JPH05331489A - Solvent composition for cleaning - Google Patents

Abstract

PURPOSE:To provide a solvent composition for cleaning containing a cyclic hydrofluorocarbon having a specific carbon number and 4-membered ring and containing at least one hydrogen atom, capable of effectively removing the flux and oil on an electronic part, etc., and free from the problem of ozonosphere destruction. CONSTITUTION:The solvent composition for cleaning is produced by compounding (A) a >=4C cyclic hydrofluorocarbon having 4-membered ring and containing at least one hydrogen atom (e.g. 1,1,2,2,3,3-hexafluorocyclobutane), (B) a solvent soluble in the component A and selected from >=5C alkanes (e.g. n-pentane), >=5C cycloalkanes (e.g. cyclohexane), alcohols (e.g. methanol), ketones (e.g. acetone), esters (e.g. ethyl acetate), hydrohalocarbons (e.g. dichloromethane), etc., and (C) a nonionic surfactant (e.g. alkylpolyoxyethylene ether).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent composition used for cleaning, and in particular, it is used for cleaning suitable for removing fluxes, oils and fats, etc. adhering to ICs, electronic parts, precision machine parts and the like. It relates to a solvent 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 and the like 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. Further, R113 has an excellent feature that it selectively dissolves only dirt without damaging the base material such as metal, plastic, and elastomer. A printed circuit board that is cleaned by removing flux is a good example of a product made of a base material such as metal, plastic, and elastomer. From this point as well, R113 is useful.

[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, these alternative cleaning solvents have a slight effect on the ozone layer because they contain chlorine atoms. Therefore, it has been desired to develop a more excellent alternative cleaning solvent that does not affect the ozone layer at all.

An object of the present invention is to provide a cleaning solvent composition which does not destroy the ozone layer and has the ability to effectively clean flux, oil and the like.

A further object of the present invention is to provide a cleaning solvent composition having a characteristic that it selectively dissolves only dirt without damaging a substrate such as metal, plastic and elastomer.

[0008]

The present invention has been made to achieve the above-mentioned object. First, it has a carbon number of 4 or more and a 4-membered ring, and at least one hydrogen atom. The present invention provides a solvent composition for cleaning, which comprises a cyclic hydrofluorocarbon (A) containing

The above hydrofluorocarbon (A) is characterized in that it does not contain chlorine atoms and therefore does not affect the ozone layer at all. Further, since the hydrofluorocarbon (A) contains at least one hydrogen atom and has a structural strain derived from the cyclobutane ring, the decomposition rate in the atmosphere is extremely fast. That is, the hydrofluorocarbon (A) has an advantage that it has a short life in the atmosphere and does not contribute to global warming.

Secondly, the present invention provides a solvent composition for cleaning which comprises the hydrofluorocarbon (A) and a solvent (B) soluble in the hydrofluorocarbon (A).

Thirdly, the present invention provides a solvent composition comprising the above-mentioned hydrofluorocarbon (A) and a nonionic surfactant (C) for cleaning.

Fourthly, the present invention provides a solvent composition for cleaning, which comprises the hydrofluorocarbon (A), the solvent (B) and the nonionic surfactant (C).

In the present invention, it is important to use the above-mentioned hydrofluorocarbon (A) (hereinafter referred to as "specific HFC"), and such compounds have hitherto been used as cleaning agents for removing flux, oil and fat. There wasn't.

Further, in the present invention, alkanes having 5 or more carbon atoms (b-1), cycloalkanes having 5 or more carbon atoms (b-2) and alcohols (b- 3), ketones (b-4), ethers (b-
5), at least one selected from the group of esters (b-6), hydrohalocarbons (b-7), and hydrochlorofluorocarbons (b-8) and / or a nonionic surfactant (C). ), At least one selected from the group of ether type, ether ester type, ester type, and nitrogen-containing type can be used by being mixed with the specific HFC.

As the specific HFC, a specific HFC in which the number of hydrogen atoms does not exceed the number of fluorine atoms is preferably used because it is flame-retardant. Further, the specific HFC has 4 or more carbon atoms, preferably one having about 4 to 7 carbon atoms is selected.
Those having a boiling point of about 0 have a suitable boiling point from the viewpoints of cleaning applications and solvent recovery, and are therefore preferably used.

The specific HFC can be variously exemplified in a wide range, for example, 1,1,2,2,3,3-
Hexafluorocyclobutane, 1,1,2,2,3,4
-Hexafluorocyclobutane, 1,1,2,2,3-
Pentafluoro-3- (trifluoromethyl) cyclobutane, 1,1,2,3-tetrafluoro-2- (trifluoromethyl) cyclobutane, 1,1,2,2-tetrafluoro-3- (trifluoromethyl) Preferred examples include cyclobutane and 1,1,2,2,3-pentafluoro-4,4-dimethyl-3- (trifluoromethyl) cyclobutane. These specific HF
C can be used alone or in combination of two or more.

Alkanes having 5 or more carbon atoms (b-1) and cycloalkanes having 5 or more carbon atoms (b-2) as the solvent (B) soluble in the specific HFC 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, 2,2,3-trimethylpentane, 2,2,4-
Examples thereof include trimethylpentane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane, but are not limited thereto.

As the alcohol (b-3) as the solvent (B) soluble in the specific HFC, 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 (b-4) as the solvent (B) soluble in the specific HFC include, but are not limited to, acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone. is not.

The ethers (b-5) as the solvent (B) soluble in the specific HFC include diethyl ether, methyl cellosolve, tetrahydrofuran, methyl-t-butyl ether, 1,4-dioxane and the like. However, it is not limited to this.

Examples of the ester (b-6) as the solvent (B) soluble in the specific HFC include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and the like. Examples thereof include, but are not limited to:

Hydrohalocarbons (b-7) as a solvent (B) soluble in a specific HFC include dichloromethane, cis-1,2-dichloroethylene and trans-.
Examples thereof include 1,2-dichloroethylene and 2-bromopropane, but are not limited thereto.

The hydrochlorofluorocarbons (b-8) as the solvent (B) soluble in the specific HFC include 2,2-dichloro-1,1,1-trifluoroethane and 1,1-dichloro. -1-fluoroethane, 3,3-
Dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1,2,2,3
3-pentafluoropropane, 1,2-dichloro-1,
1,3,3,3-pentafluoropropane, 1,2-dichloro-1,1,2,3,3-pentafluoropropane, 2,3-dichloro-1,1,1,2,3-pentafluoro Propane or 2,2-dichloro-1,1,
Examples thereof include 1,3,3-pentafluoropropane, but are not limited thereto.

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

The nonionic surfactant (C) used in the composition of the present invention is not particularly limited, but preferably, for example, alkyl and alkylallyl polyoxyethylene ether, alkylallyl formaldehyde condensed polyoxy. Ethylene ether, glycerin ether and its polyoxyethylene ether, block polymer having polyoxypropylene as a lipophilic group, ether type such as alkylthiopolyoxyethylene ether, propylene glycol ester polyoxyethylene ether, glycerin ester polyoxyethylene ether , Sorbitan ester type ether ester such as polyoxyethylene ether, polyoxyethylene fatty acid ester type, glycerin ester, sorbitan ester type ester type, fatty acid Luke alkanolamides include a nitrogen-containing type such as polyoxyethylene fatty acid amides. Regarding the above-mentioned surfactant (C), one kind alone or two
A mixture of two or more species can be used.

When used as a mixed composition in the present invention, the mixing ratio is not particularly limited, but the content of the solvent (B) soluble in the specific HFC is preferably 0.1% by weight to 50%. The content by weight and / or the content of the nonionic surfactant (C) is 0.001% by weight to 10% by weight.

The cleaning solvent composition of the present invention contains a specific HFC.
Hydrofluorocyclobutanes other than those that do not destroy the ozone layer can be blended. Examples of such hydrofluorocyclobutanes include 1,2-difluoroethane,
1,1,1,2,3-pentafluoropropane, 1,
1,2,2,3-pentafluoropropane, 1,1,
Examples thereof include 1,3-tetrafluoropropane and 1,3-difluoropropane, but are not limited thereto.

Further, to the cleaning solvent composition of the present invention, the components which have been appropriately added to the cleaning solvent composition of this type conventionally according to 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 solvent composition of the present invention used for cleaning, which has a specific HFC, has a dissolving power similar to that of the conventional R113 system and can be suitably used for various purposes. Specific examples of such applications include flux, grease, oil, wax, ink 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.

[0032]

EXAMPLES In Examples 1-44, SUS-304
Test piece (25 mm × 30 mm × 2 mm) was immersed in 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 machine oil. .. The results are shown in Tables 1 and 2 below, which are evaluated as ⊚: good removal is possible, ∘: almost good, Δ: very small amount remains, x: considerably remains.

In Examples 45 to 88, a printed circuit board made of glass epoxy (50 mm × 100 mm × 1.6) was used.
(mm) Flux (Speedy Flux AGF-J-1 manufactured by Asahi Chemical Laboratory) was applied to the entire surface, and soldering was performed using a wave solder machine at a soldering temperature of 260 ° C. 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 is possible, ○: almost good,
Table 3 to Table 4 below show the evaluations of Δ: small amount remaining, x: considerable remaining.

Specific HFCs used in the following examples are 1,1,2,2,3,3-hexafluorocyclobutane (C336), 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,2,3-pentafluoro-3- (trifluoromethyl) cyclobutane,
1,1,2,3-tetrafluoro-2- (trifluoromethyl) cyclobutane, 1,1,2,2-tetrafluoro-3- (trifluoromethyl) cyclobutane, and 1,1,2,2,3 -Pentafluoro-4,4-dimethyl-3- (trifluoromethyl) cyclobutane.

Specific HFC-soluble solvents used in the following examples are n-pentane (n-Pet), cyclopentane (c-Pet) and n-hexane (n-He).
x), cyclohexane (c-Hex), n-heptane (n-Hep), methanol (MeOH), ethanol (EtOH), n-propanol (n-PA), 2-propanol (IPA), acetone (Acet), Methyl ethyl ketone (MEK), ethyl acetate (EtA
c), dichloromethane (DCM), 1,1-dichloro-
1-fluoroethane (R141b), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R2
25A), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R225B), and 2,2-
Dichloro-1,1,1-trifluoroethane (R12
3) selected from the group.

As the surfactant used in the following examples, alkyl polyoxyethylene ether (APO
EE), glycerin ester polyethoxyethylene ether (GEPEE), polyoxyethylene fatty acid ester (POEFE), ester of glycerin ether (G
RETES), alkyl polyoxyethylene ether ester (APOEES), sorbitan ester (SO
RES), glycerin ester (GRES), fatty acid alkanolamide (FAAD), and glycerin ether (GRET).

[0037]

[Table 1]

[0038]

[Table 2]

In Examples 1 to 44, C3 having a solvent composition was used.
36 is 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,2,3-pentafluoro-3-
(Trifluoromethyl) cyclobutane, 1,1,2,3
-Tetrafluoro-2- (trifluoromethyl) cyclobutane, 1,1,2,2-tetrafluoro-3- (trifluoromethyl) cyclobutane, or 1,1,2,
When 2,3-pentafluoro-4,4-dimethyl-3- (trifluoromethyl) cyclobutane was used for the evaluation, the same result was obtained.

[0040]

[Table 3]

[0041]

[Table 4]

In Examples 45 to 88, C having a solvent composition was used.
336 to 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,2,3-pentafluoro-3
-(Trifluoromethyl) cyclobutane, 1,1,2,
3-tetrafluoro-2- (trifluoromethyl) cyclobutane, 1,1,2,2-tetrafluoro-3- (trifluoromethyl) cyclobutane, or 1,1,2,
When 2,3-pentafluoro-4,4-dimethyl-3- (trifluoromethyl) cyclobutane was used for the evaluation, the same result was obtained.

[0043]

INDUSTRIAL APPLICABILITY The solvent composition used in the present invention, which comprises a cyclic hydrofluorocarbon (A) having 4 or more carbon atoms and a 4-membered ring and containing at least one hydrogen atom, is chlorine. It has the advantages that it does not contain atoms and does not affect the ozone layer at all, has a short life in the atmosphere, and does not contribute to global warming. Besides, conventional R11
3 has the advantages of satisfying the excellent characteristics and being capable of effectively cleaning dirt such as fats and oils and flux.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H05K 3/26 7511-4E // (C11D 7/60 7:30) (C11D 10/02 1: 66 7:30) (72) Inventor Keiichi Onishi, 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture AZ Technology Co., Ltd. (72) Yoko Usami 1160, Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Address inside AZ Technology Co., Ltd.

Claims (10)

[Claims] 1. A solvent composition used for washing, which comprises a cyclic hydrofluorocarbon (A) having 4 or more carbon atoms and a 4-membered ring and containing at least one hydrogen atom. 2. The hydrofluorocarbon (A) and a solvent (B) soluble in the hydrofluorocarbon (A).
A solvent composition used for cleaning. 3. A solvent composition for cleaning, comprising the hydrofluorocarbon (A) and a nonionic surfactant (C). 4. A solvent composition for cleaning, which comprises the hydrofluorocarbon (A), the solvent (B) and a nonionic surfactant (C). 5. The solvent (B) is an alkane (b-1) having 5 or more carbon atoms, and a cycloalkane (b-) having 5 or more carbon atoms.
2), alcohols (b-3), ketones (b-4),
At least one selected from the group consisting of ethers (b-5), esters (b-6), hydrohalocarbons (b-7), and hydrochlorofluorocarbons (b-8).
The solvent composition used for cleaning according to claim 2 or 4, which is a seed. 6. The solvent composition used for washing according to claim 3, wherein the nonionic surfactant (C) is at least one selected from the group consisting of ether type, ether ester type, ester type and nitrogen-containing type. object. 7. The solvent (B) is an alkane (b-1) having 5 or more carbon atoms, and a cycloalkane (b-) having 5 or more carbon atoms.
2), alcohols (b-3), ketones (b-4),
At least one selected from the group consisting of ethers (b-5), esters (b-6), hydrohalocarbons (b-7), and hydrochlorofluorocarbons (b-8).
And the nonionic surfactant (C) is an ether type,
The solvent composition used for cleaning according to claim 4, which is at least one selected from the group consisting of ether ester type, ester type, and nitrogen-containing type. 8. The content of the solvent (B) is 0.1% by weight to.
50% by weight of the solvent composition for cleaning according to claim 2, 4, 5 or 7. 9. A nonionic surfactant (C) is contained in an amount of 0.001% by weight to 10% by weight.
Alternatively, the solvent composition used for the cleaning of 7. 10. The content of the solvent (B) is 0.1% by weight.
The solvent composition used for cleaning according to claim 4 or 7, wherein the content of the nonionic surfactant (C) is 0.001% by weight to 10% by weight.