JPS61155497A - Detergent for automatic dish washer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: One aspect of the invention is to combine dissolved tripolyphosphate, silicate and alkali metal ions and a dispersed non-swellable clay thickener, preferably attapulgite. The present invention relates to an aqueous thixotropic automatic washing machine detergent consisting of a liquid phase, which is water, containing (clay), and a solid phase, which is primarily sodium tripolyphosphate. The composition preferably also contains a chlorine whitening agent (advantageously dissolved sodium hypochlorite).
and bleach-resistant anionic surfactants. The composition also preferably includes an alkali metal carbonate.

Prior Art: U.S. Patent Application S, N, 497.615 (19B!1 Year 5
(Registered March 24, 2013) discloses several compositions of this type, the entire disclosure of which is incorporated herein by reference.

Problems and Means to Solve the Problems: Including in the composition a limited proportion of a water-bathable potassium compound, such as a potassium salt (or KOH), such that the K:Na weight ratio is from about 0.04 to 0.5, preferably about 0.07 to 0.4
, for example about 0.08 or about 0.15, it has now been discovered that greatly improved results can be obtained.

The resulting product is much more stable in that it has less tendency to undesirably thicken or to undergo separation upon aging at, for example, 1 oo"F (58 °C) K. Also, the sodium salt Replacement with an equal amount of the corresponding potassium salt at a fraction of ) resulting in greater stability against separation during storage, and inhibition of the growth of relatively large crystals during storage. Clay reduction allows for easier handling in the manufacturing plant, easier aliquoting at the time of use, and lower consumption. This makes it easier for the person to break the sicuntroscopic structure of the product (by photographing the container it is tied to) and thus to easily pour it into the detergent cup of a household automatic washing machine.

In formulating the product, the proportions and ingredients set forth in the above-mentioned US patent application S.N. 497.615 may be used. In that patent application, the proportion range for the - group is broad, with one amount: (a) 8 to 65% alkali metal tripolyphosphate, (bl 2.5 to 20% sodium silicate, (C)
0 to 9% alkali metal carbon 6' (salt, tdl 0.
(e) 1 to 5% salt-tolerant, water-dispersible organic detergent active; (e) 0 to 5% chlorine bleach-stable suds suppressor; % of available chlorine, and a sufficient amount of a thixotropic thickener to give the composition a thixotropic index of about 2.5 to 10. Preferably, In the compositions disclosed herein, the proportion of IJium tripolyphosphate is greater than 15% (more preferably in the range of about 20 to 25% or 60%) and the proportion of sodium silicate is at least about 4%.
% (for example in the range of about 5 to 10% or 15%) and the proportion of alkali metal carbonates is about 2 to 6 or 7%.
The chlorine-whitening agent ratio is 0.5% or more of available chlorine (
For example, the proportion is such as to provide about 1 to 2% available chlorine) and the proportion of detergent actives is in the range of 0.1 to 0.5%. A preferred range of proportions of sodium silicate, calculated as S s Oz, represents about 6.5 to 7% SiO2 in the composition.

The proportion of water in the composition (measured by a "Senco Moisture Analyzer", in which the sample is heated by an infrared lamp until it reaches a mass) is preferably in the range of about 40-50%, more preferably is about 45-48%, for example about 44% or 46%.

The compositions disclosed herein typically have a pH well above 11 or 12. In one preferred type of formulation, the composition has a pH in the range of about 10.7 to 11.6 when diluted with water to a concentration of 0.75%.

The compositions disclosed herein preferably have a composition of about soo.

Centiboise or less, preferably about 2,000! Or 3.000 000 centiboise For example, about 4.0
It is formulated to have a viscosity U (measured on a Brookfield viscometer at 25° C. and 2 Orpm using Svirindol #4) of 0.00 to 6,000 centiboise. Viscosity and other properties may be measured several days (eg, one week) after composition production, and it is a good practice to shake the sample and run the FrIJVc for approximately 90 seconds before measuring the viscosity.

The compositions disclosed herein have yield values well above 200 dynes/cn1, preferably about 1100 dynes/cn1.
2 to about 600 dy/cm2, more preferably less than about 900 dy/cm2, such as about 40
It can be formulated to have a yield value of 0 to 600 dynes/α2. Yield value is a measure of the shear rate at which the thixotropic structure fails. It is Hague RV12 or R
Spindle MVIP 2 with a V 100 rotational viscometer
Measured using at 5[deg.]C, the shear rate increases linearly from zero to 20 s-1 in 5 minutes (after a 5 minute rest period). In a Hague viscometer, a thin layer of material is subjected to shear between a rotating cylinder and closely adjacent cylindrical walls of a surrounding container.

Figures 1-6 are graphs obtained in such tests of the three sample products shown therein, with the beak Y indicating the yield value.

Another factor measured with the Haag viscometer is the ability of the composition to recover its thixotropic structure.

In one method, after the 5 minute shear rate increase described above, the rotation is slowed to zero over 5 minutes, then after a 50 second rest, the rotation is accelerated again to increase the shear rate from zero to 20 in 5 minutes. Increase linearly to s-1. This gives a second yield value, ie Y'' in Figure 1. Preferably this second (recovery) yield value is at least 200 dia/an
2, for example, 50% of the initially measured yield value, 7
5% or more.

FIG. 4 is a photomicrograph (taken at the magnification indicated therein) of the composition of Example 4.

The following examples are presented to further illustrate the invention.

In these examples, Attagel #50 is a powdered acpargite clay (Enkelhard Mineral x
Manufactured by Ban&Chemicalme. Its sales literature states that as manufactured it has a BET surface area of about 12% free moisture measured by heating to 220"F' (105C) and about 210F?//? calculated on anhydrous pace); Grafdor Green is a coloring agent; LPKN158 is an antifoam agent manufactured by American Hoechst (Natpsack) consisting of a 2=1 mixture of heptano and di(C+6-C+8) alkyl esters of phosphoric acid; :
It has a Na20:SrOz ratio of 2.4; Dowfax 5B2 is a 45% aqueous solution of Na monodecyl/didecyl diphenyl oxide disulfonate, a bleach-resistant anionic surfactant; 5TPP is sodium tripolyphosphate It is. 5TPP unless otherwise specified
is in the form of a commercially available anhydride in the form of a fine powder with a water content of about 0.5%, in which substances such as pyro-g4 & salt are typically present at about 4.5-6.5%. There is. The water used is deionized water unless otherwise specified.

Example 1 The following ingredients are warmed in the order shown below while mixing in a container and a small laboratory stirrer.

The temperature and mixing time at various stages are also shown below = 130
F (54℃) water 1746 melt LPKN158
(Defoaming agent) 8 Daufax 6B2 (surfactant) 40126 (2 minutes) 122 (1 minute) 120 (5 minutes) Soda ash 275 to 2CO375 134 (1 minute) 132 (5 minutes) Fine powder 5TPP/hexahydrate 750127 (1
125 (5 minutes) 124 (5 minutes) 47.5% water bath solution of sodium silicate 42150% Na
Mix with OH aqueous solution 150118 (5 minutes) 16% aqueous solution of NaOCL 500108 (5 minutes)
minute) fine & fine 5TPP-hexahydrate 750 108 (1
minutes) Total 5000P 107 (5 minutes) The viscosity of the mixture measured as above is approximately 5000 centivoise after 5 weeks of aging at 100F (58C) and 100"F (58C).
After aging for 6 months at 68°C), it is approximately 4800 centipoise.

In this example, the 5TPP hexahydrate has the following approximate particle size distribution: #10 Remained 0 #40 Remained 0 #100 Remained 25.4 #200 Remained 51.5 #625 Remained 16.5 #625 Passed 25. 9 Example 2 The following formulation was made and the two ingredients whose properties were determined as shown below are mixed in the following order: water, colorant, clay, half of the phosphate, antifoam, chlorine. acid salt, sodium carbonate, potash carbonate, NaOH1 silicate, second half of phosphate,
surfactant.

component! Clay (Atagel 50) 5
．． 285STPP
23.0 Potassium tripolyphosphate
-Potassium pyrophosphate
-Sodium carbonate
5.0 Potassium carbonate -
Sodium hypochlorite (12%) 9.
375 Sodium hydroxide (50%)
2.05 Sodium silicate (415%>
10.53 Surfactant (Dowfax 1-2)
0.80 Colorant o, 16 Water
0.381 Properties Capillary flow time (min) 8.2 Viscosity (centiboise) Aging for 1 week at 1007 (i°C) 90802 weeks - 9200 5 weeks” 9300%
3.2855.2B53.2853.28523.0
17.0116.5 23.0--6.5 - - 5.99 0 - 5.0 5.02.5 5.0 2.5 9.3759.3759.3759.5752.05
2.05 2.05 2.0510.5310.531
0.5310.530.80 0.80 0.80 0
．． 800.16 0.16 0.16 0.160.5
81 1.3810.3810.381 remaining 12.1 10.9 11.4
11.2 The capillary outflow time was determined by drawing a circle with a diameter of 6.8α on a 15CM Whatman size 41 door paper and using a plastic annular body (inner diameter 6.5α, outer diameter 4.2
on, height 6.0 cm) is placed vertically on the door paper concentrically with a circle, and this annular body is filled with the composition to be tested. The liquid from the composition is thereby absorbed into the P paper and slowly spreads into the drawn circle. The elapsed time until the liquid contacts the circle is measured at three predetermined positions, and the average value is calculated. This predictive test indicates the relative stability of these systems. Composition (b) thus has a lower viscosity and higher stability than composition (a) above.

Example 6 The following formulation is made by mixing the M ingredients in the order indicated. The compositions were then centrifuged at 275 G until the volume of the clear separated (continuous) phase did not increase, and the resulting liquid was divided; thus, these compositions were:
They are the same except for the NaO ratio.

Product properties Viscosity After 1 day at room temperature 8520 5520 4200 21
20 After 6 weeks at room temperature 8550 6200 4500
2420 ratio 1 [1,571,571,401,59 ratio 1
m 1.257 1.262 1.276
1.50 Product viscosity for this example is 8011i
' (26.7°C) using a Brookfield RVT viscometer spindle shop 5.

Examples 4-6 below demonstrate a new and useful method for making the above-mentioned product (containing limited amounts of potassium) of another inventor, which is claimed separately in a co-dated invention of the present invention. It is explained. It is also the aforementioned U.S. patent application S.
, N, 497.615 (for example, in which no potassium compounds are present) K and other products of the type indicated, as well as water containing dissolved builder salts, viscosity or other colloidal thickening agents, and surfactants. It can also be used to make other detergent slurries consisting of fine particles of water-bathable inorganic builder salts dispersed in water. In these examples (in which the builder salt particles in the product are primarily 5TPP hexahydrate and aqueous sodium carbonate)
A viscous (e.g., 20,000-60,000 centipoise viscosity) mixture is formed of a limited amount of water, a highly alkaline saturated solution of builder salt, and undissolved particles of water-bathable builder salt as the main component. This viscous mixture is subjected to attrition of undissolved particles in a high-speed disperser, followed by the addition of solid particles of clay thickener to deagglomerate the viscosity and then to the remaining components of the formulation (e.g. liquid phase with high electrolyte content). other liquids or substances that are easily dissolved or dispersed therein). This mixture is then subjected to additional high shear mechanical action to further deagglomerate the clay. It has been found that with this method no predispersion of the clay in the aqueous medium is required. Clay solid particles are easily dispersed even in highly alkaline media.

Attrition of undissolved builder salt particles occurs much more effectively and easily in the substantial absence of clay.

In the method described in Example 4-6', the builder salt, which should constitute the main part of the undissolved particles, is removed because its addition causes the builder salt to precipitate out of solution (e.g. due to the common ion effect). Preferably, it is added to high concentrations of other dissolved builder salts that are recrystallized as microcrystals.

Another feature of the mixing method explained in Examples 4-6 is that
It is possible to make reproducible repeat batches using the entire remainder of a previously formed batch as a component of each subsequent batch.

As indicated above, the use of the methods described in Examples 4-6 is not limited to producing compositions containing potassium salts. So far the method has found its greatest utility in the production of formulations in which the clay is attapulgite, but all or part of the clay is of a swellable type, such as bentonite (e.g. Gel White GP). Alternatively, compositions that are smectite type clays such as pectolite can also be used.

Example 4 Sunset Pigment (i.e. 0.028 parts Graff d'Or
Green, an aqueous paste containing 28% pigment) in 52.0 parts of deionized water mixed with 2.0 parts of 2CO3
(The water solubility is 10 parts per 100 parts of water even at 0°C.
0 parts or more) and 5.0 parts of granular carbonic acid) IJ cum (its water solubility is about 45 parts per 100 parts at 65°C)
The temperature of the solution is approximately 90″F.
(32°C). 23.116 parts of powdered 5TPP containing approximately 0.5% water of hydration are then added while constantly subjecting the mixture to the action of a high speed disperser. The amount of 5TPP is much greater than that which is soluble in the amount of water present; its solubility in water is approximately 2 per 100 d at 25°C.
It is 0F. In an illustrative example, 5TPP is a product of Olin Corporation and contains approximately 50% 7Aze I.
It has a sodium sulfate content of approximately 2% and a very fine particle size; it is a mixture of granular anhydrous 5TPP and powdered 5TPP hexahydrate made by the known "wet method".

When this 5TPP is added to a solution, it easily hydrates and forms a hard crystalline mass that also consists of 5TPP hexahydrate. (
It is observed that 23 parts of s'rpp has the ability to take up about 7 parts of water in forming the hexahydrate salt). This mixture is initially a thin slurry of undissolved 5TPP in a liquid that is a supersedation solution. The temperature increases due to the hydration reaction,
A peak of about 140"F (60C) is reached. In about 3 to 4 minutes the mixture becomes much more viscous, with a viscosity of 20.
000 centivoise (e.g., measured at 10 RPM with a Brookfield RVT, Sub/Dollar #6, at the slurry temperature, about 40.
000-50.000 centipoise). During this process, it is believed that the IJium carbonate crystallizes out of the liquid phase (in the form of very fine crystals) due to the common ion effect (of the sodium in STPP). When the mixture becomes viscous, the high-speed disperser acts to grind the particles (e.g. of hydrated TPP) to a fine particle size, and the grinding action, in part, increases the power consumption of the disperser. and concomitant temperature increases (e.g. 150″F
(66℃). This increases the dissolution of the builder salts, which in turn recrystallize in fine form upon cooling)'
Therefore, it is shown. This milling was continued for approximately 5 minutes after the initial thickening of the slurry, during which the visible rings disappeared and the size of the undissolved particles decreased until virtually all particles were
It comes to be believed that it has a diameter of less than 0 microns.

Next, add another 9667 parts of water to bring the viscosity to 10.0.
00 centivoise or less (for example, 5 when measured as above)
000 centiboise) and then add 6.3 parts of Attagel #50 and 0.752 parts of Why) Ti02 (anatase) pigment to the highly alkaline mixture (whose pH is well above 9, e.g. 10.5). Meanwhile, the mixture was subjected to the action of a high speed disperser, which greatly dispersed (deagglomerated) the clay so that the viscous mixture had a homogeneous to smooth appearance. Next, 2.7 parts of 50% NaOH aqueous solution, 0.16 parts of antifoaming agent (Natpsack LPKN (5
8), 10.53 parts of 47.5% sodium silicate aqueous solution (its Na2O:5i02 ratio is 1:2,4), 10.0 parts of 12% hypochlorous acid +7um aqueous solution, and Add 0.8 parts of a bleach-resistant anionic surfactant (Dowfax 6B2); these additions can be carried out under any desired mixing conditions, such as with simple stirring (although this It may be convenient to continue the high shear dispersion action for seed mixing). The mixture is then subjected to a comminution action, for example by passing it through an in-line mill such as the Chikmar "Dispax Reactor" (which operates at a top speed of 22 m/s), and the mixture is kept at a high temperature for a relatively short period of time. Subject to shear rate (eg, residence time in the mill may be as little as 2 seconds or less). The main effect of this is to further deagglomerate the clay particles, as shown by a significant increase in yield value, e.g., raising the yield value of the mixture by almost 33%.

The resulting mixture is thixotropic. The particle size of the dispersed solid particles therein is very small, with 801% or more having a particle size of less than 10 microns. The mixture is at a temperature in the vicinity of 120-1301 i' (!19-54 °C) (at this temperature its viscosity is e.g. 70"
(higher than the viscosity at 21°C). It is withdrawn from the mixing vessel (eg, through a valve in the bottom when the volume has a conical bottom, or from the lower side pulp of a substantially plain-bottomed mixing vessel). Approximately 10% of the mixture remains in the container as residual material, and due to its flow properties it is difficult to remove the entire composition from the container.

The entire procedure described above is then repeated many times in the same mixing vessel without drawing out any "leftovers".

A high-velocity disperser consists of a circular horizontal plate with alternating upwardly and downwardly extending peripheral teeth that rotates rapidly to achieve a peripheral velocity (of teeth) of 75 feet per second (e.g. 90 feet per second). ) is mounted so that it is larger (on the vertically downward-pointing axis of the K).

For laboratory operations, a Colorless high speed disperser is suitable; for large scale operations, a Mayer Model 800 series high speed disperser can be used. These high speed dispersers reduce particle size by impact milling with toothed plates and by laminar shear stress on the mixture. This shear generates heat in the batch in addition to the heat generated by K such as dissolution, hydration, etc.

At the resulting relatively high temperatures, the chain components are more soluble and crystallization upon cooling gives relatively small particles that do not quickly settle out. The high speed disperser induces "rolling" of the mixture, i.e. the path of motion of the mixture is downward in the center of the vessel, outward on the rotating plate, upward along the vessel side walls, and the mixture is Inward-looking. In the course of this movement, the desired degassing takes place, ie air (which is always introduced during powder addition) leaves the mixture during the inward step of the circuit.

Apparently, after processing the composition described above, crystal growth occurs to form many larger and relatively uniformly sized crystals (as shown by optical microscopy). In this way the fourth
The figure shows the presence of crystals with diameters on the order of 80 microns. It has been suggested that these crystals contain boilIII salts, but this has not yet been fully identified.

Example 5 Example 4 is repeated, except that 5TPP powder is
Monsanto Anhydrous 5, consisting of anhydrous 5TPP made by the "dry method" K and humidified to such an extent that the hydration water content is 1% (or somewhat higher, e.g. 1-%).
It is TPP. Its Phase I content is approximately 20%. This 5TPP was also used in Example 3.

Example 6 Example 4 is repeated except that the initial proportion of water is 28.
0 parts and the second part of water is 13.637 parts, K, 1.11 parts of a 45% aqueous solution of sodium polyacrylate (Acrisol LMW-45N with a molecular weight of about 4500) before addition of the attapulgite clay. Added. Here, 2CO3t is 6 parts, and the amount of Na2CO3 is 4 parts.

The products of Examples 4-6 were found to have the following properties: Example Viscosity (ゞ7chi'i''> 4000 6000 4
40 [1 yield value (dia/z2) 4 s
0 600 a.s.

Capillary flow time (min) 8.2 5.6
6.1 centrifugation minute 1111t (%)
16 26.5 12 thixotropic index
5 4.3 4.1 "Centrifugation Volume" was determined by centrifuging at 275 G as described in Example 6 above and determining the volume of the clear layer relative to the total volume.

"Sixotrope index" is the above S, N, 497.615
Brookfield HATD viscometer, as described in
Ratio of viscosity at 60 rpm to 5 rpm, measured at room temperature with a #4 spindle.

In Example 6, a soluble chlorine bleach resistant polymer is present. It has been found that the presence of this polymer improves the separation resistance of the product upon standing or centrifugation without imparting a correspondingly large increase in viscosity of the product. This polymer is here expected to be present in a very concentrated (saturated) electrolyte solution. It has also been found that the presence of polymers leads to an improved protection of the glaze layer of tableware (fine china). In previous studies, these effects were observed with polyacrylates, which were found to be quite compatible with chlorine bleach and the clay in this system, e.g. The active chlorine content is maintained as in clay. Polymers of various molecular weights can be used; for example, polymers of 10.
000 or less, or 100
．． It can have a molecular weight of 0.000 or more.

Preferred molecular weights range from about 1.000 to 50.000.

Molecular weights of about 1.000 to 50.000 are particularly notable for not forming films on glass. The proportion of polymers ranges from 0.01 to 6%, with lower proportions being suitable for higher molecular weight polymers (e.g.
! 0.06 for a molecular weight polymer of 100.000
%). Other bleach-resistant polymers such as Tancol 76
1, which is a sodium salt of a polymeric carboxylic acid with a molecular weight of about 15,000.

In this invention, all parts are by weight unless otherwise specified. In these examples, atmospheric pressure is used unless otherwise specified.

It is understood that the foregoing detailed description has been presented for illustrative purposes only and that changes may be made without departing from the spirit of the invention.

[Brief explanation of drawings]

Figures 1-'5 are graphs obtained by rotational viscometer testing of the products of the examples shown in each figure, where Y at the peak indicates the yield value. FIG. 4 is an optical micrograph of the composition of Example 4 (taken at the indicated magnification). (Other 5 people) TJF Seven Shiji & (Tai 1 In/6-Rumor-) 1 岨区lateral (Gain/1-Fal-2 FIG, 4 Procedures Amendment Book December 2, 1985 - Day 1) Display of the case Patent Application No. 178476 filed in 1985 2 Name of the invention Automatic dishwasher detergent 3 Person making the amendment Relationship to the case Patent applicant address Name Colgate Palmolive Power/Panny 4 Agent 5. The specification to be amended is amended as follows. Page Line Before amendment After amendment 28 3 Optical micrograph More than a micrograph of crystal structure 9 Akira A Ko Shie Ao 11 Relationship with the case of the person making the fifth amendment Patent applicant's address" 4th stem ri...y'L F -7%'-Molyb'
-f)'/res-4, agent

Claims (1)

[Claims] 1. An aqueous thixotropic automatic dishwashing composition; water containing a dissolved alkali metal tripolyphosphate, an alkali metal silicate, and a dispersed non-swelling clay thickener. a liquid phase that is primarily sodium tripolyphosphate; and a solid phase that is primarily sodium tripolyphosphate; the weight ratio of K:Na is in the range of about 0.04 to 0.5. 2. Has a yield value of at least 200 dynes/cm^2;
A composition according to claim 1. 3. The composition of claim 2, comprising a chlorine bleach, an alkali metal carbonate and a bleach-resistant surfactant. 4. The composition of claim 1, wherein said composition comprises about 20% to 25% sodium tripolyphosphate. 5. The composition according to claim 3, wherein potassium carbonate is present. 6. The composition according to claim 3, wherein potassium tripolyphosphate is present. 7. The composition according to claim 3, comprising potassium pyrophosphate.