JPH06136387A - Cleaning composition - Google Patents

Abstract

(57) [Abstract] [Purpose] It has excellent solubility and storage stability as an alternative to specific CFC-based detergents, and has an antistatic effect on the item to be washed without impairing the appearance of the item to be washed. To provide a cleaning composition containing a cheap petroleum solvent as a main component. [Composition] A petroleum solvent as a main component, an anionic surfactant of 0.05 to 1.0% by weight, and a solubility parameter of 10
~14 (cal / cm ^{3) 1/2,} and a polar organic solvent 0.3 dipole moment is 1.0 to 2.5 (D)
A cleaning composition containing 10 to 10% by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition containing a petroleum-based solvent as a main component for washing a plastic or metal surface. More specifically, a polar organic solvent is added to dissolve a surfactant. The present invention relates to a detergent composition that improves performance and does not stain the surface of the article to be washed after cleaning, and imparts an antistatic effect to the article to be washed as well as the detergent composition itself.

[0002]

2. Description of the Related Art Plastic products are used in household products, electric appliances, automobiles and other daily necessities. Among them, urethane foam is used as a cushioning material for seat cushions, sofas, beds, mattresses, etc., or as a heat insulating material, soundproofing material, building materials, vehicles, ships, air conditioners,
Widely used in audio equipment.

Products such as cushions, laminated sheets, vehicle instrument panels, and the like include those having a vinyl chloride skin material on the surface thereof and a reinforcing material such as a metal inside thereof as other constituents.

Wax, silicone oil, etc. are used as a mold release agent when molding (molding) a plastic product made of such urethane foam and skin material, and vinyl chloride, metal, etc. are used at the time of molding. In many cases, a mold release agent adheres to the surface of the constituent material of (1), resulting in insufficient adhesion with each material, or impairing the appearance of the molded product. Also, if you want to post-paint this product,
Release agents that adhere to the skin may interfere with painting.

Therefore, it is necessary to remove the release agent such as wax and silicone oil after molding. As a cleaning agent for removing the release agent, a petroleum-based cleaning agent such as normal hexane is generally used. However, petroleum-based solvents have a risk of being ignited by static electricity generated when the release agent is wiped off, and in order to avoid this, chlorine such as trichlorotrifluoroethane (CFC113), which has excellent heat resistance, is included. It is used with a CFC-based solvent blended to lower the flash point and improve safety. In some cases, cleaning is performed only with a fluorocarbon solvent.

However, in order to obtain the flame retardant effect,
Since an expensive CFC-based solvent must be added at a high concentration, the cost of the cleaning agent becomes high and the economy is poor. Further, in recent years, the use of solvents containing fluorine has tended to be significantly restricted due to environmental problems such as ozone layer depletion, and in particular, CFCs such as CFC113 are beginning to move toward total abolition worldwide and will be used in the future. Can not do.

[0007]

On the other hand, the present inventors have
As a result of various studies focusing on cheap petroleum solvents such as normal hexane, benzine, and cleaning solvent, a cleaning agent in which an anionic surfactant is added to petroleum solvents has the effect of preventing static electricity generation to some extent, It has been found to be useful as a cleaning agent for materials. However, the anionic surfactant does not always dissolve well, or even once it dissolves, it may cause a stain over time.
There is a problem with the storage stability of the solution, and further, when the molded product is washed with a detergent having such a problem, a white powdery product is produced on the surface of the molded product after drying, and the surface is soiled, which is satisfactory. There is a problem that it is difficult to obtain a product with an external appearance.

Therefore, an object of the present invention is to obtain excellent solubility,
Has storage stability and does not impair the appearance of the object to be washed,
It is an object of the present invention to provide a cleaning composition that imparts an antistatic effect to an object to be cleaned and is an alternative to a specific CFC-based cleaning agent containing an inexpensive petroleum solvent as a main component.

[0009]

Means for Solving the Problems The present inventors have found that when a specific organic compound is added to a detergent prepared by adding an anionic surfactant to a petroleum solvent, the solution stability of the surfactant is improved. In addition, they have found that an antistatic effect is imparted to the article to be cleaned without impairing its appearance, and have completed the present invention. That is, the present invention comprises a petroleum solvent as a main component, an anionic surfactant of 0.05 to 1.0% by weight, and a solubility parameter of 10 to 14 (cal / c).
m ^{3) 1/2,} and dipole moment 1.0 to 2.
5 (D) is a detergent composition containing 0.3 to 10% by weight of a polar organic solvent.

The petroleum solvent used in the present invention is, for example,
Separation of specific compounds or components from industrial gasoline such as benzine, white gasoline, mineral spirits, cleaning solvent, kerosene or petroleum-based solvents of these,
Examples include purified products (eg, normal hexane and normal paraffins extracted from kerosene fraction).
These petroleum-based solvents may adversely affect the constituent materials of the object to be cleaned, in consideration of various characteristics such as solubility, volatility, odor, flash point, specific gravity and color, alone or in combination of two or more kinds. Instead, those having a good solubility for the object to be removed may be appropriately selected and combined depending on the application. In order to wipe off the release agent from a molded product such as urethane foam of vinyl chloride skin, special care must be taken in handling to avoid damage to health, low content of aromatic hydrocarbons and normal hexane, Volatile industrial gasoline is preferred.

The anionic surfactant used in the present invention plays a role as an antistatic agent, and examples thereof include alkyl sulfonates, alkyl sulfates, alkylaryl sulfonates and α-olefin sulfones. Examples thereof include acid salts, alkylphosphonates, and alkyl phosphate ester salts. Of these salts, sodium salts are preferable from the viewpoint of availability, but alkali metal salts such as lithium and potassium or alkaline earth metal salts such as magnesium and calcium can also be used.

The anionic surfactant is contained in an amount of 0.05 to 1.0% by weight based on the finished detergent composition.
If it is less than 0.05% by weight, the antistatic effect cannot be imparted to the article to be cleaned. If it exceeds 1.0% by weight,
The antistatic effect does not improve as much as the added amount increases, so it is economically unfavorable, and it takes a long time to dissolve, and the storage stability of the solution after dissolution is impaired, and it is easy to cause a cage. And further stain the surface of the object to be cleaned, which is not preferable.

Even if the above-mentioned mixed composition of the petroleum solvent and the anionic surfactant is used as the cleaning agent, the cleaning effect is naturally obtained, and a certain degree of antistatic effect is given to the object to be cleaned. . However, it takes a long time to dissolve the anionic surfactant until it becomes completely transparent, and even if the anionic surfactant is completely dissolved, when the obtained mixed composition is left for a long time, a floating substance is generated in the liquid. In some cases, the phenomenon of white turbidity occurs, and a homogeneous solution having good storage stability cannot be obtained. The use of the above-mentioned heterogeneous mixed composition as a cleaning agent is not preferable because powdery white matter adheres to the surface of the object to be cleaned, significantly reducing the commercial value.

Therefore, in the present invention, the dissolution parameter is 10 to 14 and the dipole moment is 1.0 to.
A polar organic solvent that is 2.5 is used. This polar organic solvent improves the dissolution performance of the anionic surfactant in the petroleum solvent, and when the polar organic solvent is added, the dissolution time is shortened and the detergent can be prepared efficiently. At the same time, even if the mixed composition thus obtained is left for a long time, it does not form a suspended matter or becomes cloudy, and the storage stability of the cleaning composition is significantly improved. .

Examples of polar organic solvents having a solubility parameter of 10 to 14 and a dipole moment of 1.0 to 2.5 include ethanol, 2-ethoxyethanol, 1-propanol, 2-propanol, 1-butanol, and secondary. Butanol, tert-butanol, cyclohexanol, etc. are mentioned, and these can be used individually or in combination of 2 or more types. The solubility parameter is 10 to 14 and the dipole moment is 1.0 to 2.
If a polar organic solvent other than 5 is used, the excellent effects of accelerating the dissolution rate and imparting storage stability of the solution cannot be obtained. That is, when the dissolution parameter is less than 10, the dissolution rate of the surfactant is low, and when it exceeds 14, the dissolution rate is good, but the storage stability is poor and it cannot be used.
Further, even if the dissolution parameter is in the range of 10 to 14, if the dipole moment exceeds 2.5, or if it falls below 1.5, layer separation occurs and crystals are likely to precipitate, so that it cannot be used. A more preferable range is the solubility parameter 10 to 1.
3, the dipole moment is in the range of 1.5 to 2.1.

The solubility parameter is the square root of the cohesive energy density due to the intermolecular action in a non-electrolyte solution, and its numerical value is as described in Solvent Handbook, Asahara Teruzo et al., Kodansha (1976), K. L. Hoy, Ne
w Values of the Solubilit
y Parameters from VaporP
pressure Data, Journal of P
aint Technology, Vol. 42, No.
541, Feb. It can be obtained from literature such as 1970. The solubility parameter varies depending on the temperature, but in the present invention, the data is at about 25 ° C.

The dipole moment is a property of a molecule that has a geometrical structure or a valence bond, and the electric capacity of a capacitor is measured by using a sample vapor or solution as a dielectric material between electrode plates. Is obtained by doing.

The polar organic solvent is contained in an amount of 0.3 to 10% by weight based on the finished detergent composition. 0.3% by weight
If it is less than 10% by weight, the dissolution rate of the anionic surfactant is slow, and the storage stability of the solution is insufficient. On the other hand, if it exceeds 10% by weight, the dissolution rate is accelerated, but the additive is separated into layers from the petroleum solvent. However, it is not preferable because it deteriorates the storage stability of the solution.

The detergent composition of the present invention can be used as a lubricant or a processing oil after cleaning the above-mentioned urethane foam or other plastic products to which a release agent such as wax or silicone oil adheres after molding or after processing a metal. It can be preferably used for cleaning a metal work to which various oils are attached. As a cleaning method, a known cleaning method may be used, for example, a method in which a cleaning agent is sprayed onto an object to be cleaned and then wiped off with a cloth or a brush, a cloth, a sponge, or a felt containing a cleaning agent in advance. The method can be performed by wiping off with, or by soaking in a detergent solution, so-called soaking, and then air-drying, and an appropriate method can be selected depending on the application and the characteristics of the detergent.

In this way, the cleaned plastic products, metal processed products, etc. have their surfaces cleaned of oils and are not contaminated by the cleaning agent. Furthermore, since the antistatic effect is given to the object to be cleaned, dust and the like are less likely to adhere to it, and a clean surface is always retained, so that the product value is not impaired or extra cleaning is performed in the manufacturing or processing process. And cleaning can be omitted.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0022]

EXAMPLES The following materials were used as the constituents of the detergent compositions of the examples and comparative examples of the present invention.

Petroleum solvent : Industrial gasoline having the properties shown in Table 1 [R5N manufactured by Nippon Mining Co., Ltd.].

[0024]

[Table 1]

Anionic surfactant : alkanesulfonic acid sodium salt having the properties shown in Table 2 [manufactured by Nippon Mining Co., Ltd.,
SAS-195, SAS-495].

[0026]

[Table 2]

Polar organic solvent : Commercially available polar organic solvents shown in Table 3 [all reagents special grade or equivalent manufactured by Katayama Chemical Co., Ltd.].

Ethanol to ethyl cellosolve in Table 3 are examples of polar organic solvents that can be used in the present invention, and examples of comparative polar organic solvents that cannot be used after methanol.

[0029]

[Table 3]

The measurement and evaluation of each evaluation item carried out in Examples and Comparative Examples were carried out by the following methods.

Dissolution Time After the predetermined amount of each of the above materials was placed in a beaker, the magnetic stirrer was immediately rotated and stirred to measure the time until the SAS particles disappeared. The dissolution was performed under room temperature (18 to 23 ° C) conditions.

Storage stability of the solution The appearance of the sample solution subjected to the dissolution time test was allowed to stand at room temperature and visually observed immediately after dissolution, 1 day and 7 days later, and visually observed for evaluation.

The evaluation was performed according to the following criteria.

Symbol Dissolution time 1 day or 7 days after the test ◎ Transparent Transparent ○ Almost transparent Almost transparent △ -Slight amount of slag produced × White turbidity, layer separation scent generated, or layer separation Charged object to be washed Commercially available thickness A 25 mm × 100 mm test piece was cut out from a 0.1 mm polyethylene bag (manufactured by Taiyo Co., Ltd.), and the whole was immersed in a cleaning agent, and then air-dried at room temperature in the atmosphere (relative humidity 40 to 60%). The test piece was placed on the filter paper and the entire surface was rubbed strongly three times with a washed cotton cloth. The presence or absence of electric charge existing in the test piece after the treatment was detected by a foil electroscope [EB type manufactured by Yagami Corporation].

Surface contamination of the object to be cleaned 0.03 g / cm ^{2 of a} mold release agent (polydimethylsiloxane, KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly applied to the entire surface of the inside of the mold with a brush, and the mold temperature was 30 ° C. Warm to. Pre-manufactured vinyl chloride sheet (300 mm x 300 mm x 1
mm) is spread over the mold, and then semi-rigid polyurethane obtained by mixing 100 parts by weight of isocyanate (manufactured by Nippon Polyurethane, MR-200) and 60 parts by weight of polyol (manufactured by Inoac, SKLA631) is injected into the mold. After injection, the mold was clamped, and after 6 minutes, the mold was released, and the soft vinyl chloride-polyurethane composite (300 mm × 300 mm × 10 m
m, and the thickness of the polyurethane part was 9 mm).

The composite thus obtained was wiped with a cotton cloth impregnated with a cleaning agent (3 times of hand-wiping), and the soft vinyl chloride surface of the composite after wiping and washing was JIS L 87.
The lightness (L), the yellowness (a) and the redness (b) were measured with a color difference meter manufactured by Minolta Co., Ltd. according to 30, and the surface of the clean vinyl chloride sheet used for the production of the soft vinyl chloride-polyurethane composite was measured. The difference (ΔL, Δa and Δb) is calculated, and JI
According to S Z 8741, 60 degree specular gloss [Gs (60 °)] is measured with a gloss meter manufactured by Suga Co., and the difference from the clean vinyl chloride sheet surface [ΔGs (60 °)] is obtained. The surface contamination after cleaning was evaluated.

Examples 1 to 14 and Comparative Examples 1 to 23 As anionic surfactants, 0.1 g of the above SAS-195, various polar organic solvents shown in Tables 4 and 5 in g numbers shown in Table 4, and The industrial gasoline was placed in a beaker in a balanced amount and mixed to prepare a detergent composition having a total amount of 50 g to prepare detergent compositions of Examples and Comparative Examples. Then, the dissolution time and the storage stability of the solution of each of these trial-produced detergent compositions were measured and evaluated.

The results of these tests are shown in Table 4.

[0039]

[Table 4]

[0040]

[Table 5]

From Table 4, all of the cleaning agents of the present invention shown as examples have a dissolution rate of less than 5 minutes and good storage stability. However, although some of the cleaning agents of the comparative examples have a dissolution rate of less than 5 minutes, the storage stability cannot be satisfied.

Examples 15 to 28 Cleaning agents were prepared in the same manner as in Examples 1 to 14 except that SAS-195 as the anionic surfactant in Examples 1 to 14 was replaced with SAS-495. Then, each dissolution rate and the storage stability of the solution were measured and evaluated.

The results are shown in Table 5.

Comparative Examples 24 to 31 The above SAS-495 was used as an anionic surfactant in an amount of 0.1.
g, the number of g of the polar organic solvent shown in Table 5, and the balance amount of the industrial gasoline were placed in a beaker and mixed to prepare 50 g of the detergent as a whole, thereby preparing the detergent compositions of Comparative Examples 24 to 31. Then, each dissolution rate and the storage stability of the solution were measured and evaluated. The results are shown in Table 5.

[0045]

[Table 6]

From this result and comparison with Table 4, SAS-
Although 495 has better solubility than SAS-195, none of the detergents of Comparative Examples satisfy both dissolution rate and storage stability.

Examples 29 to 36, Comparative Examples 32 to 35 As the anionic surfactant, 0.1 g of the above SAS-195 and ethanol or i-propanol as the polar organic solvent in the weights (g) shown in Table 6, Table 6 shows the test results of the dissolution rate, the storage stability, and the presence or absence of electrification after cleaning the test pieces of the detergents prepared by adding the above-mentioned and industrial gasoline so that the total detergent content was 50 g.

[0048]

[Table 7]

From Table 6, the dissolution rates of the anionic surfactants are all 5> (5 minutes or less) and no difference is observed, but when the amount of the polar organic solvent is small, the dissolution rate tends to be slow. It can be seen that the storage stability of the solution deteriorates when the amount of the polar organic solvent is too large or too small.

Examples 37 to 42, Comparative Examples 36 to 39 The above SAS-195 was used as the anionic surfactant in Table 7.
For the detergents prepared by adding the weights (g), ethanol or i-propanol 0.5 g as a polar organic solvent, and industrial gasoline to make the total detergent 50 g, the test in Table 6 and the article to be washed are shown. The surface contamination test was conducted and the results are shown in Table 7.

[0051]

[Table 8]

Further, it can be seen from Table 7 that if the amount of the SAS compounded is too small, the antistatic effect is not exhibited, and if it is too large, the surface of the object to be cleaned is contaminated.

[0053]

The cleaning composition of the present invention comprises a petroleum solvent,
Since it contains a specific amount of anionic surfactant and a specific polar organic solvent, it has excellent additive solubility and solution stability. It can be stored, and after cleaning, it has an extraordinary effect such as imparting an antistatic effect without spoiling the appearance of the object to be cleaned, and it adheres to the surface of plastic or metal during processing. It can be suitably used as a cleaning agent for cleaning dirt such as oil content and the like, as a substitute for the specified CFC cleaning agent.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Kenichi Matsuda 25 Kitahama-cho, Chita-shi, Aichi Japan Mining Co., Ltd. Chita Refinery (72) Inventor, Kazumi Kato 3-chome, Imaike-cho, Anjo-shi, Aichi Inoac Corporation

Claims (1)

[Claims] 1. A petroleum based solvents, anionic surface active agent 0.05 to 1.0 wt%, the solubility parameter is 10~14 (cal / cm ^{3) 1/2,} and the dipole A cleaning composition comprising 0.3 to 10% by weight of a polar organic solvent having a moment of 1.0 to 2.5 (D).