JP3207432B2 - CLEANING COMPOSITION COMPRISING A Saturated Dialkylcationic Surfactant - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a hard surface cleaning composition comprising both a fully saturated dialkyl cationic surfactant and a nonionic surfactant.

Background of the Invention Conventionally, for example, when cleaning hard surfaces such as wood, decorative tiles, painted metal, and the like, after removing dirt using a composition based on a surfactant or a solvent, as another operation, the surface is cleaned. It is known to apply lacquers, waxes or polishes to seal and protect and to reduce the degree of soil redeposition. This two-step cleaning and sealing operation is time consuming and complicated.

It is known to incorporate certain components into surfactant-based compositions. This is intended to provide a protective layer in a one-step washing operation by attaching such components to the surface.

GB 1528592 (1978) discloses alkaline floor cleaning compositions. The composition has a molecular weight of 100,000 to 100, which is soluble in aqueous solutions at pH 8.5 or higher.
Contains 2,500,000 organic polycarboxylic acid copolymers. These polymers are commercially available in large quantities.

GB 1534722 (1978) discloses a particulate hard surface cleaning composition. The composition comprises a surfactant and, as "improvement mixture for soil removal", polyvinyl alcohol or pyrrolidone and a biopolysaccharide. These polymers have a molecular weight of about 5,000-36.
0,000 and can be obtained in industrially usable amounts. These compositions form an alkaline solution.

In US 07/297807 (EP379256), EP0467472 A2 (Co
lgate Palmolive) for cationic surface cleaning of poly [beta (methyldiethylammonium) ethyl-methacrylate] for hard surface cleaning.
It is disclosed that the incorporation of 2.3% of a 15-20% aqueous solution into a mixed nonionic surfactant system makes it easier to clean and rewash the soiled ceramic tile.

EP 0467472 A2 is an antifouling action promoting polymer such as cationic poly [beta (methyldiethylammonium)
Ethyl-methacrylate] (but not limited to) are also disclosed to be effective when combined with anionic and cationic surfactants. The published application states that "the adsorbed polymer forms a residual stain-preventing hydrophilic layer of an antifouling action-promoting polymer on the surface,
As a result, it is less time-consuming to remove dirt adhering to the surface than it would be without the residual layer ". The molecular weight range of the polymer is between 4,000 and 100,000. However, it is not recommended to use a polymer having a molecular weight of 50,000 or more because of a solubility problem.

EP 0379256 is similar to the above-mentioned literature and optionally contains 2% by weight of an antistatic quaternary polymer having a molecular weight of 2,000 to 500,000.
And compositions comprising: This composition has an acidic pH
2 to 4 and is characterized by containing 2 to 4% by weight of a nonionic surfactant system. A composition having a pH of 2.5 and comprising 2.2% by weight of a mixed nonionic system and 0.07% of a special cationic polymer is illustrated. It is also said that the modified polymer functions as an antifouling agent.

US-A-4065409 discloses a hard surface cleaning detergent composition comprising a low level of a nonionic detergent (which may be an ethoxylated alcohol) and a quat. (Eg dimethyldidecyl ammonium chloride: DDAC). I have. This document does not mention the antifouling effect.

WO-A-8605199 discloses a composition comprising a glycoside nonionic surfactant. It should be noted that the prior art compositions disclosed in this document are said to leave essentially no residue on the surface. It is also believed that the compositions of this reference are intended to leave no residue.

WO-A-9406899 discloses a composition comprising quaternary mono- and di-tallowates in combination with a glycoside nonionic surfactant.

In addition to the above, it is also known from US Pat. No. 4,606,842 to use low molecular weight polyacrylic resins as builders for spray-on and wipe-off glass cleaning compositions. Baker et al. In US Pat. No. 4,690,779 disclose the use of a combination of a polyacrylic acid polymer having a molecular weight of 5,000 or less and certain nonionic surfactants in a hard surface cleaning composition. In these systems, the polymer functions as a builder.

It can be seen from the above that the first cleaning effect is obtained when the composition is first used on the surface, or that the surface is modified to prevent the adherence of dirt or to facilitate repeated cleaning. In order to obtain a generally alkaline hard surface cleaning composition,
It is known to contain certain polymers.

Other surface treatments, including special cationic detergents, have also received attention. WO 91/09930 (Ques Industries)
Discloses the use of "ETHOQUAT" (TM) on aluminum, for example on metal surfaces found on car bodies.

BRIEF DESCRIPTION OF THE INVENTION The present inventors have developed an improved composition which is believed to wash a surface and at the same time deposit a cationic surfactant layer on said surface which serves to release soils subsequently adhering to said surface. Devised things.

Accordingly, the present invention provides an aqueous composition for cleaning hard surfaces comprising a surfactant mixture, said surfactant mixture comprising: a) at least 65% by weight of the total surfactants of a hydrophilic alkylene oxide group and a hydrophobic fatty acid; A nonionic surfactant obtained by condensation with an aromatic compound or an alkyl aromatic compound; b) less than 1% by weight of total surfactant of anionic surfactant; c) 0.1 to 35% by weight of total surfactant. C ₁₂ or longer dialkyl cationic surfactants include, when the composition is used, by attaching a layer of cationic surfactant to the surface, thereby to liberate the dirt adhering thereafter to the surface A composition is provided that assists in

DETAILED DESCRIPTION OF THE INVENTION A series of cationic dialkyl quaternary ammonium compounds are useful in the compositions of the present invention. These compounds may contain moieties such as, for example, C = O, but the alkyl chain does not contain moieties such as C = C (ie, ethylene saturated). It is further important that the molecule contains at least two medium-length alkyl chains, although these compounds may contain more than one such alkyl chain. In the present invention, at least two of these alkyl groups contain 12 or more carbons.

Typically, the cationic surfactant has the general formula: In the above formula, R ₁ , R ₂ and R ₃ are each independently C _1-6 alkyl or hydrogen, n and m are 0 to 4, and OOR ₄ and OOR ₅ have 8 to 26 carbon atoms. Wherein X is a monovalent anion equivalent. More typically, it is a cationic surfactant comprising a cation of the above formula wherein m = 1 and n = 1.

Preferably, it is a cationic surfactant containing a cation of the above formula (where R ₁ RR ₂ RR ₃ CHCH ₃ ). Most preferred are cationic surfactants comprising a cation of the above formula wherein R ₄ and R ₅ are independently C ₁₂ -C ₂₀ .

Fully saturated dialkyl quaternary ammonium compounds include the _{^{following: X - [CH 3 (CH}} 2) n CO · NH (CH 2) m] 2 · N + R 1 R ₂ above formulas, R ₁ And R ₂ are independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and alkylene glycol residues, or polymers thereof; n is 8-26; m is 1-4. And X is a monovalent anion equivalent.

Preferably, R ₁ is methyl, R ₂ is - _{(CH 2 CH 2 O) x} H or methyl.

Fully saturated dialkyl quaternary ammonium compounds include:

^{_{X - [CH 3 (CH 2}} ) n COO (CH 2) m] in ₂ · N ⁺ R ₁ R ₂ above formulas, R ₁ and R ₂ are independently hydrogen, C ₁ -C ₄ alkyl, C ₁ selected from -C ₄ hydroxyalkyl and alkylene glycol residues or polymers thereof,, n is 8 to 26, X is a monovalent anion equivalent.

Preferably, R ₁ is methyl, R ₂ is — (CH ₂ CH ₂ O) _x H, where x is on average 1-2, or methyl, and m is 2.

Fully saturated dialkyl quaternary ammonium compounds include:

^{_{X - [CH 3 (CH 2}} ) n] in ₂ · N ⁺ R ₁ R ₂ above formulas, R ₁ and R ₂ are independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and It is selected from an alkylene glycol residue or a polymer thereof, n is 8 to 26, m is 1 to 4, and X is a monovalent anion equivalent. Preferably, R ₁ is methyl and R ₂ is — (CH ₂ CH ₂ O) _x H
Wherein x is 1-2, or methyl. Preferably, n is chosen such that the chain length distribution of the longer alkyl chains is similar to that of tallow.

The pH of the composition according to the invention is acidic, alkaline or neutral.

A typical composition according to the invention has a pH of less than 7.5,
In this case, an ester group is used. If the cationic surfactant does not have an ester group as a conjugate, the pH will be
Higher than 7.5.

Preferred cationic surfactants are the _{following: [(CH 3) 3 N} -CH 2 -CH (OOCR 4) -CH 2 OOCR 5] + X - in the above formulas, R ₄ and R ₅ are independently C ₁₂ -C ₂₀ alkyl, and the composition is substantially free of anionic surfactants. Materials falling within this general category are available from Hoechst. Most preferably, R ₄ and R ₅
Is a fatty acid residue whose alkyl chain length distribution corresponds to that of tallow.

Another preferred cationic surfactants are those of the _{^{following: X - [CH 3 (CH}} 2) n CO · NH (CH 2) 2] 2 · N + R 1 R 2 in the above formulas, n 11 ~ 19, R ₁ is methyl, R ₂ is-(CH ₂ CH
₂ O) _x (where x is 1-2), hydrogen or methyl. A substance within this general category is marketed as ACCOSOFT 440/75 ™ by Stepan.

In said composition, the ethoxylation number x is close to 1.7. That is, it is preferably 1.5 to 2.0.

The cationic surfactant present in the composition of the present invention comprises
Alter the surface energy of the surface to which the composition is applied. It is believed that this increases the contact angle of dirt that later adheres to the modified surface. Preferred cationic surfactants have a significant effect on the contact angle of the test liquid applied to the surface treated with said cationic surfactant. Thus, for untreated microscope slides, the contact angle of a 10 microliter dodecane droplet is less than 10 °. When treated with a composition according to the present invention, i.e., an aqueous solution containing 5% nonions and 1% cations as described in more detail below, the contact angle of the dodecane droplets is typically
Increase to over 20 ゜.

Therefore, the present invention also provides a net negative charge.
It also extends to methods for cleaning hard surfaces with harge). The method comprises the step of treating said surface with a composition of the invention.

It is important that the compositions of the present invention include an alkoxylated alcohol nonionic surfactant. It is believed that the presence of the nonionic surfactant significantly contributes to the cleaning effect of the composition of the present invention.

Suitable nonionic detergent active compounds may be broadly described as compounds obtained by condensing an inherently hydrophilic alkylene oxide group with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature.

The length of a hydrophilic or polyoxyalkylene group condensed with a particular hydrophobic group can be easily adjusted, resulting in a water-soluble compound having the desired HLB.

A special example is the condensation product of ethylene oxide with an aliphatic alcohol having 6 to 22 carbon atoms having a straight or branched chain structure. For example, coconut alcohol 1
Examples include coconut oil ethylene oxide condensates of from 2 to 15 moles of ethylene oxide per mole, and alkyl phenol condensates of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol, wherein the alkyl group has from 6 to 12 carbon atoms.

Particularly preferred nonionic surfactants are ethoxylated alcohols having 6 to 14 carbon atoms having a degree of ethoxylation of 2 to 9 moles. Suitable materials include IMBENTIN 91/35
OFA (TM), there is a C ₁₀ nonionic surfactant having 5 moles of ethoxylation on average.

Many other nonionic surfactants obtained by condensation of alkylene oxides with aliphatic or alkyl-aromatic compounds are known to those skilled in the art. For example, MJSchick
"Nonionic surfactants" by Marcel Dekker (1967
Year) and its reprint.

The amount of nonionic detergent active used in the compositions of the present invention is generally between 1 and 30%, preferably between 2 and 20%, most preferably between 5 and 10% by weight.

The ratio of nonionic surfactant to anionic and cationic surfactant is> 75 of the total surfactant present in the composition.
% Should be a nonionic surfactant.

It is important that the compositions of the present invention contain only low levels of anionic detergent active. Alternatively, an anionic detergent activator may not be included if there is no problem. It is believed that the presence of the anionic detergent forms a complex between the cationic detergent and the anionic detergent, thus reducing the effectiveness of the composition.

The overall surfactant content of the compositions of the present invention is generally 1
~ 30%.

Hydrophobic oil is an optional component of the composition of the present invention. Suitably the oil includes an oil that rapidly dissolves triglycerides. If oil is present, limonene, paracimen,
Dibutyl ether and butyl butyrate are preferred.

The composition of the present invention may contain other components that assist its cleaning performance.

For example, the composition may include a detergent builder. Suitable builders include, for example, carbonate, bicarbonate, nitrilotriacetate, polycarboxylate,
Citrates, dicarboxylic acids, water-soluble phosphates, especially polyphosphates, mixtures of orthophosphate and pyrophosphate, zeolites and mixtures thereof. Such builders (particularly phosphates and carbonates) can function as abrasives if present in amounts above their aqueous solubility. However, it is preferable that the composition of the present invention essentially does not contain an abrasive. Generally, the builder will be 0.1 to 25% by weight of the composition.

 Sequestering agents such as ethylenediaminetetraa
Acetate, amino-polyphosphonate (DEQUES
T ), Phosphates and various other polyfunctionalities
Organic acids and salts can also be optionally used.

Another optional component of the composition of the present invention is a foam control agent. This can be used in compositions of the present invention that tend to produce excessive foam during use. Examples of foam control agents include organic solvents, hydrophobic silica, silicone oils and hydrocarbons.

The solvent is one of the optional components of the composition of the present invention.
When a solvent is present, R ₁ —O— (EO) _m — (PO) _n —R ₂
Wherein R ₁ and R ₂ are independently C _2-6 alkyl or hydrogen, but two cannot be hydrogen and m and n are independently 0-5. . More preferably, it is selected from the group consisting of diethylene glycol mono-n-butyl ether, monoethylene glycol mono-n-butyl ether, propylene glycol-n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof. Another solvent includes pyrrolidone (pyrrolidinone), for example, N-methylpyrrolidinone.

The compositions of the present invention may also include, in addition to the components described above, various other optional ingredients, such as pH adjusters, colorants, optical brighteners, soil suspending agents, cleaning enzymes, compatible bleaches, gel modifiers. Agents, freeze-thaw stabilizers, bactericides, preservatives, washing hydrotropes, flavors and opacifiers.

In embodiments intended for cleaning burnt or crosslinked soils, the composition preferably comprises 1 to 10% alkanolamine. Levels of 2 to 6% by weight are particularly preferred. Particularly suitable alkanolamines include 2-amino-2-methyl-1-propanol (AM
P), monoethanolamine and diethanolamine.

The inventors have found it particularly advantageous to incorporate polymers into the compositions of the present invention to reduce the extent to which very fine droplets are formed when the compositions are sprayed as relatively fine mist. I thought. A suitable polymer is polyvinylpyrrolidone, commercially available as polymer PVP K-90.

Suitable levels of PVP polymer range is 50 ppm or more. 300-2000 ppm is particularly preferred.

The compositions of the present invention may be alkaline, acidic or neutral, but for kitchen soils the compositions are generally alkaline, preferably pH> 6.

Particularly preferred compositions are pH> 10, mixed with water following components a) alkoxylated alcohols nonionic surfactant (EO5-8 nonionic surfactant preferably C ₉ ~C ₁₂₎ 3~15
%, B) solvent (preferably diethylene glycol mono-n-
Butyl ether) 2-10%, c) alkanolamine (preferably 2-amino-2-
Methyl-1-propanol) 2~6%, d) a buffer / alkali (preferably an alkali metal carbonate) 0~5%, e) the polymer (preferably PVP) 0~2000ppm, and f) the general formula: X ^- [ CH ₃ (CH ₂ ) _n CO · NH (CH ₂ ) _m ] ₂ · N ⁺ R ₁ R ₂ (wherein R ₁ and R ₂ are independently hydrogen, C ₁ -C ₄ alkyl, C _1- Selected from C ₄ hydroxyalkyl and alkylene glycol residues, or polymers thereof, wherein n is 8
26, m is 1-4, and X is a monovalent anion equivalent) 0.1 to 2% of a cationic surfactant comprising a cation of the formula: 1.5
Packed in containers adapted to produce a spray volume of ml. The spray has an average droplet size of 30 to 300 microns.

In order that the present invention may be better understood, it will be described by the following examples.

EXAMPLES Aqueous compositions containing a nonionic surfactant and a relatively low level of a cationic surfactant were prepared as shown in Tables 1 and 2 below using the following materials (all compositions are unless otherwise noted): % By weight).

NONI: IMBENTIN 91/35 OFA (TM) CTAB: cetyl trimethyl ammonium bromide _{HEQ: [(CH 3) 3} N-CH · OOCR 4 -CH 2 · OOCR 5] + Cl - ( wherein, OOR ₄ and OOR ₅ is And a fatty acid whose fatty acid chain length is equivalent to tallow.) (Manufactured by Hoechst) ACCO: ACCOSOFT 440/75 (manufactured by Stepan).

AMP: amino-2-methyl-1-propanol digol: Butyl Digol ™ The composition was prepared by mixing at room temperature except when using HEQ and ACCO. These two substances are dissolved in 3 parts of propylene glycol at 70 ° C under stirring,
To water.

The results "ETh" and "EPh" are described below. CT
AB, a typical monoalkyl cation surfactant, was selected as a control because of its small effect on the contact angle of dodecane droplets mounted on a (microscope) glass slide. This slide glass was treated with a 1% solution of a dialkyl cation surfactant in a 5% aqueous solution of NONI.

The surface energy (gamma _s / mN · m ⁻¹ ) of this CTAB-treated (microscope slide) glass surface is considered to be about 25 mN · m ⁻¹ (Grifalco, Good, Fowkes and Young's method (Physical Chemistry of Surfaces , AAAdamso
n, Wiley, New York, 1990). On the other hand, the surface energy of the surface treated with a similar solution of the cationic surfactant used in the composition of the present invention was less than 25 mN · m ⁻¹ .

100 g of dehydrated castor oil (manufactured by UNICHEMA) was weighed and placed in a glass bottle. This includes Fat Red ™ dye (SIMGA
0.2 g) and the mixture was stirred vigorously (2000 RPM) for 6 hours using a Heidolph stirrer. The stirred mixture was refrigerated when not in use.

Enamel container (380 × 300mm) is replaced with new wet J-CLOT
Washed sequentially with JIF LAC ™ (liquid dishwashing product by hand) and calcite powder using H ™. After drying, the remaining calcite was removed by polishing with a paper towel.

1 ml of the composition shown in Table 1 was added to a new wet J-CLOTH
And smeared it on a clean tile. The tile was rinsed with tap water for 15 seconds to remove excess composition and drained. 25ps
215 x 1 of tiles by spraying from a position 27 cm away for 35 seconds with a DeVilbiss ™ gravity feed spray gun (Model MPS-514 / 515) using compressed air
Dirt was sprayed on an area of 50 mm. Dirty tile, 85 ℃
And placed in an oven horizontally at a temperature of 2 hours, heat aged for 2 hours and stored overnight or exposed to sunlight for 3-6 days to photochemically age. The tiles were hand washed with wet J-CLOTH and, for the examples shown in Table 1, with 1-2 ml of a control composition containing the formulation shown in Table 3 below.

The cleaning power required to clean the tiles was measured in Table 1 as "ETh" for heat aged tiles and "EPh" for photochemically aged tiles.

2 ml of the composition listed in Table 2 was added to a new wet JC
Using LOTH, smeared on clean tile. The tiles were soiled and aged as described above, and washed with the same formulation used for the pretreatment, but not the control formulation.

From the results shown in Tables 1 and 2, the composition according to the present invention has no cationic surfactant, or when compared to a control composition containing a cationic surfactant that is not a saturated dialkyl cationic surfactant. It can be seen that the required cleaning power is significantly reduced.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C11D 1/86 C11D 1/62

Claims (13)

(57) [Claims] 1. An aqueous composition for cleaning hard surfaces comprising a surfactant mixture, said surfactant mixture comprising: a) a condensate or a carbon atom of an aliphatic alcohol having 6 to 22 carbon atoms and ethylene oxide. Alkyl phenols having alkyl groups of 6 to 12 and alkyl phenols 1
A nonionic surfactant of at least 65% by weight of the total surfactant selected from condensates with 5 to 25 moles of ethylene oxide per mole; b) an anionic surfactant of less than 1% by weight of the total surfactant; and c. ) 0.1 to 35% by weight of a total surfactant having at least 2 alkyl groups having 8 or more carbon atoms selected from the compounds represented by the following general formulas I to III, and ethylene-saturated dialkyl cation surfactant activity of 0.1 to 35% by weight. Agent: General formula I: Wherein R ₁ , R ₂ and R ₃ are independently C _1-6 alkyl or hydrogen, n and m are 0-4, and OOCR ₄ and OOCR ₅ have 8 to 26 carbon atoms. X is a fatty acid residue of
Monovalent anion equivalent thereof) general formula II _{^{are: X - [CH 3 (CH}} 2) n CO · NH (CH 2) m] 2 · N + R 1 R 2 ( wherein, R ₁ and R ₂ Independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and alkylene glycol residues, or polymers thereof;
~ 26, m is 1 to 4, X is a monovalent an anion equivalent) general formula _{^{III: X - [CH 3 (}} CH 2) n COO (CH 2) m] 2 · N + R 1 R 2 Wherein R ₁ and R ₂ are independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and alkylene glycol residues, or polymers thereof, and n is 8
26, m is 1-4 and X is a monovalent anion equivalent). 2. The total amount of the surfactant is from 1 to 30% by weight,
The composition according to claim 1. 3. The composition according to claim 1, wherein the saturated dialkyl cationic surfactant is a compound represented by the general formula II. 4. The method according to claim 1, wherein the saturated dialkyl cation surfactant is R ₁
Wherein R ₂ is a methyl group and m and n are 1
The composition according to claim 3, which is a compound represented by II. 5. The composition according to claim 1, wherein the saturated dialkyl cationic surfactant is a compound represented by the general formula (I). 6. The method of claim 1, wherein the saturated dialkyl cation surfactant is R ₁
Is a methyl group, and R ₂ is — (CH ₂ CH ₂ O) _x H (where x is an average number of 1 to 2) or a methyl group. A composition according to claim 1. 7. The compound according to claim 1, wherein the saturated dialkyl cationic surfactant is a compound represented by the general formula III.
A composition according to claim 1. 8. The method of claim 1, wherein the saturated dialkyl cation surfactant is R ₁
Is a methyl group, R ₂ is — (CH ₂ CH ₂ O) _x H (where x is an average number of 1 to 2) or a methyl group, and m is 2; The composition of claim 7, which is 9. The composition according to claim 1, further comprising 1 to 10% by weight of an alkanolamine. 10. The composition according to claim 1, which is substantially free of anionic surfactant. 11. The composition according to claim 1, wherein the composition has a pH> 6. 12. The group consisting of carbonates, bicarbonates, nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates, in particular polyphosphates, mixtures of orthophosphate and pyrophosphate, zeolites and mixtures thereof. A builder selected from the group consisting of:
The composition according to Item. 13. A method for cleaning a hard surface, comprising the step of treating said surface with a composition according to claim 1. Description: