JP2899946B2 - Aqueous detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous detergent composition. More specifically, glass containing a modified oxide consisting of metal ions and electrical equipment using it, electronics, optics, exists on the solid surface of electronic components and precision components for the precision industry,
Fats and oils, adhesives, masks, waxes, cream solders,
The present invention relates to an aqueous detergent composition for washing and removing dirt such as flux.

[0002]

2. Description of the Related Art Glass is modified with glass-forming oxides such as phosphorus, boron, silicon and germanium and intermediate oxides such as aluminum and beryllium, and with magnesium, zinc, calcium, lead and sodium. It is composed of oxide. These intermediate oxides and modified oxides are compounded to enhance chemical stability and to adjust various properties such as optical constant, hardness, elastic modulus, coefficient of thermal expansion, and melting point.

[0003] Specific examples of glass include optical glass such as lenses, solder glass used for sealing, coating and bonding electronic parts, and functional glass having various optical and electrical functions.

Heretofore, oils, fats, adhesives, masking agents, and the like which exist on the solid surface of glass containing a modified oxide composed of metal ions and electronic parts and precision parts for the electric, electronic, optical and precision industries using the same. For removing stains such as waxes, cream solder, and flux, alcohol-based solvents such as ethanol and isopropanol; hydrocarbon-based solvents such as kerosene, benzene, and xylene; chlorine-based solvents such as trichloroethylene and tetrachloroethylene; trichlorotrifluoroethane and the like Solvent-based cleaning agents such as CFC-based solvents have been used.

However, alcohol solvents have safety problems, and hydrocarbon solvents, especially benzene,
Xylene and the like are compounds having high toxicity and are designated as harmful substances for occupational safety and health, and it is not preferable to use them as cleaning agents in view of the danger and complexity of handling such substances.

On the other hand, it has been revealed that cleaning agents using chlorine-based and chlorofluorocarbon-based solvents have serious problems in safety, toxicity, environmental pollution, and the like, and are being abolished on an international level. I have.

Recently, a water-based cleaning agent or water rinse has been used for cleaning stains on glass containing a modified oxide composed of metal ions and electronic parts and precision parts for the electric, electronic, optical and precision industries using the same. The use of possible cleaning agents is being considered. These detergents have the same or better detergency as solvent-based detergents by appropriately selecting and blending surfactants and builders used in detergents, and have various advantages such as low risk of fire and explosion. Having.

However, when cleaning glass containing a modified oxide composed of metal ions and electronic parts and precision parts for electric, electronic, optical, and precision industries using the same with these cleaning agents, it is difficult to use a metal. Elution of so-called "burn" of metal ions and the like in the modified oxide occurs from the surface layer of the glass containing the modified oxide composed of ions. Along with that,
In the case of optical glass, the surface layer of the glass is discolored or turbid (cloudy). Furthermore, in the case of the solder glass, there is a disadvantage that the melting point rises and, when used as a bonding agent, poor adhesion occurs.

[0009] There have been many attempts to use water-based cleaning agents for glass materials. For example, Japanese Patent Application Laid-Open No. Hei 5-271699 discloses that a quaternary ammonium hydroxide base is used as an alkali base material, and an organic alkali aqueous solution obtained by adding a nonionic surfactant and an alkanolamine is used as a detergent. It is shown.
However, these have insufficient cleaning properties for low-polarity stains. JP-A-5-302099 discloses that a composition containing ethylene glycol monohexyl ether, a surfactant, an auxiliary solvent and water is used as a detergent. However, these have insufficient effect of preventing "burn" of glass containing a modified oxide composed of metal ions.

Further, Japanese Patent Application Laid-Open No. 4-57899 discloses an invention relating to a solder flux detergent containing a polyoxyalkylene phosphate ester-based surfactant. An example in which a salt or the like is formed is also shown. However, when the phosphate ester does not form a salt, when the ester is added in a large amount to the detergent composition, the pH of the system is lowered, the solubility in water is deteriorated, and the viscosity of the cleaning solution itself is increased. There is a problem that is easy to occur. On the other hand, those forming an ammonium salt or a sodium salt are inferior in compatibility with organic stains such as oils, fats, waxes and flux, so that not only good cleaning properties cannot be obtained, but also the effect of preventing "burn" is poor. Is enough. Further, there are problems such as rusting due to the residual and deterioration of the electric characteristics.

On the other hand, regarding the “burnt” of the glass material,
For example, Journal of the Ceramic Society of Japan VOL87, No. 1, (1979) states that erosion of a surface layer by an alkali solution of alkali glass, so-called "latent wound", is caused by Ca ²⁺ , tetramethylammonium ion (N (CH ₃ ) ₄ ⁺ ). It is disclosed that it can be delayed by the presence of However, in the glass containing the modified oxide composed of the metal ion targeted in the present invention, the content of the modified oxide is large, so that more severe elution occurs.
In addition, some of the components contained in the dirt are apt to bond with the metal ions of these modified oxides.
This is due to a mechanism different from the above-mentioned etching, because the above-mentioned etching is remarkably promoted.

An object of the present invention is to solve a problem which has not been solved thus far. That is,
It is an object of the present invention to provide a water-based cleaning composition which improves the drawbacks of the conventional ordinary water-based cleaning agents, prevents "burn" of glass containing a modified oxide composed of metal ions, and at the same time enhances detergency.

[0013]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a glass containing a modified oxide composed of a metal ion and electric, electronic, optical, When cleaning electronic components and precision components for precision industry with a water-based cleaning agent, by using a composition containing a specific compound as a cleaning agent, a glass containing a modified oxide composed of metal ions can be used. It has been found that it can prevent "burn" and increase the cleanability,
The present invention has been completed.

That is, the gist of the present invention is as follows: (a) The following general formula (1)

[0015]

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(Wherein, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms, and X ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms). (B) 50 to 100% equivalent of the alkyl phosphate represented by the general formula (1) has 1 to 5 nitrogen atoms and has a molecular weight of 50 to 300.
The aqueous detergent composition according to the above (a), which is neutralized with an amine compound represented by the following general formula (2):

[0017]

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(Wherein R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group or a C ⁸ to C 12
Represents a phenyl group substituted with a linear or branched alkyl group, and q represents an integer of 0 to 20. X ² is a hydroxyl group or the following general formula (3) R ³ —O— (CH ₂ CH ₂ O) _q − (3) (wherein, R ³ is a linear or branched alkyl group having 1 to 20 carbon atoms; A phenyl group or a phenyl group substituted with a straight-chain or branched-chain alkyl group having 8 to 12 carbon atoms q
Represents an integer of 0 to 20. ). An aqueous detergent composition containing a phosphate ester represented by the formula (1), wherein 50 to 100% equivalent of the phosphate ester has 1 to 5 nitrogen atoms and a molecular weight of 50 to 300. An aqueous detergent composition neutralized with an amine compound, (d)
The following general formulas (4), (5) and (6)

[0019]

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(Wherein, R ⁴ represents a hydrocarbon group having 1 to 8 carbon atoms, R ⁵ and R ⁶ each represent an alkylene group having 2 to 4 carbon atoms. Y represents a hydrogen atom or a C 1 to C ⁴ alkyl group). M represents 1 to 7, n represents 0 to 7, and l represents an alkyl group or an acyl group.
Represents an integer of 0 to 5, and p represents an integer of 0 to 5. (A) to (c) further containing one or more alkylene oxide compounds selected from the group consisting of the compounds represented by
The aqueous cleaning composition according to any one of (a) to (d), further comprising (e) one or more surfactants; (f) a carbon number of 10; ~
(A) to (a) to (18), further containing 18 hydrocarbons.
(E) The aqueous cleaning composition according to any one of the above.

Among the components used in the aqueous detergent composition of the present invention, the alkyl phosphate is represented by the general formula (1)
It is represented by In the general formula (1), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and X ¹ is required to be a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. When the number of carbon atoms of the hydrocarbon group of R ¹ or X ¹ exceeds this range, the solubility in water becomes poor when the pH is lowered, and the viscosity of the cleaning liquid itself is also increased, so that the rinsing property tends to be reduced.

Specific examples of such alkyl phosphate esters include alkyl phosphate monoesters such as methyl phosphate monoester, ethyl phosphate monoester, isopropyl phosphate monoester and butyl phosphate monoester.
Alkyl phosphate diesters such as methyl phosphate diester, ethyl phosphate diester, isopropyl phosphate diester, and butyl phosphate diester; a mixture of the above alkyl phosphate monoester and alkyl phosphate diester (hereinafter, this mixture is referred to as alkyl phosphate sesquiester) In addition, even if the alkyl chains of the diester are the same,
It may be different. ). Specific examples of the alkyl phosphate sesquiester include methyl phosphate sesquiester, ethyl phosphate sesquiester, isopropyl phosphate sesquiester, and butyl phosphate sesquiester. Of the above compounds, methyl phosphate monoester, ethyl phosphate monoester, isopropyl phosphate monoester, butyl phosphate monoester, methyl phosphate sesquiester, ethyl phosphate sesquiester, isopropyl phosphate sesquiester, and butyl phosphate sesquiester are particularly preferably used. be able to.

The above alkyl phosphate monoester, alkyl phosphate diester and alkyl phosphate sesquiester can be obtained, for example, as follows. First, a method of reacting an alcohol having 1 to 4 carbon atoms with a highly active phosphorus derivative such as diphosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride, or phosphoric acids such as orthophosphoric acid or condensed phosphoric acid (polyphosphoric acid). Yields an alkyl phosphate sesquiester. To use an alkyl phosphate monoester, the alkyl phosphate sesquiester obtained as described above is neutralized with an inorganic alkali such as sodium hydroxide or an organic amine in water, for example, to form a salt. Allow to dissolve. This is added to an organic solvent such as acetone or ethanol to precipitate an alkyl phosphate monoester, or the sesquiphosphate phosphate is dissolved in a heated organic solvent such as n-hexane and then cooled. , And an alkyl phosphate monoester may be isolated by a conventional separation method such as precipitation. Also, to use an alkyl phosphate diester,
It may be isolated by a conventional separation method such as concentration to dryness from the organic solvent solution from which the precipitate of the alkyl phosphate monoester has been removed.

These alkyl phosphates are present in the detergent composition in an amount of from 0.1 to 6% by weight, especially from 0.2 to 3% by weight.
It is preferable to mix them. If it is less than this range, the effect of preventing "burn" of the glass containing the modified oxide composed of metal ions tends to be insufficient, and if it exceeds this range, the pH decreases, the solubility in water becomes poor, and the cleaning solution itself becomes poor. Since the viscosity also increases, the rinsability tends to decrease. Furthermore,
In particular, glass containing boron as a glass-forming oxide tends to cause surface corrosion called “latent flaw” when the pH is low.

The alkyl phosphate represented by the general formula (1) used in the aqueous detergent composition of the present invention is:
Further, by neutralizing 50 to 100% of the equivalent with an amine compound, a decrease in pH when the ester is added in a large amount to the detergent composition is suppressed, deterioration of solubility in water and viscosity of the washing solution itself are suppressed. Can be prevented, and a decrease in rinsing properties can be suppressed. Further, "latent scratches" of glass containing boron as a glass forming oxide can be prevented. Neutralization is achieved by mixing the two components described above. At this time, the mixing ratio of the above-mentioned two components for neutralization of a desired% equivalent can be easily obtained from the acid value of the alkyl phosphate ester and the base value of the amine compound.

The amine compound which neutralizes the alkyl phosphate ester has 1 to 5 nitrogen atoms and a molecular weight of 50 to 300, preferably 1 to 2 nitrogen atoms. Having a molecular weight of 100 to 250. If the molecular weight is less than this range, the obtained detergent composition tends to have a strong odor, and if the molecular weight exceeds this range, the viscosity of the neutralized product with the alkyl phosphate ester increases, and as a result, the cleaning solution itself , The rinsing properties tend to decrease.

Specific examples of such an amine compound include:
The following substances may be mentioned. (A) Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, dibutylethanolamine and methyldiethanolamine. (B) Morpholines such as morpholine and ethyl morpholine. (C) cyclohexylamine, dicyclohexylamine, polyoxyalkylenecyclohexylamine and the like, and alicyclic amines obtained by addition polymerization of 1 to 20 moles of ethylene oxide, propylene oxide and the like per 1 mole of these cyclohexylamines. (D) hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine,
Linear alkylamines having a linear alkyl group having 6 to 22 carbon atoms, such as laurylamine, tridecylamine, myristylamine, pentadecylamine, cetylamine, heptadecylamine, stearylamine, nonadecylamine, eicosylamine and the like. (E) s-butylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylpropylamine, 2-methylbutylamine, isoamylamine, dimethylpropylamine, t-amylamine, 1,
3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, 1-methylheptylamine, 2-ethylhexylamine, 1,5
-Dimethylhexylamine, t-octylamine, t-
4 carbon atoms such as tridecylamine and t-nanodecylamine
Branched alkylamines having from 22 to 22 branched alkyl groups. (F) In addition, piperazine, triethylenediamine, pentamethyldiethylenetriamine, tetramethylpropylenediamine and the like.

Among the above compounds, alicyclic amine compounds (hereinafter referred to as (POE)) obtained by addition-polymerizing 2 mol of ethylene oxide per 1 mol of diethanolamine, methyldiethanolamine, ethylmorpholine, piperazine, triethylenediamine, cyclohexylamine, and cyclohexylamine Abbreviated as ₂ cyclohexylamine)), hexylamine, octylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, t-butylamine, t-amylamine, t-octylamine, t-tridecylamine,
T-nanodecylamine can be preferably used from the viewpoint of performance and availability.

The alkyl phosphate represented by the general formula (1) and the neutralized product of these amine compounds are contained in the detergent composition in an amount of 0.2 to 15% by weight, particularly 0.5 to 10% by weight. It is preferable to mix them. If it is less than this range, the effect of preventing "burning" of the glass containing the modified oxide composed of metal ions tends to be insufficient. There is a tendency that the viscosity increases and the cleaning agent or the like is not sufficiently rinsed in the rinsing step.

Among the components used in the aqueous detergent composition of the present invention, the phosphate ester represented by the general formula (2) is obtained by neutralizing 50 to 100% equivalent of the phosphate ester with an amine compound. In addition, it is possible to suppress a decrease in pH when a large amount of the ester is added to the detergent composition, prevent deterioration in solubility in water and increase in viscosity of the washing liquid itself, and suppress a decrease in rinsing properties. Further, "latent scratches" of glass containing boron as a glass forming oxide can be prevented. The amine compound used for neutralizing the phosphate ester is
The same compounds as the amine compounds used for neutralizing the alkyl phosphate can be used. Neutralization is achieved by mixing the two components described above. At this time, the mixing ratio of the above-mentioned two components for neutralization of a desired% equivalent can be easily obtained from the acid value of the alkyl phosphate ester and the base value of the amine compound.

In the general formula (2), R ² is a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group or a phenyl group substituted with a linear or branched alkyl group having 8 to 12 carbon atoms. And q is an integer of 0 to 20; X ² is a hydroxyl group or a general formula (3) (wherein, R ³ is a group having 1 to 20 carbon atoms)
And a phenyl group substituted with a linear or branched alkyl group having 8 to 12 carbon atoms. q is an integer of 0 to 20. ). Therefore, the phosphate ester in the present invention includes an alkyl phosphate ester.

In the general formula (2) or (3), when the carbon number of the hydrocarbon group of R ² or R ³ exceeds the above range,
Since the solubility in water deteriorates and the viscosity of the cleaning liquid itself also increases, the rinsing property tends to decrease. Also,
q is an integer in the range of 0 to 20, but more preferably 3 to 14. When q exceeds this range, the viscosity of the cleaning liquid tends to increase, and the rinsing property decreases. Hereinafter, such a phosphate ester is referred to when q is 0 and q is 1 to
20 cases are specifically listed.

(A) When q is 0: methyl phosphate monoester, ethyl phosphate monoester, isopropyl phosphate monoester, butyl phosphate monoester, pentyl phosphate monoester, hexyl phosphate monoester, heptyl phosphate monoester, octyl phosphate Monoester, nonyl phosphate monoester,
Monoester of decyl phosphate, monoester of isodecyl phosphate, monoester of undecyl phosphate, monoester of lauryl phosphate, monoester of tridecyl phosphate, monoester of myristyl phosphate, monoester of pentadecyl phosphate, monoester of cetyl phosphate, monoester of heptadecyl phosphate And phosphoric acid monoesters such as stearyl phosphate monoester, oleyl phosphate monoester, octylphenyl phosphate monoester, nonylphenyl phosphate monoester and dodecylphenyl phosphate monoester.

Methyl phosphate diester, ethyl phosphate diester, isopropyl phosphate diester, butyl phosphate diester, pentyl phosphate diester, hexyl phosphate diester, heptyl phosphate diester, octyl phosphate diester, nonyl phosphate diester, decyl phosphate diester, isodecyl phosphate diester, undecyl phosphorus Acid diester, lauryl phosphate diester, tridecyl phosphate diester, myristyl phosphate diester, pentadecyl phosphate diester, cetyl phosphate diester, heptadecyl phosphate diester, stearyl phosphate diester, oleyl phosphate diester, octylphenyl phosphate diester, nonylphenyl Phosphoric diesters such as phosphoric diester and dodecylphenyl phosphoric diester.

Sesquiester of methyl phosphate, sesquiester of ethyl phosphate, sesquiester of isopropyl phosphate, sesquiester of butyl phosphate, sesquiester of pentyl phosphate, sesquiester of hexyl phosphate, sesquiester of heptyl phosphate, sesquiester of octyl phosphate, sesquiester of nonyl phosphate Sesquiester decyl phosphate, sesquiester isodecylphosphate, sesquiester undecylphosphate, sesquiester lauryl phosphate, sesquiester tridecylphosphate, sesquiester myristyl phosphate, sesquiester pentadecylphosphate, sesquiester cetylphosphate, sesquiester heptadecylphosphate , Stearyl phosphate sesquiester, oleyl phosphate sesquiester, octylphenyl phosphate sesquiester, nonyl Enirurin acid sesqui esters, phosphoric acid sesqui esters such as dodecyl phenyl phosphate sesqui esters.

(B) When q is 1 to 20 (at this time, the compound represented by the general formula (2) is hereinafter referred to as polyoxyethylene phosphate. In the general formula (2), R ² Is a phosphoric acid monoester in which the hydrocarbon group is a methyl group and q is 1. (POE) _1- methylphosphoric acid monoester. Hereinafter, similar compounds are abbreviated as described above in corresponding expressions. Also, (POE) ₁
Methyl phosphate monoester, abbreviated as (POE) ₂ methyl phosphate monoester and (POE) ₃ methyl phosphate monoester collectively (POE) ₁ ~ ₃ methyl phosphate monoester. Hereinafter, similar abbreviations mean those compounds corresponding thereto. ) (POE) ₁ ~ ₂₀ methyl phosphate monoester, (PO
E) ₁ to ₂₀ ethyl phosphate monoester, (POE) ₁ to
₂₀ isopropyl phosphoric acid monoester, (POE) ₁ ~ ₂₀
Butyl phosphate monoester, (POE) ₁ ~ ₂₀ Penchirurin acid monoester, (POE) ₁ ~ ₂₀ Hekishirurin acid monoester, (POE) ₁ ~ ₂₀ Hepuchirurin acid monoester, (POE) ₁ ~ ₂₀ octyl phosphate monoester, (POE) ₁ ~ ₂₀ Nonirurin acid monoester, (P
OE) ₁ ~ ₂₀ decyl acid monoester, (POE) ₁
~ ₂₀ Isodeshirurin acid monoester, (POE) ₁ to ₂₀
Undeshirurin acid monoester, (POE) ₁ ~ ₂₀ lauryl phosphate monoester, (POE) ₁ ~ ₂₀ tridecyl acid monoester, (POE) ₁ ~ ₂₀ Mirisuchirurin acid monoester, (POE) ₁ ~ ₂₀ pentadecyl phosphate monoester, (POE) ₁ ~ ₂₀ cetyl phosphate monoester, (POE) ₁ ~ ₂₀ heptadecyl phosphoric acid monoester, (POE) ₁ ~ ₂₀ stearyl acid monoester,
(POE) ₁ ~ ₂₀ oleyl phosphate monoester, (PO
E) ₁ ~ ₂₀ octylphenyl phosphoric acid monoester, (P
OE) ₁ ~ ₂₀ nonylphenyl phosphoric acid monoester, (P
OE) polyoxyethylene phosphoric acid monoesters such as _1-20 dodecylphenyl phosphate monoester.

[0037] (POE) ₁ ~ ₂₀ methyl phosphate diesters, (POE) ₁ ~ ₂₀ ethyl phosphoric acid diester, (PO
E) ₁ ~ ₂₀ isopropyl phosphodiester, (POE)
_1-20 butyl phosphate diesters, (POE) _1-20 Penchirurin acid diesters, (POE) _1-20 Hekishirurin acid diesters, (POE) _1-20 Hepuchirurin acid diesters, (POE) _1-20 octyl phosphate diester,
(POE) ₁ ~ ₂₀ Nonirurin acid diester, (POE)
_1-20 decyl diester, (POE) _1-20 Isodeshirurin acid diesters, (POE) _1-20 Undeshirurin acid diesters, (POE) _1-20 lauryl phosphoric acid diester, (POE) _1-20 tridecyl diesters, (POE ) ₁ to ₂₀ Mirisuchirurin acid diester,
(POE) ₁ ~ ₂₀ pentadecyl phosphodiester, (P
OE) ₁ to ₂₀ cetyl phosphate diester, (POE) ₁ to
₂₀ heptadecyl phosphodiester, (POE) ₁ ~ ₂₀ stearyl phosphate diesters, (POE) ₁ ~ ₂₀ oleyl phosphate diesters, (POE) ₁ ~ ₂₀ octylphenyl phosphoric acid diester, (POE) ₁ ~ ₂₀ nonylphenyl phosphate diesters, (POE) polyoxyethylene phosphoric acid diesters such as _1-20 dodecylphenyl phosphate diester. The polyoxyethylene chains of the diester may be the same or different.

[0038] (POE) ₁ ~ ₂₀ methyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ ethyl phosphate sesqui esters,
(POE) ₁ ~ ₂₀ isopropyl phosphate sesqui esters,
(POE) ₁ to ₂₀ butyl sesquiphosphate, (PO
E) ₁ ~ ₂₀ Penchirurin acid sesqui esters, (POE)
₁ to ₂₀ hexyl phosphoric acid sesquiester, (POE) ₁ to
₂₀ Hepuchirurin acid sesqui esters, (POE) ₁ ~ ₂₀ octyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ Nonirurin acid sesqui esters, (POE) ₁ ~ ₂₀ decyl acid sesqui esters, (POE) ₁ ~ ₂₀ Isodeshirurin acid sesqui esters , (POE) ₁ ~ ₂₀ Undeshirurin acid sesqui esters, (POE) ₁ ~ ₂₀ lauryl phosphate sesqui esters, (POE) ₁ ~ ₂₀ tridecyl acid sesqui esters, (POE) ₁ ~ ₂₀ Mirisuchirurin acid sesqui esters, (POE) _1-20 pentadecyl phosphoric acid sesqui esters, (POE) _1-20 cetyl phosphate sesqui esters,
(POE) ₁ ~ ₂₀ heptadecyl phosphoric acid sesqui esters,
(POE) ₁ ~ ₂₀ stearylphosphate sesqui esters,
(POE) ₁ ~ ₂₀ oleyl acid sesqui esters, (P
OE) ₁ ~ ₂₀ octylphenyl phosphoric acid sesqui esters,
(POE) _1-20 nonylphenyl phosphoric acid sesqui esters, (POE) or the like _1-20 dodecylphenyl phosphate sesqui esters. The sesquiester referred to herein is a mixture of polyoxyethylene phosphate monoester and polyoxyethylene phosphate diester.

Of the above compounds, methyl phosphate monoester, ethyl phosphate monoester, isopropyl phosphate monoester, butyl phosphate monoester, hexyl phosphate monoester, octyl phosphate monoester, decyl phosphate monoester, lauryl phosphate monoester Esters, myristyl phosphate monoester, cetyl phosphate monoester, stearyl phosphate monoester, oleyl phosphate monoester, nonylphenyl phosphate monoester, methyl phosphate sesquiester, ethyl phosphate sesquiester, isopropyl phosphate sesquiester, butyl phosphate sesquiester , Hexyl phosphate sesquiester, octyl phosphate sesquiester, decyl phosphate sesquiester, lauryl phosphate sesquiester, myristyl phosphate sesquiester Cetyl phosphate sesqui esters, stearyl acid sesqui esters, oleyl acid sesqui esters, nonylphenyl phosphoric acid sesqui esters, (POE) ₁ ~ ₂₀ methyl phosphate monoester, (P
OE) ₁ ~ ₂₀ ethyl phosphate ester, (POE) ₁
~ ₂₀ isopropyl phosphate monoester, (POE) ₁ ~
₂₀ butyl phosphate monoester, (POE) ₁ ~ ₂₀ Hekishirurin acid monoester, (POE) ₁ ~ ₂₀ octyl phosphate monoester, (POE) ₁ ~ ₂₀ decyl acid monoester, (POE) ₁ ~ ₂₀ lauryl phosphoric acid mono ester, (POE) ₁ ~ ₂₀ Mirisuchirurin acid monoester,
(POE) ₁ ~ ₂₀ cetyl phosphate monoester, (PO
E) ₁ ~ ₂₀ stearyl acid monoester, (POE)
_1-20 oleyl phosphate monoester, (POE) _1-20
Octyl phenyl phosphate monoester, (POE) _1
20 nonylphenyl phosphate monoester, (POE) _1-
20 methyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ ethyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ isopropyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ butyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ Hekishirurin acid sesqui esters , (POE) ₁ ~ ₂₀ octyl phosphate sesqui esters, (POE) ₁ ~ ₂₀ decyl acid sesqui esters, (POE) ₁ ~ ₂₀ lauryl phosphate sesqui esters,
(POE) ₁ ~ ₂₀ Mirisuchirurin acid sesqui esters,
(POE) ₁ ~ ₂₀ cetyl phosphate sesqui esters, (PO
E) ₁ ~ ₂₀ stearylphosphate sesqui esters, (PO
E) ₁ ~ ₂₀ oleyl acid sesqui esters, (POE)
_1-20 octylphenyl phosphoric acid sesqui esters, (PO
E) ₁ ~ ₂₀ nonylphenyl phosphoric acid sesqui esters can be preferably used in terms of performance and easy availability.

Among these phosphoric acid esters, the phosphoric acid ester in (a) has an alcohol having 1 to 2 carbon atoms.
Except for making it 0, it can be produced by the same method as the method for producing the alkyl phosphate represented by the general formula (1). The polyoxyethylene phosphate in (b) is obtained by adding ethylene oxide in a gaseous state to an alcohol or phenol having a hydrocarbon group having 1 to 20 carbon atoms while heating in the presence of a catalyst such as caustic soda. By doing so, first, an ethylene oxide compound is obtained. The desired compound is obtained by reacting the obtained ethylene oxide compound with a phosphorus derivative such as phosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride or the like, or phosphoric acid such as orthophosphoric acid or condensed phosphoric acid (polyphosphoric acid). .

The neutralized product of the phosphate ester and the amine compound is preferably incorporated in the detergent composition in an amount of 0.2 to 15% by weight, particularly 0.5 to 10% by weight. Below this range, the effect of preventing "burning" of the glass containing the modified oxide composed of metal ions is insufficient, and if it exceeds this range, not only is it not advisable to increase the cost,
The viscosity of the cleaning agent tends to increase, and the cleaning agent and the like tend not to be sufficiently rinsed in the rinsing step.

The detergency can be improved by further using the alkylene oxide compounds represented by formulas (4), (5) and (6) in the aqueous detergent composition of the present invention.

In the general formulas (4), (5) and (6), R ⁴
Is required to be a hydrocarbon group having 1 to 8 carbon atoms, but is preferably a hydrocarbon group having 2 to 6 carbon atoms. When R ⁴ is not a hydrocarbon group, the affinity with organic stains such as oils and fats, adhesives, masking agents, waxes, cream solder, and flux is reduced. Further, when the carbon number of the hydrocarbon group of R ⁴ exceeds this range, solubility in water deteriorates and the viscosity of the cleaning solution itself tends to increase. It is not suitable for cleaning used electronic parts and precision parts for electric, electronic, optical and precision industries.

M is 1 to 7, n is 0 to 7, and l is 0 to 7.
5, p needs to be an integer of 0-5. Also,
m + n is in the range of 1 to 14, and p + 1 is in the range of 0 to 10. In particular, m + n is in the range of 2 to 4, and p + 1
Is preferably in the range of 0 to 4. If m + n is less than this range, the solubility in water tends to be insufficient, and if m + n exceeds this range, the affinity for water tends to be too strong, and the detergency of organic stains decreases. I do.

Specific examples of such alkylene oxide compounds include methanol, ethanol, propanol,
Alcohols having a linear or branched alkyl group such as butanol, isobutanol, hexanol and octanol; phenols such as phenol and cresol; alicyclic alcohols such as cyclohexanol; acetic acid, propionic acid, hexanoic acid, Fatty acids having a linear or branched alkyl group such as isooctylic acid; organic carboxylic acids such as methacrylic acid and benzoic acid; linear acids such as ethylamine, diethylamine, hexylamine, dibutylamine, octylamine, benzylamine and cyclohexylamine;
An amine compound having a branched chain, an aromatic or alicyclic hydrocarbon group, or the like, to which an alkylene (ethylene, propylene, butylene) oxide is added alone or in combination is mentioned. Compounds in which terminal hydroxyl groups are methylated, ethylated, or butylated with alkyl chloride or the like, or esterified with acetic acid, propionic acid, or the like. One of the alkylene oxide compounds may be used alone, or two or more thereof may be used in combination.

Specific examples include the following compounds. (A) Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoallyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether And monoethylene glycol monoethers such as ethylene glycol monooctyl ether, ethylene glycol monophenyl ether, and ethylene glycol monobenzyl ether.

(B) diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoallyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol monooctyl ether ,
Diethylene glycol monoethers such as diethylene glycol monophenyl ether and diethylene glycol monobenzyl ether;

(C) Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monoisobutyl ether, triethylene glycol monoallyl ether, triethylene glycol monoethyl ether Hexyl ether, triethylene glycol mono 2
Triethylene glycol monoethers such as ethylhexyl ether, triethylene glycol monooctyl ether, triethylene glycol monophenyl ether, and triethylene glycol monobenzyl ether;

(D) Tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monoisobutyl ether, tetraethylene glycol monoallyl ether, tetraethylene glycol monoethyl ether Tetraethylene glycol monoethers such as hexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monooctyl ether, tetraethylene glycol monophenyl ether, and tetraethylene glycol monobenzyl ether.

(E) pentaethylene glycol monomethyl ether, pentaethylene glycol monoethyl ether, pentaethylene glycol monopropyl ether, pentaethylene glycol monobutyl ether, pentaethylene glycol monoisobutyl ether, pentaethylene glycol monoallyl ether, pentaethylene glycol monoethyl ether Pentaethylene glycol monoethers such as hexyl ether, pentaethylene glycol mono 2-ethylhexyl ether, pentaethylene glycol monooctyl ether, pentaethylene glycol monophenyl ether, and pentaethylene glycol monobenzyl ether;

[0051] _{(f) (POE) 6 ~} 7 monomethyl ether, (POE) ₆ ~ ₇ monoethyl ether, (POE)
_6-7 monopropyl ether, (POE) _6-7 monobutyl ether, (POE) _6-7 monoisobutyl ether, (POE) _6-7 monoallyl ether, (POE)
_6-7 monohexyl ether, (POE) _6-7 monomethyl 2
- ethylhexyl ether, (POE) ₆ ~ ₇ monooctyl ether, (POE) ₆ ~ ₇ monophenyl ether, (POE) ₆ ~ ₇ polyoxyethylene monoethers of monobenzyl ether.

(G) Monoethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether and ethylene glycol diallyl ether.

(H) Diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol 2-ethylhexyl methyl ether, and diethylene glycol diallyl ether.

(I) Triethylene glycol diethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, and triethylene glycol diallyl ether.

(J) Tetraethylene glycol diethers such as tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether and tetraethylene glycol diallyl ether.

[0056] _{(k) (POE) 6 ~} 7 dimethyl ether, (POE) ₆ ~ ₇ diethyl ether, (POE) ₆
Polyoxyethylene diethers such as ₇ to ₇ dipropyl ether, (POE) ₆ to ₇ dibutyl ether, and (POE) ₆ to ₇ diallyl ether.

(L) Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoallyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, propylene glycol Monopropylene glycol monoethers such as monooctyl ether, propylene glycol monophenyl ether and propylene glycol monobenzyl ether;

(M) dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoallyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoethyl Dipropylene glycol monoethers such as 2-ethylhexyl ether, dipropylene glycol monooctyl ether, dipropylene glycol monophenyl ether, and dipropylene glycol monobenzyl ether;

(N) tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoallyl ether, tripropylene glycol monohexyl ether, tripropylene glycol monoethyl ether Tripropylene glycol monoethers such as 2-ethylhexyl ether, tripropylene glycol monooctyl ether, tripropylene glycol monophenyl ether, and tripropylene glycol monobenzyl ether.

[0060] _{(o) (POP) 4 ~} 7 monomethyl ether, (POP) ₄ ~ ₇ mono ethyl ether, (POP)
_4-7 monopropyl ether, (POP) _4-7 monobutyl ether, (POP) _4-7 monoallyl ether,
(POP) ₄ to ₇ monohexyl ether, (POP) ₄
~ ₇ mono 2-ethylhexyl ether, (POP) ₄ ~
₇ monooctyl ether, (POP) _4-7 monophenyl ether, (POP) polyoxypropylene monomethyl ethers such as _4-7 monobenzyl ether. (PO
P) is (PO) except that ethylene is propylene.
Abbreviations similar to E).

(P) Monopropylene glycol diethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and propylene glycol diallyl ether.

(Q) Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol isopropyl methyl ether, dipropylene glycol isopropyl ethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diallyl ether, etc. Dipropylene glycol diethers.

(R) Tripropylene glycol diethers such as tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, and tripropylene glycol diallyl ether.

[0064] _{(s) (POP) 4 ~} 7 dimethyl ether, (POP) ₄ ~ ₇ diethyl ether, (POP) _4
1-7 dipropyl ethers, (POP) _4-7 dibutyl ether, (POP) polyoxypropylene di- ethers such as _4-7 diallyl ether.

(T) Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoallyl ether acetate, ethylene glycol monohexyl ether acetate, ethylene glycol monooctyl Monoethylene glycol monoether acetates such as ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monobenzyl ether acetate;

(U) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoallyl ether acetate, diethylene glycol monohexyl ether acetate, diethylene glycol monooctyl ether acetate, diethylene glycol monophenyl ether Diethylene glycol monoether acetates such as acetate and diethylene glycol monobenzyl ether acetate;

[0067] _{(v) (POE) 3 ~} 7 monomethyl ether acetate, (POE) ₃ ~ ₇ monoethyl ether acetate, (POE) ₃ ~ ₇ monopropyl ether acetate, (POE) ₃ ~ ₇ monobutyl ether acetate, (POE ) _3-7 monoallyl ether acetates,
(POE) ₃ ~ ₇ monohexyl ether acetate,
(POE) ₃ ~ ₇ mono-octyl ether acetate,
(POE) ₃ ~ ₇ monophenyl ether acetate,
(POE) polyoxyethylene monoether acetates, such as _3-7 monobenzyl ether acetate.

(W) Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monoallyl ether acetate, propylene glycol monohexyl ether acetate, propylene glycol monooctyl Monopropylene glycol monoether acetates such as ether acetate, propylene glycol monophenyl ether acetate, propylene glycol monobenzyl ether acetate;

[0069] _{(x) (POE) 2 ~} 7 monomethyl ether acetate, (POE) ₂ ~ ₇ monoethyl ether acetate, (POE) ₂ ~ ₇ monopropyl ether acetate, (POE) ₂ ~ ₇ monobutyl ether acetate, (POE ) _2-7 monoallyl ether acetates,
(POE) ₂ ~ ₇ monohexyl ether acetate,
(POE) ₂ ~ ₇ mono-octyl ether acetate,
(POE) ₂ ~ ₇ monophenyl ether acetate,
(POE) polyoxypropylene monobutyl ether acetates, such as _2-7 monobenzyl ether acetate.

(Y) Monopropylene glycol diacetates such as propylene glycol diacetate. (Z) a compound obtained by blocking and randomly adding ethylene oxide and propylene oxide to an alcohol having a linear or branched alkyl group, which is a raw material of the hydrocarbon group, or an alicyclic alcohol, (POE) ₁ to
₇ (POP) ₁ ~ ₇ monoethers; (POE) ₁ ~ ₇
(POP) ₁ ~ ₇ diethers.

(Α) Instead of alcohols and alicyclic alcohols having a straight-chain or branched-chain alkyl group, which are raw materials for the above-mentioned hydrocarbon groups, acetic acid, propionic acid, hexanoic acid, isooctylic acid, etc. Compounds using an organic carboxylic acid such as a fatty acid having a chain or branched chain alkyl group, methacrylic acid, benzoic acid and the like. For example, (POE) _1-7 monomethyl ester, (POE) _1-7 monoethyl ester, methacrylic acid (POE) _1-7 adducts, benzoic acid (POE) glycol monoesters such as _1-7 adduct ; (POE) ₁ ~ _7-dimethyl ester, (POE) ₁
To ₇ glycol diesters such as diethyl ester. (Β) Instead of alcohols having a straight-chain or branched-chain alkyl group and alicyclic alcohols, which are raw materials for the hydrocarbon group, ethylamine, diethylamine, hexylamine, dibutylamine, octylamine, benzylamine, Compounds using amines having a linear, branched, aromatic or alicyclic hydrocarbon group, such as cyclohexylamine. For example, (POE) ₁ ~ ₇ ethylamine, (PO
E) ₁ ~ ₇ diethylamine, (POE) ₁ ~ ₇ hexylamine, (POE) ₁ ~ ₇ dibutylamine, (POE)
Examples thereof include glycol monoamines such as ₁ to ₇ octylamine, (POE) ₁ to ₇ benzylamine, and (POE) ₁ to ₇ cyclohexylamine.

Of the above compounds, those listed below are preferably used from the viewpoint of performance and availability. (A) Ethylene glycol monoethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monoallyl ether, ethylene glycol monohexyl ether, ethylene glycol mono2 −
Ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether;

Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoallyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monophenyl ether Benzyl ether;

Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol monophenyl ether, triethylene glycol monobenzyl ether;

Tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether,
Tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monophenyl ether, tetraethylene glycol monobenzyl ether;

Pentaethylene glycol monomethyl ether, pentaethylene glycol monoethyl ether,
Pentaethylene glycol monopropyl ether, pentaethylene glycol monobutyl ether, pentaethylene glycol monophenyl ether, pentaethylene glycol monobenzyl ether;

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether;

Diethylene glycol dimethyl ether,
Diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether,
Diethylene glycol 2-ethylhexyl methyl ether; triethylene glycol dimethyl ether; tetraethylene glycol dimethyl ether.

(B) propylene glycol propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, propylene glycol monobenzyl ether;

Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, dipropylene glycol monobenzyl ether; tripropylene glycol monomethyl ether, tripropylene glycol Propylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monophenyl ether, tripropylene glycol monobenzyl ether;

Propylene glycol dimethyl ether,
Propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol isopropyl methyl ether, dipropylene glycol isopropyl ethyl ether; tripropylene Glycol dimethyl ether.

(C) Acetate Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol diacetate.

These alkylene oxide compounds are
For example, an alcohol having a hydrocarbon group having 1 to 8 carbon atoms,
Phenols, fatty acids, organic carboxylic acids, and amine compounds are heated to 2 carbon atoms in the presence of a catalyst such as caustic soda.
To alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) in a liquid or gaseous state and reacted. Further, those obtained by alkylating the terminal hydroxyl groups of these alkylene oxide adducts with an alkyl chloride or the like or esterifying them with an organic acid or the like can be used.

In the case of adding an alkylene oxide, random addition polymerization in which two or more alkylene oxides are mixed and reacted or block addition polymerization in which an alkylene oxide is sequentially added may be performed.

These alkylene oxide compounds are
It is preferable to add 5 to 95% by weight, particularly 10 to 70% by weight in the detergent composition. If the compounding amount is less than this range, the effect of adding the alkylene oxide compound tends to fail to sufficiently exert the detergency and its sustainability.
In addition, if the compounding ratio exceeds this range, there is a danger of flammability.

The water-based detergent composition of the present invention further increases the detergency by adding a surfactant. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a zwitterionic surfactant can be used.

More specifically, fatty acid salts, higher alcohol sulfate salts, liquid fatty oil sulfate salts,
Anions such as sulfates of aliphatic amines and aliphatic amides, phosphate salts of fatty alcohols, sulfonates of dibasic fatty acid esters, fatty acid amide sulfonates, alkylallyl sulfonates, and naphthalene sulfonates of formalin condensation Cationic activators such as aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts; polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene alkylamines, and polyoxyalkylene alkyl Nonionic activators such as esters, sorbitan alkyl esters and polyoxysorbitan alkyl esters; or zwitterions such as alkyl betaines, alkyl dimethyl amine oxides and alkyl alanines Active agent and the like as those were the main. Here, polyoxyalkylene refers to a polymer of ethylene oxide, propylene oxide or butylene oxide. Among these surfactants,
In particular, nonionic activators having an average HLB of 4 to 18 exhibit excellent effects.

Specifically, (POE) ₁ to ₄₀ octyl ether, monomeric to _40- mer ethylene oxide and ether of a synthetic alcohol having 12 to 14 carbon atoms ((PO
E) abbreviated as ₁ ~ ₄₀ C ₁₂ ~ ₁₄ Synthesis alcohol ether. ), (POE) ₁ ~ ₄₇ lauryl ether, (PO
E) ₂ to ₂₀ cetyl ether, (POE) ₂ to ₃₀ stearyl ether, (POE) ₂ to ₃₅ oleyl ether, (P
OE) ₂ to ₄₀ octyl phenyl ether, (POE) ₂
Polyoxyethylene alkyl ethers such as _-45 nonylphenyl ether; sorbitan monolauryl ester,
Sorbitan monoalkyl esters such as sorbitan monopalmityl ester, sorbitan monostearyl ester, sorbitan monooleyl ester; (POE) _1-
25 sorbitan lauryl ester, (POE) ₁ ~ ₂₅
Sorbitan mono palmityl ester, (POE) ₁ ~ ₃₀
Sorbitan monostearyl ester, (POE) ₁ ~ ₃₀
Polyoxyethylene sorbitan monoalkyl esters such as sorbitan monooleyl ester; (POE) _10
40 Sorbitan tristearyl ester, (POE) ₁₀ ~
_And polyoxyethylene sorbitan trialkyl esters such as ₄₀ sorbitan trioleyl ester.

Of the above compounds, (POE) ₅ to ₉ C
_12-14 synthetic alcohol ether, (POE) ₄ ~ ₁₀ lauryl ether, (POE) ₅ ~ ₈ cetyl ether, (P
OE) ₁₀ to ₁₅ stearyl ether, (POE) ₅ to ₁₅ oleyl ether, (POE) ₆ to ₁₀ octyl phenyl ether, (POE) ₅ to ₁₃ nonyl phenyl ether, sorbitan monolauryl ester, sorbitan monopalmityl ester, sorbitan mono stearyl ester, sorbitan mono-oleyl ester, (POE) ₅ ~ ₂₀ sorbitan monolauryl ester, (POE) ₅ ~ ₂₀ sorbitan palmityl ester, (POE) ₅ ~ ₂₀ sorbitan monostearyl ester, (POE) ₅ ~ ₂₀ sorbitan oleyl ester, (POE) ₁₅ ~ ₃₀ sorbitan tristearate Lil ester, (POE) ₁₅ ~ ₃₀ sorbitan trioleyl esters are preferably used.

These surfactants are preferably incorporated in the aqueous detergent composition of the present invention in an amount of 0.5 to 35% by weight, particularly 3 to 30% by weight. If the amount is less than this range, no special effect due to the addition of the surfactant tends to be exhibited. Further, even if the compounding amount exceeds this range, the effect of further addition tends not to be exhibited.

The water-based detergent composition of the present invention further increases the detergency against dirt having a small polarity by adding a hydrocarbon.

The hydrocarbon includes 10 to 1 carbon atoms.
8, straight-chain or branched-chain saturated or unsaturated hydrocarbons such as decane, dodecane, tetradecane, hexadecane, octadecane, decene, dodecene, tetradecene, hexadecene and octadecene; nonylbenzene, dodecyl Alkylbenzenes such as benzene; naphthalene compounds such as methylnaphthalene and dimethylnaphthalene; and cyclo compounds such as cyclodecane and cyclododecene. Among them, straight-chain or branched-chain saturated or unsaturated hydrocarbons having 12 to 18 carbon atoms are preferable, and olefin-based hydrocarbons are particularly preferable in consideration of detergency, handling, and the like.

These hydrocarbons are preferably incorporated in the aqueous detergent composition of the present invention in an amount of 5 to 80% by weight, particularly preferably 20 to 70% by weight. If the amount is less than this range, no special effect due to the addition of hydrocarbons tends to be exhibited.
If the amount exceeds this range, the cleaning agent and the like tend not to be sufficiently rinsed in the rinsing step.

Further, the cleaning composition of the present invention can contain water as appropriate from the viewpoint of safety and workability. Water is preferably incorporated in the detergent composition at 5 to 30%.

The detergent composition of the present invention may contain, if necessary, other hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, etc., as far as the effect is not impaired. Compounds having organic or inorganic chelating power such as aminocarboxylates, preservatives, rust preventives, defoamers such as silicon, amine and phenolic antioxidants, coconut fatty acid methyl and benzyl acetate, etc. Esters, amine-based additives, alcohols, and the like can be appropriately used in combination.

The cleaning composition of the present invention can be produced by mixing the above-mentioned components and optional components in a conventional manner.

To clean a glass containing a metal oxide-modified oxide and to use the cleaning composition of the present invention for cleaning electronic parts and precision parts for electric, electronic, optical and precision industries using the same, For example, using the cleaning composition of the present invention, immersion method, ultrasonic cleaning method, immersion rocking method, spray method,
Various cleaning methods such as a hand wiping method can be adopted, and a method of continuously performing a method such as rinsing with a solvent or warm water at the end,
It is cited as an efficient cleaning method, and favorable results can be obtained.

[0098]

EXAMPLES The present invention will be described in detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples.

Production Example 1 (Methylphosphoric acid monoester) In a reaction vessel, 2 mol (64.0 g) of methanol, 1 mol (18.0 g) of ion-exchanged water, and 1 mol of diphosphorus pentoxide (14 mol)
1.9 g) and immersed in an oil bath with good stirring.
The temperature was raised to 5 ° C. Thereafter, the reaction was carried out for 20 hours to obtain a reaction product of methyl phosphate monoester 80% (molar ratio).

Production Example 2 (ethyl sesquiphosphate, phosphoric acid) In a reaction vessel, 3 mol (138.3 g) of ethanol and 1 mol (141.9 g) of diphosphorus pentoxide were put, and immersed in an oil bath with good stirring. The temperature rose. Thereafter, the reaction was carried out for 15 hours to obtain ethyl phosphate monoester 61% (molar ratio) and ethyl phosphate diester 39% (molar ratio) to obtain ethyl phosphate sesquiester.

Production Example 3 (Isopropyl phosphoric acid monoester) 2 mol of isopropyl alcohol (120.2
g), 1 mol of ion-exchanged water (18.0 g) and 1 mol of diphosphorus pentoxide (141.9 g) were immersed in an oil bath with good stirring, and the temperature was raised to 80 ° C. Thereafter, the reaction was carried out for 20 hours to obtain a reaction product of 81% (molar ratio) of isopropyl phosphate monoester.

Production Example 4 (Busethyl sesquiphosphate) 3 mol (222.3 g) of butanol and 1 mol (141.9 g) of diphosphorus pentoxide were placed in a reaction vessel, and immersed in an oil bath with good stirring. The temperature rose. Thereafter, the mixture was reacted for 15 hours to obtain butyl phosphate monoester 62% (molar ratio) and butyl phosphate diester 38% (molar ratio), thereby obtaining butyl phosphate sesquiester.

Production Example 5 (Methylphosphoric acid sesquiester) Into a reaction vessel, 3 mol (96.0 g) of methanol and 1 mol (141.9 g) of diphosphorus pentoxide were immersed in an oil bath while stirring well, and the mixture was heated to 65 ° C. The temperature rose. Thereafter, the mixture was reacted for 20 hours to obtain a methyl phosphate monoester 63% (molar ratio) and a methyl phosphate diester 37% (molar ratio) of methyl phosphate sesquiester.

Production Example 6 (Ethyl Phosphate Monoester) In a reaction vessel, 2 mol (92.2 g) of ethanol, 1 mol (18.0 g) of ion-exchanged water, and 1 mol of diphosphorus pentoxide (14 mol)
1.9 g) and immersed in an oil bath with good stirring.
The temperature was raised to 0 ° C. Thereafter, the reaction was carried out for 20 hours to obtain a reaction product of ethyl phosphate monoester 81% (molar ratio).

Production Example 7 (Butyl phosphoric acid monoester) In a reaction vessel, 1 mol (74.1 g) of butanol, 0.5 mol (9.0 g) of ion-exchanged water, and 0.5 mol (71 g) of diphosphorus pentoxide were placed. Immerse in oil bath with good agitation, 9
The temperature was raised to 0 ° C. Thereafter, the reaction was carried out for 20 hours to obtain a reaction product of butyl phosphate monoester 78% (molar ratio).

Production Example 8 (Hexylphosphoric acid sesquiester) 3.2 mol (330.7 g) of hexanol was placed in a reaction vessel.
1.1 mol (153.0 g) of diphosphorus pentoxide was added, immersed in an oil bath with good stirring, and heated to 90 ° C. Thereafter, the mixture was reacted for 15 hours, and 55% (molar ratio) of hexyl phosphate monoester and 45% of hexyl phosphate diester were used.
(Molar ratio) of hexyl phosphate sesquiester was obtained.

Production Example 9 (Octyl phosphoric acid monoester) 1.7 mol (220.4 g) of octanol was placed in a reaction vessel.
0.85 mol (15.24 g) of ion-exchanged water and 0.85 mol (120.1 g) of diphosphorus pentoxide were added, immersed in an oil bath with good stirring, and heated to 90 ° C. Then 1
The reaction was performed for 5 hours. Further, this reaction product was dissolved in hexane at 50 ° C. and cooled to 20 ° C. to precipitate octyl phosphate monoester, which was separated by filtration to obtain octyl phosphate monoester having a purity of 91%.

Production Example 10 (stearyl phosphate monoester) 1.0 mol of stearyl alcohol (271.
0 g), 0.5 mol (9.0 g) of ion-exchanged water and 0.5 mol (71.0 g) of diphosphorus pentoxide were immersed in an oil bath with good stirring, and the temperature was raised to 90 ° C. Then 15
Allowed to react for hours. Further, the reaction product was dissolved in hexane at 50 ° C. and cooled to 20 ° C. to precipitate stearyl phosphate monoester, which was separated by filtration to obtain stearyl phosphate monoester having a purity of 92%.

Production Example 11 ((POE) ₃ sesquiester of lauryl phosphate) A reaction vessel was charged with ethylene oxide 3 of lauryl alcohol.
1 mol (321.34 g) of a molar adduct (Emulgen 103: manufactured by Kao Corporation), 0.33 mol of diphosphorus pentoxide (4
7.3 g) and immersed in an oil bath with good stirring.
The temperature was raised to 0 ° C. Thereafter, the mixture was reacted for 15 hours to obtain (POE) ₃ lauryl phosphate sesquiester of 56% (molar ratio) and 44% (molar ratio) of diester.

Production Example 12 ((POE) ₉ Olesylphosphoric acid sesquiester) Ethyl oxide 9 of oleyl alcohol was placed in a reaction vessel.
Molar adduct (Emulgen 409: manufactured by Kao Corporation) 0.5
Mol (336.7 g), diphosphorus pentoxide 0.17 mol (2
3.7 g) and immersed in an oil bath with good stirring.
The temperature was raised to 0 ° C. Thereafter, the mixture was reacted for 15 hours to obtain (POE) ₉ oleyl phosphate sesquiphosphate having 55% (molar ratio) of monoester and 45% (molar ratio) of diester.

Production Example 13 ((POE) ₆ Nonylphenyl Phosphate Monoester) A reaction vessel was charged with 0.5 mol (245.2 g) of a 6 mol adduct of nonylphenol with ethylene oxide (Emulgen 906, manufactured by Kao Corporation), 0.25 mol of exchanged water (4.
5 g) and 0.25 mol (35.5 g) of diphosphorus pentoxide were immersed in an oil bath with good stirring, and the temperature was raised to 90 ° C. Thereafter, the reaction was carried out for 15 hours. The reaction product was further dissolved in hexane at 50 ° C., and then cooled to 20 ° C. to precipitate a monoester, which was separated by filtration and (POE) having a purity of 92%.
_6- Nonylphenyl phosphate monoester was obtained.

Examples 1 to 13 and Comparative Examples 1 to 11 Washing tests were carried out by washing with an aqueous detergent composition comprising the components shown in Tables 1, 2, 3 and 4. Table 5 shows the results. Tables 6 and 7 correspond to Table 1,
It shows the origin of the compounds shown in 2, 3, and 4.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

[0116]

[Table 4]

[0117]

[Table 5]

[0118]

[Table 6]

[0119]

[Table 7]

The test conditions are as follows. (Preparation of Test Pieces) On a 50 mm × 50 mm × 2 mm plate of optical glass having two kinds of compositions, 1 g of each different fixing wax was dissolved and applied thinly. What was cooled and left at room temperature for 24 hours was used as a test piece. Table 8 shows the composition of the glass and the fixing wax used.

[0121]

[Table 8]

(Cleaning test) The above test piece was heated at 60 ° C.
And washed with a 39 kHz, 200 W ultrasonic cleaning device (SILENTSONIC UT-204, manufactured by Sharp Corporation) for 5 minutes. Next, it was immersed in ion-exchanged water at 30 ° C. and rinsed for 1 minute with the same ultrasonic cleaner as used for cleaning. After air blowing for one minute, the air is blown at a constant temperature of
Dried for minutes.

(Evaluation Method and Evaluation Criteria) The detergency was evaluated visually with an optical microscope at a magnification of 100 times according to the following criteria. ◎: very clean without any wax residue on the surface, very good ：: little wax residue on the surface, good △: slight wax residue on the surface, slightly poor ×: wax on the surface Poor residue and "burn" of the optical glass after washing was visually evaluated with an optical microscope at a magnification of 100 times according to the following criteria. ：: No discoloration or etching was observed on the glass surface, and there was no change from before cleaning. ：: Slightly brownish discoloration is observed on the glass surface. Δ: The entire glass surface is observed to be discolored from brown to blue. ×: Not only discoloration of the glass surface but also loss of gloss due to etching is observed.

From Table 5, it was found that the water-based cleaning composition of the present invention has good cleaning properties and has an excellent property of preventing "burn" (Examples 1 to 13).
On the other hand, those containing neither alkyl phosphate ester, its amine neutralized product nor phosphate amine neutralized product (Comparative Examples 1 and 2) and those obtained by neutralizing alkyl phosphate ester with inorganic alkali (Comparative Example 3) 4), alkyl phosphate ester having a large number of carbon atoms (Comparative Examples 5 and 6), phosphate ester not neutralized with an amine compound (Comparative Example 7), and amine-based neutralized product Compounds with small amounts of compounds (Comparative Examples 8 and 9), alkyl phosphate esters and amine neutralized products thereof, and those containing inorganic phosphoric acid instead of phosphate amine neutralized products (Comparative Example 10,
In the case of 11), the cleaning properties were all poor, and "burn" could not be prevented.

[0125]

The water-based detergent composition of the present invention has excellent properties of preventing "burn" of glass containing a modified oxide composed of metal ions, and at the same time, having high detergency.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1:72 3:30 3:20 1:44 1:74)

Claims (6)

(57) [Claims] 1. The following general formula (1): (Wherein, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms, X ¹
Represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. An aqueous detergent composition comprising an alkyl phosphate ester represented by the formula: 2. An alkyl phosphate ester represented by the general formula (1) having an equivalent amount of 50 to 100% and an alkyl phosphate having a nitrogen atom number of 1 to 1.
The aqueous detergent composition according to claim 1, wherein the aqueous detergent composition is neutralized with an amine compound having a molecular weight of 5 to 50 and having a molecular weight of 50 to 300. 3. The following general formula (2): (Wherein, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a phenyl group or a phenyl group substituted with a linear or branched alkyl group having 8 to 12 carbon atoms, and q
Represents an integer of 0 to 20. X ² is a hydroxyl group or the following general formula (3) R ³ —O— (CH ₂ CH ₂ O) _q − (3) (wherein, R ³ is a linear or branched alkyl group having 1 to 20 carbon atoms; A phenyl group or a phenyl group substituted with a straight-chain or branched-chain alkyl group having 8 to 12 carbon atoms q
Represents an integer of 0 to 20. ). An aqueous detergent composition containing a phosphate ester represented by the formula (1), wherein 50 to 100% equivalent of the phosphate ester has 1 to 5 nitrogen atoms and a molecular weight of 50 to 300. An aqueous detergent composition neutralized with an amine compound. 4. The following general formulas (4), (5) and (6): (Wherein, R ⁴ represents a hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ each represent an alkylene group having 2 to 4 carbon atoms.
Represents a hydrogen atom or an alkyl or acyl group having 1 to 4 carbon atoms. m is 1 to 7, n is 0 to 7, l is 0 to 5, p
Represents an integer of 0 to 5. The aqueous detergent composition according to any one of claims 1 to 3, further comprising at least one alkylene oxide compound selected from the group consisting of compounds represented by the formula (1). 5. The aqueous cleaning composition according to claim 1, further comprising one or more surfactants. 6. The aqueous detergent composition according to claim 1, further comprising a hydrocarbon having 10 to 18 carbon atoms.