DE1617203A1 - Dishwashing detergent - Google Patents

Description

Alfred Hceppener Nov. 25, 1968

DE ä Wlff

Wolff

Dr, Hani Car, hatchet

Rcefcts & jwäite

Frankfurt a, M. «Höchst

Adelonetraße 58 - Tel 312649

^ ur No. 15 322

Stauffer Chemical Company Xorkj H ₀ L ₅ Y ₀ St.A.

Wash dishes

The invention relates to a detergent, which in particular when Washing off Ga (Is and glazed ceramic and porcelain parts in Water can be used without attacking the surfaces of the parts to be washed.

It is known that the previously used strong alkaline solutions, especially containing the caustic and industrially for washing bottles wiü other, en dlaswarss, Yerwendat are the surfaces of the glass etch or "roughen and thus impair their appearance · It is also known that less alkaline cleaning solutions (pH 8-13) _f predominantly in automatic Haushaitsabwasch-Buuichinen verweaüet werä © a _s äi® surface of Gläs @ r and porcelains

-2 - 1Ο9δΦΟ / 1

BATH ORIGINAL

etch, in iaanciien cases even completely on porcelain or Remove stoneware printed or painted patterns. Bs are already a whole series of protective devices against the attack of alkalis Additives have become known, e.g. from the USA patents 2.2-41.984, 2.419.805, 2.447.297 and 2.575-576. Be the ones known so far protective additives, which are also referred to as inhibitors, are mainly water-soluble zinc, beryllium Aluminum compounds. Although these have a certain effect, however, have not proven to be satisfactory overall.

The object of the present invention is to provide a dishwashing detergent to find which does not have the disadvantages that have been accepted so far. As has now been found * can be alkaline and acidic Alkaline aluminum oritophosphates in alkaline dishwashing liquids for reduction added to the attack on glass and glazed porcelain It is completely surprising that the alkali aluminum orthophosphate the one commonly used for this purpose up to now Inhibitory are far superior to sodium aluminate.

The acidic orthophosphates according to the present invention correspond the following empirical formula:

In this formula, M represents an alkali metal, preferably sodium and / or potassium, sine ganae number χ between 1 uad 5 inclusive, y is an integer counting 2-4, inclusive, and ζ is an integer from 11 to 17 inclusive, wherein the sum of χ + 3y + ζ correspond numerically to the sum of the talences of the phosphate residues (POf), ie must be between 21 and 30. The acidic sodium aluminum orthophosphates, which have hitherto been used essentially as leavening agents in baking powders and as additives for other foods, can be used for the purposes of the present invention. These bonds and processes for their production are described, for example, in the USA patents and patent applications 3,223,480, 5,223,479, 3-205,073, 2,995-421, 2,957-750, 2,550,490 and Serial ITq ... 173-054. Compounds of the following composition, _

Can be used with a special part of the gate: ___

. BAD ORlGiNAL

_ 3. 109809/1884

COPY

.2. b H ₂ O

The alkaline orthophosphates, which according to Torliegender invention can be used, as well as their manufacture are in the USA Patent 3,097,949. Alkaline Uatrium-Aluminumortt Phosphates have the following empirical composition:

In this formula, ^ means a number between 6 and 1 >>, y a number between T, i3 and 4.5 ¹ JHd ζ a number between A and 40. The terms "alkali aluminum or" phosphate used in the context of the present invention "or" potassium aluminum orthophosphates "should include both the acidic and the alkali orthophosphates»

The dishwashing agents according to the present invention are egg are mixtures which externally unite the inhibitors according to the invention A wide variety of well-known ingredients - which are usually about 8t

■■ - ■■■■ ". · - - - ■" - "■ -" ■ - " make up to 99 weight percent and one or more of the fo ".

These consist of: a caustic alkali such as sodium hydroxide, an alkali metal salt such as alkali carbonates, phosphates, borates, silicates and sulfates, an organic or inorganic "active chlorine bond" such as chlorinated alkali metal cyanurates, chlorinated cyanuric acid, chlorinated trisodium phosphate or other halogenated nitrogen-containing compounds , eg If-Ghlorbernsteinsäureamid as well as allows a what or ohst off or a surface-active compound, vorz-. wise of the little or non-foaming type, for example, 3. a non-ionic alkyiaryl polyether such as Triton oil ¹ 10 ", a non-ionic amine-polyglycol condensate such as" Triton.Cj? 52 "or an anionic liatriümdoäecyldiphenylätherdisulfonat such as" Benox 2Al ". If necessary, mt can also use a moderately or strongly foaming raw laundry detergent together with a foam inhibitor, 2 ^ 3, a silicone. Furthermore, such detergents are generally added quaternary ammonium compounds such as benzethionium chloride as formicides . to carry out the rinsing process, the washing or rinsing agent in water, a sufficient temperature welcl (typically about 5O ⁰ Q) having dissolved

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WG bei the ratio of detergent to water depending on the requirements (i.e. use for industrial Z-wec & e or in the household) set weö.

Purely industrial Plasehenwaschaniagen one uses highly alkaline (pH 12 or above) detergent types, which about 5U "to 9 !? percent by weight caustic alkali (Fatriumbyäroriö) jU" to 40 percent by weight of one or more of the following compounds, namely sodium carbonate. iDrinatriumphosphat ₅ iEetranatriumpjrophosphat or ITatriummetasiiikat, as well as u, ^> to 2ü weight percent of an etching inhibitor of the type described above.

A detergent for household purposes normally consists of about 2u to 0% of a condensed phosphate as a builder (liatric tripolyphosphate, tetrasodium pyrophosphate, potassium pyrophosphate, etc.) and about 5 to 65 percent by weight of one or more of the following constituents, a sodium silicate such as sodium silicate, preferably sodium pentahydrate a detergent raw material or a surface-active substance as well as one or more special ingredients or puilaxic agents such as matri-omcliloriä-disodium phosphate, sodium borate; chlorinated trisodium pliosphate "clilorierta cyanuric acid derivatives" sodium sulf & t, sodium carbonate - as well as a disinfectant. Furthermore, the agent can contain a XompexDi.Ldner which serves to soften the water, for example. Salts of ethylenediaminetetraacetic acid or of nitrile / acetic acid _? a part or the total amount of "PhOsphätgerüststofie \ ^r erw6naet v / ground ÖIE can also be used instead. Sowob.3, the detergent for Haushaltsswecke and the -who inäustrielie for purposes may in dissolved Porm _f is preferably dissolved in water, in ueen marketed The agents can also be put on the market in .perm. of suspensions consequently stated on a dry weight basis! What or other solvents that may be used to convert a mixture of ingredients into a liquid form _? are not taken into account. EABORIGiNAL

-0S80 S / 1884 COPY

TB 17203

A household dishwashing detergent can also contain borax (sodium tetraborai and common salt (sodium chloride). Dishwashing detergent for industrial purposes, sodium glueonate, Contain sodium nitrate or sodium tartrate. :

The alkali aluminum orthophosphates according to the present invention can be used in amounts of about 0.5 up to about 20 percent by weight, based on the dry weight of the constituents _y The inhibitor mentioned is used in amounts between 2 and 6 percent by weight.

The dishwashing detergents according to the present invention can, for example consist of the following components in the specified quantities:

Ingredient * ■■ '.'. "; Na tr iumt r ip olypho sphat irisodium phosphate

Sodium methosilicate "'..-, -

Sodium carbonate washing raw material · alkali aluminum orthophoephate

The irisodium osphat in the formulation described above can be chlorinated. As far as "are ¹¹ ISTY talk Erikiatrium-PhOSPhBt both chlorinated as you do not chlorinated! Dvpen be included up to the MLIE, which expressly only chlorierteis trisodium phosphate is talk. Should Furthermore, the term" in the present context of metasilicate "in The present context encompasses both the water- containing and the anhydrous porms of sodium metasilicate, with the exception of the palls, which expressly refer to anhydrous sodium metasilicate.

A dishwashing detergent according to the present invention which contains a chlorinated isocyanurate can, for example, have the following composition:

^: ■. : - ■■ "- ■■ - / · ■" ■ ■ - "\ '." - ■: ^:: - ■'"'■ - copy

Parts by weight ■ "-" ■ 60 30th ■ ... ■■ ..; 'i> - - 50 10 20th 0 0 2

Ingredients Parts by weight sodium tripolyphosphate 40

Trisodium phosphate 10

E Sodium Metasilicate, Anhydrous 35

Sodium carbonate 9

surfactant (Triton CP

10). 1

Potassium chloroisocyanurate 1

Alkali aluminum orthophosphate 4

The unexpected superiority of acidic alkali aluminum orthophosphates as inhibitors in G-eschirrspül ^ means results from the values of the following Table I. The values were obtained by placing porcelain plates in washing-up solutions according to the determinations Chemical Specialties Manufacturers Association, Inc. using a standard procedure (CSMA Bulletin Ho. 19bt> 7, July 31, 1957) washed. The dry dish soap was in water dissolved so that there are solutions with a concentration of pesticides of 0.305ε.

TABLE I. Composition of the agent to be tested

Constituent Gkawielitstsile sodium tripolyphosphate 40 Trine & triumphal phosphate 10 H & trium metasilicate, anhydrous 35 Sodium carbonate 10 surfactant (Triton OP-10) 1 Inhibitor 4th

BATH ORIGINAL

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Results :

Delay the attack on you glaze of the Porcelain (IO hours of flushing time / at -ΐθθί

I ⁰ C

Inhibitor

no (control)

Sodium aluminate (standard)

Soaking time on the glaze

H ₂ U

i < ^P0 ₄ V

. (PO ₄ ) ₉ .2.5 H ₂ O

- _s ' \ 4H ₂ O

1U4-10 + 10+

finally observed degree of attack (i)

1U

4 7

3 1

(i) Visual inspection of the nut and egg glaze on the porcelain after 10 hours using a rating scale 1 to IU; 10 means maximum damage "bsvi .. Ser fault: 1 means minimum Damage c

The compound of the formula KTa ^ Al ₅ JB-Jc (PO /) _o . _{-2.5 B P} U mentioned in the above and a process for its production have not yet been started. The compound can be produced as follows If 10 moles of egg ₅ JO (B ^ ig) are added 1.35 moles of SSgCO ^; the oil mixture is kept at '8G ° Q. Then, 1.15 moles of Al ₂ O ^, 3 H ₂ O The mixture is heated too uno again to S ¹ O ⁰ G ₀ The reaction mixture is then left under reflux at 90 "G until a finely larger mixture has formed :! iTstriuiaal-uaaiTiiiaiaphospliatkrista: le are sr £ t Kit ktiitexa water unö ösim: washed with It] s6.nol and finally dried at IUO ⁰ O. PI's element analysis shows that the compound corresponds to the formula Ka ^ Al ^ H ^ (PO ₄ ) q.2.5 E ₂ G. The RöatgenbeugurLg ^ SiagraiHm äsr Verbinöiaxg showing main lines at 3 _f 07, 4-foue laid.8,1 υ .feBestrela "The LöslichkBit the compound in water is 4 g per 100 El H ₉ O at low decomposition; the pE- ¥ ert a: 1 $ LdEimg is 3? 0. Its absolute density is 2.47 g / cm; Refractive indexes Έ-J ³ = 1.518 and 1.564. In the case of the step-by-step thermal analogs, jumps can be seen at 210 ^° C. (loss of about '

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BATH ORIGINAL

6 moles of H ₂ O), 24ü-255 ° C (loss of an additional 1.5 moles of H ₂ O), 32O ⁰ G (loss of an additional 1.5 moles of H ₂ O) and ⁰ C 4-3O (loss of further 1 mole of H 0). On microscopic examination, the crystals appear rhombohedral with transverse extinction under crossed ITicols.

The following examples serve to further illustrate the present Invention.

example 1

Dishwashing detergents were made and according to the above CSM / L standard procedure tested.

40 g sodium tripolyphosphate, 35 g anhydrous sodium tetasilicate, 10 g of trisodium phosphate and 10 g of sodium carbonate were in a Put wide-necked flask and mix with a spatula. 1 cm one surfactant (Triton CT-IO) was added dropwise and while mixing the dry ingredients from a wide-necked Pipette added. Thereafter, 4 g of the inhibitor compound were admixed with the dry ingredients. Part of this mixture was made dissolved in distilled water in such a way that a solution was obtained which contained 0.3 percent by weight of the mixture. The solution was heated to boiling and kept boiling. Small glazed plates with a colored pattern were 10 hours in the simmering Solution immersed. During this 10 hour trial, the Plates removed from the boiling solution every hour dried with soft white paper towels and visually for a change in the intensity of the pattern as well as the Checked for damage to the glaze. An apparatus-based examination of the changes the pattern and glaze were measured with a Hunter glossometer (Model D 36) made; the values thus obtained agreed well with those obtained by visual inspection. The results are compiled in the following table.

BAD ORiGfNAL

109809/1884

Attack on the glaze of porcelain (immersion time for 10 hours: 10O ⁰ + 1 ⁰ C)

a) Inhibitor: sodium aluminate (standard) pH value of the solution at the beginning

12.5; at the end of 12.02

Time in hours Comments

ü strong shine - pattern intense

1 μ w-

2 "n

5 ■ 'ti it

4 »n

5 several weak "water marks ¹¹ *

are to be observed

6th ⁿ - ■. ■■■ '■■ · ^: - 7 η

8th "

9 it

10 compared to an untreated one

Teller, the "coloring of the treated Seiler appears only slightly weaker; some ^M water ^marks are present

♦ -

The word "water markings" means very fine lines that

appear on the glaze of the plate surface. As these lines go through the attack of the alkali on the glaze can be caused they are not removed by washing, rubbing or normal post-treatment of the plates.

b) Inhibitor: HaAl ^ H _1. (PO.) _R. 4H ₉ O pH of the solution at the beginning

^{p 14 4} - * 12.3; at the end 10.9

Time in hours Comments

0 strong gloss - pattern intense

2 »ι η

4,; »." "■ =. it

BATH

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- to -

Time in hours 6

7 8 9

10

Remarks

Strong shine - pattern intense

"Water marks ¹ 'are observed

compared to untreated plates, the treated plates seem to mean

to show deteriorated imprint.

) Inhibitor:

pH of the solution at the beginning 12.4; at the end of 12.05

Time in hours

υ 1 2

3 4 5 6

7 8

9 10 Comments

strong shine - intense cough

η η

weak spots appear but disappear again

η
η
n

η η

n η

Picks no longer visible η η

η η

treated plates showed no water marks or fading Colors in comparison with untreated plates

Inhibitor: Ka ^ Al

time in hours 0 1 2.

I (PO ^) ₉ .2.5H ₂ O pH of the solution at the beginning 12.30 at the end 11.75

Remarks

strong gloss - pattern intense η η

some very faint water marks are visible

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BATH ORIGINAL

Time in hours Comments

some very faint watermark

rungs are visible

η η

η ■ η η

if η

ο η η

Plates show no degradation

the gloss or the color and • have only small water marks on

e) Inhibitor: keiD & r (i: ontrolle) pH value of the solution at the beginning 12.4b;

at the end 11.8

Time in hours Comments

0 strong gloss - pattern intense

• j - η ti

2 η it

3 patterns less intense

4 "- haze of gloss t> slightly more clouding of the gloss

- 3 marks on the towel

6 paring marks on the towel

7 The gold rim is starting to fade

9 Pattern becomes even paler

in comparison with untreated Tel

the treated person is visibly paler and duller

Example 2

Using the same procedure as in Example 1 but with Various sodium aluminum phosphates were added to a chlorine-based dishwashing detergent tested for the effect in preventing the attack on the porcelain glaze. The following means were used

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middle

Ingredients Parts by weight sodium tripolyphosphate 45

Sodium Metasilicate Pentahydrate 20
Sodium carbonate 10

chlorinated trisodium phosphate 20

surfactant (Triton
)

1 .
Inhibitor 4

The test results are summarized in the following table.

Attack on the porcelain glaze (lOstündige Immersion time: 1OO ° ± 1 ⁰ C)

(a) Inhibitors sodium aluminate pH of the solution initially 11.8;

at the end 11.0

Time in hours Comments

0 strong gloss - pattern intense

• y at

2 μ η

5 mm

4 M Il

There are 5 faint water marks

bar - cloudiness of the gold rim

6 μ η.

7 ^wn

8 water marks are becoming more numerous

9 »

Clouding of the gold rim. Some were black

The water marks are visible. No fading of the colors of the cough and no clouding of gloss.

(b) Inhibitor: 15 Na ₉ O, 2.8 Al ₉ O,. 8P ₉ Op..xH _P ü pH value of the solution am

^{c 7} ° beginning 10.8; at the end of 10,

95

Tent in hours Comments '

0 strong gloss - pattern intense

BATH ORIGINAL

_ ₁₃ _ 109809/1884

Time in hours Comments

1 strong shine - pattern intense

2 ti n

3 η ν

4 hm

5 it it

6 spots are visible everywhere

7 most stains will fade

9 red and red painted ropes show plug-in

pin-sized holes on small water marks are at the bottom

ren rope visible; painted red and roajT The ropes' ropes have holes the size of a pin

(c) Inhibitor: ITaAl _x H ^ (PO.) _Q. 4H _O Q pH of the solution initially 10.9

^{3 14 4 ö} / at the end 10.8

Time in hours Comments

0 strong gloss - pattern intense

■ \ η ti

2 gold rim more orange; small

Water markings become visible

5 'Μ μ

4 η «

5 η η

6 ti it

7 dark red colors have faded; the

Underside is dull

8 "" g η η

10 * small water marks are on the

Underside visible; dark red colors have faded; Gold rim a little more orange; no reduction in Glansef

-H-

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• * r

(d) Inhibitor: none (control) pH of the solution at the beginning 12.00

at the end 10.65

Time in hours Comments

0 'strong shine - intense haster

1 red color can be passed through the

Remove towel. The glaze on the patterns has disappeared; brown deposits appear

2 red color is more distant.

3 red and green colors are removable

the green has darkened

4 more red color has been removed;

the gold rim begins to fade

5 more red color has been removed;

faded green

6 η η

7 more red color is removed

8th "

9 Gold edge faded more

10 the floral pattern is almost conspicuous

the; the gold rim has faded considerably; the shine is just a little dimmer.

From the above observations it can be seen that the alkaline sodium aluminum phosphate in chlorinated TSP detergents gave the longest initial protection (hours of protective action: b>a>c> d). The acidic sodium aluminum phosphate gave the highest values for protection that extended over the full 10 hours (extent of protection: c>a>b> d).

Example 3

A bottle washing agent for industrial purposes is produced by dissolving 48 parts of caustic soda and 7 parts of inhibitor in 1,430 ropes of water. In this solution, which is brought to a temperature of 85-3 ⁰ G and kept at this temperature , nan places new GIaa bottles weighing about 400 g. The bottles are left in this solution for 6 days, the egg is then removed from the solution and the weight loss is determined. It turned out to be acidic and alkaline latrium

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aluminum phosphate prevents the alkali from attacking glass bottles reduce the above procedures to a considerable extent.

BATH ORIGINAL

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Claims (1)

Claims 1) Dishwashing detergent with reduced aggressiveness against glass, and glazed porcelain, characterized in that it comprises about 8 "to 99 percent by weight of at least one of the following Components, namely caustic alkali, alkali carbonate, phosphate, silicate, borate, sulfate, chlorinated alkali cyanurate, chlorinated Cyanuric acid, chlorinated trisodium phosphate and ash raw material, and about 0.5 to 20 percent by weight of at least an alkali aluminum orthophosphate. 2) dishwashing agent according to claim 1, characterized in that it is 85 to 98 percent by weight of caustic alkali and about 2 to 15 percent by weight consists of at least one sodium aluminum orthophosphate. 3) Alkaline dishwashing detergent for automatic dishwashers with reduced aggressiveness against glass and glazed earthenware and porcelain, characterized in that it 20 to 80 percent by weight of a condensed phosphate as a builder, 5 to 65 percent by weight of one or more of the following ingredients, namely sodium silicate, detergent raw material Sodium chloride, trisodium phosphate, disinfectant, sodium sulfate, Sodium borate, sodium carbonate, chlorinated cyanuric acid derivative and chlorinated irisodium phosphate and at 0.5 to 20 percent by weight consists of at least one sodium aluminum orthophate. 4) Alkaline dishwashing agent according to claim 3, characterized in that that it essentially consists of the following components in the specified proportions: Parts by weight Sodium tripolyphosphate 30-60 Trisodium phosphate 5-30 Sodium metasilicate 10-50 ORIGINAL INSPECTED - 2 - 109809/1884 Components Parts by weight 20th Sodium 0 - 4th Laundry raw material 0 - 6th Alkaline aluminum orthophosphate 2 - ;?) Alkaline dishwashing detergent according to claim 3, characterized in that that it essentially consists of the following components in the specified proportions: Components parts by weight Sodium tripolyphosphate = 40 Irisodium Phosphate Sodium Metasilicate, Anhydrous Sodium Carbonate low-foaming detergent raw material sodium aluminum orthophosphate 6) Alkaline dishwashing agent according to claim 3, characterized in that that it essentially consists of the following components in the specified proportions: Components parts by weight Sodium tripolyphosphate 45 Sodium metasilicate 20 Sodium carbonate 10 chlorinated trisodium phosphate 20 low-foaming detergent 1 Sodium aluminum orthophosphate 4 7) Alkaline dishwashing agent according to claim 3, characterized in that that it consists essentially of the following ingredients in the specified There is a quantitative ratio: Ingredients Parts by weight sodium tripolyphosphate 40 Trisodium phosphate 10 liatrium metasilicate, anhydrous 35 latriuacarbonat 10 BATH ORIGINAL _ 109809/1884 - 5 - Components parts by weight low-foaming laundry detergent 1) Q. 4H ₂ O 4 Alkaline dishwashing agent according to Claim 3, characterized in that it is marked net that it essentially consists of the following components in the specified proportions: Components parts by weight Sodium tripolyphosphate 40 Irisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Low-foaming washing raw material 1 Na ₅ Al ₅ H ₁₅ (PO ₄ ) ₉ . 2, i> H ₂ 0 4 ) Alkaline Greschirrwaschmittel according to claim 3, characterized gekennzeict net that it essentially consists of the following components in the specified proportions: Components parts by weight Sodium tripolyphosphate 40 Trisodium phosphate 10 Sodium metasilicate, anhydrous 35 Sodium carbonate 10 Little foaming laundry fabric 1 ) Q 4 ) Alkaline dishwashing detergent according to claim 3, characterized gekennzeicfc net that it consists essentially of the following components in the given proportions: Components Parts by weight Sodium tripolyphosphate 45 Sodium metasilicate pentahydrate 20 Sodium . 10 chlorinated irisodium phosphate 20 BAD ORIGINAL low-foaming washing raw material 1 - 4 - 109809/1884 COPY Components parts by weight 15 Ha ₉ 0.2,8Al ₉ O ,,. 8P ₉ Uc.XH ₉ O (X =
6-15) ^ ^ 4 11) Alkaline dishwashing detergent according to Claim 3 »marked thereby net that it consists essentially of the following ingredients in the specified There is a quantitative ratio: Components parts by weight Sodium tripolyphosphate 45 Sodium metasilicate pentahydrate 20 Sodium carbonate 10 chlorinated irisodium phosphate 20
Low-foaming washing raw material 1 ü 4 12) Alkaline dishwashing agent according to claim 3, characterized net that it consists essentially of the following ingredients in the specified There is a quantitative ratio: Components Parts by weight Sodium tripolyphosphate 40 Irinatriumpho sphat 1U ■ Sodium metasilicate 35 sodium 9 Laundry raw material 1 Potassium dichloroisocyanurate 1 Sodium aluminum orthophosphate 4th 13) dishwashing agent according to claim 1 to 3, characterized in that that the content of alkali aluminum orthophosphate 5 to 20 percent by weight amounts to. 14) Method of reducing the aggressiveness of aqueous alkaline rinsing solutions against glass and glazed earthenware and porcelain, thereby £ indicates that the alkaline solutions are $ 0.5 to $ 20 109809/1884 ^G0PY on the dry weight of the Beatand parts of the cleaning solution, one Exposing alkali aluminum orthophosphates. Process according to claim 12, characterized in that sodium aluminum orthophosphate is used in amounts of 2 to bfo if the detergent is one for automatic dishwashing machines. For Stauffer Chemical Company Uew Iö6rk. , U.Y., Y.St.A. Law SAD GRIGiHAL 109809/1884