JPH0617096A - Solvent mixture composition - Google Patents

Abstract

PURPOSE:To obtain a fluorinated hydrocarbon solvent mixture composition that can be used as a cleaning solvent substitute which does not affect the ozonosphere while satisfying the excellent characteristics of the conventional trichlorotrifluoroethane, by mixing a specified linear fluorinated hydrocarbon with a nonionic surface active agent. CONSTITUTION:The solvent mixture composition is obtained by mixing a linear fluorinated hydrocarbon (A) comprising a 4C or higher linear hydrocarbon having part or the whole of the hydrogen atoms substituted by fluorine atoms and a nonionic surfactant (B). A solvent (C) soluble in the component A can be incorporated in addition into this composition. It is desirable that the amounts of the components A, B and C respectively are at least 50wt.%, 0.01-10wt.% and 0.1-50wt.%. Examples of the component A include 1,1,1,3,3,4,4- heptafluoroethane and 1,1,1,2,4,4,4-heptafluorobutane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixed solvent composition, and more particularly to a mixed solvent suitable for removing fluxes, oils and fats, etc. adhering to ICs, electronic parts, precision machine parts and the like. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, in the manufacture of ICs, electronic parts and precision machine parts, cleaning with an organic solvent has been carried out in order to remove flux, grease, dust, etc. adhering to the parts during assembly. For such cleaning, 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as R113) has been widely used as an organic solvent. R113 is nonflammable, has little toxicity, and is excellent in stability. Furthermore, R113 has an excellent feature that it selectively dissolves only various stains without damaging the base material such as metal, plastic, and elastomer. Therefore, various precision parts or various electronic parts made of metal, plastic, elastomer, etc. Moreover, it was most suitable for cleaning the printed circuit boards on which these electronic components were mounted.

[0003]

[Problems to be Solved by the Invention]
Although 113 has various advantages, it has a long chemical life in the troposphere and diffuses into the stratosphere, where it is decomposed by ultraviolet rays to generate chlorine radicals. Chlorine radicals cause a chain reaction with stratospheric ozone, which destroys the ozone layer.

Therefore, in place of the conventional R113, an alternative cleaning solvent that is less likely to destroy the ozone layer is being actively searched. As the alternative cleaning solvent, 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 3,3-dichloro-1,
1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane and the like have been developed.

These alternative cleaning solvents have the same excellent cleaning properties as R113, and have a very small effect on the ozone layer. However, since these alternative cleaning solvents contain chlorine atoms, they slightly affect the ozone layer, albeit only slightly. Therefore, it is desired to develop a more excellent alternative cleaning solvent that does not affect the ozone layer at all.

The present invention provides a novel fluorinated hydrocarbon-based mixed solvent composition which can be used as an alternative cleaning solvent which satisfies the excellent properties of conventional R113 but does not affect the ozone layer at all. That is the purpose.

[0007]

The present invention has been made to achieve the above-mentioned object. Firstly, a part or all of hydrogen atoms of a chain hydrocarbon having 4 or more carbon atoms is fluorine. A mixed solvent composition comprising a chain fluorinated hydrocarbon (A) substituted with atoms and a nonionic surfactant (B) is provided.

In the present invention, it is important to use the chain fluorinated hydrocarbon (A) and the nonionic surfactant (B), and conventionally, such a mixed solvent composition has a flux, oil and fat. It has never been used as a cleaning agent to remove.

The chain fluorinated hydrocarbon (A) is characterized in that it does not contain chlorine atoms and therefore does not affect the ozone layer at all. Further, the mixed solvent composition comprising the chain fluorinated hydrocarbon (A) and the nonionic surfactant (B) has high selective solubility in oil and the like and is suitable as a cleaning solvent.

Secondly, the present invention comprises a chain fluorinated hydrocarbon (A), a nonionic surfactant (B) and a solvent (C) soluble in the chain fluorinated hydrocarbon (A). And a mixed solvent composition comprising

The nonionic surfactant (B) used in the present invention is not particularly limited, but preferably, for example, alkyl polyoxyethylene ether, alkyl allyl polyoxyethylene ether, alkyl allyl formaldehyde condensation. Polyoxyethylene ether, glycerin ether and its polyoxyethylene ether, block polymer having polyoxypropylene as lipophilic group, ether type such as alkylthiopolyoxyethylene ether, polyoxyethylene ether of propylene glycol ester, polyoxy of glycerin ester Ethylene ether, ether ester type of sorbitan ester such as polyoxyethylene ether, polyoxyethylene fatty acid ester, glycerin ester, sorbitan ester, etc. Ether type, or fatty acid alkanolamides, it can be mentioned nitrogen-containing type such as polyoxyethylene fatty acid amides. These nonionic surfactants (B) can be used alone or in combination of two or more.

The composition of the present invention comprises the above chain fluorinated hydrocarbon (A) and a nonionic surfactant (B), which is soluble in the above chain fluorinated hydrocarbon (A). Alkanes having 5 or more carbon atoms as solvent (C) (c-
1), cycloalkanes having 5 or more carbon atoms (c-2), alcohols (c-3), ketones (c-4), ethers (c-5), esters (c-6), halogen At least one selected from the group of chlorinated hydrocarbons (c-7) and chlorinated fluorinated hydrocarbons (c-8) can be blended and used.

The above chain fluorinated hydrocarbon (A) (hereinafter,
As the specific FC), those containing at least one hydrogen atom are preferably used because they have a high decomposition rate in the atmosphere and a short life and therefore do not contribute to global warming. Further, the specific FC in which the number of hydrogen atoms does not exceed the number of fluorine atoms is flame-retardant and is preferably used. Further, the specific FC having about 4 to 10 carbon atoms is preferably used because it has a suitable boiling point from the viewpoint of cleaning application and solvent recovery.

The specific FC can be variously exemplified in a wide range, but for example, 1,1,1,3,3,4,4
-Heptafluorobutane, 1,1,1,2,4,4,4
-Heptafluorobutane, 1,1,1,4,4,4-hexafluorobutane, 1,1,1,2,4,4,4-heptafluoro-2- (trifluoromethyl) butane,
1,1,2,2,3,3,4,4-octafluoropentane, 1,1,1,2,2,5,5,6,6,6-decafluorohexane, 1,1,1, 3, 3, 4, 4, 6,
6,6-decafluorohexane, 1,1,1,2,2
3,3,4,4-nonafluorohexane, 1,1,2,
2,3,3,4,4,5,5,6,6-dodecafluoroheptane, 1,1,1,2,2,3,3,4,5,5
5,6,6-tridecafluorooctane, or 1,
1, 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6,
Preferred examples include 7,7,8,8-heptadecafluorodecane and the like. These specific FCs may be used alone or in combination of two or more.

Alkanes having 5 or more carbon atoms (c-1) and cycloalkanes having 5 or more carbon atoms (c-2) as the solvent (C) soluble in the specific FC include pentane, 2-
Methylbutane, 2,2-dimethylpropane, hexane,
2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, 2
-Methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, octane,
Examples thereof include 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane, but are not limited thereto.

As the alcohol (c-3) as the solvent (C) soluble in the specific FC, methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, s-butanol, or Examples thereof include t-butanol and the like, but the invention is not limited thereto.

Examples of the ketones (c-4) as the solvent (C) soluble in the specific FC include, but are not limited to, acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone. is not.

As the ethers (c-5) as the solvent (C) soluble in the specific FC, diethyl ether, methyl cellosolve, tetrahydrofuran, methyl-t-butyl ether, 1,4-dioxane and the like can be mentioned. However, it is not limited to this.

The esters (c-6) as the solvent (C) soluble in the specific FC include methyl formate, ethyl formate,
Examples thereof include propyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate, but are not limited thereto.

The halogenated hydrocarbons (c-7) as the solvent (C) soluble in the specific FC include dichloromethane, cis-1,2-dichloroethylene and trans-.
Examples thereof include 1,2-dichloroethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, and tetrachloroethylene, but are not limited thereto.

The chlorinated fluorinated hydrocarbons (c-8) as the solvent (C) soluble in the specific FC are 2,
2-dichloro-1,1,1-trifluoroethane, 1,
1-dichloro-1-fluoroethane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, etc. However, the present invention is not limited to this.

The solvent (C) may be used alone or in combination of two or more.

The mixed composition ratio of the composition of the present invention is not particularly limited, but from the viewpoint of not affecting the ozone layer, the specific FC is preferably used in a content of 50% by weight or more. The preferred content of the nonionic surfactant (B) is about 0.001% by weight to 10% by weight, and the preferred content of the solvent (C) is 0.
It is about 1 to 50% by weight.

The cleaning solvent composition of the present invention may contain fluorinated hydrocarbons other than the specific FC that do not destroy the ozone layer. Examples of such fluorinated hydrocarbons include 1,2-difluoroethane, 1,1,1,2,3
-Pentafluoropropane, 1,1,2,2,3-pentafluoropropane, 1,1,1,3-tetrafluoropropane, 1,3-difluoropropane and the like can be mentioned, but are not limited thereto. is not.

Further, to the cleaning solvent composition of the present invention, the components which have been appropriately added to this type of cleaning solvent composition in accordance with its use can be added. Examples of such components are auxiliaries and stabilizers for cleaning solvent compositions.

Examples of the above components include nitro compounds such as nitromethane, nitroethane, nitropropane and nitrobenzene, amines such as diethylamine, triethylamine, i-propylamine, butylamine and i-butylamine, phenol, o-cresol and m. −
Cresol, p-cresol, thymol, p-t-butylphenol, t-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-
Dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate,
Phenols such as 2,6-di-t-butyl-p-cresol, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-).
Of 3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 1,2,3-benzotriazole, or 1-[(N, N-bis-2-ethylhexyl) aminomethyl] benzotriazole Examples thereof include triazoles.

The mixed solvent composition comprising the specific FC in the present invention has a dissolving power comparable to that of the conventional R113 system, and can be suitably used for various purposes. Such specific applications include flux, grease, oil, wax, ink and other removers, paint solvents, extractants, glass, ceramics, plastics, rubber, various metal parts, especially IC parts, electrical equipment, Examples include cleaning agents for precision machines and optical lenses.

As a cleaning method, hand-wiping, dipping, spraying, shaking, ultrasonic cleaning, steam cleaning, a combination of these, or the like may be adopted.

[0029]

EXAMPLES In Examples 1 to 22, SUS-304 was used.
Test piece (25 mm × 30 mm × 2 mm) was immersed in a machine oil (CQ-30 manufactured by Nippon Oil Co., Ltd.) and then immersed in the cleaning solvent composition of the present invention for 5 minutes to determine the degree of removal of the machine oil. . The results are shown in the following Tables 1 and 2 as ⊚: good removal possible, ∘: almost good, Δ: very small amount remaining, ×: considerably remaining.

In Examples 23 to 33, a glass epoxy printed circuit board (50 mm × 100 mm × 1.6) was used.
mm) The entire surface was coated with flux (Speedy Flux AGF-J-1 manufactured by Asahi Chemical Laboratory) and soldered at a soldering temperature of 260 ° C. using a wave solder machine. Then, it was immersed in the cleaning solvent composition of the present invention for 3 minutes for cleaning, and the degree of flux removal was determined. The result is taken as the degree of removal, ◎: good removal possible, ○: almost good,
Table 3 below shows the evaluation of Δ: trace amount remaining, ×: considerable remaining.

Specific FCs used in the following examples include 1,1,1,3,3,4,4-heptafluorobutane (R347A), 1,1,1,2,4,4,4. −
Heptafluorobutane (R347B), 1,1,1,
4,4,4-hexafluorobutane (R356), 1,
1,1,2,4,4,4-heptafluoro-2- (trifluoromethyl) butane (R43-10), 1,1,
2,2,3,3,4,4-octafluoropentane (R
458), 1,1,1,2,2,5,5,6,6,6-
Decafluorohexane (R55-10A), 1,1,
1,3,3,4,4,6,6,6-decafluorohexane (R55-10B), 1,1,1,2,2,3,3
4,4-nonafluorohexane (R569), 1,1,
2,2,3,3,4,4,5,5,6,6-dodecafluoroheptane (R65-12), 1,1,1,2,2
3,3,4,4,5,5,6,6-tridecafluorooctane (R76-13), and 1,1,1,2,2
3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorodecane (R96-17).

As the nonionic surfactant (B) used in the following examples, alkyl polyoxyethylene ether (APOEE), alkylallyl polyoxyethylene ether (AAPOEE), glycerin ester polyethoxy ether (GEPEE), Polyoxyethylene ether of propylene glycol ester (PGE
POEE), polyoxyethylene ether of glycerin ester (GREPOEE), polyoxyethylene ether of sorbitan ester (SBEPOEE), glycerin ester (GRE), sorbitan ester (SB
E), ester of alkyl polyoxyethylene ether (APOEES), polyoxyethylene fatty acid ester (POEFE), fatty acid alkanolamide (FAA)
And polyoxyethylene alkylamine (POEA
Selected from the group A).

As the solvent (C) soluble in the specific FC used in the following examples, n-pentane (n-Pe) is used.
t), n-hexane (n-Hex), cyclohexane (c-Hex), methanol (MeOH), ethanol (EtOH), 2-propanol (IPA), n-butanol (NBA), i-butanol (IBA), Acetone (Acet), diethyl ether (DEE), ethyl acetate (EtAc), methyl propionate (MePr),
Dichloromethane (DCM), cis-1,2-dichloroethylene (c-DE), trans-1,2-dichloroethylene (t-DE), 1,1-dichloro-1-fluoroethane (R141b), 2,2-dichloro. -1,1,
It was selected from the group of 1-trifluoroethane (R123) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R225cb).

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

EFFECTS OF THE INVENTION A chain fluorinated carbon which is obtained by substituting a part or all of hydrogen atoms of a chain hydrocarbon having 4 or more carbon atoms as an active ingredient of the mixed solvent composition used in the present invention with fluorine atoms. Hydrogen has the advantage that it contains no chlorine atoms and has no effect on the ozone layer. Further, the mixed solvent composition of the present invention satisfies the excellent properties of the conventional R113, and since it contains a nonionic surfactant, it has high selective solubility in oils, etc., There is an advantage that dirt such as flux can be effectively cleaned.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keiichi Onishi, Keiichi Onishi, 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture A-G Technology Co., Ltd. (72) Yoko Usami, Hazawa-machi, Kanagawa-ku, Yokohama 1160 Matsubara AGC Technology Co., Ltd.

Claims (8)

[Claims] 1. A chain fluorinated hydrocarbon (A) obtained by substituting a part or all of hydrogen atoms of a chain hydrocarbon having 4 or more carbon atoms with fluorine atoms, and a nonionic surfactant (B). A mixed solvent composition comprising: 2. A chain fluorinated hydrocarbon (A) obtained by substituting a part or all of hydrogen atoms of a chain hydrocarbon having 4 or more carbon atoms with fluorine atoms, a nonionic surfactant (B). ,
And a mixed solvent composition comprising the solvent (C) soluble in the chain fluorinated hydrocarbon (A). 3. The nonionic surfactant (B) is at least one surfactant selected from the group consisting of ether type, ether ester type, ester type, and nitrogen-containing type surfactants. Mixed solvent composition. 4. The solvent (C) is an alkane having 5 or more carbon atoms (c-1) and a cycloalkane having 5 or more carbon atoms (c-).
2), alcohols (c-3), ketones (c-4),
It is at least one selected from the group consisting of ethers (c-5), esters (c-6), halogenated hydrocarbons (c-7), and chlorinated fluorinated hydrocarbons (c-8). The mixed solvent composition according to claim 2. 5. The nonionic surfactant (B) is at least one surfactant selected from the group of ether type, ether ester type, ester type and nitrogen-containing type, and the solvent (C) is Alkanes having 5 or more carbon atoms (c-1),
Cycloalkanes (c-2) having 5 or more carbon atoms, alcohols (c-3), ketones (c-4), ethers (c
-5), esters (c-6), halogenated hydrocarbons (c-7), and chlorinated fluorinated hydrocarbons (c-
The mixed solvent composition according to claim 2, which is at least one selected from the group of 8). 6. The content of nonionic surfactant (B) is
The amount is 0.001% by weight to 10% by weight.
Or the mixed solvent composition of 5. 7. The content of the solvent (C) is 0.1% by weight.
The mixed solvent composition according to claim 2, 4 or 5, which is ˜50% by weight. 8. The content of the nonionic surfactant (B) is
0.001% to 10% by weight of the above solvent (C)
The mixed solvent composition according to claim 2 or 5, wherein the content is 0.1% to 50% by weight.