JP2003027091A - Cleaning liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleaning liquid composition which has good detergency against a substance to be cleaned with a cured resin such as an epoxy resin and a polyurethane resin adhering thereto and excellent safety and, simultaneously, does not react even with the resin raw materials. SOLUTION: This cleaning liquid composition comprises 90-20 wt.% 10-18C aromatic hydrocarbon compound and 10-20 wt.% 5-11C dicarboxylic acid diester, >=50 wt.% of the above aromatic hydrocarbon compound being a dicyclic aromatic hydrocarbon compound. The cleaning liquid composition is suitably used in cleaning a hard substance to which a curable resin such as a two-pack type curable resin or its raw materials have adhered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid composition, and more specifically, a casting resin and a container to which a curable resin such as a polyurethane resin or an epoxy resin, a raw material body during the curing of these resins, etc. are attached. The present invention relates to a cleaning liquid composition used when cleaning a hard substance such as.

[0002]

2. Description of the Related Art Conventionally, a two-part curable resin such as an epoxy resin or a polyurethane resin is hardened and molded by mixing at least two parts of raw material components. At this time, a chlorofluorocarbon-based solvent or a chlorine-based solvent such as trichloroethane is used for cleaning and removing the pre-curing resin adhering to the devices during the mixing of the respective components or the storage after the mixing. However, the production of these solvents is prohibited as a substance that destroys the ozone layer at the end of 1995, and chlorine-based solvents are highly toxic and prevent water pollution, so their regulations are strict.

For such cleaning and removal, 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 and their ignition. There are safety issues such as relatively low points and toxicity. In addition, the use of water-based cleaning agents with added surfactants and inorganic alkalis, and aqueous-based cleaning agents such as phosphates is also being considered, but they lack cleaning power and require a large space for wastewater treatment facilities, making them economical. It is not preferable from the aspect. For this reason, there is a problem that methylene chloride, which is highly toxic, must be used when sufficient cleaning power is required for cleaning and removing the epoxy resin or polyurethane resin before curing, especially for peeling the polyurethane resin film.

As a cleaning agent for such an epoxy resin or polyurethane resin before curing, Japanese Patent Laid-Open No. 9-2089 has been proposed.
As disclosed in 9, there is known a detergent containing three components of (a) a dialkyl ester such as adipic acid, (b) a hydrocarbon, and (c) a fatty acid ester, a glycol ether or an acetic acid ester thereof as essential components. Has been. However, this cleaning agent may not have sufficient cleaning power. In addition, (c) fatty acid ester, glycol ether or acetic acid ester thereof is decomposed to generate alcohol,
This alcohol has a problem that it reacts with an isocyanate which is a raw material of the polyurethane resin to form a resin.

[0005]

SUMMARY OF THE INVENTION The present invention is directed to an article to be cleaned,
In particular, it provides a cleaning liquid composition which has a good cleaning effect on an object to be cleaned to which a cured resin such as an epoxy resin or a polyurethane resin is attached, has excellent safety, and does not react with a resin raw material. Is.

[0006]

The cleaning liquid composition according to the present invention contains 90 aromatic hydrocarbon compounds having 10 to 18 carbon atoms.
-20% by weight and 10 to 80% by weight of a dicarboxylic acid diester having 5 to 11 carbon atoms, and 50% by weight or more of the aromatic hydrocarbon compound is a bicyclic aromatic hydrocarbon compound.
This cleaning liquid composition is preferably used for cleaning a hard material to which a curable resin such as a two-component curable resin or a raw material thereof is attached.

In the cleaning method according to the present invention, an object to be cleaned, preferably a curable resin such as a two-component curable resin or a hard substance to which a raw material thereof is attached is treated with an aromatic hydrocarbon compound having 10 to 18 carbon atoms. 90 to 20% by weight and 5 to 5 carbon atoms
10 to 80% by weight of the dicarboxylic acid diester of No. 11, and 50% by weight or more of the aromatic hydrocarbon compound is brought into contact with the cleaning liquid composition which is a bicyclic aromatic hydrocarbon compound.

[0008]

The operation and effect of the present invention has a good cleaning effect on a wide range of stains, particularly on a hard material to be cleaned to which a curable resin or a raw material thereof is attached, and in particular, it is cured. Suitable for cleaning urethane resin before curing and epoxy resin before curing. Since the urethane resin for elastomers is cured at a low temperature for a short time, it is easy to form a cured film on a casting machine, a container or the like, but the cleaning liquid composition of the present invention has a remarkable effect on peeling of such a cured film. In addition, it has low flammability, low odor, low toxicity, and is extremely excellent in terms of safety.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the cleaning liquid composition of the present invention,
The aromatic hydrocarbon compound having 10 to 18 carbon atoms includes a monocyclic or polycyclic aromatic hydrocarbon compound, an alkyl-substituted compound thereof, and the like, for example, iso-butylbenzene, sec-butylbenzene, 1, 3-diethylbenzene, 1-methyl-3-n-propylbenzene, 1,
4-diethylbenzene, 1,3-diethyl-5-ethylbenzene, 1,2-diethylbenzene, 1-methyl-2
-N-propylbenzene, 1,4-dimethyl-2-ethylbenzene, 1,3-dimethyl-2-ethylbenzene,
1,2-dimethyl-4-ethylbenzene, 1,2-dimethyl-3-ethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, methylindane, ethylindane, Examples thereof include tetralin, naphthalene, methylnaphthalene, ethylnaphthalene, propylnaphthalene, dimethylnaphthalene, diethylnaphthalene, dimethylisopropylnaphthalene, ethylpropylnaphthalene and dipropylnaphthalene. In addition, these may be used alone or as a mixture of two or more kinds as necessary. Carbon number 10
The content of the aromatic hydrocarbon compound of -18 is 40-80.
%, Especially 50 to 75% by weight is preferred. A petroleum fraction containing this aromatic hydrocarbon compound can also be used.

In the present invention, it is necessary that 50% by weight or more, particularly 80% by weight or more of the aromatic hydrocarbon compound is a bicyclic aromatic hydrocarbon compound. The bicyclic aromatic hydrocarbon compound contains an alkyl-substituted naphthalene such as naphthalene, methylnaphthalene, ethylnaphthalene, propylnaphthalene, dimethylnaphthalene, diethylnaphthalene, and dipropylnaphthalene. By using such an aromatic hydrocarbon compound, compatibility with the dicarboxylic acid diester is improved, and excellent detergency is obtained.
In addition, even if only an aliphatic hydrocarbon compound and a dicarboxylic acid diester are mixed, they are phase-separated and cannot be used as a detergent.

Dicarboxylic acid diesters having 5 to 11 carbon atoms include dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, dimethyl glutarate,
Examples thereof include diethyl glutarate, dimethyl adipate, diethyl adipate, dimethyl pimelic acid, and diethyl pimelic acid. Particularly, a diester of a dicarboxylic acid having 3 to 6 carbon atoms and an alcohol having 1 to 2 carbon atoms is preferably used. These may be used alone or as a mixture of two or more, if necessary. The content of the dicarboxylic acid diester having 5 to 11 carbon atoms is preferably 20 to 60% by weight, and particularly preferably 25 to 50% by weight. 5 to 1 carbon atoms
When the content of the dicarboxylic acid diester of 1 is less than 10% by weight, it is difficult to remove the curable resin such as urethane, and
Even if the content is more than 0% by weight, the detergency will not be significantly improved. Further, in the scope of the present invention, since the cleaning liquid composition belongs to the dangerous substances Class 4 second and third petroleum, it is highly safe.

The cleaning liquid composition of the present invention may contain conventional additives such as a surfactant, an antioxidant, an ultraviolet absorber and an anticorrosive agent as long as the object of the present invention is not impaired. Usually, in order not to impair the object of the present invention, the components other than the aromatic hydrocarbon compound and the dicarboxylic acid diester are preferably 5% by weight or less, and particularly preferably 1% by weight or less.
Further, the content of the compound having an OH group such as alcohol is preferably 1% by weight or less because it is reactive with the raw material of the resin. The surfactant as an optional substance that can be blended is used for improving the permeability and dissolution rate into oils, polymers, scales and the like attached to the surface of pre-cured epoxy resin, polyurethane resin and the like. The surfactant is preferably a nonionic surfactant, for example, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, sorbitol and sorbitan fatty acid ester, Any of sucrose fatty acid ester, silicon type, fluorine type and the like can be used.

Further, other optional substances such as ultraviolet absorbers and antioxidants are useful for improving the stability of the cleaning solution during long-term storage, and examples of the ultraviolet absorbers include benzotriazole type, benzophenone type and hindered amine type. As the antioxidant, any of those that are soluble in the cleaning liquid composition of the present invention, such as phenol-based, amine-based, sulfur-based, and phosphorus-based antioxidants can be used. It is particularly preferable to add a phenolic antioxidant in an amount of 100 to 1000 ppm.

In the cleaning method of the present invention, a cleaning liquid composition
There is no particular limitation on the method of contacting with
Either method can be used. For example, including a cleaning liquid composition
Wipe with a damp sponge, etc.
It is preferable to contact by dipping or spraying.
In cleaning by immersion, in order to enhance the cleaning effect,
Simultaneously combine stirring, rocking, ultrasonic waves, air bubbling, etc.
It is more preferable to match. In this case, the use of ultrasound
Conditions are, for example, oscillation frequency: 20 to 100 kHz, cleaning
Oscillation output per liter of liquid: 10 to 200 W is preferable. D
In the bubbler, fine air bubbles are preferably washed with gas:
By aerating the volume ratio of the purified solution at 1: 1 to 5: 1,
Raises dirt that does not dissolve in the cleaning liquid composition along with air bubbles,
Can be separated. Pressure in cleaning by spray
Is, for example, 0.5 to 10 kg / cm ² G is preferred. I
Even in the case of deviation, the cleaning time is 15 seconds to 2 hours, especially 3
0 second to 20 minutes is preferable. Washing below this range
Insufficient to remove dirt sufficiently. On the other hand, this range
Even if it exceeds, the cleaning effect does not improve significantly. The cleaning temperature is
20-120 degreeC is preferable and it processes at 60-120 degreeC.
As a result, the cleaning effect can be significantly increased.

The cleaning liquid composition of the present invention can be used for cleaning hard substances such as mechanical parts, electric / electronic parts and optical parts. Examples of such industrial parts include electronic / electrical parts, optical parts, and precision machine parts. The target electrical and electronic parts are printed wiring boards, wiring boards such as ceramic wiring boards, semiconductor package parts such as lead frames, contact members such as relays and connectors, display parts such as liquid crystal and plasma displays,
Examples include hard disk storage media, magnetic storage parts such as magnetic heads, piezoelectric parts such as crystal oscillators, electric motor parts such as motors and solenoids, and sensor parts. Examples of optical components include glasses, lenses for cameras, and their housings. Examples of precision machine parts include parts such as precision bearings used in VTRs and the like. Examples of stains to be cleaned include processing oil, wax, pitch and adhesive.

In particular, the cleaning liquid composition of the present invention is used for cleaning polyurethane resins and industrial equipment handling polyurethane resin compositions, such as mixers, molding machines, storage tanks, and processing machines, or epoxy resins before curing and epoxy before curing. It can be preferably used for cleaning industrial equipment handling resin compositions, such as storage tanks, mixing tanks, and casting machines.
Further, it can be similarly used for other curable resins such as two-component curable resins.

The cleaning liquid composition of the present invention does not have a curing accelerating effect on each of the above-mentioned pre-curing resins, particularly the pre-curing resin composition. In addition, the physical properties of each resin are not adversely affected.
Therefore, the cleaning liquid composition of the present invention after cleaning, for example, even if some remains in the tank, the above-mentioned each pre-curing resin,
In particular, there is no risk of curing during storage of the resin composition before curing, and premature curing does not occur in the curing step.

Examples of the polyurethane resin to be washed include reaction products with diisocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI) and polyols such as polypropylene glycol. Polyurethane resin contains hardener, hardening accelerator, and additives such as emulsifier, foaming agent, stabilizer, plasticizer, flame retardant, antistatic agent, colorant, sway modifier, impact modifier. May be done.

Examples of the epoxy resin to be cleaned include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, polyglycidyl ether of polyhydric alcohol, polyglycidyl ester of polybasic acid, 3, ( 3,4-epoxycyclohexane) carboxylate, vinylcyclohexene diepoxide, cresol novolac type epoxy resin, epoxy resin having a hydantoin ring, and the like. Also, epoxy resin is an epoxy resin curing agent,
Addition of curing accelerators, fillers, stabilizers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, colorants, charge imparting agents, sway modifiers, impact modifiers, etc. The agent may be blended. Here, the epoxy resin curing agent may be any one commonly used, and examples thereof include polyhydric phenols, aromatic polybasic acids, aromatic polyamines, and the like. For example, phenol novolac and biphenol novolac. , Novolaks such as bisphenol A type novolacs, acid anhydrides such as phthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and amines such as diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, and hexamethylenetetramine. To be Examples of the curing accelerator include tertiary amines and organic phosphorus compounds.

[0020]

EXAMPLES 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. Table 1 shows the compositions of the cleaning liquids prepared as Examples 1 to 3 and Comparative Examples 1 to 3.

[0021]

[Table 1]

[Evaluation of Compatibility] The washing solution was stirred and
After leaving for a minute, the presence or absence of phase separation was visually observed. In the case of Comparative Example 1, the phases cannot be separated and used as a cleaning liquid.

[Evaluation of Detergency] A cleaning test of the polyurethane resin composition A before curing was carried out. As the polyurethane resin composition A, Super Urethane Foam S-20 of Tokyo Aerosol Chemical was used. The polyurethane resin has a room temperature of 12
The surface hardens in 0 seconds. Super urethane foam S-
20 was applied to a 5 cm × 5 cm 200-mesh stainless steel wire net, and then cured at room temperature for 30 seconds. Then 2
In a 00 ml beaker, 100 g of each cleaning liquid composition shown in Table 1 and a rotor were put, a wire net with the resin composition was immersed in the cleaning liquid composition, and the mixture was stirred for 3 minutes at room temperature with a magnetic stirrer. I went. After washing, the wire net was taken out and visually judged whether the urethane foam was removed. The judgment was indicated by ◯ when there was no urethane residue and could be washed cleanly, and by x when the urethane resin remained.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 3B201 AA23 AA46 AB01 BA08 BB01                       BB21 BB82 BB83 BB87 BB88                       BB92                 4H003 DA12 DB03 EB09 ED03 ED32

Claims (3)

[Claims] 1. 90 to 20% by weight of an aromatic hydrocarbon compound having 10 to 18 carbon atoms and 10 to 80% by weight of a dicarboxylic acid diester having 5 to 11 carbon atoms, and 50% by weight of the aromatic hydrocarbon compound. A cleaning liquid composition characterized in that the above is a bicyclic aromatic hydrocarbon compound. 2. The substance to be cleaned contains 90 to 20% by weight of an aromatic hydrocarbon compound having 10 to 18 carbon atoms and 10 to 80% by weight of a dicarboxylic acid diester having 5 to 11 carbon atoms. A cleaning method comprising contacting a cleaning liquid composition in which 50% by weight or more of the compound is a bicyclic aromatic hydrocarbon compound. 3. The cleaning method according to claim 2, wherein the object to be cleaned is a hard material to which a curable resin or a raw material thereof is attached.