KR100948497B1 - A cleaning composition comprising a fatty acid ester compound derived from vegetable oils - Google Patents

Abstract

The present invention relates to a detergent composition comprising a vegetable oil-derived fatty acid ester-based compound, an aliphatic alcohol, a surfactant, and water. The present invention relates to a field of electrical, electronic and precision instruments, metals and polymer materials, manufacturing, processing, and post-treatment. It is widely applicable to the removal of oil and other contaminants and fluxes in the process.

Vegetable-derived fatty acid esters, cleaners, oily ingredients, fluxes, eco-friendly

Description

Cleaner composition containing a fatty acid ester compound derived from vegetable oils {A CLEANING COMPOSITION COMPRISING A FATTY ACID ESTER COMPOUND DERIVED FROM VEGETABLE OILS}

The present invention relates to an environment-friendly, low-toxic compliance cleaning agent composition that can be widely applied to the removal of oil and other contaminants and flux in the process of manufacturing, processing and post-treatment in the field of electrical and electronic equipment, metal and polymer materials In detail, by using a vegetable oil-derived fatty acid ester compound, an aliphatic alcohol, a nonionic or anionic surfactant, and water, the penetration and wettability is good, lowering the interfacial tension of the contaminant, it is easy to remove the contaminant from the substrate Rather, the present invention relates to an environmentally friendly detergent composition having excellent cleaning power, high flash point, and easy biodegradation after a washing process by emulsifying free contaminants.

1,1,2-trichlorofluoroethane (CFC-113) and 1,1,1-trichloroethane (1,1,1-) Trichloroethane (hereinafter referred to as 1,1,1-TCE) and methylene chloride (MC) have been widely applied in domestic and overseas industrial cleaning fields based on excellent cleaning. However, these are chlorine-based volatile organic compounds (VOCs) having a relatively high vapor pressure and are likely to enter the human body through the respiratory organs and the skin of workers, and are known as substances having human toxicity such as carcinogenicity. In addition, it has been found that it can be released into the atmosphere to cause smog by photochemical reactions, and furthermore, to destroy the ozone layer in the stratosphere, causing global climate change and extreme weather such as global warming. Each country is regulated in accordance with their cut, cut and abatement schedules set forth in the 1987 Montreal Protocol. In Korea, the CFC-based compounds will be totally decommissioned from 2010, 1,1,1-TCE from 2015, and the chlorofluorocarbon series from 2040. In recent years, opinions on the need for a shorter timeline have been raised in many countries, and it is time for further efforts to develop alternative materials.

In the electronics industry, the use of CFC-113 and 1,1,1-TCE is mainly used to remove the flux residues left in the components after the soldering process. The reason for removing the flux from the electronic components is corrosive. By removing the flux components, visual inspection can be facilitated, inspection can be automated, current leakage can be minimized, and the appearance of the product can be seen.

When the electronics are exposed to high temperature and high humidity, most of the flux residues are susceptible to corrosion. In the past, rosin-based materials were mainly used. The main component of rosin is abietic acid, and the structural formula is C ₂₀ H ₃₀ O ₂ . Conventionally, there have been a number of methods for producing a di-limonene-based cleaner with a flux cleaner, but the types and amounts of the surfactants to be added are different. For example, US Pat. No. 4,511,488 describes non-ionic surfactants of nonylphenol added with 4-15 moles of ethylene oxide and anionic surfactants of dodecylbenzene sulfonic acid to water and di-limonene to be used as general industrial cleaning agents. Used. However, the method has a lot of kinds and amounts of surfactants used, and thus there is an economic problem with waste water.

US Pat. No. 4,740,247 also discloses 1: 1 to 1: 4 with 90% di-limonene, 6.5% poly (7) ethoxy nonylphenol, 2.1% poly (10) ethoxy nonylphenol, 1.4% sodium dioctyl sulfosuccinate. The rosin-based flux was removed using a detergent diluted with water. In Japanese Patent No. 3-215689, a residue prepared for through hole substrates was removed by using a detergent such as di-limonene, L-limonene, dipentene, and a straight chain alkylbenzene as a terpene compound. However, limonene tends to remain in the object to be cleaned after cleaning as a non-volatile factor, and therefore, especially in the indentation part of the machine element having a gap between parts, such as a joint part and an assembly part among the objects to be cleaned. There is a problem. In addition, limonene has a weak cleaning power against polar contaminants.

Accordingly, the present invention, by solving the problems of the prior art, is widely used in the removal of oil and other contaminants and flux in the process of manufacturing, processing, post-treatment, etc. in the field of electrical and electronic equipment, precision metals and polymer materials It is an object of the invention to provide an environmentally friendly, low toxicity compliant detergent composition that can be applied.

The above object of the present invention is achieved by a detergent composition comprising a vegetable oil-derived fatty acid ester compound, an aliphatic alcohol, a surfactant and water. Accordingly, the present invention, in particular, as an alternative cleaning agent of CFC-113 or 1,1,1-TCE, which does not have an ozone depletion index, is a low toxicity, environmentally friendly system that can be used as an aqueous / compliant system depending on the pollutant and the application field and the desired cleaning ability. A cleaning composition, preferably a cleaning composition for rosin flux removal, is provided. In addition, the present invention provides a cleaning composition excellent in the physical properties of the cleaning agent, material compatibility of the cleaning agent and the object to be cleaned, removal efficiency for contaminants, and the like.

Specifically, the present inventors have studied in various angles to solve the problems of the prior art as described above to improve the VOC-induced problem that significantly affects environmental pollution while maintaining the cleaning power for oil, grease and flux, cleaning composition In the preparation, using a fatty acid ester solvent derived from vegetable oil, using a fatty acid ester having a high solubility and excellent biodegradability to rosin flux, water is added to increase the flash point of pure fatty acid ester, water and fatty acid ester The present invention was completed by adding a glycol-based binding material and finally adding a surfactant to uniformly mix the two materials of water and fatty acid esters, making the liquid transparent and having a low viscosity.

Accordingly, the present invention relates to an environment-friendly, low-toxic detergent composition that can be widely applied to the removal of oily, other contaminants and flux in the process of manufacturing, processing, post-treatment, etc. in the field of electrical and electronic equipment, metals and polymer materials. As the detergent composition, a fatty acid ester solvent derived from vegetable oil is used. Specifically, the cleaning composition according to the present invention is characterized by comprising (1) a fatty acid ester solvent, (2) an aliphatic alcohol, (3) a surfactant, (4) water and optionally (5) alkyl pyrrolidones.

The present invention will be described in more detail as follows.

The cleaning composition of the present invention contains a fatty acid ester alone or a mixture thereof as a main component. In the present invention, the fatty acid ester has no generation of VOC, and a fatty acid ester system derived from vegetable oil having excellent biodegradability is used. The fatty acid ester system may be a fatty acid ester derived from vegetable oil, preferably a compound represented by the following general formula (1), but is not particularly limited thereto.

[Formula 1]

R ¹ -COO-R ²

In the formula, R ¹ is a higher fatty acid group having 12 or more carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms.

The fatty acid group R ¹ is 12 or more carbon atoms, preferably 22 or less carbon atoms, specifically, can be used fatty acid groups of vegetable oil as stearic acid, oleic acid, linoleic acid, ricinoleic acid, or a mixture thereof, Vegetable oils having a glycerol ester structure of higher fatty acids such as soybean oil, castor oil, rapeseed oil, sunflower oil, rapeseed oil, corn oil and palm oil can be used as the vegetable oil used in the preparation of the ester and amide mixture.

The fatty acid ester according to the present invention is characterized by excellent solubility in oils, greases and fluxes and excellent biodegradability at disposal. The fatty acid ester is used in a blending ratio in the range of 50 to 90 parts by weight relative to the total weight of the composition, and preferably used in the range of 65 to 90 parts by weight. If the fatty acid ester is less than 50 parts by weight, solubility in oil, grease and flux is inferior, and if it exceeds 90 parts by weight, there is a disadvantage in that it remains on the surface of the workpiece as a residue when dried with water.

In the present invention, an aliphatic alcohol containing one or more ether functional groups (-O-) and containing 3 to 8 carbon atoms can be used. Aliphatic alcohols can increase the stability of the composition and help to maintain a stable composition over a wide temperature range to enable smooth cleaning at various cleaning temperature ranges. In addition, the cleaning power, the rinse characteristics, and the like can be improved.

As the aliphatic alcohol, a compound represented by the following general formula (2) may be preferably used, but is not particularly limited thereto.

[Formula 2]

R ¹ -O- [CH (R ² )] _l -{[O] _m- [CH (R ³ )] _n } _p -OH

Wherein R ¹ , R ² and R ³ are H or an alkyl group, l and n are natural numbers, m is 0 or 1, p is 0 or natural numbers, and R ¹ , R ² , R ³ , l, n and p are It satisfies the condition that carbon number of the compound represented by the said General formula (2) becomes 3-8.

Materials that can be easily applied industrially as the compound of Formula 2 include 2-methoxyethanol, 1-methoxy-2-propanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxy Ethoxy) ethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxy-1-propanol, 3-methoxy-1-butanol, 2- (2-butoxyethoxy) ethanol, triethylene glycol And tetraethylene glycol.

The aliphatic alcohol is used in a blending ratio in the range of 5 to 50 parts by weight relative to the total weight of the composition, and preferably used in the range of 10 to 30 parts by weight. If the aliphatic alcohol is less than 5 parts by weight, the stability of the composition is lowered, solubility in oil, grease and flux is lowered, and if it exceeds 50 parts by weight, the biodegradability of the composition is not environmentally friendly.

It is important to select and apply a suitable surfactant to increase the cleaning power, to facilitate the washability with water in the post-process, and to unify the discontinuous or discontinuous phase. In order to facilitate the penetration of the cleaning agent, it is generally advantageous to use compounds of high density, low viscosity and surface tension, and the surfactants contribute a great deal to this role. In addition, surfactants and other metal salts in the compliant cleaner mainly provide a function of increasing the limit of the amount of dilutable water used, so that the economic efficiency of the cleaner can be improved when compared to expensive cleaning base materials.

Surfactants are typically classified into ionic and nonionic surfactants, and in principle, both aqueous and non-aqueous surfactants can be applied. However, in the compliance system, the surfactants can be selectively used in consideration of phase stability, or other builders, It is desirable to apply a solubilizer, other metal salts, etc. to form a single phase at least at the micrometer level or below.

Nonionic surfactants applicable to the present invention include polyoxyethylene type, sorbitan type, glucose type, and hydroxyl type. The polyoxyethylene type includes polyoxyethylene alkyl ethers, alkyl phenol ethers, fatty acid esters and the like obtained by adding ethylene oxide (EO) to higher alcohols, alkyl phenols, and higher fatty acids. They are widely used as emulsifiers because they can easily control the degree of hydrophilicity by controlling the number of moles of EO. However, in recent years, the use of alkyl phenyl ethers is considerably reduced because phenolic compounds are problematic. There is a trend. The sorbitan type is the form of sorbitol and aliphatic ester of sorbitan, and the glucose type corresponds to alkyl glucoside obtained by condensation reaction between higher alcohol and glucose. As the hydroxyl group, an aliphatic amide may be used in which an fatty acid and an ester are formed in an alkanol amine.

The most widely known anionic surfactants are alkyl benzene sulfuonate, alkyl sulfuonate, alkyl polyoxyethylene sulfuonate, and the like. It is obtained through sulfonation and post neutralization by acting fuming sulfuric acid or sulfur trioxide (SO ₃ ) on alcohol, alkylpolyoxyethylene ether. However, alkylbenzene sulfonate has recently been slowed due to environmental problems.

Except for the surfactants containing the benzene and phenolic structural units mentioned above, they are industrially easy to manufacture and biodegradable. They are very suitable as eco-friendly cleaners. In particular, various levels of hydrophilic lipo can be adjusted by adjusting the amount of EO added. It is very useful in that it can implement a hydrophilic lipophilic balance (HLB). In the present invention, ionic and nonionic surfactants having a HLB value in the range of 4 to 18 are suitable.

In addition, when the ionic and nonionic surfactants are used together, the phase safety may be somewhat deteriorated. Therefore, in the corresponding composition, an appropriate metal salt is added as a builder or a solubilizer to solve the problem. Representative metal salts that may be used include NaOH, KOH, NaHCO ₃ , Na ₂ CO ₃ and the like, and metal neutralizers of aliphatic carboxylic acids. However, it should be noted that if the amount of the metal salts and water is excessively used, the pH of the detergent may be affected, and thus, phase separation of the aqueous detergent may occur, resulting in a decrease in the cleaning power.

The surfactant is used in a mixing ratio in the range of 0.5 to 20 parts by weight based on the total weight of the composition, and preferably used in the range of 1 to 10 parts by weight. If the surfactant is less than 0.5 parts by weight of the composition has affinity with water, solubility in oil, grease and flux is lowered, if more than 20 parts by weight of the biodegradability of the composition is not environmentally friendly.

In the present invention, water improves the stability to flammability of the composition and washability, and preferably purified water such as ion-exchanged water or distilled water is used. Water is used in the range of 0.5 to 10 parts by weight based on the weight of the total composition, and preferably in the range of 1 to 5 parts by weight based on the weight of the total composition.

The cleaning composition according to the present invention may further include a compound of alkyl pyrrolidone, and as the compound of alkyl pyrrolidone, N-methyl pyrrolidone, N-ethyl pyrrolidone, N-propyl pyrrolidone and the like have. Alkyl pyrrolidone compounds have compatibility and compatibility with fatty acid esters and aliphatic alcohols, and have very good compatibility with water, and thus can be applied as an aqueous / complementary cleaning agent or raw material for cleaning. Do. The amount used may be used in the range of 0 to 10 parts by weight based on the total weight of the composition, and preferably in the range of 1 to 5 parts by weight based on the weight of the total composition.

The cleaning composition mainly composed of vegetable oil-derived fatty acid esters according to the present invention is an alternative cleaning agent of CFC-113 or 1,1,1-TCE which does not have an ozone layer destructive index, depending on the pollutant and the application field and the desired cleaning ability. It is a low-toxic, eco-friendly detergent composition that can be used as a system, and has excellent physical properties of the cleaner, material compatibility of the cleaner and the object to be cleaned, removal efficiency of contaminants, etc. It can be widely applied to the removal of oily, other contaminants and flux in the process of processing, post-treatment, etc., and can be preferably used for rosin-based flux removal.

Hereinafter, the present invention will be described in more detail, but the following examples are not intended to limit or limit the protection scope of the present invention.

EXAMPLES Examples 1-8 and Comparative Examples 1-4

As shown in Table 1 below, a fatty acid ester, an aliphatic alcohol, a surfactant, and water were used to prepare a detergent composition, and then the stability, washing ability, rinsability, and biodegradability of the phase were evaluated. Comparative Example 4 shows a limonene hydrocarbon cleaner. The stability of the phase was determined by observing the degree of cloudiness and whether it was present as a single phase after 24 hours of stasis after the detergent was prepared. For the evaluation of the cleaning ability, the contaminants were selected by selecting grease and flux. The grease and flux were applied thinly on the slide glass and then ultrasonically treated at room temperature (20 kHz). The cleaning time was fixed to 30 minutes, and after cleaning, the glass surface was visually inspected and the presence of residue was observed under a microscope to evaluate the cleanliness. ◎ means that there is no residue at all, ○ means that there is almost no residue, and △ means that some residue remains. The weight change of the contaminants before and after cleaning confirmed that the grease and flux contaminants were removed by this cleaning process, suggesting that they can be widely applied to cleaning contaminants in general industrial sites. The biodegradability of the cleaning composition was evaluated by the OECD 301C method to determine whether the cleaning composition is environmentally friendly when the cleaning composition is leaked into the soil after cleaning.

 compound Example Comparative Example One 2 3 4 5 6 7 8 One 2 3 4 Fatty acid ester 70 70 70 70 70 70 60 60 - - - - Octanoic acid methyl ester 70 50 70 Aliphatic alcohols1 20 20 20 20 5 10 20 20 - Aliphatic alcohol 2 20 20 10 10 20 - Aliphatic alcohol 3 20 5 10 4 10 - Nonionic surfactant 5 5 5 5 5 5 One 5 - Anionic surfactant 5 - Cationic surfactant 5 - water 5 5 5 2.5 5 5 5 5 5 5 - Alkyl pyrrolidone 2.5 5 5 - Sum 100 100 100 100 100 100 100 100 100 100 100 - Stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ - Detergency ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ △ △ ◎ Rinseability ◎ ◎ ◎ ◎ ○ ○ ◎ ◎ △ ○ △ △ Biodegradability,% 80 75 70 85 75 75 70 70 80 50 75 30 [◎; No residue, ○: almost no residue, △: some residue remaining] aliphatic alcohol 1: 2- (2-methoxyethoxy) ethanol aliphatic alcohol 2: 2- (2-ethoxyethoxy) ethanol Aliphatic alcohol 3: 2- (2-n-butoxyethoxy) ethanol (wherein the figures refer to parts by weight)

Claims (10)

Aliphatic alcohols, surfactants, and water and vegetable oil-derived fatty acid ester-based compounds, the fatty acid esters in the range of 50 to 90 parts by weight based on the total weight of the composition, A cleaning composition, wherein the vegetable oil-derived fatty acid ester compound is a compound of the following general formula (1): [Formula 1] R ¹ -COO-R ² In the formula, R ¹ is a higher fatty acid group having 12 to 22 carbon atoms, and R ² is an alkyl group having 1 to 6 carbon atoms. The cleaning composition according to claim 1, comprising 5 to 50 parts by weight of aliphatic alcohol, 0.5 to 20 parts by weight of surfactant, and 0.5 to 10 parts by weight of water based on the weight of the total composition. delete The cleaning composition according to claim 1, wherein R ¹ is a fatty acid group of vegetable oil which is stearic acid, oleic acid, linoleic acid, ricinoleic acid, or a mixture thereof. The detergent composition according to claim 1, wherein the aliphatic alcohol is a C3-C8 aliphatic alcohol represented by the following General Formula (2) and containing one or more ether functional groups (-O-): [Formula 2] R ¹ -O- [CH (R ² )] _l -{[O] _m- [CH (R ³ )] _n } _p -OH Wherein R ¹ , R ² and R ³ are H or an alkyl group, l and n are natural numbers, m is 0 or 1, p is 0 or natural numbers, and R ¹ , R ² , R ³ , l, n and p are It satisfies the condition that carbon number of the compound represented by the said General formula (2) becomes 3-8. The method of claim 1, wherein the aliphatic alcohol is 2-methoxyethanol, 1-methoxy-2-propanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2 Ethoxyethanol, 2-butoxyethanol, 2-ethoxy-1-propanol, 3-methoxy-1-butanol, 2- (2-butoxyethoxy) ethanol, triethylene glycol, and tetraethylene glycol The cleaning composition is selected from the group consisting of. The cleaning composition according to claim 1, wherein the alkyl pyrrolidone compound is contained in the range of 0 to 10 parts by weight based on the total weight of the composition. The cleaning composition of claim 1, wherein the surfactant is a nonionic or anionic surfactant having an HLB value in the range of 4-18. The nonionic surfactant according to claim 8, wherein the nonionic surfactant is a polyoxyethylene type, sorbitan type, glucose type or hydroxyl type surfactant, and the anionic surfactant is alkyl benzene sulfuonate. ), Alkyl sulfuonate or alkyl polyoxyethylene sulfuonate. The cleaning composition according to any one of claims 1, 2 or 4 to 9, wherein the cleaning composition is for flux removal.