DE1508348A1 - Soldering liquid - Google Patents

Description

OR. ELISABETH JUNQ AND DR. VOLKER VO88IU8 FATtNTANWXLTt 1 b U ö 3 A

• MONCHtN ι * · IHOIIITRAtIEM · TtLCFON MIOtT · TtLIOHAMM-ADfItIIt: INVtNT / MONCHtN

P 7556 December 23, 1966

Shell International? Research MaatBchappij N.V. Ben Haag / Holland

"Soldering"

Priority; December 27, 1965 / USA registration number * 526 313

The present relates to a charge-trt LötilUeeiglceit containing novel components.

In the multi-layer process carried out in the technical MaSatab, a bath consisting of molten ventilation material (customary οληο Miiiohtinc made of lead and tin) must be kept at a high temperature for a long period of time. .Dia T * ap "rntur kaiua while above 232 ⁰ C and are oalbst ⁰ G above 40O. Boi such high Temperatureu can calibrated the goschJBolsene Lötmaos "3 oxidize in air and about form Aich _e 10 unl""3iöhs Miitalloxyde, also ale Kräts" are referred to. S Dp © It is good soldering would be achieved, but the scabies are removed, otherwise the scabies in ^; (5er LQtverbindunc can be located and thereby »Elfc & trizi- ^ t ^iitete ü ^ßnen i ^Q dfsr LötvevbiräüRi and thereby the Kleictriiiitätaleitimß is interrupted or the mechanical

MDUCHtM MlTI ■ 9AMKKONTOi StUJJCMi P * »IK A. O. KCKCKf!). lüC'OLt> 3Ta TI. KTO. MR. W, t BADORIQINAL

See strength is impaired «In the case of a printed electrical circuit, even a very small debris particle can completely interrupt the continuity of the current

In order to report such dross formation, the surface of the molten solder can be covered with a liquid that is in the presence of both the molten metal ala is also relatively stable from air and the dross particles transferred into a soluble state »A liquid with these properties are used in the present description alo means solder liquid>

The soldering fluid according to the invention consists of a) a polyphenyl ether of the general formula

in which η is an integer from 2-6, R is hydrogen or an O ^ _ ₄ -alkyl group and the radicals R can be identical or different, and

1-5o wt .- ^ ό of a Folyphenyläthercarbonsäure the general a formula

(COOH).

(COOH),

• 0-

in which η is an integer from 2-5, χ the value 0, 1, 2 or 3, y is 0, 1, 2 or 3 and the sum χ + y <* 1, 2 or 3 where y is for each benzene ring

90984W075S

BATH ORIGINAL

can be the same or different.

In the formula for the polyphony lather means; preferably each R is hydrogen _t eich the polyphenyl ether is preferably a compound of the following general formula »in which η is a whole number from 2-6,

The ether units in the polyphenyl ether are preferably linked to one another in the meta position, such as in m ~ .'ß.B (m-phenoxyphenoxy) benzene. The soldering liquid preferably contains more than one polyphenyl ether, regardless of whether or not each Heat R is a chemical substance. In this case, the Lb'tflUssigkeit preferably contains a major proportion of connected in taeta position _f polyphenyl ethers wherein nB wenigstenn 50 $ of the phenylene metal'henyleiißruppen aind.

eti of polyphenylethers with f> or wrestle for Benao, which of your preferred formulas en a aind available in landol. I will be coming soon added Iaomer (itiinificlie liexUglioh their Äueammenöetzunf? ange give:

- "-" ■} · ■ ο Πι; ·; '.; ph 'it) ;; y

90984 ^ / 0751 BAD

p-Bia (m-phenoxyphenoxy) - 35

benzene

o-BiB (m-phenoxyphenoxy) - 5

benzene ——

100

m-Bia (m-phenoxyphenoxy) - 65

benaol

1- (m-Phenoxyphenoxy) "? - 28

(p-ph.noxyphenoxy) benzene

p-bin (m-phsnoxyphenoxy) benzene 7

Examples of preferred polyphenyl ethers _β that can be used alone or in mixture are the following:

Bis (m-phenoxyphenoxy) ether; m-phenoxyphenyl-p-phenoxyphenyl etherj ra-Bia (ra-phenoxyphenoxy) benzene; p-Bia (m-phenoxy phenoxy) benzene; o-bio (m-phenoxyphenoxy) benzene} bis ynfm-phenoxyphenoxy) phenylj ^ ether »bis Q> - (m-phenoxyphenoxy) phenyfather; To Jj) - (m-phenoxyphenoxy) phenyl ether;

and m bit ßb ~ { m-phenoxy phenoxy) phenoxs7 beneol ·

Such polyphenyl ethers and their preparation are described in "Synthetic Lubricant"", Chapter 11 (editors" Gundereon & Hart j Reinhold Publishing Company, 1962)

The er: ^;> lncung8i-enjrU3en solder liquids can be 3-50 wt. - 'f.ri'; UßPv, ßlH ^ S - TO Gev / r - '/ o and innb ^ a:: 3Ί »Γ'3 10

9098AWQ7 5I

BATH ORIGINAL

or 10-20 Gew .- ^ contain the polyphenyl ether carbonic acid.

In the given formula for the polyphenyletheroarboxylic acid

may n, den ffert 31 have 4 or 5, with 4 preferably iet.

The solvent preferably contains more than one poly-

phenylätheroorbonsäure «In this case the molecule contains the

Polyphenyl ether carboxylic acid generally preferred 1-3

and in particular 1-2 carbonic acid groups, if more ale 3 carboxylic acid groups per molecule of the acid are present, eo the solubility of the lead and zinc salts of such acids λ in the "Lötflü88igkeit become too low.

Examples of suitable ones are given in Table I below Polyphenyl ether carboxylic acids listed.

»G9-84 4 / Q7 5 · _B AD

TABLE I.

ra- (aenoxy) -m-oarboxy phenoxy ban «β ■

COOH ^ COOH

nH & ie (p-carboxy pheno

OOOH 3- (p-arboxy phenoxy) -3 '-phenoxy jii phenyl «ether

4- (p-fiarboxyphenoxy) -3'-phenoxy ^ diphenyl ether

3-Bhenoxy-5-carboxy-3 '- (p-carboxy phenoxy), _ £! pheny l «ther

Cr ⁰ Xr ⁰ Xr ⁰ Xr ⁰ X) ^

- (m-Bhenoxy) phenoxy-m- (p-oarboxyphenoxy) phenoxyben

«Tie

HOOC COOH

ra- (p-carboxyphenoxy) phenoxyl bensem

Xr ⁰ Xr ⁰ X ^ - ⁰ Or ⁰ -

Γπ> - (p-omfrboxyphenoxy) phenoxy!

BATH ORIGINAL

These polyphenyl ether carbonic acids can according to any one of Working method "hereeetellt are used for the production of carbonic acids is known to eich · For example can a Grignard method can be used for this purpose. In In this case the ether used as the exit surface can be used with e.g. bromine to form the corresponding bread derivatives halogenated, which is then reacted with magnesium and then carbonated with dry ice «That too can Bromine derivative with 2.B. Hodium cyanide are implemented and the The cyano groups formed are then hydrolyzed to the corresponding carboxylic acid groups. A different way of working consists in the etcher used in all output material react with phosgene in the presence of AlCl ^ and hydrolyze the reaction product. Another possibility

9098AA / 0756

is to provide a Alkylpolyphenylather with a etarken Oxidant _t like to oxidize, for example, a permanganate, nitric acid or Chromsäurs. The preparation of carboxylic acid using the above and other procedures is described in "Synthetic Organic Chemistry", Chapter 13 (Wagner and Zook, Wiley & Sons, 1955).

The invention is illustrated by the following example explained in more detail.

a) Manufacture of polyphenyl & therd ioarboxylic acids Kt? Polyphenyl ether dibrcmine were prepared in the following manner from bromine and an isomeric mixture of unsubstituted polyphonyl ethers with 5 benzene rings in the molecule, with ra-bio (m-phenoxyphenoxy) benzene predominating. 669 g (1.5 mol) dee Isomerengomisches were dissolved using a Dreihalskalbens of 3 liters of capacity, equipped with a Rührer5 dropping funnel and a condenser in 500 cc of carbon tetrachloride ο The resulting mixture was heated to 40 - heated 50 ⁰ C, and 480 g of bromine were then added dropwise. This mixture was heated with stirring for about 10 hours, the original red-orange color in the light (Jeil) above would The reaction mixture was then cooled and poured into Wanser, and the organic layer was separated _o v This organic layer / URRE zweofcs removal of nichturageeetztem bromine and ¹ ■ .viihrend tfsr reaction Brorswasserstoffes formed with eirer

9098 A A / 07 5d

- ■ ■ ORIGINAL BATHROOM

- * - 15083A8

Washed with a dilute base « Kb was followed by a wash until the wash was neutral. The organic layer was then dried over calcium sulfate and the carbon tetrachloride was removed by vacuum distillation, whereby the desired polyphenyl ether dibromito with a Bronf content of 25 _f 2 wt. In the form of an orange syrup was obtained. The calculated bromine content is 26.4 wt <, - # and the yield of the dibroinides, based on this bromine "content, was 95.4?" the theory. '

Using 200 g of the polyphenyl ether dibromides produced in this way, A solution was prepared from 162.8 g of n-propyl bromide and 200 eom of dry tetrahydrofuran. o This solution was added to 52.2 g (2.15 mol) of magnesium napkins, which were covered with dry tetrahydrofuran and placed in a three-necked flask with a capacity of 5 liters " the one with a stirrer, a dropping funnel, one with drying tubes provided condenser and a gas inlet was provided. To get the action going, a few drops were made the polyphenyl ether bromide solution and an iodine crystal added = Further addition of the dibromide solution was made to such an extent that a gentle reflux was maintained After the addition was completed, the mixture was left reflux for several hours and then cool it down.

Dry carbon dioxide was then passed into the reaction mixture in order to remove the Grignard compound formed au carbonate, whereby the heating flask is removed

the heat of reaction was cooled. The mixture was then filtered through a plug of glass wool to remove excess magnesium, and then diluted old Hydrochloric acid acidified to release the carboxylic acid. The mixture was diluted with benzene and the sioh formed Layers were separated from one another in a separating funnel. The benzene layer was nibbled several times with ./asaer to remove the butyric acid formed. The washed benzene layer was then dried and vacuum distilled to give a brown, glassy residue. This fiückatand could be powdered, but sintered when Let stand together again to a glass * This residue represents the desired polyphenylatherdicarboxylic acids. Er showed $ 65.3 of the theoretically calculated acid number of 210. It contained 1.01% residual bromine and an average of about 1.2 Carboxylic acid groups per molecule, whereby this carboxylic acid « groups mainly in the para position at the terminal ends ^ Phenylene groups were located.

b) Production and Properties of the Liquids The polyphenylene carboxylic acids and polyphenyl ethers obtained in this way were used to produce the L liquids given in Table II, which also contain solder liquids for comparison which do not correspond to the invention specified for a solder bath with a temperature of 371 ⁰ C «

90984 4/07 58

The polyphenyl ethers used are ee eich a A mixture of phenyl ethers with 5 benzene rings in the molecule, m-bis (m-phenoxyphenoxy) benzene predominating.

TABE LLE ^ Π

Lptflüealg Celtic Lebenadauer h _t Polyphenyl ether +> 8 1/2

10 wt. ^{1/5 of} the dicarboxylic acids

Polyphenyl ether> 11

20 wt.% Of dicarboxylic acids, etc.

Polyphenylenes! Alone '1 1 / 2-2 Commercially available lot 2.4

liquid consisting of a mineral oil and a considerable amount of fatty acids

The lifespan of the different soldering fluids was determined by means of an Ilollia "Peewee" wave soldering device. The soldering fluid was located above the molten solder in a pot, never let the melt melt and susacmen with oil through an elongated nozzle pumped, whereby a fountain of the wave deo Ltjtmittelc formed T / urde. The point in time only the occurrence of the individual Metnlloxyd «n in this ao produced VZeIIa oJer I'ontHnc otellt (Ji »I-leveledauQT dar ·

According to the numerical values in Table II, it can be seen that the addition of 10 or 20 % by weight of the polyphenyl fctherdici i>v'l : - ν

acids a significant extension of the service life can be achieved «In the absence of these dicarboxylic acids , sludge collects very quickly in the soldering liquid and large amounts of metal oxide form on the molten metal melt, which prevents effective operation.

90984 4/0758

Claims (1)

Claims a) a polyphenyl ether of the general formula in which η is an integer from _{2-6, R is hydrogen or a G 1} , -Alky! group and the radicals If. can be the same or different, as well as up to 50% by weight of a polyphenyl scheroarboxylic acid of the general formula (GOOH) _x O- - (COOH) ₁ in which η is an integer from 2-5, χ has the value 0, Ip 2 or 3, y has the value 0, 1, 2 or 3 and the sum χ fy = 1, 2 or 3, where y is each Benzolrixig can be the same or different. 2c soldering flux according to claim 1 ₉ characterized _s that it comprises a polyphenylene ether, wherein each R 7 / asseratoff meant 3-1 soldering liquid according to claim 1 or 2, characterized in that that it contains a polyphenyl ether with a meta bond \ -, ijöt.Qüeaigkeit according to Amiprueh 3 » characterized in that c'5 contains i \ 'Uiü (jn-pbenoxyphenoxy) benzene. 90S84A / 075 « -t *. 15083A8 5. soldering liquid according to claims 1-4, characterized in that it contains more than one polyphenyl ether. 6ο soldering liquid according to claim 5 »characterized in that In the mixture of polyphenyl ethers a larger proportion of Ether with meta-bonds is included. 7. soldering liquid according to claim 6, characterized in that) it contains an isomeric mixture of polyphenyl ethers. 8 »soldering flux according to claims 1-7, characterized in that it _o 5-30 - contains the $ Polyphenyläthercarboneäure" 9ο soldering liquid according to claim 8, characterized in that it contains 10-20% by weight of the polyphenyl ether carbonic acid. 1Oo soldering liquid according to claims 1-9 _f, characterized in that it contains a polyphenyl ether carboxylic acid in which η has the value 3 »4 or 5 o ο soldering liquid according to claim 10, characterized in that it contains a polyphenyl ether carboxylic acid in which η has the value 4, 12ο soldering liquid according to claim 1-11, characterized in that it contains more than one polyphenyl ether carboxylic acid » BAD ORJGINAL 909844/0758 13 · Soldering liquid according to claim 12, characterized in that that the polyphenyl ether carbonic acids contain on average 1-3 carboxyl groups in the molecule. 14ο Lötflüesigkeit according to claim 13, that the polyphenyl ether carbonic acids on average 1-2 carboxyl groups in the molecule contain. 909844/0758