JPH09310095A - Cleanser composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleanser composition comprising a specific hydrocarbon compound, a nonionic surfactant, an alcoholic compound and water, excellent in cleansability, storability and long-term performance maintainability, without foaming and useful for removing oils stuck to various kinds of parts, etc. SOLUTION: This cleanser composition comprises (A) 1-30wt.% of a hydrocarbon compound selected from the partial or perfect hydrogenation product of a monoterpene, a (branched) paraffin base hydrocarbon of the formula: Cm H2m+2 [(m) is 15-24] and a naphthene base hydrocarbon of the formula: Cx H2x [(x) is 3-14], (B) 0.2-20wt.% of a nonionic surfactant of the formula: R-Pb-O-(CH2 CH2 O)n H [R is a 5-17C alkyl; Ph is phenyl; (n) is 2-12], (C) 0-10wt.% of an alcoholic compound selected from propargyl alcohol and a compound of the formula: R'(OH)y [R' is a 2-8C (un)saturated hydrocarbon group; (y) is 2, 3], and (D) is 50-98.8wt.% of water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can substitute for an organic halogen-based detergent such as 1,1,1-trichloroethane and specific freon, and has a strong detergency and an economically useful long life. The present invention relates to a low foaming detergent composition having no layer destruction and little environmental pollution. This detergent composition is useful as a detergent for oil attached to metals and resins, non-metals such as ceramics, and a flux remover.

[0002]

2. Description of the Related Art Conventionally, in various industries such as automobile, electric, electronic equipment, shipbuilding, machinery, machine parts, electric / electronic parts, heat treatment parts, etc. are various oils such as motor oil, machine oil, lubricating oil, etc. at the time of manufacturing and processing. Has been used, and organic halogen-based detergents such as 1,1,1-trichloroethane and specific freon have been used as detergents for removing the adhered oil.

However, since these organic halogen-based detergents have been found to be substances that destroy the ozone layer and have been regarded as a problem, a wide variety of alternative detergents have been developed. Categorizing the developed products, hydrocarbon cleaners such as toluene, xylene, paraffin, and naphthene,
It is roughly classified into three types: semi-aqueous detergents and aqueous detergents.

In the conventional water-based cleaning agents, a surfactant and a builder component are mainly used, and the oil adhering to the object to be cleaned is dispersed in a fine emulsion by using mechanical force and the like to prevent re-adhesion and improve the cleaning power. It is exerting. In the state of the new liquid at the initial stage of washing, the surfactant is sufficiently present in the oil, and thus the washing performance is good. However, when the amount of oil to be treated increases, the surfactant is consumed and the emulsion agglomerates and the like, and the cleaning ability deteriorates. Therefore, replacement of the liquid is repeated. It is possible to add a large amount of surfactant in advance, but foaming trouble occurs in the cleaning tank or rinse tank, or rinse failure in the rinse tank due to surfactant etc. brought out to adhere to the object to be cleaned Because troubles occur,
It becomes difficult to increase a large amount of the surfactant in the cleaning liquid.

On the other hand, since the hydrocarbon type detergent dissolves oil, the cleaning ability gradually decreases as the amount of oil to be treated increases. In order to maintain the cleaning performance, it is necessary to purify the cleaning agent by distillation etc. and always maintain a low oil solubility, but in reality, an oil having a boiling point close to that of the main component of the cleaning agent, hydrocarbon, is used. Since problems such as inclusion in the distillation component and removal of the additive component occur, it is impossible to maintain the initial liquid composition, and the performance is degraded in a relatively short period of time. Also, it is a combustible material and there is a risk of fire.

In the case of a semi-aqueous detergent, the solubility of oil is lowered by adding water, so that the amount of dissolved oil can be kept smaller than that of a hydrocarbon detergent. It is also known that the addition of salt or the like reduces the amount of dissolved oil and temporarily increases the cleaning ability. As described above, each cleaning agent has advantages and disadvantages, and there is no example in which it is explosively replaced. What the market demands for a conventional detergent alternative to trichloroethane and freon is to satisfy the following performance requirements as an alternative detergent that simultaneously satisfies the properties of conventional halogenated hydrocarbons.

(1) The cleaning agent is a non-combustible material. (2) It is non-toxic. (3) The ability to dissolve oil or the like is large, or the oil can be dispersed and removed. (4) Easy to dry. (5) It is inexpensive. The cleaning equipment used should be inexpensive. (6) There is no stain on the object to be cleaned. (7) There should be no rust. (8) No need for wastewater treatment, atmospheric gas treatment, etc. (9) Use life is long. (10) There is no corrosion due to the difference in materials (one side is not corroded when cleaning different kinds of composite materials).

The biggest problem with the alternative cleaning agent is that all of the above 10 items are satisfied at the same time. However, in the case of the conventional water-based cleaning agent, (4) (6) (7) (8) (9) It does not meet the conditions. However, compared to other hydrocarbon-based cleaning agents and semi-water-based cleaning agents, water-based cleaning agents are in a position to easily overcome the above problems by devising the cleaning agent itself and the cleaning system. For example, the drying of (4) can be dealt with by raising the temperature of the rinsing water, and the stain countermeasure of (6) can be dealt with by cleaning the rinsing water. The rust of (7) can be dealt with by adding an anticorrosive agent, and the wastewater treatment of (8) can be dealt with by cleaning and recycling the rinse water. Therefore, improving the water-based cleaning agent is the most important issue regarding the service life of (9).

[0009]

DISCLOSURE OF THE INVENTION The present invention provides a detergent composition which is excellent in oil removal performance, has a low foaming property, is free from air pollution, and has a long service life.

[0010]

Means for Solving the Problems The present invention provides (A) a partially or completely hydrogenated monoterpene, a linear or branched paraffinic hydrocarbon represented by the formula (I), and a formula (II). Hydrocarbon compound selected from naphthenic hydrocarbons 1 to 30% by weight

[0011]

[Chemical _formula 5] C _m H _{2m + 2} (I)

[In the formula, m is a number from 15 to 24. ]

[0013]

_{Embedded image} C _x H _2x (II)

[Wherein x is a number from 3 to 14]. ] (B) Nonionic surfactant represented by the formula (III): 0.2 to 20% by weight

[0015]

Embedded image R—Ph—O— (CH ₂ CH ₂ O) _n H (III)

[In the formula, R is an alkyl group having 5 to 17 carbon atoms, and Ph is a phenyl group. n is a number of 2-12. ] (C) Propargyl alcohol, alcoholic compound selected from polyhydric alcohols represented by formula (IV) 0 to 10% by weight

[0017]

Embedded image R ′ (OH) _y (IV)

[In the formula, R'is a saturated hydrocarbon group having 2 to 8 carbon atoms, or an unsaturated hydrocarbon group having a carbon-carbon double bond or a triple bond, and y is a number of 2 to 3. . ] (D) Water 50-98.8% by weight It is intended to provide a detergent composition containing the components (A), (B), (C) and (D).

[0019]

[Function] A hydrogenated product of a monoterpene or / and a paraffinic hydrocarbon or / which is compatible with oil (or oil)
If an emulsion having a fine particle size is prepared in advance from naphthenic hydrocarbon and nonionic surfactant, the oil (oil) on oil deposits such as metals, resins and ceramics will be dissolved during washing, and the oil Hold the emulsion in the state of wrapping it. The dissolved oil is incorporated into the particles of the emulsion together with the compatible monoterpene hydrogenated product and the like, thus suppressing the consumption of the surfactant. As a result, the long life of the cleaning agent is maintained. Since the emulsion generated in this washing step maintains the particle size, the degree of washing does not become uneven.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION

(A) Hydrocarbon Compound The component (A) that contributes to the solubility of the oil is a partial hydrogenated product (C ₁₀ H ₁₈ ) or a complete hydrogenated product (C ₁₀ H ₂₀ ) of a monoterpene (C ₁₀ H ₁₆ ). Yes, the offensive odor of monoterpenes is reduced by hydrogenation.

The component (A) is a partially hydrogenated product (C ₁₀
H ₁₈ ) and the completely hydrogenated product (C ₁₀ H ₂₀ ) may be used alone or in combination as a mixture. Further, a monoterpene (C ₁₀ H ₁₆ ) may be contained in a small amount (5% by weight or less). Preferably, 80% by weight or more of complete hydrogenation is free from odor problems. Also, the formula (I) C
A linear or branched paraffinic hydrocarbon represented by _m H _{2m + 2} and a naphthenic hydrocarbon represented by the formula (II) C _x H _2x can also be used as the oil dissolving agent.

These may be used alone or in combination of two or more. Preferably, the monoterpene hydrogenation product and paraffin hydrocarbon are 1: 0.1.
A weight mixing ratio of 1: 0.5 is preferred. In the detergent composition, the hydrocarbon compound as the component (A) is 1 to 30% by weight,
It is preferably used in a proportion of 5 to 20% by weight. If it is less than 1% by weight, the number of emulsion particles is small and the life becomes short. If it exceeds 30% by weight, the oil dispersed particles cannot be made small and the life becomes short.

(B) Nonionic Surfactant The above formula (III) R-Ph-O capable of simultaneously removing water-soluble stains and oil-soluble stains and having an action of emulsion-dispersing the separated oil in water. - non-ionic surfactant represented by _{(CH 2 CH 2 O) n} H is a polyoxyethylene alkyl phenyl ether-based surfactant.

Specific examples thereof include 4 to 8 mol of ethylene oxide adduct of nonylphenol, ethylene oxide adduct of t-butylphenol, and ethylene oxide adduct of amylphenol. In addition to the above, it is also possible to use a compound obtained by simultaneously polymerizing and adding ethylene oxide and propylene oxide as a hydrophilic group to an alkylphenol, and a compound into which a fatty acid, a higher alcohol, an alkylphenol, a sorbitan ester or the like is introduced as a hydrophobic group.

The nonionic surfactant has an HLB value of 10 to 10.
14 is preferred. In the detergent composition, the content of the nonionic surfactant is 0.1 to 20% by weight, preferably 0.2 to 10% by weight. If it is less than 0.1% by weight, the oil dispersibility is insufficient. If it exceeds 20% by weight, foaming in the cleaning tank and the rinse tank becomes remarkable. The amount of the nonionic surfactant as the component (B) is 1/6 to 3/4 (weight basis) of the hydrocarbon compound as the component (A), preferably 1/3 to 2/3. To use.

(C) Propargyl alcohol or polyhydric alcohol Used in combination with the nonionic surfactant of the component (B), it suppresses foaming in the washing step and keeps the emulsified oil emulsion in a small particle size. Examples of alcoholic compounds useful for the purpose include propargyl alcohol, ethylene glycol, propylene glycol, butanediol, butenediol, butynediol, 2-butene-1,4-
Examples thereof include diol, glycerin, diethylene glycol, pentaerythritol and the like.

The alcoholic compound as the component (C) is
In the detergent composition, 0 to 10% by weight, preferably 0.2 to
Used in a proportion of 5% by weight. Above 10% by weight,
The long-term stability of the detergent composition emulsion is reduced.
This alcoholic compound is 1/10 to 2/3, preferably 1/10 to 1/5 of the hydrocarbon compound as the component (A).
Use (weight basis) as a guide, and use 1/4 to 1/2 (weight basis) of the nonionic surfactant of the component (B) as a guide.

Cleaning method Machine parts, electric parts, etc. to which oil is attached are placed in a wire netting basket, and the wire netting basket is placed in a hanging state in a cleaning tank containing a cleaning agent composition, and is vertically moved and left and right half-rotational motions. Repeat the above to separate and emulsify the oil, overflow the oil / water emulsion from the liquid surface, guide it to the oily oil separation tank, separate the oil layer and water layer here, and put the water layer in the cleaning tank. By returning, washing can be stably performed for a long time. A method of emulsifying and dispersing oil by putting oil deposits in a cleaning tank containing a detergent composition and applying ultrasonic vibration or by spraying a fluid under pressure onto the oil deposits Good. The washing is performed at a temperature of room temperature to 60 ° C. The oil-separated object to be cleaned is rinsed with water and dried. If the temperature of the rinse water is raised to 50 to 70 ° C., the drying time can be shortened.

[0029]

【Example】

Example 1 2-Butyne-1,4-diol (2B1-4D) as a polyhydric alcohol and ion-exchanged water were stirred and mixed at a weight ratio of 1: 1 and the mixture was used as a nonionic surfactant. Kao Corporation's HLB value of 12.4 is polyoxyethylene nonylphenyl ether (n = 7 to 11) (PONP
E) was stirred and mixed at a weight ratio of 1: 1 to obtain a uniform solution.

Next, a completely hydrogenated product of monoterpene (C ₁₀ H ₂₀ ) methylisopropylcyclohexane (paramenthane) was sequentially added to the homogeneous solution under stirring until the weight ratio became 1: 4, and a transparent gel was obtained. Made an emulsion. This is diluted with ion-exchanged water about 5 times and Oil i
An emulsion of n Water type emulsion (average particle diameter 1 μm, maximum particle diameter 4 μm) was prepared and used as a washing liquid.

[0031]

[Table 1] Composition of cleaning liquid Completely hydrogenated monoterpene (paramentan) 15% by weight Ethylene oxide adduct of nonylphenol (PONPE) 2% by weight 2-butene-1,4-diol (2B1-4D) 1% by weight Ion-exchanged water 82 weight%

The cleaning liquid did not separate even after being left for 6 months, and had good storability. As a cleaning device, as shown in FIG. 1, an ultrasonic wave generator 2 is provided at the bottom of a cleaning tank 1 having a capacity of 500 liters, and a wire net cage 3 capable of accommodating an object 4 to be cleaned is vertically provided at the center of the cleaning tank 1. A cleaning liquid containing oil that can be swung and overflowed on the upper surface of the cleaning tank 1 is guided to the oil separation tank 5, where the oil is collected by the oil skimmer 5a, and the cleaning liquid after the oil removal is pumped up and passed through the filter 8 to the cleaning tank. The structure which can be recycled to 1 was used.

As the object to be cleaned 4, 15 kg of bolts were selected and immersed in cutting oil (Diacut C1B: Type 2 No. 3 cutting oil) and placed in a cage 3 of wire mesh, which was washed with the cleaning liquid 7 described above.
It was suspended in the washing tank 1 in which was stored and operated while applying ultrasonic waves of 28 KHz. Washing for 2 and a half minutes, hang the wire net basket 3 and rinse tank 9 containing tap water at 60 ° C
And rinsed by ultrasonic method. The rinse solution dirt was evaporated and concentrated and then purged out of the system. After the rinse, the hot air dryer 10 was used to dry the hot air 11 at 85 to 90 ° C.

When this operation was repeated 300 times, the residual oil content on the bolt surface of the object to be cleaned was 150 μg / cm at the first time.
² , 180th microgram / cm ² at the 400th time, there was almost no difference between the initial and final stages. In the micrograph of the washing solution after washing 400 times, the emulsion particle size was exactly the same as the initial stage. The oil recovery rate was 30%, and 70% of the oil was taken into the cleaning liquid, but no significant deterioration in cleaning power was observed, and long-term use (long life) function was possible. I was satisfied enough.

Comparative Example 1 The same test as in Example 1 was carried out except that a cleaning agent containing only water and a nonionic surfactant was used. The initial residual oil content of 100 μg / cm ² is 3 after washing 400 times.
It was increased to 50 μg / cm ² and residual oil was recognized by visual observation. By microscopic observation, emulsions were formed, but the emulsions were agglomerated into aggregates. Although it had a cleaning power in the initial stage, the cleaning performance gradually decreased as the cleaning was repeated. For this reason, it was necessary to replace the cleaning solution every 20 cleaning batches.
The oil could not be recovered and was totally incorporated in the form of an emulsion. Also, the foaming was large.

COMPARATIVE EXAMPLE 2 In Example 1, an attempt was made to prepare an emulsion by using an ultrasonic homogenizer with the other components being the same without blending the polyhydric alcohol. Immediately after the production, an emulsion was formed, but after 1 day, it was divided into an oil phase and an aqueous phase. When mixed with ultrasonic waves or the like, an emulsion is temporarily produced, but washing and incorporating oil facilitates phase separation.

Observation under a microscope revealed that an emulsion was formed, but the emulsion particle size was 5 microns on average. During the initial emulsion formation, the residual oil content on the bolt surface was 150 μg / cm ² , and the residual oil content on the washed bolt surface increased as the emulsion broke,
It became g / cm ² . It was also confirmed that when the emulsion was broken, the degree of cleaning was non-uniform.

Examples 2 to 5 and Comparative Example 3 A cleaning test was conducted in the same manner as in Example 1 except that the cleaning liquid having the composition shown in Table 1 was used. The results are shown in the table.

[0039]

[Table 2]

[0040]

EFFECT OF THE INVENTION It is a cleaning liquid which has no foaming, has excellent long-term storability, does not deteriorate in performance even after long-term use, and has excellent cleaning properties.

[Brief description of drawings]

FIG. 1 is a plan view of a cleaning device.

[Explanation of symbols] 1 cleaning tank 2 ultrasonic generator 3 wire netting basket 4 object to be cleaned 5 oil separation tank 6 overflow weir 7 cleaning liquid 8 filter 9 rinse tank 10 hot air dryer 11 hot air

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kasuke Yamada 7-29-19 Misaki Funabashi, Chiba Prefectural Research Institute (72) Riichiro Kawashima 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Kagaku Co., Ltd. Functional Chemicals Company (72) Inventor Shiota Vertical 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Chemical Co., Ltd. Functional Chemicals Company

Claims (1)

[Claims] 1. A selected from (A) a monoterpene partially or completely hydrogenated product, a linear or branched paraffinic hydrocarbon represented by the formula (I), and a naphthenic hydrocarbon represented by the formula (II). 1 to 30% by weight of a hydrocarbon compound [Chemical formula 1] C _m H _{2m + 2} (I) [wherein, m is a number of 15 to 24]. Embedded image C _x H _2x (II) [wherein x is a number of 3 to 14]. (B) Nonionic surfactant represented by the formula (III) 0.2 to 20% by weight: embedded image R—Ph—O— (CH ₂ CH ₂ O) _n H (III) [wherein R is an alkyl group having 5 to 17 carbon atoms, and Ph
Is a phenyl group. n is a number of 2-12. (C) Propargyl alcohol, alcoholic compound selected from polyhydric alcohol represented by formula (IV) 0 to 10% by weight R '(OH) _y (IV) [wherein R'is carbon It is a saturated hydrocarbon group having a number of 2 to 8, or an unsaturated hydrocarbon group having a carbon-carbon double bond or a triple bond, and y is a number of 2 to 3. ] (D) Water 50-98.8% by weight A cleaning composition containing the components (A), (B), (C) and (D).