JP3233887B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a detergent composition used for degreasing and cleaning various metal parts. More specifically, cleaning compositions used for degreasing machine oils, greases, waxes, and other oils adhering to electrical, electronic, mechanical, and precision processed parts, and for removing flux and flux residues after soldering these parts. About things.

[0002]

2. Description of the Related Art Conventionally, degreasing detergents for oils such as machine oils, greases, waxes and the like are roughly classified into non-aqueous and aqueous ones. Non-aqueous detergents include 1,1,1-trichloroethane and chlorofluorocarbon.
13. Halogen solvents such as trichloroethylene, tetrachloroethylene, and methylene chloride; petroleum solvents such as gasoline and kerosene; and alcohol solvents such as methyl alcohol and isopropyl alcohol are used, whereas aqueous detergents are acids, alkalis, and surfactants. And the like have been used. In addition, fluxes and flux residues used in soldered electric circuits of electronic devices, electric devices, mechanical parts, etc., have the same degreasing agent because of the deterioration of the electric characteristics of the circuit and the problem of corrosion. Has been used.

As a cleaning agent, a chlorine-based or chlorofluorocarbon-based solvent which has no flash point and is hardly changed chemically has been used. However, since these are substances that cause ozone layer depletion, their use will be restricted in the future. For this reason, many water-based or solvent-based cleaning agents have been proposed as cleaning agents in place of chlorine-based or chlorofluorocarbon-based solvents. Also, in recent years, an example using a terpene such as limonene, pinene, dipentene or the like as a cleaning agent having low environmental pollution and high flux removal properties is disclosed in US Pat. No. 4,451,148.
No. 8 and JP-T-63-501908 (U.S. Pat. Nos. 4,640,719 and 4,740,247).

[0004] However, these detergents sufficiently satisfy the conditions required for detergent compositions such as low environmental pollution, low deterioration, low corrosion, low flammability, low toxicity and high flux removal. It was not something. That is, cleaning agents using chlorine and chlorofluorocarbon-based solvents have great problems in safety, toxicity, environmental pollution, etc.
Although it is preferable in that it is less dangerous and toxic than solvent-based cleaning agents, it has problems such as generation of rust, adhesion of dry bleeding (watermark), reduced drying property, and wastewater treatment. Solvent-based cleaning agents containing a non-hydrocarbon-based solvent as a main component have excellent flux removal properties, but have problems such as poor cleaning properties with respect to general working oil, toxicity, and deterioration during use and poor durability. Also, terpenes represented by limonene are:
Although it has excellent flux removal properties, it has problems such as low flash point, easy deterioration during use and poor durability.In addition, it is difficult to obtain stable quality because it is derived from natural products, it is expensive and the supply amount is limited. There is.

[0005] When a hydrocarbon-based cleaning agent is used alone, there is a problem in the ability to remove the flux, though the environmental pollution is low. For this reason, JP-A-3-146597 discloses a detergent in which a polar substance such as an alcohol, an ether or a ketone is added to a hydrocarbon solvent to improve the flux removing property and the part washing property.
And Japanese Patent Publication No. 7-503032. Further, JP-A-3-146597 discloses that benzotriazole or the like can be added for the purpose of preventing corrosion of a metal surface.

[0006] In order to reduce the cost and reduce the impact on the environment, such a cleaning agent is usually reused by distillation and regeneration. However, when the polar substance is decomposed during the distillation regeneration or washing, the detergent may be deteriorated or explosive peroxide may be generated. JP-A-7-268391 discloses an example in which an antioxidant such as 2,6-di-tert-butyl-p-cresol (BHT) is added to prevent this. Although it is more stable than polar substances, it is known that saturated aliphatic hydrocarbons are also oxidized during heating or distillation regeneration of the liquid, and a phenolic antioxidant such as BHT is used to prevent this oxidation. An example of the addition is disclosed in JP-A-6-293898.

As described above, a detergent to which a phenolic antioxidant such as BHT is added has a somewhat improved stability against oxidative decomposition. However, it was revealed that the effect of suppressing oxidative decomposition was insufficient under the condition of being exposed to a high temperature under the condition of contact with a metal such as copper. Metals such as copper are used for printed wiring boards and the like, and are used in a state of being in direct contact with a cleaning agent. For this reason, there has been a demand for an additive which is less oxidatively degraded even when used in contact with a metal such as copper.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a detergent composition which can prevent oxidative deterioration for a long period of time even when a detergent comprising a hydrocarbon solvent and / or a polar substance is used in contact with a metal. The purpose is to provide things.

[0009]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that p, p'-
Amine antioxidant comprising dioctyldiphenylamine and bis (2,4-di-t-butylphenyl) penta
At least one selected from phosphorus-based antioxidants consisting of erythritol diphosphite ; and 2,6-di-t-butyl-
It has been found that by using a mixture with a phenolic antioxidant composed of p-cresol , it is possible to suppress the oxidative deterioration of the organic solvent caused by heating in the presence of a metal. In addition, such a mixed system is more oxidatively degraded in the organic solvent than when only one or more selected from amine-based antioxidants and phosphorus-based antioxidants are added, or when only phenol-based antioxidants are added. It was confirmed that the prevention effect could be further improved. That is, by using at least one selected from amine-based antioxidants and phosphorus-based antioxidants and a phenol-based antioxidant in a mixture, it is possible to prevent the solvent from being oxidized and degraded in the presence of a metal.

[0010] The detergent composition of the present invention can significantly reduce the oxidative deterioration of a detergent used in contact with a metal by containing the above-mentioned specific additive. It is suitable as a detergent composition for cleaning electronic components, electrical components, mechanical components, and the like.

The organic solvent-based detergent used in the present invention comprises:
A commercially available solvent-based solvent can be used, and there is no particular limitation, but it is desirable to select a solvent that has less environmental pollution. Hydrocarbon cleaning agents suitable for such purposes include:
A saturated aliphatic hydrocarbon having 5 to 20 carbon atoms, preferably 7 to 16 carbon atoms, particularly preferably 9 to 15 carbon atoms can be mentioned. Among the saturated aliphatic hydrocarbons, normal paraffin has advantages such as easy availability of a pure substance and excellent biodegradability, and can be said to be suitable as a washing solvent. If the number of carbon atoms is less than 5, the risk of fire or explosion during the cleaning operation is large and there is a problem in safety.
On the other hand, if it exceeds 20, there is a problem that not only a large amount of energy is required for distillation regeneration due to a high boiling point, but also a large amount of flux components are recovered at the time of distillation regeneration, and the properties of the cleaning agent are changed.

When the flux cannot be sufficiently washed using only a hydrocarbon solvent, the carbon number is 5 to 20.
And an organic compound having a polar group. Examples of such an organic compound having a polar group include alcohols, ketones, ethers, and esters. These need to have 5 to 20 carbon atoms. If the number of carbon atoms is 5 or less, there is a large risk of fire or explosion during operation and there is a problem in safety. On the other hand, if it exceeds 20, the flux-removing property is reduced, and furthermore, since the boiling point is high, not only much energy is required for distillation regeneration, but also a large amount of flux components are recovered at the time of distillation regeneration, and the properties of the detergent change. There are problems such as. Among them, carbon number 6-1
7, especially those having 7 to 15 carbon atoms can be suitably used.

When an alcohol is used as the organic compound having a polar group, an alcohol having one or two hydroxyl groups is selected. When the number of hydroxyl groups is 3 or more, not only the flux removal property becomes insufficient, but also the solubility in hydrocarbons decreases, which is not preferable. Specific examples of alcohols include 2-ethyl-1-hexanol, hexyl alcohol, 1-octanol, 2-octanol, lauryl alcohol, oleyl alcohol, Guerbet alcohol of C20, 2-cyclo-2-propanol, 1,2 -Natural or synthetic alcohols such as -dodecanediol and 1,2-octadecanediol.

As the ether compound, a hydrogen atom of the hydroxyl group of the alcohol is converted to a hydrocarbon group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-
Substituted with a propyl group, an n-butyl group, an i-butyl group, or a t-butyl group, and having 5 to 20 carbon atoms in the molecule.
Can be used. These are obtained, for example, by reacting the above-mentioned alcohols with corresponding halogenated hydrocarbons. Further, a cyclic ether having five or more ring members can also be used. When the ether compound has a hydroxyl group, it is preferable to select an ether compound having 0 to 2 hydroxyl groups similarly to the alcohol. These ether compounds have excellent flux removal properties. Of these, ethers having a methyl group or an ethyl group at one end are preferred from the viewpoint of flux removal. Specific examples of the ether compound include dibutyl ether, propylene glycol monobutyl ether, 1,2-diethoxyethane, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol methyl ether, anisole, and dihexyl ether.

Examples of the ketone compound include hydrocarbon groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, and the like.
A compound having a -butyl group and a hydrocarbon group having 1 to 15 carbon atoms and having 5 to 20 carbon atoms in the molecule can be used. These can be synthesized by oxidation or catalytic dehydrogenation of the corresponding secondary alcohol. Ketone compounds also have excellent flux removal properties, similar to ether compounds. Among them, those having a methyl group or an ethyl group at one end can be suitably used from the viewpoint of flux removal.

Similarly, the ester compound is also a hydrocarbon group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-group.
A compound having a -butyl group and a hydrocarbon group having 1 to 15 carbon atoms and having 5 to 20 carbon atoms in the molecule can be used. These can be synthesized by directly reacting an acid and an alcohol. Ester compounds also have excellent flux removal properties, similar to ether compounds and ketone compounds. Among them, those having a methyl group or an ethyl group at one end can be suitably used from the viewpoint of flux removal. Specific examples of the ester compound include butyl acetate, isopentyl acetate, 3-methoxybutyl acetate, butyl propionate, butyl butyrate, isopentyl isovalerate, methyl benzoate, diethyl malonate, and ethylene glycol monoacetate. .

These organic compounds having a polar group can be used alone or in combination of two or more. The compounding amount may be any amount that can ensure the flux removal property, and is usually about 3 to 50%, preferably about 5 to 30%, and more preferably about 10 to 25%.

The phenolic antioxidants used in the present invention include, for example, 2,6-di-t-butylphenol, 2-t-butyl-4-methoxyphenol, 2,4
-Dimethyl-6-t-butylphenol, 2,4-diethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-
Ethylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, 2,6-di-t-butyl-4
-(N, N-dimethylaminomethyl) phenol, n-
Octadecyl-β- (4′-hydroxy 3 ′, 5-di-
t-butylphenyl) propionate, 2,4- (n-
(Octylthio) -6- (4-hydroxy3 ', 5'-di-t-butylanilino) -1,3,5-triazine, styrenated phenol, styrenated cresol, tocophenol, 2-t-butyl-6- ( 3'-t-butyl-
5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,2′-methylenebis (4
-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'- Dihydroxy-
3,3′-di (α-methylcyclohexyl) -5,5 ′
-Dimethyldiphenylmethane, 2,2'-ethylidene-
Bis (2,4-di-t-butylphenol), 2,2 ′
-Butylidene-bis (4-methyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-
Butylphenol), 4,4'-butylidenebis (3-
Methyl-6-t-butylphenol), 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], triethylene glycol-bis-3-(-t-butyl-4-hydroxy-5-methylphenyl) propionate, N, N'-
Bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N'-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy) hydrocinnamide , 2,2'-thiobis (4
-Methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol),
2,2-thiodiethylenebis- [3 (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
Bis [2-t-butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,1,3-tris (2-methyl-4-hydroxy- 5-t-butylphenyl) butane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, tetrakis [methylene-3-
(3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, calcium (3,5-di-t-butyl-4-hydroxybenzylmonoethylphosphonate), propyl gallate, gallic Octyl acid,
Lauryl gallate, 2,4,6-tri-t-butylphenol, 2,5-di-t-butylhydroquinone, 2,5
-Di-t-amylhydroquinone, 1,1,3-tris-
(2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 3,9-bis [2- {3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,8,
Examples thereof include 10-tetraoxaspiro [5,5] undecane, and one or more of these can be used. The concentration of phenolic antioxidant is 3-1000p
pm, preferably 5 to 200 ppm, more preferably 1
0 to 100 ppm. If the amount is less than 3 ppm, the effect may not be obtained, and if it exceeds 1000 ppm, the insulation performance of the parts to be cleaned may be deteriorated.

The amine antioxidants used in the present invention include, for example, p, p'-dioctyldiphenylamine, N-phenyl-N'-isopropyl-p-phenylenediamine, poly 2,2,4-trimethyl-1 , 2-dihydroquinoline, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, thiodiphenylamine, 4-amino-p-diphenylamine, and the like. The above can be used.
The concentration of the amine antioxidant is 3 to 1000 ppm, preferably 5 to 200 ppm, more preferably 10 to 100 ppm.
ppm. If the amount is less than 3 ppm, the effect may not be obtained, and if it exceeds 1000 ppm, the insulation performance of the parts to be cleaned may be deteriorated.

On the other hand, as the phosphorus antioxidant used in the present invention, bis (2,4-di-t-butylphenyl)
Pentaerythritol diphosphite, phenyl diisodecyl phosphite, diphenyl diisooctyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, tris nonyl phenyl phosphite, tris-di-nonyl phenyl phosphite, tris- (2,4- Di-t-butylphenyl) phosphite,
Distearyl-pentaerythritol diphosphite,
Bis (nonylphenyl) pentaerythritol diphosphite, 4,4'-isopropylidenediphenol alkyl phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyldi-tridecyl phosphite), , 1,3-Tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl)-
4,4′-bisphenylenediphosphite, 3,4
5,6-dibenzo-1,2-oxaphosphane-2-oxide, trilauryltrithiophosphite, tris (isodecyl) phosphite, tris (tridecyl)
Phosphite, phenyldi (tridecyl) phosphite, diphenyltridecylphosphite, phenyl-bisphenol A pentaerythritol diphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid diethyl ester and the like can be mentioned. And one or more of these can be used. The concentration of the phosphorus antioxidant is 3 to 1000 ppm, preferably 5 to 1000 ppm.
２００200 ppm, more preferably 10-100 ppm. If the amount is less than 3 ppm, the effect may not be obtained. If the amount exceeds 1000 ppm, the insulation performance of the parts to be cleaned may be deteriorated.

The detergent composition of the present invention uses a mixture of the phenolic antioxidant and at least one selected from amine-based antioxidants and phosphorus-based antioxidants. Also,
The cleaning composition is distilled and regenerated because dirt from the cleaning object accumulates, but the phenol-based antioxidant, the amine-based antioxidant, and the phosphorus-based antioxidant are largely present in the residue. Therefore, it is only necessary to newly add a predetermined concentration of a phenolic antioxidant and one or more mixtures selected from amine-based antioxidants and phosphorus-based antioxidants to the liquid regenerated by distillation.

The concentration ratio of the phenolic antioxidant and one or more antioxidants selected from the amine type and the phosphorus type is defined as follows. The concentration of one or more antioxidants selected from the system can be suitably used in the range of 0.3 to 3. If this is less than 0.3 or more than 3, the effect of preventing the organic solvent-based cleaning agent from being oxidized and deteriorated is reduced.

[0023] If necessary, other additive components can be included. As such other additives, sulfur-based antioxidants, surfactants, rust inhibitors and the like can also be used. As the sulfur-based antioxidant, dilauryl-3,3 ′
Thiodipropionate, dimyristyl-3,
3'-thiodipropionate, distearyl-
3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3-n -Alkylthiopropionyloxy) -5-t-butylphenyl] sulfide;
Pentaerythritol tetra (β-lauryl-thiopropionate) ester, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole and the like can be mentioned. As the surfactant, any of an anionic surfactant, a cationic surfactant, a zwitterionic surfactant and the like can be used, but a nonionic surfactant is most preferred in that it has little effect on a cleaning surface. Good. For example, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene alkyl fatty acid ester, polyoxyalkylene allyl phenol ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine, sorbitan fatty acid ester, polyoxyalkylene and the like are preferable. Can be used for Also,

Examples of the rust preventive include benzotriazole, tolyltriazole, benzotriazole derivatives having a hydrocarbon group having 2 to 10 carbon atoms, benzimidazole, imidazole derivatives having a hydrocarbon group having 2 to 20 carbon atoms, and 2 carbon atoms. Examples thereof include thiazole derivatives having from 20 to 20 hydrocarbon groups, 2-mercaptobenzothiazole and the like, and one or more of these can be used. Among these, benzotriazole, tolyltriazole, 2-mercaptobenzothiazole, an imidazole derivative having a C2-20 hydrocarbon group, etc., which have a large rust-preventing effect on copper used in wiring materials, are widely used. It can be used particularly preferably. The concentration of the nitrogen-containing organic rust inhibitor is 0.01 to 2% by mass, preferably 0.1 to 2% by mass.
03 to 1% by mass. If the amount is less than 0.01% by mass, the effect may not be obtained. If the amount exceeds 2% by mass, the insulation performance of the parts to be cleaned may be deteriorated.

The cleaning composition of the present invention can be used in various cleaning methods such as an immersion method, an ultrasonic cleaning method, an oscillating method, and a spray method, and preferable results can be obtained.

When the cleaning agent of the present invention is used in a step of cleaning a printed circuit board to which a flux has adhered, for example, first, the cleaning agent of the present invention is ultrasonically cleaned in an ultrasonic cleaning tank, and then the cleaning agent of the present invention is used. By continuously performing a method such as rinsing with the agent composition, efficient cleaning can be achieved.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

(Test Method) Assuming that the hydrocarbon-based cleaning agent is used in contact with the metal, 70 mL of the hydrocarbon-based cleaning agent was placed in a 100-mL eggplant-shaped flask, and 12.5 m
One copper plate having a size of mx 75 mm and a thickness of 3.0 mm was placed and heated in an oil bath at 180 ° C for 5 hours in an air atmosphere. Inject a part of the heated liquid into the gas chromatograph,
The concentration of ketone produced by oxidative decomposition was measured.

(Example 1) Normal paraffin having 10 carbon atoms (NS-Clean 100 manufactured by Nikko Petrochemical Co., Ltd.)
A test was conducted by adding 50 ppm of 2,6-di-t-butyl-p-cresol (BHT) as a phenolic antioxidant and 50 ppm of p, p'-dioctyldiphenylamine (DOPPA) as an amine antioxidant. Was. As a result, the concentration of ketone generated by oxidative decomposition was lower than the lower limit of measurement.

Example 2 A test was conducted in the same manner as in Example 1 except that DOPPA was changed to bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (PEP). The concentration of the ketone formed after the test was below the lower limit of measurement.

(Embodiment 3) The BHT of the embodiment 1 is 25 pp
m, 25 ppm of DOPPA was added and a test was conducted.
As a result, the concentration of ketone produced by oxidative decomposition was 0.03% by mass.

Comparative Example 1 Normal paraffin having 10 carbon atoms to which no antioxidant was added was tested in the same manner as in Example 1. The concentration of ketone formed after the test is
0.32% by mass.

(Comparative Examples 2 and 3) The test was conducted in the same manner as in Example 1 except that only 25 ppm and 50 ppm of BHT were added as the antioxidant of Example 1. The concentrations of the ketones formed after the test were 0.12% by mass and 0.1%, respectively.
It was 1% by mass.

(Comparative Example 4) A test was conducted in the same manner as in Example 1 except that only 50 ppm of DOPPA was added as the antioxidant of Example 1. The concentration of ketone formed after the test was 0.41% by mass.

Comparative Example 5 Example 1 was repeated except that only 50 ppm of PEP was added as the antioxidant of Example 1.
The test was performed in the same manner as described above. The concentration of the ketone formed after the test was 0.29% by mass.

[0036]

The cleaning composition of the present invention has very little oxidative deterioration of the cleaning agent even when it is heated in contact with the copper of the printed circuit board. For this reason, it is possible to use the electronic parts, the electric parts, the mechanical parts, etc. for a long time in a heated state.

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. ⁷ identification mark FI C23G 5/02 C23G 5/02 H05K 3/26 H05K 3/26 E (58) investigated the field (Int.Cl. ^7, DB name ) C11D 7/32 C11D 7/36 C11D 7/50 C23G 5/02-5/036 H05K 3/26 CA (STN)

Claims (4)

(57) [Claims] 1. p, p'-dioctyldiphenylamine
Amine antioxidant and bis consisting (2,4-di -t
-Butylphenyl) pentaerythritol diphosphite
At least one selected from phosphorus-based antioxidants consisting of
Containing a metal which comprises a Fe <br/> Nord antioxidant consisting of 2,6-di -t- butyl -p- cresol
An organic solvent-based cleaning composition which is a cleaning composition for parts . 2. The organic solvent according to claim 1, wherein the organic solvent is mainly composed of a hydrocarbon having 5 to 20 carbon atoms and / or an organic compound having a polar group having 5 to 20 carbon atoms. The organic solvent-based cleaning composition according to the above. 3. The method according to claim 1, wherein the hydrocarbon having 5 to 20 carbon atoms is a branched and / or straight-chain saturated aliphatic hydrocarbon. An organic solvent-based cleaning composition. 4. The organic solvent-based cleaning composition according to claim 1, which is a cleaning composition for parts containing copper as a metal.