Classifications

• • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • 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
  • C11D1/825—Mixtures of compounds all of which are non-ionic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/78—Neutral esters of acids of phosphorus

Definitions

• the present invention relates to a surfactant composition, and a degreasing composition and a degreasing bath containing the surfactant composition, and more particularly to a surfactant composition suitable for a degreasing composition having excellent detergency and antifoaming properties at room temperature, and a degreasing composition and a degreasing bath containing such surfactant composition.
• degreasing is usually conducted to remove oil substances (mineral oils, animal or vegetable fats and oils, etc.) from the surfaces of metal members to be formed with chemical coatings.
• oil substances mineral oils, animal or vegetable fats and oils, etc.
• Degreasing detergents used for degreasing treatments contain as main components builders based on acids or alkalis and nonionic surfactants, and they are used in the form of aqueous solutions by a spraying method or an immersion method at 40 - 70°C for 1 - 10 minutes.
• Japanese Patent Laid-Open No. 61-60892 discloses an alkali detergent usable at room temperature which contains polyoxyalkylene alkyl ether as a surfactant.
• the polyoxyalkylene alkyl ether in this detergent has the following general formula: RO(EO) m (PO) n H, wherein R: Alkyl group, EO: Ethylene oxide group, P O: Propylene oxide group, and m,n : Moles.
• an object of the present invention is to provide a surfactant composition having excellent detergency at room temperature which is equal to or even higher than under heated conditions (40°C or higher), with little foaming.
• Another object of the present invention is to provide a degreasing composition having excellent detergency at room temperature which is equal to or even higher than under heated conditions (40°C or higher), with little foaming.
• a further object of the present invention is to provide a degreasing bath having excellent detergency at room temperature which is equal to or even higher than under heated conditions (40°C or higher), with little foaming.
• a still further object of the present invention is to provide a degreasing composition and a degreasing bath showing excellent detergency even when oil materials are accumulated.
• a surfactant composition obtained by mixing a polyoxyalkylene ether-type nonionic surfactant containing a predetermined amount of ethylene group with a phosphate-polyethylene oxide adduct shows excellent detergency and antifoaming properties at room temperature when combined with an alkali builder.
• the present invention is based upon this finding.
• the surfactant composition according to the present invention comprises a compound (a) represented by the general formula: R1O(AO) n H, wherein R1 is a substituted or unsubstituted hydrocarbon group having 6 or more carbon atoms; A is at least one group selected from the group consisting of an ethylene group, a propylene group, a butylene group and a styrene group, provided that an ethylene group in A is 5 mol % or more per 1 mol % of R1, and that the ethylene group is 50 mol or more per 100 mol of the A; and n is an integer of 5 - 50; and a compound (b) represented by the general formula: (R2O) x (O(EO) n ) y H, wherein R2 is a substituted or unsubstituted hydrocarbon group having 6 or more carbon atoms, E is an ethylene group, n is an integer of 1 - 20, x and y are 1 or 2, and x + y
• the degreasing composition according to the present invention comprises a compound (a) represented by the general formula: R1O(AO) n H, wherein R1 is a substituted or unsubstituted hydrocarbon group having 6 or more carbon atoms; A is at least one group selected from the group consisting of an ethylene group, a propylene group, a butylene group and a styrene group, provided that an ethylene group in A is 5 mol or more per 1 mol of R1, and that the ethylene group is 50 mol % or more per 100 mol % of the A; and n is an integer of 5 - 50; and a compound (b) represented by the general formula: (R2O) x (O(EO) n ) y H, wherein R2 is a substituted or unsubstituted hydrocarbon group having 6 or more carbon atoms, E is an ethylene group, n is an integer of 1 - 20, x and y are 1 or 2, and x +
• the degreasing bath according to the present invention comprises:
• the compound (a) used in the present invention is represented by the following general formula (1): R1O(AO) n H, (1) wherein n is an integer of 5 - 50.
• R1 is, as described below in detail, a hydrocarbon group having 6 or more carbon atoms. When the number of carbon atoms is 5 or less, sufficient surfactant activity cannot be obtained, failing to provide good detergency.
• a in the above general formula (1) is at least one group selected from the group consisting of an ethylene group, a propylene group, a butylene group and a styrene group.
• the number of the ethylene group in “A” is 5 mol or more per 1 mol of R1.
• the proportion of the ethylene group in “A” is 50 mol % or more per 100 mol % of "A.”
• the proportion of the ethylene group is lower than 50 mol %, the resulting surfactant composition does not show sufficient detergency.
• the antifoaming properties of the surfactant composition according to the present invention can be freely adjusted by changing the proportion of the ethylene group relative to 100 mol % of "A" in the compound (a) within the above range.
• the number (n) of an AO group in the compound (a) is 5 - 50.
• the number (n) of the AO group is less than 5, sufficient detergency cannot be obtained.
• n exceeds 50 detergency also becomes insufficient.
• n 5
• n 6
• a portion exceeding 5 may be a group other than the ethylene group.
• the ethylene group should be 50 mol % or more based on the total "A.”
• the AO group may be contained in the compound (a) in the form of random addition, block addition or a mixture of block addition and random addition.
• R2 is a hydrocarbon group having 6 or more carbon atoms. When the number of carbon atoms is 5 or less, good detergency cannot be obtained.
• the mole number (n) of an oxyethylene group represented by EO is 1 - 20. When there is no oxyethylene group or when the oxyethylene group exceeds 20 mol, sufficient detergency cannot be obtained.
• R1 and R2 in the compound (a) and the compound (b) used in the present invention may be the same or different from each other, and as long as they are hydrocarbon groups having 6 or more carbon atoms, they may be substituted or unsubstituted.
• R1 and R2 are alkyl groups such as a hexyl group, an octyl group, a decyl group, a dodecyl group, a stearyl group; alkenyl groups such as an oleyl group; cycloalkyl groups such as a cyclohexyl group; alkyl-substituted or phenyl-substituted phenyl groups such as a xylene group, an octyl phenyl group, a nonyl phenyl group, a dodecyl phenyl group, a dinonyl phenyl group, a paracumyl phenyl group, a styrene-­added phenyl group; an unsubstituted phenyl group, etc.
• the compound (a) and the compound (b) may be used in combination.
• compound (a)/compound (b) is 10/90 - 95/5, preferably 25/75 - 75/25.
• weight ratio of the compound (a) to the compound (b) is lower than 10/90 or larger than 95/5, sufficient detergency cannot be obtained.
• alkali builders which may be used in the present invention include alkali metal salts, alkali phosphate, alkali carbonates, alkali silicates, alkali nitrites, alkali borates, etc., and they may be used alone or in combination.
• a proportion of the alkali builder to the surfactant composition [weight ratio of (compound (a) + compound (b))/alkali builder] is 1:0.1 - 1:2000, preferably 1:1 - 1:100.
• the degreasing composition of the present invention may further contain 5-­100 parts by weight of an antifoaming agent per 100 parts by weight of the surfactant composition.
• an antifoaming agent is less than 5 parts by weight, sufficient improvement of antifoaming properties cannot be obtained, and when it exceeds 100 parts by weight, the detergency of the degreasing composition decreases.
• the antifoaming agents include higher alcohols, higher ethers, higher aliphatic acids, higher aliphatic acid esters, and alkyl alkylates or alkyl phenol alkylates having HLB values of 10 or less, polypropylene glycols polyethylene glycol ethers, etc. having cloud points of 40°C or lower, and they may be used alone or in combination.
• the degreasing bath of the present invention contains the above surfactant composition and the alkali builder.
• the amount of the surfactant composition is 0.005 - 0.5 weight %, preferably 0.05 - 0.3 weight %.
• the amount of the surfactant composition is lower than 0.005 weight %, sufficient degreasing activity cannot be obtained.
• it exceeds 0.5 weight % further increase in degreasing activity cannot be achieved.
• the amount of the alkali builder is 0.05 - 10 weight %, preferably 1 - 5 weight %.
• the degreasing detergent solution has a low pH, making it likely that the metal members to be treated are rusted, and making it difficult to emulsify oil materials removed from the metal members being treated.
• the amount of the alkali builder exceeds 10 weight %, it is difficult to dissolve the alkali builder, deteriorating operability.
• composition of the degreasing bath of the present invention can be adjusted by introducing the surfactant composition and the alkali builder separately into a degreasing bath (hereinafter called “separate system”) or by mixing them in advance and then introducing the resulting mixture into the degreasing bath (hereinafter called “premixed system”).
• the premixed system is preferable, but from the viewpoint of stability with time, the separate system is preferable.
• the amount of the alkali builder is preferably 80 weight % or more based on the surfactant composition to avoid swelling.
• the surfactant composition of the present invention comprises the compound (a) which is a particular polyoxyalkylene ether-type nonionic surfactant, and the compound (b) which is a phosphate-ethylene oxide adduct in a particular proportion.
• the compound (a) itself does not have sufficient detergency at room temperature, and the compound (b) itself does not have detergency at all. Nevertheless, a combination of the compound (a) and the compound (b) provides a degreasing detergent with good detergency.
• the degreasing bath of the present invention utilizing the synergistic effect of the compound (a) and the compound (b) can maintain degreasing detergency and antifoaming properties equally at start and even after oil accumulation in the bath.
• the following compounds A1 - A9 are synthesized by adding alkylene oxides to various alcohols and phenols having various R1 groups in the general formula (1), in the presence of an alkali catalyst by a usual method.
• the following compounds B1 - B6 are synthesized by preparing phophates of various alcohols and phenols having R2 groups in the fomula (2) using phosphorus pentoxide by a usual method, and then adding ethylene oxide thereto in the presence of an alkali catalyst by a usual method.
• the following compound C1 is synthesized by adding 10 mol of ethylene oxide to 1 mol of nonyl phenyl having an R2 group in the general formula (2) in the presence of an alkali catalyst by a usual method, and preparing a phosphate thereof by using phosphorus pentoxide by a usual method.
• C1 Phosphate of a nonyl phenol -10 mol ethylene oxide adduct.
• Each of surfactant compositions containing the above compounds A1 - A9, B1 - B6 and C1 as shown in Table 1 is mixed with an alkali builder in a proportion shown in Table 2 to prepare each degreasing composition.
• each degreasing composition 2 parts by weight of each degreasing composition is mixed with 98 parts by weight of water to prepare each degreasing detergent solution bath.
• detergency is evaluated at start (fresh composition) and after oil accumulation in the bath.
• Each degreasing detergent solution is introduced into a 50.0 ml-beaker and kept at 15°C.
• a steel test piece (JIS G-3141) is immersed in the solution, and the solution is stirred at 200 rpm for 10 minutes. Thereafter, the steel test piece is removed and rinsed by running water for 30 seconds to measure water wettability of the steel test piece surface.
• This is regarded as detergency at start. Incidentally, the detergency is regarded as 100% when the entire surface of the steel test piece is still wet with water 30 seconds after the removal from the bath, and the water wettability is expressed by percentage of surface area wet with water observed by the naked eye.
• Table 2 Composition Parts by Weight Surfactant Composition 10 Alkali Builder Sodium Metasilicate ⁇ 5H2O 45 Anhydrous Sodium Carbonate 18 Sodium Phosphate 18 Sodium Nitrite 9
• each surfactant composition is mixed with an alkali builder in a proportion shown in Table 2 to prepare a degreasing composition.
• 2 parts by weight of each degreasing composition is mixed with 98 parts by weight of water to prepare a degreasing detergent solution.
• the evaluation of antifoaming properties is conducted on the resulting degreasing detergent solution by a Ross-Miles Test Method. Specifically, 200 ml of the degreasing composition solution is dropped from a height of 90 cm onto a 50 ml of degreasing composition solution contained in a glass cylinder of 50 mm in inner diameter at 25°C for 30 seconds to measure the height (mm) of a foam generated immediately after dropping and the height (mm) 5 minutes after dropping. The height of a foam is expressed as a level of foaming.
• the degreasing composition solution of the present invention is more excellent in antifoaming properties than those containing conventional surfactants in Compartive Examples 17-19.
• A5 and B1 are selected as the compound (a) and the compound (b), and mixed in a weight ratio of 50/50 to prepare a surfactant composition, and the surfactant composition is mixed with an alkali builder in the proportion shown in Table 4 to prepare a degreasing composition.
• each degreasing composition is mixed with water in a proportion shown in Table 4 to prepare a degreasing composition solution.
• the resulting degreasing composition solution is evaluated with respect to detergency and antifoaming properties in the same method as above. The evaluation results are shown in Table 4. Table 4 Example No. Comparative Example No.
• the degreasing composition solutions in Examples 22 and 23 are much better in detergency than that of Comparative Example 20 in which the proportion of the surfactant composition to the alkali builder is less in detergency than 1/2000.
• Comparative Example 22 in which the content of the alkali builder in the degreasing composition solution is less than 0.05 weight %, the steel test piece is rusted in the evaluation process of detergency. Therefore, a proper amount of the alkali builder is important to adjust pH, thereby achieving the object of the present invention.
• the surfactant composition of the present invention contains the compound (a) and the compound (b) in a weight ratio [compound (a)/compound (b)] of 10/90 - 95/5, the degreasing composition and degreasing bathcontaining such surfactant composition and an alkali builder are excellent in detergency and antifoaming properties at room temperature.
• the degreasing detergent of the present invention can advantageously maintain detergency and antifoaming properties even after oil accumulation in the bath on an equal level to that at start.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Detergent Compositions (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

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Cited By (2)

Citations (3)

• 1989
  • 1989-04-11 JP JP1091504A patent/JP2578367B2/ja not_active Expired - Lifetime
• 1990
  • 1990-04-06 DE DE1990600812 patent/DE69000812T2/de not_active Expired - Fee Related
  • 1990-04-06 EP EP19900106663 patent/EP0392394B1/de not_active Expired - Lifetime
  • 1990-04-06 CA CA 2014085 patent/CA2014085A1/en not_active Abandoned
  • 1990-04-06 ES ES90106663T patent/ES2054135T3/es not_active Expired - Lifetime

Patent Citations (3)

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