JPH04122800A - Halogen-free detergent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can be substituted for fluorocarbon detergents by incorporating a specific amount of a specific nonionic surfactant and/or amine compound in a specific glycol or its ether used as the main component. CONSTITUTION:A halogen-free detergent composition is obtained by mixing 100 pts. glycol or its ether of formula I (wherein R<1> and R<2> are each a 1-12C alkyl, 1-12C alkenyl or H; A is a 2-3C alkylene; (n) is 1-20) with 0.5-30 pts.wt. nonionic surfactant of formula II (wherein R<3> is a 6-26C alkyl or 6-26C alkenyl; A is as defined above; (m) is 1-16) and/or 0.1-30 pts.wt. amine compound of formula III (wherein R<4> is a cycloalkyl, 8-18C alkyl, 8-18C alkenyl or 8-18C acyl; X and Y are each H or (AO)rH; A is as defined above, both X and Y are not H, and (r) is an integer of one or more). The above composition exhibits a high solvency against dirt, and hence it is characterized by short washing time, high safety, good workability due to low foaming property, prevention of environmental problem, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a non-halogen cleaning composition that is effective for electronic parts, various metal surfaces, surfaces such as plastics, textile products, and the like.

[Conventional technology] Freon has many advantages such as low toxicity, non-flammability, chemical stability, does not attack materials to be cleaned such as plastics, maintains strong permeability, and dries quickly. Because of its properties, it has been used in a wide range of fields, including as a refrigerant for coolers and refrigerators, a propellant for sprays, a foaming agent for insulation materials such as urethane foam, and a cleaning agent for electrical and electronic parts and precision machinery. It has been.

However, in recent years, it has been scientifically revealed that CFCs destroy the stratospheric ozone layer, and CFC-11, CFC-12,
Five types of fluorocarbons, including fluorocarbon 113, are now regulated.

Freon 113 accounts for approximately 50% of all Freon products.
Most of these are used as cleaning agents, and currently there are cleaning agents that can replace them, such as terpene-based compositions, hydrocarbon-based compositions, and alcohol-based compositions centered on ethanol. have been proposed, but they generally have a low flash point, making them unfavorable in terms of work safety, and there is still room for improvement in detergency.

[Problems to be Solved by the Invention] The present inventors have discovered that the excellent properties of conventionally known fluorocarbon-based cleaning agents, that is, they have excellent cleaning power, are chemically stable, and are free from halogens such as chlorine and fluorine. While conducting intensive studies to develop a cleaning composition that does not contain any substances and has no risk of damaging the environment, we have determined that certain glycols and glycol ethers have a kauributanol value (hereinafter abbreviated as "rKB value") of 200. The above (measured values) are very high, and we focused on the fact that its flash point is also relatively high. Here, the KB value is an index for evaluating the dissolving power of a solvent measured by the following method. That is, when the test substance is dropped into 20 g of Kauributanol solution at 25°C, it is the volume (d) of the test substance required until the solution becomes cloudy.

Glycols are a type of polyhydric alcohol, and glycol ethers have an ether group or an ether group and a hydroxyl group in their molecules, and can be used for resins, oils, waxes,
It is an excellent low-odor solvent for fats, dyes and other organic compounds, and is also miscible with water and most organic solvents.

Due to these properties, it is currently used as a solvent in the textile industry, leather industry, printing industry, etc., as a diluent for brake fluid, and as a refrigerant. Also, water, organic solvents, resins,
Because it is compatible with soaps and the like, it is used as a coupling agent in soluble oils and other soap-organic solvent systems, and is also used in heavy-duty cleaners by adding it to detergents.

As a result of subsequent studies, we found that by blending certain types of glycols or glycol ethers as the main ingredients with a specified amount of specific nonionic surfactants and/or amine compounds, The number of substances that can be dissolved and cleaned is expanded compared to the case in which the composition can be dissolved and cleaned, resulting in a more general-purpose cleaning composition; ■An anti-rust effect can be expected. ■Furthermore, it is an aqueous composition prepared by adding a predetermined amount of water. It has been recognized that the composition has excellent properties such as being less flammable, suppressing irritation, and improving work safety.
We have discovered that this is a cleaning composition that can fully achieve the intended purpose, and have completed the present invention based on this knowledge.

That is, an object of the present invention is to provide a new and useful non-aqueous and aqueous non-halogen-based cleaning composition that can replace fluorocarbon-based cleaning agents.

1. Means for Solving the Problem] The non-halogen cleaning composition according to the present invention has the formula (I>
It is expressed as (A>for 100 parts by weight of component, - formula (
0.5 to 30 parts by weight of the component (B) represented by II> and/or 0.1 to 30 parts by weight of the component (C) represented by the formula (In>
It is characterized by blending 1 part of 30M.

(A) - Formula (I> R10(AO)n R2(I> [wherein R1 and R2 are the same or different and have a carbon number of 1 to 12
represents an alkyl group having , an alkenyl group having 1 to 12 carbon atoms, or a hydrogen atom. A represents an alkylene group having 2 to 3 carbon atoms. n represents an integer of 1 to 20. ] One or more glycols or glycol ethers represented by (B) - formula (I[) R30(AO>m H(II> group or alkenyl group having 6 to 26 carbon atoms, A is 2 to 26 carbon atoms
3 represents an alkylene group. m represents an integer of 1 to 16. ] One or more nonionic surfactants represented by (C)-formula (III) \ [wherein R4 is a cyclohexyl group, an alkyl group having 8 to 18 carbon atoms, and 8 to 18 carbon atoms] alkenyl group or carbon number 8
~18 acyl groups. X and Y are the same or different and represent a hydrogen atom or (CH2CH20)rH.

However, neither X nor Y is a hydrogen atom.

r represents an integer of 1 or more. ] An amine compound represented by

(A> Component glycols or glycol ethers have the property of being compatible with water, and depending on the purpose of use, they can be used alone to prepare non-aqueous compositions, or with a predetermined amount of water. A water-based composition is constituted by using it in combination with.

Examples of the (A> component) include the following compounds: ethylene glycol, propylene glycol, and alkylene oxide adducts thereof exemplified by dipropylene glycol (hereinafter abbreviated as rDPGJ). Glycols such as ethylene glycol monomethyl ether (rMGJ)
It is abbreviated as. 〉, diethylene glycol 7-methyl ether, triethylene glycol 7-methyl ether (hereinafter abbreviated as rMTGJ), polyethylene glycol monomethyl ether (hereinafter rM
It is abbreviated as PGJ. ), propylene glycol monomethyl ether (rMF
It will be abbreviated as GJ. ), dipropylene glycol monomethyl ether (rM
It is abbreviated as FDGJ. ), ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, propylene glycol monopropyl ether (hereinafter abbreviated as rPFGJ).

), dipropylene glycol monopropyl ether, ethylene glycol monoisopropyl ether (hereinafter referred to as “i5
It is abbreviated as oPGJ. ), diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether , diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, and other glycol monoethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether (rDEDGJ)
It is abbreviated as. ), glycol diethers such as diethylene glycol dibutyl ether and triethylene glycol dimethyl ether.

Among them, DPG, MG, MTG, MPG, MFG, M
FDG, PFG, +5oPG, DEDG, etc. are preferred.

These compounds may be used alone or in combination of two or more.

The number of moles of alkylene oxide having 2 to 3 carbon atoms present in glycols or glycol ethers is 1 to 20
A suitable amount is about mol, preferably about 1 to 8 mol. 2
If more than 0 mol is added, the dissolving power for the material to be cleaned will decrease, which is not preferable. Here, as the alkylene oxide according to the present invention, ethylene oxide (
Hereinafter, it will be abbreviated as rEOJ. ), propylene oxide (
Hereinafter, rpoJ will be abbreviated. ) and their co-adducts are exemplified. The same applies to the following components (B) and (C).

The nonionic surfactant that is the component (B) has 6 or more carbon atoms.
It is a compound formed by adding 1 to 16 moles of alkylene oxide to a saturated aliphatic alcohol or an unsaturated aliphatic alcohol having 26, and can be used alone or in combination of two or more types. Here, specific examples of the aliphatic alcohol include lauryl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol. It may also be a synthetic alcohol made from. If the number of moles of alkylene oxide added exceeds 16, it is not preferable because the dissolving power for the material to be cleaned decreases.

When a surfactant obtained by co-adding EO and PO to the above alcohol is applied, foaming of the cleaning composition can be suppressed.

Examples of the amine compound as component (C) include EO adducts of cyclohexylamine, lauric acid monoethanolamide, lauric acid jetanolamide, coconut oil fatty acid monoethanolamide, etc. Used in combination of more than one species.

Among them, E of cyclohexylamine as component (C)
When the O adduct is applied, a detergent composition having very good dissolving power can be obtained. Furthermore, by adding alkylene oxide to cyclohexylamine, the boiling point can be raised to improve safety as a cleaning composition, and the odor peculiar to cyclohexylamine can be reduced, thereby improving the working environment. I can do it.

In this case, the number of moles of alkylene oxide added is 1 to 6.
A molar level is preferable. In particular, 2 molar adducts (e.g.
When the product name "Wondermin CHE-20PJ, manufactured by Shin Nippon Rika ■" is applied, the detergent composition obtained has high detergency and low foaming properties, making it even more practical.

The blending ratio of component (B) and component (C) to component (A> can be appropriately selected depending on the type of system of the cleaning composition. Namely, [1] In the non-aqueous composition, (A) >The blending ratio of component (B) to 100 parts by weight of component is 1 to 30 parts by weight, preferably 2 to 10 parts by weight.

If the amount of component (B) is less than 1 part by weight, the dissolving power for the material to be cleaned will decrease, which is undesirable.
Even if more than 1 part by weight is added, no significant difference is observed in terms of effectiveness, which is economically disadvantageous.

On the other hand, the blending ratio of component (C) to 100 parts by weight of component (A) is 0.5 to 30 parts by weight.

Preferably it is 1 to 15 parts. If the amount of component (C) is less than 0.5 parts by weight, the dissolving power for the material to be cleaned will decrease, which is undesirable, and even if it exceeds 30 parts by weight, there will be no noticeable difference in effectiveness. is not allowed and is economically disadvantageous.

12] The aqueous cleaning composition according to the present invention usually has (A>
It is prepared by blending up to 100 parts by weight of water, preferably about 10 to 50 parts by weight, to 100 parts by weight of the ingredients, making it less likely to catch fire and improving environmental and operational safety. If more than 100 parts by weight of water is added, K
The B value decreases rapidly, making it difficult to obtain a desired effect. However, in fields such as the cleaning industry, where even if the KB value is low, the composition can be applied as long as it has a predetermined function that can be practically achieved, the composition according to the present invention may be further applied in a desired amount. It can be used after being diluted with water.

The amount of component (B) blended into the above water-based composition is (A>
The amount is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the component. (B) The blending amount of the component is 0.
If the amount is less than 5 parts by weight, the dissolving power for the material to be cleaned will decrease, which is undesirable, and even if the amount exceeds 30 parts by weight, no significant difference in effectiveness will be observed, which is economically disadvantageous.

On the other hand, the blending ratio of component (C) to 100 parts by weight of component (A) is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight. If the amount of component (C) is less than 1 part by weight, the dissolving power for the material to be cleaned will decrease, which is undesirable, and even if it exceeds 30 parts by weight, the effect will be
There are no obvious differences, which is economically disadvantageous.

In the cleaning composition according to the present invention, by using a predetermined amount of the component (B) and the component (C) with respect to the component (A), each component acts synergistically, and the component (B) or (
C) Compared to the case where each component is used alone, the KB value and the cleaning efficiency can be dramatically improved.

Additionally, additives such as antioxidants and antifungal agents may be added as appropriate.

The cleaning composition thus obtained is useful in fields where fluorocarbon-based cleaning agents have been conventionally used, for example, as a flux cleaning agent for IC parts such as printed wiring boards, precision mechanical parts, optical equipment parts, automobile-related parts, etc. I'll go. in this case,
Examples of materials for the object to be cleaned include metals, plastics, lastomers, and composites thereof. Furthermore, it is fully applicable as a cleaning agent.

Furthermore, the cleaning composition according to the present invention can be widely applied not only as a substitute for fluorocarbon-based cleaning agents, but also in various fields where halogen-based cleaning agents have been used.

[Example] The present invention will be described in detail below with reference to Examples.

Examples 1-14 300m! ! The cleaning compositions listed in Table 1 were prepared by pouring the specified ingredients into a glass beaker and stirring at a temperature of room temperature to 40°C. The properties of the composition were comprehensively evaluated on the following four levels. The results obtained along with the KB values are listed in Table 1.

◎: Excellent in cleanability and work safety ○: Good cleanability and work safety △：Cleanability and work safety require improvement X: Poor cleaning performance The products used for each side in Table 1 are listed below.

(A>Ingredients・DPG-Dipropylene glycol (reagent)・MG-Methyl glycol [Including the following products, all Nippon Nyukazai ■Cleaving product names]・+5oPG-Isopropyl glycol・M-D-G-Methyl triglycol・MPG - Methylpolyglycol・PFG=Propylpropylene glycol・MFG-Methylpropylene glycol・DEDG=Diethyl diglycol・MFDG=Methylpropylene diglycol (B) component・Licanon EN-909 (manufactured by Shin Nippon Rikaken)=209 of oleyl alcohol Molar adduct (C) component - Wondermin CHE-20P (manufactured by Shin Nihon Rika ■) = EO2 molar adduct of cyclohexylamine Comparative example 1 The KB value of glycol ethers (MG) alone was measured, and the KB value of glycol ethers (MG) alone was measured. The performance was comprehensively evaluated.The obtained results are shown in Table 1.

Comparative Example 2 The KB value of a glycol ether (MG)/water mixed solution (weight ratio -2/]) was measured, and its performance as a cleaning agent was comprehensively evaluated. The results obtained are shown in Table 1.

Comparative Example 3 Comprehensive evaluation of the performance as a cleaning agent of a composition prepared by blending a predetermined nonionic surfactant based on an ethanol/water mixed solution (weight ratio -10/1, KB value -46) did. The results obtained are shown in Table 1. Incidentally, the KB value of ethanol alone was 92.

[Effects of the Invention] The non-halogen cleaning composition according to the present invention has the following excellent properties and can replace conventional fluorocarbon cleaning compositions. That is, (1) It exhibits high solubility in the object to be cleaned (high KB value), so the cleaning time is short.

(2) High safety, especially in aqueous compositions.

(3) Good workability due to low foaming properties.

(4) Unlike Freon and other chlorine-based cleaning agents, it does not contain any halogen, so there are no environmental problems.

(5) Compared to fluorocarbon-based cleaning agents, it is less likely to volatilize and escape and can be recovered and reused, which is advantageous in terms of cost.

Patent applicant: Shin Nippon Rika Co., Ltd. North incident display 1990 Patent application No. 244219 2. Name of the invention non-ha Rogen-based cleaning composition 3. Person who makes corrections Relationship with the incident

Claims (2)

[Claims] 1. 0.5 parts of component (B) represented by general formula (II) per 100 parts by weight of component (A) represented by general formula (I)
~30 parts by weight and/or represented by general formula (III) (
A non-halogen cleaning composition characterized by containing 0.1 to 30 parts by weight of component C). (A) General formula (I) R^1 O(AO)nR^2 (I) [In the formula, R^1 and R^2 are the same or different and have a carbon number of 1 to
represents an alkyl group having 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a hydrogen atom. A represents an alkylene group having 2 to 3 carbon atoms. n represents an integer of 1 to 20. ] One or more glycols or glycol ethers represented by (B) General formula (II) R^3 O(AO)mH(II) [wherein R^3 is a carbon number of 6 to 26 or an alkenyl group having 6 to 26 carbon atoms, A is 2 carbon atoms
~3 represents an alkylene group. m represents an integer of 1 to 16. ] One or more nonionic surfactants represented by (C) General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, R^4 is a cyclohexyl group, It represents an alkyl group having 8 to 18 carbon atoms, an alkenyl group having 8 to 18 carbon atoms, or an acyl group having 8 to 18 carbon atoms. X and Y are the same or different and represent a hydrogen atom or (CH_2CH_2O)rH. However, neither X nor Y is a hydrogen atom. r represents an integer of 1 or more. ] An amine compound represented by: 2. A non-halogen aqueous cleaning composition comprising the cleaning composition according to claim 1 and water.