WO2017208472A1 - Composition détergente pour lave-vaisselle automatique - Google Patents

Composition détergente pour lave-vaisselle automatique Download PDF

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Publication number
WO2017208472A1
WO2017208472A1 PCT/JP2016/077325 JP2016077325W WO2017208472A1 WO 2017208472 A1 WO2017208472 A1 WO 2017208472A1 JP 2016077325 W JP2016077325 W JP 2016077325W WO 2017208472 A1 WO2017208472 A1 WO 2017208472A1
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Prior art keywords
group
cleaning composition
carbon atoms
cleaning
acid
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PCT/JP2016/077325
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English (en)
Japanese (ja)
Inventor
正 稲本
健 黒瀬
隆平 福島
美里 吉村
吉田　健二
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Niitaka Co Ltd
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Niitaka Co Ltd
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Priority to CN201680003793.XA priority Critical patent/CN107709531B/zh
Publication of WO2017208472A1 publication Critical patent/WO2017208472A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen

Definitions

  • the present invention relates to a cleaning composition for an automatic cleaning machine.
  • automatic washing machines such as an automatic dishwasher are used to wash used dishes or cooking utensils from the viewpoints of work efficiency and hygiene management.
  • automatic washing machines In general households, automatic washing machines have been rapidly spreading in recent years.
  • the performance required of a detergent composition used in an automatic washer includes low foaming (low foaming).
  • Patent Document 1 discloses (a) 0.1 to 5% by mass of a nonionic surfactant and (b) 0.1 to 10% by mass of polypropylene glycol as a detergent composition for a low-foam automatic dishwasher. Etc., the total surfactant concentration is 10% by mass or less, and a viscosity of 1000 to 4000 mPa ⁇ s is disclosed.
  • Patent Document 2 contains a nonionic surfactant (a) having a specific structure and a polyoxypropylene (b) having an average degree of condensation of oxypropylene groups of 10 to 90 in total of 0.1 to 20% by weight.
  • Patent Document 3 discloses a cleaning composition for an automatic dishwasher containing polyoxypropylene having an average degree of condensation of oxypropylene groups of 30 to 90.
  • the main type of automatic washing machine is a type that sprays high temperature (for example, 40 to 70 ° C) cleaning liquid to remove dirt such as dishes, but when the automatic cleaning machine is started up (starts operation), the water temperature of the cleaning liquid Is often as low as room temperature.
  • the temperature of the cleaning liquid is low (at a low temperature)
  • components such as a surfactant contained in the cleaning composition for an automatic cleaning machine tend to foam.
  • the foaming of the cleaning liquid is caused not only by a component such as a surfactant contained in the cleaning composition, but also by a substance brought in from dirt (food residue or the like) attached to the tableware or the like.
  • fouling is caused by food-derived soils such as oil stains, protein stains and starch stains.
  • the detergent compositions for automatic dishwashers of Patent Documents 1 to 3 have room for improvement to further improve the effect of suppressing such foaming at low temperatures and foaming due to dirt.
  • the automatic cleaning machine for business use usually has a higher foam suppression because it is washed with a high-pressure water flow than the automatic cleaning machine for home use, and higher foam suppression is required.
  • the detergent compositions for automatic dishwashers disclosed in Patent Documents 1 to 3 have insufficient foam suppression when used in commercial automatic washing machines, and there is room for improvement to further improve foam suppression.
  • the present invention has been made in order to solve the above-described problems, and can suppress foaming caused by low temperature foaming and dirt, and foaming even when used in a commercial automatic washing machine. It aims at providing the cleaning composition for automatic washing machines which can be controlled.
  • the cleaning composition for an automatic cleaning machine of the present invention comprises (a) an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl represented by the following general formula (2): 0.01 to 10% by mass in total of at least one compound selected from the group consisting of ethers, and (b) reverse pluronic block polymer, reverse tetronic block polymer, pluronic block polymer and tetronic type A total of 0.1 to 10% by mass of at least one surfactant selected from the group consisting of block polymers is included.
  • R 1 represents a residue obtained by removing all hydroxyl groups from a tri- to octavalent polyhydric alcohol having 3 to 20 carbon atoms, and A 1 O is the same or different and has 3 or 4 carbon atoms.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms
  • a 2 O is the same or different and represents an oxyalkylene group having 3 or 4 carbon atoms
  • t represents the average number of moles of oxyalkylene group added and is a number from 2 to 100.
  • the content (% by mass) of each component of the cleaning composition is the content of a pure component (in the cleaning composition) relative to the cleaning composition unless otherwise specified.
  • the cleaning composition for an automatic cleaning machine of the present invention includes (a) an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a general formula: 0.01 to 10% by mass in total of at least one compound selected from the group consisting of the polyoxyalkylene monoalkyl ethers represented by (2) (hereinafter also referred to as component (a)), and (b ) Total of at least one surfactant selected from the group consisting of reverse pluronic block polymer, reverse tetronic block polymer, pluronic block polymer and tetronic block polymer (hereinafter also referred to as component (b)) 0.1 to 10% by mass.
  • the detergent composition of the present invention can exhibit excellent foam suppression and detergency by containing the components (a) and (b) in the above amounts. For this reason, excellent foam suppression can be exhibited at low temperatures and in the presence of dirt such as food residues. Moreover, foaming can be suppressed even when the detergent composition is used in a commercial automatic washer.
  • foaming at low temperatures can be suppressed, and in washing dishes and the like by an automatic washing machine, for example, even when the washing liquid is cold when the washing machine is started up, the temperature is low.
  • the foaming of the cleaning liquid can be suppressed in the temperature range of the cleaning temperature.
  • contamination can be suppressed by containing the amount of a component (b), and even when a large amount of stain
  • the cleaning composition of the present invention has a high detergency by including the components (a) and (b) in the above amounts.
  • the cleaning liquid means an aqueous cleaning solution obtained by diluting or dissolving a cleaning composition for an automatic cleaning machine with water.
  • the low temperature in the present invention includes, for example, the case where the cleaning liquid temperature is less than 40 ° C., preferably the cleaning liquid temperature is 10 to 30 ° C., and more preferably the cleaning liquid temperature is 10 to 20 ° C.
  • the cleaning composition of the present invention can exhibit high foam suppression properties at such low temperatures.
  • R 2 preferably represents an alkyl group having 1 to 20 carbon atoms.
  • the polyoxyalkylene monoalkyl ether is such a polyoxyalkylene monoalkyl ether, the foam suppression at a low temperature is further improved.
  • R 2 represents an alkyl group having 3 to 15 carbon atoms
  • a 2 O represents an oxypropylene group
  • t is a number of 2 to 60. More preferred.
  • the polyoxyalkylene monoalkyl ether represented by the general formula (2) is more preferably polyoxypropylene tridecyl ether. When polyoxypropylene tridecyl ether is contained, the foam suppression at a low temperature can be further improved.
  • R 1 represents a residue obtained by removing all hydroxyl groups from a trivalent aliphatic alcohol having 3 to 5 carbon atoms
  • a 1 O represents an oxypropylene group
  • n represents 2 to Preferably, the number is 250 and m is 3.
  • the alkylene oxide adduct of polyhydric alcohol in component (a) is such a propylene oxide adduct of trivalent aliphatic alcohol, the foam-suppressing property at low temperature is further improved.
  • the molar ratio (EO / PO) of oxyethylene groups (EO) to oxypropylene groups (PO) in the reverse pluronic block polymer is preferably 1/10 to 1/2. More preferably, the molar ratio (EO / PO) is 1/6 to 1/2.
  • the foam suppression property in the presence of dirt is further improved.
  • the cleaning composition of the present invention preferably further contains at least one selected from the group consisting of an alkali agent, a chelating agent, a solubilizer, a bleaching agent, a corrosion inhibitor, a disinfectant, and an enzyme. It is preferable that the cleaning composition contains at least one of the above components in addition to the component (a) and the component (b) because the cleaning power and the like are further improved.
  • the cleaning composition for an automatic washing machine of the present invention is suitable as a cleaning composition for an automatic dishwashing machine or a container washing machine.
  • ⁇ 1-1> (a) Selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the above general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2)
  • a cleaning composition for an automatic cleaning machine comprising a total of 0.01 to 10% by mass of at least one compound and 0.1 to 10% by mass of (b) a reverse pluronic block polymer.
  • R 2 in the general formula (2) represents an alkyl group having 1 to 20 carbon atoms.
  • R 2 represents an alkyl group having 3 to 15 carbon atoms
  • a 2 O represents an oxypropylene group
  • t is a number of 2 to 60 -1> or ⁇ 1-2>
  • the automatic according to any one of ⁇ 1-1> to ⁇ 1-3>, wherein the polyoxyalkylene monoalkyl ether represented by the general formula (2) is polyoxypropylene tridecyl ether A cleaning composition for a cleaning machine.
  • R 1 represents a residue obtained by removing all hydroxyl groups from a trivalent aliphatic alcohol having 3 to 5 carbon atoms
  • a 1 O represents an oxypropylene group
  • n is a number from 2 to 250 and m is 3.
  • m is 3.
  • ⁇ 1-7> The above ⁇ 1-1> to ⁇ 1> further containing at least one selected from the group consisting of an alkali agent, a chelating agent, a solubilizer, a bleaching agent, a corrosion inhibitor, a disinfectant, and an enzyme 1-6>
  • ⁇ 1-8> The cleaning composition for automatic washing machines according to any one of the above ⁇ 1-1> to ⁇ 1-7>, which is a cleaning composition for automatic dishwashing machines.
  • the detergent composition for automatic washing machines which can suppress foaming at the time of low temperature, and foaming resulting from dirt, and can also suppress foaming when used for a commercial cleaning machine is provided. Is done.
  • the cleaning composition for an automatic cleaning machine of the present invention comprises (a) an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl represented by the following general formula (2): 0.01 to 10% by mass in total of at least one compound selected from the group consisting of ethers, and (b) reverse pluronic block polymer, reverse tetronic block polymer, pluronic block polymer and tetronic type A total of 0.1 to 10% by mass of at least one surfactant selected from the group consisting of block polymers is included.
  • R 1 represents a residue obtained by removing all hydroxyl groups from a tri- to octavalent polyhydric alcohol having 3 to 20 carbon atoms, and A 1 O is the same or different and has 3 or 4 carbon atoms.
  • R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms
  • a 2 O is the same or different and represents an oxyalkylene group having 3 or 4 carbon atoms
  • t represents the average number of moles of oxyalkylene group added and is a number from 2 to 100.
  • the component (a) is at least one selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2).
  • a kind of compound As a component (a), only 1 type of these compounds may be used and 2 or more types may be used together.
  • excellent foam suppression can be exhibited.
  • the foam-suppressing property at a low temperature is improved, and foaming at the start-up of the automatic washing machine can be suppressed.
  • foaming can also be suppressed when the cleaning composition is used in a commercial automatic cleaning machine.
  • R 1 in the general formula (1) represents a residue obtained by removing all hydroxyl groups from a tri- to octavalent polyhydric alcohol having 3 to 20 carbon atoms.
  • the trivalent to octavalent polyhydric alcohol having 3 to 20 carbon atoms include glycerol (glycerin), 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2, 3,4-pentanetriol, 3-methylpentane-1,3,5-triol, 2,4-dimethyl-2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3, Trivalent alcohols such as 4,5-heptanetriol, 1,3,5-cyclohexanetriol, pentamethylglycerin, trimethylo
  • trivalent to hexavalent polyhydric alcohols having 3 to 20 carbon atoms are preferable, and trivalent to hexavalent polyhydric alcohols having 3 to 10 carbon atoms are more preferable.
  • glycerol, sorbitol, pentaerythritol, and trimethylolpropane are preferable.
  • trivalent aliphatic alcohols having 3 to 5 carbon atoms are particularly preferable, and glycerol is most preferable.
  • the oxyalkylene group having 3 or 4 carbon atoms represented by A 1 O is an oxypropylene group or an oxybutylene group.
  • a 1 O preferably contains an oxypropylene group, and the ratio of the oxypropylene group in all oxyalkylene groups is preferably 50 mol% or more, more preferably 80 mol% or more, and 95 mol % Or more is more preferable.
  • a 1 O is an oxypropylene group.
  • a 1 O has an oxypropylene group and an oxybutylene group, these addition forms may be random or block-like.
  • n is preferably 2 to 250, more preferably 2 to 200, more preferably 2 to 100, still more preferably 10 to 100, and particularly preferably 15 to 100, most preferably 15-70.
  • m is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3.
  • the alkylene oxide adduct of the polyhydric alcohol represented by the general formula (1) preferably has an average addition mole number (n ⁇ m) of oxyalkylene groups per molecule of 10 to 300, more The preferred range is 40 to 150.
  • the mass average molecular weight of the alkylene oxide adduct of the polyhydric alcohol represented by the general formula (1) is preferably 250 to 40,000, and more preferably 500 to 10,000.
  • the mass average molecular weight is determined by gel permeation chromatography using polyethylene glycol (PEG) as a standard substance using N, N-dimethylformamide (DMF) as a developing solvent.
  • An example of a preferred embodiment of an alkylene oxide adduct of a polyhydric alcohol in the component (a) is a residue obtained by removing all hydroxyl groups from a trivalent aliphatic alcohol having 3 to 5 carbon atoms in R 1 in the general formula (1).
  • the three [—O— (A 1 O) n—H] may be the same or different.
  • R 1 represents a residue obtained by removing all hydroxyl groups from trimethylolpropane, pentaerythritol, or sorbitol
  • a 1 O represents oxypropylene.
  • n is a number of 5 to 50 (preferably 8 to 30) and m is 3, 4 or 6 is also preferred.
  • m [—O— (A 1 O) n—H] may be the same or different.
  • Component (a) in the present invention is preferably a polyoxyalkylene monoalkyl ether represented by the general formula (2).
  • R 2 in the general formula (2) represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms
  • a 2 O is the same or different and represents an oxyalkylene group having 3 or 4 carbon atoms
  • T represents the average number of moles added of the oxyalkylene group and is a number from 2 to 100.
  • R 2 is preferably an alkyl group having 1 to 20 carbon atoms.
  • the polyoxyalkylene monoalkyl ether in the present invention is preferably a polyoxyalkylene monoalkyl ether in the general formula (2) in which R 2 represents an alkyl group having 1 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, t-pentyl group, n-hexyl group, s-hexyl group, t-hexyl group, isohexyl group, n-heptyl group, s-heptyl group, t-heptyl group, isoheptyl group, n-octyl group, s-octyl group, t-octyl group , Isooctyl group, 2-ethylhexyl group, 3-ethylhexyl group, n-nonyl group, s-nonyl group, t-nonyl group, isononyl group, n-dec
  • an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 4 to 15 carbon atoms is more preferable, an alkyl group having 12 to 15 carbon atoms is further preferable, and an alkyl group having 13 carbon atoms is particularly preferable.
  • the alkyl group is preferably a branched alkyl group.
  • alkenyl group having 2 to 20 carbon atoms examples include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, hexenyl group and heptenyl.
  • linear or branched alkenyl groups such as a group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group and the like.
  • an alkenyl group having 4 to 15 carbon atoms is preferable.
  • a 2-butenyl group, 3-butenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, and pentadecenyl group are preferable, and a carbon number of 5 to 15 is preferable.
  • a tridecenyl group is particularly preferable.
  • the oxyalkylene group having 3 or 4 carbon atoms represented by A 2 O is an oxypropylene group or an oxybutylene group.
  • a 2 O preferably contains an oxypropylene group, and the ratio of the oxypropylene group in all oxyalkylene groups is preferably 50 mol% or more, more preferably 80 mol% or more, and 95 mol % Or more is more preferable.
  • a 2 O is an oxypropylene group.
  • t is preferably 2 to 60, more preferably 2 to 55, and still more preferably 2 to 10.
  • the mass average molecular weight of the polyoxyalkylene monoalkyl ether represented by the general formula (2) is preferably 150 to 5000, and more preferably 250 to 4000.
  • the mass average molecular weight is obtained by using DMF as a developing solvent and gel permeation chromatography using PEG as a standard substance.
  • R 2 represents an alkyl group having 3 to 15 carbon atoms
  • a 2 O represents an oxypropylene group
  • t is a number of 2 to 60.
  • R 2 represents an alkyl group having 4 to 15 carbon atoms (more preferably 12 to 15 carbon atoms)
  • a 2 O represents an oxypropylene group
  • t is 2 to A number of 60.
  • the polyoxyalkylene monoalkyl ether represented by the general formula (2) is preferably a polyoxypropylene monoalkyl ether in which R 2 is an alkyl group having 12 to 15 carbon atoms. Particularly preferred is propylene tridecyl ether. When polyoxypropylene tridecyl ether is contained, the foam suppressing property at low temperature is particularly good, which is preferable.
  • the polyoxypropylene monoalkyl ether (preferably polyoxypropylene tridecyl ether) in which R 2 is an alkyl group having 12 to 15 carbon atoms preferably has an average addition mole number (t) of oxypropylene group of 2 to 50 (more It is preferably 2 to 10, more preferably 2 to 8).
  • the cleaning composition of the present invention contains 0.01 to 10% by mass of component (a).
  • component (a) When the content of the component (a) is in the above range, the antifoaming property at a low temperature is good. If the component (a) exceeds 10% by mass, the cleaning action may be reduced.
  • the content of component (a) is preferably from 0.01 to 8% by mass, more preferably from 0.1 to 5% by mass, since foam suppression at a low temperature becomes better.
  • the said content is defined as those totals.
  • Component (b) in the present invention is at least one surfactant selected from the group consisting of a reverse pluronic block polymer, a reverse tetronic block polymer, a pluronic block polymer, and a tetronic block polymer.
  • Each of these surfactants may be used alone or in combination of two or more.
  • the component (b) preferably contains at least one surfactant selected from the group consisting of a reverse pluronic block polymer and a reverse tetronic block polymer, and the component (b) includes a reverse pluronic block polymer and It is preferably at least one selected from the group consisting of reverse tetronic block polymers.
  • component (b) is a reverse pluronic block polymer or a reverse tetronic block polymer. These may be used alone or in combination of two or more. Among these, as the component (b), a reverse pluronic block polymer is particularly preferable.
  • the mass average molecular weight of the reverse pluronic block polymer is preferably 1000 to 6000, more preferably 2000 to 5000.
  • the mass average molecular weight of the reverse tetronic block polymer is preferably 1000 to 6000, more preferably 3000 to 5000.
  • the mass average molecular weight of the pluronic block polymer is preferably 1000 to 6000, more preferably 1000 to 4000.
  • the mass average molecular weight of the tetronic block polymer is preferably 1000 to 6000, more preferably 1500 to 4000.
  • the molar ratio (EO / PO) of oxyethylene group (EO) to oxypropylene group (PO) in the reverse pluronic block polymer is preferably 1/10 to 1/2, and 1/6 to 1/2. It is more preferable that The molar ratio (EO / PO) of oxyethylene groups (EO) to oxypropylene groups (PO) in the reverse tetronic block polymer is preferably 1 / 0.5 to 1/10, and preferably 1 / 0.0. It is more preferably 5 to 1/5, and further preferably 1/1 to 1/3.
  • the molar ratio (EO / PO) of EO and PO in the pluronic block polymer is preferably 1 / 0.5 to 1/15, more preferably 1/2 to 1/12, and 1/4. More preferable is 1/9.
  • the molar ratio (EO / PO) of EO and PO in the tetronic block polymer block polymer is preferably 1 / 0.5 to 1/15, more preferably 1/2 to 1/12. 1/4 to 1/9 is more preferable.
  • the component (b) includes one or more of a reverse pluronic block polymer, a reverse tetronic block polymer, a pluronic block polymer, and a tetronic block polymer having an EO / PO molar ratio of the above ratio It is preferable because the foam suppression property in the presence of dirt is further improved.
  • the cleaning composition of the present invention contains 0.1 to 10% by mass of component (b).
  • component (b) By containing the component (b) in the above amount, excellent foam suppression can be exhibited. In particular, foam suppression in the presence of dirt is improved, and foaming can be suppressed even when a large amount of dirt is present in the cleaning liquid. Moreover, foaming can also be suppressed when the cleaning composition is used in a commercial automatic cleaning machine. Furthermore, a high detergency can be exhibited by including the component (b) in the above amount.
  • the content of the component (b) is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 8% by mass. When 2 or more types of compounds are contained in a component (b), the said content is defined as those totals.
  • the cleaning composition of this invention may also contain components other than a component (a) and a component (b).
  • the cleaning composition of the present invention may further contain at least one selected from the group consisting of an alkaline agent, a chelating agent, a solubilizer, a bleaching agent, a corrosion inhibitor, a disinfectant, and an enzyme. preferable. These may be used alone or in combination of two or more.
  • the cleaning composition contains an alkaline agent because the cleaning power is improved.
  • the alkali agent may be a water-soluble alkali agent, and for example, an alkali metal salt or an alkaline earth metal salt can be used.
  • the alkali metal salt is preferably at least one compound selected from the group consisting of alkali metal hydroxides, alkali metal phosphates, alkali metal carbonates, and alkali metal salts of silicic acid.
  • Alkali metal hydroxides such as sodium oxide and potassium hydroxide; Alkali metal phosphates such as trisodium phosphate; Alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; Sodium silicate (sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, sodium silicate 1, sodium silicate 2, sodium silicate 3, sodium silicate 4), potassium silicate (potassium metasilicate, sesquisilicate) An alkali metal salt of silicic acid such as potassium or potassium orthosilicate) is preferred. These alkaline agents may be hydrated.
  • alkali metal hydroxides and alkali metal salts of silicic acid are more preferred, and alkali metal salts of silicic acid are more preferred.
  • the compound illustrated as a chelating agent mentioned later is not contained in the alkaline agent in this invention.
  • the content of the alkaline agent is preferably 5 to 85% by mass with respect to the cleaning composition.
  • the content of the alkaline agent is within the above range, the detergency becomes higher.
  • the content of the alkali agent is preferably 10 to 50% by mass.
  • the content is determined as the total content of the alkali agents.
  • the cleaning composition contains a chelating agent because the cleaning power becomes higher.
  • the chelating agent include aminocarboxylic acid-based, hydroxycarboxylic acid-based, phosphoric acid-based, ether carboxylate, and phosphonic acid-based chelating agents.
  • aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), Ethylenetetramine hexaacetic acid (TTHA), glutamic acid diacetic acid (GLDA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2 -Hydroxypropane hexaacetic acid (DPTA-OH), aspartic acid diacetic acid (ASDA), ethylenediaminesuccinic acid (EDDS), or salts thereof.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotri
  • Examples of the hydroxycarboxylic acid-based chelating agent include malic acid, succinic acid, citric acid, lactic acid, tartaric acid, gluconic acid, and salts thereof.
  • Examples of the phosphoric acid-based chelating agent include tripolyphosphoric acid and hexametaphosphate.
  • phosphonic acid-based chelating agent examples include hydroxyethylidene diphosphonic acid (HEDP), nitrilotrismethylenephosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), and salts thereof. Is mentioned.
  • Examples of the salt in the chelating agent include salts of alkali metals such as potassium and sodium; salts of alkaline earth metals such as magnesium and calcium. Among them, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.
  • aminocarboxylic acid-based and phosphonic acid-based chelating agents are preferable, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid, or these.
  • a salt or the like is more preferable, and nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid or a salt thereof is more preferable.
  • the content of the chelating agent is preferably 5 to 85% by mass with respect to the cleaning composition. If the chelating agent is less than 5% by mass, generation of scale may be a problem. When a chelating agent exceeds 85 mass%, a detergency may become low.
  • the content of the chelating agent is preferably 30 to 50% by mass. When two or more chelating agents are included, the content is determined as the total content of the chelating agents.
  • the detergent composition contains a solubilizer
  • the solubilizer include aromatic acids or salts thereof, carboxylic acids or salts thereof, and alkyl polyglucosides. These may be used alone or in combination of two or more.
  • the aromatic acid include xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzoic acid and the like.
  • the carboxylic acid include citric acid, malic acid, succinic acid, tartaric acid, octylic acid, caprylic acid, and the like.
  • Examples of the salt include salts of alkali metals such as potassium and sodium, and amines such as monoethanolamine, diethanolamine and triethanolamine, among which sodium salt is preferable.
  • Examples of the alkyl polyglucoside include butyl polyglucoside. Among them, as the solubilizer, one or more of octylic acid, caprylic acid and butyl polyglucoside are preferable.
  • the content of the solubilizing agent is preferably 0.1 to 10% by mass, and preferably 1 to 8% by mass with respect to the cleaning composition. More preferred is 1 to 5% by mass.
  • the content is determined as the total content of the solubilizers.
  • bleaching agents for example, chlorinated isocyanurate (chlorinated sodium isocyanurate (sodium dichloroisocyanurate), chlorinated isocyanurate potassium (potassium dichloroisocyanurate), etc.), trichloroisocyanuric acid, hypochlorite (hypochlorite) And chlorine bleach such as sodium chlorate, potassium hypochlorite, calcium hypochlorite).
  • chlorinated isocyanurate and hypochlorite are preferable, and chlorinated sodium isocyanurate and sodium hypochlorite are more preferable.
  • the content of the bleaching agent is preferably 0.1 to 20% by mass with respect to the cleaning composition.
  • the bleaching agent is less than 0.1% by mass, the improvement of the cleaning power and disinfection effect, deodorizing action or bleaching action obtained by adding the bleaching agent may not be sufficient. If the bleaching agent exceeds 20% by mass, for example, when the bleaching agent is a chlorine bleaching agent, the chlorine odor may be a problem.
  • the content of the bleaching agent is preferably 2 to 10% by mass. When two or more kinds of bleaching agents are contained, the content is determined as the total content of each bleaching agent.
  • the corrosion preventing action (anticorrosive action) of the cleaning composition is improved.
  • the corrosion inhibitor it is preferable to use a corrosion inhibitor for aluminum, copper or a copper alloy.
  • corrosion inhibitors include benzotriazole or its derivatives (for example, benzotriazole, tolyltriazole, 5-dodecylbenzotriazole, 5-octylbenzotriazole, 5-hexylbenzotriazole, 5-butylbenzotriazole, 5- Methylbenzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, carboxybenzotriazole methyl ester, carboxybenzotriazole butyl ester, carboxybenzotriazole hexyl ester, benzotriazole octyl ester, dicarboxypropylbenzotriazole, etc.), benzimidazole or Derivatives thereof (for example, benzimidazo
  • the content of the corrosion inhibitor is preferably 0.001 to 5% by mass with respect to the cleaning composition. If the corrosion inhibitor is less than 0.001% by mass, there may be cases where sufficient corrosion prevention action cannot be exhibited. When the corrosion inhibitor exceeds 5% by mass, the influence of the odor peculiar to the corrosion inhibitor may become strong.
  • the content of the corrosion inhibitor is preferably 0.1 to 2% by mass. When two or more types of corrosion inhibitors are included, the content is determined as the total content of the respective corrosion inhibitors.
  • the cleaning composition contains a disinfectant
  • the disinfecting effect is improved.
  • the disinfectant include N, N ′, N ′′ -tris (hydroxyethyl) hexahydro-s-triazine, 4,4-dimethyloxazolidine, 2-octyl 4-isothiazolin-3-one, and alkyldimethylbenzylammonium.
  • the content of the disinfecting agent is preferably 0.1 to 30% by mass, and more preferably 0.1 to 15% by mass with respect to the cleaning composition.
  • the content is determined as the total content of each disinfectant.
  • the cleaning power is improved.
  • the enzyme include protease, esterase, lipase, nuclease, cellulase, amylase, and pectinase.
  • the cleaning power is improved by the function of the enzymes.
  • protease, amylase, and lipase are preferable.
  • proteases Commercially available enzymes that can be used as proteases include, for example, alcalase, sabinase, everase, cannase, esperase, ovozyme (Novozymes Japan Co., Ltd.), Pract, Properase, Plast OX (Genencor International).
  • Examples of commercially available enzymes that can be used as amylase include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry), Plaster ST, Plaster OxAm (Genencor International). It is done.
  • Examples of commercially available enzymes that can be used as the lipase include Entilon AKG-2000 (Santo Kasei Kogyo Co., Ltd.) and Lipozyme (Novozymes Japan Co., Ltd.).
  • the content of the enzyme is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, as the amount of enzyme protein, with respect to the cleaning composition.
  • the content is determined as the total content of each enzyme.
  • an enzyme stabilizer in order to suppress enzyme deactivation in a neutral to weak alkaline aqueous solution containing the alkaline agent.
  • the enzyme stabilizer it is preferable to blend at least one selected from boric acid or a boron compound capable of forming boric acid and a water-soluble calcium salt.
  • the compounding amount of the enzyme stabilizer is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, and still more preferably 1 to 5% by mass with respect to the detergent composition.
  • the cleaning composition of the present invention may contain a polymer dispersant having a mass average molecular weight of 3000 to 300,000. When such a polymer dispersant is contained, the scale preventing ability is improved. Only one type of polymer dispersant may be used, or two or more types may be used in combination. Examples of the polymer dispersant having a mass average molecular weight of 3000 to 300,000 include polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly- ⁇ -hydroxyacrylic acid, and polyvinyl.
  • Phosphonic acid sulfonated polymaleic acid, olefin-maleic acid copolymer, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer, Maleic anhydride ethylene cross-linked copolymer, maleic anhydride acrylic copolymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene Mutual weight , Maleic anhydride isoprene copolymer, poly- ⁇ -ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid, ethylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer Examples thereof include
  • the metal salt examples include salts of alkali metals such as potassium and sodium; alkaline earth metal salts such as magnesium and calcium. Among them, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.
  • the polymer dispersant having a mass average molecular weight of 3,000 to 300,000 in the present invention polyacrylate and olefin-maleic acid copolymer salt are preferable, and sodium polyacrylate and sodium salt of olefin-maleic acid copolymer are preferable. More preferred.
  • the cleaning composition contains a polymer dispersing agent having a mass average molecular weight of 3000 to 300,000
  • the content is preferably 0.1 to 20% by mass relative to the cleaning composition, 0.1 to 10 mass% is more preferable.
  • the content is determined as the total content of the respective polymer dispersants.
  • the mass average molecular weight can be obtained by using a phosphate buffer solution and acetonitrile as a developing solvent and gel permeation chromatography using polyacrylic acid as a standard substance.
  • a surfactant other than the component (b) may be used in the cleaning composition of the present invention.
  • the component (a) is not included in the surfactant in the present invention.
  • anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used, and nonionic surfactants are preferred.
  • nonionic surfactant examples include polyoxyalkylene dialkyl ether, polyoxyalkylene alkylphenyl ether, fatty acid alkanolamide, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester Sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, polyoxyethylene methyl ether fatty acid ester, polyoxyalkylene alkylamine and the like.
  • the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, substantially, relative to the detergent composition. Most preferably, no surfactant other than component (b) is contained.
  • the cleaning composition of the present invention may contain other components blended in the cleaning composition such as a solvent and a bulking agent as necessary. Moreover, you may contain an antifoamer in addition to a component (a) and a component (b) as needed. These may be used alone or in combination of two or more.
  • the solvent include water and organic solvents. As the organic solvent, a monohydric to trihydric alcohol can be preferably used.
  • Monohydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, polyethylene glycol, polypropylene glycol and the like divalent or trivalent polyhydric alcohols, etc. Is mentioned. Of these, divalent or trivalent polyhydric alcohols are preferable, and polypropylene glycol, propylene glycol, and 1,2-propanediol are more preferable.
  • the extender include sodium sulfate (sodium salt) and powdered silica.
  • the antifoaming agent include silicone-based antifoaming agents.
  • the dosage form of the cleaning composition of the present invention may be liquid or solid (powder, granules (granular), tablets, tablets, flakes, blocks, etc.). Preferred are liquid and solid.
  • the cleaning composition of the present invention is also suitably used for cartridge cleaning agents and the like.
  • the manufacturing method of the cleaning composition of the present invention is not particularly limited, and may be appropriately selected depending on the dosage form. For example, it can be produced by mixing or stirring the component (a), the component (b), and other components blended as desired. The order of mixing each component, the method of mixing or stirring, etc. are not particularly limited.
  • a solid detergent composition such as a block
  • water and raw materials of the detergent composition other than water are mixed by stirring to prepare a slurry liquid, and then the slurry liquid is prepared. It is preferable to put into a desired mold or container and cool and solidify.
  • a raw material for the cleaning composition other than water is added to water, and then maintained at 30 to 100 ° C. and stirred to prepare a slurry liquid containing water and the raw material for the cleaning composition.
  • the input amount of the raw material of the cleaning composition other than water is preferably 35 to 100% by mass relative to the total amount of the slurry liquid.
  • the slurry liquid is charged into a desired mold or container, and then the slurry liquid is allowed to solidify at room temperature for 1 to 24 hours to be solidified into a mold or container shape. Manufacturing things.
  • the ingredients (a) and (b), which are the ingredients of the detergent composition, and the particulate ingredients of other ingredients blended as desired are mixed. do it.
  • a ribbon mixer, a nauter mixer, and a drum mixer are preferably used.
  • the components (a) and (b), which are the raw materials of the cleaning composition, and other powdered raw materials mixed as desired are mixed. do it.
  • a ribbon mixer, a nauter mixer, and a drum mixer are preferably used.
  • the manufacturing method of a liquid cleaning composition is not specifically limited, It can manufacture by mixing or stirring arbitrary components. The order of mixing each component, the method of mixing or stirring, etc. are not particularly limited.
  • the automatic washing machine in which the cleaning composition for an automatic washing machine of the present invention is used is not particularly limited, examples thereof include a spray type automatic washing machine.
  • the spray type automatic washing machine include an automatic dishwashing machine and a container washing machine.
  • An example of the container is a plastic container used for transporting food or the like.
  • the cleaning composition of this invention is used suitably as a cleaning composition for automatic dishwashers or a container washing machine, and is used more suitably as a cleaning composition for automatic dishwashers.
  • the cleaning composition of the present invention is preferably used for commercial or household automatic washing machines, but is more suitable for commercial automatic washing machines, and is used for commercial automatic dishwashers. It is particularly suitable as an agent composition.
  • the cleaning composition diluted with water or dissolved in water.
  • the tableware or the like may be brought into contact with each other, and the concentration of the cleaning composition in the cleaning liquid is preferably 0.04 to 0.3% by mass.
  • Examples 1 to 100 The components shown in Tables 1 to 8 were blended so as to have the ratios shown in Tables 1 to 8, and mixed or heated and dissolved to prepare the cleaning compositions of Examples 1 to 100.
  • the numerical values in Tables 1 to 8 are ratios (mass%) of pure components of the respective components with respect to the cleaning composition.
  • ⁇ Detergency> (Cleaning conditions)
  • the cleaning composition was introduced into the cleaning liquid so that the concentration of the cleaning composition was 0.15% with respect to the amount of water in the automatic dishwashing machine.
  • a sample for washing test (a lunch box made of polypropylene coated with 1 g of composite dirt) was washed and the appearance was visually evaluated.
  • a door type washing machine (model number JW-650UF) manufactured by Hoshizaki Corporation was used, and washing conditions were a washing time of 60 seconds, a washing temperature of 60 ° C., a rinsing time of 5 seconds, and a rinsing temperature of 80 ° C.
  • Tap water was used as the washing water.
  • the cleaning power of the cleaning composition was evaluated as follows. A: No adhesion of dirt is observed. ⁇ : Almost no dirt is observed. X: Obvious residue of dirt is observed.
  • Tables 1 to 18 show the compositions and evaluation results of the cleaning compositions prepared in Examples and Comparative Examples.
  • the polyoxypropylene triol in the table is a propylene oxide adduct of glycerol.
  • PO means propylene oxide.
  • the “residue” in the table means that the balance obtained by subtracting the mass% of components other than water and mirabilite from 100 mass% of the cleaning composition is water or mirabilite.
  • the compounds of component (b) in Tables 1 to 16 are as follows.
  • Reverse pluronic block polymer (mass average molecular weight 4000): EO / PO molar ratio is 1/3 Reverse pluronic block polymer (mass average molecular weight 4500): EO / PO molar ratio is 1 / 3.5
  • Reverse tetronic block polymer (mass average molecular weight 4000) Reverse tetronic block polymer (mass average molecular weight 5000)
  • Pluronic block polymer (mass average molecular weight 2000): molar ratio of EO / PO is 1/7
  • Pluronic block polymer (mass average molecular weight 3000): EO / PO molar ratio is 1/7 Tetronic block polymer (mass average molecular weight 2500): EO / PO molar ratio is 1/7 Tetronic block polymer (mass average molecular weight 3000): EO / PO molar ratio is 1/7
  • the compounds used as the component (a ′) are as follows.
  • Polyoxyethylene triol mass average molecular weight 3000: glycerol ethylene oxide adduct polyoxyethylene polyoxypropylene triol (mass average molecular weight 2500): glycerol ethylene oxide and propylene oxide adduct aliphatic alcohol alkoxylate: manufactured by BASF, Product name Plurafac LF403
  • Polyoxyethylene polyoxypropylene alkyl ether 1 manufactured by Toho Chemical Industry Co., Ltd., trade name Pepol AS-054C
  • the detergent compositions of Examples 1 to 100 exhibited high foam suppression properties at low temperatures and in the presence of dirt. Further, the cleaning compositions of the examples were excellent in cleaning power. The cleaning compositions of Comparative Examples 1 to 116 could not suppress foaming at a low temperature or in the presence of dirt.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

L'invention concerne une composition détergente pour lave-vaisselle automatique qui comprend : (a) de 0,01 à 10 % en masse au total d'au moins un composé choisi dans un groupe constitué par un adduit d'oxyde d'alkylène comportant 3 ou 4 atomes de carbone d'un polyalcool et d'un éther de monoalkyle de polyoxyalkylène avec un groupe oxyalkylène comportant 3 ou 4 atomes de carbone ; et (b) de 0,1 à 10 % en masse au total d'au moins un type de tensioactif choisi dans un groupe constitué par un polymère séquencé pluronique inverse, un polymère séquencé tétronique inverse, un polymère séquencé pluronique et un polymère séquencé tétronique.
PCT/JP2016/077325 2016-05-30 2016-09-15 Composition détergente pour lave-vaisselle automatique Ceased WO2017208472A1 (fr)

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