JPH06306400A - Proximate three critical point composition - Google Patents

Abstract

PURPOSE: To obtain a cleaning compsn. excellent in cleaning grease, tar, etc., by incorporating a polar solvent, a water-soluble or water-dispersible low- molecular amphiphatic substance, and a nonpolar or weakly polar solvent in a specified manner into the same.

CONSTITUTION: A liq. cleaning compsn. is prepd. which contains a polar solvent (A) (e.g. water), a water-soluble or water-dispersible low-molecular amphiphatic substance (B) (e.g. triethylene glycol monohexyl ether), and a nonpolar or weakly polar solvent (C) (e.g. an aliph. hydrocarbon), has a surface tension of about 10-35 mN/m, and is derived from three kinds of almost chemically same, compatible liq. phases. The three kinds of compatible liq. phases are in such a state that the instantaneous change of the state can convert the total into a single phase through a reversible equilibrium. The first phase is rich in ingredient A; the second phase, in ingredient B; and the third phase, in ingredient C. The interfacial tension between the first and the second phase, that between the second and the third phase, and that between the first and the third phase are each 0 - about 1×10^-3 mN/m.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to aqueous detergent compositions, optionally surfactant-free and useful for the removal of fats or tars without the use of any mechanical action. In particular, the composition comprises three liquid phases which together form a continuum near the three critical points, wherein each of the three phases is a polar solvent, a non-polar solvent or a weak solvent. It essentially comprises a polar solvent and a water soluble or water dispersible low molecular weight amphiphile.

[0002]

Liquid phase synthetic organic detergent compositions have long been used as shampoos for human hair and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing in which the dishes are machine washed). Liquid detergent compositions have also been used as hard surface cleaners, as is the case with pine oil liquids for cleaning floors and walls. More recently, they are obviously convenient to use, instantly insoluble in wash water, and easy to use in "press potting" applications to remove dirt and stains from laundry by subsequent washing. It was demonstrated that they were also successful as laundry detergents. Liquid detergent compositions consisted of anionic, cationic and nonionic surfactants, builders and auxiliaries, which were lipophilic substances which could act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic organic detergent compositions described above serve to emulsify lipophilic substances, including oily soils, in aqueous media such as wash water by forming micellar dispersions and emulsions.

The cleaning action can be considered as a somewhat complex process of removing soil from a given surface. The driving force generally required in this process is mechanical energy (friction, abrasion, sonication, etc.), solvation with liquid,
Thermal agitation, soil-solvent interfacial tension reduction, chemical modification (caustic, acidic, oxidative, reductive hydrolysis with or without catalyst or enzyme assistance), soil or soil residual suspension (eg. , In a micelle solution) and the like.

When the cleaning action occurs in a water-based vehicle, it is generally an auxiliary cleaning agent for removing hydrophobic soil,
In particular, surfactants are needed. Furthermore, in most home cleaning operations, the success of the cleaning mechanism is based on the reduction of water / oil interfacial tension. The generally accepted theory is that oily soils are easily dispersed or evenly dissolved in the composition due to the low interfacial tension present between the composition and the oil.

Another explanation can be drawn.
Due to the low interfacial tension, the liquid detergent composition readily diffuses throughout the soil or between the support and the soil, thereby weakening the overall cohesion; subsequently removing the soil spontaneously from the support. This is the reason for removing the oily soil without actually solubilizing the soil that is finally emulsified. Although emulsification is one mechanism for removing dirt, it has recently been discovered how to produce microemulsions that are much more effective than conventional emulsions in removing lipophilic substances from a support. Such a microemulsion is
British Patent No. 2,190,681 and US Patent Application Nos. 06 / 866,029 and 07/08
Nos. 5,902,07 / 120,250 and 07 / 267,872, most of which are for cleaning hard surface objects such as bathtubs and sinks. It relates to a useful acidic microemulsion which is particularly effective in removing soap scum and lime scale therefrom. In US patent application Ser. No. 07 / 267,872, microemulsions may be essentially neutral and are themselves believed to be effective in microemulsifying lipophilic soils from a support. To be U.S. patent application Ser. No. 07 / 313,664 describes a soft microemulsion liquid detergent composition that is useful for washing dishes and removing fatty deposits therefrom, either neat or diluted. ing. Such compositions include a complex of anionic and cationic detergents as the surface-active component of the microemulsion.

The various microemulsions discussed include lipophilic substances which may be hydrocarbons; surfactants which may be one or more anionic and / or nonionic detergents; poly (lower alkylene glycols). Co-surfactants, which may be lower alkyl ethers such as tripropylene glycol monomethyl ether; as well as water.

While the manufacture and use of detergent compositions in the form of microemulsions significantly improves detergency and greasy soil removal, the present invention has improved cleaning as compared to microemulsions. They are further improved by the production of aqueous near-tricritical detergent compositions.

The present aqueous detergent compositions, which are optionally surfactant-free, provide increased fat and tar removal capabilities comparable to water-based microemulsions without the use of mechanical action. All of these water-based microemulsions contain surfactants that are comparable to the preferred surfactant-free compositions of the present invention.

In most home cleaning operations, the success of the cleaning mechanism is based on the reduction of water / oil interfacial tension. In this mechanism, the thermodynamics of the phases are expected to allow ultra-low interfacial tensions to be achieved in the immediate vicinity of a unique composition called the "critical point", especially the near "three critical point", and their properties are (Griffiths) (Robert (Rober
t) B. ) Wheeler (John (J
oh) C.I. ), The critical point in multi-component systems (Criti
cal points in multicompon
ent systems) Phys. Rev. A , New York, 1970, 2, (3), (September), 104
7-1064; Griffith (Robert B.), a thermodynamic model for the three critical points in ternary and quaternary fluid mixtures.
r tricritical points in te
ranny and quaternary flui
d mixtures. ) J. Chem. Phy
s. , Lancaster, 1974, 60, (1), 195
~ 206; Widom. B. Tricritical point in ternary and quaternary fluid mixtures
al pointsin three-and fo
ur-component fluidmixture
s) J. Phys. Chem. , Washington, 197
3, 77, (18), pp. 2196-2200; Widom (B.), interfacial tension of three fluid phases in equilibrium (Int
erfacial tensions of three
efluid phases in equilibr
ium. ) J. Chem. Phys. Lancaster, 1975, 62 (4) 1332-13360 and Lang (JC) Widom (B.),
Approach to Equilibrium of Three Liquid Phases and Three Critical Points in Benzene-Ethanol-Water-Ammonium Sulfate Mixture (E
quilibrium of three liqui
d phases and approach to
the critical point in
benzene-ethanol-water-amm
onium sultate fixtures) Ph
ysics A , Amsterdam, 1975, 81A,
190-213; and Widom (B.) Three-Phase Equilibrium and Three-Critical Equilibrium.
brium and the tritical
point. ) Kinan, Mexico, 1981, 3,
A, pages 143-157, described extensively.

It is necessary to point out that a surfactant is not essential in such a critical composition. Moreover, correctness at the tricritical point is not absolutely necessary to obtain a much lower surface tension than is currently achieved with today's cleaning systems. It is worth noting that the three-critical point theory has already been highly scrutinized to facilitate oil recovery. These studies are based on Fleming (F
leming) (P.D.) Vinatieri (Vina)
tieri) (JE), phase behavior of multi-component fluids (Ph
as behavior of multicomp
onent fluids. ) J. Phys. Che
m. , Washington 1977, 66, (7), 3147
Pp. 3154 and Vinatieri (James (Ja
mes) E. ) Fleming (Paul)
D. ), The use of pseudo-components in the expression of the phase behavior of surfactant systems (Use of pseudocomponent)
ts in the representation
of phase behavior of surf
actant systems. ) Soc. Pet.
Eng. J. , Dallas, 1979, 19, 289-30
P. 0; Fleming (Paul D.) Vinatieri (James E.), Quantitative Interpretation of the Phase Volume Behavior of Multicomponent Systems Near the Critical Point.
rotation of phase volume b
environment of multicomponent
systems near critical po
ints. ) AlChE J. , New York 19
79, 25, (3), pp. 493-502; Fleming (Paul D.) Vinatieri (James
E. ), The role of critical phenomena in oil recovery systems using surfactants (Role of critical p
henomena in oil recovery
systems emulating surfact
ants. ) J. Colloid Interfac
e Sci. , New York 1981, 81,
(2), 319-331; Vinatieri (James) Fleming (Paul D.), Third Multivariate Optimization of Surfactant Systems for Oil Recovery (Multivariate).
optimization of surfacta
nt systemsfor tertiary oi
l recovery. ) Soc. Pet. Eng.
J. , Dallas 1981, (2), pp. 77-88; Smith (Duane, H.),
Interfacial tension near the critical point of classical liquids. Experimental evidence for the correctness of the prediction of critical scaling theory (Inter
physical tensions near the
tritical points of cla
social liquids: experiment
al evidence for the valid
itity of the prediction of c
critical scaling theory. )
J. Chem. Phys. , Lancaster 1986,
85, 1545-1558 and Smith (Duane
H. ), The Tricritical point as an aid to the design of surfactants for low tension enhanced oil recovery.
al points as an aid to th
e design of surfactants f
or low-tension enhanced o
il recovery. ) AOSTRA J. Re
s. Edmonton (Alberta) 1984,
(4), pp. 245-265, extensively.
In 1926, Kornstamm
Have developed the theoretical possibility of a "second order" critical point in a ternary liquid mixture where the three coexisting fluid phases come together and are identical. Corn stam (P
h. ), Handbuchder physik , 19
26, 10 Volume, Chapter 4, Thermodynamics of Mixtures (Thermod
ynamik der Gemische), 270-
271, H .; Geiger and K.K. Seal (Springer)
R), Berlin). Kornstam further emphasized that finding such points is extremely difficult.

The near-three critical point composition for aqueous cleaning of the present invention is
Suitable for use in concentrated residential and personal care products. The near tricritical point composition of the present invention contains harmless components. The present near tricritical point composition allows for the production of ultra-dense cleaning or conditioning liquid products, which are optionally surfactant-free.

According to the present invention, a near-three critical point detergent composition suitable for pretreatment and cleaning of materials contaminated with lipophilic soils at room temperature or cooler or even higher temperatures is a polar composition such as water. It contains a solvent, a water-soluble or water-dispersible low molecular weight amphiphile and a non-polar or weakly polar solvent, where the three phases together form a continuum at the three critical points. The present invention further provides for the treatment of objects and materials contaminated with soil, such as lipophilic soil, with a composition of the invention to release or remove the soil relative to the location of the soil on the material. It relates to a method of releasing and removing such soils without the use of mechanical action by applying the tricritical point composition of the present invention.

The present aqueous detergent composition exists at or near the three critical points which are the boundaries of the three series of critical points. The tricritical point is a thermodynamic point at which all three coexisting phases are the same at the same time. At the critical point, polar solvent (water)
The interfacial tension between the mixed phase of low molecular weight amphiphiles is substantially zero, and the interfacial tension between the mixed phase of low molecular weight amphiphiles and nonpolar solvents (oils) or weakly polar solvents is Is substantially zero, and the interfacial tension between the polar solvent and the non-polar or weakly polar solvent is substantially zero. Therefore, the cleaning mechanism of the cleaning composition of the present invention is based on its reduction such that the polar solvent / nonpolar solvent interfacial tension approaches a value of zero.

The phase inversion temperature (PIT) of the compositions of the present invention is about 0 to about 80 ° C, more preferably about 15 to about 40 ° C. The phase inversion temperature is the temperature at which low molecular weight amphiphiles of equal affinity for water and oil are present. It is the temperature at which the partition of the low molecular weight amphiphile between the rich water phase and the non-polar or weakly polar solvent phase is one. That is, the weight fraction of the low molecular weight amphiphile in the rich water phase is equal to the weight fraction of the low molecular weight amphiphile in the non-polar solvent phase.

The tricritical point composition is

[Equation 1] (In the formula, the weight fraction of water is (1-g) (1-a) (1-
e), a is about 0.1 to about 0.9, more preferably about 0.3 to about 0.7, and g is about 0.1 to about 0.
6, more preferably about 0.2 to about 0.4, and e is about 0 to about 0.5, more preferably about 0.05 to.
About 0.25 and the additive is a water soluble additive, polar cosolvent or electrolyte).

Additives are water-soluble molecules (electrolytes or organic substances) that can modify the structure of water so as to enhance or destroy the solvent structure. Therefore, the addition of such chemicals modifies the solubility of uncharged organic components in water, especially amphipathic molecules. The above chemical substances are classified into two types. That is, salting out (or kosmotropic) substances reinforce the structure of water and render it largely unavailable for hydration of organic molecules. (The salting-out and salt-soluble substances are also referred to as lyotrope and hydrotrope, respectively.)
Salt-soluble (or chaotropic) substances disrupt the structure of water, thereby producing an action comparable to a "hole". As a result, they increase the solubility of polar organic molecules in water.

In fact, lyotropic substances make water more incompatible with both oils and amphiphiles. The result is a decrease in PIT and an increase in super-tricritical properties. The amount of low molecular weight amphiphile needed to "associate" water and oil is generally increased in the presence of salting out substances. Hydrotropes have the opposite effect.

[0018]

The present invention has an apparent viscosity of about 1 to about 1,000 cps at 10 ² sec ^-1 , more preferably about 1 to about 100 cps and a surface tension of about 1.
An aqueous near-three critical point composition of 0 to about 35 mN / m, wherein the weight is about 15 to 85% by weight of polar solvent; 15 to 55% by weight of nonpolar or weakly polar solvent; and water soluble or water. About 5 to about 60 dispersible low molecular weight amphiphiles
% Of the above composition.

Accordingly, it is an object of the present invention to provide an aqueous tricritical point detergent composition which is useful in cleaning operations that do not use or use mechanical action, particularly for removing fats and tars. The critical point is to provide a composition for permeating into the porous surface to destroy the attachment of soil to the support.

[0020]

The present invention has an apparent viscosity of 1
0.2 second to about 1,000 cp at 0 ² sec ^-1 and 25 ° C
s, more preferably from about 1 to about 100 cps and having a surface tension of from about 10 to about 35 mN / m, an aqueous near-three critical point composition comprising: (a) a non-polar solvent or a weakly polar solvent. Or 15-55%, more preferably 25-50%, and most preferably 30-45% of a mixture thereof; (b) 5 water-soluble or water low molecular weight dispersible amphiphiles
-60%, more preferably 10-50%, and most preferably 15-40%; (c) 15-55%, more preferably 20-55% polar solvent.
40%, and most preferably 25-35%, wherein the composition is optionally surfactant-free; and (d) 0-20% water-soluble additives, more preferably 0.
5 to 15%, and most preferably 1.0 to 10%.

The aqueous near-tri-critical point composition of the present invention can be used as a base formulation for the manufacture of both commercial and industrial applications by including selective ingredients in the tri-critical point composition. Typical compositions that can be produced for various uses are oral compositions, cosmetics, hand creams, facial creams, eye shadows, lipsticks, metal polishes, textile cleaners, shampoos, floors. Washing soap,
Cleaning paste, tile cleaner, bath cleaner, bleaching composition, ointment, oven cleaner, stain remover, fabric softener, bleach presspotter, dishwashing presspotter, automatic dishwashing composition, laundry presspotter, pharmaceutical composition Materials, coal slurries, oil drilling muds, cleaning press potters and graffiti or paint removers, anti-mold cleaners for grouts, flux removers for printed circuit boards, engine cleaners and degreasers, deinking compositions for printing presses, and leaked Shoreline cleaners for crude oil contaminated coastlines, as well as cleaning mechanisms for medical procedures such as the treatment of oral diseases or the need to be delivered into cavities or porous surfaces for delivery of drug use. Any composition containing an active ingredient.

The present invention is derived from three coexisting liquid phases, optionally surfactant-free, having a surface tension of about 10 to about 35 mN / m at 25 ° C. and being substantially chemically identical to each other. Wherein the three coexisting liquid phases together form a continuum to form the composition, wherein the first phase is predominantly A polar solvent, the second phase is predominantly a water-soluble or water-dispersible amphiphile, and the third phase is predominantly a non-polar or weakly polar solvent, the first phase and the second phase The interfacial tension between the two phases is 0 to about 1 × 10 ⁻³ mN / m,
The interfacial tension between the second and third phases is 0 to about 1 × 10 ^−3.
mN / m, and the interfacial tension between the first and third phases is 0 to about 1 × 10 ⁻³ mN / m.

In a preferred composition, the polar solvent [which is the first phase] is water [for example] at a concentration of about 15 to about 85% by weight and the low molecular weight amphiphile is both about 5 (M).
Pa) water-insoluble hydrophobic moieties with partial Hansen polar and hydrogen-bonding parameters less than ^1/2 and water-soluble hydrophilic moieties with partial Hansen hydrogen-bonding solubility parameters greater than about 10 (MPa) ^1/2 An amphiphile is present at a concentration of about 5 to about 60% by weight; and the nonpolar or weakly polar solvent is a Hansen dispersion solubility parameter greater than about 10 (MPa) ^1/2. And has a Hansen hydrogen-bonding solubility parameter of less than about 15 (MPa) ^1/2 and is present at a concentration of about 15 to about 55% by weight.

The main characteristics of polar solvents are that they have the ability to form hydrogen bonds with low molecular weight amphiphiles and that the polar solvent has a dielectric constant higher than 35. Besides water,
Other polar solvents suitable for use in the composition are formamide, glycerol, glycol and hydrogen peroxide and mixtures thereof. The polar solvents described above can be mixed with water to form a mixed polar solvent system. The concentration of polar solvent such as water in the near-three critical point composition is about 15 to about 55.
%, More preferably about 20 to about 40% by weight.

The organic non-polar or weakly polar solvent component of the present aqueous near tricritical point composition comprises a solvent for dirt, is lipophilic, and is a suitable oil, eg, from about 5 to about 25 carbon atoms. Are non-polar oils having the formula C _n H _{2n + 2} , where n is 5 to 25, and more preferably 6 to 16. Such aliphatic hydrocarbons are preferably straight chain paraffins or isoparaffins, among which saturated ones having 6 to 16 carbon atoms are preferable,
Also preferred are isoparaffins having 8 to 18 carbon atoms. The most preferred aliphatic hydrocarbon solvent is decane. Hansen dispersion solubility parameters for non-polar or weakly polar solvents are at least 10 (MP
a) ^1/2 , more preferably at least about 14.8
(MPa) ^1/2 , the Hansen polar solubility parameter is less than about 10 (MPa) ^1/2 , and the Hansen hydrogen bonding solubility parameter is about 15 (MPa).
It is less than ^1/2 . In selecting a non-polar or weakly polar solvent, important parameters to be considered are the length and configuration of the hydrophobic chain, the polarity of the molecule and its molecular volume.

Non-polar or weakly polar solvents which are less than 5% by weight soluble in water at 25 ° C. have from about 5 to about 25 carbon atoms, more preferably from about 6 to about 16 carbon atoms. Alkanes and cycloalkanes; about 12 to about 2
Arylalkyl having 4 carbon atoms; about 10 to
About 40 carbon atoms, more preferably about 10 to about 30.
Having 1 carbon atom; and a formula

[Chemical 4] Where R and R ₁ are alkyl groups having from about 7 to about 24 carbon atoms, and more preferably from about 8 to about 20 carbon atoms with each other. Selected from the group. Some typical non-polar or weakly polar solvents are hexadecane, tetradecane, phenylhexane, decyl acetate, 2-undecanone, limonene, diethylene glycol monohexyl ether, diisopropyl adipate, cetyl lactate and dioctyl malate and mixtures thereof. is there.

The concentration of the non-polar or weakly polar solvent in the near tricritical point composition is about 15 to about 55% by weight, more preferably about 25 to about 40% by weight.

The concentration of the low molecular weight amphiphile in the near tricritical point composition is about 5 to about 60% by weight, more preferably about 15%.
Is about 40% by weight.

The low molecular weight amphiphile of the composition is a molecule composed of at least two moieties capable of binding polar and non-polar solvents. Increasing the molecular weight of the low molecular weight amphiphile increases the water / oil binding capacity, indicating that less low molecular weight amphiphile is needed to bind polar and non-polar or weakly polar solvents. means. At least a portion is hydrophobic in nature and the Hansen partial polarity and hydrogen bonding solubility parameters are 5
(MPa) is less than ^1/2 . At least a portion is water-soluble in nature, and the Hansen partially hydrogen-bonding solubility parameter is 10 (MPa) ^1/2 or greater.

In order to determine the hydrophilic and hydrophobic moieties, low molecular weight amphipathic molecules (amphiphiles) need to be cleaved according to the following rules. That is, the hydrophobic portion should not include any nitrogen or oxygen atoms; the hydrophilic portion generally includes heteroatoms that include carbon atoms directly bonded to the oxygen or nitrogen atoms.

[0031]

[Table 1] This table shows the solubility parameters of various groups. Since the hydrogen-bonding solubility parameter is always greater than 10, the first series can be used as the hydrophilic part of amphipathic molecules. The last group can be used as the hydrophobic part of the amphiphile because their polar and hydrogen bonding solubility parameters are less than 1. The central groups (esters and ketones) cannot be used as a significant contributor to the amphipathic molecule. Although amphiphiles may include ketone or ester functions, it should be noted that these functions do not directly contribute to amphiphile performance. d _d is the Hansen dispersion solubility parameter measured at room temperature; d _p is the Hansen polar solubility parameter measured at room temperature; d _H is the Hansen hydrogen bonding solubility parameter measured at room temperature. In particular, the concentration is about 5 to about 60% by weight, more preferably about 15 to
Preferred low molecular weight amphiphile is present at about 40% by weight, formula _{C x H 2x + 1 -O- (} CH 2 CH 2 -O-) y -H ( wherein, x and / or y is 1 to 6, More preferably from 1 to 6), a polyoxyethylene derivative having from about 4 to about 8 carbon atoms, from about 5 to
Polyamines having about 7 carbon atoms, polyamides having about 5 to about 7 carbon atoms, alkanols having about 2 to about 4 carbon atoms and formulas

[Chemical 5] Where R ″ is an alkylene group having from about 1 to about 8 carbon atoms, x is 0 to 2 and y is about 1
From about 5 to about 5). The low molecular weight amphiphile has a molecular weight of about 76 to about 300, more preferably about 100 to about 250. Particularly preferred low molecular weight amphiphiles are propylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, propylene glycol-t-butyl ether, propylene glycol methyl ether, hexanediol,
Diethylene glycol monobutyl ether, triethylene glycol monohexyl ether and tetraethylene glycol monohexyl ether and mixtures thereof, such as propylene glycol-n-butyl ether and propylene glycol methyl ether in a ratio of about 2: 1 to about 1.5: 1. is there.

The near tricritical point compositions formed from the low molecular weight amphiphiles described above are surfactant-free because these low molecular weight amphiphiles are not classified as surfactants. .

However, the near-three critical point composition may optionally be formed from a polar solvent, a non-polar or weakly polar solvent and a surfactant in a mixture of low molecular weight amphiphile and surfactant. When a surfactant is used without the low molecular weight amphiphile, the surfactant is present in the composition at a concentration of about 5.0 to about 25.0% by weight. When the surfactant is used in a composition containing a low molecular weight amphiphile, the concentration of the surfactant is about 0.1 to about 25% by weight and the concentration of the low molecular weight amphiphile is about 5 to about 6%.
It is 0% by weight. Surfactants that can be used in the present invention are selected from the group consisting of nonionic, anionic, amine oxide, cationic and amphoteric surfactants and mixtures thereof. When using the surfactant alone and no low molecular weight amphiphile, the HLB of the surfactant should preferably be from about 7 to about 14. It should be understood that surfactants are a subset of the set of low molecular weight amphiphiles. Low molecular weight amphiphiles do not form aggregates at interfaces, eg oil and water interfaces, but rather low molecular weight amphiphiles are evenly distributed in solution. However, the surfactant tends to concentrate at the interface between various phases (air / liquid; liquid / liquid; liquid / solid), thereby forming aggregates at the interface and increasing the interfacial tension between the coexisting phases. Reduce. For example,
Surfactants form aggregates at the oil / liquid interface and the surfactant is not evenly distributed in the solution.

Further, the composition optionally contains, in addition to the polar solvent, a non-polar or weakly polar solvent, a water-dispersible amphiphile, and a water-soluble acid in a concentration of about 0.1 to about 15.0% by weight, More preferably, it can be contained at about 1 to about 10% by weight.

The active acidic component of the near tricritical point composition can optionally be a carboxylic acid that is strong enough to reduce the pH of the near tricritical point composition to the range of 1-4. Although various carboxylic acids can perform this function, it was polycarboxylic acids that were found to effectively remove soap scum and lime scale from bathroom surfaces while still not destabilizing the composition. Of these, dicarboxylic acids are preferred. 2 from oxalic acid to sebacic acid
Of the dicarboxylic acid groups, including those with 10 carbon atoms, suberic acid, azelaic acid and sebacic acid have a lower solubility, and therefore other dibasic fats in the near-three critical point composition. Less useful than family fatty acids,
Both of them are preferably saturated and linear.
Oxalic acid and malonic acid are also useful as reducing agents, but may be too strong for delicate hard surface cleaning. Preferred such dibasic acids are those in the central part of the acid range of 2 to 10 carbon atoms, succinic acid, glutaric acid, adipic acid and pimelic acid, especially fortunately commercially available in admixture. It is the first three of them that can be transformed. The diacid may be partially neutralized after being included in the near tricritical point composition of the present invention to successfully produce the pH in the near tricritical point composition that is desirable for maximum functional effectiveness. it can.

Phosphoric acid is one of the additional acids that serves to protect the acid sensitive surface being cleaned by its presence. Even tribasic acids can be partially neutralized to obtain a desired range of composition pH. For example, it may be partially neutralized to give a diphosphate such as NaH ₂ PO.
_{It can be 4} or NH ₄ H ₂ PO ₄ .

Phosphonic acid, the other of the two additional acids for protecting the acid-sensitive surface from the solubilizing action of the dicarboxylic acids of the present composition, is obviously only theoretically present, but its derivatives are stable. And is useful in the practice of the invention. Such is considered to be the phosphonic acid as that term is used herein. Phosphonic acid has the structure

[Chemical 6] Wherein Y is any suitable substituent, but preferably Y is alkylamino or N-substituted alkylamino. For example, a preferred phosphonic acid component of the composition, amino tris has the formula _{N (CH 2 PH 2 O 3} ) - is (methylene phosphonic) acid. Other useful phosphonic acids are ethylenediamine-tetra (methylenephosphonic) acid, hexamethylenediamine-tetra (methylenephosphonic) acid and diethylenetriamine-penta (methylenephosphonic) acid. Compounds of this type include 1 to 3 amino nitrogens; 3 or 4 lower alkylenephosphonic acid groups in which the lower alkylene has 1 or 2 carbon atoms; It may be described as an aminoalkylenephosphonic acid containing in the range of 0 to 2 alkylene groups having 6 carbon atoms, one or more alkylenes are present and a large number of such alkylenes in the aminoalkylenephosphonic acid. A new amino nitrogen is bound to the amino nitrogen when present. Such an aminoalkylenephosphonic acid, which may be partially neutralized at the desired pH of the near tricritical point composition, provides the desired stability in the detergents of the present invention, especially when present with phosphoric acid. It has a detergency and protection effect, and is a cleaning agent
It has been found to prevent harmful effects on the surface of European enamel by one or more diacid components. Generally, the phosphate salt, if present, is a mono-salt of each of the phosphate and / or phosphonate groups present. Works effectively on soap dregs and on hard surfaces such as ceramic tiles, Portland cement between tiles and acrylic latex grout, porcelain, porcelain enamel, glass,
Glutaric acid or partially neutralized of all organic acids with sufficient acidity to convert it to a form that can be easily removed from glass fibers and metal (eg, chrome and nickel plated) surfaces The salt or their ionic form is highly preferred because it works effectively and has few detrimental negative properties, but in some cases calcium and magnesium higher fatty acids are in the acidic or partially neutralized form. Other acids that can convert to and help remove them from hard surfaces that are contaminated (in the form of soap dregs) (if their harmful properties are acceptable, if any) Can be used.

Some of these acids do not form water-insoluble calcium salts. For example, acetic acid, succinic acid, propionic acid and citric acid can be used in certain circumstances. However, citric acid is a sequestering acid, has the property of removing calcium from the calcium carbonate in the grout used between adjacent ceramic tiles and is detrimental to its use, and the other aforementioned acids are , Often unsatisfactory due to unacceptable odors and / or as they cause irritation of the human nose and / or breath. Of course, it is also preferable to avoid such acids, which are toxic under the conditions of use. Therefore, it is preferable to use glutaric acid as an acid that acts on such soap scum. Subsequently, it is common (and common) to partially neutralize it to the desired pH range during the production of the detergents of the invention, but it is possible to use salts of such acids and to bring them to the desired pH range. It is further within the scope of the present invention to convert to and the products of both such operations are understood to be identical. Thus, by referring to "partially neutralized glutaric acid", it is possible to derive a partially neutralized glutarate of desired pH from the partially acidified glutarate together with the other ingredients of the detergent. It is meant to also include such products obtained by direct inclusion.

The composition may optionally comprise from about 0.1 to about 15% by weight, more preferably from about 1 to about 5% by weight of a water soluble chaotropic additive which may be hydrotropic or kosmotropic. . Hydrotropic substances weaken the structure of water (salt-dissolving effect), thereby making water an improved solvent for amphiphiles, and cosmotropic (lyotropic) substances enhance water structure (salting-out effect). , Thereby making water an even worse solvent for amphiphiles. Typical hydrotropic substances are
Acetic acid, ethanol, isopropanol, sodium benzoate, sodium toluene sulfonate, sodium xylene sulfonate, ethylene glycol, propylene glycol, metal salts of iodide, metal salts of thiocyanate,
It is a metal salt of perchlorate, a guanidinium salt. The use of chaotropic additives can change the weight percentages of polar solvent, amphiphile and non-polar solvent used to produce the near tricritical point composition.

In addition to the listed components of the aqueous near-tricritical point composition of the present invention, auxiliary materials for dental, dishwashing, laundering and other detergency applications may also be present and they Examples of materials include foam enhancers such as lauric acid or myristic acid diethanolamide; foam inhibitors (if desired) such as silicones, higher fatty acids and higher fatty acid soaps; preservatives and antioxidants such as formalin and Mention may be made of 2,6-di-t-butyl-p-cresol; pH adjusting agents such as sulfuric acid and sodium hydroxide; perfumes; and colorants (dyes and pigments).

Aqueous near-tri-critical point compositions include detergent compositions containing enzymes and / or bleaches, such as bleach, at least one enzyme and a suitable phosphate or non-phosphate builder system. It can be used to produce a possible textile detergent composition or automatic dishwashing composition.

A typical detergent composition is: H ₂ O 19.24% Na benzoate 1.0% Triethylene glycol hexyl ether 32.5% Heptyl acetate 35.44% Nonyl acetate 11.81% Tricritical point. Alternatively, changes in the formulation of compositions within the scope of the present invention in the near tricritical state can be readily ascertained, and the present invention discusses the specification, including its experimental examples, together with the phase diagrams. It is easily understood when it reaches.

1-2 show compositions C and D of Example 1.
Is a phase diagram of 13 in which 13 indicates a tricritical point composition. With reference to the drawing, the composition of point 23 marked with an "x" in FIG.
% By weight and oil (heptyl acetate / nonyl acetate ratio 3:
1 mixture) 18.15% by weight.

In the preceding description of the components of the composition of the invention and their proportions which may be functional, a boundary for preferred compositions within the scope of the invention was obtained, but the near tricritical point composition of the invention. It is clear that the investigator who manufactures the article will select the proportion of the composition indicated by the phase diagram of the particular composition so that the desired composition is within the near-three critical region. Similarly, the selected tri-critical point composition should be such that contact with water removes lipophilic contamination from the support.

A number of different compositions within the scope of the present invention were manufactured and characterized in the experiments undertaken by the inventor with respect to the plotting of phase diagrams and in determining the formulation of the desired tricritical point composition. It was

The preparation of the near tricritical point compositions of the present invention tends to generate spontaneously as they tend to spontaneously require little additional energy to promote the transition to the tricritical point state. Is simple. However, in order to promote homogeneity of the composition, mixing is usually done and, although not compulsorily, the amphiphile and water are first mixed together followed by the non-polar solvent or weak solvent components. It turned out to be desirable. It is generally not necessary to use heat, and most mixing is preferably done at about 20-25 ° C or higher.

The use of prepotting and manual cleaning of the near tricritical point composition of the present invention is uncomplicated and does not require unique or anomalous operation. Thus, such near tricritical point compositions can be used in the same manner as other liquid prepotting and detergent compositions.

The near tricritical point composition of the present invention can be applied by pouring onto such a surface, by applying with a cloth or sponge, or by various other contacting means. Depending on their viscosity, it is preferably applied to them in the form of a spray by spraying them onto the support from a hand or finger pressure spray or squeeze bottle. Such an application is
Lipophilic (usually fatty or oily) stains can be applied on hard surfaces such as dishes, walls or floors to be removed, or laundry pre-contaminated with lipophilic stains such as motor oil Can be applied on textiles. The compositions of the present invention can be used as detergents and as such can be used in the same manner as liquid detergents are commonly used in dishwashing, floor and wall washing and laundering, but using them as pre-potting agents. Further use is preferred and in that application they have been found to be very useful for liberating the attachment of lipophilic soils to the support, whereby a large number of similar detergent compositions of the invention are also provided. Cleaning is much easier facilitated by the application of the product or by applying various commercial detergent compositions in liquid, bar or granular form.

[0049]

EXAMPLES Example 1 The following examples illustrate, but do not limit, the invention. Unless otherwise noted, all parts in this specification and in the claims are percentages by weight and all temperatures are at 0 ° C.

Formulations AG were made according to the following procedure.

[0051]

[Table 2] (*) Performance is evaluated as the extent to which the stain is removed after pouring a few drops of the composition onto the stain, allowing it to act on it without any mechanical action for about 1 minute and allowing it to react with water. Rinse and wash with.

XXX = Completely removed. XX = Partially removed. X = hardly removed.

Compositions A to G were prepared by first forming the amphiphile and water or a solution of water and additives at room temperature with mixing. A non-polar solvent (oil) or a weakly polar solvent was added to this solution with mixing at room temperature to produce near-three critical point compositions A to G. Apparent viscosity measurement is 25 at Carrimed
Performed at ° C. Surface tension measurements were carried out on a Lauda at 25 ° C.

While the present invention has been described with respect to its various embodiments and drawings, it will be apparent to those skilled in the art that alternatives and equivalents may be used by those earlier herein without departing from the invention. As such, they should not be considered limited to these.

[Brief description of drawings]

1 illustrates the phase diagram of the aqueous tricritical point composition of Example 1. FIG.

2 illustrates a phase diagram of the aqueous tricritical point composition of Example 1. FIG.

Claims (45)

[Claims] 1. A surface tension of about 10 to 35 mN / m, comprising at least a polar solvent, a water-soluble or water-dispersible low molecular weight amphiphile and a non-polar or weakly polar solvent,
A liquid detergent composition derived from three types of coexisting liquid phases that are substantially chemically identical to each other, wherein the three types of coexisting liquid phases are reversible equilibrium Either they can all be converted into one single phase or they can be combined with each other into one continuum to form the composition, the first phase being most rich in polar solvents, The second phase is richest in water-soluble or water-dispersible low molecular weight amphiphiles, and the third phase is richest in nonpolar or weakly polar solvents, and the interfacial tension between the first and second phases is zero. To about 1 × 10 ⁻³ mN / m, and the interfacial tension between the second and third phases is 0 to about 1 × 10 ⁻³ m.
The above composition, which is N / m and the interfacial tension between the first and third phases is 0 to about 1 × 10 ⁻³ mN / m. 2. The polar solvent is water at a concentration of about 15 to about 85% by weight and the amphiphile is both about 5 (MP
a) having a water-insoluble hydrophobic moiety having a partial polarity parameter and a hydrogen-bonding parameter that is less than ^1/2 and a water-soluble hydrophilic moiety having a partial hydrogen-bonding solubility parameter that is greater than about 10 (MPa) ^1/2. An organic compound; the amphiphile is present in a concentration of about 5 to about 60% by weight; and the non-polar or weakly polar solvent has a dispersive solubility parameter of greater than about 10 (MPa) ^1/2 and about The composition of claim 1 having a hydrogen-bonding solubility parameter of less than 15 (MPa) ^1/2 , wherein the non-polar or weakly polar solvent is present in a concentration of about 15 to about 55% by weight. Wherein the low molecular weight amphiphile, alkylene glycol alkyl ether of the formula _{C x H 2x + 1 -O- (} CH 2 CH 2 -O-) y -H ( wherein, x or y is 1 to 6 A polyoxyethylene derivative having about 5 to about 7 carbon atoms, a polyol having about 4 to about 8 carbon atoms, a polyamine having about 5 to about 7 carbon atoms, having about 5 to about 7 carbon atoms. The composition of claim 2 selected from the group consisting essentially of a polyamide and an alkanol having from about 2 to about 4 carbon atoms. 4. The non-polar or weakly polar solvent comprises alkanes and cycloalkanes having from about 5 to about 25 carbon atoms, aryl alkanes having from about 12 to about 24 carbon atoms, about 6. To aliphatic and aromatic oils having from about 14 carbon atoms, terpenes having from about 10 to about 40 carbon atoms, and formulas A composition according to claim 3 selected from the group consisting of esters having R and R ₁ are alkyl groups having from about 7 to about 24 carbon atoms with each other. 5. The non-polar solvent or weakly polar solvent is 6
A composition according to claim 1, which is an aliphatic hydrocarbon having 1 to 16 carbon atoms and is present in the composition in a concentration of 15 to 55% by weight. 6. A composition according to claim 1, wherein the polar solvent is water and is present in the composition at a concentration of 15-85% by weight. 7. The composition of claim 1, wherein the composition is sprayable by manual pump spray. 8. A composition according to claim 1, which comprises at least one solid particle and / or immiscible liquid in the composition. 9. The composition of claim 6, wherein the non-polar or weakly polar solvent is an aliphatic hydrocarbon having from about 6 to about 16 carbon atoms. 10. The composition according to claim 9, wherein the low molecular weight amphiphile is triethylene glycol monohexyl ether. 11. The composition of claim 6, wherein the amphiphile is triethylene glycol monohexyl ether. 12. A surface tension of about 10 to 35 mN / m, containing at least a polar solvent, a water-soluble or water-dispersible surfactant and a non-polar or weakly polar solvent, and being substantially chemically identical to each other 3. A liquid detergent composition derived from two kinds of coexisting liquid phases, wherein the three kinds of coexisting liquid phases are converted into one single phase by reversible equilibrium due to an instantaneous change of the state. In a state such that they can be converted or they can be brought together into one continuous body to form the composition, the first phase being most enriched in polar solvents and the second phase being water-soluble or water-dispersible. Rich in surfactants, and the third phase is most rich in non-polar or weakly polar solvents, and the interfacial tension between the first phase and the second phase is between 0 and.
About 1 × 10 ⁻³ mN / m, the interfacial tension between the second and third phases is 0 to about 1 × 10 ⁻³ mN / m, and the interfacial tension between the first and third phases is 0 to about 1 × 10.
^{-3 The} above composition which is mN / m. 13. The polar solvent is water at a concentration of about 15 to about 85% by weight and the amphiphile is both about 5 (MP
a) having a water-insoluble hydrophobic moiety having a partial polarity parameter and a hydrogen-bonding parameter that is less than ^1/2 and a water-soluble hydrophilic moiety having a partial hydrogen-bonding solubility parameter that is greater than about 10 (MPa) ^1/2. An organic compound; the amphiphile is present in a concentration of about 5 to about 60% by weight; and the non-polar or weakly polar solvent has a dispersive solubility parameter of greater than about 10 (MPa) ^1/2 and about The composition of claim 15 having a hydrogen bonding solubility parameter of less than 15 (MPa) ^1/2 , wherein the non-polar or weakly polar solvent is present in a concentration of about 15 to about 55% by weight. 14. The non-polar solvent or weakly polar solvent comprises:
Alkanes and cycloalkanes having from about 5 to about 25 carbon atoms, aryl alkanes having from about 12 to about 24 carbon atoms, aliphatic oils and aromatics having from about 6 to about 14 carbon atoms. Oils, terpenes having from about 10 to about 40 carbon atoms and of the formula 14. The composition of claim 13, selected from the group consisting of esters having R and R < ₁ > are alkyl groups having from about 7 to about 24 carbon atoms with each other. 15. The non-polar solvent or weakly polar solvent comprises:
A composition according to claim 12 which is an aliphatic hydrocarbon having 6 to 16 carbon atoms and is present in the composition in a concentration of 15 to 55% by weight. 16. A composition according to claim 15, wherein the polar solvent is water and is present in the composition at a concentration of 15-85% by weight. 17. The composition of claim 12, wherein the composition is sprayable by manual pump spray. 18. A composition according to claim 12, which comprises at least one solid particle and / or an immiscible liquid in the composition. 19. The non-polar solvent or weakly polar solvent,
13. The composition of claim 12, which is an aliphatic hydrocarbon having about 6 to about 16 carbon atoms. 20. The composition of claim 12, wherein the surfactant is an anionic surfactant. 21. The composition of claim 12 (ie, 6?), Wherein the surfactant is an anionic surfactant. 22. A method of treating soil-contaminated material to release or remove it, wherein the soil release or removal amount is at the location of the soil on the material. A method as described above comprising applying the described composition. 23. The composition is applied to a material contaminated with stains that are difficult to remove at the location of the stain on the material as a pretreatment agent, and after that the stain is removed by the application of water. 22. 24. The method of claim 22, wherein the composition is applied as a pretreatment agent to a dish having a pre-handwash deposit or to such dish in dishwashing water containing a dishwashing detergent composition. the method of. 25. The composition is pre-applied onto the soiled area of the laundry contaminated with oily or fatty soil prior to washing the laundry in wash water containing the laundry detergent composition. The method according to claim 22, which is applied as a spotting treatment agent. 26. A surface tension of about 10 to 35 mN / m, comprising at least a polar solvent, a water-soluble or water-dispersible low molecular weight amphiphile and a non-polar or weakly polar solvent and a water-soluble acid, and approximately to each other. Chemically identical 3
A liquid detergent composition derived from two kinds of coexisting liquid phases, wherein the three kinds of coexisting liquid phases are converted into one single phase by reversible equilibrium due to an instantaneous change of the state. In a state such that they can be converted or they can be brought together into one continuous body to form the composition, the first phase being most enriched in polar solvents and the second phase being water-soluble or water-dispersible. Rich in low molecular weight amphiphiles, and third rich in non-polar or weakly polar solvents, water-soluble acids contained in the first, second and third phases, and the first phase And the interfacial tension between the second phase is 0 to about 1 × 10 ⁻³ mN /
m, and the interfacial tension between the second and third phases is 0 to about 1
x10 ^-3 was mN / m, and the composition interfacial tension between first phase and third phase is 0 to about ^1x10 -3 mN / m. 27. The polar solvent is water at a concentration of about 15 to about 85% by weight and the amphiphile is both about 5 (MP
a) having a water-insoluble hydrophobic moiety having a partial polarity parameter and a hydrogen-bonding parameter that is less than ^1/2 and a water-soluble hydrophilic moiety having a partial hydrogen-bonding solubility parameter that is greater than about 10 (MPa) ^1/2. An organic compound; the amphiphile is present in a concentration of about 5 to about 60% by weight; and the non-polar or weakly polar solvent has a dispersive solubility parameter of greater than about 10 (MPa) ^1/2 and about 27. The composition of claim 26, having a hydrogen bonding solubility parameter of less than 15 (MPa) < ^1/2 >, wherein the non-polar or weakly polar solvent is present in a concentration of about 15 to about 55% by weight. 28. The low molecular weight amphiphiles, alkylene glycol alkyl ether of the formula _{C x H 2x + 1 -O- (} CH 2 CH 2 -O-) y -H ( wherein, x or y is 1 to 6 A polyoxyethylene derivative having about 5 to about 7 carbon atoms, a polyol having about 4 to about 8 carbon atoms, a polyamine having about 5 to about 7 carbon atoms, having about 5 to about 7 carbon atoms. 28. The composition of claim 27, selected from the group consisting of polyamides and alkanols having about 2 to about 4 carbon atoms. 29. The non-polar solvent or weakly polar solvent,
Alkanes and cycloalkanes having from about 5 to about 25 carbon atoms, aryl alkanes having from about 12 to about 24 carbon atoms, aliphatic oils and aromatics having from about 6 to about 14 carbon atoms. Oils, terpenes having from about 10 to about 40 carbon atoms and of the formula 29. The composition of claim 28, wherein the composition is selected from the group consisting of esters having R and R ₁ are alkyl groups having from about 7 to about 24 carbon atoms with each other. 30. The non-polar solvent or weakly polar solvent,
27. A composition according to claim 26 which is an aliphatic hydrocarbon having 6 to 16 carbon atoms and is present in the composition in a concentration of 15 to 55% by weight. 31. The composition according to claim 26, wherein the polar solvent is water and is present in the composition at a concentration of 15-85% by weight. 32. The composition according to claim 26, wherein the composition comprises at least one solid particle and / or immiscible liquid. 33. The non-polar solvent or weakly polar solvent,
32. The composition of claim 31, which is an aliphatic hydrocarbon having about 6 to about 16 carbon atoms. 34. The low molecular weight amphiphile is triethylene glycol monohexyl ether.
The composition according to. 35. A method of treating soil-contaminated material to release or remove it, wherein the soil release or removal amount at the location of the soil on the material. A method as described above comprising applying the described composition. 36. The composition is applied to a material contaminated with stains that are difficult to remove at the location of the stain on the material as a pretreatment agent, and after that the stain is removed by the application of water. The method according to 37. 37. The method of claim 37, wherein the composition is applied as a pretreatment to dishes with pre-handwash deposits or to such dishes in dishwashing water containing a dishwashing detergent composition. . 38. Pre-applying the composition onto the soil location of the laundry contaminated with oily or fatty soil prior to washing the laundry in wash water containing the laundry detergent composition. The method according to claim 37, which is applied as a spotting treatment agent. 39. A method of treating soil-contaminated material to release or remove it, wherein a soil-releasing or removing amount of soil is provided at the location of the soil on the material. A method as described above comprising applying the described composition. 40. The composition is applied to a material contaminated with stains that are difficult to remove at the location of the stains on the material as a pretreatment agent, after which the stains are removed by the application of water. The method according to 39. 41. The method of claim 39, wherein the composition is applied as a pretreatment agent to a dish having a pre-handwash deposit or to such dish in dishwashing water containing a dishwashing detergent composition. the method of. 42. The composition is pre-applied onto the soiled area of the laundry contaminated with oily or fatty soil prior to washing the laundry in the wash water containing the laundry detergent composition. The method according to claim 39, which is applied as a spotting treatment agent. 43. The method of claim 39, wherein the composition is sprayed onto a lipophilic soil on a surface, where it remains as a surface-adhesive liquid until it is absorbed by it. 44. The method of claim 35, wherein the composition is sprayed onto a lipophilic soil on a surface, where it remains as a surface-adhesive liquid until it is absorbed by it. 45. The method of claim 22, wherein the composition is sprayed onto a lipophilic soil on a surface, where it remains as a surface-adhesive liquid until it is absorbed by it.