, wherein the cationic compound is an ethoxy cationic polyamine, R ⁴ is a substituted C ₃ -C ₆ alkyl, hydroxyalkyl or aryl group, and A ¹ is

And p is 3 to 6. 7. The composition of claim 4, wherein R ² is each methyl or residue —LX and R ³ is each methyl. 7. The composition of claim 4, wherein M ¹ and each M ² is an N ⁺ group. The method according to claim 1, wherein the cationic compound is an ethoxylated cationic polymer, and the polymer backbone is polyurepan, polyester, polyether, polyamide, polyimide, polyacrylate, polyacrylamide, polyvinyl ether, poly Group consisting of alkylene, polyalkylene, polyalkyleneimine, polyvinylamine, polyallylamine, polydiallylamine, polyvinylpyridine, polyaminotriazole, polyvinylalcohol, amino polyureylene and mixtures thereof A composition, characterized in that selected from among. The composition of claim 9, wherein the ratio of group M: group X is from about 2: 1 to about 1:10. The composition of claim 9 or 10, wherein the polymer unit containing groups M and L-X contains about 50 to 100% of the polymer. The composition of claim 9 or 10, wherein the number of groups M and L-X is about 3 to about 40, respectively. 10. The method of any of claims 4, 6 and 9, wherein m and n are numbers such that the residues-(CH ₂ CH ₂ O) n- contain at least about 85% by weight of the polyoxyalkylene residues. Composition. 10. The composition of any one of claims 4, 6 and 9, wherein m is 0 and n is at least about 12. 10. The composition of any one of claims 4, 6 and 9, wherein X is H or methyl ether. 10. The composition of claim 9, wherein the polymer contains units selected from general formulas (I), (II) and (III).

Wherein A ¹ is

or

X is 0 or 1, R is H or C ₁ -C ₄ alkyl or hydroxyalkyl, R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene Or is alkarylene or a C ₂ -C ₃ oxyalkylene moiety containing 2 to about 20 oxyalkylene units, provided that no OO or ON bond with A ¹ is formed and x is 1, ² is R ^3- (where A ¹ is |

Or (OR ⁸ ) _y -or -OR ^5- , provided that no OO or NO bond is formed with A ^1, and R ³ is -R ^5- (where A ¹ is

Or-(R ⁸ 0) _y ,-or -R ⁵ O-, provided that no OO or ON bond with A ¹ is formed and x is 0, then R ² is-( OR ⁸ ) _y- , -OR ^5- ,

,

,

,

,

,

or

R ⁵ , R ₃ is -R ^5- , R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, or residues-(R ⁵ ) k-[(C ₃ H ₆ O) _m (CH ₂ CH | ₂ O) _n ] -X, R ⁵ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, and R ⁶ is C ₁ -C ₄ alkyl or hydroxyalkyl, respectively Or a residue-(CH ₂ ) rA ^2- (CH ₂ ) s-, A ² is -O- or -CH _2- , R ⁷ is H or R ⁴ , and R ⁸ is C ₂ -C | ₃ alkylene or hydroxyalkylene, X is H,-

R ⁹ , -R ⁹ or a mixture thereof, R ⁹ is C ₁ -C ₄ alkyl or hydroxyalkyl, k is 0 or 1, m and n are residues-(CH ₂ CH ₂ 0) n-valent residues At least about 85% by weight of-(C ₃ H ₆ O) _m (CH ₂ CH ₂ 0) _n ]-, m is 0 to about 5, n is about 3 or more, and r is 1 or 2, s is 1 or 2, r + s is 3 or 4, y is 2 to about 20, u, v and w are numbers such that at least two N centers and at least two X groups are present . The compound of claim 16, wherein A ¹ is

or

And, R ¹ is a C ₂ -C ₅ alkylene, R ² is -OR ⁵ or - (OR ⁸⁾ y-, and, R ³ is -R ⁵ O- or - (R ⁸ O) y-, and, R ⁴ and R ⁵ are each methyl, R ⁵ is C ₂ -C ₃ alkylene, R ⁷ is H or methyl, R ⁸ is ethylene, X is H or methyl, k is 0, y is 2 To about 12. 10. The composition of claim 9, wherein the polymer contains units selected from general formulas (IV), (V) and (Vl).

Wherein A ¹ is -O-,

, ,

,

,

,

,

,

, or

R is H, C ₁ -C ₄ alkyl or hydroxyalkyl, R ¹ is substituted C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, or C _2- C ₃ oxyalkylene, R ² is each C ₁ -C ₂ alkylene, hydroxyalkylene, alkenylene, arylene or alxarylene, R ³ is each C ₁ -C ₄ alkyl or hydroxyalkyl, Or residues-(R ² ) _k -[(C ₃ H ₆ O) m (CH ₂ CH ₂ 0) n] -X, or together form residues-(CH ₂ ) rA ^2- (CH ₂ ) s- R is each C ₁ -C ₄ alkyl or hydroxyalkyl, or two R ⁴ together form the residue-(CH ₂ ) rA ^2- (CH ₂ ) s-, and A ² is -0- or -CH _2- , X is H,-

R ⁵ , -R ⁵ or a mixture thereof, R ⁵ is C ₁ -C ₄ alkyl or hydroxyalkyl, j is 1 or 0, k is 1 or 0, m and n are residues-(CH ₂ A number such that CH ₂ O) n- contains at least about 85% by weight of the residue-[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) n]-, m is 0 to about 5, and n Is at least about 3, r is 1 or 2, s is 1 or 2, r + s is 3 or 4, u, v and w are two or more N ⁺ centers and two or more X groups are present. It is a number. The compound of claim 18, wherein A ¹ is

,

Or -O-, R ¹ is -CH ₂

H- or -CH ₂

And each of R ⁴ is methyl, X is H or methyl, and k is zero. 20. The composition of any one of claims 16-19, wherein v and w are zero and u is about 3 to about 40. 10. A composition according to claim 9, wherein the polymer contains units selected from general formulas (iii), (iii) and (iii).

Wherein R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alxarylene, or C ₂ -C containing 2 to about 20 oxyalkylene units ₃ oxyalkylene moiety, provided that no 0-N bond is formed and R ² is C | ₁ -C ₄ alkyl or hydroxyalkyl, or residues-(R ³ ) k-((C ₃ H ₆ O) m (CH ₂ CH ₂ O) n] -X, R ³ is C ₁ -C ₁₂ alkyl Ylene, hydroxyalkylene, alkenylene, arylene, or alxarylene, M ¹ is N ⁺ or N center; X is H,-

R ⁴ , -R ⁴ or a mixture thereof, R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, d is ¹ when M ¹ is N ⁺ , 0 when M ¹ is N, e Is 2 when M ¹ is N ⁺ , ¹ when M ¹ is N, k is 1 or 0, and m and n are residues-(CH ₂ CH ₂ O) n- is a residue-[(C ₃ H ₆ O) _m (CH ₂ CH | ₂ O) n] is a number containing at least about 85% by weight, m is 0 to about 5, n is at least about 3, x, y and z are It is a number such that at least two M ¹ groups, at least two N ⁺ centers and at least two X groups exist. The compound of claim 21, wherein R ¹ is ethylene, R ² is each methyl or a residue [(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] -X, X is H, k is 0 A composition characterized in that. 23. The composition of claim 21 or 22, wherein the M ¹ group is a mixture of about 50 to 100% N ⁺ center and 0 to about 50% N center. 23. The composition of claim 21 or 22, wherein the sum of x, y and z is 2 to about 40. 10. The composition of claim 9, wherein the polymer contains units selected from the general formulas (X) and (XI).

Wherein R ¹ is C ₁ -C ₄ alkyl or hydroxyalkyl, or residues — (R ² ) _k — [(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] —X, R ² Is C ₁ -C ₁₂ alkylene, hydroxyalkylene, arylene or alxarylene, R ³ is each C ₁ -C ₄ alkyl or hydroxyalkyl, or together is the residue-(CH ₂ ) rA- ( CH ₂ ) s, A is -0- or -CH _2- , X is H,-

R ⁴ , -R ⁴ or a mixture thereof, R ⁴ is C ₁ -C ₄ alkyl or hydroxyalkyl, k is 1 or 0, m and n are residues-(CH ₂ CH ₂ O) _n -valent residues At least about 85% by weight of — [(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] —, m is from 0 to about 5, n is at least about 3, r Is 1 or 2, s is 1 or 2, r + s is 3 or 4, x is 1 or 0, y is 1 when x is 0, 0 when x is 1, u And v is a number such that at least two N ⁺ centers and at least two X groups are present. 27. The composition of claim 25, wherein R ¹ is methyl, R ³ is each methyl, X is H and k is 0. 27. The composition of claim 25 or 26, wherein v is 0 and u is about 3 to about 40. 26. The composition of any one of claims 16, 18, 21 and 25, wherein m is 0 and n is at least about 12. The composition of claim 1 containing from about 0.1 to about 10 weight percent cationic compound. 30. The composition of claim 29, containing from about 1 to about 3 weight percent cationic compound. The composition of claim 1 containing up to about 80% by weight detergent builder.