JP2631621B2 - Cleaning liquid composition for epoxy resin before curing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an epoxy resin before curing,
In particular, the present invention relates to a cleaning liquid composition used for cleaning a container or the like containing an uncured epoxy resin composition.

[0002]

2. Description of the Related Art Conventionally, in industrial equipment that handles epoxy resin, chlorofluorocarbon is used for washing and removing the uncured epoxy resin and the uncured epoxy resin composition adhering to the equipment during the compounding step of the components or during storage after the compounding. Although chlorinated solvents such as trichloroethane are used, these solvents are scheduled to be banned in the near future as substances that destroy the ozone layer, and chlorinated solvents are highly toxic. The laws and regulations are strict to prevent water pollution.

[0003] Further, aqueous detergents and aqueous solutions such as phosphates have a low detergency and require a large space for wastewater treatment equipment, which is not preferable in terms of economy.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a cleaning solution which has not only a good cleaning effect but also excellent safety and which has no curing-acceleration effect on an epoxy resin before curing, especially on an epoxy resin composition before curing. It provides a composition.

[0005]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned drawbacks of various cleaning liquids and to find a cleaning liquid having a good cleaning effect on the epoxy resin before curing. Stacked. As a result, N-methyl-2-
It has been found that the above-mentioned problems can be effectively solved by using a cleaning liquid composition containing pyrrolidone (hereinafter, sometimes abbreviated as NMP) and water at a specific mixing ratio.

That is, the cleaning composition for an epoxy resin before curing of the present invention has a good cleaning effect on the epoxy resin before curing, has no flash point, has low odor, has low toxicity, and has a high safety. Is also very good. In addition, there is no curing acceleration effect on the pre-cured epoxy resin, particularly on the pre-cured epoxy resin composition. Therefore, even if the cleaning liquid composition of the present invention remains slightly after washing, for example, in a tank or the like, there is no danger of curing during the storage of the epoxy resin before curing, particularly the epoxy resin composition before curing, and the curing Premature curing does not occur in the process. Further, NMP has a high boiling point, a small loss due to evaporation, can be reused by distillation, and is excellent in terms of economy.

[0007] The present invention relates to N-methyl-2-pyrrolidone 7
The cleaning liquid composition for an epoxy resin before curing contains 0 to 85 parts by weight and 30 to 15 parts by weight of water.

In the cleaning liquid composition for epoxy resin before curing of the present invention, the mixing ratio of NMP and water is NMP 70-85.
30 to 15 parts by weight of water, preferably 25 to 15 parts by weight of water to 75 to 85 parts by weight of NMP, particularly preferably 80 to 85 parts by weight of NMP, 15 parts by weight. If NMP is less than 70 parts by weight and water exceeds 30 parts by weight, the solubility of the epoxy resin before curing and the epoxy resin composition before curing significantly decreases,
Good cleaning effect cannot be obtained. If NMP exceeds 85 parts by weight and water is less than 15 parts by weight, the flash point of NMP cannot be extinguished, which is not preferable from the viewpoint of safety.

The cleaning liquid composition for an epoxy resin before curing of the present invention contains conventional additives such as a surfactant, an antioxidant, an ultraviolet absorber and a rust inhibitor within a range not to impair the object of the present invention. Can be included. Here, the surfactant as an optional substance is used for improving the permeability and dissolution rate of the epoxy resin before curing, particularly the epoxy resin composition before curing. As the surfactant, nonionic surfactants are preferable, for example, higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, sorbitol and fatty acid esters of 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 for an epoxy resin before curing of the present invention is not particularly limited, and generally known means can be employed.

The cleaning method itself with the cleaning liquid composition for an epoxy resin before curing 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, for example, an oscillation frequency of 20 to 100 kHz, an oscillation output of 1
0 to 200 W / l is preferred. In 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 air bubbles and separate insoluble dirt. can do. In cleaning by spraying, the pressure is preferably, for example, 0.5 to 10 kg / cm ² G. In any case, the cleaning time is preferably 30 seconds to 2 seconds.
Time, particularly preferably 3 to 20 minutes. If the time is less than 30 seconds, the cleaning is insufficient and the adhered dirt cannot be sufficiently removed. On the other hand, if the time exceeds 2 hours, the cleaning effect is not particularly improved. The washing temperature is preferably 30 to 80C. The temperature is particularly preferably 50 to 65 ° C., and the treatment at a high temperature can significantly increase the cleaning effect. 30 ° C
If the temperature is less than 80 ° C., the cleaning becomes insufficient. If the temperature is higher than 80 ° C., the evaporation rate of water is large and the management of the water concentration of the cleaning liquid composition becomes complicated, which is not preferable.

The cleaning liquid composition for an epoxy resin before curing according to the present invention is widely used for cleaning an epoxy resin before curing and an epoxy resin composition before curing. It is effectively used for washing and removing the pre-cured epoxy resin, particularly the pre-cured epoxy resin composition, which has adhered to the equipment during the subsequent storage.

Examples of the epoxy resin before curing include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, polyglycidyl ether of polyhydric alcohol, polyglycidyl ester of polybasic acid, and 3,4-epoxy. Examples include cyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, vinylcyclohexene diepoxide, cresol novolak type epoxy resin, and epoxy resin having a hydantoin ring. Further, as the epoxy resin composition before curing, for example, an epoxy resin curing agent, a curing accelerator is added to the epoxy resin, and further, a filler, a stabilizer,
Plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, colorants, charge imparting agents, foldability improvers, those blended with conventional additives such as impact resistance improvers, and the like. . here,
As the epoxy resin curing agent, any one may be used as long as it is generally used, and examples thereof include polyhydric phenols, aromatic polybasic acids, and aromatic polyamines. For example, phenol novolak, biphenol type novolak, bisphenol A Examples include novolaks such as type novolaks, acid anhydrides such as phthalic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride; and amines such as diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, and hexamethylenetetramine. Examples of the curing accelerator include tertiary amines and organic phosphorus compounds.

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.

[0015]

EXAMPLES The substances in the pre-cured epoxy resin compositions used in the following Examples and Comparative Examples and the mixing ratios thereof are as follows. <Epoxy resin composition A before curing> Epoxy resin (CT-200, trademark, manufactured by Ciba-Geigy Corporation): 100 parts by weight Curing agent (HT-903, trademark, manufactured by Ciba-Geigy Corporation): 40 parts by weight Inorganic filler: 210 parts by weight Parts (silica, HHH, trademark,
<Epoxy resin composition B before curing> Epoxy resin (Epicoat 828, trademark, manufactured by 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-methyl-imidazole,
Shikoku Chemicals Co., Ltd.): 0.5 parts by weight The aqueous cleaning liquid and petroleum cleaning liquid used in Comparative Examples are as follows. <Water-based cleaning liquid> 5% by weight aqueous solution of TOYOZOL SS-20 (trademark, manufactured by Toyoda Chemical Co., Ltd.) <Petroleum-based cleaning liquid> ACTEL 1178L (trademark, manufactured by Exxon Chemical Co., Ltd.)

[0016]

Examples 1 to 5 Ten grams of each of the uncured epoxy resin compositions A and B prepared by mixing the components at room temperature were applied to a glass watch glass having a diameter of 10 cm and the temperature was adjusted to 60 ° C.
For 4 hours. An 85% by weight aqueous solution of NMP
Temperature 50 ° C., pressure 1.0 kg / cm ² G, flow rate 2.2
The cleaning test was performed by spraying at liters / minute for each time shown in Table 1. After washing, keep the watch glass at 90 ° C for 5
After drying for minutes, the weight was measured to determine the residual ratio of each resin composition. Table 1 shows the results.

[0017]

Table 1 Example 1 2 3 4 5 Precured epoxy resin composition type A A B B B Spray time (min) 3 5 0.5 13 Residual rate (% by weight) 0.3 0 0 0 0 , 85% by weight NMP aqueous solution, the epoxy resin composition before curing could be satisfactorily removed in a short time.

[0018]

EXAMPLES 6 TO 7 AND COMPARATIVE EXAMPLE 1 A pre-cured epoxy resin composition B prepared by mixing the components at room temperature was used as a sample and subjected to a washing test by immersion combined with stirring. First, a 200-mesh stainless steel wire mesh of 5 cm × 5 cm was immersed in the sample, 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 sample attached to the wire mesh was measured. It was measured. Next, a wire mesh with the sample attached to a 150 ml sample bottle was heated at 60 ° C.
Then, the heated washing liquid and the rotor were put in, and the mixture was stirred by a magnetic stirrer having a heating function at 60 ° C. for 1 minute to perform washing. After washing, take out the wire mesh and
After drying for 0 minutes and then cooling at room temperature for 30 minutes, the weight of the sample was measured to determine the removal rate of the epoxy resin composition. Table 2 shows the results.

[0019]

[Table 2] Table 2 Example Comparative example 6 7 1 Washing liquid type 85% by weight NMP aqueous solution 75% by weight NMP aqueous solution 50% by weight NMP aqueous solution Amount of wire mesh resin (mg) 231.5 261.5 176.7 Removal rate (% by weight) 99.9 99.8 89.8 Execution Examples 6 and 7 are 85% and 75% by weight NM, respectively.
Although the cleaning was performed using the P aqueous solution, the removal rate of the pre-cured epoxy resin composition was better as compared with Comparative Example 1. In Examples 6 and 7, there was almost no change in the removal rate.

[0020]

Examples 8 to 9 and Comparative Examples 2 to 3 The epoxy resin composition B before curing prepared by mixing the components at room temperature was stored at 0 ° C. for 2 weeks and then returned to room temperature. A washing test by immersion in combination with was carried out. First,
A 100-mesh stainless steel wire mesh of 5 cm × 7 cm was immersed in the sample, pulled up, allowed to stand at room temperature for 1 hour on a metal bat covered with filter paper, drained, and the weight of the sample attached to the wire mesh was measured. . Next, the wire net having the sample attached thereto and the cleaning solution heated to 40 ° C. are placed in a 150 ml sample bottle, and the ultrasonic cleaning machine (oscillation frequency 28
Washing was performed at 40 ° C. using a frequency of 80 kHz and an oscillation output of 80 kHz. 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 the epoxy resin composition. Table 3 shows the results.

[0021]

Table 3 Example 3 Comparative Example 8 9 2 3 Type of cleaning liquid 85% by weight NMP aqueous solution 85% by weight NMP aqueous solution Water-based cleaning liquid Water-based cleaning liquid Cleaning time (seconds) 30 60 30 60 Amount of wire netting resin (mg) 508.3 527.3 512.1 517.6 Removal rate (% by weight) 99.7 99.9 67.4 70.0 In Examples 8 and 9, the cleaning time was 30 and 60 seconds, respectively, using 85% by weight NMP, and Comparative Example 2 was used.
And 3 use a water-based cleaning agent and also set the cleaning time to 3
0 and 60 seconds. In Examples 8 and 9, the removal rate of the epoxy resin before curing was lower than that in Comparative Examples 2 and 3.
Very good. Further, since the cleaning ability of 85% by weight NMP was large, the effect of the difference in the cleaning time between 30 seconds and 60 seconds on the removal rate was hardly observed.

[0022]

Example 10 and Reference Examples 1 and 2 Next, the effect of accelerating the curing of the cleaning liquid composition for an epoxy resin before curing of the present invention was examined. Each component was added at 12 at the mixing ratio (parts by weight) shown in Table 4.
After heating and mixing at 0 ° C., the gelation time was measured while maintaining at 115 ° C. For reference, the gel time was also measured when the cleaning solution of the present invention was not added and when benzyldimethylamine as a curing accelerator was added instead of the cleaning solution. The gel time is measured according to ASTM D353.
2 was performed. The results are shown in Table 4 below.

[0023]

Table 4 Table 4 Example Reference Example 10 1 2 Epikote 828 100 100 100 penta hard 5000 90 90 90 85 wt% NMP aqueous solution 2 - - benzyldimethylamine - - 1 gel time (min) gelling not gel Example 25 In Example 10, an 85% by weight NMP aqueous solution was added, but no gelation occurred as in Reference Example 1 in which this was not added. In the case of Reference Example 2 in which benzyldimethylamine, which is a typical curing accelerator, was added, gelation occurred in 25 minutes. Therefore, 85% by weight NMP
The aqueous solution does not show a curing acceleration effect up to a temperature of about 115 ° C., and it can be said that there is no adverse effect even if a small amount of the cleaning liquid of the present invention remains in the tank after cleaning. That is, after cleaning the storage tank for pre-cured epoxy resin composition using the pre-cured epoxy resin cleaning liquid composition of the present invention, without completely removing the remaining cleaning liquid composition, a new pre-cured pre-curing liquid is used. The storage of the epoxy resin composition is possible.

[0024]

Examples 11 to 13 and Comparative Examples 4 to 6 Epoxy resin compositions B before curing prepared by mixing the components at room temperature were used as samples. Using 100 g of each of the cleaning solutions shown in Table 5, the dissolved weight of the epoxy resin composition B before curing at room temperature was measured. Table 5 shows the results.

[0025]

[Table 5] Table 5 Example Cleaning liquid type Dissolution weight State at the time of dissolution (g / 100g-washing liquid) 11 85% by weight NMP aqueous solution> 570 Dissolves very well and is considered to dissolve in almost any proportion 12 80% by weight % NMP aqueous solution 140 Emulsified once and became homogeneous after several minutes 13 70% by weight NMP aqueous solution 114 Emulsified once and became homogeneous after several hours Comparative Example 4 50% by weight NMP aqueous solution <10 Emulsified but uniform 5 aqueous cleaning liquid <10 hardly dissolved 6 petroleum cleaning liquid <10 hardly dissolved The cleaning liquid compositions of Examples 11 to 13 all dissolved the epoxy resin composition before curing well. In contrast, 5
Comparative Example 4 using a 0% by weight aqueous solution of NMP, Comparative Example 5 using an aqueous cleaning liquid, and Comparative Example 6 using a petroleum cleaning liquid all had extremely small dissolved weights. Also,
In Examples 11 to 13, the NMP aqueous solution concentration was changed to 85, 80, and 70% by weight. The higher the concentration of the NMP aqueous solution, the higher the solubility of the pre-cured epoxy resin composition, but any of them can sufficiently achieve the effects of the present invention.

[0026]

The cleaning liquid composition for an epoxy resin before curing of the present invention has a good cleaning effect on an epoxy resin before curing, particularly an epoxy resin composition before curing, and has no flash point, low odor and toxicity. Has excellent safety. In addition, there is no curing promoting effect on the pre-cured epoxy resin, particularly on the pre-cured epoxy resin composition. Therefore, it is extremely useful industrially as a substitute for the conventional cleaning liquid.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masayuki Asami 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Tonen Co., Ltd. (72) Inventor Hiroshi Ueno Nishitsuruga, Oimachi, Iruma-gun, Saitama 1-3-1 Oka, Tonen Co., Ltd.

Claims (1)

(57) [Claims] 1. N-methyl-2-pyrrolidone 70 to 85
A cleaning liquid composition for an epoxy resin before curing, comprising parts by weight and 30 to 15 parts by weight of water.