WO2017208472A1 - Detergent composition for automatic dishwasher - Google Patents

Detergent composition for automatic dishwasher 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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WIPO (PCT)
Prior art keywords
group
cleaning composition
carbon atoms
cleaning
acid
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PCT/JP2016/077325
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French (fr)
Japanese (ja)
Inventor
正 稲本
健 黒瀬
隆平 福島
美里 吉村
吉田　健二
Original Assignee
株式会社ニイタカ
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Application filed by 株式会社ニイタカ filed Critical 株式会社ニイタカ
Priority to CN201680003793.XA priority Critical patent/CN107709531B/en
Publication of WO2017208472A1 publication Critical patent/WO2017208472A1/en

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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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Abstract

A detergent composition for an automatic dishwasher that includes: (a) 0.01 to 10% by mass in total of at least one compound selected from a group consisting of an alkylene oxide adduct having 3 or 4 carbon atoms of a polyalcohol and a polyoxyalkylene monoalkyl ether with an oxyalkylene group having 3 or 4 carbon atoms; and (b) 0.1 to 10% by mass in total of at least one type of surfactant selected from a group consisting of a reverse pluronic block polymer, a reverse tetronic block polymer, a pluronic block polymer, and a tetronic block polymer.

Description

自動洗浄機用洗浄剤組成物Cleaning composition for automatic cleaning machine
本発明は、自動洗浄機用洗浄剤組成物に関する。 The present invention relates to a cleaning composition for an automatic cleaning machine.
ホテル、レストラン等においては、作業の効率化、衛生管理などの観点から、使用後の食器又は調理器具の洗浄に自動食器洗浄機等の自動洗浄機が用いられている。また、一般家庭においても、近年急速に自動洗浄機が普及している。自動洗浄機に用いられる洗浄剤組成物に求められる性能として、洗浄力が高いことに加えて、泡立ちが少ないこと（低泡性）が挙げられる。 In hotels, restaurants, etc., 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. In general households, automatic washing machines have been rapidly spreading in recent years. In addition to high detergency, the performance required of a detergent composition used in an automatic washer includes low foaming (low foaming).
特許文献１には、低泡性の自動食器洗浄機用の洗浄剤組成物として、（ａ）非イオン界面活性剤０．１～５質量％、（ｂ）ポリプロピレングリコール０．１～１０質量％等を含有し、全界面活性剤濃度が１０質量％以下であって、粘度１０００～４０００ｍＰａ・ｓの液状洗浄剤組成物が開示されている。特許文献２には、特定構造の非イオン界面活性剤（ａ）と、オキシプロピレン基の平均縮合度が１０～９０であるポリオキシプロピレン（ｂ）とを合計で０．１～２０重量％含有し、且つ（ａ）と（ｂ）の重量比が（ａ）／（ｂ）＝１／２～１／１である自動食器洗浄機用洗浄剤組成物が開示されている。特許文献３には、オキシプロピレン基の平均縮合度が３０～９０であるポリオキシプロピレンを含有する自動食器洗浄機用洗浄剤組成物が開示されている。 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. In addition, a detergent composition for an automatic dishwasher in which the weight ratio of (a) and (b) is (a) / (b) = 1/2 to 1/1 is disclosed. 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.
特許第５０６４０４５号公報Japanese Patent No. 5064045 特許第３４１３３５１号公報Japanese Patent No. 3413351 特許第２９３１５７１号公報Japanese Patent No. 2931571
自動洗浄機は、高温（例えば、４０～７０℃）の洗浄液を噴射して食器等の汚れを落とすタイプのものが主流であるが、自動洗浄機の立ち上げ（運転開始）時には、洗浄液の水温は室温程度の低温である場合が多い。このように洗浄液の温度が低い場合（低温時）には、自動洗浄機用洗浄剤組成物に含まれる界面活性剤等の成分が泡立ち易い。また、洗浄液の泡立ちは、洗浄剤組成物に含まれる界面活性剤等の成分に起因するだけでなく、食器等に付着した汚れ（食品残渣等）から持ち込まれる物質によっても発生する。例えば、油汚れ、タンパク質汚れ、デンプン汚れ等の食品由来の汚れによって、泡立ちが引き起こされる。特に激しい泡立ちを引き起こすのはタンパク質汚れであり、代表的なものとして卵汚れが挙げられる。特許文献１～３の自動食器洗浄機用洗浄剤組成物は、このような低温時の泡立ちや、汚れに起因する泡立ちの抑制効果をより向上させる改善の余地があった。
また、業務用自動洗浄機では、通常家庭用自動洗浄機よりも高圧の水流で洗浄を行うため泡立ちも多く、より高い抑泡性が必要とされる。特許文献１～３の自動食器洗浄機用洗浄剤組成物は、業務用自動洗浄機で使用する場合に抑泡性が不充分であり、抑泡性をより高める改善の余地があった。 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. Thus, when 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. In addition, 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. For example, fouling is caused by food-derived soils such as oil stains, protein stains and starch stains. In particular, protein fouling causes intense foaming, and typical examples include egg fouling. 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.
In addition, 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.
本発明は、上記のような課題を解決するためになされたものであり、低温時の泡立ち及び汚れに起因する泡立ちを抑制することができ、業務用自動洗浄機に使用した場合にも泡立ちを抑制することができる自動洗浄機用洗浄剤組成物を提供することを目的とする。 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.
本発明の自動洗浄機用洗浄剤組成物は、（ａ）下記一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び下記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物を合計で０．０１～１０質量％、及び、（ｂ）リバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤を合計で０．１～１０質量％含むことを特徴とする。 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.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式中、Ｒ１は、炭素数３～２０の３～８価の多価アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｎは、オキシアルキレン基の平均付加モル数を表し、２～１０００の数であり、ｍは、３～８の整数を表し、ｍ個の〔－Ｏ―（Ａ１Ｏ）ｎ－Ｈ〕は同一であってもよく、異なっていてもよい。） (Wherein 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. Represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, is a number of 2 to 1000, m is an integer of 3 to 8, and m [—O— (A 1 O NH] may be the same or different.)
（式中、Ｒ２は、炭素数１～２０のアルキル基又は炭素数２～２０のアルケニル基を表し、Ａ２Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｔは、オキシアルキレン基の平均付加モル数を表し、２～１００の数である。） (Wherein R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and 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.)
本明細書中、洗浄剤組成物の各成分の含量（質量％）は、特に断らない場合には洗浄剤組成物に対する（洗浄剤組成物中の）純分の含量である。 In the present specification, 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.
本発明の自動洗浄機用洗浄剤組成物（以下、単に本発明の洗浄剤組成物ともいう）は、（ａ）一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物（以下、成分（ａ）ともいう）を合計で０．０１～１０質量％、及び、（ｂ）リバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤（以下、成分（ｂ）ともいう）を合計で０．１～１０質量％含む。本発明の洗浄剤組成物は、成分（ａ）及び（ｂ）を上記量含むことにより、優れた抑泡性及び洗浄力を発揮することができるものである。このため、低温時及び食品残渣等の汚れの存在下において優れた抑泡性を発揮することができる。また、洗浄剤組成物を業務用自動洗浄機で使用する場合でも、泡立ちを抑制することができる。特に、成分（ａ）を上記量含むことにより、低温時の泡立ちを抑制することができ、自動洗浄機による食器等の洗浄において、例えば洗浄機の立ち上げ時に洗浄液が低温であっても、低温～洗浄温度の温度範囲において、洗浄液の泡立ちを抑制することができる。また、成分（ｂ）を上記量含むことにより、汚れに起因する泡立ちを抑制することができ、汚れが多量に存在する場合でも高い抑泡性を示す。さらに、本発明の洗浄剤組成物は、成分（ａ）及び成分（ｂ）を上記量含むことにより、洗浄力が高いものである。
洗浄液とは、自動洗浄機用洗浄剤組成物を水で希釈した又は水に溶解させた洗浄剤水溶液を意味する。 The cleaning composition for an automatic cleaning machine of the present invention (hereinafter also simply referred to as the cleaning composition 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. In particular, by containing the above component (a), 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. Moreover, the foaming resulting from a stain | pollution | contamination can be suppressed by containing the amount of a component (b), and even when a large amount of stain | pollution | contamination exists, a high foam suppression property is shown. Furthermore, 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.
本発明における低温時とは、例えば、洗浄液温度が４０℃未満の場合が挙げられ、好ましくは洗浄液温度が１０～３０℃、より好ましくは洗浄液温度が１０～２０℃の場合である。本発明の洗浄剤組成物は、このような低温時において高い抑泡性を発揮することができる。 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.
本発明においては、上記一般式（２）において、Ｒ２が炭素数１～２０のアルキル基を表すことが好ましい。上記ポリオキシアルキレンモノアルキルエーテルが、このようなポリオキシアルキレンモノアルキルエーテルであると、低温時の抑泡性がより向上する。 In the present invention, in the general formula (2), R 2 preferably represents an alkyl group having 1 to 20 carbon atoms. When the polyoxyalkylene monoalkyl ether is such a polyoxyalkylene monoalkyl ether, the foam suppression at a low temperature is further improved.
本発明においては、上記一般式（２）において、Ｒ２が炭素数３～１５のアルキル基を表し、上記Ａ２Ｏがオキシプロピレン基を表し、ｔが、２～６０の数であることがより好ましい。
ポリオキシアルキレンモノアルキルエーテルが、このようなポリオキシアルキレンモノアルキルエーテルであると、低温時の抑泡性をさらに向上させることができる。
上記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルは、さらに好ましくはポリオキシプロピレントリデシルエーテルである。ポリオキシプロピレントリデシルエーテルを含むと、低温時の抑泡性をさらに向上することができる。 In the present invention, in the general formula (2), R 2 represents an alkyl group having 3 to 15 carbon atoms, A 2 O represents an oxypropylene group, and t is a number of 2 to 60. More preferred.
When the polyoxyalkylene monoalkyl ether is such a polyoxyalkylene monoalkyl ether, it is possible to further improve the antifoaming property at low temperatures.
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.
上記一般式（１）においては、Ｒ１が炭素数３～５の３価の脂肪族アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏがオキシプロピレン基を表し、ｎが２～２５０の数であり、ｍが３であることが好ましい。
成分（ａ）における多価アルコールのアルキレンオキサイド付加物がこのような３価の脂肪族アルコールのプロピレンオキサイド付加物であると、低温時の抑泡性がより向上する。 In the general formula (1), 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, and n represents 2 to Preferably, the number is 250 and m is 3.
When 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.
本発明においては、上記リバースプルロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）が１／１０～１／２であることが好ましい。より好ましくは、上記モル比（ＥＯ／ＰＯ）は１／６～１／２である。
上記リバースプルロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）が上記範囲であると、汚れ存在下での抑泡性がより向上する。 In the present invention, 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.
When the molar ratio (EO / PO) of the oxyethylene group (EO) to the oxypropylene group (PO) in the reverse pluronic block polymer is in the above range, the foam suppression property in the presence of dirt is further improved.
本発明の洗浄剤組成物は、さらに、アルカリ剤、キレート剤、可溶化剤、漂白剤、腐食防止剤、除菌剤及び酵素からなる群より選択される少なくとも１種を含有することが好ましい。
洗浄剤組成物が成分（ａ）及び成分（ｂ）に加えて上記の成分の少なくとも１種を含有すると、洗浄力等がより向上するため好ましい。
本発明の自動洗浄機用洗浄剤組成物は、自動食器洗浄機用又はコンテナ洗浄機用の洗浄剤組成物として好適である。 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.
本発明の実施態様の一例を記載する。
＜１－１＞（ａ）上記一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び下記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物を合計で０．０１～１０質量％、及び、（ｂ）リバースプルロニック型ブロックポリマーを０．１～１０質量％含むことを特徴とする自動洗浄機用洗浄剤組成物。
＜１－２＞上記一般式（２）において、Ｒ２が炭素数１～２０のアルキル基を表す上記＜１－１＞に記載の自動洗浄機用洗浄剤組成物。
＜１－３＞上記一般式（２）において、Ｒ２が炭素数３～１５のアルキル基を表し、上記Ａ２Ｏがオキシプロピレン基を表し、ｔが２～６０の数である上記＜１－１＞又は＜１－２＞に記載の自動洗浄機用洗浄剤組成物。
＜１－４＞上記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルが、ポリオキシプロピレントリデシルエーテルである上記＜１－１＞～＜１－３＞のいずれかに記載の自動洗浄機用洗浄剤組成物。
＜１－５＞上記一般式（１）において、Ｒ１が炭素数３～５の３価の脂肪族アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏがオキシプロピレン基を表し、ｎが２～２５０の数であり、ｍが３である上記＜１－１＞～＜１－４＞のいずれかに記載の自動洗浄機用洗浄剤組成物。
＜１－６＞上記リバースプルロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）が１／１０～１／２である上記＜１－１＞～＜１－５＞のいずれかに記載の自動洗浄機用洗浄剤組成物。
＜１－７＞さらに、アルカリ剤、キレート剤、可溶化剤、漂白剤、腐食防止剤、除菌剤及び酵素からなる群より選択される少なくとも１種を含有する上記＜１－１＞～＜１－６＞のいずれかに記載の自動洗浄機用洗浄剤組成物。
＜１－８＞自動食器洗浄機用洗浄剤組成物である上記＜１－１＞～＜１－７＞のいずれかに記載の自動洗浄機用洗浄剤組成物。 An example of an embodiment of the present invention will be described.
<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.
<1-2> The cleaning composition for an automatic cleaning machine according to the above <1-1>, wherein R 2 in the general formula (2) represents an alkyl group having 1 to 20 carbon atoms.
<1-3> In the above general formula (2), R 2 represents an alkyl group having 3 to 15 carbon atoms, A 2 O represents an oxypropylene group, and t is a number of 2 to 60 -1> or <1-2> The cleaning composition for an automatic cleaning machine.
<1-4> 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.
<1-5> In the general formula (1), 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, The cleaning composition for automatic cleaning machines according to any one of the above <1-1> to <1-4>, wherein n is a number from 2 to 250 and m is 3.
<1-6> The above <1-1>, wherein the molar ratio (EO / PO) of oxyethylene group (EO) to oxypropylene group (PO) in the reverse pluronic block polymer is 1/10 to 1/2 A cleaning composition for an automatic cleaning machine according to any one of <1-5>.
<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> The cleaning composition for an automatic cleaning machine according to any one of 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.
本発明によれば、低温時の泡立ち及び汚れに起因する泡立ちを抑制することができ、業務用洗浄機に使用した場合にも泡立ちを抑制することができる自動洗浄機用洗浄剤組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, 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.
以下、本発明の実施形態について具体的に説明する。しかしながら、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。 Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and can be applied with appropriate modifications without departing from the scope of the present invention.
本発明の自動洗浄機用洗浄剤組成物は、（ａ）下記一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び下記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物を合計で０．０１～１０質量％、及び、（ｂ）リバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤を合計で０．１～１０質量％含むことを特徴とする。 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.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式中、Ｒ１は、炭素数３～２０の３～８価の多価アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｎは、オキシアルキレン基の平均付加モル数を表し、２～１０００の数であり、ｍは、３～８の整数を表し、ｍ個の〔－Ｏ―（Ａ１Ｏ）ｎ－Ｈ〕は同一であってもよく、異なっていてもよい。） (Wherein 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. Represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, is a number of 2 to 1000, m is an integer of 3 to 8, and m [—O— (A 1 O NH] may be the same or different.)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ２は、炭素数１～２０のアルキル基又は炭素数２～２０のアルケニル基を表し、Ａ２Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｔは、オキシアルキレン基の平均付加モル数を表し、２～１００の数である。） (Wherein R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and 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.)
上記成分（ａ）は、一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び下記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物である。成分（ａ）として、これらの化合物を１種のみ用いてもよく、２種以上を併用してもよい。
成分（ａ）を上記量含むことにより、優れた抑泡性を発揮することができる。特に低温時の抑泡性が向上し、自動洗浄機の立ち上がり時の泡立ちを抑制することができる。また、洗浄剤組成物を業務用自動洗浄機に使用した場合にも泡立ちを抑制することができる。 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.
By including the component (a) in the above amount, excellent foam suppression can be exhibited. In particular, the foam-suppressing property at a low temperature is improved, and foaming at the start-up of the automatic washing machine can be suppressed. Moreover, foaming can also be suppressed when the cleaning composition is used in a commercial automatic cleaning machine.
上記一般式（１）におけるＲ１は、炭素数３～２０の３～８価の多価アルコールから全部の水酸基を除いた残基を表す。炭素数３～２０の３～８価の多価アルコールとして、例えば、グリセロール（グリセリン）、１，２，３－ブタントリオール、１，２，４－ブタントリオール、１，２，３－ペンタントリオール、１，２，４－ペンタントリオール、２－メチル－１，２，３－プロパントリオール、２－メチル－２，３，４－ブタントリオール、２－エチル－１，２，３－ブタントリオール、２，３，４－ペンタントリオール、３－メチルペンタン－１，３，５－トリオール、２，４－ジメチル－２，３，４－ペンタントリオール、２，３，４－ヘキサントリオール、４－プロピル－３，４，５－ヘプタントリオール、１，３，５－シクロヘキサントリオール、ペンタメチルグリセリン、トリメチロールエタン、トリメチロールプロパン等の３価のアルコール；テトラメチロールメタン（ペンタエリスリトール）、ジグリセリンなどの４価のアルコール；アラビトール、ガラクトース、キシリトール、グルコース、フルクトース、マンノース、アロース、グロース、イドース、タロース等の５価のアルコール；ジペンタエリスリトール、ソルビトール、マンニトール、イジトール、イノシトール等の６価のアルコール；ペルセイトールの７価のアルコール；スクロース、マルトース、ラクトース等の８価のアルコール等の多価の脂肪族アルコール等が挙げられる。中でも、炭素数３～２０の３～６価の多価アルコールが好ましく、炭素数３～１０の３～６価の多価アルコールがより好ましく、例えば、グリセロール、ソルビトール、ペンタエリスリトール、トリメチロールプロパンがさらに好ましい。中でも、炭素数３～５の３価の脂肪族アルコールが特に好ましく、グリセロールが最も好ましい。 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. Examples of 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, trimethylolethane, trimethylolpropane Tetramethylolmethane (pentaerythritol), tetravalent alcohols such as diglycerin; pentavalent alcohols such as arabitol, galactose, xylitol, glucose, fructose, mannose, allose, gulose, idose, talose; dipentaerythritol, sorbitol, mannitol And polyhydric aliphatic alcohols such as octavalent alcohols such as sucrose, maltose, and lactose. Among them, 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. For example, glycerol, sorbitol, pentaerythritol, and trimethylolpropane are preferable. Further preferred. Among these, trivalent aliphatic alcohols having 3 to 5 carbon atoms are particularly preferable, and glycerol is most preferable.
Ａ１Ｏで表される炭素数３又は４のオキシアルキレン基は、オキシプロピレン基、オキシブチレン基である。Ａ１Ｏは、オキシプロピレン基を含むことが好ましく、全オキシアルキレン基中のオキシプロピレン基の割合は、５０モル％以上であることが好ましく、８０モル％以上であることがより好ましく、９５モル％以上がさらに好ましい。特に好ましくは、Ａ１Ｏはオキシプロピレン基である。
Ａ１Ｏとしてオキシプロピレン基及びオキシブチレン基を有する場合、これらの付加形式は、ランダム状でもよく、ブロック状でもよい。 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. Particularly preferably, A 1 O is an oxypropylene group.
When A 1 O has an oxypropylene group and an oxybutylene group, these addition forms may be random or block-like.
一般式（１）において、ｎは、好ましくは２～２５０であり、より好ましくは２～２００であり、より好ましくは２～１００であり、さらに好ましくは１０～１００であり、特に好ましくは１５～１００であり、最も好ましくは１５～７０である。
ｍは、好ましくは３～６であり、より好ましくは３～５であり、さらに好ましくは３である。
また、一般式（１）で表される多価アルコールのアルキレンオキサイド付加物は、１分子あたりのオキシアルキレン基の平均付加モル数（ｎ×ｍ）が、１０～３００であることが好ましく、より好ましくは４０～１５０である。 In the general formula (1), 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.
In addition, 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.
一般式（１）で表される多価アルコールのアルキレンオキサイド付加物の質量平均分子量は、２５０～４００００であることが好ましく、５００～１００００であることがより好ましい。
質量平均分子量は、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）を展開溶媒とし、ゲルパーミエーションクロマトグラフィーでポリエチレングリコール（ＰＥＧ）を標準物質として求められる。 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.
成分（ａ）における多価アルコールのアルキレンオキサイド付加物の好ましい態様の一例は、一般式（１）において、Ｒ１が炭素数３～５の３価の脂肪族アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏがオキシプロピレン基を表し、ｎが２～２５０の数であり、ｍが３である化合物である。多価アルコールのアルキレンオキサイド付加物は、より好ましくは、一般式（１）において、Ｒ１が、グリセロールから全部の水酸基を除いた残基を表し、Ａ１Ｏが、オキシプロピレン基を表し、ｎが、１０～２００（好ましくは、１５～１００）の数であり、ｍが、３を表す化合物である。３個の〔－Ｏ―（Ａ１Ｏ）ｎ－Ｈ〕は同一であってもよく、異なっていてもよい。
また、多価アルコールのアルキレンオキサイド付加物として、一般式（１）において、Ｒ１が、トリメチロールプロパン、ペンタエリスリトール又はソルビトールから全部の水酸基を除いた残基を表し、Ａ１Ｏが、オキシプロピレン基を表し、ｎが、５～５０（好ましくは、８～３０）の数であり、ｍが、３、４又は６を表す化合物も好ましい。この場合、ｍ個の〔－Ｏ―（Ａ１Ｏ）ｎ－Ｈ〕は同一であってもよく、異なっていてもよい。
多価アルコールのアルキレンオキサイド付加物としてこのような化合物を含むと、低温時の抑泡性をより向上させることができる。このため自動洗浄機の立ち上がり時の泡立ちをより充分に抑制することができる。 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). A compound in which A 1 O represents an oxypropylene group, n is a number from 2 to 250, and m is 3. Alkylene oxide adducts of polyhydric alcohols, more preferably, in the general formula (1), R 1 is a residue obtained by removing all hydroxyl groups from glycerol, A 1 O is, represents oxypropylene radical, n Is a number of 10 to 200 (preferably 15 to 100) and m is 3. The three [—O— (A 1 O) n—H] may be the same or different.
Further, as an alkylene oxide adduct of a polyhydric alcohol, in general formula (1), R 1 represents a residue obtained by removing all hydroxyl groups from trimethylolpropane, pentaerythritol, or sorbitol, and A 1 O represents oxypropylene. A compound in which n is a number of 5 to 50 (preferably 8 to 30) and m is 3, 4 or 6 is also preferred. In this case, m [—O— (A 1 O) n—H] may be the same or different.
When such a compound is contained as an alkylene oxide adduct of a polyhydric alcohol, it is possible to further improve the antifoaming property at a low temperature. For this reason, foaming at the time of starting of an automatic washing machine can be controlled more fully.
本発明における成分（ａ）は、一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルであることが好ましい。 Component (a) in the present invention is preferably a polyoxyalkylene monoalkyl ether represented by the general formula (2).
上記一般式（２）におけるＲ２は、炭素数１～２０のアルキル基又は炭素数２～２０のアルケニル基を表し、Ａ２Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｔは、オキシアルキレン基の平均付加モル数を表し、２～１００の数である。 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, and 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.
一般式（２）において、Ｒ２は、好ましくは炭素数１～２０のアルキル基である。本発明におけるポリオキシアルキレンモノアルキルエーテルは、一般式（２）において、Ｒ２が、炭素数１～２０のアルキル基を表すポリオキシアルキレンモノアルキルエーテルであることが好ましい。 In the general formula (2), 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.
炭素数１～２０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、ｔ－ペンチル基、ｎ－ヘキシル基、ｓ－ヘキシル基、ｔ－ヘキシル基、イソヘキシル基、ｎ－ヘプチル基、ｓ－ヘプチル基、ｔ－ヘプチル基、イソヘプチル基、ｎ－オクチル基、ｓ－オクチル基、ｔ－オクチル基、イソオクチル基、２－エチルへキシル基、３－エチルへキシル基、ｎ－ノニル基、ｓ－ノニル基、ｔ－ノニル基、イソノニル基、ｎ－デシル基、ｓ－デシル基、ｔ－デシル基、イソデシル基、ｎ－ウンデシル基、ｓ－ウンデシル基、ｔ－ウンデシル基、イソウンデシル基、ｎ－ドデシル基、ｓ－ドデシル基、ｔ－ドデシル基、イソドデシル基、ｎ－トリデシル基、ｓ－トリデシル基、ｔ－トリデシル基、イソトリデシル基、ｎ－テトラデシル基、ｓ－テトラデシル基、ｔ－テトラデシル基、イソテトラデシル基、ｎ－ペンタデシル基、ｓ－ペンタデシル基、ｔ－ペンタデシル基、イソペンタデシル基、ｎ－ヘキサデシル基、ｓ－ヘキサデシル基、ｔ－ヘキサデシル基、イソヘキサデシル基、ｎ－ヘプタデシル基、ｓ－ヘプタデシル基、ｔ－ヘプタデシル基、イソヘプタデシル基、ｎ－オクタデシル基、ｓ－オクタデシル基、ｔ－オクタデシル基、イソオクタデシル基等の直鎖又は分岐鎖アルキル基が挙げられる。中でも、炭素数３～１５のアルキル基が好ましく、炭素数４～１５のアルキル基がより好ましく、炭素数１２～１５のアルキル基がさらに好ましく、炭素数１３のアルキル基が特に好ましい。また、アルキル基は、分岐鎖アルキル基が好ましい。 Examples of the alkyl group having 1 to 20 carbon atoms 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-decyl group, s-decyl group, t-decyl group , Isodecyl group, n-undecyl group, s-undecyl group, t-undecyl group, isoundecyl group, n-dodecyl group, s-dodecyl group, t-dodecyl group, isododecyl group, n-tridecyl group Group, s-tridecyl group, t-tridecyl group, isotridecyl group, n-tetradecyl group, s-tetradecyl group, t-tetradecyl group, isotetradecyl group, n-pentadecyl group, s-pentadecyl group, t-pentadecyl group, Isopentadecyl group, n-hexadecyl group, s-hexadecyl group, t-hexadecyl group, isohexadecyl group, n-heptadecyl group, s-heptadecyl group, t-heptadecyl group, isoheptadecyl group, n-octadecyl group, s- Examples thereof include linear or branched alkyl groups such as octadecyl group, t-octadecyl group, and isooctadecyl group. Among them, 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.
炭素数２～２０のアルケニル基としては、例えば、ビニル基、１－プロペニル基、２－プロペニル基、２－ブテニル基、３－ブテニル基、３－ペンテニル基、４－ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基等の直鎖又は分岐鎖アルケニル基が挙げられる。中でも、炭素数４～１５のアルケニル基が好ましく、例えば、２－ブテニル基、３－ブテニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基が好ましく、炭素数５～１５のアルケニル基がより好ましく、トリデセニル基が特に好ましい。 Examples of the alkenyl group having 2 to 20 carbon atoms 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. And 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. Among them, an alkenyl group having 4 to 15 carbon atoms is preferable. For example, 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. Are more preferable, and a tridecenyl group is particularly preferable.
Ａ２Ｏで表される炭素数３又は４のオキシアルキレン基は、オキシプロピレン基、オキシブチレン基である。Ａ２Ｏは、オキシプロピレン基を含むことが好ましく、全オキシアルキレン基中のオキシプロピレン基の割合は、５０モル％以上であることが好ましく、８０モル％以上であることがより好ましく、９５モル％以上がさらに好ましい。特に好ましくは、Ａ２Ｏはオキシプロピレン基である。
Ａ２Ｏとしてオキシプロピレン基及びオキシブチレン基を有する場合、これらの付加形式は、ランダム状でもよく、ブロック状でもよい。
ｔは、好ましくは２～６０であり、より好ましくは２～５５であり、さらに好ましくは２～１０である。 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. Particularly preferably, A 2 O is an oxypropylene group.
When A 2 O has an oxypropylene group and an oxybutylene group, these addition forms may be random or block-like.
t is preferably 2 to 60, more preferably 2 to 55, and still more preferably 2 to 10.
一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルの質量平均分子量は、１５０～５０００であることが好ましく、２５０～４０００であることがより好ましい。
上記質量平均分子量は、ＤＭＦを展開溶媒とし、ゲルパーミエーションクロマトグラフィーでＰＥＧを標準物質として求められる。 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.
一般式（２）の好ましい態様の一例として、Ｒ２が炭素数３～１５のアルキル基を表し、Ａ２Ｏがオキシプロピレン基を表し、ｔが、２～６０の数であることが挙げられる。より好ましくは、一般式（２）において、Ｒ２が炭素数４～１５（より好ましくは炭素数１２～１５）のアルキル基を表し、Ａ２Ｏがオキシプロピレン基を表し、ｔが、２～６０の数である。ポリオキシアルキレンモノアルキルエーテルがこのような化合物であると、低温時の抑泡性をより向上させることができる。 As an example of a preferred embodiment of the general formula (2), R 2 represents an alkyl group having 3 to 15 carbon atoms, A 2 O represents an oxypropylene group, and t is a number of 2 to 60. . More preferably, in the general formula (2), 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, and t is 2 to A number of 60. When the polyoxyalkylene monoalkyl ether is such a compound, the antifoaming property at low temperature can be further improved.
本発明においては、上記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルが、Ｒ２が炭素数１２～１５のアルキル基であるポリオキシプロピレンモノアルキルエーテルであることが好ましく、ポリオキシプロピレントリデシルエーテルであることが特に好ましい。ポリオキシプロピレントリデシルエーテルを含有すると、低温時の抑泡性が特に良好であるため好ましい。Ｒ２が炭素数１２～１５のアルキル基であるポリオキシプロピレンモノアルキルエーテル（好ましくはポリオキシプロピレントリデシルエーテル）は、好ましくはオキシプロピレン基の平均付加モル数（ｔ）が２～５０（より好ましくは２～１０、さらに好ましくは２～８）である。 In the present invention, 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).
本発明の洗浄剤組成物は、成分（ａ）を０．０１～１０質量％含有する。成分（ａ）の含量が上記範囲であると、低温時の抑泡性が良好となる。成分（ａ）が１０質量％を超えると、洗浄作用が低下する場合がある。成分（ａ）の含有量は、低温時の抑泡性がより良好となることから、好ましくは０．０１～８質量％であり、より好ましく０．１～５質量％である。成分（ａ）に２種以上の化合物が含まれる場合、上記含有量は、それらの合計として定める。 The cleaning composition of the present invention contains 0.01 to 10% by mass of 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. When 2 or more types of compounds are contained in a component (a), the said content is defined as those totals.
本発明における成分（ｂ）は、リバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤である。これらの界面活性剤をそれぞれ１種のみ用いてもよく、２種以上を併用してもよい。中でも、成分（ｂ）はリバースプルロニック型ブロックポリマー及びリバーステトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤を含むことが好ましく、成分（ｂ）がリバースプルロニック型ブロックポリマー及びリバーステトロニック型ブロックポリマーからなる群より選択される少なくとも１種であることが好ましい。成分（ｂ）がリバースプルロニック型ブロックポリマー又はリバーステトロニック型ブロックポリマーであることも好ましい。これらはそれぞれ１種のみ用いてもよく、２種以上を併用してもよい。中でも、成分（ｂ）としては、リバースプルロニック型ブロックポリマーが特に好ましい。 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. Among them, 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. It is also preferred that 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.
リバースプルロニック型ブロックポリマーの質量平均分子量は、好ましくは１０００～６０００であり、より好ましくは２０００～５０００である。
リバーステトロニック型ブロックポリマーの質量平均分子量は、好ましくは１０００～６０００であり、より好ましくは３０００～５０００である。
プルロニック型ブロックポリマーの質量平均分子量は、好ましくは１０００～６０００であり、より好ましくは１０００～４０００である。
テトロニック型ブロックポリマーの質量平均分子量は、好ましくは１０００～６０００であり、より好ましくは１５００～４０００である。
質量平均分子量が上記範囲であると、汚れ存在下での抑泡性がより向上する。
上記質量平均分子量は、ＤＭＦを展開溶媒とし、ゲルパーミエーションクロマトグラフィーでＰＥＧを標準物質として求められる。 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.
When the mass average molecular weight is in the above range, the foam suppression property in the presence of dirt is further improved.
The mass average molecular weight is obtained by using DMF as a developing solvent and gel permeation chromatography using PEG as a standard substance.
上記リバースプルロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）は１／１０～１／２であることが好ましく、１／６～１／２であることがより好ましい。
上記リバーステトロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）は１／０．５～１／１０であることが好ましく、１／０．５～１／５であることがより好ましく、１／１～１／３がさらに好ましい。
プルロニック型ブロックポリマー中のＥＯとＰＯのモル比（ＥＯ／ＰＯ）は１／０．５～１／１５であることが好ましく、１／２～１／１２であることがより好ましく、１／４～１／９がさらに好ましい。テトロニック型ブロックポリマー型ブロックポリマー中のＥＯとＰＯのモル比（ＥＯ／ＰＯ）は１／０．５～１／１５であることが好ましく、１／２～１／１２であることがより好ましく、１／４～１／９がさらに好ましい。
成分（ｂ）として、ＥＯ／ＰＯのモル比が上記割合であるリバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーの１種又は２種以上を含むと、汚れ存在下での抑泡性がより向上するため好ましい。 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.
When 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.
本発明の洗浄剤組成物は、成分（ｂ）を０．１～１０質量％含有する。成分（ｂ）を上記量含むことにより、優れた抑泡性を発揮することができる。特に、汚れ存在下での抑泡性が向上し、洗浄液中に汚れが多量に存在する場合でも泡立ちを抑制することができる。また、洗浄剤組成物を業務用自動洗浄機に使用した場合にも泡立ちを抑制することができる。さらに、成分（ｂ）を上記量含むことにより、高い洗浄力を発揮することができる。成分（ｂ）の含有量は、好ましくは０．５～１０質量％であり、より好ましく１～１０質量％であり、さらに好ましくは１～８質量％である。成分（ｂ）に２種以上の化合物が含まれる場合、上記含有量は、それらの合計として定める。 The cleaning composition of the present invention contains 0.1 to 10% by mass of 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.
本発明の洗浄剤組成物は、本発明の効果を損なわない限り、成分（ａ）及び成分（ｂ）以外の成分を含んでもよい。
例えば、本発明の洗浄剤組成物は、さらに、アルカリ剤、キレート剤、可溶化剤、漂白剤、腐食防止剤、除菌剤及び酵素からなる群より選択される少なくとも１種を含有することが好ましい。これらはそれぞれ１種のみ用いてもよく、２種以上を併用してもよい。 Unless the effect of this invention is impaired, the cleaning composition of this invention may also contain components other than a component (a) and a component (b).
For example, 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.
洗浄剤組成物がアルカリ剤を含有すると、洗浄力が向上するため好ましい。
アルカリ剤としては、水溶性のアルカリ剤であればよく、例えば、アルカリ金属塩又はアルカリ土類金属塩を用いることができる。アルカリ金属塩としては、アルカリ金属の水酸化物、アルカリ金属のリン酸塩、アルカリ金属の炭酸塩及びケイ酸のアルカリ金属塩からなる群より選択される少なくとも１種の化合物が好ましく、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物；リン酸三ナトリウム等のアルカリ金属のリン酸塩；炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属の炭酸塩；ケイ酸ナトリウム（メタケイ酸ナトリウム、セスキケイ酸ナトリウム、オルソケイ酸ナトリウム、ケイ酸ソーダ１号、ケイ酸ソーダ２号、ケイ酸ソーダ３号、ケイ酸ソーダ４号）、ケイ酸カリウム（メタケイ酸カリウム、セスキケイ酸カリウム、オルソケイ酸カリウム）等のケイ酸のアルカリ金属塩が好ましい。これらのアルカリ剤は、水和物となっていてもよい。中でも、アルカリ金属の水酸化物、ケイ酸のアルカリ金属塩がより好ましく、ケイ酸のアルカリ金属塩がさらに好ましい。なお、後記するキレート剤として例示される化合物は、本発明におけるアルカリ剤には含まれない。 It is preferable that 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. Of these, alkali metal hydroxides and alkali metal salts of silicic acid are more preferred, and alkali metal salts of silicic acid are more preferred. In addition, the compound illustrated as a chelating agent mentioned later is not contained in the alkaline agent in this invention.
洗浄剤組成物がアルカリ剤を含有する場合、アルカリ剤の含有量は、洗浄剤組成物に対して５～８５質量％であることが好ましい。アルカリ剤の含有量が上記範囲であると、洗浄力がより高くなる。上記アルカリ剤の含有量は、好ましくは１０～５０質量％である。アルカリ剤が２種以上含まれる場合、上記含有量は、各アルカリ剤の含有量の合計として定める。 When the cleaning composition contains an alkaline agent, the content of the alkaline agent is preferably 5 to 85% by mass with respect to the cleaning composition. When 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. When 2 or more types of alkali agents are contained, the content is determined as the total content of the alkali agents.
洗浄剤組成物がキレート剤を含有すると、洗浄力がより高くなるため好ましい。
キレート剤としては、アミノカルボン酸系、ヒドロキシカルボン酸系、リン酸系、エーテルカルボン酸塩、ホスホン酸系等のキレート剤が挙げられる。後記する質量平均分子量３０００～３０００００の高分子分散剤として例示されるポリアクリル酸ナトリウム等の化合物は、本発明におけるキレート剤には含まれない。 It is preferable that the cleaning composition contains a chelating agent because the cleaning power becomes higher.
Examples of the chelating agent include aminocarboxylic acid-based, hydroxycarboxylic acid-based, phosphoric acid-based, ether carboxylate, and phosphonic acid-based chelating agents. A compound such as sodium polyacrylate exemplified as a polymer dispersant having a mass average molecular weight of 3000 to 300,000, which will be described later, is not included in the chelating agent in the present invention.
上記アミノカルボン酸系のキレート剤としては、エチレンジアミン四酢酸（ＥＤＴＡ）、ニトリロ三酢酸（ＮＴＡ）、メチルグリシン二酢酸（ＭＧＤＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、ヒドロキシエチルエチレンジアミン三酢酸（ＨＥＤＴＡ）、トリエチレンテトラミン六酢酸（ＴＴＨＡ）、グルタミン酸二酢酸（ＧＬＤＡ）、ヒドロキシエチルイミノ二酢酸（ＨＩＤＡ）、ジヒドロキシエチルグリシン（ＤＨＥＧ）、１，３－プロパンジアミン四酢酸（ＰＤＴＡ）、１，３－ジアミノ－２－ヒドロキシプロパン六酢酸（ＤＰＴＡ－ＯＨ）、アスパラギン酸二酢酸（ＡＳＤＡ）、エチレンジアミンコハク酸（ＥＤＤＳ）又はこれらの塩等が挙げられる。 Examples of the 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.
上記ヒドロキシカルボン酸系のキレート剤としては、例えば、リンゴ酸、コハク酸、クエン酸、乳酸、酒石酸、グルコン酸又はこれらの塩が挙げられる。
上記リン酸系のキレート剤としては、トリポリリン酸、ヘキサメタリン酸塩等が挙げられる。 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.
上記ホスホン酸系のキレート剤としては、ヒドロキシエチリデンジホスホン酸（ＨＥＤＰ）、ニトリロトリスメチレンホスホン酸（ＮＴＭＰ）、ホスホノブタントリカルボン酸（ＰＢＴＣ）、エチレンジアミンテトラメチレンホスホン酸（ＥＤＴＭＰ）又はこれらの塩等が挙げられる。 Examples of the phosphonic acid-based chelating agent include hydroxyethylidene diphosphonic acid (HEDP), nitrilotrismethylenephosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), and salts thereof. Is mentioned.
上記キレート剤における塩としては、例えば、カリウム、ナトリウム等のアルカリ金属の塩；マグネシウム、カルシウム等のアルカリ土類金属の塩を挙げることができる。中でも、アルカリ金属の塩が好ましく、ナトリウム塩又はカリウム塩がより好ましい。 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.
本発明におけるキレート剤としては、アミノカルボン酸系、ホスホン酸系等のキレート剤が好ましく、ニトリロ三酢酸、エチレンジアミン四酢酸、メチルグリシン二酢酸、エチレンジアミンテトラメチレンホスホン酸、ホスホノブタントリカルボン酸又はこれらの塩等がより好ましく、ニトリロ三酢酸、エチレンジアミン四酢酸、メチルグリシン二酢酸又はこれらの塩がさらに好ましい。 As the chelating agent in the present invention, 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.
洗浄剤組成物がキレート剤を含有する場合、キレート剤の含有量は、洗浄剤組成物に対して５～８５質量％であることが好ましい。キレート剤が５質量％未満であると、スケールの発生が問題となる場合がある。キレート剤が８５質量％を超えると、洗浄力が低くなる場合がある。上記キレート剤の含有量は、好ましくは３０～５０質量％である。キレート剤が２種以上含まれる場合、上記含有量は、各キレート剤の含有量の合計として定める。 When the cleaning composition contains a chelating agent, 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.
洗浄剤組成物が可溶化剤を含有すると、液体の場合、保管安定性が向上するため好ましい。
可溶化剤としては、例えば、芳香族酸又はその塩、カルボン酸又はその塩、アルキルポリグルコシド等が挙げられる。これらは、単独で用いても、２種以上を組み合わせて用いてもよい。
芳香族酸としては、キシレンスルホン酸、トルエンスルホン酸、クメンスルホン酸、安息香酸等が挙げられる。
カルボン酸としては、クエン酸、リンゴ酸、コハク酸、酒石酸、オクチル酸、カプリル酸等が挙げられる。
塩としては、例えば、カリウム、ナトリウム等のアルカリ金属や、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミン類等の塩を挙げることができ、中でも、ナトリウム塩が好ましい。
アルキルポリグルコシドとして、ブチルポリグルコシド等が挙げられる。
中でも、可溶化剤として、オクチル酸、カプリル酸及びブチルポリグルコシドの１種又は２種以上が好ましい。 When the detergent composition contains a solubilizer, it is preferable in the case of a liquid because the storage stability is improved.
Examples of 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.
Examples of the aromatic acid include xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzoic acid and the like.
Examples of 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.
洗浄剤組成物が可溶化剤を含有する場合、可溶化剤の含有量は、洗浄剤組成物に対して０．１～１０質量％であることが好ましく、１～８質量％であることがより好ましく、１～５質量％がさらに好ましい。可溶化剤が２種以上含まれる場合、上記含有量は、各可溶化剤の含有量の合計として定める。 When the cleaning composition contains a solubilizing agent, 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. When two or more solubilizers are included, the content is determined as the total content of the solubilizers.
洗浄剤組成物が漂白剤を含有すると、洗浄力、除菌効果、脱臭作用及び漂白作用が向上する。
漂白剤として、例えば、塩素化イソシアヌル酸塩（塩素化イソシアヌル酸ナトリウム（ジクロロイソシアヌル酸ナトリウム）、塩素化イソシアヌル酸カリウム（ジクロロイソシアヌル酸カリウム）等）、トリクロロイソシアヌル酸、次亜塩素酸塩（次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウム等）等の塩素系漂白剤が挙げられる。これらの漂白剤は１種を用いてもよく、２種以上を併用してもよい。また、これらの漂白剤は、水和物であってもよい。中でも、漂白剤として、塩素化イソシアヌル酸塩、次亜塩素酸塩が好ましく、塩素化イソシアヌル酸ナトリウム、次亜塩素酸ナトリウムがより好ましい。 When the cleaning composition contains a bleaching agent, the detergency, sterilizing effect, deodorizing action and bleaching action are improved.
As 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). These bleaching agents may be used alone or in combination of two or more. These bleaching agents may be hydrates. Among them, as the bleaching agent, chlorinated isocyanurate and hypochlorite are preferable, and chlorinated sodium isocyanurate and sodium hypochlorite are more preferable.
洗浄剤組成物が漂白剤を含有する場合、漂白剤の含有量は、洗浄剤組成物に対して０．１～２０質量％が好ましい。漂白剤が０．１質量％未満であると、漂白剤を添加することによる得られる洗浄力と除菌効果、脱臭作用又は漂白作用の向上が充分でない場合がある。漂白剤が２０質量％を超えると、例えば漂白剤が塩素系漂白剤の場合に塩素臭が問題となる場合がある。漂白剤の含有量は、好ましくは２～１０質量％である。漂白剤が２種以上含まれる場合、上記含有量は、各漂白剤の含有量の合計として定める。 When the cleaning composition contains a bleaching agent, the content of the bleaching agent is preferably 0.1 to 20% by mass with respect to the cleaning composition. When 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.
洗浄剤組成物が腐食防止剤を含有すると、洗浄剤組成物の腐食防止作用（防食作用）が向上する。
腐食防止剤としては、アルミニウム、銅又は銅合金に対する腐食防止剤を用いることが好ましい。このような腐食防止剤として、例えば、ベンゾトリアゾール又はその誘導体（例えば、ベンゾトリアゾール、トリルトリアゾール、５－ドデシルベンゾトリアゾール、５－オクチルベンゾトリアゾール、５－ヘキシルベンゾトリアゾール、５－ブチルベンゾトリアゾール、５－メチルベンゾトリアゾール、４－カルボキシベンゾトリアゾール、５－カルボキシベンゾトリアゾール、カルボキシベンゾトリアゾールメチルエステル、カルボキシベンゾトリアゾールブチルエステル、カルボキシベンゾトリアゾールヘキシルエステル、ベンゾトリアゾールオクチルエステル、ジカルボキシプロピルベンゾトリアゾール等）、ベンゾイミダゾール又はその誘導体（例えば、ベンゾイミダゾール、２－メルカプトベンゾイミダゾール、チアゾリルベンゾイミダゾール、チアベンダゾール等）、ベンゾチアゾール又はその誘導体（例えば、ベンゾチアゾール、２－メチルベンゾチアゾール、２－アミノベンゾチアゾール、２－メルカプトベンゾチアゾール等）を好適に使用することができる。中でも、ベンゾイミダゾール、ベンゾトリアゾール、トリルトリアゾールが好ましく、ベンゾトリアゾール、トリルトリアゾールがより好ましい。 When the cleaning composition contains a corrosion inhibitor, the corrosion preventing action (anticorrosive action) of the cleaning composition is improved.
As the corrosion inhibitor, it is preferable to use a corrosion inhibitor for aluminum, copper or a copper alloy. Examples of such 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, benzimidazole, 2-mercaptobenzimidazole, thiazolylben) Imidazole, thiabendazole, etc.), benzothiazole or derivatives thereof (e.g., benzothiazole, 2-methyl-benzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, etc.) can be suitably used. Among these, benzimidazole, benzotriazole, and tolyltriazole are preferable, and benzotriazole and tolyltriazole are more preferable.
洗浄剤組成物が腐食防止剤を含有する場合、腐食防止剤の含有量は、洗浄剤組成物に対して０．００１～５質量％が好ましい。腐食防止剤が０．００１質量％未満であると、充分な腐食防止作用を発揮できない場合がある。腐食防止剤が５質量％を超えると、腐食防止剤特有の臭いの影響が強くなる場合がある。上記腐食防止剤の含有量は、好ましくは０．１～２質量％である。腐食防止剤が２種以上含まれる場合、上記含有量は、各腐食防止剤の含有量の合計として定める。 When the cleaning composition contains a corrosion inhibitor, 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.
洗浄剤組成物が除菌剤を含有すると、除菌効果が向上する。
除菌剤としては、例えば、Ｎ，Ｎ’，Ｎ’’－トリス（ヒドロキシエチル）ヘキサヒドロ－ｓ－トリアジン、４，４－ジメチルオキサゾリジン、２－オクチル４－イソチアゾリン－３―オン、アルキルジメチルベンジルアンモニウムクロライド、塩化ベンゼトニウム、ジデシルジメチルアンモニウムクロライド、ジオクチルジメチルアンモニウムクロライド、ヘキサデシルピリジニウムクロライド、塩化アルキルジメチルヒドロキシアンモニウム、塩化アルキルジメチルヒドロキシアンモニウム、４，４’－（テトラメチレンジカルボニルアミノ）ビス（１―デシルピリジニウムブロマイド）、グルコン酸クロルヘキシジン、クロルヘキシジン塩酸塩、ポリヘキサメチレンビグアナイド塩酸塩、ピリジン－２－チオール－１－オキシドナトリウム、イソプロピルメチルフェノール、２，４，４’－トリクロロ―２’－ヒドロキシジフェニルエーテル、アルキルポリアミノエチルグリシン、ソルビン酸、安息香酸、プロピオン酸、アルキルジメチルヒドロキシエチルアンモニウムクロライド等が挙げられる。中でも、ジデシルジメチルアンモニウムクロライド、ジオクチルジメチルアンモニウムクロライド、アルキルジメチルヒドロキシエチルアンモニウムクロライド等が好ましい。 When the cleaning composition contains a disinfectant, the disinfecting effect is improved.
Examples of the disinfectant include N, N ′, N ″ -tris (hydroxyethyl) hexahydro-s-triazine, 4,4-dimethyloxazolidine, 2-octyl 4-isothiazolin-3-one, and alkyldimethylbenzylammonium. Chloride, benzethonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, hexadecylpyridinium chloride, alkyldimethylhydroxyammonium chloride, alkyldimethylhydroxyammonium chloride, 4,4 '-(tetramethylenedicarbonylamino) bis (1-decyl) Pyridinium bromide), chlorhexidine gluconate, chlorhexidine hydrochloride, polyhexamethylene biguanide hydrochloride, sodium pyridine-2-thiol-1-oxide, Examples thereof include isopropylmethylphenol, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, alkylpolyaminoethylglycine, sorbic acid, benzoic acid, propionic acid, and alkyldimethylhydroxyethylammonium chloride. Of these, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, alkyldimethylhydroxyethylammonium chloride and the like are preferable.
洗浄剤組成物が除菌剤を含有する場合、除菌剤の含有量は、洗浄剤組成物に対して０．１～３０質量％が好ましく、０．１～１５質量％がより好ましい。除菌剤が２種以上含まれる場合、上記含有量は、各除菌剤の含有量の合計として定める。 When the cleaning composition contains a disinfectant, 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. When two or more disinfectants are included, the content is determined as the total content of each disinfectant.
洗浄剤組成物が酵素を含有すると、洗浄力が向上する。
酵素として、例えば、プロテアーゼ、エステラーゼ、リパーゼ、ヌクレアーゼ、セルラーゼ、アミラーゼ及びペクチナーゼ等が挙げられる。これらの酵素が含まれていると、酵素の機能により洗浄力が向上する。中でも、プロテアーゼ、アミラーゼ、リパーゼが好ましい。 When the cleaning composition contains an enzyme, the cleaning power is improved.
Examples of the enzyme include protease, esterase, lipase, nuclease, cellulase, amylase, and pectinase. When these enzymes are contained, the cleaning power is improved by the function of the enzymes. Of these, protease, amylase, and lipase are preferable.
プロテアーゼとして使用できる市販の酵素として、例えば、アルカラーゼ、サビナーゼ、エバラーゼ、カンナーゼ、エスペラーゼ、オボザイム（ノボザイムズジャパン（株））、プラフェクト、プロペラーゼ、プラフェクトＯＸ（ジェネンコア・インターナショナル社）等が挙げられる。 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).
アミラーゼとして使用できる市販の酵素として、例えば、ラピダーゼ（ギスト－ブロカーズ社）、ターマミル、デュラミル、ステインザイム（ノボノルディスクバイオインダストリー（株））、プラスターＳＴ、プラスターＯｘＡｍ（ジェネンコア・インターナショナル社）等が挙げられる。
リパーゼとして使用できる市販の酵素として、例えば、エンチロンＡＫＧ－２０００（洛東化成工業（株））、リポザイム（ノボザイムズジャパン（株））等が挙げられる。 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.).
洗浄剤組成物が酵素を含有する場合、酵素の含有量は、洗浄剤組成物に対して、酵素タンパク質量として０．１～１０質量％が好ましく、０．１～５質量％がより好ましい。酵素が２種以上含まれる場合、上記含有量は、各酵素の含有量の合計として定める。 When the cleaning composition contains an enzyme, 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. When two or more enzymes are included, the content is determined as the total content of each enzyme.
本発明の洗浄剤組成物に酵素及びアルカリ剤を配合する場合、アルカリ剤を含有する中性～弱アルカリ性水溶液中での酵素失活を抑制するため、酵素安定化剤を配合することが好ましい。酵素安定化剤としては、ホウ酸又はホウ酸を形成することが可能なホウ素化合物、水溶性カルシウム塩から選択される１種以上を配合することが好ましい。酵素安定化剤の配合量は、洗浄剤組成物に対して０．００１～１０質量％が好ましく、より好ましくは０．０１～８質量％、さらに好ましくは１～５質量％である。 When an enzyme and an alkaline agent are blended in the cleaning composition of the present invention, it is preferable to blend an enzyme stabilizer in order to suppress enzyme deactivation in a neutral to weak alkaline aqueous solution containing the alkaline agent. As 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.
本発明の洗浄剤組成物は、質量平均分子量３０００～３０００００の高分子分散剤を含有してもよい。このような高分子分散剤を含有すると、スケール防止能が向上する。高分子分散剤は１種のみ用いてもよく、２種以上を併用してもよい。
上記質量平均分子量３０００～３０００００の高分子分散剤としては、例えば、ポリアクリル酸、ポリアコニット酸、ポリイタコン酸、ポリシトラコン酸、ポリフマル酸、ポリマレイン酸、ポリメタコン酸、ポリ－α－ヒドロキシアクリル酸、ポリビニルホスホン酸、スルホン化ポリマレイン酸、オレフィン－マレイン酸共重合体、無水マレイン酸ジイソブチレン共重合体、無水マレイン酸スチレン共重合体、無水マレイン酸メチルビニルエーテル共重合体、無水マレイン酸エチレン共重合体、無水マレイン酸エチレンクロスリンク共重合体、無水マレイン酸アクリル酸共重合体、無水マレイン酸酢酸ビニル共重合体、無水マレイン酸アクリロニトリル共重合体、無水マレイン酸アクリル酸エステル共重合体、無水マレイン酸ブタジエン共重合体、無水マレイン酸イソプレン共重合体、無水マレイン酸と一酸化炭素から誘導されるポリ－β－ケトカルボン酸、イタコン酸、エチレン共重合体、イタコン酸アコニット酸共重合体、イタコン酸マレイン酸共重合体、イタコン酸アクリル酸共重合体、マロン酸メチレン共重合体、イタコン酸フマール酸共重合体、エチレングリコールエチレンテレフタレート共重合体、ビニルピロリドン酢酸ビニル共重合体、これらの金属塩等が挙げられる。
金属塩としては、例えば、カリウム、ナトリウム等のアルカリ金属の塩；マグネシウム、カルシウム等のアルカリ土類金属の塩を挙げることができる。中でも、アルカリ金属の塩が好ましく、ナトリウム塩又はカリウム塩がより好ましい。
本発明における質量平均分子量３０００～３０００００の高分子分散剤としては、ポリアクリル酸塩、オレフィン－マレイン酸共重合体の塩が好ましく、ポリアクリル酸ナトリウム、オレフィン－マレイン酸共重合体のナトリウム塩がより好ましい。 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-α-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-β-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 a copolymer, an itaconic acid acrylic acid copolymer, a malonic acid methylene copolymer, an itaconic acid fumaric acid copolymer, an ethylene glycol ethylene terephthalate copolymer, a vinylpyrrolidone vinyl acetate copolymer, and metal salts thereof.
Examples of the metal salt 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.
As 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.
洗浄剤組成物が質量平均分子量３０００～３０００００の高分子分散剤を含有する場合、その含有量は、洗浄剤組成物に対して０．１～２０質量％であることが好ましく、０．１～１０質量％がより好ましい。質量平均分子量３０００～３０００００の高分子分散剤が２種以上含まれる場合、上記含有量は、各高分子分散剤の含有量の合計として定める。
上記質量平均分子量は、リン酸緩衝溶液とアセトニトリルを展開溶媒とし、ゲルパーミエーションクロマトグラフィーでポリアクリル酸を標準物質として求められる。 When 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. When two or more kinds of polymer dispersants having a mass average molecular weight of 3000 to 300,000 are contained, 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.
本発明の洗浄剤組成物には、本発明の効果を損なわない限り、成分（ｂ）以外の界面活性剤（以下、その他の界面活性剤という）を使用してもよい。なお、上記成分（ａ）は、本発明における界面活性剤には含まれない。
その他の界面活性剤としては、陰イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤、非イオン界面活性剤等を使用することができ、好ましくは非イオン界面活性剤である。非イオン界面活性剤として、例えば、ポリオキシアルキレンジアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、脂肪酸アルカノールアミド、ポリオキシアルキレン脂肪酸アルカノールアミド、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、アルキルポリグリコシド、ポリオキシエチレンメチルエーテル脂肪酸エステル、ポリオキシアルキレンアルキルアミン等が挙げられる。 As long as the effects of the present invention are not impaired, a surfactant other than the component (b) (hereinafter referred to as other surfactant) may be used in the cleaning composition of the present invention. The component (a) is not included in the surfactant in the present invention.
As other surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and the like can be used, and nonionic surfactants are preferred. Examples of the nonionic surfactant 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.
洗浄剤組成物が成分（ｂ）以外の界面活性剤を含有する場合、その含有量は、洗浄剤組成物に対して１０質量％以下であることが好ましく、５質量％以下がより好ましく、実質的に成分（ｂ）以外の界面活性剤を含有しないことが最も好ましい。 When the detergent composition contains a surfactant other than the component (b), 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.
本発明の洗浄剤組成物は、必要に応じて溶媒、増量剤等の洗浄剤組成物に配合される他の成分を含有してもよい。また、必要に応じて、成分（ａ）及び成分（ｂ）に加えて消泡剤を含有してもよい。これらは１種のみ用いてもよく、２種以上を併用してもよい。
上記溶媒としては、水、有機溶媒等が挙げられる。有機溶媒としては、１～３価のアルコールを好適に用いることができ、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メトキシエタノール、２－エトキシエタノール等の１価アルコール；エチレングリコール、プロピレングリコール、ジプロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、グリセリン、ポリエチレングリコール、ポリプロピレングリコール等の２価又は３価の多価アルコール類等が挙げられる。中でも、２価又は３価の多価アルコールが好ましく、ポリプロピレングリコール、プロピレングリコール、１,２－プロパンジオールがより好ましい。
上記増量剤としては、硫酸ナトリウム（芒硝）、粉末シリカ等が挙げられる。
上記消泡剤としては、シリコーン系消泡剤等が挙げられる。 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.
Examples of the solvent include water and organic solvents. As the organic solvent, a monohydric to trihydric alcohol can be preferably used. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol 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.
Examples of the extender include sodium sulfate (sodium salt) and powdered silica.
Examples of the antifoaming agent include silicone-based antifoaming agents.
本発明の洗浄剤組成物の剤形は、液体、固体（粉末、顆粒（粒状）、錠剤、タブレット、フレーク又はブロック等）のいずれでもよい。好ましくは、液体及び固体である。また、本発明の洗浄剤組成物は、カートリッジ洗浄剤等にも好適に使用される。 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.
本発明の洗浄剤組成物の製造方法は特に限定されず、剤形に応じて適宜選択すればよい。例えば、成分（ａ）及び成分（ｂ）、並びに、所望により配合される他の成分を混合又は撹拌等することにより製造することができる。各成分を混合する順番、混合又は撹拌の方法等は特に限定されない。 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.
例えば、ブロックなどの固形体の洗浄剤組成物を製造する際には、例えば、まず、水及び水以外の洗浄剤組成物の原料を撹拌混合し、スラリー液を調製した後、上記スラリー液を所望の型又は容器等に投入し、冷却して固化させることが好ましい。 For example, when producing a solid detergent composition such as a block, for example, first, 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.
具体的には、まず、水に水以外の洗浄剤組成物の原料を加えた後、３０～１００℃に維持し、攪拌することにより、水及び洗浄剤組成物の原料を含むスラリー液を調製する。
水以外の洗浄剤組成物の原料の投入量は、上記スラリー液の全量に対して３５～１００質量％が好ましい。
次に、上記スラリー液を所望の型又は容器に投入し、その後、上記スラリー液を常温で１～２４時間放置して固化させ、型又は容器の形状に固化された固形体からなる洗浄剤組成物を製造する。 Specifically, first, 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. To do.
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.
Next, 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.
顆粒状（粒状）の洗浄剤組成物を製造する際には、洗浄剤組成物の原料となる成分（ａ）及び成分（ｂ）、並びに、所望により配合される他の成分の粒状原料を混合すればよい。混合にはリボンミキサー、ナウターミキサー、ドラムミキサーが好適に用いられる。
また、粉末状の洗浄剤組成物を製造する際には、洗浄剤組成物の原料となる成分（ａ）及び成分（ｂ）、並びに、所望により配合される他の成分の粉状原料を混合すればよい。混合にはリボンミキサー、ナウターミキサー、ドラムミキサーが好適に用いられる。
液体の洗浄剤組成物の製造方法は特に限定されず、任意の成分を混合又は攪拌等をすることにより製造することができる。各成分を混合する順番、混合又は攪拌の方法等は特に限定されない。 When producing a granular (granular) detergent composition, 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. For mixing, a ribbon mixer, a nauter mixer, and a drum mixer are preferably used.
In addition, when producing a powdery cleaning composition, 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. For mixing, 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.
本発明の自動洗浄機用洗浄剤組成物が使用される自動洗浄機は特に限定されないが、例えば、スプレー式自動洗浄機等が挙げられる。スプレー式自動洗浄機として、例えば、自動食器洗浄機、コンテナ洗浄機等が挙げられる。コンテナとして、食品等の運搬に使用されるプラスチック製コンテナが挙げられる。中でも、本発明の洗浄剤組成物は、自動食器洗浄機用又はコンテナ洗浄機用の洗浄剤組成物として好適に使用され、自動食器洗浄機用洗浄剤組成物としてより好適に使用される。また、本発明の洗浄剤組成物は、業務用又は家庭用の自動洗浄機用として好適に使用されるが、業務用自動洗浄機用としてより好適であり、業務用の自動食器洗浄機用洗浄剤組成物として特に好適である。 Although 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. Examples of 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. Especially, 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. Further, 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.
本発明の自動洗浄機用洗浄剤組成物を用いて自動洗浄機により食器等を洗浄する場合には、自動洗浄機中で、上記洗浄剤組成物を水で希釈した又は水に溶解させた洗浄液と食器等とを接触させればよく、該洗浄液中の洗浄剤組成物の濃度は０．０４～０．３質量％が好ましい。 When washing dishes and the like with an automatic washing machine using the cleaning composition for an automatic washing machine of the present invention, in the automatic washing machine, the cleaning composition diluted with water or dissolved in water. And 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.
以下、本発明をより具体的に説明する実施例を示す。なお、本発明はこれらの実施例のみに限定されるものではない。 Examples that more specifically describe the present invention are shown below. In addition, this invention is not limited only to these Examples.
＜実施例１～１００＞
表１～表８に示す成分を、表１～表８に示す割合となるように配合し、混合又は加温溶解することにより実施例１～１００の各洗浄剤組成物を製造した。表１～表８中の数値は、洗浄剤組成物に対する各成分の純分の割合（質量％）である。 <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.
＜比較例１～１１６＞
表９～１８に示す成分を、表９～１８に示す割合となるように配合し、混合又は加温溶解することにより比較例１～１１６の各洗浄剤組成物を製造した。表９～１８中の数値は、洗浄剤組成物に対する各成分の純分の割合（質量％）である。 <Comparative Examples 1-116>
The components shown in Tables 9 to 18 were blended so as to have the ratios shown in Tables 9 to 18, and mixed or heated to dissolve, whereby the cleaning compositions of Comparative Examples 1 to 116 were produced. The numerical values in Tables 9 to 18 are ratios (mass%) of pure components of the respective components with respect to the cleaning composition.
実施例１～１００及び比較例１～１１６で製造した洗浄剤組成物について、以下の方法で抑泡性及び洗浄力の評価を行った。 The detergent compositions produced in Examples 1 to 100 and Comparative Examples 1 to 116 were evaluated for foam suppression and detergency by the following methods.
＜抑泡性＞
（抑泡性条件）
抑泡性の試験は、洗浄工程において、自動食器洗浄機内の水量に対して洗浄剤組成物の濃度が０．１５質量％になるように洗浄剤組成物を投入して洗浄液とし、自動食器洗浄機を運転し、２分後の泡立ちと運転を停止してから３０秒後の泡立ちを観測した。
自動食器洗浄機として、ホバート社製１槽コンベアタイプの洗浄機（型番Ｃ４４Ｂ）を用いた。
（１）低温時の抑泡性
自動食器洗浄機を洗浄温度２０℃で運転した場合の泡の高さを観測した。
（２）汚れ存在下での抑泡性
全卵（鶏卵の卵液）４５gを自動食器洗浄機に投入し、洗浄温度５０℃で運転した場合の泡の高さを観測した。
（抑泡性の評価基準）
◎：抑泡性が高い（運転開始２分後の泡の高さが１００ｍｍ未満かつ運転停止３０秒後の泡の高さが７０ｍｍ未満）
〇：抑泡性が低い（運転開始２分後の泡の高さが１００ｍｍ以上又は運転停止３０秒後の泡の高さが７０ｍｍ以上）
×：抑泡性が非常に低い（運転開始２分後の泡の高さが１００ｍｍ以上かつ運転停止３０秒後の泡の高さが７０ｍｍ以上） <Foam suppression>
(Foam suppression condition)
The anti-foaming test was conducted in an automatic dishwashing process in which a cleaning composition was added so that the concentration of the cleaning composition was 0.15% by mass with respect to the amount of water in the automatic dishwashing machine. The machine was operated, and the foaming after 2 minutes and the foaming after 30 seconds were observed.
As an automatic dishwasher, a 1-bath conveyor type washer (model number C44B) manufactured by Hobart was used.
(1) The foam height when the automatic anti-foaming dishwasher at low temperature was operated at a washing temperature of 20 ° C. was observed.
(2) 45 g of foam-suppressing whole eggs (egg egg liquid) in the presence of dirt was placed in an automatic dishwasher, and the height of the foam was observed when the dish was operated at a washing temperature of 50 ° C.
(Evaluation criteria for foam suppression)
A: High foam suppression (the height of the foam after 2 minutes from the start of operation is less than 100 mm and the height of the foam after 30 seconds of operation is less than 70 mm)
◯: Low foam suppression (bubble height after 2 minutes of operation is 100 mm or more, or foam height after 30 seconds of operation is 70 mm or more)
X: Very low foam suppression (the height of the foam after 2 minutes of operation is 100 mm or more and the height of the foam after 30 seconds of operation is 70 mm or more)
＜洗浄力＞
（洗浄条件）
洗浄力の試験は、洗浄工程において、自動食器洗浄機内の水量に対して洗浄剤組成物の濃度が０．１５％となるように、洗浄剤組成物を投入して洗浄液とし、自動食器洗浄機を用いて洗浄試験用試料（ポリプロピレン製の弁当箱に１ｇの複合汚垢を塗布したもの）を洗浄してその外観を目視で評価することにより行った。
自動食器洗浄機として、ホシザキ社製ドアタイプの洗浄機（型番ＪＷ－６５０ＵＦ）を用い、洗浄条件は洗浄時間６０秒、洗浄温度６０℃、すすぎ時間５秒、すすぎ温度８０℃とした。洗浄水には、水道水を用いた。 <Detergency>
(Cleaning conditions)
In the cleaning process, in the cleaning process, 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.
As an automatic dishwasher, 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.
（洗浄力の評価基準）
洗浄剤組成物の洗浄力を次のように評価した。
◎：汚れの付着は見られない。
○：汚れの付着はほとんど見られない。
×：明らかな汚れの残留が見られる。 (Evaluation criteria for cleaning power)
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.
実施例及び比較例で製造した各洗浄剤組成物の組成並びに評価結果を表１～１８に示した。 Tables 1 to 18 show the compositions and evaluation results of the cleaning compositions prepared in Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
表中のポリオキシプロピレントリオールは、グリセロールのプロピレンオキサイド付加物である。表中、ＰＯは、プロピレンオキサイドを意味する。
表中の「残分」は、洗浄剤組成物１００質量％から水及び芒硝以外の成分の質量％を引いた残りが水又は芒硝であることを意味する。 The polyoxypropylene triol in the table is a propylene oxide adduct of glycerol. In the table, 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.
表１～１６中の（ｂ）成分の化合物は、以下の通りである。
リバースプルロニック型ブロックポリマー（質量平均分子量４０００）：ＥＯ／ＰＯのモル比が１／３
リバースプルロニック型ブロックポリマー（質量平均分子量４５００）：ＥＯ／ＰＯのモル比が１／３．５
リバーステトロニック型ブロックポリマー（質量平均分子量４０００）
リバーステトロニック型ブロックポリマー（質量平均分子量５０００）
プルロニック型ブロックポリマー（質量平均分子量２０００）：ＥＯ／ＰＯのモル比が１／７
プルロニック型ブロックポリマー（質量平均分子量３０００）：ＥＯ／ＰＯのモル比が１／７
テトロニック型ブロックポリマー（質量平均分子量２５００）：ＥＯ／ＰＯのモル比が１／７
テトロニック型ブロックポリマー（質量平均分子量３０００）：ＥＯ／ＰＯのモル比が１／７ 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
（ａ’）成分として使用した化合物は、以下の通りである。
ポリオキシエチレントリオール（質量平均分子量３０００）：グリセロールのエチレンオキサイド付加物
ポリオキシエチレンポリオキシプロピレントリオール（質量平均分子量２５００）：グリセロールのエチレンオキサイド及びプロピレンオキサイド付加物
脂肪族アルコールアルコキシレート：ＢＡＳＦ社製、商品名Ｐｌｕｒａｆａｃ　ＬＦ４０３
ポリオキシエチレンポリオキシプロピレンアルキルエーテル１：東邦化学工業社製、商品名ペポールＡＳ－０５４Ｃ 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
表１～８から、実施例１～１００の洗浄剤組成物は、低温時及び汚れ存在下において高い抑泡性を示した。さらに、実施例の洗浄剤組成物は、洗浄力に優れるものであった。比較例１～１１６の洗浄剤組成物は、低温時又は汚れ存在下での泡立ちを抑制できなかった。 From Tables 1 to 8, 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.

Claims (8)

  1. （ａ）下記一般式（１）で表される多価アルコールのアルキレンオキサイド付加物及び下記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルからなる群より選択される少なくとも１種の化合物を合計で０．０１～１０質量％、及び、（ｂ）リバースプルロニック型ブロックポリマー、リバーステトロニック型ブロックポリマー、プルロニック型ブロックポリマー及びテトロニック型ブロックポリマーからなる群より選択される少なくとも１種の界面活性剤を合計で０．１～１０質量％含むことを特徴とする自動洗浄機用洗浄剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、炭素数３～２０の３～８価の多価アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｎは、オキシアルキレン基の平均付加モル数を表し、２～１０００の数であり、ｍは、３～８の整数を表し、ｍ個の〔－Ｏ―（Ａ１Ｏ）ｎ－Ｈ〕は同一であってもよく、異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ２は、炭素数１～２０のアルキル基又は炭素数２～２０のアルケニル基を表し、Ａ２Ｏは、同一又は異なって、炭素数３又は４のオキシアルキレン基を表し、ｔは、オキシアルキレン基の平均付加モル数を表し、２～１００の数である。）     (A) At least one compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2) 0.01 to 10% by mass in total, and (b) at least one 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 A cleaning composition for automatic cleaning machines, comprising a total of 0.1 to 10% by weight of surfactants.
    Figure JPOXMLDOC01-appb-C000001
     (Wherein 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. Represents an oxyalkylene group, n represents the average number of moles added of the oxyalkylene group, is a number of 2 to 1000, m is an integer of 3 to 8, and m [—O— (A 1 O NH] may be the same or different.)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and 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.)
  2. 前記一般式（２）において、Ｒ２が炭素数１～２０のアルキル基を表す請求項１に記載の自動洗浄機用洗浄剤組成物。 The cleaning composition for an automatic cleaning machine according to claim 1, wherein, in the general formula (2), R 2 represents an alkyl group having 1 to 20 carbon atoms.
  3. 前記一般式（２）において、Ｒ２が炭素数３～１５のアルキル基を表し、前記Ａ２Ｏがオキシプロピレン基を表し、ｔが２～６０の数である請求項１又は２に記載の自動洗浄機用洗浄剤組成物。 3. The general formula (2), wherein R 2 represents an alkyl group having 3 to 15 carbon atoms, the A 2 O represents an oxypropylene group, and t is a number of 2 to 60. A cleaning composition for automatic cleaning machines.
  4. 前記一般式（２）で表されるポリオキシアルキレンモノアルキルエーテルが、ポリオキシプロピレントリデシルエーテルである請求項１～３のいずれかに記載の自動洗浄機用洗浄剤組成物。 The cleaning composition for an automatic cleaning machine according to any one of claims 1 to 3, wherein the polyoxyalkylene monoalkyl ether represented by the general formula (2) is polyoxypropylene tridecyl ether.
  5. 前記一般式（１）において、Ｒ１が炭素数３～５の３価の脂肪族アルコールから全部の水酸基を除いた残基を表し、Ａ１Ｏがオキシプロピレン基を表し、ｎが２～２５０の数であり、ｍが３である請求項１～４のいずれかに記載の自動洗浄機用洗浄剤組成物。 In the general formula (1), 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, and n is 2 to 250. The cleaning composition for an automatic cleaning machine according to any one of claims 1 to 4, wherein m is 3.
  6. 前記リバースプルロニック型ブロックポリマー中のオキシエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）のモル比（ＥＯ／ＰＯ）が１／１０～１／２である請求項１～５のいずれかに記載の自動洗浄機用洗浄剤組成物。 The molar ratio (EO / PO) of oxyethylene groups (EO) to oxypropylene groups (PO) in the reverse pluronic block polymer is 1/10 to 1/2. A cleaning composition for automatic cleaning machines.
  7. さらに、アルカリ剤、キレート剤、可溶化剤、漂白剤、腐食防止剤、除菌剤及び酵素からなる群より選択される少なくとも１種を含有する請求項１～６のいずれかに記載の自動洗浄機用洗浄剤組成物。 The automatic cleaning according to any one of claims 1 to 6, further comprising 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. Machine cleaning composition.
  8. 自動食器洗浄機用又はコンテナ洗浄機用の洗浄剤組成物である請求項１～７のいずれかに記載の自動洗浄機用洗浄剤組成物。 The cleaning composition for an automatic washing machine according to any one of claims 1 to 7, which is a cleaning composition for an automatic dishwashing machine or a container washing machine.
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