JP2003502480A - Detergent composition - Google Patents

Abstract

  (57) [Summary] The present invention relates to a composition suitable for cleaning the outer surface of a vehicle, comprising an anionic surfactant, a chelating agent, a re-staining inhibitor, a soil-sedimenting inhibitor or a mixture thereof. The composition of the invention provides an excellent cleaning effect by contacting the surface to be cleaned.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to the technical field of compositions suitable for cleaning the exterior surfaces of vehicles, in particular motor vehicles.

BACKGROUND OF THE INVENTION Cleaning compositions for vehicle exterior surfaces are well known in the art. Generally, the composition is used diluted and applied to the vehicle using a sponge or cloth. However, these products typically require the user to scrub or scrub the vehicle. For example, if the surface is wide, high, or has a complicated contour with relatively inaccessible parts, such as a truck, large freight car, or aircraft, it may be The need for scrubbing is particularly problematic. However, the most serious existing problem is that manual scrubbing requires time and enormous effort. Accordingly, it is an object of the present invention to provide a vehicle cleaner composition that does not require the user to polish or rub the surface to be cleaned.

International Patent Application No. WO 99/13036 relates to a hard surface cleaning composition that does not require scrubbing of the surface and can be used to clean large structures. The composition is
It contains alcohol ethoxylates and _C8-16 alkyldimethylamine oxide in a weight ratio of 5-15: 1, and a nitrogen-containing chelating agent.

International Patent Application No. WO 97/43372 relates to a hard surface cleaner that can be used for cleaning difficult-to-contact surfaces, such as the outer surface of windows and the outer surface of automobiles. The compositions described herein contain a silicate, a hydrophobic acrylic polymer and a surfactant, and optionally a chelant.

Applicants have identified a combination of components in the form of a vehicle cleaner composition that is cleaned by contact with the vehicle and does not require scrubbing or scrubbing. In addition, the compositions of the present invention provide benefits in subsequent cleaning. That is, the composition of the present invention is not only easy to wash the vehicle at the time of the first use, but also the second use of the composition of the present invention, and the subsequent cleaning, compared with the conventionally available vehicle cleaners. With continued use, cleaning is even easier. It is believed that this new added benefit comes from recontamination prevention or soil settling prevention polymers in the compositions described herein, or mixtures thereof. Further, it is believed that during use of the compositions described herein, the polymer deposits and adheres to the surface of the vehicle to be cleaned. During continued washing of the vehicle, the polymer forms a protective layer on which soil components are deposited. Then, in the next vehicle cleaning, the polymer layer is removed together with the dirt components deposited thereon, and the alternative polymer layer is deposited.

In another aspect of the invention, the compositions described herein provide, in addition to the benefits described above, the benefit of not requiring drying, and the surface cleaned by the composition remains intact. Water marks do not remain on the surface even if left unattended.

SUMMARY OF THE INVENTION According to the present invention, a chelating agent and an anionic surfactant are used in a ratio of 4: 1 to 1: 4.
A cleaning composition suitable for cleaning the outer surface of a vehicle is provided, which contains a polymer compound selected from the group consisting of a redeposition prevention polymer, a soil precipitation inhibitor polymer, and a mixture thereof. It

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention comprises a chelating agent, an anionic surfactant, and an anti-fouling polymer, a soil-precipitation inhibitor polymer, or a mixture thereof as an essential component of the present specification. A polymer compound selected from

Chelating Agent The composition of the present invention contains a chelating agent. Typically, the compositions of the present invention contain no more than 20% by weight, preferably 0.01 to 15% by weight, more preferably 0.01 to 10% by weight, based on the total composition, of a chelating agent.

Suitable chelating agents include phosphonate chelating agents, aminocarboxylate chelating agents, other carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, ethylenediamine N, N′-disuccinic acid. Or any of those known to those skilled in the art, such as those selected from the group consisting of:

The presence of chelating agents contributes to further increasing the chemical stability of the composition.

Suitable phosphonate chelating agents for use herein include ethane 1-hydroxydiphosphonic acid alkali metal salt (HEDP), alkylene poly (alkylenephosphonate), and aminoaminotri (methylenephosphonic acid) (ATMP). )
, Nitrilotrimethylenephosphonate (NTP), ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate (D
Aminophosphonate compounds including TPMP) are included. The phosphonate compounds may be present as salts with various cations, either in their acid form or in some or all of their acid functionality.

Polyfunctionally substituted aromatic chelating agents may also be useful in the compositions of the present invention. Co
U.S. Pat. No. 3,812 issued May 21, 1974 to Nnor et al.
, 044. Preferred compounds of this type in the acid state are:
Examples thereof include dihydroxydisulfobenzene such as 2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use in the present invention are ethylenediamine N, N′-disuccinic acid, or its alkali metal or alkaline earth salts, ammonium salts or substituted ammonium salts, or mixtures thereof. Is. Ethylenediamine N, N'-disuccinic acid, and in particular its (S, S) isomer, is broadly described in US Pat. No. 4,704,233 issued Nov. 3, 1987 to Hartman and Perkins. Have been described. Ethylenediamine N, N
'-Disuccinic acid can be obtained, for example, by Palmer Research Labo with ssEDDS®.
It is marketed by ratories.

Suitable aminocarboxylates that can be used in the present invention include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropionic acid,
Included are triethylenetetraaminehexaacetic acid, ethanoldiglycine, propylenediaminetetraacetic acid (PDTA) and methylglycinediacetic acid (MGDA), which are either in the acid form or of alkali metal, ammonium and substituted ammonium salts. In form. In particular, suitable aminocarboxylates that can be used in the present invention are diethylenetriaminepentaacetic acid, such as propylenediaminetetraacetic acid (PDTA) and methylglyminediacetic acid (MGDA) marketed by BASF under the name Trilon FS®.

Furthermore, the carboxylic acid chelating agents used in the present invention include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid and mixtures thereof.

[0017]   Another chelating agent used in the present invention includes the following formula:

[0018]

[Chemical 1]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO ₂ , —C (O) R ′ and -SO ₂ R
Each independently selected from the group consisting of R ', wherein R'is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy;
"Is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy, and R ₅ , R ₆ , R ₇ and R ₈ are each independently selected from the group consisting of -H and alkyl). is there.

Particularly preferred chelating agents that can be used in the present invention are aminoaminotri (methylenephosphonic acid), diethylenetriaminopentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamine N, N′-disuccinic acid. And mixtures thereof.

Other chelating agents include polycarboxylates, especially citrate and the following formula: CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (
A complex having COOX) (B) may be mentioned. (In the formula, A is H or OH; B is H or _{-O-CH (COOX) -CH 2} (
COOX); X is H or a salt-forming cation. For example, when both A and B in the above general formula are H, the compound is oxydisuccinic acid and its water-soluble salts. When A is OH and B is H, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. A is H and B is -O-CH (C
When it is OOX) -CH ₂ (COOX), the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these chelating agents are particularly preferred for use in the present invention. With particular reference to TMS, TDS, these chelating agents are described by Bush et al., US Pat.
No.

Still other polycarboxylic acid ethers suitable for use in the present invention include maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid. And a copolymer thereof.

Other useful polycarboxylate chelating agents are: HO- [C (R) (COOM) -C (R) (COOM) -O] _n- H _where M is hydrogen or a cation. And the resulting salt is water soluble, preferably an alkali metal, ammonium, or substituted ammonium cation, and n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n). Is about 2 to about 4), and each R is the same or different and is hydrogen, C _1-4 alkyl, or C _1-4 substituted alkyl (preferably, R is hydrogen). Hydroxypolycarboxylic acid ethers are mentioned.

Suitable polycarboxylic acid ethers include cyclic compounds, especially cycloaliphatic compounds, which are described in US Pat. Nos. 3,923,679, 3,835,163, 4,158,635. No. 4,120,874, and 4,102,903.
No., etc., the contents of which are incorporated herein by reference.

Preferred among these cyclic compounds are dipicolinic acid and chelidanic acid.

Preferred polycarboxylates suitable for use in the present invention also include mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benzenepentacarboxylic acid, carboxymethyloxysuccinic acid and them. Soluble salts of

Further suitable carboxylate chelating agents have been given to Diehl 19
Mention may be made of the carboxylated carbohydrates disclosed in U.S. Pat. No. 3,723,322 issued Mar. 28, 1973.

Among the carboxylates suitable for other uses in the present invention, less preferred because they do not meet the above criteria are alkali metal salts, ammonium salts and substituted ammonium salts of polyacetic acid. To be Examples of polyacetic acid chelating agents include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

As other suitable but less preferred polycarboxylates, alkyliminoacetic acid chelating agents are also known, such as methyliminodiacetic acid, alaninediacetic acid, methylglycinediacetic acid, hydroxypropyleneiminodiacetic acid and Other alkyliminoacetic acid chelating agents and the like can be mentioned.

Suitable for the composition of the present invention is 3,3-dicarboxy-4-oxa-1.
, 6-hexanediote and related compounds, such as Bush
U.S. Pat. No. 4,566,984 issued Jan. 28, 1986, which is hereby incorporated by reference. Useful succinic chelating agents include alkyl succinic acids and salts thereof C _{5-C 20.} Particularly preferred as this type of compound is dodecenyl succinic acid. Alkyl succinic acids typically of the general formula _{R-CH (COOH) CH 2} (C
OOH) is a derivative of succinic acid, wherein R is a hydrocarbon, C _10- C ₂₀
Is an alkyl or alkenyl group, preferably C ₁₂ -C ₁₆ , or R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all of which are described in the above-identified US patents.

The succinic acid chelating agents are preferably used in the form of their water-soluble salts including sodium, potassium, ammonium and alkanol ammonium salts and the like.

Specific examples of the succinic acid chelating agent include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate. Is mentioned. Lauryl succinate is a preferred chelating agent of this group and is described in European Patent Application No. 86200690.5 / 0 200 263 published Nov. 5, 1986.

Examples of useful chelating agents are sodium and potassium carboxymethyloxymalonates, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, water-soluble polyacrylates and maleic anhydride. Mention may be made of copolymers of acids with vinyl methyl ether or ethylene.

Other suitable polycarboxylates have been described by Crutchfield et al.
Polyacetal carboxylate disclosed in US Pat. No. 4,144,226, issued Mar. 13, the description of which is incorporated herein by reference. These polyacetal carboxylates are prepared by bringing together an ester of glyoxylic acid and a polymerization initiator under polymerization conditions (bring together). Next, the polyacetal carboxylate ester thus obtained is
It is attached to a chemically stable end group to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt and added to the surfactant.

Polycarboxylate chelating agents have also been assigned to Diehl 3 1967.
It is also disclosed in U.S. Pat. No. 3,308,067, issued March 7, the content of which is incorporated herein by reference. Such materials include water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Suitable polyphosphonates for use in the present invention include polyphosphonates (
Alkali metal salts, typified by tripolyphosphoric acid, pyrophosphoric acid and vitreous polymeric metaphosphoric acid), ammonium salts, and alkanol ammonium salts.

The most preferred chelating agent for use in the present invention is selected from diethylenetriaminepentamethylenephosphonate (DTPMP) or ethane 1-hydroxydiphosphonate (HEDP). Such phosphonate chelating agents are DEQUE
Commercially available from Monsanto under the ST® trademark.

Anionic Surfactant The composition of the present invention also contains an anionic surfactant as an essential component thereof. The anionic surfactant is 0.01 to 40% by weight of the composition, preferably 0.1.
-20% by weight, more preferably less than 10% by weight, most preferably 0.2-10%
% By weight.

Suitable anionic surfactants for use in the compositions of the present invention include those of the formula RO
It includes water-soluble salts or acids represented by SO ₃ M, wherein, R is preferably C ₇ ~
A C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C _{7 to} C ₂₄ alkyl moiety, more preferably a C _{12 to} C ₁₈ alkyl or hydroxyalkyl, M being hydrogen or a cation, for example Alkali metal cations (eg sodium, potassium, lithium) or ammonium or substituted ammonium cations (eg methyl-, dimethyl- and trimethylammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperdinium cations , And quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.

[0040]   Other suitable anionic surfactants have the formula RO (A)_mSO₃Water represented by M
Soluble salts or acids may be mentioned, where R is C_Ten~ C_{twenty four}Alkyl or C_Ten~ C_{twenty four} A hydroxyalkyl group having an alkyl component of, preferably C₁₂~ C ₂₀ Alkyl or hydroxyalkyl, more preferably C₁₂~ C₁₈of
Alkyl or hydroxyalkyl, where A is an ethoxy or propoxy unit
And m is greater than 0, usually about 0.5 to about 6, and more preferably about 0.
Is between 5 and about 3, and M is hydrogen or a cation, such as a metal ion (eg, nato).
Lithium, potassium, lithium, calcium, magnesium, etc.) or ammoniu
Can be a ammonium or substituted ammonium cation. Alkyl ethoxylated sulf
And alkylpropoxylated sulfates are contemplated herein.
Be done. Specific examples of the substituted ammonium cation include methyl-, dimethyl-, and
Limethylammonium cation, as well as quaternary ammonium cations such as the
Tramethylammonium and dimethylpiperdinium cations and alal
Cananolamines such as ethylamine, diethylamine, triethylamine,
The cation obtained from the mixture etc. of these is mentioned. An example of a surfactant is C₁₂~
C₁₈Alkyl polyethoxylate (1.0) sulfate (C₁₂~ C₁₈E (
1.0) M), C₁₂~ C₁₈Alkyl polyethoxylate (2.25) sulphate
(C₁₂~ C₁₈E (2.25) M), C₁₂~ C₁₈Of alkyl polyethoxy
(3.0) Sulfate (C₁₂~ C₁₈E (3.0)) and C₁₂~ C₁₈of
Alkyl polyethoxylate (4.0) sulfate (C₁₂~ C₁₈E (4.0
) M), where M is conveniently selected from sodium and potassium.
.

[0041]   Other particularly suitable anionic surfactants for use in the present invention include those of the formula RSO ₃ Alkyl sulfonates containing a water-soluble salt or acid represented by M include
Medium, R is C₆~ C_{twenty two}A linear or branched, saturated or unsaturated alkyl group of
, Preferably C_Ten~ C₁₆An alkyl group of, more preferably C₁₂~ C₁₆A
Is a alkyl group, M is hydrogen or a cation, such as a metal ion (eg, sodium).
Ammonium, potassium or lithium) or ammonium or substituted ammonium (eg
Methyl-, dimethyl- and trimethylammonium cations, and quaternary
Ammonium cations such as tetramethyl ammonium and dimethyl piper
Dinium cations, and alkylamines such as ethylamine, diethylami
Quaternary ammonium cations derived from amines, triethylamine and mixtures thereof
Etc.).

Alkylaryl sulfonates suitable for use in the present invention have the formula RSO ₃ M
Is a water-soluble salt or acid represented by the formula, wherein R is a C _{6 to} C ₂₂ linear or branched, saturated or unsaturated alkyl group, preferably a C _{10 to} C ₁₈ alkyl group, and more preferably Is an aryl group substituted with a C ₁₂ -C ₁₆ alkyl group, preferably a benzyl group, M is hydrogen or a cation, such as an alkali metal ion (eg sodium, potassium, lithium, calcium, magnesium etc.) or ammonium or Substituted ammonium cations (such as methyl-, dimethyl- and trimethylammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperdinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Etc. Quaternary ammonium cations) and the like.

Alkyl sulfonates and alkyl aryl sulfonates for use in the present invention include primary and secondary alkyl sulfonates and primary and secondary alkyl aryl sulfonates. The term "secondary C ₆ -C ₂₂ alkyl or C ₆ -C ₂₂ alkylaryl sulfonate" as used herein means that SO ₃ M or an aryl-SO ₃ M group is an alkyl group as defined above. It is meant to be attached to a carbon atom in the chain which is located between two other carbon atoms in the alkyl chain (second carbon atom).

For example, a C ₁₄ -C ₁₆ alkyl sulfonate salt can be prepared by using Hostapur (
It is marketed by the company Hoechst under the trademark ® SAS and the sodium salt of C ₈ -alkyl sulfonate is marketed by the company Witco SA under the brand Witconate NAS 8 ®. An example of a commercially available alkylaryl sulfonate is lauryl aryl sulfonate from Su. Ma. A particularly preferred alkylaryl sulphonate is the alkyl benzene sulphonate marketed by Albright & Wilson under the trade name Nansa®.

[0045]   Other useful anionic surfactants for cleaning purposes may also be used in the compositions of the present invention.
Wear. These include soap salts (e.g. sodium, potassium, ammonium).
And substituted ammonium salts such as mono-, di- and triethanolamine salts.
Including), C₈~ C_{twenty four}Olefin sulfonates, such as British Patent 1,082,
Sulfate, a thermal decomposition product of an alkaline earth metal citrate, as described in US Pat.
A sulfonated polycarboxylic acid prepared by sulfonation, C₈~ C_{twenty four}Alkyl polyg
Recall ether sulphate (containing 10 mol or less of ethylene oxide); C ₁₄ ~ C₁₆Sulfonic Acid Methyl Ester; Acylglycerol Sulfonate, Fat
Group oleyl glycerol sulfate, alkylphenol ethylene oxide
Ether sulfate, paraffin sulfonate, alkyl phosphate, iseti
Onates (eg, acyl isethionates), N-acyl taurates, alkyls
Xinamate and sulfosuccinate, monoester of sulfosuccinate (
Especially saturated and unsaturated C₁₂~ C₁₈Monoester) and sulfosuccinate
Diesters (especially saturated and unsaturated C₆~ C₁₄Diester), ethoxylated
Rufosuccinate, sulfates of alkyl polysaccharides such as alkyl polyglucos
Sid sulfates (nonionic nonsulfated compounds described below), branched chain
Monoalkyl sulphates and alkyl polyethoxycarboxylates, eg
Ba RO (CH₂CH₂O)_kCH₂COO-M⁺(In the formula, R is C₈~ C_{twenty two}The archi
, K is an integer from 0 to 10 and M is a soluble salt-forming cation).
There are things to do. Resin acids and hydrogenated resin acids are also suitable, rosin, hydrogen
Rosin, and resin acids present in or derived from tall oil and
Examples thereof include hydrogenated resin acids. Further examples are “Surface Active Agents and
Detergents ”(Vol. I and II by Schwartz, Perry and Berch)
It A variety of such surfactants are generally described in US Pat. No. 3,929,678.
Issue (column 23 line 58 to column 29 line 23, Laughlin et al., Issued December 30, 1975)
(This description is incorporated herein by reference).

Other particularly suitable anionic surfactants for use in the present invention are alkylcarboxyls having 4 to 24 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 16 carbon atoms in the alkyl chain. And alkylalkoxycarboxylates, where alkoxy is propoxy and / or ethoxy, preferably ethoxy with a degree of alkoxylation of 0.5-20, preferably 5-15. Preferred alkyl alkoxy carboxylates for use in the present invention, laureth 11 carboxylate _{(i.e., RO (C 2 H 4 O} ) 10 -CH 2 COONa, wherein R is C ₁₂ -C ₁₄₎ are, Akiposofuto ( It is commercially available from Kao Chemical Gbmh under the trade name Akyposoft® 100 NV.

Particularly preferred surfactants are alkyl sulphates, alkyl sulphonates,
It is selected from the group consisting of alkyl ethoxy sulphates, alkyl benzene sulphonates, alkyl carboxylates, alkyl ethoxy carboxylates, alkyl sulphosuccinates and mixtures thereof. In a preferred embodiment of the present invention, the anionic surfactant is a system consisting of at least two anionic surfactants. Particularly suitable anionic surfactants are linear alkyl or alkylbenzene sulfonate and sulfosuccinate surfactants. More specifically preferred as existing anionic surfactants in the surfactant system are C ₁₂ linear alkyl benzene sulfonates (LAS) and dioctyl sulfosuccinates.

The chelating agent and the anionic surfactant of the present invention are present in a ratio of 4: 1 to 1: 4.

Recontamination Inhibiting Component The compositions of the present invention can include a recontamination inhibiting polymer. If there,
The anti-redeposition polymer is preferably 20% or less, more preferably 0.001%.
-10%, more preferably 0.01% -5%, most preferably 0.1% -2%
Exist at the level of.

Suitable antifouling ingredients include those well known to those skilled in the art, including polyalkoxylen glycol diesters, homopolymers or copolymers of vinylpyrrolidone except those already mentioned, polysaccharide polymers, polyalkoxylen glycols. , Mono- or di-capped polyalkoxylen glycols, which are defined below, or mixtures thereof.

[0051]   Vinylpyrrolidone homopolymers suitable for use in the present invention include:

[0052]

[Chemical 2] (In the formula, n (degree of polymerization) is 10 to 1,000,000, preferably 20 to 100.
, And more preferably an integer of 20 to 10,000) is a homopolymer of N-vinylpyrrolidone.

Accordingly, vinylpyrrolidone homopolymers (“PV
P ") has an average molecular weight of 1,000 to 100,000,000, preferably 2,
000 to 10,000,000, more preferably 5,000 to 1,000,0
00, most preferably 50,000 to 500,000.

Suitable vinylpyrrolidone homopolymers are PVP K-15® (viscous molecular weight 10,000), PVP K-30® (average molecular weight 40,000).
), PVP K-60® (average molecular weight 160,000) and PVP
Product name of K-90 (registered trademark) (average molecular weight 360,000), ISP Corporatio
n (New York, NY and Montreal, Canada). Other suitable vinylpyrrolidone homopolymers that are commercially available include Sokalan HP165 (registered trademark) and Sokalan HP that are commercially available from BASF.
12 (R), vinylpyrrolidone homopolymers known to those skilled in the detergent art (e.g. EP-A-262,897 and EP-EP-A).
A-256,696).

Vinylpyrrolidones suitable for use in the present invention include copolymers of N-vinylpyrrolidone and alkylene unsaturated monomers or mixtures thereof.

The alkylene unsaturated monomer of the copolymer of the present invention includes unsaturated acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, and vinyl acetate. Dicarboxylic acids are included. Any anhydride of the unsaturated acid can be used, and acrylate and methacrylate are exemplified. Aromatic monomers such as styrene, sulfonated styrene, alpha-methyl styrene, vinyltoluene, t-butyl styrene and similar known monomers can also be used.

The molecular weight of the vinylpyrrolidone copolymer is determined by the liquid composition or solution containing the copolymer so that it is water soluble, has some surface activity and can enhance the hydrophilicity of hard surfaces (ie, diluted use). Conditions), it is not particularly limited as long as it is adsorbed on the hard surface. However, with N-vinylpyrrolidone,
Preferred copolymers of alkylene unsaturated monomers or mixtures thereof are 1
It has a molecular weight of 1,000 to 1,000,000, preferably 10,000 to 500,000, and more preferably 10,000 to 200,000.

N-vinylpyrrolidone, such as PVP / vinyl acetate copolymers, and such copolymers of alkylene unsaturated monomers are commercially available from BASF under the Luviskol® series of trade names.

Other polymers suitable for use in the present invention are polysaccharide polymers, which include carboxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycans and naturally occurring polysaccharide polymers include substituted cellulosic materials such as xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, and mixtures thereof.

A polysaccharide polymer to be used especially in the present invention is xanthan gum and its derivatives. Xanthan gum and its derivatives are, for example, Ketrol
It may be commercially available from Kelko under the trade names RD®, Kelzan S®, Kelzan T®.

Additional antifouling components suitable for use in the present invention further include polyalkoxylen glycols, mono- and di-capped polyalkoxylenglycols or mixtures thereof, which are defined below. It

Suitable polyalkoxylene glycols for use in the present invention have the formula H—O— (C
Represented by _{H 2 CHR 2 O) n -H} .

Suitable monocapped polyalkoxylen glycols for use in the present invention have the formula R ₁ —O— (CH ₂ CHR ₂ O) _n —H.

Suitable dicapped polyalkoxylen glycols for use have the formula R ₁ —O—
Represented by _{(CH 2 CHR 2 O) n} -R 3.

In these formulae, the substituents R ₁ and R ₃ are each independently substituted or unsubstituted,
Saturated or unsaturated, linear or branched hydrocarbon chain having 1 to 30 carbon atoms, or amino group-containing linear or branched, substituted or unsubstituted hydrocarbon chain having 1 to 30 carbon atoms And R ₂ is hydrogen or linear or branched 1 to 30
Is a hydrocarbon chain having a carbon number of n, and n is an integer greater than zero.

Preferably, R ₁ and R ₃ are each independently substituted or unsubstituted, linear or branched 1 to 30, preferably 1 to 16, more preferably 1 to 8, and most preferably 1 to An alkyl group having 4 carbon atoms, an alkenyl group or an aryl group, or an amino group containing (amino bearing) straight or branched, substituted or unsubstituted 1 to 30,
It is preferably an alkyl group, an alkenyl group or an aryl group having 1 to 16 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Preferably R ₂
Is hydrogen, or a linear or branched 1-30, preferably 1-16, more preferably 1-8, alkyl, alkenyl, or aryl group, and most preferably R ₂ is a methyl group. Or hydrogen. Preferably n is greater than 1, more preferably 5 to 1000, more preferably 10 to 100, even more preferably 20 to 60 and most preferably 30 to 50.

Preferred polyalkoxylen glycols, mono- and di-capped polyalkoxylen glycols for use in the present invention are at least 200, more preferably 4
It has a molecular weight of 00 to 5000, most preferably 800 to 3000.

Suitable monocapped polyalkoxylene glycols for use in the present invention include:
2-aminopropyl polyethylene glycol (MW 2000), methyl propylene glycol (MW 1800) and the like are included. Such mono-capped polyalkoxylene glycol is a polyglycol series from Hoechst,
Alternatively, it is commercially available from Hunstman under the trade name of XTJ (registered trademark). Polyalkoxylen glycols suitable for use in the present invention include polyethylene glycol (MW
2000) and other polyethylene glycols.

Suitable dicapped polyalkoxylen glycols for use in the present invention include O
, O'-bis (2-aminopropyl) polyethylene glycol (MW 2000
), O, O′-bis (2-aminopropyl) polyethylene glycol (MW
400), O, O'-dimethyl polyethylene glycol (MW 2000), dimethyl polyethylene glycol (MW 2000) or mixtures thereof. A preferred dicapped polyalkoxylen glycol for use in the present invention is dimethyl polyethylene glycol (MW 2000). For example, dimethyl polyethylene glycol is a polyglycol series (eg PEG DME-
2000) or from Hunstman under the trade names Jeffamine® and XTJ®.

Preferred recontamination inhibitors include oligomeric terephthalate esters, which are typically prepared by a process involving at least one transesterification / oligomerization in which a metal catalyst such as a titanium (IV) alkoxide is often used. To be done. Such esters include, of course, additional monomers that can be incorporated into the ester structure at one, two, three, four or more positions without forming a dense, cross-linked overall structure. May be.

Suitable antifouling agents include a substantially straight chain consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and an allyl-derived sulfonated terminal moiety attached to the backbone in the form of a covalent bond. Sulfonation products of chain ester oligomers are included and are described, for example, in US Pat. No. 4,968,451 issued Nov. 6, 1990 to JJ Scheibel and EP Gosselink. Such ester oligomers are ethoxylated of (a) allyl alcohol; (b) the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in two stages. It is prepared by reacting in the exchange / oligomerization process; reacting the product of (c) (b) with sodium metabisulfite in water. Other anti-redeposition agents include US Pat. No. 4,7,8 issued Dec. 8, 1987 to Gosselink et al.
Nonionic end-capped 1,2-propylene / as described in 11,730
Polyoxyethylene terephthalate polyesters such as poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) (“PE
G ") include compounds produced by transesterification / oligomerization. Other anti-redeposition agents include Gosselink et al., Jan. 26, 1988.
Partially or fully anionically end-capped oligomeric esters described in U.S. Pat. No. 4,721,580 issued to Sun, such as ethylene glycol ((
G "), PG, DMT and oligomers derived from Na-3,6-dioxa-8-hydroxyoctanesulfonate; assigned to Gosselink, October 1987 2
Derived from nonionic capped block polyester oligomeric compounds, such as DMT, methyl (Me) -capped PEG and EG and / or PG, as described in US Pat. No. 4,702,857 issued 7th, or DMT. , EG and / or PG, derived from a combination of Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; Maldonado, Gosselink et al., Issued Oct. 31, 1989. Anionic, especially sulfoaroyl, end-capped terephthalate esters as described in US Pat. No. 4,877,896,
For example, prepared from m-sulfobenzoic acid monosodium salt, PG and DMT,
An optional but preferable example is an ester composition or the like, which further contains PEG such as PEG3400 optionally added.

The antifouling agents include simple copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide (these patents to Hays, issued May 25, 1976). No. 3,959,230 and Basadur, 8 July 1975.
See U.S. Pat. No. 3,893,929 issued daily; cellulosic derivatives such as hydroxy ether cellulosic polymers (from Dow
L); C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkyl cellulose (see US Pat. No. 4,000,093 issued Dec. 28, 1976 to Nicol et al.); And the average degree of substitution (methyl) for the anhydroglucose unit is about 1.6 to about 2.3, and the viscosity of the solution is a 2% aqueous solution,
Included is methyl cellulose ether which is about 80 to about 120 centipoise measured at 20 ° C. Such substances are METOLOSE SM100 and METOLOSE SM200 (these are Shin-etsu Kagaku Kogyo KK
Is a trade name of methyl cellulose ether manufactured in (1).

Suitable antifouling agents characterized by a poly (vinyl ester) hydrophobic segment include graft copolymers of polyvinyl esters, eg, C ₁ -C ₆ vinyl esters, preferably polyalkylene oxide backbones. Is a poly (vinyl acetate) graft-bonded to. See European Patent Application No. 0,219,048, published April 22, 1987, by Kud et al. Commercially available examples include SOKALAN recontamination inhibitors such as SOKALAN HP-22, BASF
, Available from Germany. Other antifouling agents are repeating units containing 10 to 15 wt% ethylene terephthalate with 80 to 90 wt% polyoxyethylene terephthalate derived from polyoxyethylene glycol with an average molecular weight of 300 to 5,000. Is a polyester having. As a commercial example
Examples include Dupont's ZELCON 5126 and ICI's MILEASE T.

Another preferred recontamination inhibitor is the empirical formula: (CAP) ₂ (EG / PG) ₅ (T) ₅ (
An oligomer having SIP) ₁ , terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (E
G / PG) unit, preferably terminated with an end cap (CAP), 1 unit of sulfoisophthaloyl, 5 units of terephthaloyl, oxyethyleneoxy and oxy-1,2-propylene (EG / PG) a specific ratio,
Preferably about 0.5: 1 to about 10: 1, and 2- (2-hydroxyethoxy)
A modified isethionate with 2 units of endcaps derived from sodium ethanesulfonate. The anti-redeposition agent is preferably an oligomer of 0.5
.About.20% by weight of a crystallinity-reducing stabilizer, such as an anionic surfactant (for example selected from linear dodecylbenzene sulphonate sodium or xylene-, cumene- and toluene-sulphonate or mixtures thereof). However, these stabilizers or modifiers are disclosed in US Pat. No. 5,415,807 issued May 16, 1995 to Gosselink, Pan, Kellett and Hall.
It is introduced into the synthesis vessel as taught in the specification. Suitable monomers for the antifouling agent include Na-2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

Yet another group of preferred recontamination inhibitors are (1) (a) dihydroxy sulfonates, polyhydroxy sulfonates, units that are at least trifunctional,
At least one unit selected from the group consisting of a unit thereby forming an ester bond to form a branched oligomer main chain, and a combination thereof;
(B) at least one unit that is a terephthaloyl moiety, and (c) 1,2-
A backbone containing at least one unsulfonated unit that is an oxyalkyleneoxy moiety; and (2) a nonionic cap unit, an anionic cap unit (eg, alkoxylated, preferably ethoxylated, isethionate, alkoxylated propane sulfonate). , An alkoxylated propane disulfonate, an alkoxylated phenol sulfonate, a sulfoaroyl derivative and a mixture thereof, which is an oligomeric ester having at least one cap unit, and preferably has an empirical formula: {(CAP) x (EG / PG). y '(DEG) y "(PE
G) y ″ ′ (T) z (SIP) z ′ (SEG) q (B) m} may be mentioned, in which CAP, EG / PG, PEG, T and SIP are as described above. , (DEG) represents a di (oxyethylene) oxy unit, and (SEG
) Represents a unit derived from sulfoethyl ether of glycerin and a unit related thereto, and (B) is a branched unit having at least trifunctionality, whereby an ester bond is formed to form a branched oligomer main chain. X is about 1 to about 12
, Y'is about 0.5 to about 25, y "is 0 to about 12, y"'is 0 to about 10, y' + y.
The sum of "+ y"'is about 0.5 to about 25, z is about 1.5 to about 25, and z'is 0 to about 1.
2, the sum of z + z 'is about 1.5 to about 25, q is 0.05 to about 12, and m is about 0.0.
1 to about 10, wherein x, y ', y ", y"', z, z ', q and m represent the average number of moles of units corresponding to the moles of said ester, said ester being from about 500 About 5
It has a molecular weight in the range of 1,000.

Preferred SEG and CAP monomers for the above ester include Na-2- (
2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na
-{2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3
)) And homologues thereof and mixtures thereof, as well as ethoxylated and sulfonated products of allyl alcohol. Preferred antifouling agent esters of this class include sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or 2- using a suitable titanium (IV) catalyst.
[2- {2- (2-hydroxyethoxy) ethoxy} ethoxy] sodium ethanesulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG, and PG by transesterification and oligomerization The resulting products are included, which are (CAP) ₂ (T) ₅ (EG / PG) _1.4 (SEG
) _2.5 (B) _0.13 , where CAP is (Na ⁺ -O ₃ S [CH ₂ CH ₂ O] 3.
5)-and B are units derived from glycerin, and the EG / PG molar ratio is about 1.7.
1 (measured by conventional gas chromatography after complete hydrolysis).

An additional class of antifouling agents is (I) a nonionic terephthalate linked to a polymeric ester structure using a diisocyanate coupling agent, see Violland et al., US Pat. No. 4,201. , 824 and Lagasse et al., U.S. Pat. No. 4,240,918; and (II) made by adding trimellitic anhydride to known redeposition inhibitors to convert the hydroxyl end groups to trimellitic acid esters. Recontamination inhibitors having carboxylated end groups. With the proper choice of catalyst, trimellitic anhydride can react with the chemical bond of the anhydride.
The conjugate with the polymer end is formed through the ester of the carboxylic acid isolated from trimellitic anhydride rather than unraveling the kage). Any nonionic or anionic antifouling agent, so long as it has a hydroxyl end group that can be esterified,
It can be used as a starting material. U.S. Pat. No. 4,525 to Tung et al.
See No. 524. Another class of (III) antifouling agents for urethane-bonded manifolds based on anionic terephthalates, for which Vi
See U.S. Pat. No. 4,201,824 to Olland et al .; (IV) Poly (vinylcaprolactam) and copolymers related thereto, wherein the following monomers (e.g. vinylpyrrolidone and / or dimethylaminoethylmethacrylate,
(Including nonionic and anionic polymers),
See U.S. Pat. No. 4,579,681 to Ruppert et al .; (V) BASF SOKALAN type graft graft copolymers made by graft bonding acrylic monomers to sulfonated polyesters, Is mentioned. These antifouling agents have soil release and antiredeposition activity similar to known cellulose esters for which Rhone-Poulenc Chemie
． See European Patent Application Publication No. EP 279,134A (1988). As another class, a graft bond of vinyl monomers in which acrylic acid and vinyl acetate are bonded to the surface of a protein such as (VI) casein,
BASF (1991) European Patent Application Publication No. EP 457,205A; and (VI
I) Polyester-recontamination inhibitors, which are prepared by condensing adipic acid, caprolactam and polyethylene glycol and are assigned to Bevan et al. In Unilever NV (1974) German patent. Second DE 2,33
See 5,044. Other redeposition inhibitors are described in US Pat. No. 4,240,918.
No. 4,787,989, and No. 4,525,524.

Other suitable antifouling agents include hydrophobically modified cellulosic polymers. Suitable cellulose-based polymers for use in the present invention preferably have the formula:

[0079]

[Chemical 3]

Wherein each R is R ₂ , R _c and

[Chemical 4] Wherein each R ₂ is independently selected from the group consisting of H and C ₁ -C ₄ alkyl, and each R _c is

[Chemical 5] Wherein each Z is independently selected from the group consisting of M, R ₂ , R _c and R _H , each R _H is C ₅ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl , C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl,
C ₁ -C ₂₀ alkoxy-2-hydroxyalkyl, C ₇ -C ₂₀ alkylaryl-2-hydroxyalkyl, (R _{4) 2} N- _{alkyl, (R 4) 2 N-} 2- hydroxy-alkyl, (R ₄ ) ₃ N-alkyl, (R ₄ ) ₃ N-2-hydroxyalkyl, C ₆ -C ₁₂ aryloxy-2-hydroxyalkyl,

[Chemical 6] Are each independently selected from the group consisting of, - each R ₄ is, H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, Each independently selected from the group consisting of aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each R ₅ is H, C ₁ -C ₂₀ alkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₂₀ alkylaryl, C ₇ -C ₂₀ arylalkyl, substituted alkyl, hydroxyalkyl, from (R _{4) 2} N- alkyl and (R _{4) 3} N- alkyl Independently selected from the group consisting of Na, K, 1 / 2Ca, and 1 / 2Mg. With a suitable cation, each x is from 0 to about 5, each y is from about 1 to about 5, and the degree of substitution for the -R _H groups is between about 0.001 to 0.1 , More preferably between about 0.005-0.05, most preferably between about 0.01-0.05, and the degree of substitution with the —R _C group is such that when Z is H or M, Between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, most preferably about 0.4 to 0.
． 7 and-if either R _H carries a positive charge, it is balanced by a suitable anion, and-the two R ₄ bound to the same nitrogen are jointly piperidine and It is capable of forming a cyclic structure selected from the group consisting of morpholine).

In the present specification, “degree of substitution” for the R _H group, which may be abbreviated as “DS _RH ”.
The, R _H group component substituted by anhydroglucose units (group R _H component
), The anhydrous glucose unit is a 6-membered ring as shown in the above general structural formula.

[0082]   In this specification, "DS_RC] May be abbreviated, R_C"Substitution degree" for groups
And Z is H or M, which is R substituted by an anhydroglucose unit. _c Means the number of moles of the base component, the anhydrous glucose unit is shown in the general structural formula above.
It is a 6-membered ring. Z being H or M means that the resulting polymer is soluble.
To ensure that there are a sufficient number of carboxymethyl groups to be degradable,
This is a mandatory condition. The required number of R, where Z is H or M_cIn addition to the ingredients,
An additional R, where Z is H or less than M_cIngredients may be present and are most preferred
It is better to understand that it exists.

These polymers are described, for example, in co-pending International Patent Application No. PCT / US98.
/ 19139 and the production method described in PCT / US98 / 19142.

Particularly preferred antifouling polymers are selected from the group consisting of vinylpyrrolidone, polysaccharide polymers, polyalkoxylenglycols and mixtures thereof.

Soil Settling Agent Polymer The compositions of the present invention can contain a soil settling inhibitor polymer. When such a soil-dispersing polymer is present, its proportion is preferably 0.001-1.
It is 0%, more preferably 0.01 to 5%, most preferably 0.1 to 3%. Any of the soil precipitation inhibitor polyamine polymers known to those skilled in the art can be used in the present invention. A particularly suitable polyamine polymer is a polyalkoxylated polyamine. Such a material has a molar structural formula (molecul) containing repeating units.
es of the empirical structure).

[0086]

[Chemical 7]

In the formula, R is usually a hydrocarbon group having 2 to 6 carbon atoms, R ¹ is a C _{1 to} C ₂₀ hydrocarbon group; the alkoxy group is ethoxy, propoxy and the like, and y is 2 to 30, most preferably. Is 10 to 20; n is an integer of at least 2, preferably 2 to 20, most preferably 3 to 5; X ⁻ is an anion such as halide or methylsulfate, and is quaternized. It is caused by the reaction.

The most preferred polyamine used here is the so-called ethoxylated polyethyleneamine, ie the reaction product of the polymerization of ethylene oxide with ethyleneimine,
It is represented by the following general formula.

[0089]

[Chemical 8]

Embedded image wherein y is 2 to 30. Particularly preferred for use herein are ethoxylated polyethyleneamines, especially ethoxylated tetraethylenepentamine, and quaternary ethoxylated hexamethylenediamine. .

Particularly preferred soil settling prevention polymers are polyalkoxylated polyamine polymers, more preferably ethoxylated polyethyleneamines.

Optional Ingredients The composition according to the invention may contain various optional ingredients, depending on the technical advantage sought and the treated surface.

Optional components suitable for use herein include surface direct acting polymers.
tive polymer), additional surfactants, enzymes, hydrotropes, antifoams,
Solvents, buffers, thickeners, radical scavengers, dyes, dyes, preservatives and / or
Alternatively, it can be selected from the group consisting of fragrances.

Surface Direct Action Polymer The compositions of the present invention may contain a surface direct action polymer as an optional but preferred component. By surface-direct acting polymer is meant a polymer that can be modified by attaching to or otherwise binding to the surface to be washed such that it remains on the surface during and after the washing step. To do. Such attachment or bonding is due to, for example, covalent interactions, electrostatic interactions, hydrogen bonds, Van der Waals forces. The polymer modifies the surface by rendering it hydrophilic, ie the contact angle between water and the surface is less than 50 degrees, preferably less than 40 degrees after surface treatment with the polymer containing composition. , And more preferably 30
It is less than 40 degrees, most preferably 20 degrees or less. The contact angle is the American Standard Test Method for measuring contact angle, designation number D57.
Kruss under the trade name Contact Angle Measuring System G10 according to 25-95
Is measured by using an apparatus marketed by.

In another aspect of the invention, the polymer can permanently modify the surface to make it hydrophilic and has a surface contact angle between water and the surface of less than 50 degrees, preferably less than 40 degrees. It is more preferably less than 30 degrees, and most preferably 20 degrees or less. "Permanent"
Means at least 1 rinse, preferably at least 3 rinses, more preferably at least 5 rinses, even more preferably at least 7 rinses, most preferably at least 10 rinses, or at least 30 rinses. Rinsing also means that the surface modification to hydrophilic is retained while performing the rinse test methods described herein.

Rinsing Test Method The rinsing test method used in accordance with the invention was 24 French hardness (French degr
ee hardness) water is sprayed onto the surface for 30 seconds from a location 1.0 meter away from the surface to be cleaned using a normal garden hose. The water flow rate from the hose was about 10 liters per minute.

The polymers used in the present invention are homo or copolymers and preferably contain at least one hydrophobic or cationic moiety and at least one hydrophilic moiety. The hydrophobic moiety is preferably aromatic, straight chain or branched C ₈
~ _C18 carbon chain, vinylimidazole or propoxy group. The cation moiety includes all groups that are either positively charged or have a positive dipole. The hydrophilic moieties can be selected from all moieties that form a dipole with hydrogen bonding capacity. Suitable examples of such hydrophilic moieties include vinylpyrrolidone, carboxylic acids (eg acrylic acid, methacrylic acid, maleic acid) and ethoxy groups.

In a preferred embodiment of the present invention said polymer is selected from the group consisting of copolymers of polyvinylpyrrolidone. A particularly preferred copolymer of polyvinylpyrrolidone is N-vinylimidazole N-vinylpyrrolidone (PVPVI) polymer, available for example from BASF under the trade name Luvitec VP155K18P. Preferred PVP VI polymers are 1,000 to 5,000,000, more preferably 5,000 to 2,000,000, and even more preferably 5,000 to 500.
It has an average molecular weight of 5,000, most preferably 5,000 to 15,000. Preferred PVPVI polymers contain at least 55%, preferably at least 60% N-vinylimidazole monomer. Also, other preferred polymers are quaternary PVPVI, such as under the trade name Luvitec Quat 73W.
It may be a compound sold by BASF.

Other vinylpyrrolidone copolymers suitable for use in the compositions of the present invention are quaternary vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers. Suitable quaternary vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers for use in the compositions of the present invention have the formula:

[0100]

[Chemical 9]

(In the formula, n is between 20 and 99 mol%, preferably 40 to 90 mol%, m
Is between 1 and 80 mol%, preferably between 5 and 40 mol%; R ₁ represents H or CH ₃ ; y represents 0 or 1; R ₂ is —CH ₂ —CHOH—CH ₂ - or C _x H _2x (where x is 2 to 18); R ₃ is a lower alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, or the following compounds:

[0102]

[Chemical 10] Represents

R ₄ represents a lower alkyl group having 1 to ₄ carbon atoms, preferably a methyl group or an ethyl group, and X ⁻ is Cl, Br, I, 1 / 2SO ₄ , HSO ₄ and CH ₃ SO _3. Selected from the group. ). The polymer is a French patent No. 2
, 077,143 and 2,393,573.

Preferred quaternary vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers for use herein are from 1,000 to 1,000,0.
00, preferably between 10,000 and 500,000, more preferably 10
It has a molecular weight between 1,000 and 100,000.

The vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers described above are copolymers 845®, Gafquat 734® or Gafquat 75.
5 (registered trademark) under the trade name of ISP Corporation, New York, NY and Montreal,
Commercially available from Canada and from BASF under the trade name Luviquat®.

Optimal herein is a quaternary copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (polyquaternium-11), available from BASF.

Another preferred polymer is polyvinyl pyridine N-oxide (PVNO).
Polymers available, for example, from Reilly. Preferred PVNO polymers have an average molecular weight of 1,000 to 2,000,000, more preferably 5,000 to 50.
It is 50,000, most preferably 15,000 to 50,000.

The range of the average molecular weights described above is as described in Barth H. G. And Mays J. W., Chemical
Analysis Volume 113, "Modern Methods of Polymer Characterization"
It was identified by light scattering described in.

The polymer is preferably 0.001% to 10% by weight, more preferably 0.01% to 5% by weight, most preferably 0.1% by weight, based on the weight of the composition.
Present in the composition at a level of ˜2% by weight.

Other Surfactants The compositions of the present invention may also contain additional surfactants as an optional but preferred ingredient. Such additional surfactants include nonionic, cationic, zwitterionic and / or amphoteric surfactants.

Amphoteric surfactants suitable for use herein include those of the formula R ₁ R ₂ R ₃ NO, where R ₁ ,
R ₂ and R ₃ each independently represent a saturated, substituted or unsubstituted, linear or branched hydrocarbon chain having a carbon number of 1 to 30) and an amine oxide. A preferred amine oxide surfactant used in the present invention has the following formula: R ₁ R ₂ R ₃ NO (wherein R ₁ is 1 to 30, preferably 6 to 20, more preferably 8 to 16).
, Most preferably a hydrocarbon chain of 8 to 12 carbon atoms, wherein R ₂ and R ₃ are each 1
To 4, preferably a substituted or unsubstituted, straight or branched hydrocarbon chain having 1 to 3 carbon atoms, and more preferably a methyl group). R ₁ may be substituted or unsubstituted and may be a linear or branched hydrocarbon group. Suitable amine oxides for use herein are, for example, natural mixed C ₈
-C ₁₀ amine oxide and C ₁₂ -C ₁₆ amine oxide commercially available from Hoechst.

Zwitterionic surfactants suitable for use herein have the same cationic hydrophilic groups, ie, quaternary ammonium groups, and anionic hydrophilic groups, under a fairly wide range of pH conditions. Have on the molecule. Typical anionic hydrophilic groups are carboxylates and sulfonates, but other groups such as sulphates, phosphonates and the like can also be used. Here zwitterionic surfactants for use in the following general ^{_{formula: R 1 -N + (R 2}} ) (R 3) R 4 X -

Wherein R ₁ is a hydrophobic group; R ₂ is hydrogen, C ₁ -C ₆ alkyl, hydroxyalkyl or another substituted C ₁ -C ₆ alkyl group; R ₃ is bound to R ₂ and together with N C ₁ -C ₆ alkyl, hydroxyalkyl or other substituted C ₁ which can also form a cyclic structure
To C ₆ alkyl group, or C _{1 to} C ₆ carboxylic acid group or C _{1 to} C ₆ sulfonate group; R ₄ is a moiety for connecting a cationic nitrogen atom and a hydrophilic group, and typically, It is an alkylene, hydroxyalkylene or polyalkoxy group having 1 to 10 carbon atoms, and X is a hydrophilic group which is a carboxylate or sulfonate group.
) Is represented by.

Preferred as the hydrophobic group R ₁ is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain which can contain a binding group such as an amide group or an ester group. More preferable R ₁ is an alkyl group having 1 to 24, preferably 8 to 18, and more preferably 10 to 16 carbon atoms. These simple alkyl groups are preferable in terms of cost and stability. However, the hydrophobic group R ₁ has the formula:
_Ra- C (O) -NH- (C ( _Rb ) ₂ ) _m (wherein _Ra is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably, An alkyl group having 8 to 20, preferably 18 or less, more preferably 16 or less carbon atoms, R _b
Is selected from the group consisting of hydrogen and hydroxy groups, m is 1-4, preferably 2-.
3, more preferably 3, and any amide radical represented by ((C (R _b ) ₂ ) moiety has 1 or less hydroxy groups) may be used.

[0115]   Preferred R₂Is hydrogen or C₁~ C₃Alkyl, more preferably methyl
. Preferred R₃Is C₁~ C_FourCarboxylic acid group or C₁~ C_FourSulfonate group
Is C₁~ C₃Alkyl, more preferably methyl. Preferred R_FourIs (CH₂) _n And n is an integer of 1 to 10, preferably 1 to 6, and more preferably 1 to 3.

General examples for betaines / sulfobetaines are given in US Pat. No. 2,082,
275, 2,702,279 and 2,255,082, the contents of which are incorporated herein by reference.

Examples of particularly preferable alkyldimethyl betaines include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl ammonia) acetate, 2- (N-coco-N). , N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. For example, coconut-dimethyl betaine is available as Amonyl 265 (
It is marketed by Seppic under the registered trademark). Lauryl betaine is commercially available from Albright & Wilson under the trade name of Empigen BB / L®.

Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine, or C ₁₀ -C ₁₄ aliphatic acylamido propylene (hydropropylene) sulfobetaine. For example, C ₁₀ -C ₁₄ aliphatic acyl amides propylene (hydro propylene) sulfobetaine is commercially available from Sherex Company under the trade name "baryon (Varion) CAS (R) sulfobetaine".

Another example of betaine is lauryl iminodipropionate, commercially available from Rhone-Poulenc under the tradename Mirataine H2C-HA ™.

Cationic surfactants suitable for use in the present invention are derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants for use herein are quaternary ammonium compounds (wherein
1 or 2 hydrocarbon group bonded to nitrogen is saturated and is a straight-chain or branched-chain alkyl group having 6 to 30 carbon atoms, preferably 10 to 25 carbon atoms, and more preferably 12 to 20 carbon atoms, Other hydrocarbon groups bonded to nitrogen (that is, three when one hydrocarbon group is the above-mentioned long-chain hydrocarbon group, and two hydrocarbon groups when it is the above-mentioned long-chain hydrocarbon group) Are two or more) each independently a saturated or unsaturated, straight-chain or branched, alkyl chain having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a methyl group. ). Preferred quaternary ammonium compounds suitable for use herein are non-chloride / non-halogen quaternary ammonium compounds.

Particularly suitable for use in the compositions of the present invention are trimethyl quaternary ammonium compounds, such as myristyl trimethyl sulphate, cetyl trimethyl sulphate, and / or tallow trimethyl sulphate. Such trimethyl quaternary ammonium compounds are available from Hoechst
It is commercially available from Albright & Wilson under the trade name of MPIGEN) CM (registered trademark).

In one embodiment of the invention, the composition contains a nonionic surfactant in addition to the anionic surfactant. Any nonionic surfactant known in the art is suitable for use herein. Preferred nonionic surfactants are alkoxylated nonionic surfactants. The alkoxylated nonionic surfactant preferably has 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms,
Most preferably, it is an alkoxylated alcohol having a carbon chain of 10 to 15 carbon atoms. The alkoxylation can be carried out with ethoxylate, propoxylate or butoxylate groups, preferably ethoxylate groups. In a preferred embodiment, the ethoxylated alcohol is 0.5-20, more preferably 2
10 to 10, most preferably 4 to 6 ethoxy groups. Preferred alcohol ethoxylates are described in Example 1.

Suitable capped alkoxylated nonionic surfactants for use herein have the formula: R ₁ (O—CH ₂ —CH ₂ ) _n — (OH ₂ ) _m —O—R ₃ ( In the formula, R ₁ is a C _{8 to} C ₂₄ linear or branched alkyl or alkenyl group,
An aryl group or an alkaryl group, preferably R ₁ is a C ₈ -C ₁₈ alkyl or alkenyl group, more preferably a C ₁₀ -C ₁₅ alkyl or alkenyl group, and even more preferably C ₁₀ -C _15. alkyl group, R ₂ is an alkyl group of C ₁ -C ₁₀ straight or branched chain, preferably C ₂ -C _{1 0} straight or branched chain alkyl group, R ₃ is C ₁ To C ₁₀ alkyl or alkenyl groups, preferably C _{1 to} C ₅ alkyl groups, more preferably methyl groups, and n and m are each independently 1 to 20, preferably 1 to 10, and more preferably Preferably, it is an integer in the range of 1 to 5, or a mixture thereof.

These surfactants are known under the trade name Plurafac®.
It is marketed by BASF by HOECHST under the trade name of Genapol® or by ICI under the trade name of Symperonic®. Preferred capped nonionic alkoxylated surfactants of the above formula are those from Hoechst under the tradename Genapol® L2.5NR and also from Plurafac®. It is marketed by BASF under the product name.

If the composition according to the invention also contains a nonionic surfactant, this may have a ratio of anionic surfactant to nonionic surfactant of from 6: 1 to 1: 1 and more preferably 5: 1. It is preferably present as being from 1: 1 to 3: 1, more preferably about 4: 1.

Other suitable surfactants include silicone surfactants such as organosilanes and organosiloxanes. Preferably, the molecular weight of the silicone surfactant is 600-10,000, more preferably 900-6,000, most preferably about 3000. Such compounds are well known in the art and are described, for example, in U.S. Patents 3,299,112, 4,311,695 and 4,782,095.
No. 6,096,096, the contents of which are incorporated herein by reference. Suitable siloxane oligomers are described in US Pat. No. 4,005,028. Preferred silicone surfactants include polysiloxane polyethylene glycol copolymers and polyalkylene oxide modified polydimethylsiloxane copolymers.

Other suitable surfactants include fluorosurfactants containing hydrophilic and hydrophobic moieties. The hydrophilic portion contains an alkyl group having 2 to 12 carbon atoms and an ester, sulfonate or carboxylate portion. The hydrophobic part is fluorinated. Preferred fluorosurfactants include alkylfluorocarboxylates, examples of which include ammonium perfluoroalkylcarboxylates and potassium fluoroalkylcarboxylates. A particularly preferable fluorosurfactant is a water-soluble mixture of potassium fluoroalkylcarboxylate, which contains 40 to 44% of fluoroalkylcarboxylic acid having an alkyl chain of 8 carbon atoms and 6 carbon atoms.
1 to 5% of fluoroalkylcarboxylic acid having an alkyl chain, 1 to 5% of fluoroalkylcarboxylic acid having an alkyl chain of 4 carbon atoms, and 1 to 3% of fluoroalkylcarboxylic acid having an alkyl chain of 7 carbon atoms And 0.1 to 1% of a fluoroalkylcarboxylic acid having an alkyl chain of 5 carbon atoms.

Enzymes As an optional component, the compositions of the present invention may contain enzymes or mixtures thereof.

Preferred enzyme-based substances are commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases,
Examples include pectinase, lactase, and peroxidase, which are conventionally contained in detergent components and detergent compositions. Suitable enzymes are described in US Pat. Nos. 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include Alcalase, Savinase, Primaze, Durazym and Esperases sold by Novo Industries A / S (Denmark).
se) product name, Maxatase sold by Gist-Brocades
Under the trade names of Maxacal and Maxapem, Genenc
and those sold under the trade names of Opticlean and Optimase sold by Solvay Enzymes. Protease enzymes may be included in the compositions of the present invention at active enzyme levels of 0.0001% to 4% by weight, based on the weight of the composition.

Preferred amylases include, for example, α-obtained from a B licheniformis specific strain.
Amylase can be mentioned, but the details thereof are described in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold by Gist-Bracades under the trade name Rapidaze, Termamyl (T
Novo Industr under the trade names of ermamyl), Duramyl and BAN
Some are sold by ies A / S. Particularly preferred amylase enzymes are PCT / US9703635 and WO95 / 26397 and WO96 / 2.
3873.

Amylase enzymes may be included in the compositions of the invention at active enzyme levels of 0.0001% to 2% by weight, based on the weight of the composition.

The lipolytic enzyme is present in the composition of the invention in an amount of 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably 0.1% by weight, based on the weight of the composition.
It may be present at an active lipolytic enzyme level of 001% to 0.5% by weight.

Lipases are derived from fungi and bacteria, for example Humicola sp., Th.
genus ermomyces, or Pseudomonas pseudoalc
It is obtained from a lipase producing strain of the genus Pseudomonas containing aligenes or Pseudomonas fluorescens. Lipases obtained from mutant strains obtained by chemically or genetically modifying these strains are also useful. A preferred lipase is Pseudomonas pseudoalcaligen.
es, which is described in patent EP-B-0218272.

Other suitable lipases herein are Humicola lanugi.
It was obtained by cloning the gene of Nosa and expressing it using Aspergillus oryza as a host, which is described in European Patent Application Publication No. EP-A-025.
No. 8068 and the Novo Indu under the trade name of Lipolase.
Commercially available from stri A / S, Bagsvaerd, Denmark. This lipase is described by Huge-Jensen et al. In US Pat. No. 4,810,4 issued Mar. 7, 1989.
No. 14 is also described.

[0136]   Hydrotrope   The composition of the present invention may contain a hydrotrope as an optional component.

Suitable hydrotropes herein include sulfonated hydrotropes. All sulfonated hydrotropes known to those skilled in the art are suitable for use herein. Alkylaryl sulphonates or alkylaryl sulphonic acids are used in preferred embodiments. Preferred alkylaryl sulfonates are sodium, potassium, calcium and ammonium salts of xylene sulfonate, sodium, potassium, calcium and ammonium salts of toluene sulfonate, sodium, potassium, calcium and ammonium salts of cumene sulfonate, substituted or unsubstituted naphthalene. Included are the sodium, potassium, calcium and ammonium salts of sulfonic acids, and mixtures thereof. Preferred alkylaryl sulfonic acids include xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid and mixtures thereof. More preferably, xylene sulfonic acid or p-toluene sulfonate or mixtures thereof are used.

The composition of the present invention is generally 0.01% to 20% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, based on the total composition. % Sulfonated hydrotop.

Sulfonated hydrotropes, when present, contribute to the physical and chemical stability of the compositions described herein.

Ions The composition of the present invention may further comprise ions, which are preferably added to the composition as salts. Preferred ions used herein are sodium, ammonium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium,
And / or magnesium, more preferably calcium, zinc and / or magnesium. The ions may be added as chlorides, acetates, sulphates, formates, carbonates and / or nitrates or salts of metal complexes. For example, calcium may be added as calcium chloride, magnesium as magnesium acetate or magnesium sulfate, zinc as zinc chloride and ammonium as ammonium carbonate. Generally, such ions may be present in the composition at levels of up to 20% by weight, preferably 0.001% to 10% by weight, based on the total composition.

Antifoam Agent The composition of the present invention may further contain an antifoam agent such as a 2-alkylalkanol or a mixture thereof as a suitable optional component. Particularly suitable for use in the present invention have an alkyl chain having 6 to 16 carbon atoms, preferably 8 to 12 carbon atoms and a terminal hydroxyl group, said alkyl chain having 1 to 10 carbon atoms in the α position, preferably 2 to. 8-alkyl alkanols substituted with 8, more preferably 3-6 alkyl chains. Such suitable compounds include, for example, Isofol (
There is a registered trademark) series, Isofol (registered trademark) 12 (2-butyloctanol) or Isofol (registered trademark) 16 (2-hexyldecanol), which are commercially available.

Other antifoaming agents include alkali metal (for example, sodium or potassium) salts of fatty acids, or saponified products (soaps) thereof, wherein the fatty acids have about 8 to about 24 carbon atoms, preferably. Is about 10 to about 20.

The above-mentioned fatty acids, including those used in the production of soaps, include, for example, glycerides of plant or animal origin (eg palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow, Obtained from natural sources such as grease, lard, and mixtures thereof). Fatty acids can also be synthesized (eg, by oxidation of petroleum feedstocks or Fisher-Tropsch manufacturing processes). Alkali metal soaps can be made by directly saponifying fats and oils or by neutralizing free fatty acids prepared by a separate manufacturing process. Particularly effective are the sodium and potassium salts of a mixture of fatty acids derived from coconut oil and tallow, i.e. tallow and coconut sodium and potassium soaps. The term "tallow" as used herein typically has an approximate distribution of carbon chain lengths of 2.5%.
C _14, 29 percent of C _16, 23% of the C _18, 2% of the palmitoleic acid, 41.5% oleic acid and 3% linoleic acid (the first three fatty acids listed are saturated fatty acid) is the , Used in connection with a mixture of fatty acids. Other mixtures with similar partitioning, such as tallow of various animals and fatty acids obtained from lard, are also included in tallow herein. Tallows can also be cured (ie, hydrogenated) to convert some or all unsaturated fatty acid moieties to saturated fatty acid moieties. As used herein, "coconut"
When using the term, C ₈ typically has a distribution of about carbon chain length of about 8%,
7% C ₁₀ , 48% C ₁₂ , 17% C ₁₄ , 9% C ₁₆ , 2% C ₁₈ , 7% oleic acid and 2% linoleic acid (the first 6 fatty acids listed). Is a saturated fatty acid)
Is a mixture of fatty acids. Other sources with similar carbon chain length distribution are also included in the term coconut oil, such as palm kernel oil, babassu oil.

Other suitable foam control agents include silicones and mixtures of silica and silicones. Silicones are commonly represented by alkylated polysiloxane materials, while silica is commonly used in finely divided form, typified by silica aerogels and xerogels and various types of hydrophobic silica. These materials are incorporated as particles and the foam control agent within the particles is conveniently releasably bound to a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. Alternatively, the defoamer may be dissolved or dispersed in a liquid carrier and applied by spraying on the surface of one or more other components.

A preferred silicone antifoam agent is US Pat. No. 3,933,6 by Bartollota et al.
72. Another particularly useful defoamer is a self-emulsifying silicone defoamer, German Patent Application No. DTOS 2,64 issued Apr. 28, 1977.
No. 6,126. As an example of such a compound, DC-544
Is commercially available from Dow Corning, which is a siloxane-glycol copolymer.

A particularly preferred silicone antifoam agent is the ongoing European patent application No. 92201649.
No. 8. The composition may contain a silicone / silica mixture with fumed non-porous silica such as Aerosil.

A particularly preferred foam control agent is a foam control system comprising a mixture of silicone oil and a 2-alkyl-alkanol. Typically, the composition herein is 4% or less by weight, preferably 0.1% to 1.5% by weight, most preferably 0.1% by weight, based on the total composition.
% To 0.8% by weight of antifoam or mixtures thereof may be contained.

Solvent The composition of the present invention may further contain a solvent or a mixture thereof. The solvent used here includes all those known to those skilled in the art. Preferred solvents for use herein include ethers or diethers having 4 to 14, preferably 6 to 12 and more preferably 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, Aliphatic branched alcohol, alkoxylated aliphatic branched alcohol, alkoxylated straight chain C ₁
-C ₅ alcohols, linear C ₁ -C ₅ alcohols, C ₈ -C ₁₄ alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons, C ₆ -C ₁₆ glycol ethers, and mixtures thereof.

Suitable glycols for use herein have the formula: HO-CR ₁ R ₂ —OH, where R ₁
And R ₂ are each independently H or a C ₂ -C ₁₀ saturated or unsaturated aliphatic hydrocarbon chain and / or cyclic hydrocarbon chain). Suitable glycols for use herein are dodecane glycol and / or propanediol.

[0150] alkoxylated glycols suitable for use herein have the formula R- (A) _n R ₁ -O
Is represented by H, in which R is H, OH or 1 to 20, preferably 2 to 15 carbon atoms;
More preferably, it is a linear saturated or unsaturated alkyl having 2 to 10 carbon atoms, and R ₁ is H or a linear saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. , A is an alkoxy group, preferably an ethoxy, methoxy and / or propoxy group, and n is 1-5, preferably 1-2. Suitable alkoxylated glycols for use herein are methoxyoctadecanol and / or ethoxyethoxyethanol.

Alkoxylated aromatic alcohols suitable for use herein have the formula: R (A) _n-
OH (In the formula, R has 1 to 20 carbon atoms, preferably 2 to 15, and more preferably 2-1.
0 is an alkyl-substituted or non-alkyl-substituted aryl group, A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy group, n is 1 to 5,
Preferably it is an integer of 1-2). Suitable alkoxylated aromatic alcohols are benzoxyethanol and / or benzoxypropanol.

Aromatic alcohols suitable for use herein include those of the formula: R-OH, where R is C 1-20, preferably 1-15, more preferably 1-10 alkyl-substituted or non-alkyl. A substituted aryl group). Aromatic alcohols suitable for use herein are, for example, benzyl alcohol.

Aliphatic branched chain alcohols suitable for use herein are of the formula: R—OH, where R is a branched type having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, Which is a saturated or unsaturated alkyl group). Aliphatic branched chain alcohols particularly suitable for use herein include 2-ethylbutanol and / or 2-methylbutanol.

Alkoxylated aliphatic branched alcohols suitable for use herein have the formula: R (A
) _N- OH (wherein R is a branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, A is an alkoxy group, preferably butoxy, A propoxy and / or ethoxy group, n being an integer of 1-5, preferably 1-2. Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol.

Alkoxylated straight chain C ₁ -C ₅ alcohols suitable for use herein are of the formula R (A
) _N- OH (wherein R is a straight-chain, saturated or unsaturated alkyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, and A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy group. And n is an integer of 1 to 5, preferably 1 to 2)
Follow Suitable alkoxylated aliphatic linear C ₁ -C ₅ alcohols are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxypropoxypropanol is commercially available from Dow Chemical under the tradename n-BPP®.

Suitable straight chain C ₁ -C ₅ alcohols for use herein are of the formula: R-OH, where R is a straight chain, saturated or unsaturated, having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. Is a saturated alkyl group). Suitable straight chain C ₁ -C ₅ alcohol is methanol, ethanol, propanol and mixtures thereof.

Other suitable solvents include butyl diglycol ether (BDGE), butyl triglycol ether, ter amilic alcohol.
) And the like. Particularly preferred solvents for use herein are butoxypropoxypropanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.

Other suitable solvents include mineral spirits, more preferably mineral spirits commonly known as white spirits.

Typically, the composition of the present invention, if it is substantially aqueous, is 30% by weight or less, preferably 10% by weight or less, more preferably 8% by weight, based on the total composition.
It contains the following solvents or mixtures thereof:

However, as described below, the composition, when it is substantially non-aqueous, preferably comprises from 60% to 99.5% by weight of the total composition, more preferably 70% to 99% by weight, more preferably 90% to 99% by weight, most preferably 95% to 99% by weight solvent or mixture thereof.

PH Buffering Agents In an embodiment of the invention, the composition is in a neutral pH range, typically pH 5.5-8.5, more preferably pH 7-8. The compositions of the present invention are pH buffers or mixtures thereof, i.e. systems consisting of one compound or a combination of compounds, the pH of which changes slightly when a strong acid or base is added. It is a system that does not.

Suitable pH buffers for use herein include those in the neutral to basic state including borate pH buffers, phosphonates, silicates and mixtures thereof.
Preferred borate pH buffers for use herein include alkali metal salts of boric acid and alkylboric acids and mixtures thereof. Suitable borate pH buffers for use herein include borate, metaborate, tetraborate, octoborate, pentaborate, dodecabolone, boron trifluoride, and / or C1-12. , Preferably 1 to 4 alkylboric acid alkali metal salts. Suitable alkyl borates are methyl borate, ethyl borate, and propyl borate. Particularly preferred here are alkali metal salts of metaboric acid (eg sodium metaborate), alkali metal salts of tetraborate (eg sodium tetraborate decahydrate) and mixtures thereof.

Borate salts such as sodium metaborate and sodium tetraborate include sodium metaborate® and Borax.
x) (registered trademark), sold by Borax and Societa Chimica Larderello.

Suitable pH buffering agents for use herein include those in the acidic state, organic acids and mixtures thereof. Suitable organic acids for use herein include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids or mixtures thereof. Suitable carboxylic acids for use herein include acetic acid, citric acid, malonic acid, maleic acid, malic acid, lactic acid, glutaric acid, glutamic acid, aspartic acid, methyl succinate,
There is succinic acid or a mixture of these. Particularly preferred here is citric acid, succinic acid or mixtures thereof.

Citric acid is sold as an aqueous solution by Jungbunzlauer under the trade name of Citric acid®.

Typically, the composition of the present invention is not more than 15% by weight, preferably 0.01% to 10% by weight, more preferably 0.01% to 5% by weight, based on the weight of the total composition. %
, Most preferably from 0.1% to 3% by weight of pH buffer or mixtures thereof.

Thickener The composition of the present invention may preferably contain a thickener. A thickener is a component added to a composition of the present invention especially for the purpose of increasing the viscosity of the composition.

Suitable thickeners are known in the art. Examples of thickeners are gum type polymers (eg xanthan gum), polyvinyl alcohol and its derivatives, cellulose and its derivatives, and polycarboxylate polymers.

In a particularly preferred embodiment of the invention, the thickening agent comprises a gum type polymer or a polycarboxylate polymer. Examples of particularly preferred thickeners include xanthan gum and crosslinked polycarboxylate polymers, respectively.

The gum-type polymer may be selected from the group consisting of polysaccharide aqueous colloids, xanthan gum, guar gum, succinoglucan gum, cellulose, derivatives of any of the above, and mixtures thereof. In a preferred embodiment of the invention, the gum type polymer is xanthan gum or a derivative thereof.

Polycarboxylate polymers include acrylic acid, methacrylic acid, maleic acid,
It may be a homo- or copolymer composed of a monomer unit selected from malic acid and maleic anhydride. The preferred polycarboxylate polymer is BF Goodrich
It is a carbopol made from. Suitable polymers have a molecular weight of 10,000 to
It is in the range of 100,000, most preferably 1,000,000 to 10,000,000.

Radical Scavengers The compositions of the present invention can contain radical scavengers or mixtures thereof.

Suitable radical scavengers for use herein are the known substituted mono- and dihydroxybenzenes, and their analogs, alkyl and aryl carboxylates and mixtures thereof. Suitable radical scavengers for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone,
tert-butylhydroxyanisole, benzoic acid, toluic acid, catechol,
t-Butylcatechol, benzylamine, 1,1,3-tris (2-methyl-4)
-Hydroxy-5-t-butylphenyl) butane, -n-propyl gallate (n
-Propyl-gallate) or mixtures thereof, particularly preferred is di-t
ert-butylhydroxytoluene. Radical scavengers such as -n-propyl gallate are N under the tradename of Nipanox S1 (R).
It can be purchased from ipa Laboratories.

If a radical scavenger is used, it is typically contained in an amount of up to 10% by weight, preferably 0.001% to 0.5% by weight, based on the weight of the total composition.

Fragrances Fragrances suitable for use herein include substances that provide an olfactory aesthetic benefit and / or cover a "chemical" odor that the product may have. The main function of the high volatility, low boiling point (having low boiling point) small fraction of the fragrance compound in these fragrances is:
It is intended to improve the odor of the product itself, rather than impacting the odor from the cleaned surface. However, some of the low-volatility, high-boiling point fragrance ingredients give the surface a fresh and clean impression, and it is desirable that these ingredients remain deposited on the surface after drying. The perfume ingredient can be easily dissolved in the composition, for example by means of an amphoteric surfactant. Perfume ingredients and fragrance compositions suitable for use herein include conventional ones as known in the art. The selection of the perfume ingredients and the amount of the perfume blended are determined only from an aesthetic point of view.

Suitable perfume compounds and compositions are described by Brain and Cummins in US Pat. No. 4,145,184 issued Mar. 20, 1979, Whyte in US Pat. No. 24 Jun. 1,980. No. 4,209,417, 19 by Moeddel
Found in the technical literature, including US Pat. No. 4,515,705 issued May 7, 1985, and US Pat. No. 4,152,272 issued May 1, 1979 by Young. All of the above patent documents are incorporated herein by reference. Generally, the degree of substantivity of a perfume is roughly proportional to the percentage of the substantive perfume raw material used. Relatively substantial perfume contains at least about 1%, preferably at least about 10% by weight of substantial perfume raw material. The substantial fragrance raw material is a scented compound that is deposited on the surface through the washing process, and can be recognized by the normal sense of smell of humans. Typically, such ingredients have a lower vapor pressure than the average perfume ingredient. Also, such ingredients have a molecular weight of about 200 or higher, and are perceivable at levels lower than the average perfume ingredient. Perfume ingredients useful in the present invention include "Pe
rfume and Flavor Chemicals (Aroma Chemicals) ", Steffen Arctander
It is described together with its odor characteristics and physical / chemical characteristics such as boiling point and molecular weight in 1969, published by the author, and is incorporated herein by reference.

Examples of the highly volatile and low boiling point perfume ingredients include anethole, benzaldehyde,
Benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, ciscitral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethylphenylcarbinol , Eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methylanthranilate, alpha -Methylionone, methylnonylacetaldehyde, methylphenylcarbinyl acetate, laevo-menthyl acetate, menthone, iso Menthone, mycrene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenylethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate. And Vertenex (para-tertiary butyl cyclohexyl acetate). Certain natural oils also contain large amounts of volatile perfume ingredients. For example, Labandhan (l
avandin) contains linalool, linalyl acetate, geraniol and citronellol as main components. Both lemon oil and orange terpenes contain about 95% d-limonene.

Examples of perfume ingredients with moderate volatility include amyl cinnamaldehyde, iso-amyl salicylate, beta-caryophyllene, sedrene, cinnam alcohol, coumarin, dimethylbenzylcarbinyl acetate, ethyl vanillin, eugenol, Iso-eugenol, flor acetate, heliotropin, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiary butyl-alpha-methylhydrocinnamaldehyde),
Gamma-methylionone, nerolidol, patchouli alcohol, phenylhexanol, beta-serinene, trichloromethylphenylcarbinyl acetate, triethyl citrate, vanillin, and veratraldehyde.
Is mentioned. Sederterpene oil is alpha-cedrene,
Beta - Sedoren (beta-cedrene), and mainly composed of other C ₁₅ H ₂₄ sesquiterpenes.

Examples of perfume components having low volatility and high boiling points are benzophenone, benzyl salicylate, ethylene brushlate, galaxolide (1,
3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-
Cyclopenta-gamma-2-benzopyran), hexylcinnamaldehyde, lyral (4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-
10-carboxaldehyde), methylcedrilone, methyldihydrojasmonate, methyl-beta-naphthylketone, muskindanone, muskketone, musktibetane and phenylethylphenylacetate.

[0180]   The choice of any particular perfume ingredient is primarily verified from an aesthetic perspective.

The compositions of the present invention may contain up to 5% by weight, preferably 0.1% to 1.5% by weight, of perfume ingredients or mixtures thereof, based on the weight of the total composition.

[0182]   Trace component   Colorants, including known dyes and pigments, can be added in small amounts to the compositions of the present invention.

Other preferred minor compounds include preservatives. Preservatives are microorganisms (
It means compounds which kill or at least inactivate (for example bacteria and fungi) and which are added to the compositions of the invention in a stable manner. Preservatives currently available on the market include, for example, those listed in HAPPI, May 1999, pages 78-94, which are incorporated herein by reference. .
As a particularly preferred preservative, phenoxyethanol is available, for example, from BASF under the trade name Protectol PP, or gluteraldehyde is available, for example, from BASF under the trade name Protectol GDA. It is possible.

Dosage Form of Composition The composition of the present invention may be in any dosage form such as liquid, gel, foam, particles or tablets.

When the composition of the present invention is a solution, it may be water-soluble or water-insoluble, diluted or concentrated. If the composition is water soluble, preferably 1-9
9% by weight, more preferably 50-99% by weight, most preferably 80-95% by weight water is included in the composition. Alternatively, as mentioned above, the composition of the invention comprises
It may be water-insoluble. Water-insoluble means that the composition is substantially free of water. More precisely, the composition does not contain water added intentionally,
Therefore, it is meant that only water is present in the composition, for example from the crystallization resulting from the combination of raw materials.

Packaging Forms for Compositions The compositions of the present invention can be packaged in a variety of suitable containers known to those of skill in the art depending on the dosage form of the composition. The liquid composition is preferably filled in well-known bottles which do not chemically react with the composition to be filled. Such bottles are preferably made of plastic.

In one particularly preferred embodiment, the compositions of the present invention can be filled into spray dispensers. This type of container is usually made of synthetic organic polymeric plastic material. The spray device of the container can be manual or electric. Manual-operated spray devices include trigger-operated spray dispensers and pump-operated spray dispensers. Spray-type dispensers suitable for use in the present invention include manually operated, trigger-type, foam-producing dispensers, such as Specialty Packaging Products or Continental Spr.
Some are sold by ayers. These types of dispensers are described, for example, in US Pat. No. 4,701,311 to Dunnining et al. And Focarra.
US Pat. No. 4,646,973 and US Pat. No. 4,538 to cci
, 745. Especially preferred for use herein are eg Cont
T8500 (trade name) available from inental Spray International, or C
It is a spray type dispenser of T8100 (trade name) that can be purchased from anyon, Northern Ireland. In such dispensers, the liquid composition is dispersed into fine droplets which then splash into a direct deposit on the surface to be treated. In fact, in such a spray type dispenser, when the user actuates the pump mechanism, the energy of the pump mechanism causes the composition of the present invention filled in the dispenser body to pass through the head of the spray type dispenser. To migrate. More particularly, at the head of such a spray type dispenser, the composition impacts and impacts obstacles, such as a grid or cone, which atomizes the liquid composition. To assist in forming droplets.

Alternatively, the composition may be loaded into an electrically operated spray device, in which a power source is used to power the spraying operation.

In another preferred embodiment of the present invention, the liquid composition of the present invention is applied to the surface using a dispensing device, preferably a spray dispenser. The spray dispenser has at least one opening through which the composition is dispensed to create a droplet of droplets.

Such spray dispensers may have a means for pumping the composition (“pump spray dispenser”) or may be operated by any source of pressurized gas, such as an aerosol can or pressurized container. Sometimes. The pump spray dispenser can be operated manually or electrically. The spray dispenser is particularly preferred for use in a wide range of surface treatments and / or for application of large amounts of product to heavily soiled surfaces as it is easy for the consumer to use. The spray dispenser ensures that a large quantity of product is applied to a heavily soiled surface and that it evenly covers the area to be treated. In addition, the electrically operated spray device described above applies the product in the best atomized state, thereby allowing the composition to run for an acceptable period of time so that the product remains substantially dry over the area to be treated. Optimize.

The preferred spray dispenser in the present invention is a manually or electrically operated pump spray dispenser. Typical manually operated pump spray dispensers include push button operated or trigger operated pump spray dispensers. A preferred spray dispenser suitable in the present invention is
A container equipped with an electric pump and a spray arm as a means for transporting the composition. The spray arm is long enough or extendable,
Due to the provision of at least one opening, during operation the composition is pumped from the container through the spray arm to the opening by the electric pump and dispensed from this opening. The spray arm and the container are preferably connected by a freely bendable connector. The spray arm may have at least one opening along its length. The spray arm simplifies adjusting the position at which the composition is sprayed, thereby increasing the accuracy of application of the composition by the arm. Electric pumps are, for example, gear pumps, impeller pumps, piston pumps, screw pumps, peristaltic pumps, diaphragm pumps or other small pumps. A highly preferred embodiment of the electric pump used in the present invention has a typical speed of 60.
Gear-pump between 00 rpm and 12000 rpm. The electric pump is typically 1 to 20 mN. m. It is operated by means of a torque electric motor or the like.
The electric motors must be sequentially powered. Such power source may be the main power source (optionally through a transformer), or it may be a disposable battery or a rechargeable battery. The spray arm may be rigidly stretched beforehand. However, in such a case, it may be difficult to store, and therefore the spray arm is preferably extendable by a telescopic structure or a foldable structure.

Cleaning Step The present invention includes a method of cleaning a surface (eg the outer surface of a vehicle such as an automobile), characterized in that the surface to be cleaned is contacted with a composition of the invention. To do. Surface as used herein refers to surfaces typically found in the home, such as kitchen, kitchen, bathroom surfaces or exterior surfaces of vehicles, such as floors, walls, tiles, windows, sinks, showers, Plastic shower curtains, washbasins, toilets,
A variety of different materials such as dishes, furniture and furniture, such as ceramics, vinyl materials, wax-free vinyl materials, linoleum materials, melamine resins, glass, various plastics,
It refers to plastic wood, metal, etc., or the surface coated with paint, varnish, or the like. The surface mentioned here includes the surface of household appliances, and includes, for example, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, etc., but is not limited to these. Absent. The composition of the present invention is particularly effective for cleaning the outer surface of a vehicle (for example, an automobile) coated with a paint.

The surface to be cleaned may optionally be rinsed prior to cleaning with water.
Thereafter, the composition of the present invention is applied to the surface. This composition can also be applied by applying the composition to a cloth or sponge. It can also be applied by pouring the composition onto the surface. The composition can also be applied by spraying it onto the surface using the above-mentioned spray device.

Once the composition has been applied to the surface, it is typically rinsed with water,
It can be naturally dried as it is. Optionally, the user may wait between application and rinse of the composition for the composition to be most effective.
A notable advantage of the composition according to the invention is that the surface can be cleaned as described above and does not leave water stains or water marks even if the surface is naturally dried after cleaning.

[0195]

【Example】

The invention is further described by the following examples. Each number is shown as a percentage of the weight of the composition.

[Table 1] In the table, SSP has a molecular weight of about 3000, a propoxylation degree of 3, and an ethoxylation degree of 2.
7 is a polyethylene amine.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 1/72 C11D 1/72 3/36 3/36 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, E , FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG , US, UZ, VN, YU, ZA, ZW (72) Inventor Bertre, Jean Belgium, 1860 Maze, Regelbos Strad 1 (72) Inventor Sedeno, Alex Belgium, 1050 Brussels, Avuni, Louise 341 ( 72) Inventor Xavi, Ivano Belgium, 1060 Brussels, Ryu, De, La, Sluth 113 F term (reference) 3D026 AA15 4H003 AB19 AB22 AB27 AC07 AC15 DA11 EA15 EA21 EB07 EB08 EB13 EB15 EB19 EB22 EB24 EB28 EB34 EB46 ED29 FA04 FA21

Claims (10)

[Claims] 1. A chelating agent and an anionic surfactant in a ratio of 4: 1 to 1: 4, and a polymer compound selected from the group consisting of a redeposition prevention polymer, a soil precipitation inhibitor polymer and a mixture thereof. A cleaning composition suitable for cleaning the outer surface of a vehicle, which comprises: 2. The cleaning composition according to claim 1, wherein the chelating agent is a phosphonic acid-containing chelating agent or a salt thereof. 3. The chelating agent is ethane 1-hydroxydiphosphonic acid alkali metal salt, alkylene poly (alkylene phosphonate), aminotrimethylene phosphonic acid, nitrilotrimethylene phosphonate, ethylenediamine tetramethylene phosphonate, diethylene triamine pentamethylene phosphonate and the like. The cleaning composition according to claim 2, which is selected from a mixture of 4. The method according to claim 1, wherein the anionic surfactant is selected from alkyl sulfates, alkyl or alkylaryl sulfonates, sulfosuccinate surfactants and mixtures thereof. Cleaning composition. 5. The cleaning composition according to any one of claims 1 to 4, further comprising a nonionic surfactant, preferably an alkoxylated alcohol nonionic surfactant. 6. The antifouling polymer as claimed in claim 1, wherein the polymer is a antifouling polymer selected from homo- or copolymers of vinylpyrrolidone, polysaccharide polymers, polyalkoxylenglycols and mixtures thereof. Cleaning composition. 7. The cleaning composition according to claim 1, wherein the polymer is a soil-precipitation inhibitor polymer selected from the group consisting of polyalkoxylated polyamines, preferably ethoxylated polyethyleneamines. object. 8. The cleaning composition according to any one of claims 1 to 7, further comprising a surface-direct acting polymer. 9. The following steps: (i) optionally pre-wetting the vehicle; (ii) contacting the composition of any one of claims 1-8 with the vehicle; and iii) A method of cleaning the outer surface of a vehicle, comprising the step of rinsing the vehicle with water. 10. Use of the cleaning composition according to any one of claims 1 to 9 for cleaning the outer surface of a vehicle.