KR101999100B1 - Non-water soluble eco-friendly metal detergent and non-metal detergent - Google Patents

Abstract

The present invention relates to a metal, non-metal detergent for electronic components and, more specifically, to a detergent for removing contaminants such as metal-processed oil and punched oil. A detergent composition according to the present invention does not comprise trichloroethylene (TCE), methylene chloride (MC), 1,2 dichloropropane (1,2 DCP), thereby avoiding regulated substances, being environmentally friendly, imparting excellent physical properties, and being economical in price.

Description

TECHNICAL FIELD [0001] The present invention relates to a non-water-soluble environmentally friendly metal and non-metal detergent composition,

The present invention relates to water-insoluble eco-friendly metal and non-metal detergent compositions.

As the electronic industry and the semiconductor industry develop, the electronic parts industry is rapidly gaining market. In the process of manufacturing and molding the electronic component, the oil component such as the tack oil or the metal shale is used in the metal. Finally, the oil component and the contamination source must be removed. A detergent is used to remove such oil components and contaminants, and an excellent detergent which is excellent in cleaning effect, has no risk of fire in the washing process, and has no influence on the human body and the environment is needed.

Chlorinated solvents such as trichlorethylene (TCE), methylene chloride (MC) and 1,2-dichloropropane (DCP), which have been used for a long time as detergents, have no fear of fire, . However, these chlorine-based solvents are subject to severe regulations in various countries along with various reports that cause human carcinogenicity and reproductive toxicity. Therefore, it is necessary to develop an environmentally friendly detergent which can ensure flammability and washing without using chlorinated solvents such as trichlorethylene (TCE), methylene chloride (MC) and 1,2-dichloropropane (DCP).

As an alternative cleaning agent, the non-chlorinated organic solvent type has good cleaning power, but it is difficult to use it as an alternative detergent because it has a high fire risk, a high volatility, a human carcinogen, and an environmental problem such as ozone layer destruction.

In order to solve these problems, Korean Patent No. 10-1127112 proposes 1,2-dichloropropane (DCP) as a component replacing trichlorethylene (TCE). However, 1,2-dichloropropane (DCP) is difficult to use as a cleaning substance as a regulated substance since 2019 due to a problem of reproductive toxicity. Korean Patent No. 10-1747387 discloses that 60 to 70 parts of dimethyl carbonate and 20 to 35 parts of dibromomethane are used as the skin. However, the cleaning agent containing the above-described components has a low cost due to high cost, and the cleaning liquid is consumed due to the rapid volatility of the dimethyl carbonate, resulting in low economic efficiency. Therefore, it is a reality that a company that uses the detergent to perform a cleaning operation tends to use the detergent.

Therefore, it is urgent to develop an environmentally friendly detergent that solves economic problems, has excellent cleaning power.

1. Korean Patent No. 10-1127112 2. Korean Patent No. 10-1747387

Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a process for producing a polycarbonate resin composition which does not contain a solvent such as trichlorethylene (TCE), methylene chloride (MC) and 1,2-dichloropropane The present invention aims to develop an environmentally friendly detergent composition which does not affect carcinogenicity, reproductive toxicity and reproductive variability by using dimethyl carbonate, bromide and fluoride as main ingredients.

Further, the present invention has developed a detergent which does not contain an organic solvent which is a T-Voc-inducing material but has excellent washing property, corrosion resistance and flame resistance while minimizing the content of bromide such as methylene bromide (DBM) .

The present invention relates to a process for the production of a catalyst comprising dimethyl carbonate (carbonate), bromide and fluoride,

The bromide is one selected from the group consisting of methylene bromide (DBM), isobutyl bromide and tert-butyl bromide,

The fluoride provides at least one detergent composition selected from the group consisting of para-chlorobenzotrifluoride (PCBTF), hexafluoroxylene, and benzotrifluoride.

The present invention also provides a method of cleaning a metal or nonmetal comprising cleaning a metal or nonmetal containing impurities with the detergent composition described above.

The detergent composition according to the present invention does not contain chlorine-based solvents such as trichlorethylene (TCE), methylene chloride (MC) and 1,2-dichloropropane (DCP) which have been conventionally used as detergents, , Excellent in corrosion resistance and resistance to ignition, and can inhibit carcinogenicity, reproductive toxicity and reproductive variability.

In addition, it is possible to reduce the amount of bromide having a high raw material cost, that is, methylene bromide (DBM), to be economical and to ensure flammability, thereby preventing a fire hazard that may occur during a cleaning operation.

In addition, the detergent composition according to the present invention is an environmentally friendly and human-friendly detergent, which can meet all of the washing conditions at normal temperature and high temperature since it compensates for the rapid volatility and flammability of dimethyl carbonate (DMC).

In addition, the surface corrosiveness of the metal or non-ferrous metal to be cleaned can be completely compensated for, thereby replacing the conventional cleaning agents.

The present invention provides a detergent composition comprising dimethyl carbonate, bromide and fluoride.

The dimethyl carbonate has a good cleaning power for removing contaminants, but it has flammability and there is a fear of fire for use alone. Therefore, in the present invention, it is possible to provide a non-aqueous detergent composition which can solve the flammability problem by mixing the dimethyl carbonate and the bromide and fluoride, which are flame retardant raw materials, and which is excellent in price competitiveness.

In addition, the detergent composition of the present invention does not contain a solvent of trichlorethylene (TCE), methylene chloride (MC) and 1,2-dichloropropane (1,2 DCP) and is environmentally friendly.

Hereinafter, the cleaning composition of the present invention will be described in detail.

In the present invention, dimethyl carbonate is the main component of the detergent composition and is an environmentally friendly solvent that can be used alone.

The dimethyl carbonate has dissolution and cleansing properties similar to those of 1,2-dichloropropane used in the prior art, but causes corrosion on the surface of the metal substrate to be cleaned and has flammability, which may cause instability in cleaning conditions.

The content of the dimethyl carbonate is not particularly limited and may be 50 to 65% by weight or 52 to 59% by weight based on the total weight of the detergent composition (100% by weight). It can have excellent solubility and cleaning property in the above content range. If the content is more than 65% by weight, it is difficult to ensure flammability. If the content is less than 50% by weight, the washing property is deteriorated and the cost of the cleaning agent may increase.

In the present invention, the bromide is a flame retardant solvent that complements the detergency of the dimethyl carbonate as a flame retardant raw material and imposes flame retardancy.

The bromide may be one selected from the group consisting of methylene bromide (Dibromo methane, DBM), isobutyl bromide, and tert-butyl bromide, and may specifically be methylene bromide (DBM).

The content of the bromide is not particularly limited and may be 10 to 25% by weight, 15 to 20% by weight or 16 to 19% by weight based on the total weight (100% by weight) of the detergent composition. If the content exceeds 25% by weight, stability to fl usability and flame retardancy can be imparted. However, bromide, especially methylene bromide (DBM), has a high price, which may reduce the cost burden when used as a detergent composition. If the amount is less than 10% by weight, the detergency is lowered and the flame retardancy can not be imparted to the dimethyl carbonate.

In the present invention, the fluoride is a solvent capable of imparting flame retardancy to the cleaning agent and reducing the consumption of the cleaning liquid. The above-mentioned bromides such as methylene bromide (DBM) are indispensable for a detergent composition containing dimethyl carbonate as a flame-retardant raw material. However, since the cost is high, the cost of the detergent increases and the cost is not economical. Therefore, in the present invention, the fluoride can be further used to lower the cost while maintaining the flame retardancy.

The fluoride may be at least one selected from the group consisting of para-chlorobenzotrifluoride (PCBTF), hexafluoroxylene, and benzotrifluoride, and specifically may be para-chlorobenzotrifluoride (PCBTF). The para-chlorobenzotrifluoride (PCBTF) has a high boiling point of 139 占 폚, thereby imparting flame retardancy to the cleaning agent and reducing the consumption of the cleaning agent.

The content of the fluoride is not particularly limited and may be 15 to 35 wt%, 20 to 30 wt%, or 21 to 29 wt% based on the total weight (100 wt%) of the detergent composition. Accordingly, in the present invention, flame retardancy can be ensured while using bromide in an amount of 25% by weight or less. If the content exceeds 35% by weight, the detergency is weakened, the drying speed of the metal surface is slowed, and a residual image may remain on the metal surface. If the amount is less than 15% by weight, flammability can not be ensured and the amount of the cleaning liquid is reduced during the cleaning process because of the volatilization of the cleaning liquid.

In the present invention, in addition to the above-mentioned components, namely, dimethyl carbonate, bromide, and fluoride, corrosion inhibitors and antioxidants may be further included. Since the detergent components corrode the surface of the metal or non-metal, and cause the oxidation reaction, the corrosion inhibitor and the antioxidant can be used to suppress the detergent component. The above corrosion inhibitor and antioxidant can be used together to more effectively prevent metal or nonmetal surface corrosion.

Examples of the corrosion inhibitor include N, N-dimethyl acetamide, Tri ethanol amine, Tri ethyl amine, Mercapto benzotriazole, Nitroethane (Nitro ethane) and nitro propane, and the content thereof may be 1 to 5% by weight or 2 to 4% by weight based on the total weight (100% by weight) of the detergent composition have. If the content is more than 5% by weight, there is a possibility that the color of the detergent composition, which is in a liquid state, is changed due to a strong smell of the detergent composition. If it is less than 2% by weight, there is a fear that the surface of the metal after washing is smudged due to corrosion.

Examples of the antioxidant include butylated hydroxy toluene, 2,6-di tert butyl methyl phenol and 2,6-di-3-butyl cresol ( 2,6-Di-3-butyl cresol), and the content thereof may be 0.005 to 0.03% by weight or 0.01 to 0.02% by weight based on the total weight (100% by weight) of the detergent composition have. If the content is more than 0.03% by weight, scum or residue may be generated in the cleaning agent after the cleaning operation to shorten the period of use of the cleaning agent, and the surface of the metal remains uneven There is a possibility that a problem may occur.

In the present invention, various additives used in the present invention may be used in addition to the above-mentioned components as long as the object of the present invention is not impaired.

In addition, the detergent composition may be prepared by adding detergent components to a compounding machine generally used in the art, followed by blending. At this time, nitrogen gas may be injected for stability.

The present invention also relates to a cleaning method of a metal or a nonmetal comprising the step of cleaning a metal or a nonmetal containing an impurity with the cleaning composition described above.

The object to be cleaned, that is, metal or nonmetal, may be a metal such as iron, a ceramic, glass, polycarbonate, polystyrene, polyacrylate, acrylonitrile-butadiene-styrene copolymer, natural and synthetic fibers (and fabrics derived therefrom) , And complexes of the foregoing materials.

The method of the present invention can be used, for example, to remove oil used in metal working, flux of electronic substrates and contaminants of metal workpieces.

The present invention will be described in more detail with reference to the following examples. It will be apparent to those skilled in the art, however, that the scope of the present invention is not limited to the following embodiments, and that various changes, modifications, and / or other applications may be made without departing from the spirit and scope of the invention, will be.

Example

Example  One

57.0 parts by weight of dimethyl carbonate, 19.0 parts by weight of methylene bromide (DBM), 21.0 parts by weight of para-chlorobenzotrifluoride (PCBTF), 0.015 part by weight of 2,6-Di-3-butyl cresol, (Nitro Propane) were precisely mixed in a glass lined mixing tank or a stainless steel (SUS 306) having a lid, and stirred with stirring at 60 rpm for 30 minutes while injecting nitrogen gas to prepare a cleaning agent do.

Example  2.

52.0 parts by weight of dimethyl carbonate, 17.0 parts by weight of methylene bromide (DBM), 29.0 parts by weight of para-chlorobenzotrifluoride (PCBTF), 0.020 part by weight of 2,6-Di-3-butyl cresol, (Nitro Propane) were precisely mixed in a glass lined mixing tank or a stainless steel (SUS 306) with a lid, followed by stirring for 30 minutes at a stirring rate of 60 rpm while injecting nitrogen gas, thereby preparing a cleaning agent do.

Example  3.

59.0 parts by weight of dimethyl carbonate, 16.0 parts by weight of methylene bromide (DBM), 25.0 parts by weight of para-chlorobenzotrifluoride (PCBTF), 0.010 part by weight of 2,6-Di-3-butyl cresol, (Nitro Propane) were precisely mixed in a glass lined mixing tank or a stainless steel (SUS 306) with a lid, followed by stirring for 30 minutes at a stirring rate of 60 rpm while injecting nitrogen gas, thereby preparing a cleaning agent do.

Example  4.

55.0 parts by weight of dimethyl carbonate, 17.0 parts by weight of methylene bromide (DBM), 26.0 parts by weight of para-chlorobenzotrifluoride (PCBTF), 0.020 parts by weight of 2,6-Di-3-butyl cresol, (Nitro Propane) were precisely mixed in a glass lined mixing tank or a stainless steel (SUS 306) having a lid, followed by stirring for 30 minutes at a stirring speed of 60 rpm while introducing nitrogen gas, thereby preparing a cleaning agent do.

Comparative Example  One.

 67.0 parts by weight of dimethyl carbonate, 30.0 parts by weight of methylene bromide (DBM), 0.020 parts by weight of 2,6-Di-3-butyl cresol and 3.0 parts by weight of nitropropane were mixed with a glass lined mixture Tank or stainless steel (SUS 306), nitrogen gas is injected and stirring is carried out at a stirring speed of 60 rpm for 30 minutes to prepare a cleaning agent so that the composition can be sufficiently mixed.

Comparative Example  2.

45 parts by weight of dimethyl carbonate, 40.0 parts by weight of methylene bromide (DBM), 10.0 parts by weight of para-chlorobenzotrifluoride (PCBTF), 0.050 parts by weight of 2,6-Di-3-butyl cresol, (Nitro Propane) were precisely mixed in a glass lined mixing tank or a stainless steel (SUS 306) having a lid, followed by stirring for 30 minutes at a stirring speed of 60 rpm while injecting nitrogen gas, thereby preparing a cleaning agent do.

Comparative Example  3.

, 92.0 parts by weight of 1,2-dichloropropane (DCP), 5.0 parts by weight of methylene bromide (DBM), 0.030 part by weight of 2,6-Di-3-butyl cresol and 3.0 parts by weight of Nitropropane (SUS 306), followed by stirring at a stirring speed of 60 rpm for 30 minutes while injecting nitrogen gas to prepare a cleaning agent so that the composition can be sufficiently mixed.

Example Comparative Example Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Dimethyl carbonate 57.0 52.0 59.0 55.0 67.0 45.0 0 Methylene bromide 19.0 17.0 16.0 17.0 30.0 40.0 5.0 Para-chlorobenzotrifluoride 21.0 29.0 25.0 26.0 0 10.0 0 1,2-dichloropropane 0 0 0 0 0 0 92.0 2,6-Di-3-butyl cresol 0.015 0.020 0.010 0.020 0.020 0.050 0.030 Nitropropane 3.5 2.5 2.5 2.0 3.0 5.0 3.0

Experimental Example . Property measurement

One) Flammability .

A polyester fiber (cloth) was prepared in a size of a length x width = 10 cm x 8 cm, impregnated into the washing liquid prepared in Examples and Comparative Examples and taken out, followed by ignition to evaluate flammability.

The evaluation criteria are as follows.

◎: No combustion at all

○: Partially burned and burned

△: After one minute, it is burned and burned.

X: Printed immediately

2) Cleanliness .

A copper foil (Cu plate) was prepared in the form of a length X width = 5 cm X 2 cm, impregnated with a metal shavings (tung oil), taken out, and left at room temperature for 5 minutes. Then, the cleaning solution prepared in Examples and Comparative Examples was impregnated for 2 minutes, washed and dried to evaluate the cleaned state.

The evaluation criteria are as follows.

◎: The state where the oil component and the contamination source are completely removed from the surface of the copper foil (very good)

O: The state where the oil component and the contamination source are removed from the surface of the copper foil (good)

?: Part of the oil component and contamination source remained on the surface of the copper foil (somewhat poor)

X: A state in which at least 30% of an oil component and a contamination source remain on the surface of the copper foil (insufficient)

3) Corrosion resistance

A copper foil (Cu plate) was prepared in the form of a length X width = 5 cm X 2 cm, impregnated with a metal shavings (tung oil), taken out, and left at room temperature for 5 minutes. Then, the rinse solution prepared in Examples and Comparative Examples was impregnated and cleaned for 2 minutes and then dried to evaluate the corrosion state of the surface of the copper foil.

The evaluation criteria are as follows.

◎: Corrosion does not occur on the surface of copper foil (very good)

○: Some corrosion (less than 5%) appears on the surface of the copper foil (good)

△: Part of copper (less than 10%) appears on the surface of copper (somewhat insufficient)

×: Corrosion on the surface of the copper foil shows 50% or more (insufficient)

4) Liquid phase Discoloration

After washing solutions prepared in Examples and Comparative Examples were heated at 90 캜 for 2 hours, the discoloration degree of the liquid phase was evaluated.

The evaluation criteria are as follows.

◎: No color change after heating and heating at 90 ℃

○: The color slightly changes after heating (at 90 ℃)

Δ: Change in color after heating before and after heating at 90 ° C. (yellow)

×: The color greatly changes after heating (at 90 ° C.) (yellowing, yellowing)

5) Cleaning liquid consumption

In order to measure the amount of cleaning liquid that could be consumed by volatilization during the cleaning process, 100 mL of the cleaning agent prepared in Examples and Comparative Examples was placed in a distillation tester and maintained at 100 ° C. for 4 hours, and the consumability was evaluated by volatilization .

The evaluation criteria are as follows.

⊚: Amount to be volatilized is less than 3% (very good)

○: Volatilization amount is less than 10% (good)

?: The amount of volatilization is 10% or more (somewhat insufficient)

×: Amount of volatilization is 30% or more (insufficient)

6) Eco-friendliness

Environmental friendliness was assessed in the metallic detergent according to whether or not the environmentally hazardous substance contained in the chemical information of the Industrial Safety and Health Agency was included.

 The evaluation criteria are as follows.

◎: Does not contain

×: Contains environmentally harmful substances such as TCE and DCP

7) Cost-effectiveness

In consideration of the manufacturing cost of the cleaning liquid prepared in Examples and Comparative Examples and the consumption of cleaning liquid, it was evaluated as the purchase cost of the cleaning liquid to be determined by the customer.

The evaluation criteria are as follows.

Example Comparative Example Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Manufacturing cost 3 7 5 6 8 10 One Consumption of cleaning liquid 4 One 3 2 8 7 5 Total points 7 8 8 8 16 17 6

* Manufacturing cost: 1 (lowest) to 10 (highest)

* Cleaning fluid consumption: 1 (lowest) to 10 (highest)

(The lower the combined standard, the better the cost efficiency)

◎: Total score less than 7 (very good) _

○: Total score 7-10 (good)

△: Total score 11-14 (somewhat poor)

×: Sum total score 15 or more (insufficient)

The results of the physical properties test are shown in Table 3 below.

Example Comparative Example Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Flammability ◎ ○ ○ ○ ○ ◎ ○ Washability ◎ ○ ○ ○ Х Х △ Corrosion resistance ◎ ○ ○ ○ ○ △ △ Liquid discoloration ◎ ◎ ◎ ◎ ○ △ △ Cleaning liquid consumption (90 ° C) ○ ◎ ○ ○ △ △ △ Eco-friendly ◎ ◎ ◎ ◎ ◎ ◎ Х Cost-effectiveness ◎ ○ ○ ○ △ Х ◎

As shown in Table 3 above, in the case of flameproof resistance, the detergent compositions of the Examples were prepared using 13 to 19%, 15 to 21%, respectively, of para-chlorobenzotrifluoride (PCBTF) and methylene bromide Excellent results in flammability. In Comparative Example 2, methylene bromide (DBM) was used in a high content to give very high stability in flammability, but there was a fear of a burden due to high cost.

In the case of washability, the most excellent physical properties were shown when the amounts of dimethyl carbonate (DMC), para-chlorobenzotrifluoride (PCBTF) and methylene bromide (DBM) were used as in Example 1. As a result, it can be confirmed that the use of dimethyl carbonate (DC), methyl bromide (DBM), and para-chlorobenzotrifluoride (PCBTF) As in Comparative Example 1 and Comparative Example 2, when the antioxidant and nitropropane were used in an amount exceeding the content range of the present invention, they were inferior in flammability, washability and cost.

In the case of the cleaning liquid consumption, the least amount was found when the content of para-chlorobenzotrifluoride (PCBTF) was increased. However, when the content of the substance itself was over the content range of the present invention, the problem of high cost and washing power were finely deteriorated .

When the antioxidant and nitropropane were used in an amount exceeding the content range of the present invention as in Comparative Example 1 and Comparative Example 2 in the case of corrosiveness, the stain and cleaning property of the object to be cleaned were poor.

Eco-friendliness and price are the most important parts, and 1,2-dichloropropane (DCP) can be used to produce the lowest cost product, but DCP can not be used as a regulated substance.

It is possible to manufacture the detergent composition by using an environmentally friendly composition as in the examples, thereby avoiding the substances to be regulated, and it is possible to impart excellent physical properties by using the components in appropriate ratios. Further, a detergent composition which is economical in terms of cost can be produced.

Claims (5)

50 to 65% by weight of dimethyl carbonate, 15 to 21% by weight of bromide and 20 to 30% by weight of fluoride,
The bromide is one selected from the group consisting of methylene bromide (DBM), isobutyl bromide and tert-butyl bromide,
Wherein the fluoride is at least one selected from the group consisting of para-chlorobenzotrifluoride (PCBTF), hexafluoroxylene, and benzotrifluoride.
delete delete delete The method according to claim 1,
But does not comprise trichlorethylene (TCE), methylene chloride (MC), and 1,2 dichloropropane (1,2 DCP).