JP3232300B2 - Cleaning liquid composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning liquid composition,
More specifically, the present invention relates to a cleaning liquid composition suitable for cleaning oils, polymers, scales, soldering fluxes, metal soaps and the like attached to the surface of metals or resins.

[0002]

2. Description of the Related Art Conventionally, hydrocarbons such as aromatic and aliphatic solvents, terpene solvents and alcohol solvents have been used for washing the above oils and the like. There are safety problems such as a relatively low flash point and toxicity.

[0003] In addition, CFC-based solvents and chlorine-based solvents are also used, but these solvents are scheduled to be banned in the near future as substances that destroy the ozone layer. It is strong and its regulations are strict to prevent water pollution.

Aqueous detergents, aqueous solutions such as phosphates,
A large space is required for the wastewater treatment equipment, which is not preferable in terms of economy.

JP-A-56-92999 and JP-A-57-8
Japanese Patent No. 3598 discloses a household detergent and cleaning agent obtained by adding succinic diester, an anionic surfactant and a nonionic surfactant to 60% by weight or more of water.
In addition, Japanese Patent Application Publication No. 4-502638 discloses that the carbon
Cleaning agents for printing plates comprising six dialkyl alkyl esters and 0 to 40% by weight of a nonionic surfactant are disclosed.

[0006]

SUMMARY OF THE INVENTION The present invention provides a cleaning liquid composition having a good cleaning effect and excellent safety.

[0007]

Means for Solving the Problems The present inventors have a good cleaning effect, do not show flammability, have low odor, have low toxicity, have good biodegradability, and have a good biodegradability. Various investigations were repeated in order to find a new cleaning solution which is very excellent and more economical. As a result, when a cleaning liquid composition containing γ-butyrolactone (hereinafter, may be abbreviated as GBL), diethyl succinate (hereinafter, may be abbreviated as DES), and water at a predetermined compounding ratio is used, the above-described problem occurs. Can be effectively solved.

That is, the gist of the present invention comprises 50 to 88 parts by weight of γ-butyrolactone, 2 to 25 parts by weight of diethyl succinate, and 10 to 48 parts by weight of water, the total of which is 1
100 parts by weight of the cleaning liquid composition.

The cleaning liquid composition of the present invention has the above-mentioned advantages, and does not leave scales on the surface of a metal or resin product even when the rinsing step is simplified, as compared with other water-based cleaning agents. And wastewater treatment is also easy. Furthermore, both GBL and DES have a high boiling point, low loss due to evaporation, and can be reused by distillation.

[0010] In the cleaning composition of the present invention, GBL,
The mixing ratio of DES and water is GBL 50 to 88 parts by weight,
2 to 25 parts by weight of DES and 10 to 48 parts by weight of water, preferably 55 to 83 parts by weight of GBL, 2 to 20 parts by weight of DES, and 15 to 40 parts by weight of water, particularly preferably GBL6
0 to 80 parts by weight, 5 to 15 parts by weight of DES, and 15 to water
25 parts by weight, the sum of which is 100 parts by weight. In the range of the compounding ratio of the present invention, the cleaning liquid composition is uniform at room temperature and does not show flammability when its flash point is measured in accordance with JIS K2274 using a Cleveland open type flash point measuring device. .

When the GBL content is less than 50 parts by weight, the components do not dissolve uniformly at room temperature, and the washing solution may become non-uniform during storage. If GBL exceeds 88 parts by weight, or if the total of GBL and DES exceeds 90 parts by weight and water is less than 10 parts by weight, the flammability of GBL and DES cannot be extinguished, which is not preferable from the viewpoint of safety. . On the other hand, if DES exceeds 25 parts by weight, the ratio of GB for maintaining the cleaning solution composition at room temperature is uniform.
It is not preferable because the flammability of L and DES cannot be extinguished. If the DES is less than 2 parts by weight, sufficient detergency cannot be obtained for stains of low polarity such as machine oil. Also,
If the amount of water is more than 48 parts by weight, the cleaning effect is not significantly reduced.

FIG. 1 shows the mixing state at room temperature (21 ° C.) of the cleaning liquid compositions having various mixing ratios. In FIG. 1, the cleaning liquid composition which was completely colorless and transparent without phase separation was made uniform (indicated by ○), and the one in which phase separation or white turbidity was made nonuniform (indicated by x). When GBL is contained in an amount of 50 parts by weight or more based on the entire cleaning liquid composition, the cleaning liquid composition is uniform regardless of the mixing ratio of DES and water.

FIG. 2 shows the presence / absence of a flash point for cleaning liquid compositions having various mixing ratios. The flash point is measured using a Cleveland open-type flash point measuring device in accordance with JIS K2274. In FIG. 2, も の indicates one having no flash point, and X indicates one having a flash point. 15 water
A cleaning liquid composition containing not less than 20 parts by weight of DES and not having a flash point does not correspond to a dangerous substance specified by the Fire Service Law. For example, in a cleaning liquid composition having a GBL / DES / water weight ratio of 75/10/15, the flash point measurement was attempted by gradually increasing the sample temperature.
The liquid boiled at about 2 ° C., and at a temperature of 124 ° C. or higher, a small flame was extinguished due to steam, and it was impossible to measure the flash point. Therefore, the cleaning liquid composition does not have a flash point and does not fall under the category of dangerous substances specified by the Fire Service Law. GBL / DES
In the cleaning liquid composition having a water / water weight ratio of 80/15/5, ignition was observed at 120 ° C.

The cleaning liquid composition of the present invention is widely suitable for cleaning oils and the like adhered to the surface of metals, resins, etc., for example, polyolefin resins such as bumpers for automobiles described in Japanese Patent Application No. 5-111195. Cleaning of products, peeling of paint and coating resin, removal of rust, grease and dirt on metal surfaces, cleaning of molding dies, removal of solder flux, cleaning of electronic and precision equipment, cleaning of printing equipment, cleaning of polymerization equipment Used for etc.
Further, it has a good cleaning effect in a wide range from a highly polar stain to a weakly polar stain. In the washing of a saturated hydrocarbon oil such as a metal working oil, the oil hardly dissolves in the washing liquid and an emulsion is hardly formed, so that the oil can be floated on the upper part of the washing liquid by standing separation for a short time. Therefore, the oil can be easily removed by a simple oil-water separator, and the service life of the cleaning liquid is long.

Further, the cleaning liquid composition of the present invention may contain conventional additives such as a surfactant, an antioxidant, an ultraviolet absorber, and a rust preventive as long as the object of the present invention is not impaired. Here, the surfactant as an optional substance is used for improving permeability and dissolution rate into oils, polymers, scales, soldering fluxes, metal soaps and the like. As the surfactant, a nonionic surfactant is preferable, for example, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid ester of sorbitol and sorbitan, Any of sucrose fatty acid ester, silicon type, fluorine type and the like can be used. Further, an ultraviolet absorber and an antioxidant, which are other optional substances, help to improve the stability for long-term storage of the liquid, and as the ultraviolet absorber, for example, benzotriazole, benzophenone, hindered amine and the like can be used. As the antioxidant, for example, any of phenol-based, amine-based, sulfur-based, phosphorus-based and the like which are soluble in the cleaning liquid composition of the present invention can be used.

The method for producing the cleaning liquid composition of the present invention is not particularly limited, and any known means can be employed, and the composition can be produced by mixing the components in any order.

The method of cleaning with the cleaning liquid composition of the present invention is not particularly limited, and any known method can be used.
For example, wiping with a sponge or the like impregnated with the cleaning liquid composition, immersion in the cleaning liquid composition and / or spraying is preferably performed. In cleaning by immersion, it is more preferable to combine stirring, rocking, ultrasonic waves, air bubbling, and the like at the same time to enhance the cleaning effect. In this case, the use conditions of the ultrasonic wave are preferably, for example, an oscillation frequency of 20 to 100 kHz and an oscillation output of 10 to 200 W / l. In the air bubbling, fine bubbles are preferably aerated at a gas: liquid volume ratio of about 1: 1 to 5: 1 to raise insoluble dirt in the cleaning liquid composition together with the air bubbles and separate insoluble dirt. can do.
In the cleaning by spraying, the pressure is, for example, 0.
5-10 kg / cm ² G is preferred. In each case, the washing time is preferably from 15 seconds to 2 hours, particularly preferably from 30 seconds to 20 minutes. If the time is less than 15 seconds, the cleaning is insufficient and the adhered dirt cannot be sufficiently removed.
Even if the time is exceeded, the cleaning effect is not particularly improved. The washing temperature is preferably 30 to 80C. Particularly preferably 5
The temperature is 0 to 65 ° C., and the treatment at a high temperature can significantly increase the cleaning effect. If the temperature is lower than 30 ° C., the washing tends to be insufficient.

In order to control the water concentration of the cleaning liquid composition of the present invention, for example, a weight measurement method by distillation separation described in ASTM D95-83, ASTM E203-7
The titration method using the Karl Fischer reagent, the quantification by near-infrared spectroscopy, the quantification method using a refractive index, and the like described in 5 can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0020]

【Example】

[0021]

Examples 1 to 8 and Comparative Examples 1 to 10 In the examples and comparative examples, the following substances for soiling and water-based cleaning liquids and petroleum-based cleaning liquids as comparative cleaning liquids were used. <Substance for dirt> Substance (a): extraction oil (Dafney master draw 533W)
D, trademark, Idemitsu Kosan Co., Ltd.) Material (b): Press oil (Unipres DP-120, trademark, manufactured by Nippon Oil Co., Ltd.) Material (c): Grease (Nichimori LE, trademark, manufactured by Nichimori Co., Ltd.) Material ( d): Flux (sparkle flux PO-
F-1010S, trademark, manufactured by Senju Metal Industry Co., Ltd.) Substance (e): Epoxy resin composition before curing The components in the resin composition and the compounding ratio thereof are as follows. Each component was mixed at room temperature, stored at 0 ° C. for 2 weeks, and then returned to room temperature.

Epoxy resin (Epicoat 828, trademark,
Yuka Shell Co., Ltd.): 100 parts by weight Curing agent (pentahard 5000, trademark, manufactured by Tonen Chemical Co., Ltd.): 90 parts by weight Curing accelerator (2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd.): 0.5 parts by weight <Comparative cleaning liquid> Aqueous cleaning liquid (a): 5% by weight aqueous solution of Toyosol SS-20 (trademark, manufactured by Toyoda Chemical Co., Ltd.) Petroleum cleaning liquid: ACTEL 1178L (trademark, manufactured by Exxon Chemical Co., Ltd.) 5 cm A 100-mesh stainless steel wire mesh of × 7 cm is immersed in each of the above soiling substances, pulled up, and left for 1 hour at room temperature on a metal vat covered with filter paper to drain the liquid. The weight of the material was measured. Next, 100 milliliters of the wire netting and the cleaning liquid to which each of the above-mentioned contaminants was adhered were placed in a 150 milliliter sample bottle, and the ultrasonic cleaning machine (28 kHz oscillation frequency, 80 W / l oscillation output) was used. Washing was performed under each of the conditions shown. After the washing, the wire net was taken out, dried at 90 ° C. for 30 minutes, then allowed to cool at room temperature for 30 minutes, and then weighed to determine the removal rate of each soiling substance. The results are shown in Tables 1 and 2.

[0023]

[Table 1]

[0024]

[Table 2] Examples 1 to 8 are the results of attempts to clean various soiling substances using the cleaning liquid composition of the present invention. A good removal rate was exhibited irrespective of the type of soiling substance or washing conditions. On the other hand, Comparative Examples 1 to 6 were GBL alone, GBL and water,
Or the case where a cleaning liquid composition containing GBL and DES is used. In each case, the stain removal rate was remarkably low as compared with the examples. Comparative Examples 7 to 10 are cases where the aqueous cleaning liquid (a) or the petroleum cleaning liquid was used. Also in this case, the stain removal rate was remarkably low as compared with the example.

[0025]

Examples 9 to 11 and Comparative Examples 11 to 14 In the examples and comparative examples, the following substances for soiling and aqueous cleaning liquids as comparative substances were used. <Stain for Substance> Substance (c): grease (same as that used in the above examples) Substance (f): release agent (silicone release agent NUC-B, trademark, manufactured by Nippon Unicar Co., Ltd.) <Comparative cleaning liquid> Water-based cleaning liquid (b): ISW32 (trademark, Tosoh Dubo)
The following polyolefin-based resin was used as a sheet to which a substance for soiling was adhered. <Polyolefin resin> Ethylene-propylene block copolymer / ethylene-propylene rubber (EPR) / talc (weight ratio of 60/30/10) Ethylene-propylene block copolymer: Melt index (based on MI: ASTM D1238) , 230
C, measured under a load of 2.16 kg) is 18 g / 10 min.
The ethylene content is 7% by weight.

EPR: melt index (MI: AS
(Measured at 230 ° C. under a load of 2.16 kg) according to TM D1238) 3.1 g / 10 min, ethylene content 7
4% by weight.

Talc: average particle size is 2.0 μm.

The above-mentioned polyolefin resin was molded by an injection molding machine set at a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C. to form a sheet of 150 × 100 × 3 mm.

After 0.4 g of a grease as a soiling substance or 0.2 g of a release agent is adhered to the sheet substantially uniformly, a spray nozzle (1/1 made by Ikeuchi Co., Ltd.) is used.
8MVNP2543) Use 1 bottle, 8-10 liters /
Washing was performed at 60 ° C. under each condition using each washing solution shown in Table 3 at a flow rate of 1 minute. After washing, rinsing was performed by rocking in ion-exchanged water at room temperature for 1 minute, and then dried by hot air blowing at 80 ° C. for 3 minutes. After cooling to room temperature, each sheet was subjected to a plasma treatment under the following conditions. Plasma processing conditions Vacuum: 0.8 torr Output: 1 kW × 2 units Processing time: 60 seconds Active gas flow rate: 220 ml / min, oxygen / nitrogen molar ratio: 1
1/1 Next, a paint (R320, trade name, manufactured by Nippon Bee Chemical Co., Ltd.) was applied in a thickness of 100 μm, and baked at 120 ° C. for 30 minutes. Using this as a test piece, the following various property tests were performed. <Peel strength> The coating film of each test piece was cut to a width of 10 mm, and 50 ° in a 180 ° direction at a temperature of 23 ° C. using a tensile tester.
The strength obtained when peeled at a speed of mm / min was measured. Further, the appearance after peeling was observed. The observation results are indicated by the following symbols.

○ The coating film was completely adhered and the material was destroyed.

X: The adhesion of the coating film was poor, and the coating film peeled off. <Warm water resistance> Each test piece was immersed in 40 ° C warm water for 240 hours, and then the presence or absence of blister generation was observed. The observation results are indicated by the following symbols.

○ The coating film adhered completely and no blister was generated.

×: The coating film is not uniformly adhered and blisters are generated. The results are shown in Table 3.

[0034]

[Table 3] Examples 9 to 11 are cases where the cleaning liquid of the present invention was used. Regardless of the type of soiling material and spray conditions,
The coating shows good peel strength, peel appearance and warm water resistance,
In each case, it was found that a good cleaning effect was obtained. On the other hand, Comparative Examples 11 to 14 are cases where the weight ratio of GBL / DES / water was set to 45/5/50 outside the range of the present invention, or the case where the aqueous cleaning liquid (b) was used. In each case, the peel strength of the coating film was remarkably inferior to that of the examples, and the peel appearance and hot water resistance were also poor, and a good cleaning effect was not obtained.

[0035]

The cleaning liquid composition of the present invention has a good cleaning effect, substantially no flammability, low odor, low toxicity and excellent safety. It is also economically superior. Therefore, it is extremely useful industrially as a substitute for the conventional cleaning liquid.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a weight ratio of GBL / DES / water and a mixed state thereof.

FIG. 2 is a graph showing the relationship between the weight ratio of GBL / DES / water and its flammability.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroshi Ueno 1-3-1, Nishi-Tsurugaoka, Oi-machi, Iruma-gun, Saitama (56) References JP-A-7-166195 (JP, A (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/50 C11D 7/26 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. 50 to 88 parts by weight of γ-butyrolactone,
A cleaning liquid composition comprising 2 to 25 parts by weight of diethyl succinate and 10 to 48 parts by weight of water, the total of which is 100 parts by weight. 2. 55 to 83 parts by weight of γ-butyrolactone,
The cleaning solution composition according to claim 1, comprising 2 to 20 parts by weight of diethyl succinate and 15 to 40 parts by weight of water.