JPH0873893A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent composition containing a specific glycol ether- based compound and a surfactant, satisfying high-grade detergency and being satisfactory from the aspects of environmental characteristics, odor, inflammability, etc., and suppressing influence of corrosion, etc., on a material to be cleaned. CONSTITUTION: This composition contains (A) at least one of glycol ether-based compounds of formula I (R<1> is H or a 1-5C alkyl; R<2> is a 1-5C alkyl; R<3> is H or methyl; (k) is 2-4), (B) a nonionic surfactant of preferably formula II [R<4> is a 6-20C alkyl on a (substituted)phenyl; (m) is 2-20], (C) a polyoxyalkylene- phosphoric acid ester-based surfactant of preferably formula III [R<3> is a 5-20C alkyl or a (substituted)phenyl; (n) is 0-20; X is OH or formula IV (R<6> is same as R<5> )] and (D) a polyoxyalkylene-amine-based surfactant of preferably formula V (R<7> is H, a 1-22C alkyl or an alkenyl; Y is H, a 1-4C alkyl or an acyl; (p) is 1-15; (q) is 0-15) as active ingredients.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.
In particular, it relates to a cleaning composition used for removing rosin-based solder flux for assembly.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbon type cleaning agents such as trichloroethylene and trichlorotrifluoroethane have been used as cleaning agents for rosin type solder flux, but they are used because of environmental pollution such as ozone layer depletion. Can not.

Therefore, the applicant has developed a non-halogen type detergent composition containing a specific glycol ether compound, a nonionic surfactant and a polyoxyalkylene phosphate ester surfactant as essential components. Then
This invention has already been disclosed (Patent 1832450).
issue). Such various non-halogen-based detergents that have been developed generally contain an ionic surfactant, etc., and have a deteriorating effect on detergency, toxicity, odor, flammability, and objects to be washed. It is excellent at. However, recently, due to the improvement of the quality of the object to be cleaned, there is a case where a high-quality cleaning property is required, and the above-mentioned non-halogen-based cleaning agent cannot sufficiently meet the requirements.

In addition, various non-halogen-based cleaning agents that have been recently developed include a water rinsing treatment (generally, a pre-rinse for removing dirt components from an object to be cleaned after cleaning the object to be cleaned). Treatment, and then a final rinse treatment for removing the detergent component) yields an object having excellent cleanliness. However, if rinse water is repeatedly used in such a rinsing step, the detergent component in the rinse water, etc. Since the concentration of (mainly ionic surfactant) increases,
There is a problem that the pH of the rinsing water becomes alkaline or acidic and a part of the material constituting the object to be cleaned is discolored or corroded. In particular, the problems of discoloration and corrosion are remarkable in the water rinsing step of the pre-rinsing treatment for peeling the dirt component from the article to be cleaned. For example, a thick film glass coating used for an on-vehicle or communication hybrid IC as an article to be washed causes blue discoloration in an acidic aqueous solution,
Causes white burns in alkaline aqueous solutions. In addition, there is a problem that a metal portion such as nickel, zinc, solder or the like of the object to be cleaned is corroded by acid or alkali, or is discolored.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a detergent composition which can satisfy high-quality detergency and is substantially satisfactory in terms of environmental characteristics, odor, flammability and the like. Furthermore, it aims at providing the cleaning composition which can suppress the influence of corrosion etc. with respect to a to-be-cleaned object in a cleaning process.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the above-mentioned problems can be solved by the following detergent composition having a specific composition. . The present invention has been completed based on this new finding.

That is, the present invention has the general formula (1):

[0008]

[Chemical 6]

(In the formula, R ¹ is a hydrogen atom or a carbon number of 1 to
5 is a linear or branched alkyl group, R ² is a linear or branched alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or a methyl group, and k is an integer of 2 to 4. . )
Of at least one glycol ether compound (A), a nonionic surfactant (B), a polyoxyalkylene phosphate ester surfactant (C), and a polyoxyalkylene amine surfactant (D). ) As the active ingredient.

As the glycol ether compound (A) represented by the general formula (1), for example, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monopropyl ether, Diethylene glycol dipropyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, diethylene glycol propyl butyl ether, diet Glycol monopentyl ether, diethylene glycol dipentyl ether, diethylene glycol methyl pentyl ether, diethylene glycol ethyl pentyl ether, diethylene glycol propyl pentyl ether, diethylene glycol butyl pentyl ether; tri- or tetraethylene glycol ethers corresponding to these; di-corresponding di-, Examples thereof include tri- or tetrapropylene glycol ethers. These glycol ether compounds can be used alone or in appropriate combination of two or more kinds. Among these, diethylene glycol monobutyl ether, from the viewpoint of cleanability, environmental characteristics, flammability,
Diethylene glycol monohexyl ether, triethylene glycol monobutyl ether and diethylene glycol dibutyl ether are preferred.

The nonionic surfactant (B) is not particularly limited as long as its ionicity is nonionic, and various known ones can be adopted. Specific examples thereof include polyalkylene glycol ether type nonionic surfactants such as polyoxyalkylene alkyl (alkyl group having 6 or more carbon atoms) ether, polyoxyalkylene phenol ether, polyoxyalkylene alkyl phenol ether; polyalkylene glycol monoester. ,
Polyalkylene glycol ester type nonionic surfactants such as polyalkylene glycol diesters; alkylene oxide adducts of fatty acid amides; polyhydric alcohol type nonionic surfactants such as sorbitan fatty acid esters and sucrose fatty acid esters; fatty acid alkanolamides I can give you. These nonionic surfactants (B) may be used alone or in an appropriate combination of two or more. The alkylene means ethylene, propylene or butylene, and the polyoxyalkylene means polyoxyethylene, polyoxypropylene, polyoxybutylene or a copolymer of these. Hereinafter, in the present invention, it is synonymous with alkylene.

Among these nonionic surfactants (B), polyethylene glycol ether type nonionic surfactants are preferable from the viewpoint of detergency. More preferably, the following general formula (2):

[0013]

[Chemical 7]

(In the formula, R ⁴ is a linear or branched alkyl group having 6 to 20 carbon atoms, a phenyl group, or 7 carbon atoms.
~ 12 represents a phenyl group substituted with a linear or branched alkyl group, and m represents an integer of 2-20. ) Is a polyoxyethylene alkyl ether. Especially R
⁴ is a linear or branched alkyl group having 10 to 16 carbon atoms, and m is preferably an integer polyoxyethylene alkyl ether of 3 to 16.

As the polyoxyalkylene phosphate-based surfactant (C), various known ones can be used without limitation, but from the viewpoint of detergency, environmental characteristics and flammability, the following general formula (3):

[0016]

Embedded image

(In the formula, R ⁵ is a linear or branched alkyl group having 5 to 20 carbon atoms, a phenyl group, or 7 carbon atoms.
A phenyl group substituted with a straight-chain or branched-chain alkyl group of ~ 12, n is an integer of 0-20, X is a hydroxyl group or the general formula (4):

[0018]

[Chemical 9]

(In the formula, R ⁶ is a linear or branched alkyl group having 5 to 20 carbon atoms, a phenyl group, or 7 carbon atoms.
~ 12 represents a phenyl group substituted with a linear or branched alkyl group, and n represents the same as above. )) Polyoxyethylene phosphate ester-based surfactants or salts thereof are preferred. Examples of the salt include metal salts such as sodium salt and potassium salt, ammonium salt, and alkanolamine salt. Particularly, R ⁵ has 7 to 16 carbon atoms
The polyoxyethylene phosphate ester-based surfactant represented by the linear or branched alkyl group of, and n is an integer of 3 to 16 is preferable. These polyoxyalkylene phosphate ester-based surfactants (C) may be used alone or in appropriate combination of two or more.

Commercially available products of the polyoxyethylene phosphate ester-based surfactant represented by the general formula (3) or a salt thereof are, for example, "Plysurf" series manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., "N-1" manufactured by Nippon Emulsifier Co., Ltd.
000FCP "," RA-574 "," RA-579 "
Can be exemplified.

As the polyoxyalkyleneamine-based surfactant (D), various known ones can be used without limitation, but from the viewpoint of detergency, environmental characteristics and flammability, the following general formula (5):

[0022]

[Chemical 10]

(In the formula, R ⁷ represents a hydrogen atom or a linear or branched C 1-22 alkyl group or an alkenyl group, and Y represents a hydrogen atom or a linear or branched C 1 -C 4 group. A polyoxyethylene amine-based surfactant represented by an alkyl group or an acyl group, p is an integer of 1 to 15 and q is an integer of 0 to 15. Among these, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, Y is a hydrogen atom, p
A polyoxyethylene amine-based surfactant in which + q is an integer of 2 to 15 is preferable. These polyoxyalkylene amine-based surfactants (D) may be used alone or in appropriate combination of two or more.

Commercially available products of the polyoxyethylene alkylamine type surfactant represented by the general formula (5) are, for example, "Newcol 4" manufactured by Nippon Emulsifier Co., Ltd.
05 "," Newcol 410 "," Pionin D-3104 "," Pionin D-31 "manufactured by Takemoto Yushi Co., Ltd.
10 "," Esomin T / 15 "manufactured by Lion Corporation,
"Esomin T / 25" etc. can be illustrated.

The glycol ether compound (A),
The proportions of the nonionic surfactant (B), the polyoxyalkylene phosphate ester-based surfactant (C) and the polyoxyalkylene alkylamine-based surfactant (D) used are not particularly limited, but usually 10 in order. About 95% by weight: about 5 to 90% by weight: about 0.1 to 90% by weight: about 0.1 to 90% by weight. Preferably 30 in order
~ 95 wt%: 1-60 wt%: 0.5-60
About wt%: about 0.5 to 60 wt%. More preferably, about 70 to 95% by weight: about 1 to 30% by weight: about 0.5 to 10% by weight: about 0.5 to 10% by weight.

The glycol ether compound (A) needs to be at least 10% by weight because it is a component having a main purpose as a cleaning agent, that is, the dissolution of stain components. Particularly, when the usage ratio is 70% by weight or more, the cleaning property is good.
Further, the nonionic surfactant (B) requires at least 5% by weight because it has a function of retaining the stain component in water during rinsing, but when it exceeds 90% by weight, the above-mentioned glycol ether compound ( Since the proportion of A) is decreased, the cleaning property is deteriorated, which is not preferable. Further, a polyoxyalkylene phosphate-based surfactant (C)
Requires an amount of at least 0.1% by weight because it has an excellent detergency-improving effect particularly when the detergent is diluted with water and is used, but if it exceeds 90% by weight, an excessive addition results. Not only the improvement is not observed, but rather the object to be cleaned may be affected by corrosion and the like, which is not preferable. Also,
The polyoxyalkyleneamine-based surfactant (D) requires an amount of at least 0.1% by weight because it has an excellent detergency-improving effect particularly when the detergent is diluted with water and used. If it exceeds%, not only is it added excessively and the effect is not improved, but also the object to be cleaned may be affected by corrosion or the like, which is not preferable.

The detergent composition can be used as it is, but it can also be dissolved in water to be used as an aqueous solution in order to reduce the risk of ignition of the detergent and the wastewater treatment load. . In such a case, the concentration of the cleaning composition is adjusted to be about 10% by weight or more. From the viewpoint of detergency, the concentration of the detergent composition is 70-
It is preferable to set it to about 98% by weight.

Further, the detergent composition of the present invention has a pH of 6 when the detergent composition is adjusted to an aqueous solution of 1% by weight.
It is preferable to adjust the use ratio of each component so that the neutrality is about -8. In the present invention, by setting the pH of the detergent composition to be around 6 to 8 as described above, even if the rinse water is repeatedly used in the rinse water treatment step (pre-rinse tank), the ionic interface in the rinse water is increased. Since it is possible to suppress the fluctuation of pH accompanying the improvement of the concentration of the activator, it is possible to prevent the corrosion of the substrate and the like.

The pH of the detergent composition of the present invention depends mainly on the ratio of the anionic polyoxyalkylene phosphate ester type surfactant (C) and the cationic polyoxyalkylene amine type surfactant (D). Therefore, the pH is adjusted by appropriately adjusting the use ratio of these. In addition,
Since the pH of the detergent composition differs depending on the type of surfactant used, it cannot be said unequivocally, but in general, the weight ratio is such that the former (C) is 1 to 10 and the latter (D) is 10 to 1.
So that Preferably, the former is 1 to 5 and the latter is 5 to 1.

The cleaning composition of the present invention is used for cleaning communication hybrid ICs, vehicle-mounted hybrid ICs, computer board cleaning, semiconductor manufacturing equipment cleaning, hard disk (HDD) component or magnetic head cover cleaning, lens cleaning. It can be used for various cleaning such as cleaning. In particular, it is suitable for cleaning applications for assemblies that use rosin-based solder flux. As the flux, an inactive rosin flux containing rosin such as rosin and modified rosin as a main component, the rosin and an activator (for example, triethanolamine hydrochloride, triethylenetetramine hydrochloride, cyclohexylamine hydrochloride) An active rosin flux composed mainly of a salt, an organic acid or an inorganic acid salt of an amine compound such as aniline hydrochloride) is generally used.

Further, the detergent composition of the present invention may optionally contain additives such as antifoaming agents and antioxidants, and the amount of the additive used is about 0.1% of the detergent. It is considered as follows.

Various methods of use can be adopted for cleaning an object to be cleaned using the cleaning composition of the present invention. Below, as a general method of use, the rosin flux on the substrate is contacted. The case will be described. That is, a method of directly immersing the substrate in the cleaning composition for cleaning,
A method of flushing the aqueous solution using a spray device, a method of brushing by a mechanical means, or the like can be appropriately selected and employed. The conditions for applying the detergent composition may be appropriately selected depending on the concentration of the detergent component in the detergent composition, the usage ratio of the component, the type of flux to be removed, etc. The cleaning agent is contacted with the flux at a temperature and for a time effective to wash away the flux. The temperature at the time of using the cleaning composition is from room temperature to about 80 ° C., and usually 50 to 7 ° C.
The temperature is preferably about 0 ° C. When removing the solder flux on the substrate by a dipping method at a temperature of, for example, about 60 ° C., generally, if the substrate having the solder flux is dipped in the cleaning composition of the present invention for about 1 to 5 minutes,
It can be removed well.

As a finishing treatment, the substrate from which the flux has been removed in this way is washed with a detergent composition and then subjected to a water rinse treatment such as a pre-rinsing treatment and a finishing rinse treatment to remove the detergent composition which may remain. Remove completely. By such a water washing treatment, the cleanliness of the substrate becomes extremely high. In particular, when the cleaning composition of the present invention is used, the pH of the rinse water hardly changes to alkaline or acidic in the pre-rinsing treatment, and the corrosion of the substrate can be suppressed.

[0034]

According to the present invention, the following effects are exhibited. (1) The detergent composition of the present invention has excellent detergency capable of sufficiently handling high-quality detergency. (2) Since the cleaning composition of the present invention is a non-halogen type cleaning agent, it does not have the problem of ozone layer depletion that is found in CFC cleaning agents. Further, it is also sufficiently satisfactory in terms of environmental damage, flammability, odor, and the like. (3) Furthermore, by adjusting the pH of the cleaning composition of the present invention to around neutral pH 6 to 8, in addition to excellent cleaning properties, it is possible to suppress corrosion of the object to be cleaned in the pre-rinsing treatment.

[0035]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The parts and% in each example are based on weight.

Example 1 70 parts of diethylene glycol dimethyl ether, a nonionic surfactant of polyethylene glycol alkyl ether type (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Neugen ET-"
135 ", R ⁴ in the general formula (2) has 12 to 1 carbon atoms.
4 branched chain alkyl group, m is 9), 10 parts of phosphoric acid monoester of polyoxyethylene alkyl ether (in the general formula (3), R ⁵ is a straight chain alkyl group having 12 carbon atoms, n is 16, X) Is a hydroxyl group) 2.5 parts, polyoxyethylene alkylamine (R in the general formula (5)
2.5 parts by weight of ⁷ is a straight-chain alkyl group having 12 carbon atoms, p + q is 10, Y is a hydrogen atom) and 10 parts of pure water were mixed to prepare a detergent composition. In addition, when the cleaning composition is diluted with pure water to prepare an active ingredient of the cleaning agent at 1%, p
H was 6.5.

Examples 2 to 19 and Comparative Examples 1 to 3 Prepared in the same manner as in Example 1 except that the kind or composition ratio of each component of the detergent composition was changed as shown in Table 1. did. Table 2 shows the results of measuring the pH in the same manner as in Example 1.

[0038]

[Table 1]

In Table 1, Component A is a glycol ether compound represented by the general formula (1), a1 is diethylene glycol monobutyl ether, a2 is diethylene glycol monohexyl ether, and a3 is triethylene glycol monobutyl ether. Component B is a nonionic surfactant, and b1 is a polyethylene glycol alkyl ether type nonionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Neugen ET-135", R ⁴ in the general formula (2). Is a branched chain alkyl group having 12 to 14 carbon atoms, m is 9, and b2 is a polyethylene glycol aralkyl ether type nonionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Neugen EA-120", In the general formula (2), R ⁴ is a nonylphenyl group and m is 5), b3 is polyoxyethylene sorbitan monolaurate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name “Sorgen TW20”, average ethylene oxide). The number of added moles 12) is shown. Component C is a polyoxyalkylene phosphate ester-based surfactant, c1 is a phosphoric acid monoester of polyoxyethylene alkyl ether (in the general formula (3), R ⁵ is a linear alkyl group having 12 carbon atoms, and n is 16). , X is a hydroxyl group), c2 is a phosphoric acid diester of polyoxyethylene aralkyl ether (in the general formula (3), R ⁵
Represents a nonylphenyl group, n represents 10, and X represents a nonylphenyl group in the general formula (4), and n represents 10. Component D is a polyoxyalkylene amine-based surfactant,
d1 is polyoxyethylene alkylamine (in the general formula (5), R ⁷ is a linear alkyl group having 12 carbon atoms, p is
+ Q is 10, Y is a hydrogen atom), d2 is a polyoxyethylene alkylamine (in the general formula (5), R ⁷ is a linear alkyl group having 18 carbon atoms, p + q is 7, and Y is a hydrogen atom), d3 is polyoxyethylene tallow amine (in the general formula (5), R ⁷ is a residue of beef tallow composed of a mixture of oleic acid, linoleic acid, myristic acid, palmitic acid, stearic acid, etc., p + q is 15, and Y is a hydrogen atom. Yes).

The various cleaning compositions obtained in Examples and Comparative Examples were subjected to the following tests. The test results are shown in Table 2 or Table 3.

(1) Detergency A rosin-based cream solder (manufactured by Tamura Kaken Co., Ltd., trade name "SOLDER P") is applied to the entire surface of the printed wiring board (copper clad laminate).
ASTE SQ-1025SA ") and apply at 250 ° C.
The test substrate was prepared by passing through the reflow furnace for 3 minutes. This substrate was immersed in the cleaning composition at room temperature, and the degree of flux removal was visually determined based on the following criteria. ◯: Can be removed well. Δ: Some remains. X: Remains considerably.

(2) Cleanliness (1) After washing and drying the substrate subjected to the cleaning test, the cleanliness (residual amount) of the substrate was measured using Omegameter 600-RC (trade name, manufactured by Alpha Metals Co., Ltd.). The ion concentration) was measured.

(3) Corrosion An aqueous solution was prepared so that the concentration of the cleaning composition was 5% by weight, the aqueous solution was heated to 40 ° C., and nickel, zinc, and lead metal pieces were placed for 1 hour. Soaked. The appearance of the metal surface before and after immersion was visually evaluated based on the following criteria. ◯: No change. Δ: Haze is seen on the metal surface. ×:
Heavy rust is seen on the metal surface.

[0044]

[Table 2]

[0045]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 1:34 1:44)

Claims (7)

[Claims] 1. General formula (1): (In the formula, R ¹ is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, R ² is a linear or branched alkyl group having 1 to 5 carbon atoms, and R ³ is a hydrogen atom. Or a methyl group, and k is an integer of 2 to 4), at least one of glycol ether compounds (A), a nonionic surfactant (B), and a polyoxyalkylene phosphate ester interface. A detergent composition comprising an activator (C) and a polyoxyalkyleneamine-based surfactant (D) as active ingredients. 2. The nonionic surfactant (B) is represented by the general formula (2): (In the formula, R ⁴ represents a linear or branched alkyl group having 6 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms,
m shows the integer of 2-20. The cleaning composition according to claim 1, which is a nonionic surfactant of polyethylene glycol ether type represented by (4). 3. The polyoxyalkylene phosphate-based surfactant (C) is represented by the general formula (3): (In the formula, R ⁵ is a linear or branched alkyl group having 5 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and n is An integer of 0 to 20, X is a hydroxyl group or general formula (4): (In the formula, R ⁶ is a linear or branched alkyl group having 5 to 20 carbon atoms, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 7 to 12 carbon atoms, and n is The detergent composition according to claim 1 or 2, which is the same as the above.)) And is a polyoxyethylene phosphate ester-based surfactant or a salt thereof. 4. The polyoxyalkyleneamine-based surfactant (D) has the general formula (5): (In the formula, R ⁷ represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms,
Y represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms or an acyl group, p is 1 to 15, q
Represents an integer of 0 to 15. The cleaning composition according to claim 1, which is a polyoxyethylene amine-based surfactant represented by the formula (1). 5. Use of the glycol ether compound (A), the nonionic surfactant (B), the polyoxyalkylene phosphate ester surfactant (C) and the polyoxyalkylene amine surfactant (D). The ratio is 10-95% by weight: 5-90% by weight: 0.1-90
% By weight: 0.1 to 90% by weight, The cleaning composition according to any one of claims 1 to 4. 6. The cleaning composition according to claim 1, wherein the cleaning composition contains water. 7. The cleaning composition according to claim 1, wherein the 1% by weight aqueous solution has a pH of 6-8.