CS611190A2 - Cleaning agent - Google Patents

Description

£ '/' / '/' 90 - 2 -

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition, in particular a composition suitable for removing impurities, fats and oils, dust and the like, deposited on micro-electronic components, precision tooling parts and the like. In the manufacture of microelectronic components, precision tooling parts, and the like, cleaning is still usually done using an organic solvent that removes dirt, dust, and the like deposited thereon. Up to now, 1,1,2-trichloro-1,2,2-trifluoroethane (R-113), which is non-flammable, low in toxicity and very stable, has been widely used as organic solvent. In addition, the substance selectively dissolves only impurities and does not cause corrosion, plastics, elastomers and the like. The printed circuits to be cleaned are mostly composite products containing metals, plastics, elastomers and the like. Also from this point of view the use of R-113 is very suitable.

However, the use of this substance must be limited, since this solvent probably destroys the ozone layer in the stratosphere and, moreover, may cause skin cancers.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cleaning composition that is harmless to the ozone layer and capable of effectively removing dirt, oil and the like.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cleaning agent which has sufficient ability to dissolve impurities but does not cause corrosion of metal, plastics, elastomers and the like.

Eyl has carried out detailed research to achieve these goals. It has been found that certain aliphatic fluorinated hydrocarbons are (1) completely free from ozone depletion because their chlorine-free molecule, (2) exceptionally capable of removing impurities, fats, oils and dust, and the like; »Only impurities can be released without corrosion of metals, plastics, elastomers and the like. Accordingly, it is an object of the present invention to provide a detergent composition comprising as its active ingredient an aliphatic fluorinated hydrocarbon of the formula:

Where n is 4 to 6 and m is 6 to 12. The detergent composition of the present invention comprises as its active ingredient an aliphatic fluorinated hydrocarbon of the formula above. This compound has never been used as a cleaning agent to remove impurities, fats and oils and the like. Examples of aliphatic fluorocarbons in the detergent composition of the present invention may be those compounds represented by the formula: C 6 F 8 H 4, C 4 F 9 H 3 ', 5 F 7 H 5', 5 F 6 -, 4 ', 5 F, 6 F 12, 2'. be 1.1.2.3.4.4- hexafluorobutane (HCF2CFHCFHCF2H), 1.1.1.2.2.3.3.4- octafluorobutane (CF3CF2CF2CH2F), 1.1.2.2.3.3.4- heptafluoropentane (HCF2 (CF2) 2CFHCH3), 1.1.2.3.3.4.5.5- octafluoropentane (HCF2CFHCF2CFHCF2H), 1.1.2.2.3.3.4.4.5- nonafluoropentane (HCFgCCFgJ2CHgF), 1.1.1.2.3.3.4.4.5.5-decafluoropentane (CF2CF (CHF2) 5'2GE2H), 1.1.1.2.2.3.3 .3.4.4-nonafluorohexane (CF3 (CF2) 2 CH3CH2), 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane (HCF2 (CF2) ^ CF8H) , 2-trifluoromethyl 1,1,1,3,4,4,5,5-nonafluoropentane ((CF 3) 2 CHCFHCF 2 CF 3) and the like.

The above-mentioned aliphatic fluorinated hydrocarbons may be used singly or at least in a mixture. The amount of these hydrocarbons in the detergent composition is not specifically limited, typically consists of hydrocarbons of 70 wt% or more, preferably 80 wt%, or more of the detergent composition.

The composition of the invention may contain at least one organic solvent from the group - 5 - hydrocarbons, alcohols, esters and ketones to increase the dissolving capacity. The amount of this organic solvent is specifically limited, typically 30% by weight or less, preferably 0.5 to 10%, especially 1 to 8%, by weight of the detergent composition. If the aliphatic fluorinated hydrocarbon mixture and the organic solvent can be azeotropic, it is advisable to use it in this form.

Hydrocarbons are not particularly limited. Preferred hydrocarbons are hexane, heptane, isoheptane, octane, isooctane, methylcyclopentane, cyclohexane, methylcyclohexane, toluene and the like.

Useful alcohols are also most specifically limited. Preference is given to saturated alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, sec-amyl alcohol, 1-ethyl- 1-propanol, 2-methyl-1-butanol, isopentyl alcohol, tert-butyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 2-ethyl-1-butanol and the like. Most preferred are methanol, ethanol, isopropanol, n-propanol and the like.

Useful esters are also most specifically limited. Preferred esters are esters of aliphatic acids having 1 to 5 carbon atoms with lower alcohols of 1 to 6 carbon atoms, such as methyl acetate, ethyl acetate, 6 propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, propyl propoinate, isopropyl propionate, methyl butyrate, ethyl butyrate , methylvalerate and the like. These materials are preferably methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.

Useful ketones are not specifically limited. The preferred ketone may be represented by the general formula R - CO - R *, wherein R and R * are saturated hydrocarbon groups having 1 to 4 carbon atoms. Examples of such ketones are acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-penta-non and the like. Of these, acetone, 2-butanone, 4-methyl-2-pentanone and the like are particularly preferred. The cleaning composition of the present invention may further comprise components that the cleaning agents have so far contained for specific purposes. These may be, for example, wetting agents and similar auxiliary agents such as hydrogen-stabilizing, chlorinated and fluorinated hydrocarbons, in which they lessen the ozone layer, fluorinated hydrocarbons containing hydrogen and other hydrocarbons that do not damage the ozone layer and the like. The use of the cleaning composition of the invention is carried out in the usual manner. For example, the composition can be used to manually wipe, form a bath, spray, use oscillation, ultrasound or vapor procedures, and the like. The cleaning agent according to the invention does not damage the ozone layer at all and guarantees the effective removal of dirt. Its solubility is similar to that of the previously used R-113, which means that the compounds selectively dissolve and remove only impurities without causing corrosion of products composed of metals, plastics, elastomers, and the like.

The following examples illustrate the invention in more detail. Example 1

The melt-removal test was carried out using detergents # 1 to 27, which will be shown in Table 1 below, containing as active ingredient 1,1,2,2,3,3,4-heptafluoropentane (7F). pentane), 1,1,2,3,3,4,5,5-octafluoro-pentane (8F pentane) or 2-trifluoromethyl-1,1,1,4,4,5,5,5-- nonafluoropurate (6FDH2).

Tamura F-Al-4, (TamuraSeisakusho) hot melt was applied to the entire surface of the printed board (laminate containing copper). The plate was then preheated at 110 ° C for 20 seconds and soldered for 5 seconds at a temperature of 250 ° C. The plate was then immersed in a cleaning composition according to the invention and ultrasound passed through the bath for 1 minute. The step of removing the flux was evaluated by the following scale i The results are shown in Table 1. 8 A: the flux was satisfactorily removed B: a small amount of flux was not removed C: A substantial amount of the melting agent was not removed.

Table 1 Composition Composition (% by weight) Evaluation of the result Number 1 7F pentane (100) 2 7F pentane (93) ethanol (7) 3 7F pentane (92) isopropanol (8) 4 7F pentane (95) ethyl acetate (5) 5 7F pentane (92) 2-butanone (8) 6 7F pentane (95) methyl acetate (5) 7 7F pentane (93) ethanol (5) ethyl acetate (2) 8 7F pentane (94) ethyl acetate (5) 2-butanone (1) 9 7F-pentane (93) 2-butanone (5) ethanol (2)

Table 1 - Continuation

means composition number (% by weight) evaluation result 10 8? pentane (100) B 11 8F pentane (97) ethanol (4) A 12 8F pentane (95) isopropanol (5) A 13 8F pentane (96) ethyl acetate (4) A 14 8F pentane (95) 2-butanone (5) A 15 8F pentane (96) methyl acetate (4) A 16 8F pentane (93) ethanol (5) ethyl acetate (2) A 17 8F pentane (94) ethyl acetate (5) 2-butanone (1) A 18 8F pentane (93) 2-butanone (4) ethanol (3) A 19 6FDH2 (100) B 20 6FDH2 (80) ethanol (20) A 10 -

Table 1 - Continuation

composition S. composition (% by weight) evaluation result 21 6FDH2 (75) isopropanol (25) A 22 6KDH2 (80) ethyl acetate (20) A 23 6FLH2 (75) 2-butanone (25) A 24 6FDH2 (80) methyl acetate (20) ) A 25 6FDH2 (80) ethanol (10) ethyl acetate (10) A 26 6FDH2 (75) ethyl acetate (15) 2-butanone (10) A 27 6FDH2 (80) 2-butanone (7) ethanol (13) A 11 - Example 2

In order to verify the effect of cleaning compositions 1 to 18 used in Example 1 on plastics, various plastics were submerged, which would be further listed in Table 2 for each of the compositions for 1 hour at 50 ° C. . After removal from the bath, the change in weight of each of the plastics used (expressed as a percentage) was measured and the degree of effect of the following grades was evaluated. The results are shown in Table 2 below. 0: Minor or no effect (0 to 1 # weight change) 1: The plastic material was somewhat habitat, but essentially no problems were encountered. (weight change 1 to 5%) 2: swelling and erosion of plastic mass at the same time (change of weight 5 to 10%). 04 honors resin detergent no co rl oO rt rt o r r o r r o rt r t o r r o r r o r t o o r t o o rt rt o rt oor — 1 t — too rt 04 rt o rt o rt o rt o rt o rt o rt o rt o rt o rt o o o o o o o o o rt rl oo O t o rt o rt o rt rt o rt o t o o rt o rt rt o o o o rt o rt o o rt o o cti o o o o o • o b • Ř j j j j j j ř ř ř ř ř ř ř ř ř ř ř ř ř ř ř ř • H o rt> 5 <0 X • rt +> >> β o> β XO β and β β rj β β and Cti Λ4 o honor honor Xt rt CO X) β si> '03 "'} β -P o> β β what 4-> Hon Ό O «3 and Λ! co Λ • rt rf w ϊ *> XO> 3 rt r — 1 rt O β rt CQ OOO and Cti O aaaoa - 13 - Results in Tables Figures 1 and 2 show that the detergent composition of the present invention is suitable for efficient removal of hot melt residue and does not cause plastic erosion.

A F-AL-4 melting agent (TamuraSeisakusho) was applied to a 10 x 10 cm printed circuit board and the plate was preheated to 110 ° C. Then soldering for 5 seconds at 250 ° C. The flux remover test was performed using the cleaning agents listed in Table 3 so that the printed circuit board was cleaned for 60 seconds using ultrasound and 60 seconds using steam.

After cleaning, the degree of removal of the melting agent with the naked eye was evaluated according to the following criteria. In addition, the amount of ionic residues was also measured by the Omega meter 500 (KENKO) and the value obtained was also used for evaluation. The results are summarized in Table 3 below.

The criteria for assessing the degree of removal of the melt additive with the naked eye are as follows: 14 - A: Seated was removed satisfactorily B: A small amount of the additive remained unresolved C: A substantial amount of the additive remained unremoved.

The criterion for evaluating ionic residues was the amount of residue left on the plate. The result was considered satisfactory if the residue 2 was at most 2 µg NaCl / cm.

Cleaning composition table hcf2cfhcfhcf2h / c2h5oh

"/ (CH 3) 2 CHOH" / CH 3 COOC 2 H 5 / CH 3 COC 2 H 5 HCF 2 (CF 2) 2 CFHCH 3 / C 2 H 5 OH "/ c 3h? Oh" / CH 3 COOC 2 H 5 "" / CH 3 COC 2 H 5

HCF2CFHCF2CFHCF2H / C2H5OH ”/ C3H7OH“ / CH3COOC2H5 ”/ CH3COC2H5 3% by weight of the remainder of the eye / UgNaCl / ca 95/5 A 1.4 95/5 A 1.5 97/3 A 1.5 95/5 A 1.8 90/10 A 1.5 92/8 A 1.6 95/5 A 1.6 90/10 A 1.9 90/10 A 1.3 95/5 A 1.5 95/5 A 1.4 90 / 10 A 1.6 - 15 -

Table 3 - Continuation of detergent composition mass% by eye remainder '2 yUgNaCl / cm ^ hcf2 (cf2) 3ch2f / c3h7oh 95/5 A 1,5 CF3CF (CHF2) CF2CF2H / C 3ΗγOH 94/6 A 1,7' ♦ / CH3COOC2H5 92/8 A 1.6 CF3 (CF2) 3CH2CH3 / (CH3) gCHOH 90/10 A 1.6 HCF2 (CF2) 4CF2H / C2H5OH 88/12 A 1.5 "/ (CH3) 2CHOH 90/10 A 1 , 6 "/ C3H7OH 92/8 A 1.7 / CH3COOC2H5 90/10 A 1.6 Example 4 100 mesh cylindrical wire mesh (diameter 25 and 15 mm height) on which spindle oil has been deposited · was immersed in the detergent bath according to the invention, heated to 60 ° C and ultra-sound passed through the bath for 60 seconds. Then, the wire mesh was immersed in a 40-60 ° C solvent while simultaneously sweeping the sieve or was ultrasonically cleaned for 60 seconds. It was then steam-cleaned for 60 seconds to terminate the 16-detergent degreasing test. The measured amount of oil adhering to the wire mesh with the appropriate equipment (Horiba, Ltd.) and the degree of oil removal was expressed as a percentage. Table 4 below shows the deposition of detergents and the removal of oil percentages.

Table 4 Composition of detergent% wt. oil removal in% HCF2CFHCFHCF2H 100 99.6 CF3CF2CF2CH2F 100 99.3 HCF2 (CF2) 2CFHCH3 100 99.5 hcf2cfhcf2cfhcf2h 100 99.6 HCF2 (CF2) 3CH2F 100 99.5 CF3CF (CHF2) CF2CF2H 100 99.3 cf3 (cf2) 3ch2ch3 100 99.2 HCF2 (CF2) 4CF2H 100 99.2 (CF3) 2CHCFHCF2CF3 100 99.1 HCF2CFHCFHCF2H / n-heptane 70/30 99.9 ”/ cyclohexane 90/10 99.7 CF3CF2CF2CH2F / n-heptane 70/30 99.9 ”/ cyclohexane 90/10 99.6 - 17 -

Table 4 - continued composition of detergent% w / w. oil removal HCF2 (CF2) 2CFHCH3 / n-heptane 70/30 99.9 ”/ cyclohexane 90/10 99.7 HCF2CFHCF2CFH / n-heptane 70/30 99.9" / cyclohexane 90/10 99.7 HCF2 (CF2) CH 3 F / n-heptane 70/30 99.9 "/ cyclohexane 90/10 99.6 CF 3 CF (CF 2) CF 2 CF 2 H / n-hept an 70/30 99.9 · / cyclohexane 90/10 99.7 CF 3 (CF 2 ) 3CH 2 CH 3 / n-heptane 70/30 99.8 "/ cyclohexane 90/10 99.6 HCF 3 (CF 2) 4CF 2 H / n-heptane 70/30 99.9" / cyclohexane 90/10 99.7 (CF 3) 2CHCFHCF 2 CF 3 / n-heptane 70/30 99.9 ”/ cyclohexane 90/10 99.6 The results given in the example section show a very good degreasing power of the compositions according to the invention.

Claims (5)

18 A Pl] TE ΝΓΟ Ε Ε ',.' Ύ; • ν ν '”’' ϋ " A detergent composition, characterized in that it contains as its active ingredient an aliphatic compound of the general formula (4) in which n is 4 to 6 and means Numbers 6 to 12. 2. A detergent composition according to claim 1 wherein the aliphatic fluorinated hydrocarbon comprises at least one compound of the group C ^ FgH4, C5F9H3, C5F7H5 &gt; G5F8H4 &apos; C5F9H3 &apos; 3. A detergent composition according to claim 1, wherein the aliphatic fluorocarbon comprises at least one compound of the group 1.1.2.3.4.4-hexafluorobutane (HCFgCFHCFHCFgH), 1.1.1.2.2.3.3.4-octafluorobutane (CF3CF2CF2CH2F), 1.1.2.2. 3.3.4- heptafluoropentane (HCF2 (CF2) 2CFHCH3, 1.1.2.3.3.4.5.5-octafluoropentane (HCF2CFHCF2CFHCF2H), 1.1.2.2.3.3.4.4.5- nonafluoropentane (HCF2 (CF2) 3CH2F), 1.1.1.2.3.3. 4.4.5.5- decaafluorentane (CF3CF (CHF2) CF2CF2H), 1.1.1.2.2.3.3.4.4- nonafluorohexane (CF3 (CF2) 3CH2CH3), 1,1,2,2,3,3,4,4,5, 5,6,6-dodecafluorohexane (HCF 2 (CF 2) 4 CF 2 H) and - 19 - 2-trifluoromethyl 1,1,1,3,4,4,5,5,5-nonafluoropentane ((0 ^ 3) 2 ^^^ 2 ^ 3) * 4. A detergent composition according to claim 1 wherein the at least one organic solvent is selected from the group consisting of hydrocarbons, alcohols, esters and acetones. 5. A detergent composition according to claim 1 comprising at least 70% by weight of a fluoro-fluorinated hydrocarbon. 6. A detergent composition according to claim 4, wherein the detergent composition comprises at most 30% by weight of an organic solvent. JUDr. Zdeňka KOR & JZ0Mz 'Advocate ^ 60 91VK0