JPH06313190A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain a detergent compsn. which exhibits a high cleaning power esp. to a liq. crystal substance, a solder flux. oil and fat, etc., and can be used as a water-base system. CONSTITUTION:The detergent compsn. contains a compd. of the general formula: R<1>-O-(PO)m-(EO)n-(XO)k-H [wherein R<1> is 10-22C alkyl, alkenyl, or alkylphenyl; PO, EO, and XO are a propylene oxide unit, an ethylene oxide unit, and a 3C or high alkylene oxide unit, respectively, provided PO, EO, and XO are each bonded in block; (m) is 1-8; (n) is 1-40; and (k) is such a number that the total number of carbon atoms in a block: (XO)k is 3-120].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition, and more particularly to an aqueous detergent composition which is useful for cleaning electronic parts and the like and which replaces a chlorofluorocarbon solvent and a chlorine solvent.

[0002]

2. Description of the Related Art For cleaning liquid crystal materials for liquid crystal display devices, solder flux on printed circuit boards, processing oils for precision parts, press oils, etc., fluorocarbon solvents and chlorine solvents have been conventionally used as cleaning agents. . However, due to various environmental hygiene problems, the use of these solvents has been regulated, and the demand for cleaning agents having cleaning performance equivalent to those of these solvents has increased.
Against this background, development of alternative cleaning agents has become active in recent years. JP-A-3-62896 discloses a detergent composition containing 70% by weight or more of a cyclic saturated hydrocarbon, and 0.1 to 30% by weight of an aliphatic alcohol and / or a surfactant is further added. Is described. However, this detergent composition is a non-aqueous detergent mainly composed of an organic solvent and has a problem in safety and working environment. Further, JP-A-3-146597 reports a detergent composition for printed circuit boards containing an aliphatic hydrocarbon having 8 to 20 carbon atoms and an organic compound having a polar group, and an organic compound having a polar group. Are listed as alcohols, ethers, esters, ketones and the like. Also, 0.
It is also described that 001 to 10% by weight of surfactant can be incorporated. However, this detergent composition is also a non-aqueous detergent mainly containing an aliphatic hydrocarbon, and has the same problems as described above.

Further, JP-A-3-153799 discloses an aliphatic hydrocarbon having 8 to 11 carbon atoms, a monohydric alcohol, an aliphatic dihydric alcohol mono-lower alkyl ether and / or an aliphatic dihydric alcohol mono. Brake device cleaners consisting of lower alkyl ether acetates are described. As described above, although it has been reported in the past to use an aliphatic hydrocarbon as a detergent, both are non-aqueous detergents that use themselves as a main solvent component, and their characteristics are alcohol or alcohol. It merely shows that it can be improved by a surfactant or the like. On the other hand, in recent years, attempts to highly utilize surfactants have become more active, and combinations of surfactants and lower alcohol ether compounds and detergent compositions containing an oily component such as a hydrocarbon solvent have been developed. (JP-A-3-62895, JP-A-3-62895)
97792, JP-A-3-162496 and JP-A-4-
57897 etc.). However, these cleaning agents are still unable to reach their target level in cleaning performance, and further improvement is desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention has an unprecedented cleaning composition, in particular, a high cleaning performance for liquid crystal substances, solder flux, oils and fats, and can be used in an aqueous system. The purpose is to provide a detergent composition.

[0005]

According to the present invention, when propylene oxide, ethylene oxide and an alkylene oxide having 3 or more carbon atoms are added in blocks to a hydrophobic group such as an alkyl group, the detergency is improved very specifically. ,
This was done based on the finding that the above problems can be efficiently solved by using this compound. That is, the present invention provides a detergent composition containing the compound represented by the general formula I. R ¹ -O- (PO) m- (EO) n- (XO) kH (I) (In the formula, R ¹ represents an alkyl group having 10 to 22 carbon atoms, an alkenyl group or an alkylphenyl group, PO, EO and XO
Are a propylene oxide unit, an ethylene oxide unit and an alkylene oxide unit having 3 or more carbon atoms, and the addition form of PO, EO and XO is a block.
m is 1 to 8, n is 1 to 40, and k is a number such that the total carbon number of (XO) k is 3 to 120. )

The compound represented by the general formula I is prepared, for example, by adding propylene oxide to a higher alcohol having 10 to 22 carbon atoms, adding ethylene oxide to the terminal hydroxyl group thereof, and further adding alkylene oxide having 3 or more carbon atoms. It can be manufactured by adding a certain XO. Here, XO itself or a polyoxyalkylene group formed by polymerization of two or more is hydrophobic, and the total number of carbon atoms of (XO) k is 3 to 120. Here, two or more kinds of alkylene oxides may be block- or random-added as XO. Examples of XO, which is an alkylene oxide having 3 or more carbon atoms, include propylene oxide, butylene oxide, butadiene monoxide, hexylene oxide, styrene oxide, and α-olefin oxide. Among these, alkylene oxides having 3 to 30 carbon atoms are preferable, and propylene oxide is particularly preferable. In formula I, m = 1 to 8, n = 1 to 40, k is a polymerized X
The total number of carbon atoms of O is 3 to 120, but 1 to 6, 10 to 40, and 5 to 40 (the total number of carbon atoms of XO) are preferable. When XO is propylene oxide, the sum of m and k is preferably 8 to 35, and particularly preferably 15 to 35.

The alcohols forming the alcohol residue of R ^{1 have} 10 to 22 carbon atoms, preferably 10 to 1 carbon atoms.
8 are linear or branched higher alcohols and phenols. Examples of such alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, nonadeca alcohol, elaidyl alcohol, behenyl alcohol, oleyl alcohol and alcohol derived from animal and vegetable oil fatty acids, such as coconut oil alcohol and beef tallow alcohol, Examples include higher alcohols such as fish oil alcohol, pork oil alcohol, soybean oil alcohol and hardened products thereof, and phenols such as phenol, octylphenol, nonylphenol, and styrenated phenol. When the number of carbon atoms of the higher alcohol of the above compound is shorter than the above range, the chain length of the alkyl group is short, resulting in insufficient hydrophobicity, and sufficient detergency cannot be obtained. On the other hand, when the alkyl group is longer than the above range, However, since the above compound is not dissolved or dispersed in water, it causes spots and the like. If the molecular weight ratio of ethylene oxide and alkylene oxide deviates from the above range, the detergency will be poor. The compound of general formula I may be used in the form of one kind or a mixture of two or more kinds, and in order to exhibit good detergency, it is necessary to add 0.5 to 100% by weight (hereinafter ,%), Preferably 10-70
%, And more preferably 20 to 50%.

In the present invention, when the compound represented by the general formula I is used in combination with the compound represented by the general formula II, a better detergency can be obtained. R ² -0 (CpH ₂ pO) qR ³ (II) (In the formula, R ² has 1 to 9 carbon atoms, preferably 4 to 4 carbon atoms.
9 is an alkyl group, an alkenyl group or an alkylphenyl group, and R ³ is a hydrogen atom or an alkyl group or an alkenyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or 1 carbon atoms.
~ 3 alkyl group, p represents a number of 2-4, q represents a number of 1-20. The (CpH ₂ pO) q may be a single alkylene oxide or a mixed addition of two or more kinds of alkylene oxides. When the compounds of general formula I and II are used in combination, the compound I is 0.5 to 80%, preferably 10 to 50%, and the compound of general formula II is 0.5 to 80%, preferably 10%. ~ 5
It is 0%. The detergent composition of the present invention may contain various conventionally known surfactants, that is, any of nonionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants. Specifically, anionic activators such as fatty acid salts, higher alcohol sulfuric acid ester salts, alkylbenzene sulfonic acids, and sulfosuccinic acid ester salts,
Polyoxyalkylene alkylamines, polyoxyalkylene (average addition mole number 3 to 40) alkyl (C10
To 22) ethers, nonionic activators such as polyoxyalkylene (average addition mole number: 3 to 40) alkyl (C5-12) phenyl ethers, and amphoteric activators such as sulfobetaine or carboxybetaine.

Of these, nonionic surfactants and sulfosuccinate salt type anionic surfactants are preferred. The sulfosuccinate type anionic activator has 2 carbon atoms.
Those having ~ 22 alkyl or alkenyl groups are preferred. Specific examples include dialkyl sulfosuccinic acid ester salts, monoalkyl sulfosuccinic acid ester salts,
Examples thereof include polyoxyethylene dialkyl sulfosuccinic acid ester salts and polyoxyethylene monoalkyl sulfosuccinic acid ester salts. Examples of salts include sodium, potassium, ammonium and alkanolamine. These surfactants may be used either individually or in combination of two or more, and by using a sulfosuccinate ester salt in combination with the nonionic surfactant, the detergency is further improved. Such a surfactant is preferably contained in the detergent composition of the present invention in an amount of 0 to 20%. Furthermore, the cleaning performance, especially the stamina cleaning property, is dramatically improved by incorporating one or more aliphatic hydrocarbons having 6 to 20 carbon atoms into the cleaning composition of the present invention. As the aliphatic hydrocarbon, various olefins, paraffins and the like can be used, and paraffins are particularly preferable. The carbon number is preferably 10-14. The content in the detergent composition is 0.01 to 50%, preferably 0.05 to 30%.

The cleaning composition of the present invention may further contain a low molecular weight nitrogen-containing compound. Specific examples thereof include alkylolamines such as monoethanolamine, diethanolamine and triethanolamine, morpholines such as morpholine, amines such as piperazine and triethylamine, and quaternary ammonium salts such as tetramethylammonium hydroxide. . The content in the detergent composition is 0 to 30%, preferably 5 to 20%. To improve liquid stability, glycols such as ethylene glycol and propylene glycol,
A lower alcohol such as methanol or ethanol, a liquid stabilizer such as a toluene sulfonate, a xylene sulfonate, or the like can be contained, for example, in an amount of about 0 to 20%.
Further, a rust preventive such as benzotriazole and a preservative such as benzoate can be added depending on the purpose. In addition, depending on the purpose of cleaning, nitrilotriacetic acid, ethylenediamine 4
Aminocarboxylic acid salts such as acetic acid, diethylenetriamine pentaacetic acid and hydroxyethyliminodiacetic acid, polycarboxylic acid salts such as oxalic acid, citric acid, malic acid and polyacrylic acid, tripolyphosphoric acid, pyrophosphoric acid, hydroxyethanediphosphonic acid It is also possible to add salts of phosphorus compounds such as The detergent composition of the present invention can be prepared as the compound of the general formula I alone or as a mixture with the various compounds described above, or as an aqueous composition dissolved or dispersed in water. it can. The detergent composition of the present invention may be used as a neat solution or may be diluted with water so that the amount of the compound of the general formula I is about 0.1 to 50% when used.

[0011]

INDUSTRIAL APPLICABILITY According to the present invention, by using the compound of general formula I as an active ingredient, excellent cleaning performance for electronic parts and the like is exhibited. Further, since no CFC-based solvent or chlorine-based solvent is used, the problem of environmental destruction does not occur. Further, by using the compound of the general formula II, a known surfactant and / or an aliphatic hydrocarbon having 6 to 20 carbon atoms in combination with the compound of the general formula I, more excellent cleaning performance can be obtained. Therefore, the cleaning composition of the present invention can be used for a wide range of cleaning, especially for cleaning electronic parts,
For example, it is suitable for cleaning liquid crystal materials of liquid crystal display elements, solder flux of printed circuit boards, processing oil for precision parts, press oil and the like. Next, the present invention will be described with reference to examples.

[0012]

【Example】

Example 1 A detergent composition having the composition shown in Table 1 was prepared (100 parts with water).
%) And its performance was evaluated by the following method.
The results are also shown in Table-1. Method for evaluating detergency of liquid crystal display device A liquid crystal material was applied to the voids of the liquid crystal cell, and the liquid crystal cell was left standing at room temperature for 10 minutes. In the stock solution of each cleaning agent prepared, 40 ℃, 10
Immersion cleaning was carried out for 1 minute, and after sufficiently rinsing with pure water, the cleaning property was judged with a polarizing microscope. The detergency evaluation criteria are as shown below, and ◯ or above is acceptable. A: The void is completely washed. ◯: Almost all voids are washed. Δ: A large amount of liquid crystal remains in the voids. X: Almost no void was washed.

Detergency Evaluation Method for Cleaning Metal Parts Ordinary Detergency An aluminum test piece (JIS H-4000) was coated with a mineral oil type cutting oil and left at 60 ° C. for 1 hour. This aluminum test piece was diluted 5 times with a cleaning agent and gently immersed in a cleaning solution adjusted to 40 ° C. to observe the rolling-up state of oil, and visually evaluated as rolling-up property. The detergency evaluation criteria are shown below. ◎: Rolls up quickly and oil is released. ◯: Rolls up and oil comes off fairly quickly. Δ: Rolling up, but oil release is slow. X: Rolling-up and oil release are slow. Stamina detergency Stamina detergency was obtained by conducting the same experiments and evaluations as the above-mentioned regular cleaning using a cleaning solution prepared by adding 1% (versus a cleaning solution) of mineral oil-based cutting oil to the cleaning solution in advance and fully emulsified and dispersed. Evaluated as. Ordinary detergency and stamina detergency are good or better.

[0014]

[Table 1] Table-1  Invention product1 2 3 4 5 6 7 8 9 10 11 12 C₁₂H_{twenty five}O (PO)₂(EO)₁₈(PO)₂₀H 10 20 50 100 C₁₂H_{twenty five}O (PO)₆(EO)₁₇(PO)_{twenty four}H 10 30 40 40 40 40 40 40 C₁₈H₃₇O (PO)₆(EO)₁₈(PO)_{twenty four}H 10 40C ₁₈ H ₃₇ O (PO) ₂ (EO) ₁₈ (PO) ₂₀ H 10 C_FourH₉O (EO)₂(PO)₂H 2 C₆H₁₃O (EO)₂H 20C ₈ H ₁₇ O (EO) ₈ H 10 10 10 10 10 C₁₄H₂₈ 1 C_TenH_{twenty two} 13C ₁₄ H ₃₀ 0.5 Ripar 870P (70% active ingredient) 10 10 10 10 10 10C ₁₂ H ₂₅ O (EO) ₁₅ H 10 Triethanolamine 0.5 30 Water 80 70 40 0 50 48 40 40 39 39 37 19 Liquid crystal cleaning ○ ○ ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ Metal parts cleaning ○ ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ Stamina ○ ○ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ The RIPAL 870P in the table has the following surface-active properties.
It is an agent.

[0015]

[Chemical 1]

Comparative Example Comparative detergent composition 1 containing 10% sodium dodecylbenzenesulfonate and the balance water, and Comparative detergent composition 1 containing 20% sodium dodecylbenzenesulfonate and the balance water. When the cleaning power of the product 2 was evaluated in the same manner as in Example 1, all of them were evaluated as x for the liquid crystal cleaning property, the metal part cleaning property and the stamina property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C11D 1:72)

Claims (3)

[Claims] 1. A detergent composition containing a compound represented by the general formula I. R ¹ -O- (PO) m- (EO) n- (XO) kH (I) (In the formula, R ¹ represents an alkyl group having 10 to 22 carbon atoms, an alkenyl group or an alkylphenyl group, PO, EO and XO
Are a propylene oxide unit, an ethylene oxide unit and an alkylene oxide unit having 3 or more carbon atoms, and the addition form of PO, EO and XO is a block.
m is 1 to 8, n is 1 to 40, and k is a number such that the total carbon number of (XO) k is 3 to 120. ) 2. The cleaning composition according to claim 1, further comprising a compound represented by the general formula (II). R ² -0 (CpH ₂ pO) qR ³ (II) (In the formula, R ² is an alkyl group having 1 to 9 carbon atoms, an alkenyl group or an alkylphenyl group, and R ³ is a hydrogen atom or 1 to 4 carbon atoms. Alkyl group or alkenyl group, p is 2
The number of ~ 4, q represents the number of 1-20. The (CpH ₂ pO) q may be a single alkylene oxide or a mixed addition of two or more kinds of alkylene oxides. ) 3. The cleaning composition according to claim 1, further comprising an aliphatic hydrocarbon having 6 to 20 carbon atoms.