JPH06184599A - Flame-retardant hydrocarbon detergent composition - Google Patents

Abstract

PURPOSE:To develop the subject composition that is excellent in safety and the ability to remove stains adherent to clothes, resin products, precision machinery, electrical and electronic parts, or soldering flux, etc., and does not cause environmental pollution. CONSTITUTION:This detergent composition consists of 100 pts.wt. hydrocarbon fraction (A) consisting mainly of a component which has a boiling point of 150-240 deg.C, is substantially free from naphthalene and biphenyl, and is obtained by subjecting a kerosene fraction having a boiling point of 150-300 deg.C to ring hydrogenation under a pressure of 10-100kg/cm<2> at 100-300 deg.C in the presence of a metal catalyst for the hydrogenation of the aromatic ring, separating and removing at least a part of n-paraffins in the kerosene fraction by using a molecular sieve made of synthetic zeolite and fractionating the obtained residual oil by a rectifier, 10-60 pts.wt. water (B), and a surfactant (C) in an amount of 20-120wt.% of the weight of the water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame retardant detergent compositions. More specifically, the present invention relates to a detergent composition which is flame-retardant, has no environmental pollution and can be easily post-treated, and has a strong detergency.

[0002]

2. Description of the Related Art Conventionally, hydrocarbon solvents such as kerosene, benzene, xylene, etc. for cleaning resin processed products and precision machine parts and removing solder flux of printed circuit boards; salts of trichloroethylene, tetrachloroethylene, trichloroethane, etc. Cable-based solvents; CFC-based solvents such as trichlorotrifluoroethane; and water-based cleaning agents such as sodium orthosilicate and caustic soda mixed with surfactants and builders are used. In particular, Freon-based solvents or chlorine-based solvents are used for parts such as machines due to their high cleanability and flame retardancy. Further, in recent years, as a detergent with less environmental pollution and high safety, detergents mainly composed of terpenes such as limonene, pinene, diterpenes and cyclic hydrocarbons have also been proposed.

[0003]

However, many of these detergents do not satisfy all the requirements of the detergent composition that are stain removability, deterioration resistance and low toxicity. In other words, cleaning agents that use chlorine-based and chlorofluorocarbon-based solvents have major problems in terms of safety, toxicity, environmental pollution, etc., and hydrocarbon solvents, especially benzene and xylene, are highly toxic and are not suitable for occupational safety. Since it is a compound designated as a toxic substance in the law, it is not preferable to use it as a detergent in consideration of the danger and complexity of the work of handling these.

On the other hand, the water-based cleaning agent is preferable in that it is less dangerous and less toxic than the solvent-based cleaning agent, but is slightly inferior in cleaning power. Terbene represented by limonene is a compound that can achieve both safety and detergency,
Not only is it easy to deteriorate during use, durability is a problem, it is difficult to obtain a stable quality product because it is derived from a natural product, it is expensive and the supply amount is limited, and it is not practical as an industrial cleaning agent. Further, in recent years, there are cases in which naphthene hydrocarbons are used for cleaning, but these are excellent in cleaning property, but have a low flash point and are dangerous to fire. Therefore, the present invention improves the drawbacks of the prior art as described above, is excellent in removing stains such as clothes, resin processed products, precision machinery, electric and electronic parts, or solder flux, and is excellent in safety and environmental pollution. The purpose of the present invention is to provide a non-cleaning composition at low cost.

[0005]

In such a difficult situation, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, through a specific hydrocarbon fraction and a surfactant or an organic solvent, The present invention has been completed by mixing water. Further, the present inventors have found that the above hydrocarbon fraction can be provided at a very low cost because it uses a hydrocarbon fraction produced as a by-product in a specific process in the petrochemical industry. That is, the present invention includes the following (A) to
A flame-retardant hydrocarbon detergent composition comprising the component (C). The kerosene fraction having the boiling point of the component (A) in the range of 150 to 300 ° C. is heated to 10 to 100 kg / cm ^{2 at} a temperature of 100 to 300 by a metal catalyst for nuclear hydrogenation of aromatic nuclei.
The residual oil obtained by nuclear hydrogenation under the condition of ° C, and then separating and removing at least a part of the n-paraffins in the kerosene fraction by using a molecular sieve made of synthetic zeolite is subjected to a precision distillation apparatus. Hydrocarbon fraction mainly composed of components having a boiling point of 150 to 240 ° C., which is substantially free of naphthalene and biphenyl, obtained by fractional distillation 10.
0 parts by weight (B) water 10 to 60 parts by weight (C) surfactant 20 to 120% by weight of water

The details of the hydrocarbon mixture of the component (A) of the present invention will be described below. In the present invention, the boiling point is 15
A kerosene fraction in the range of 0 to 300 ° C. is hydrogenated with an aromatic nuclear hydrogenation metal catalyst. Any conventionally known metal catalyst for hydrogenation of aromatic nuclei can be preferably used as this catalyst. For example, nickel, nickel oxide, nickel / diatomaceous earth, Raney nickel, nickel /
Copper, platinum, platinum oxide, platinum / activated carbon, platinum / rhodium,
Platinum / lithium / alumina, rhodium / activated carbon, palladium, cobalt, Raney cobalt, ruthenium, nickel / tungsten, tungsten sulfide / nickel sulfide /
Alumina, cobalt / molybdenum, etc. can be used favorably. The hydrogen pressure is 10 to 100 kg / cm ² , and the temperature is 100 to 300 ° C. The hydrogenation reaction does not proceed sufficiently at a pressure lower than 10 kg / cm ² or a temperature lower than 100 ° C., and a pressure higher than 100 kg / cm ² or
At a temperature higher than 300 ° C., side reactions such as decomposition reaction take precedence, which is not preferable. Reaction type is batch type,
Alternatively, any method such as continuous or flow system can be adopted.

Here, the aromatic hydrocarbons in the kerosene fraction are nuclear hydrogenated to naphthenes by the above hydrogenation, but usually 100% of the aromatic hydrocarbons contained are not nuclear hydrogenated. A certain amount of aromatic hydrocarbons remain without being hydrogenated, depending on the type of catalyst and the reaction conditions. Further, hydrogenation treatment is often accompanied by decomposition and isomerization as a side reaction, and products related to these reactions are inevitably included in the hydrogenated kerosene fraction.

In the hydrogenation treatment described above, at least a part of the kerosene fraction is separated and removed using a molecular sieve made of synthetic zeolite to obtain a residual oil. A method of separating and obtaining n-paraffins from a hydrocarbon mixture by repeating adsorption / desorption in a gas phase or a liquid layer using a molecular sieve has hitherto been an industrial method for producing n-paraffins as follows. Has been widely implemented.

That is, for example, using a molecular sieve made of synthetic zeolite having a large number of pores adjusted to 5 A as a fixed bed, n
-The paraffins are adsorbed and desorbed alternately, the molecular sieve adsorbing the n-paraffin is washed with the desorbed low molecular weight paraffin to desorb the n-paraffins, and the mixed desorbed low molecular weight paraffin is separated by distillation and re-deposited. The TSF method (Texaco Selective Selective Method) in which n-paraffins are adsorbed in the gas phase by using the Molex method of circulating and the adsorption / desorption of a molecular sieve made of synthetic zeolite also having pores of 5 A, and the desorption is washed out with low molecular weight paraffin. (Finishing method), a molecular sieve made of 5A synthetic zeolite is also used, but adsorption / desorption of n-paraffins to the molecular sieve is performed by alternately repeating pressurization and depressurization, and is an iso-sieving type, and further vapor phase / liquid bed phase. In a combination of
Adsorption of n-paraffins to a molecular sieve made of synthetic zeolite having 5 A pores was continuously carried out in a liquid bed in an adsorber, and its desorption was regenerated by operating at a temperature higher than that in the regenerator. For the molecular sieve, there is an Esso method in which the molecular sieve is returned to the adsorption device and recycled. The n-paraffins can be separated by any method using a molecular sieve made of synthetic zeolite having pores of 5A.

Generally, in separating n-paraffin,
Theoretically, only n-paraffins should be separated, but depending on the method, hydrocarbons other than n-paraffins are also separated along with n-paraffins, and in the resulting residual oil. The content of components other than n-paraffins may change. Considering such a point, there is a method of industrially separating n-paraffins by using urea crystals, but as the method of the present invention,
The method as described above using a molecular sieve made of synthetic zeolite having pores of 5 A is suitable.

The n-paraffins are separated from the hydrogenated kerosene fraction as described above to obtain a residual oil. Next, this residual oil is subjected to precision distillation. For example, a precision distillation apparatus comprising two or more distillation columns is used to remove light hydrocarbons from the top of the first tower, and the target fraction is removed from the top of the second or subsequent towers. Manufactured. Of course, if the distribution efficiency such as the number of distillation stages is appropriate, light hydrocarbons and heavy hydrocarbons are removed from the top and bottom of a precision distillation apparatus consisting of one distillation column, respectively, and the objective is from the center of the column. Fractions can also be produced. The precision distillation may be performed after the second-stage nuclear hydrogenation described below. With the above precision distillation apparatus, a hydrocarbon fraction mainly containing components having a boiling point of 150 to 240 ° C. is obtained.

The boiling point of the component of the hydrocarbon fraction of the present invention is required to be in the above range, and if it is out of this range, the existence of each component and the balance of its content may be disturbed and the initial purpose may be achieved. It is not preferable because it disappears. That is,
A component having a boiling point lower than the above boiling range is not preferable because it contains a large amount of harmful aromatic hydrocarbons such as benzene, toluene and xylene. Further, a component having a boiling point of higher than 240 ° C. is not preferable because the boiling point becomes too high and the drying property after washing becomes poor and the residual odor becomes strong. The above hydrocarbon fraction is substantially free of benzene, toluene, xylene, etc., and has a low content of other aromatic hydrocarbons, and is particularly substantially free of naphthalene and biphenyl. However, in the present invention, a second stage hydrogenation is applied to the residual oil in order to obtain higher safety, for example, in order to eliminate substantially all kinds of aromatic hydrocarbons. It is also possible to carry out a treatment to obtain a fraction substantially free from aromatic hydrocarbons.

The hydrogenation performed in the second step on the residual oil can be performed in the same manner as the hydrogenation in the first step. Alternatively, the nuclear hydrogenation may be performed under milder conditions, that is, lower temperature or lower pressure. The nuclear hydrogenation metal catalyst used in the second stage does not necessarily have to be the same as in the first stage. That is, the catalyst may be the same or different. In any case, it may be appropriately selected from the above hydrogenation conditions. Next, after the second-stage nuclear hydrogenation, fine distillation is carried out as necessary as described above. A boiling point of 150-
A hydrocarbon fraction mainly containing components in the range of 240 ° C. is obtained.

The present invention comprises mixing the hydrocarbon fraction obtained as described above with water. The above-mentioned hydrocarbon fraction of component (A) and water of component (B) must be sufficiently emulsified or dissolved via the surfactant of component (C). It is preferable to use water having low hardness. The amount of water is preferably 10 to 60 parts by weight. If it is less than 10 parts by weight, there is no flame retardant effect, and if it exceeds 60 parts by weight, it becomes difficult to incinerate, and the cleaning property also deteriorates.

As the surfactant of the component (C) of the present invention, any of cationic, anionic, nonionic and amphoteric surfactants can be used, but the nonionic surfactant is particularly advantageous in that it has little effect on the cleaning surface. The agent is the best. For example, stearic acid glyceride, polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene alkyl fatty acid ester,
Polyoxyalkylene allylphenol ether, polyoxyalkylene sorbitan fatty acid ether, polyoxylalkylene alkylamine, sorbitan acid fatty acid ester, polyoxyalkylene, alkylphenol condensate and the like are preferable, and among them, average HLB 4 to 15
The nonionic surfactant of (1) exhibits particularly excellent effects.
Here, the polyoxyalkylene is preferably a polymer or copolymer of ethylene oxide, propylene oxide or butylene oxide.

The amount of surfactant is 20 to 20% by weight of water.
It is 120% by weight, preferably 40-80% by weight. Two
If it is less than 0% by weight, it will not be sufficiently emulsified or dissolved to cause phase separation, and if it exceeds 120% by weight, problems of residual surfactant and problems of post-washing will occur.

In the present invention, the detergency can be improved and the amount of the surfactant can be reduced by adding an amphipathic solvent. The amphipathic solvent of the present invention has 3 to 1 carbon atoms.
8 of aliphatic alcohols, esters, ethers, compounds of the general formula _{R-OC n H 2n OH (} R represents an aliphatic hydrocarbon, n is an integer of 1, 2, 3), aprotic polar solvents A mixture of one or more solvents selected from the group consisting of

Examples of the above aliphatic alcohols include:
Various natural and synthetic alcohols such as propanol, butanol, pentanol, tert-butanol, hexyl alcohol, octyl alcohol, lauryl alcohol, oleyl alcohol, Guerbet alcohol and alcohols synthesized by the oxo method can be mentioned.

As the ester, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, ethyl propionate, propyl pyropionate, butyl propionate, pentyl propionate, hexyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, Examples include pentyl butyrate and hexyl butyrate.

Examples of the ether include dimethyl ether, diethyl ether, cypropyl ether, dibutyl ether, dipentyl ether, methyl ethyl ether, methyl propyl ether, methyl pentyl ether, ethyl propyl ether, ethyl butyl ether, ethyl pentyl ether, propyl butyl ether, propyl pentyl ether. , Butyl pentyl ether, glycerin methyl ether and the like.

The general formula R-OC _n H _2n OH (R is 1 carbon atom
As a compound represented by aliphatic hydrocarbons of 6 to 6, and n is an integer of 1, 2, 3, 4), for example, hydroxydimethyl ether, hydroxymethyl ethyl ether, hydroxymethyl propyl ether, hydroxymethyl isopropyl ether. , Hydroxymethyl butyl ether, hydroxymethyl pentyl ether, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, pentyl cellosolve, 3 hydroxypropyl methyl ether, 3 hydroxypropyl ethyl ether, 3 hydroxy dipropyl ether, 3 hydroxypropyl isopropyl ether, 3 hydroxy Propyl pentyl ether, 4-hydroxybutyl methyl ether, 4-hydroxybutyl ethyl ether and the like.

As the aprotic polar solvent, sulfolane, propylene carbonate and the like are preferable because they have no toxicity.

The present invention further enhances the detergency by containing a polyhydric alcohol such as ethylene glycol, propylene glycol, triethylene glycol, glycerin or the like and a mixture thereof. The amount is 0.001-
0.5 parts by weight is desirable. If the content is less than 0.001 part by weight, the effect of adding them is small, and if it exceeds 0.5 part by weight, phase separation occurs.

The cleaning composition of the present invention may further contain various organic acids such as alcohols, citric acid, tartaric acid, phthalic acid, etc., preservatives, rust preventives, as long as the effects thereof are not impaired. You may mix | blend a defoaming agent, antioxidant, an enzyme, etc.

The cleaning composition of the present invention has a particularly excellent effect in cleaning the solder flux remaining after the soldering of the printed circuit board and before cleaning the plastic molded product. It can also be used to clean parts of electrical equipment and precision equipment, or their jigs and tools.

Further, when washing with the composition of the present invention,
It can be washed by a conventionally known method. For example,
First, ultrasonic cleaning is performed in an ultrasonic cleaning tank containing the cleaning composition of the present invention, then immersion cleaning is performed in a liquid bath filled with the cleaning composition of the present invention, and finally showered with the cleaning composition of the present invention. This can be effectively performed by continuously performing a method such as washing.

After washing with the detergent composition of the present invention, it is preferable to carry out post-washing. The liquid used for the post-washing is naphthenic oil, other hydrocarbon solvent, isopropyl alcohol, water, or a kerosene fraction having a boiling point of 150 to 300 ° C., which is one of the components of the cleaning composition of the present invention. The pressure of 10 minutes by a metal catalyst for nuclear hydrogenation of aromatic nuclei.
Under the conditions of 100 kg / cm ² and temperature of 100 to 300 ° C.,
A residual oil obtained by nuclear hydrogenation and then separating and removing at least a part of n-paraffins in the kerosene fraction using a molecular sieve made of synthetic zeolite is fractionated by a precision distillation apparatus. Boiling point 150 to 24, which is substantially free of aromatic hydrocarbons such as naphthalene and biphenyl
It may be rinsed with a hydrocarbon fraction mainly composed of components in the range of 0 ° C. Further, even if it is necessary to wash with a chlorofluorocarbon-based solvent, it can be used in an extremely small amount as compared with the conventional case by using it together with the detergent of the present invention. Further, it is preferable that the object to be cleaned which does not have a fear of being oxidized on the surface or the object to be cleaned which is desired to be oxidized is cleaned with ozone or ultraviolet rays after being cleaned with the cleaning agent of the present invention.

[0028]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention. (Production of hydrocarbon fraction-1) Kerosene fraction having a boiling point range of 150 to 300 ° C (60% by weight of paraffins, 20% by weight of naphthenes, 20% by weight of aromatics) obtained by distillation of crude oil is used at 280 ° C. Under the conditions of 90 kg / cm ² , a Ni-W catalyst for nuclear hydrogenation of aromatic hydrocarbons was used as a catalyst to carry out nuclear hydrogenation, and the resulting product was prepared by the Molex method to 5 angstroms composed of synthetic zeolite. The n-paraffins were separated by feeding them to a separation column filled with a molecular sieve having holes. The obtained residual oil fraction depleted in n-paraffins was then subjected to precision distillation using a precision distillation apparatus with two columns to obtain a hydrocarbon fraction having a boiling point of 177 to 200 ° C. The composition and properties of this solvent are shown in Table 1.

(Production Example-2 of Hydrocarbon Component) The residual oil fraction depleted in n-paraffins obtained in the process of Production Example-1 of hydrocarbon component was subjected to conditions of 200 ° C. and 50 kg / cm ² . Then, a second stage hydrogenation treatment is performed using a nickel-based catalyst, and the obtained product is precision distilled using a two-column precision distillation apparatus to obtain a hydrocarbon fraction having a boiling point of 177 to 200 ° C. It was The composition and properties of this solvent are shown in Table 1.

(Production Example-3 of Hydrocarbon Component) A kerosene fraction having a boiling range of 150 to 300 ° C. (60% by weight of paraffins, 20% by weight of naphthenes, 20% by weight of aromatics) obtained by distillation of crude oil is used. Ni as a catalyst for nuclear hydrogenation of aromatic hydrocarbons under conditions of 280 ° C. and 90 kg / cm ^2.
Nuclear hydrogenation was carried out using a -W catalyst, and the resulting product was supplied by a Molex method to a separation column filled with a molecular sieve made of synthetic zeolite and having pores of 5 angstroms to separate n-paraffins. The obtained residual oil fraction depleted in n-paraffins was then subjected to precision distillation using a precision distillation apparatus with two columns to obtain a hydrocarbon fraction having a boiling point of 210 to 240 ° C. The composition and properties of this solvent are shown in Table 1.

(Examples 1 to 12, Comparative Examples 1 to 4) Cleaning agents were prepared according to the formulations shown in Table 2. Experiment is 4 cm x 2 cm x
A test piece was a 5 mm glass plate or a resin plate (polypropylene) uniformly coated with waste oil. In Examples 1 and 7 to 9, a resin plate was used and the others were glass plates. Cleaning is performed using ultrasonic waves of 28 kHz, liquid temperature 37 ° C
After 2 minutes under the above condition, the cleaning agent was wiped off with a cloth, or after further post-cleaning with water, isopropyl alcohol, and the hydrocarbon component of the component (A), the cleaning property was wiped off. The degree of cleaning of the waste oil was visually confirmed.
For flame retardancy, a flash point measuring device was used, and an open system in which the components in Table 2 did not ignite up to a liquid temperature of 80 ° C was regarded as acceptable.

The symbols used in Tables 1 and 2 are as follows. S1: Hydrocarbon component of Production Example-1 S2: Hydrocarbon component of Production Example-2 S3: Hydrocarbon component of Production Example-3 I1: Lauryl ether I2: Ethylene oxide / propylene oxide block polymer (HLB = 10.1) I3 : Sorbitan fatty acid ether (HLB = 12.5) I4: stearic acid glyceride H1: hexyl alcohol H2: propionic acid hexyl ester H3: ethyl butyl ether H4: 3 hydroxypropyl methyl ether H5: propylene carbonate

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

The cleaning composition of the present invention exhibits excellent effects in cleaning rosin flux and cleaning plastic products before coating, and is excellent in flame retardancy. The cleaning composition of the present invention has excellent removability and safety of stains such as clothes, resin processed products, precision machinery, electric and electronic parts, and solder flux, and has no environmental pollution, and thus has great industrial utility value.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C11D 1:68 1:74 7:24)

Claims (1)

[Claims] 1. A flame-retardant hydrocarbon detergent composition comprising the following components (A) to (C). The kerosene fraction having the boiling point of the component (A) in the range of 150 to 300 ° C. is heated to 10 to 100 kg / cm ^{2 at} a temperature of 100 to 300 by a metal catalyst for nuclear hydrogenation of aromatic nuclei.
The residual oil obtained by nuclear hydrogenation under the condition of ° C, and then separating and removing at least a part of the n-paraffins in the kerosene fraction by using a molecular sieve made of synthetic zeolite is subjected to a precision distillation apparatus. Hydrocarbon fraction mainly composed of components having a boiling point of 150 to 240 ° C., which is substantially free of naphthalene and biphenyl, obtained by fractional distillation 10.
0 parts by weight (B) water 10 to 60 parts by weight (C) surfactant 20 to 120% by weight of water