JPH07305097A - Cleaning agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for flux cleaning in soldering, having excellent cleaning effect, capable of sufficiently drying a material to be cleaned even in the case of drying at low temperature for a short time without rinsing the material to be cleaned, containing specific two kinds of components. CONSTITUTION:This composition contains (A) a compound selected from 3- methoxy-1-butanol, 3-methoxy-3-methylbutanol, 2-ethoxyethanol, 2-methoxy- ethanol acetic ester and 1-methoxy-2-propanol acetic ester and (B) a compound selected from N-methyl-2-pyrrolidone and gamma-butyrolactone. 20-50 pts.wt. of the component A is blended with 80-50 pts.wt. of the component B. 3-Methoxy-1- butanol and 3-methoxy-3-methylbutanol are preferably used among the component A.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a cleaning liquid composition,
More specifically, the present invention relates to a cleaning liquid composition suitable for cleaning oils, epoxy resin before curing, polymers, scales, soldering flux, metal soap, etc. attached to the surface of metal or resin.

[0002]

2. Description of the Related Art Conventionally, a chlorofluorocarbon-based solvent or a chlorine-based solvent such as trichloroethane has been used for cleaning the above oils and the like. Also, for cleaning and removing soldering flux, or in industrial equipment that handles epoxy resin,
The solvent is also used for cleaning and removing the pre-curing epoxy resin and the pre-curing epoxy resin composition which are attached to the devices during the compounding step of each component or the storage after the compounding.
However, the production of these solvents is planned to be prohibited in the near future as substances that destroy the ozone layer, and chlorine-based solvents are highly toxic and prevent water pollution, so their regulations are strict.

Petroleum-based solvents such as hydrocarbons, terpene-based solvents, alcohol-based solvents, acetone and the like can be used, but these solvents have poor detergency against inorganic ions and polar compounds, and their flash points. Is relatively low and has toxicity and other safety problems.

Aqueous detergents containing surfactants and inorganic alkalis, and aqueous solutions such as phosphates have poor detergency,
Moreover, a large space is required for the wastewater treatment facility, which is not preferable from the economical aspect. In addition, there is also a problem that after the cleaning, a rinsing step is required to remove scales, additive components, etc. that cause stains.

A cleaning liquid for soldering flux is disclosed in, for example, Japanese Patent Laid-Open No. 4-68095 and 3-243698.
No. 4,983,224 and the like.

Japanese Unexamined Patent Publication No. 4-68095 discloses (1)
A flux detergent containing a nonionic surfactant and (2) one or more selected from N-methylpyrrolidone, 2-pyrrolidone, γ-butyrolactone, dimethylsulfoxide, sulfolane, and propylene carbonate is disclosed. . However, there is a problem that a rinse process is required.

Japanese Unexamined Patent Publication (Kokai) No. 3-243698 discloses an effective method for removing flux residues containing tetrahydrofurfuryl alcohol and pyrrolidone substituted with C ₁ -C ₆ alkyl or C ₁ -C ₆ alkenyl. Detergents are disclosed. However, in the detergent,
Further, there is a problem that a step of washing with a washing solvent such as water, alcohol or fluorinated hydrocarbon is required.

US Pat. No. 4,983,224 discloses a cleaning liquid composition containing a terpene / terpenol, a surfactant, N-methylpyrrolidone and optionally water.
A method of cleaning the soldering flux is disclosed. However, there is a problem that it is preferable to finally perform water washing.

Further, the applicant has already found that (A) N-methyl-2-pyrrolidone, (B) water, and (C) 3-methoxy-3-methylbutanol, 2-ethoxyethanol, 2
-Cleansing composition for soldering flux containing at least one compound selected from acetic acid ester of methoxyethanol and acetic acid ester of 1-methoxy-2-propanol (Japanese Patent Application No. 6-80953), and (A) N- A cleaning liquid containing 30 to 73 parts by weight of methyl-2-pyrrolidone, 10 to 53 parts by weight of (B) 3-methoxy-1-butanol, and 17 to 50 parts by weight of water (C), and the total amount thereof is 100 parts by weight. I applied for a composition (filed on March 31, 1994, title of invention "cleaning liquid composition").

[0010]

The present invention has a good cleaning effect and can be sufficiently dried without rinsing the object to be cleaned and at a low temperature for a short time, and stains such as scales can be removed. And a cleaning liquid composition having excellent safety.

[0011]

The present invention provides (1)
(A) 3-methoxy-1-butanol, 3-methoxy-
3-methylbutanol, 2-ethoxyethanol, 2-
Acetate ester of methoxyethanol and 1-methoxy-
A cleaning liquid composition containing at least one compound selected from acetic acid ester of 2-propanol and (B) at least one compound selected from N-methyl-2-pyrrolidone and γ-butyrolactone, (2) (A) At least one compound selected from 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 2-ethoxyethanol, acetic acid ester of 2-methoxyethanol and acetic acid ester of 1-methoxy-2-propanol, and (C) A cleaning liquid composition containing diethyl succinate, and (3) (A) 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 2-ethoxyethanol, acetic acid ester of 2-methoxyethanol and 1 At least one compound selected from acetic acid esters of -methoxy-2-propanol, ( B) A cleaning liquid composition containing at least one compound selected from N-methyl-2-pyrrolidone and γ-butyrolactone, and (C) diethyl succinate.

In a preferred embodiment, (4) (A) 10
To 60 parts by weight and (B) 90 to 40 parts by weight, (5) (A) 10 to 70
(2) including 90 parts by weight and (C) 90 to 30 parts by weight.
(6) 10 to 50 parts by weight of (A), (B) 30 to 85 parts by weight, and (C) 5 to 50 parts by weight, and the total of these is 100 parts by weight. (3) The cleaning liquid composition described in (7), (1), (2), (4), and (5) for cleaning the soldering flux.
(8) The cleaning liquid composition according to any one of (1), (3), (4), and (6) above for cleaning an epoxy resin before curing, (8) 9)
The cleaning liquid composition according to any one of (1) to (8) above, wherein (A) is at least one compound selected from 3-methoxy-1-butanol and 3-methoxy-3-methylbutanol. Can be mentioned.

The cleaning liquid composition of the present invention has a good cleaning effect and a good drying property at low temperature. Therefore, even if the rinsing step is omitted or greatly simplified, the object to be cleaned can be easily dried. In addition, no scale remains on the surface of the object to be cleaned, and wastewater treatment is easy. Furthermore, the cleaning liquid composition of the present invention has low flammability, low odor, low toxicity, good biodegradability, and is very excellent in safety. Further, since each substance contained in the cleaning liquid composition has a high boiling point, there is little loss due to evaporation, and it can be reused by distillation, which is excellent in economic efficiency.

In the cleaning liquid composition according to claim 1, (A) 3-methoxy-1-butanol (hereinafter referred to as MB
Abbreviated as O), 3-methoxy-3-methylbutanol (hereinafter abbreviated as MMB), 2-ethoxyethanol (hereinafter abbreviated as EEO), 2-
At least one compound selected from acetic acid ester of methoxyethanol (hereinafter sometimes abbreviated as MEA) and acetic acid ester of 1-methoxy-2-propanol (hereinafter sometimes abbreviated as MPA), and (B) N -Methyl-
2-pyrrolidone (hereinafter sometimes abbreviated as NMP) and γ-butyrolactone (hereinafter sometimes abbreviated as GBL)
The compounding ratio of at least one compound selected from the following is preferably (A) 10 to 60 parts by weight, and (B) 90 to 40 parts by weight, particularly preferably (A) 20 to 50 parts by weight, and (B). 80 to 50 parts by weight. Within the above range,
It is preferable because it has both good detergency and dryness. When (A) is less than the above range and (B) exceeds the above range, the drying property at low temperature is deteriorated. If (A) exceeds the above range and (B) is less than the above range, the detergency is lowered.

In the cleaning liquid composition according to claim 3, (A) MBO, MMB, EEO, MEA and MPA
The compounding ratio of at least one compound selected from (C) diethyl succinate (hereinafter sometimes abbreviated as DES) is preferably (A) 10 to 70 parts by weight, and (C) 9
0 to 30 parts by weight, particularly preferably (A) 20 to 60 parts by weight, and (C) 80 to 40 parts by weight. Within the above range, good detergency and dryness can be combined, which is preferable. When (A) is less than the above range and (C) exceeds the above range, the drying property at low temperature is deteriorated. (A)
Is more than the above range and (C) is less than the above range, the detergency is deteriorated.

In the cleaning liquid composition according to claim 5, (A) MBO, MMB, EEO, MEA and MPA
At least one compound selected from (B) at least one compound selected from NMP and GBL, and (C)
The compounding ratio of DES is preferably (A) 10 to 50 parts by weight, (B) 30 to 85 parts by weight, and (C) 5 to 50 parts by weight, particularly preferably (A) 10 to 40 parts by weight, (B). ) 5
0 to 80 parts by weight, and (C) 10 to 30 parts by weight,
The total of these is 100 parts by weight. Within the above range, good detergency and dryness can be combined, which is preferable. When (A) is less than the above range, the drying property at low temperature is deteriorated, and when (A) exceeds the above range, detergency is deteriorated. When (B) is less than the above range, the detergency is lowered, and when (B) exceeds the above range, the drying property at low temperature is lowered. Further, if (C) is less than the above range, sufficient detergency for stains with low polarity cannot be obtained, and if (C) exceeds the above range, the drying property at low temperature is deteriorated, which is not preferable.

In each of the above cleaning liquid compositions, the component (A) is particularly preferably at least one compound selected from MBO and MMB.

The above-mentioned respective cleaning liquid compositions are widely suitable for cleaning oils and the like adhering to the surface of metals, resins and the like, and for example, polyolefin resins such as automobile bumpers described in Japanese Patent Application No. 5-111195. Product cleaning, paint and coating resin peeling, metal surface rust, oil and dirt removal, molding die cleaning, pre-cure epoxy resin removal, solder flux removal, electronic and precision equipment cleaning, printing equipment It is used for cleaning the polymer, cleaning the polymerization equipment, etc. Further, it has a good cleaning effect in a wide range from stains with strong polarity to stains with weak polarity. In the cleaning of saturated hydrocarbon oils such as metalworking oils, the oil hardly dissolves in the cleaning liquid composition and it is difficult to form an emulsion. Therefore, the oil can be floated above the cleaning liquid composition by a short standing separation. be able to. Therefore, oil can be easily removed with a simple oil-water separator,
It has a long life as a cleaning liquid. Particularly, the cleaning liquid composition according to claim 1 is for cleaning a soldering flux and an epoxy resin before curing, and the cleaning liquid composition according to claim 3 is:
The cleaning liquid composition according to claim 5 is preferable for cleaning the soldering flux, and for cleaning the epoxy resin before curing.

Further, the cleaning liquid composition of the present invention does not have a curing-accelerating action on the pre-curing epoxy resin, particularly on the pre-curing epoxy resin composition. Therefore, even if the cleaning liquid composition of the present invention after cleaning is, for example, slightly left in a tank or the like, there is no risk of curing again during storage of the epoxy resin before curing, particularly the epoxy resin composition before curing, and curing Premature curing does not occur in the process.

Examples of the above-mentioned epoxy resin before curing are bisphenol A type epoxy resin and bisphenol F.
Type epoxy resin, bisphenol AD type epoxy resin,
Polyglycidyl ether of polyhydric alcohol, polyglycidyl ester of polybasic acid, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane) carboxylate, vinylcyclohexene diepoxide, cresol novolac type epoxy resin, epoxy having hydantoin ring Resin etc. are mentioned. Further, as the pre-curing epoxy resin composition, for example, an epoxy resin curing agent and a curing accelerator are added to the above epoxy resin, and further a filler, a stabilizer, a plasticizer, a lubricant, a flame retardant, a flame retardant aid, an antistatic agent. ,
Examples thereof include those containing conventional additives such as colorants, charge imparting agents, sway-improving agents, and impact resistance-improving agents. Here, as the epoxy resin curing agent, any of those usually used may be used, and examples thereof include polyhydric phenols, aromatic polybasic acids, aromatic polyamines, and the like. For example, phenol novolac and biphenol novolac. ,
Examples thereof include novolaks such as bisphenol A type novolacs, acid anhydrides such as phthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, and amines such as diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, and hexamethylenetetramine. . Further, examples of the curing accelerator include tertiary amines and organic phosphorus compounds.

Further, the cleaning liquid composition of the present invention contains a surfactant, an antioxidant, and
Conventional additives such as ultraviolet absorbers and rust preventives may be included. Here, the surfactant as an arbitrary substance is an oil,
It is used for improving the permeability and dissolution rate into polymers, scales, metal soap, soldering flux, or pre-curing epoxy resin, especially pre-curing epoxy resin composition. The surfactant is preferably a nonionic surfactant, for example, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct,
Any of fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid ester of sorbitol and sorbitan, sucrose fatty acid ester, silicon type, fluorine type and the like can be used. Further, other optional substances such as UV absorbers and antioxidants help improve stability for long-term storage of liquids, and as the UV absorbers, for example, benzotriazole-based, benzophenone-based, hindered amine-based, etc. can be used. As the antioxidant, for example, any of those that are soluble in the cleaning liquid composition of the present invention, such as phenol-based, amine-based, sulfur-based, phosphorus-based, and the like can be used.

The method for producing the cleaning liquid composition of the present invention is not particularly limited, and commonly known means can be adopted, and the components can be produced by mixing them in any order.

The washing method itself with the washing liquid composition of the present invention is not particularly limited, and any known method can be used.
For example, it is preferable to carry out by wiping with a sponge impregnated with the cleaning liquid composition, dipping in the cleaning liquid composition and / or spraying. In the cleaning by immersion, it is more preferable to combine stirring, shaking, ultrasonic waves, air bubbling and the like at the same time in order to enhance the cleaning effect. In this case, it is preferable that the ultrasonic wave is used under an oscillation frequency of 20 to 100 kHz and an oscillation output of 10 to 200 W / l. In air bubbling, fine air bubbles are preferably aerated at a gas: liquid volume ratio of about 1: 1 to 5: 1 to raise insoluble dirt in the cleaning liquid composition together with the air bubbles and also separate insoluble dirt. can do.
In cleaning by spraying, the pressure is, for example, 0.
5 to 10 kg / cm ² G is preferable. In any case, the cleaning time is preferably 15 seconds to 2 hours, particularly preferably 30 seconds to 20 minutes. When cleaning the soldering flux, the cleaning time is preferably 10 seconds to 30 minutes, particularly preferably 20 seconds to 10 minutes. If the amount is less than the above range, the cleaning is insufficient and the attached dirt cannot be sufficiently removed. On the other hand, if the amount exceeds the above range, the cleaning effect is not particularly improved. The washing temperature is preferably room temperature to 80
℃. The temperature is particularly preferably 40 to 60 ° C., and the cleaning effect can be remarkably enhanced by treating at a high temperature. If it is less than the above range, the cleaning tends to be insufficient.
When cleaning soldering flux on electronic parts,
If the cleaning temperature exceeds 80 ° C., the electronic components mounted on the substrate are deteriorated, which is not preferable. When washing the epoxy resin composition before curing, the washing temperature is preferably room temperature to 140 ° C, particularly preferably 30 to 70 ° C.
Is. If it is less than the above range, the cleaning tends to be insufficient,
When the content exceeds the above range, the boiling point of the cleaning liquid composition is too close, which is not preferable from the viewpoint of safety.

The object to be cleaned washed with the cleaning liquid composition of the present invention can be dried by a generally known method. For example, the object to be cleaned after cleaning can be easily dried by blowing warm air. The temperature of the warm air is preferably 40 to 140 ° C, particularly preferably 40 to 80 ° C.
And the drying time is preferably 5 to 60 minutes, particularly preferably 5 to 20 minutes. When the soldering flux on the electronic component is dried after cleaning, the temperature of warm air is 80
If the temperature exceeds ℃, it is not preferable because it causes deterioration of the electronic components installed on the substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0026]

EXAMPLES In the Examples and Comparative Examples, the following substances for soiling, and water-based cleaning liquids and petroleum-based cleaning liquids as comparative cleaning liquids were used. <Staining substance> Substance (a): Rosin-based soldering flux (Sparkle flux PO-F-1010S, trademark, manufactured by Senju Metal Industry Co., Ltd.) Substance (b): Water-soluble soldering flux (Sparkle flux WF-2060, Trademark, manufactured by Senju Metal Industry Co., Ltd. Material (c): Epoxy resin composition before curing Components in the resin composition and their compounding ratios are as follows. The components were mixed at room temperature, stored at 0 ° C. for 2 weeks, and then returned to room temperature.

Epoxy resin (Epicoat 828, trademark,
Yuka Shell Co., Ltd.): 100 parts by weight Curing agent (Pentahard 5000, trademark, manufactured by Tonen Kagaku Co., Ltd.): 90 parts by weight Curing accelerator (2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Co., Ltd.): 0.5 parts by weight <Comparative cleaning liquid> Water-based cleaning liquid: 5 wt% aqueous solution of Toyosol SS-20 (trademark, manufactured by Toyota Chemical Co., Ltd.) Petroleum-based cleaning liquid: ACTREL 1178L (trademark, manufactured by Exxon Chemical Co., Ltd.)

[0028]

[Examples 1 to 17 and Comparative Examples 1 to 4] Ultrasonic cleaning test A 5 cm x 7 cm 100-mesh stainless steel wire net was immersed in the above-mentioned stain substances (a), (b) and (c) and then pulled up. The sample was drained by leaving it on a metal vat lined with filter paper for 1 hour at room temperature, and the weight of each stain substance attached to the wire net was measured. Next, 100 ml of the wire mesh and the cleaning liquid composition to which each of the above-mentioned stain substances is attached is put into a 150 ml sample bottle, and cleaning is performed using an ultrasonic cleaner (oscillation frequency 28 kHz, oscillation output 80 W / l). did. The cleaning liquid compositions and cleaning conditions used are as shown in Tables 1 to 3. After washing, the wire net was taken out, dried at 90 ° C. for 30 minutes, allowed to cool at room temperature for 30 minutes, and then weighed to determine the removal rate of each stain substance. The results are shown in Tables 1 to 3.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3] Examples 1-5 are the results of using a cleaning liquid composition comprising components (A) and (B). Examples 1 and 2 are (A)
Is used to clean the rosin-based soldering flux using MBO or MMB as the material and NMP as the material (B). In all cases, the removal rate was good. Example 3
Is a mixture of MBO, MMB, EEO, MEA and MPA used as (A) and a mixture of NMP and GBL used as (B), and the rosin-based soldering flux was washed in the same manner as above. Similar to the above, a good removal rate was obtained. In Example 4, the water-soluble soldering flux was cleaned using MBO as (A) and a mixture of NMP and GBL as (B). The removal rate was good. In Example 5, the same cleaning liquid composition as in Example 1 was used to wash the epoxy resin composition before curing. A good removal rate was achieved as well as cleaning the rosin-based soldering flux. In this way, the components (A) and (B)
It was found that the cleaning liquid composition consisting of (3) has a good cleaning effect on the rosin-based and water-soluble soldering fluxes and the pre-cured epoxy resin composition.

Examples 6-9 are the results of using a cleaning liquid composition comprising components (A) and (C). In Examples 6 and 7, MBO or MMB was used as (A) and the rosin-based soldering flux was washed. In all cases, the removal rate was good. In Example 8, the same cleaning liquid composition as in Example 6 was used to wash the water-soluble soldering flux. Similar to the above, the removal rate was good. Example 9 uses MB as (A)
It uses a mixture of O, MMB, EEO, MEA and MPA. Similarly good removal rates were achieved. Thus, the cleaning liquid composition comprising the components (A) and (C) is
It was found to have a good cleaning effect on rosin-based and water-soluble soldering flux.

Examples 10 to 17 are components (A) and (B).
The results are obtained by cleaning the pre-curing epoxy resin composition using the cleaning liquid composition consisting of (C) and (C). Examples 10 to 12 are MBO or MMB as (A),
Example 13 uses NMP as (B).
Nos. 15 to 15 use MBO or MMB as (A) and GBL as (B). All showed good removal rates. Examples 11 and 12, and Examples 14 and 15
Indicates that the compounding ratio of each component is changed within the range of the present invention. In all cases, the removal rate was good. Example 1
6 is MBO as (A), NMP and G as (B)
A mixture of BL was used and Example 17
A mixture of MBO and MMB is used as (A), and a mixture of NMP and GBL is used as (B). Good removal rates were achieved in all cases.

On the other hand, Comparative Examples 1 and 2 were prepared by cleaning the rosin-based soldering flux using an aqueous cleaning solution or a petroleum-based cleaning solution, and Comparative Examples 3 and 4 were prepared using the same cleaning solution as above. It is a result of cleaning the epoxy resin composition before curing. The removal rate was extremely low in all cases.

[0035]

Examples 18 to 41 and Comparative Examples 5 to 12 Cleaning test by rocking The above-mentioned stain substances (a) and (b) were applied to each dot printed circuit board of 4 cm × 6 cm, and left for 5 minutes.
Next, using a hot air circulation type oven, after drying at 90 ° C. for 10 minutes, the weight of each stain substance attached to each substrate was measured. Next, to 500 ml of each cleaning liquid composition,
The substrates to which the respective stain substances were attached were put in a direction in which the substrate surface was perpendicular to the liquid surface. Then, it was washed by rocking vertically with an amplitude of 25 mm and a rate of 50 cycles per minute. The cleaning liquid compositions and the cleaning conditions used are as shown in Tables 4 to 6. After cleaning, take out the substrate and
After being dried for 0 minute and then allowed to cool at room temperature for 30 minutes, the removal rate of each soiling substance was determined by weighing. The results are shown in Tables 4-6.

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

[Table 6] Examples 18-29 are the results of using a cleaning liquid composition comprising components (A) and (B). Examples 18 to 22 are
(A) is variously changed, and NMP is used as (B) to clean the rosin-based soldering flux. The removal rate was good regardless of the type of (A).
Examples 23 and 24 are MBO or MM as (A)
GBL is used as B and (B). GBL
The rosin-based soldering flux removal rate was also good in the case of using. Example 25 uses a mixture of MBO as (A) and NMP and GBL as (B). The removal rate of the rosin-based soldering flux was good. In Examples 26 to 28, the water-soluble soldering flux was washed using EEO, MEA or MPA as (A) and GBL as (B). Good removal rates were achieved in all cases. Example 29
Is MMB as (A), NMP and GB as (B)
The mixture of L was used to wash the water-soluble soldering flux. Similar to the above, the removal rate was good.

In Examples 30 to 41, the components (A) and (C) were used.
It is a result of using a cleaning liquid composition consisting of. Example 3
Nos. 0 to 34 are those in which (A) was variously changed and the rosin-based soldering flux was washed. The removal rate was good regardless of the type of (A). Example 35 is (A)
Is a mixture of MBO and MMB. The removal rate was good. Examples 36-40 are
(A) is variously changed to wash the water-soluble soldering flux. It was found that the water-soluble soldering flux can also be cleaned well. Example 41 is (A)
Using a mixture of MBO, MMB and EEO as
The water-soluble soldering flux is cleaned. The removal rate was good.

On the other hand, Comparative Examples 5 to 9 are those in which the rosin-based soldering flux was washed using only the various (A). Both compared with the cleaning liquid composition of the present invention,
Its removal rate was poor. In Comparative Example 10, isopropyl alcohol (IPA) was used and the rosin-based soldering flux was also washed. The removal rate was extremely low. Comparative Examples 11 and 12 are those in which the rosin-based soldering flux was washed using only the component (B), NMP or GBL, respectively. The removal rates were all good, but the dryness was poor as described below (see Comparative Examples 19 to 26), and it cannot be said that the cleaning solution was as good as the cleaning solution composition of the present invention.

[0041]

Examples 42 to 65 and Comparative Example 13 Washing test by stirring A 5 cm × 7 cm 100 mesh stainless steel wire net was dipped in the above-mentioned stain substance (c) and then pulled up at room temperature on a metal vat lined with filter paper. The liquid was drained by leaving it for 1 hour, and the weight of the stain substance (c) attached to the wire mesh was measured. Next, in a 150 ml sample bottle,
Washing was carried out by adding a wire net to which the stain substance was attached, 100 ml of a cleaning liquid composition and a rotor, and stirring with a magnetic stirrer. The cleaning liquid compositions and cleaning conditions used are as shown in Tables 7-8. After washing, the wire net was taken out, dried at 90 ° C. for 30 minutes, then allowed to cool at room temperature for 30 minutes, and then weighed to determine the removal rate of the stain substance. The results are shown in Tables 7-8.

[0042]

[Table 7]

[0043]

[Table 8] Examples 42 to 53 are results of cleaning the pre-curing epoxy resin composition using the cleaning liquid composition containing the components (A) and (B). Examples 42 to 46 are results obtained by changing (A) variously and using NMP as (B).
When (A) is EEO, MEA or MPA, the removal rate is slightly lowered, but the effect of the present invention can be sufficiently achieved. Examples 47 to 51 are results obtained by changing (A) variously and using GBL as (B). All showed good removal rates. Example 52 uses MBO as (A), a mixture of NMP and GBL as (B), and Example 53 uses MMB as (A),
A mixture of NMP and GBL is used as (B). In all cases, the removal rate was good.

Examples 54 to 65 are components (A) and (B).
It is a result of cleaning the epoxy resin composition before curing by using the cleaning liquid composition consisting of (C). Example 54-
58 is the result of variously changing (A) and using NMP as (B). All showed good removal rates.
Examples 59 to 63 are results obtained by changing (A) variously and using GBL as (B). All showed good removal rates. Regardless of the types of (A) and (B), all showed good removal rates. Example 64 uses a mixture of MBO as (A) and NMP and GBL as (B), Example 65 uses MM as (A).
B, a mixture of NMP and GBL is used as (B). In all cases, a good removal rate could be achieved.

On the other hand, Comparative Example 13 is the result of cleaning the pre-curing epoxy resin composition using an aqueous cleaning solution. The removal rate of the pre-cured epoxy resin composition was significantly lower than that of the cleaning liquid composition of the present invention.

[0046]

Examples 66 to 85 and Reference Examples 1 and 2 Next, the curing accelerating action of the cleaning liquid composition of the present invention on the epoxy resin was examined. Each component was heated and mixed at 120 ° C. at the compounding ratio (parts by weight) shown in Tables 9 to 10 and then kept at 115 ° C. to measure the gelation time. For reference, the gelation time was also measured when the cleaning solution of the present invention was not added and when benzyldimethylamine as a curing accelerator was added instead of the cleaning solution. The gelation time is measured by ASTM
It carried out based on D3532. The results are shown in Tables 9 to 10.
Shown in.

[0047]

[Table 9]

[0048]

[Table 10] Examples 66 to 75 are those in which a cleaning liquid composition comprising components (A) and (B) was added, and Examples 76 to 85 were
A cleaning liquid composition comprising components (A), (B) and (C) was added. In all cases, gelation did not occur, as in Reference Example 1 in which the cleaning liquid composition was not added. Further, in the case of Reference Example 2 in which benzyldimethylamine, which is a typical curing accelerator, was added, gelation occurred in 25 minutes. Therefore, the cleaning liquid composition of the present invention does not exhibit a curing accelerating action up to a temperature of at least about 115 ° C., and even if a small amount of the cleaning liquid composition of the present invention remains in the tank after cleaning, it has no adverse effect. Can be said. That is,
After cleaning the pre-curing epoxy resin composition storage tank using the cleaning liquid composition of the present invention, a new pre-curing epoxy resin composition can be stored without completely removing the remaining cleaning liquid composition. It is possible.

[0049]

Examples 86 to 133, Comparative Examples 14 to 31 Dryability Test As the article to be cleaned, a mounting board used in a Sartorius electronic balance was cut into about 8 cm × 4 cm. Two ICs, 18 resistors, and 2 sockets were installed on the object to be cleaned. The article to be cleaned was previously dried with hot air at 80 ° C. for 30 minutes with hot air. Next, the object to be cleaned was immersed in each cleaning liquid composition heated to 50 ° C., and treated for 3 minutes using an ultrasonic cleaning machine (oscillation frequency 28 kHz, oscillation output 80 W / l). Then, the liquid was drained at room temperature for 1 minute and dried with hot air using a hot dryer. Then, the dry state was visually evaluated. The cleaning liquid compositions used and the drying conditions are as shown in Tables 11 to 15.

The evaluation results are shown in Tables 11-15.

[0051]

[Table 11]

[0052]

[Table 12]

[0053]

[Table 13]

[0054]

[Table 14]

[0055]

[Table 15] Here, the symbols in Tables 11 to 15 indicate the following contents. ○: Even if filter paper is inserted into the gap of the socket of the object to be washed,
The liquid is not absorbed by the filter paper because there is no liquid Δ: No droplet is observed on the appearance of the object to be cleaned, but the liquid is absorbed by the filter paper when the filter paper is inserted into the gap of the socket, etc. A state in which droplets are visually observed in a gap or the like of the wash product Examples 86 to 109 are results of a drying test of a wash liquid composition including components (A) and (B). Examples 86 to 90 are the results of various changes in (A) and the use of NMP as (B). Regardless of the type of (A), all showed good drying properties. Examples 91 to
95 is obtained by replacing (B) with GBL with respect to Examples 86 to 90. Regardless of the type of (B), all showed good drying properties. Example 96 has M as (A)
BO, a mixture of NMP and GBL is used as (B), and Example 97 is a mixture of MMB as (A) and a mixture of NMP and GBL as (B). In all cases, good drying properties were obtained. in this way,
It was found that good dryness can be obtained even when (B) is used as a mixture. Examples 98-109 correspond to Examples 86-9, respectively.
Using the same cleaning liquid composition as in 7,
The temperature was raised to 0 ° C and the cleaning time was shortened to 5 minutes.
It was found that all of them showed good drying property, and the drying time could be shortened significantly by increasing the temperature by 20 ° C.

Examples 110 to 121 are the results of using the cleaning liquid compositions containing the components (A) and (C). Examples 110 to 114 are the results of performing the drying test by changing (A) variously. All showed good drying properties. Examples 115 to 119 are the same as Examples 110 to 110, respectively.
In comparison with 114, the compounding amount of (A) was increased, the compounding amount of (C) was decreased, and the drying time was shortened to 10 minutes. In all cases, the drying property was good. Example 120
Is a mixture of MBO and MMB used as (A), and Example 121 is a mixture of MBO and M as (A).
A mixture of MB, EEO, MEA and MPA is used. It was found that all of them exhibited good drying properties under drying conditions of 50 ° C. for 10 minutes, and that good drying properties were obtained even when (A) was used as a mixture.

Examples 122 to 133 are the components (A),
It is a result of carrying out a dryness test using the cleaning liquid composition comprising (B) and (C). Examples 122-12
No. 6 is a result of variously changing (A) and using NMP as (B). Regardless of the type of (A), all showed good drying properties. Examples 127 to 131 are results obtained by using cleaning liquid compositions in which (B) was replaced with GBL with respect to Examples 122 to 126, respectively. All showed good drying properties. Example 132 uses MB as (A)
O, a mixture of NMP and GBL as (B), Example 1
No. 33 uses MMB as (A) and a mixture of NMP and GBL as (B). In all cases, good dryness was exhibited. As described above, it was found that even when (B) was used as a mixture, good drying property was obtained.

On the other hand, in Comparative Examples 14 to 18, each component of (A) was used alone. All of them have good drying properties, but their detergency is low as described above (see Comparative Examples 5 to 9). In Comparative Examples 19 to 21, only NMP was used and the drying conditions were changed. All were poor in dryness. In Comparative Examples 22 to 26, only GBL was used and the drying conditions were changed. None of them had good drying properties. Example 27 is (C) D.
Only ES is used. Despite the long drying time of 20 minutes, the drying property was poor. Comparative Examples 28-31 showed the drying result about ion-exchanged water as a reference.

[0059]

EFFECTS OF THE INVENTION The cleaning liquid composition of the present invention has a good cleaning effect and can be sufficiently dried without rinsing an object to be cleaned and at a low temperature for a short time, and stains such as scales can be removed. It also has excellent safety. It is also economically superior. Therefore, it is industrially extremely useful as a substitute for the conventional cleaning liquid.

Claims (6)

[Claims] 1. (A) 3-methoxy-1-butanol,
At least one compound selected from 3-methoxy-3-methylbutanol, 2-ethoxyethanol, acetic acid ester of 2-methoxyethanol and acetic acid ester of 1-methoxy-2-propanol, and (B) N-methyl-
A cleaning liquid composition containing at least one compound selected from 2-pyrrolidone and γ-butyrolactone. 2. The cleaning liquid composition according to claim 1, which is used for cleaning a soldering flux and an epoxy resin before curing. 3. (A) 3-methoxy-1-butanol,
Includes at least one compound selected from 3-methoxy-3-methylbutanol, 2-ethoxyethanol, 2-methoxyethanol acetate and 1-methoxy-2-propanol acetate, and (C) diethyl succinate Cleaning liquid composition. 4. A cleaning flux cleaning soldering flux according to claim 3
The cleaning liquid composition described. 5. (A) 3-methoxy-1-butanol,
At least one compound selected from 3-methoxy-3-methylbutanol, 2-ethoxyethanol, acetic acid ester of 2-methoxyethanol and acetic acid ester of 1-methoxy-2-propanol, (B) N-methyl-2-
A cleaning liquid composition containing at least one compound selected from pyrrolidone and γ-butyrolactone, and (C) diethyl succinate. 6. The cleaning liquid composition according to claim 5, which is for cleaning an epoxy resin before curing.