JPH03239800A - Polymer-containing and phosphate-free liquid composition for use in cleaning - Google Patents

Abstract

PURPOSE: To enhance washing power especially against the contamination with food without using a phosphate builder by adding a specific water-soluble copolymer, an alkali metal hydroxide and an active chlorine source.

CONSTITUTION: A monoethylenic unsaturated monocarboxylic acid (e.g. acrylic acid) (a) in an amount of 95-30%, 5-70% of a monoethylenic unsaturated dicarboxylic acid (e.g. maleic acid) (b) and, if necessary, a carboxyl-free monoethylenic unsaturated monomer (e.g. methyl acrylate) are copolymerized to obtain a water-soluble copolymer (A) with a mol.wt. of 4000-100000. 20-25% of the component A, 2.5-35% of an alkali metal hydroxide (e.g. NaOH) (B), an active chlorine source (e.g. sodium hypochlorite) giving a washing concentrate having 1-5% of effective chlorine (C) and, if necessary, an auxiliary agent and water, etc., (D) are compounded.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an alkali metal hydroxide, an active chlorine source, a water-soluble copolymer of a monoethylenically unsaturated dicarboxylic acid and a monoethylenically unsaturated monocarboxylic acid, water, and optionally The present invention relates to alkaline aqueous cleaning concentrates and cleaning solutions comprising solutions containing alkali metal silicates. These cleaning solutions are effective in cleaning food stains. especially,
Effective in removing milk stains from cold and hot surfaces without the use of phosphate builders.

f1 views of the invention Dairy product stains consist of two components: the stains left behind by milk processing operations and the stains left behind at the end of cleaning operations. 11; Dirt resulting from hole processing operations can vary widely in composition depending on, for example, the breed of the cow, its age, and the source of the cow's feed; If the heated surface
It becomes tainted by certain components in milk that can be denatured, degraded or caramelized, making soil removal more difficult.

The second type of soiling results from the interaction between milk soiling residue and chemicals in the cleaning solution. The problem may consist of substantial accumulation of residual dirt on surfaces as a result of poor rinsing or cleaning of the equipment. This can lead to t/lJ bacterial growth which can cause serious health risks when processing additional milk with this equipment. Additionally, naturally occurring hardness ions in the water source used for rinsing or preparing concentrates or cleaning solutions constitute a further cleaning problem as they react with the cleaning solution and deactivate the builder components of the cleaning solution. There is.

Sodium polyphosphate has been used as the builder of choice in conventional aqueous cleaning solutions, but with the increasing use of liquid detergents, sodium tripolyphosphate has limited solubility in this case, and the ring J! As problems have increased, alternative compositions have been sought. However, reducing the use of phosphate also reduces the performance of the cleaning agent.

U.S. Pat. No. 4,579,676 uses polyacrylic acid in combination with phosphine polycarboxylic acid to disperse stains, eliminating the need for dirt! The patent claims a composition that purports to avoid the reduction in cleaning performance of acid-based cleaning compositions. This cleaning fluid is disclosed to be effective for cleaning previously clean food processing equipment when it becomes contaminated with fatty or oily soils. However, composition 1 disclosed in U.S. Pat.

Another patent, Belgian Patent Application No. 762,816M, discloses the use of reduced skewer phosphorus in a 61 cleaning solution. The solutions described contain low levels of alkali metal hydroxides of 0-0.4% by weight, sequestrants containing amino and carboxyl groups, 0.02-1% by weight of condensed phosphates, 0-0. 0.3% alkali metal silicon I! ! salt,
and 0.001 to 0.05 weight percent nonionic surfactant. This composition is surprisingly effective for cleaning heat exchangers used to pasteurize milk and other dairy products, as well as food industry equipment, with high efficiency and susceptibility to contamination. is low.

A third patent, European Patent No. 268.87334, discloses cleaning compositions based on quaternary ammonium compounds, alkyl ether carboxylic acids, alkali metal hydroxides, and complex-forming amino-polycarboxylic acids. ing.

This cleaning composition is claimed to be manufactured by Ryohin Kogyo, especially for dairy products.
It is effective in the al@ industry, does not foam, and has some sterilizing properties.

Summary of the Invention The present invention comprises an alkali metal hydroxide, an active chlorine source, a water-soluble copolymer of a monoethylenically unsaturated dicarboxylic acid and a monoethylenically unsaturated monocarboxylic acid, and optionally an alkali metal silicate. An aqueous cleaning condensate formulated as a water-dilutable aqueous concentrate, including: Yet another object of the present invention is to formulate an aqueous cleaning solution that does not contain any phosphorus, is suitable for removing food stains, and has efficient performance even at high levels of water hardness.

It has been found that the object of the present invention can be distantly achieved by using a copolymer of a monoethylenically unsaturated dicarboxylic acid and a monoethylenically unsaturated monocarboxylic acid in an alkaline chlorine-containing composition. The copolymer aids in the complete removal of residual fatty and oily soils.

DETAILS OF THE INVENTION Milk stains on incoming paper consist of protein-calcium-fat complexes. Although the mechanism of the method described herein is not completely understood, the copolymers contained in the detergent compositions of the present invention are capable of depositing protein-calcium-fat on the surface of stainless steel food processing 5A8. complexes and remove calcium, allowing other detergent ingredients to react with fats and proteins. When fats and proteins are in the sodified or ionized form, sodium hydroxide can saponify the fats, and chlorine can break down the proteins into water-soluble fragments. This assumption is supported by the fact that there are no cleaning problems when using non-fat milk as the soil source, as measured by the test procedure described herein. Additionally, the copolymer of the present invention has a higher affinity for calcium than the previously described acrylic homopolymer. moreover,
Since there is not enough polymer in the detergent bath to sequester all the hardness ions, especially at high concentrations, the polymer must not interact with calcium in specific localities, such as on the substrate surface. It does not modify washing by dispersing more soil or by interacting with calcium in the aqueous medium. The theory of the invention is presented here as a possible explanation for the surprising results obtained and is not intended to limit the scope of the invention in any way.

Substitution of the copolymers of the present invention in place of phosphorus-containing compounds should be considered in all areas where the use of phosphates is restricted. Most food stains are caused by fat, goshiroga,
The present invention is applicable to cleaning any hard surfaces, such as glass or metal, from which food stains must be removed. Some specific applications of the invention include automatic dishwashing detergents and standardized industrial dishwashing agents.

In general, the copolymers of the present invention are stable to effective bases, making them suitable for all situations requiring stain removal aids in alkaline, chlorinated liquids. tebrtjiI] function.

The present invention comprises an alkali metal hydroxide, an active salt source, a water-soluble J (polymer) of a monoethylenically unsaturated dicarboxylic acid and a monoethylenically unsaturated monocarboxylic acid, and optionally an alkali metal global V salt. Add 1111"g of alkaline hydrophilic cleaning concentrate and cleaning solution.

Specifically, the copolymer of the present invention, as a copolymerized monomer, contains 95 to 30% by weight of 7) J thyrenically unsaturated monocarboxylic acid and 5 to 70% by weight of monoethylenically unsaturated dicarboxylic acid. Contains units of.

A more preferred range is 90 to 70% by weight of monoethylenically unsaturated monocarboxylic acid and 10 to 30% by weight of monoethylenically unsaturated dicarboxylic acid, and more preferred t
! The range is 85 to 75% by weight of monoethylenically unsaturated monocarboxylic acid and 15 to 25% by weight of monoethylenically unsaturated dicarboxylic acid.

The starting materials used for the production of these copolymers are monoethylenically unsaturated dicarboxylic acids containing 4 to 6 carbon atoms per molecule, their alkali metal and ammonium salts,
and cis dicarboxylic acid anhydrides. Examples of suitable monomers are maleic acid, itanilic acid, mesaconic acid, fumaric acid, cy]-laconic acid, and anhydrides of cisdicarboxylic acids, such as 7-leic anhydride. , maleic anhydride is the more desirable of these monomers.

[Starting] Mono7- includes monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms per molecule, and includes acrylic acid, methacrylic acid, vinyl[1], crotonic acid, and acryloxypropionic acid. be. A more preferred monoethylenically unsaturated monocarboxylic acid is acrylic acid.

Other starting carapaces are monoethylenically unsaturated carboxyls containing no carboxyl, and include alkyl esters of acrylic or methacrylic acid, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate. , and isobutyl methacrylate: hydroxyalkyl esters of acrylic or methacrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate, human 0xyethyl methacrylate, and hydro4sibyl methacrylate; acrylamide, methacrylic 7mide, N-tert-butyl Acrylamide, N-methylacrylamide, N,N
-Di-methylacrylamide: acrylonitrile, methacrylaterile, allyl alcohol, 7lyl sulfonic acid, 7lylphosphonic acid, vinylphosphonic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, ethylene glycol diacrylate, trimethylolpropane triacrylate, diallyl phthalate,
These include vinyl acetate, styrene, vinyl sulfonic acid and its salts, and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its salts. The concentration of non-carboxyl-containing monoethylenically unsaturated monoa may be from 0 to about 80% by weight of the total hull concentration. Concentrations are typically up to 35%, depending on the solubility of the specific monomer in the reaction mixture.

These copolymers are prepared by a heel charge process in which the monoethylenically unsaturated dicarboxylic acid is placed in a reactor, an initiator is supplied to it, and the monoethylenically unsaturated monocarboxylic acid is added; It is produced by a simultaneous feeding process in which monoethylenically unsaturated dicarboxylic acid and monoethylenically unsaturated monocarboxylic acid are fed simultaneously. This simultaneous feeding process is disclosed in US Patent Application No. 353.376, commonly assigned to the same assignee of the present invention.

Aqueous gel permeation chromatography (GPC)
) has a molecular mMw range of approximately 4.0
00 to 100,000, more preferably about 10,000
~30,000. Even more preferably about 10,000
~25,000.

The alkali metal hydroxide can be of any type customary in this field, e.g.
Sodium hydroxide, potassium hydroxide, or a mixture thereof. The chlorine source may be either inorganic or organic, and includes alkali metal and alkaline earth metal hypozinc acid salts, hypochlorite addition products, lamins and chloramines, lamides and chlorimides, and the like. . Typically, these compounds include putrium hypochlorite, potassium hypochlorite, -basic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, Potassium dichloroisocyanurate,
Trichlorocyanuric acid, dichloroisocyanuric acid dihydrate, 1,3-tclIcl-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T1 dichloramine T1 chloramine B, dichloramine B1 with chlorine gas or mixtures thereof be. A more preferred chlorine source is sodium hypochlorite.

Cleaning No. 11i of the present invention! The substance is alkali metal hydroxide2.
5-35%, more preferably 5-15%, even more preferably 10%: available chlorine 1-5%, J: more preferably 2-4%, even more preferably 3%; polymer solids,
It contains 25-20%, more preferably 3-15%, more preferably 5.1%, with the balance being water or other ingredients well known to those skilled in the art. Optionally, sodium silicate may be used at a level of up to 10%, more preferably 2-7%, more preferably 4.7% sodium silicate solids.

Other ingredients which may be contained in the cleaning concentrates and/or cleaning solutions of the invention are all useful auxiliaries found in detergents of this type, such as inorganic phosphates, citrates, edgelenediamines. Tetraacetic acid, nitri-triacetic acid,
It is a homopolymer of carboxyalkylamine, surfactant, and polyacrylic acid. To produce the cleaning solution of the present invention, the cleaning concentrate may be diluted with water to about 0.1-10%.

Representative procedures for synthesizing the polymers used in the present invention are illustrated in the Examples below.

EXAMPLE - Preparation of Polymer In a 21-fourth flask equipped with a mechanical stirrer, a reflux condenser, and an addition funnel, 190 g of deionized water and 0.0 g of copper (If) sulfate pentahydrate dissolved in deionized water were added. 6 g of .15 wt% solution and 42.49 g of anhydrous maleic Fi were added. The solution was heated to reflux while adding 82009 glacial acrylic, 4 (l) deionized water and 12 liters of sodium persulfate.
,5! J initiator solution and a neutralizing solution of 50% sodium hydroxide 2179 (75 equivalent % relative to monomer) were fed linearly and separately to the flask over a period of 2 hours;
During that time, the distant current was maintained. Once the addition was complete, the system was kept at reflux for 20 minutes, then cooled to 60°C, and the solution was quenched by the addition of 525 J of 50% aqueous sodium hydroxide.

The resulting polymer solution with a pH of 6.7 had a solids content of 46.0%. Based on gel permeation chromatography (GPC), the weight average molecular weight (Mw) is 1
5.200 and the number average molecular ml (Mn) is 7
It was 440. The residual maleic acid content was 0.2% and the residual acrylic acid content was 0.01%.

Detergent Testing The detergent formulation utilized in the testing of the present invention had the following composition: 10% sodium hydroxide, 3% available chlorine, and 5.1% polymer solids. In some tests, 14% levels of sodium hydroxide were used to examine the effect of high levels of alkali on cleaning performance when compared to the use of cleaning-enhancing polymers. In addition, some tests have shown that sodium silicate has a sodium silicate solid content of 4.7%.
used at the level of This equates to approximately 3.3% silicate solids (SiO2). The performance of these detergent compositions was compared to a representative commercial product, Interest ■ (commercial product of Diversei D&T Co., Ltd.) detergent, which is a phosphate-based composition.

Both the inventive detergent and the zero interest detergent were tested at concentrations from about 0.1% usage level (relative to base) to about 2% detergent in bath concentration. The detergent was primarily tested against multi-cycle deposited cold milk stains. The soiled body in this test was a 304 stainless steel panel measuring 1" x 3" x 037". The water used for diluting the detergent and cleaning the panel was
It had a hardness of 10,001) l~aooppm as O3 and 225 ppm of sodium bicarbonate, ignoring water hardness.

The panel stained with low-temperature milk was created as follows. Pre-clean the panel with methanol and place it in the
It was soaked in a 1% solution of detergent for 15 minutes, rinsed with deionized water, and then dried. The chemically cleaned flasks (6 pieces at a time) are then immersed approximately 7/8 of their length in fresh whole milk (vitamins A & D, not skimmed or low fat); Then, it was stirred for exactly 15 minutes. This is the dirty part of the exam.

After the 15 minute staining process, the panels were removed and Ca
2001) DI(7) hardness as CO3 120
Rinse with running water from the tap below. Each test panel was then cleaned in a detergent solution kept at 60°C in a shaker tank. The detergent solution had the water hardness and detergent concentration listed in the Examples.

The detergent solution was added as an additional stress to the test.
It also contained drops of milk. Stir the panel into the detergent solution.
After 0 minutes of exposure, the test pulse was removed and 120 minutes
Rinse under running tap water at °F.

This constitutes one cycle.

The panels were then returned to the milk bath to begin the second cycle of soiling and cleaning. In all, each panel was subjected to five complete soil-clean-rinse cycles.

After the last rinse in tap water, the panels were immersed in a 1% protein dye solution for 2-3 minutes.The protein dye used was Safranin ■0. The dye solution immediately adhered to any milk stains present that were not removed by the cleaning solution. Depending on the amount of milk stain left on the panel, the degree of red staining obtained varied; the darker the red stain, the more milk stain was left on the panel. The stained panel was then dried with forced hot air and evaluated using the following scale: Appearance Panel is clean.

A cystic membrane is observed, but there is no red coloring.

Some red staining is visible.

The visible red coloration covers more than 50% of the panel.

Red coloring covers the entire panel.

A very deep red color covers the entire panel.

Test results demonstrate that the detergent of the present invention is effective in removing milk stains. The results also indicate high water hardness (>30
0(11)I), the copolymers of the invention are superior to the previously described acrylic homopolymers, even at equal molecular weights.

At high hardnesses, all polymer formulations tended to allow scale formation on the test panels. By adding sodium silicate, this scale formation was prevented in the copolymers of the present invention, but not in the acrylic homopolymers.

Example 1 Example 2 Water usage level: 10001) 1 Water pupil level: 400 ppm Staining grade 1 (2) 1 (2) 0 (1) 0 (1) 0 (1) 2 (3) No school --- −−−−−−−−−−−−−−−−−−−
---1 staining grade 3 (3) 1 (1) 2 (2) 3 (3) No scale --- 11111111 ---→Karisho: /1.500MW polyacrylic Awakening 1-rium wood invention copolymer: A-15,200Mw 80: 207 kryl: malein, NajUF3-1
5.300Mw 80: 20 Acrylic: Malein, Na salt C-30,
000 Mw 65: 35 Acrylic: Maleic, Nal Control: 4.500 Mw Sodium Polyacrylate Copolymer of the Invention: A-15,300 Mw 80: 207 Acrylic: Maleic, Na Salt B-20,
000Mw 90:10 Acrylic: Malein, Na Salt water hardness: 400
ppm Example 3 Water hardness: 400 ppm Example 4 Staining grade 3 (3) 3 (3) 0 (1) 1 (2) 3 (3) 3 (3) Scale None---------------------- −−−−−−−
-111---◆Dyeing grade 3 (3) 3 (3) 0 (1) 1 (
2) 3(3) 3(3) School None --
11------------------11→S・
1 reference: 4.500Mw Sodium polyacrylate Copolymer of the present invention: A-15,300MW 80:20 Acrylic: maleic, Na salt B-3,3
90MW 70:20:10 Acrylic: Marein = AMP81Na
Salt C-18,000Mw 45:35:20 Acrylic:Maleic:MAA.

1'4a salt control: 4.500 Mw sodium polyacrylate copolymer of the invention: A-15,300 Mw 80:20 acrylic: maleic, Na salt B-26,
000Mw 80: 207 Krill: Malein, NajMC-20
,000Mw 80: 20 Acrylic: Malein, Na Salt Seed Example 5 Actual Drop Example 6 Hydraulic Interval: 400 DI) III Ink Draft 1 Kyoka■ko L-Danichi CD Dyeing Grade 3 (4) Hll Hl)
2 (212, 5 (3) 2.5 (31 scale None - 11 - Lightly None Hydraulic interval: 4001) l) Ill Staining grade scale 3 (430 (1) ) 2(2) 2.5(3)
3 (412, 5 (3) none------------------→
Control: 4.500Mw Polyacrylic mf Thorium Copolymer of the Invention: A-15,300MW 80:20 Acrylic: Malein, Na salt t'3-1
5,200Mw 80: 20 acrylic: 7 rain, Na salt C-20,
000Mw 80: 20 acrylic; malein, Na salt D-30,
000 Mw 65:35 Acrylic: Maleic, Na salt Control: 4.500 MW Polyacrylate Zutrium Copolymer of the invention: A-15,300 MW 80:20 Acrylic; Maleic, Na salt 13-9.
100Mw 80: 20 Acrylic: Malein, Na salt C-8,6
00Mw 70:30 Acrylic: Malein, Na salt D-12,00
0Mw 65:35 Acrylic: Malein, Na Salt water hardness: 400
DpII Example 7 Hydraulic space: 400 ppm Example 8 Staining grade 3 (4) 0 (1) 1 (2) 3 (
4) 3 (4) 2 (3) School None -
11---------→ Light staining grade 3 (410 (1) 0 (1) 2 (
3) 2(3) 1(2) Scale None Light None Moderate None Control: 4.500Mw Polyacrylate Pttrium Copolymer of the Invention: A-15,300Mw 80:20 Acrylic: Malein, Na salt B -9,1
00Mw 65:35 Acrylic: Marein, NaPAC-17,6
00Mw 65:35 Acrylic: Malein, Na salt 1) -19,0
00 Mw 80:20 acrylic: maleic, Na MA control: 4.500 Mw sodium polyacrylate Copolymer of the invention: A-15,300 Mw 80:20 acrylic: maleic, Na salt B-8,4
00Mw 76: 24 Acrylic: Malein, Na salt C-17,
400Mw 84:16 Acrylic: Malene, Naffa D-14,
100Mw 76:24 Acrylic: Malein, Na salt Example 9 Example 10 Water isthmus: /Iooppm Dyeing 2q class 3 (!+) 0 (1) 1 (2) 2.5<
3) 2.5 (3) 3 (4) scale
1−−−−−−→ Medium−−−−1−−→Water hardness:
4001)l)III Ink Control Rest o ABCD Dyeing Grade 3(5) 0(1) 1(
2) 1 (2) 2 (3) 2.5 (4) School None-1
----1 sentence/1 reference: 4.500Mw Sodium polyacrylate Copolymer of Honbimei: A-15,300Mw 80: 207 Crylinimalein, Na base 13-3,
650Mw 80: 20 Acrylic: Malein, Na salt C-3,8
50Mw 80:20 Acrylic: Malein, Na salt D-5,700
Mw 70:20:10 Acrylic: Malene: MAA.

Na salts 4: 4.500Mw Polyacrylate mono-lithium Copolymer of the present invention: A-15,300Mw 80: 207 Kryl: Malein, Na mB-5
6,000Mw 80: 207 krill: 7 rain, NaJluC-1
2,000Mw 85:35 Acrylic: Malein, Na salt D-49,00
0Mw 80: 20 Acrylic: Malein, Na salt Example 11 Water tenacity: 600ppm Dyeing grade 3(3)--1(1) 1(1) 2(2)
2 (2) Scale Slightly Severe None-1-
−−−−−−−−→S4 jjlJ: 4.500Mw sodium polyacrylate Honkomei no (
Polymer: 8-15,300Mw 80:20 Acrylic: Malein, Na salt B-12
, OOOMW 65235 Acrylic: Malene, Najj: C-15,
200Mw 80: 207 Kryl: Malein, Na salt Example 12 Water hardness 2000ρρm Ink 41 L 111'1fWS + 02 1m -1
None None 1.7X 3.3m staining grade
3 (3) 0 (1) 2 (2)
2(2) 2(2) 2(2) Scale Moderate None None Slightly None None Control: 4.500Mw Sodium Polyacrylate Copolymer of the Invention: A-15,300Mw 80: 20 Acrylic: Malein, Najj :B-1
4,700Mw 80:20 Acrylic: Malene, Naj! Real JII side 1
3 Example 1 Water reflection rate: 1 factor j and 8102 9th grade scale 6001) l) III inkrest (1 re contrast no control 0 (1) 4 (5) none none ■ - once rubbed 1.7 % None 1.7x 3(4) 1(2) 1(2) None Medium None 0.9X 2(3) (Leather water hardness: Polymer product dyeing grade scale 400 ppn+ ×1 ×2 ×4 2 (3) 2(3) 1(2) 0(1) 1(2) 0(1) shi-1------------------111-→
Control: 4.500 Mw Sodium Polyacrylate Copolymer of the Invention: B-14,700 Mw 80:20 Acrylic: Maleic, Na Salt Control: 4.500 MW Sodium Polyacrylate Copolymer of the Invention: A-15, 300Mw 80: 20 Acrylic: Malein, r″+aPA water hardness: 400ppm Togoitaigaki dyeing customer grade scale x 1 4 (season 0 (1) Example 15 x 1 X, 75 X, 75X, 50 0 (1) 2 ( 3) 1(2) 2(3)
None------------------------------→S4: 4.500MW Sodium polyacrylate Copolymer of the present invention: A-15,300Mw 80: 20 acrylic : Malein, Na salt Example 16 Water hardness: 400 ppm Ink vs. -N Rest -Danichi So -〇-Dyeing grade 1 (2) 0 (1) 1 (2) 1 (2)
1(2) 1(2) Scale None-1--
-------→Medium Light control: 4.500 Mw Sodium polyacrylate Copolymer of the present invention: A-15,300 Mw 80: 20 Acrylic: maleic, Na salt B-11,
600Mw 75: 25 Acrylic: Malein, Na salt C-11,
500Mw 70:30 Acrylic: Marein, NajmD-14,7
00Mw 80: 20 Acrylic: Malein, Na salt Example 17 Example 1B Water steepness: Deionized water Ink ash Q Ripper □1 Soil dyeing Bitter grade 0 (1) 0 (1) 0 (110 (1)
0 (1) 0 (l) No scale - - - - - - - - - - - - - - - - - - - - -
→Water hardness: 600ppm Staining grade 3 (3) 3 (3)? 1n
1 (1)? 1 (1) 1.5 (2) No school Severe None Severe f, K L/-11 → Control: 4.500 MW Sodium polyacrylate Copolymer 2 of the present invention A-15,300 Mw 80: 20:/ 'Krill:? Rain, NaJnD-
11,600Mw 75: 25 acrylic; Malein, NamC-11,
500Mw 70:30 acrylnimalein, Na salt D-14,70
0 Mw 80: 20 Acrylic: maleic, Na salt Control: 4.500 Mw polyacrylic chutrium Copolymer of the present invention; A-15,300 Mw 80: 207 Acrylic: maleic, Na salt B-18,
000Mw Sodium polyacrylate C-14,700
Mw 80: 20 Acrylic: maleic, pea salt Example 1
9 Water sand 1a: 400 DDIII detergent contains 11% sodium hydroxide.

Ink raw 12 你"L-Danichi-Δ-" Length ia body suspension X1 -- Xi X2
Xl Xi staining etc'l 3(5) 1
(2) 2 (3) 2.5 (4) 0 (1)
2 (3) School None None Lightly None None Lightly Control 2 4.500Mw Sodium polyacrylate Copolymer of the present invention: A-15,300Mw 80:20 Acrylic: Malein, Na salt 8-18,00
0Mw Sodium polyacrylate C-14,700Mw

Claims (13)

[Claims] (1) (a) about 95 to 30% monoethylenically unsaturated monocarboxylic acid and about 5 to 70% monoethylenically unsaturated dicarboxylic acid and optionally a carboxyl-free monoethylenically unsaturated monomer; A water-soluble copolymer having a molecular weight of about 4,000 to 100,000 and having a monomer unit consisting of about 25 to 2
(b) about 2.5-35% alkali metal hydroxide; and (c) a source of active chlorine to provide a cleaning concentrate with about 1-5% available chlorine. (2) a patent in which the monoethylenically unsaturated dicarboxylic acid is selected from the group consisting of maleic acid, itaconic acid, mesaconic acid, fumaric acid, citraconic acid, and anhydrides of cisdicarboxylic acids such as maleic anhydride; A cleaning concentrate according to claim 1. (3) The cleaning concentrate according to claim 1, wherein the monoethylenically unsaturated dicarboxylic acid is maleic acid. (4) The cleaning concentrate of claim 1, wherein the monoethylenically unsaturated monocarboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, and acryloxypropionic acid. . (5) The cleaning concentrate according to claim 1, wherein the monoethylenically unsaturated monocarboxylic acid is acrylic acid. (6) the carboxyl-free monoethylenically unsaturated monomer is an alkyl ester of acrylic or methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and isobutyl methacrylate; hydroxyethyl Hydroxyalkyl esters of acrylic or methacrylic acid such as acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, methacrylamide, N-t
ert-butylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide; acrylonitrile, methacrylonitrile, allyl alcohol, allylsulfonic acid, allylphosphonic acid, vinylphosphonic acid, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, phosphoethyl methacrylate, N-
Vinylpyrrolidone, N-vinylformamide, N-vinylimidazole, ethylene glycol diacrylate,
Claims selected from the group consisting of trimethylolpropane triacrylate, diallyl phthalate, vinyl acetate, styrene, vinylsulfonic acid and its salts, and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its salts. Cleaning concentrate of item 1. (7) the copolymer is produced from a monomer mixture of about 85 to 75% monoethylenically unsaturated monocarboxylic acid and about 15 to 25% monoethylenically unsaturated dicarboxylic acid; A cleaning concentrate according to claim 1. (8) the copolymer is produced from a monomer mixture of 80% acrylic acid and 20% maleic acid;
A cleaning concentrate according to claim 1. (9) the alkali metal hydroxide is sodium hydroxide;
A cleaning concentrate according to claim 1, consisting of potassium hydroxide, or a mixture thereof. (10) The copolymer has a molecular weight of about 10,000 to 25,000
A cleaning concentrate according to claim 1, having a molecular weight of . (11) The cleaning concentrate according to claim 1, wherein the active chlorine source is an alkali metal hypochlorite. (12) The cleaning concentrate according to claim 1, wherein the active chlorine source is sodium hypochlorite. (13) About 0.1% of the concentrate of claim 1 in water
Cleaning solution produced by diluting to ~10%.