DE2230366A1 - METHODS OF REDUCING SURFACES - Google Patents

Description

• * · · · · • k 2230366 PATENT LAWYERS * · ·· · 21 «June 1972 DR.-INQ. H. FINOKE
DIPL.-INQ. H. BOHR. 8 MUNICH 8,
M0ll * rttra6 31 DIPL.-INQ. S. STAEQER

f · t »r μ fi · 2ί iOiO

Folder 22914 - J) r.K / hr Gases MD. 24018

IMPERIAL OHIMICAL IKI) D3! ERUäS LIMIIJBD,: ^r .ondon „· Groasbri banuien

"Procedure to reduce the tendency to cling

Surface "

Priority i June 23, 1971.

Invention relates to a YtrbesBertae process to reduce the formation of a Besohla / i? s on solid Surfaces.

Fogging is caused by the condensation of water droplets on a surface. Ee ietnöglioh _r prevent the fogging by causing inan. ,, that the condensed ViaHsar is deposited as a uniform thin pila on the surface *

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the invention is now a 1 / experienced. sjur ^! /err.lnßgiirung C.QT Preclilagin the surface, which is carried out by applying a composition to the surface which contains an odorous agent which has a hydrophilic G.rupps urii a fluorocarbon group with at least 3 Eolil _s

According to the invention, a Antibesc eotaung is also proposed, the Blch läira Anf'bvxngo-n on firm? Surfaces suitable and dia an obsrfl'lciienakuive-s means, which has a hydrophilic Qruppa and aine Perrfluorokohlsristof ^ group with at least 3 carbon atoms, in mixture; with a hydrophobic Substana, the ala ö'abstans defines eei, which is not fee- is etched, that is, that water has an account object on it, does not practice ^ is = zero

The erfindimgsgemässe Zusanaat? Ns © ti3uag may also contain other hydrophilic compounds as the Pluorokohlen fabric surface means advantageously as ZO3 _e a surfactant "for example, a Albälimetallaal? ,, vor2iug8 ¥ 3i38 a Watriumsalszi, eii Suifosuociaaatsstsrs i.at. The esters are derived from aliphatic alcohols. Ef? is preferred da.3s en trloh ii'ß d.:u; Octyl-, Jio'iyl- and Tridecylalkoho3.eater handeli; »

Thus, the invention {jernäss WSIT srhin a Antibeschlagzusaminenöetziung vorgeschiag € rii, the check S5um ei.yaet application to solid surfaces and a ob.jrflächenalilives means wölcheß a hydrophilic group and a PcrfJuorokohlsnatuffgruppe with at least '■} carbon atoms comprising in admixture with a hi'drophobic lifting punch, which defines as substance oei,

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which is not occupied by water, and one that is water-soluble hydrophilic compound that is not a fluorocarbon compound is, contains

The hydrophobic substance '1st in the ZusammensetEung as a carrier and stabilizer present »urs clae active, ^ fläclienmittc-l ale gleichmässiKen film hold Zn on the surface of the Be3ohlagen preventing Fluorokohlenstoffobe on which the Zf.sairanenseteuug has been applied * Ea is desirable that the hydrophobic substance has a high viscosity and itself has the property of forming a thin I ¹ IIm on a surface * Examples of preferred hydrophobic substances are: polysiloxanes or silicones, which can be either an oil or a fat; Hydrocarbons in the form of oils ₅ fats or waxes, such as Brdölgallertö; naturally occurring waxes or resins such as beeswax and carnauba wax; viscous oily organic liquids such as plasticizers; in particular phthalate or sebacate esterj or fluorocarbon oils, such as betrafluoroäthylenollgomere or fluorinated biphenyls "

The hydrophilic compound other than a fluorocarbon compound may be an aliphatic-hydroxy compound such as a glycol, glycerin or polyglycol. It can also be a bilozane or fo3.ysiloxane that is substituted with hydrophilic groups, such as sulfonated phenyl groups or oxyethylene chains, preferably χει ά ± ν h; rc'.rophilic compound a surface-active compound * are examples of particularly suitable compounds Alkali metal salts of sulfoauccinate esters i?

Lie FluorocolilonstorrfoberiMächf -mittel that go-Nästs d-: ir Srfin-

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BATH ORIGINAL

used as anti-fogging connections; can be usefully added to any common anti-fogging amrose composition. A considerable improvement in the durability of the anti-fogging effect can be observed in conventional compositions due to the presence of a fluorocarbon compound and the synergistic effects of the fluorocarbon compound with other surface-active compounds or anti-fogging compounds, examples of conventional anti-fogging compounds in which this effect is observed can be "are, for example, ethylene glycol *, Satriumalginat / Leija-Gemiache, Katrlumoley! sulfate, aliphatic polyvalent © compounds and compounds containing Polyäthylonglykolketten. If the conditions are so strict that fogging cannot be prevented, then the speed at which the fogging will disappear is increased if the compositions according to the invention are used *

That surface active agents containing a hydrophilic group and a perfluorocarbon group having at least 3 carbon atoms (presumably as an encoding aliphatic group) is the essential element of the present invention. The perfluorocarbon group can either completely or only partially form the fluorocarbon group of the molecule. Thus, the perfluorocarbon gj.T7.pjje can completely or only partially form a branched or straight perfluoroalkyl or perfluoroalkenyl group. Groups that contain water atoms, such as phenols, alkylene, amido or ester groups, can be present between the said terminal perfluorocarbon group and the hydrophilic part of the ϊ-molecule. or Perfluorote: ri; .- bui :: / lgruppc asin _: is a'o ^ r prefectively a «group that

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BATHROOM ORiGINAL,

a terminal chain of at least 3 carbon atoms contains, as s.B. a final part of a straight riuorο-alkyl chain ClMG]?,.) - or a terminal part of a branched en perfluoroulkeiayl or PeKTxluoroalkylgruppe. In the As a result, examples are given in advance:

(GF) JSHW ₂ )

= C

Alkali metal, ammonium and alkyl amisals of periluorocarboxylic, phoaphoric and sulfonic acid (anipnisoh) or nonionic polyoxyalkylene ketfcon with branched or straight chain perfluoro groups are materials which are suitable according to the invention. While it is preferred to use the anionic and nonionic fluorine-containing surfactants described above, it is also possible to use the middle surface area _for either a straight or a branched perfluorocarbon group, as noted above, and a cationic group Group, such as a quaternary nitrogen group, and optionally a neutralizing anion either in a covalent bond on the molecule (amphoteric) or in paired ionic ionization (cationic). Of these, the amphoteric products are preferred, but the following types of anionic and non-ionic substances are preferred for compounds that are easy to prepare:

■ ORIGINAL BATHROOM

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R _f SO

R _f

R 0 (CH ₉ CH ₉ O) R.

where R stands for a water atom or a short alkyl group

and R "stands for C F_ _j4 or C f ~ _t , where η β, 8, χ η 2η + ι η 2η-1 * * '

10 or 12 means, such as, for example, 11-O ₃ P ₁₇ or the branched groups C ₁₂ ? ₂ ,, C ₁₀ ^ q * C ₉ P ₁₅ and CgJf ₁ -, which are derived from ^ etrafluoroäthylenoligoaier · », χ stands for an integer from 1 to 40, m for an integer from 0 to 6 3teht, M for hydrogen. Alkali metal, Aliamoniuni or s-lkjlsubstituierter ammonium.

Examples of cationic surfactants are following:

R _f SO ₂ H (R) (OH

wherein R ", R and 'ra are those given above. 3eAoutu: own

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and Α "stands for an anion consisting of chloride, bromide, iodide Or methyl sulfate is selected.

It is preferred that the fluorocarbon groups derive from tetrafluoroethylene or hexafluoropropene oligomers, since these oligomers are a relatively cheap source of branched fluorocarbon chains. It is preferred to use compounds which have the perfluoroalkenyl groups C ₈ ^ ₁₅ * ^g <\ qFiq ¹ ^ ^G i 2 ^ 23 ^contain ' ^fcen '' ^Ater another group conveniently derived from the Cj ₀ F " ₀ oligomer is the group CqHF _- , g, and compounds containing this group are also included eminently suitable for the purposes of the invention.

Processes for preparing many of the above-described surfactants containing branched fluorocarbon groups are described in British Patents 1,133,822, 1,148,486, 1,176,492, 1,155,607, 1,270,661 and 1,270,662. If R * stands for an even group of the formula Q _n P _{2 +} i, then suitable compounds can be prepared according to the specification of GB-PS 1 270 838, examples of the compounds which are given by the method of the last Patent specifications that can be produced are:

O (CH ₂ CH ₂ O)

where M, A, χ and m have the meanings given above »

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It should be noted that in the main number of derivatives a hydrocarbon group or a group between the Perfluoradical and the hydrophilic group is present, Ee is clearly desired that the hydrocarbon group or other group does not have a big influence on the properties of the molecules should exert the effects of the perfluorocarbon chain get lost. Therefore ββ is preferred that the number of carbon atoms in a hydrocarbon chain, that between the fluorocarbon group and the hydrophilic center, should not be larger9, ale the total number of carbon atoms in the perfluorocarbon group. For this purpose, a Benaol ring is used as a chain with 4 carbon atoms in the hydrocarbon part. Also count Carbon atoms in branches of an aliphatic chain or substituents on an aromatic ring do not have all chains of carbon atoms.

The compositions can be prepared for application in any convenient physical form. Examples of these are liquid solutions or emulsions or a waxy solid, solutions can be prepared in water or in mixtures of water and organic solvents, preferably alcohols, for example methanol, ethanol or Ieopropanol, a gel can be prepared in a two-dimensional manner by a gel component, such as agar-agar, carboxymethyl cellulose, polyacrylamide or gelatin, is added as an aqueous solution of the other components. Jette and oils such as a "B, hydrocarbons _r silicones or esters can be advantageously incorporated WeißQ, both to increase the detention of the composition on the surface nls also in some cases, the spread of the active components on the surface to be

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BATH ORIGINAL

support. If sufficient surfactant is present is (and, if necessary, conventional surface-active hydrocarbons can also be added), then can an emulsion of the fat or oil in the aqueous solution violent beating or stirring of the vegetables can be produced. This emulsion then becomes stiff and sets when a gelling agent is present. The nature and the concentration of the gelling agent determines the viscosity of the finished Gathering. It can range from a liquid cream to au a stiff jelly. The former is used for the purpose of Preferably spread over large surfaces.

The composition is applied to the surface as uniformly as possible with a wiping action, left to stand for a short time, for example a few seconds to 5 minutes, preferably about 30 seconds, and then polished off with a white cloth or paper. A cloth or paper can also be impregnated with a composition. If necessary, the composition can be sprayed onto the surface, for example from an aerosol container. In this type of application of the fluorocarbon compound, a compound is preferably selected which is considerably soluble in the propellant. For example, 0 is _4Λ Ρ. _η 00 _£ Η _Λ 80 ~ ifeiuH for use with fluorocarbon propellants in two ways. A finished composition with the physical consistency of an ointment is desirable if the composition is to be applied to the surface by hand. However, less viscous emulsions are preferred when the compositions are to be sprayed over the surface.

The compositions according to the invention are suitable for

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bring on surfaces of solids, such as s.B. on the smooth, shaped or polished surfaces of metals, Glass and plastics. The present invention is natural especially with transparent surfaces and especially with optical glasses or optical plastic coraponents useful, duroh which Lieht should go through. But it is also equally good with light reflecting ««! surfaces usable, e.g. with metals, especially with surfaces, those with the metals chrome, aluminum, copper, nickel, gold or silver coated bind.

The invention is preferably applied to the surfaces of glass or plastics such as polystyrenes, polymethacrylates or poly (4-5 Ethyl penteG) used, which for optical Components can be used, such as ss * B. for lenses. The invention is particularly useful for keeping the outer line clear useful by optical instruments from eis ^ a fitting, such as r., B. with telescopes, binoculars * ^. cameras, spectroscopes, optical pyrometers and glasses »especially if the the latter can be used for sports purposes.

When the composition has been applied to the surface and if the surface has been wiped, then there is a tendency for water droplets to fog up and a deterioration in optical behavior, which occurs due to a distortion of the image, which o is formed by the transmitted or reflected light. Usually a fogging cannot be detected if the compositions described here are used, but if fogging occurs in extreme conditions, then this fog will not last long. The normal optical properties of the surface will be reduced after a shorter period of time

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received back as it "with an untreated surface of the Case 1st.

There are many diverse applications where fogging of the optical surfaces of mirrors and lenses is undesirable is and where the invention results in improved vision »Examples for solo applications are glasses or protective goggles, Lenses and mirrors, and “was especially good when using these come into contact with a humid atmosphere or are in close proximity to a source of water vapor, such as a “B. at Bathroom mirrors, dental mirrors or eyeglasses made by Athletes, motorcyclists or industrial workers. Other examples are large panels, such as double ones Glazing of windows, motor vehicle windshield windows, Observation windows on machines, instruments and chemical plants.

example 1

A solution containing 4 g of agar in 100 ml of water was heated ^{to 90 0 G.} At this temperature, a solution of 1. £ g of the surfactant C ₁ ^ ₁ gOCgH ^ SO "Na ⁺ in 2.0 ml of a mixture of isopropyl alcohol and water (containing 40

.-i »isopropyl alcohol) was added but the agar solution under vigorous stirring, a mechanical whisk was used. Haoh was about 1 minute; a uniform mixture was obtained, and then 1.0 g of a silicone vat was added with vigorous stirring continued until a uniform mixture was obtained. The Jrimilaion was cooled to room temperature and ₅ wurds eiiiö gelled emulsion obtained easily XAIT DSSM finger or einsm cloth was spread =

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The emulsion was spread on a glass lens, left for 1 minute and then removed with tissue paper. The lens appeared clean and let the light through clearly. ^{The lens was cooled to 10 °} C. in a stream of cold air and a person ventilated several times. But no fogging could be found,

Example 2

Compositions were prepared as gelled emulsions similar procedure as in Example 1 prepared. The components Each composition was as follows

A Fluorokohlenetoffoberflächenmittel the formula C ₈ F ₁ j-OCgELSQJHa ale solution in a Ieopropylalkohol / Waeser-Gemiech (40 vol ~ # isopropyl alcohol) at a concentration of 30 g surface means a j ~ L6 100 ml sungsmittelgemiBCh.

B is fat or oil, which is either petroleum fat, among other things (Vaseline *) (Bh) or an ällikonhahnfett (Bs), like ea used in chemical laboratories acted.

C Commercially available anti-fogging agent which is a sulfosuccinate salt, dae with the designation OT 75 is manufactured by American Cyanamid.

D agar-agar.

£ Distilled tfaeser.

The weights of each component used to make each composition are given in Table 1 below:

⁺ "Vaseline" is a registered trademark.

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Table 1

Together-
settling
Mr. weight of the component in grams 2 C. D. 85 A. B. 2 85 1 Bh Bs 10.7 2 85 2 2 10.7 2 85 3 5 2 10.7 2 85 4th 10.7 2 5 5 10.7 2 5

The relative effects of the compositions and the anti-soling preparation were tested by applying them to a glass plate and rubbing the glass plate with a cloth to polish off the composition The plate and, after 3 months of storage, the treated plate was carried out. The tea used consisted of placing the glass plates in a ^{cooling cabinet set to 0 0} O for 15 minutes, removing all glass plates from the refrigerator at the same time and observing the clarity of an object which was observed simultaneously through each plate. It was found that all panels were currently fogging up. But some became clear much more quickly than others. The order of effectiveness was determined as follows:

Immediately -4) 5 = Cb 2 > 3> 1> untreated plate

After 3 months -4> 2> 3> 5> 1>

uii treated plate

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- 14 ~

Example 3

The same compositions as in Example 2 were made up Glasses tested that were worn τοη players, who played the game of squash racquets. From three individual Players became independent on six separate occasions determines the times that occurred up to the point when the treated glasses were worn during the game " The mean times are below for each composition specified:

4th composition 1 10 Minutes 3 - 15 Minutes 4th - 60 Minutes example

Overall, a gelled emulsion was formed by a similar Procedure as produced in example 1 *

The components of any Zuaanaa neze were as in game 2, euseer that the "fluorocarbon surface agent" was replaced by an aioht-ionisohe or cationic ^ sample and that SilUconfett in a composition by oin Silicone oil was replaced. Details of each composition are given in table 2:

Table 2

Together
settlements
ITr. Weight of the components in grams Bs C. D. S. 6th
7th
8th A. 2 (oil)
2
2 10.7
10.7
10.7 2
2
2 85
85
85 h ⁵
A ₇ 2
A ₈ 2

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A, - C _n F ₁ CQO ^ H ₁ SO_Na 30 # solution in isopropyl

⁰ α 15 ö 4 ^ alcohol / water mixture

A ₇ C _1n F ₁ QO (CH ₅ OH ₅ O) ^ C _1n P ₁₀ Used as a solid, the ι lu iy id ο ι υ iy _TO rfier in hot water on ge

was resolved #

^{A "0} In ^ iO ⁰⁰ ACH ₅ (N ⁺ Cj-HjCl used as a solid which ö ι υ ι y ο 4 ά 5 5 placed in hot water previously had been dissolved.

The success of the effectiveness of the above compositions was determined in the same way as in Example 2 Resiiltates were 4> 7> 6> 8 ^^ 2, when compared with the effectiveness of compositions 2 and 4 of Example 2.-

Sb were solutions in isopropyl alcohol prepared containing 1 wt .- ^ silicone oil, 1 · ^ Qew of Batriumsalsee of Dioetyleeters of SuIfobemateineäure and 1 f »of the following Fluorokohlan- * stoffoberfläoheaaoittel.:

Mixture of ₁₀₁₉ g ₄ )
and C _Q F _4C ΟΟ, Η.δΟ, Ιίβι)

₂ CH ₂ O) ₁₄ H

C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ COONa O

(CFj ₅ CF (CF ₅ ) COO "C ₅ Hp-NH," ¹ "η = 6-9 D

A few drops of each solution were placed on separate glass plates applied and spread out with a cloth and polished clear. Fogging of each plate was determined at room temperature by ventilating the plate. The WirkBomkeil » the anti-fog coating was applied to an untreated panel compared. The untreated record was padded every time very light, but none of the treated platters, aeigto any-

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a tendency to fogging at room temperature *

The order in which anti-fogging is effective * *
ratios was thereby determined that a jedö plate to ~ 2 ° C cooled and then it was brought into the normal atmosphere. Ea it was observed that the untreated plate and plate J) have a strong padding, while plates A, B or G Bieh do not fog up. Then each became
Plate cooled down to ^{-20 0 O uno.} brought into the atmosphere.
It was observed that plates C and D es very rapidly
Rereietsn, but the plates A and B for a few minutes remained relatively clear.

Example 6

A series of compositions was prepared by carefully grinding the compounds in Table 3 with the consents given in Table 3 into a paste and dissolving the mixtures in a solvent, consisting of 2 parts by volume of leopropyl alcohol and 1 part by volume Waeser consisted, Dio solutions were in one
Aerosol container introduced, with a quantity of Difluorodiehloromethan added \ iurde.

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Tabel

Wt .- $
Wi ₉ ⁰ WS ** 0.3 Gew, - # an
CH ₂ OOOO ₈ Hj ₇ Weight - ⁰ A.
silicone Anti fog--
classification - O CHCOOC ₀ IL
I all
SOYYes 0.3 0 0 1 0.3 1 0 2 0.3 0 1 3 0 _r 15 1 0 3 0.15 1 1 4th 0.15 0 0 1 1 0.5 0 3 0 0.5 0.5 4th 1 1 + 5 0 0
i 0

The concentrations of each component are all weights · * percentage, based on the total weight of the alcohol / WaBoex · solution, printed out

The silicone used was a water-soluble silicone which contained polyethylene oxide chains attached to the silicone units were knotted «An exception was made with the composition, which is marked with +, in which the silicone is a normal one hydrophobic oil was. which was mixed with the aqueous alcoholic Solvents a Z> / e.! Phase and not a Si '& phase system formed.

Glass plates were filled with each solution of dsm aerosol

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10 ~

Miter splattered and polished off after 30 seconds. The plates were then ^{cooled to 0} ° C. and returned to the laboratory at 20 G from 0 = e instantaneous fogging to 5 * no fogging varied during the time it took for the panel to reach room temperature.

The anti-fogging ratings of each composition, which Pressure was added to the plates in Table 5.

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Claims (16)

• 19 - PATMGAHSPRtJCHEt 1 »Method of reducing the slope of a surface for fitting, daduroh marked, daes one on clie Surface applies a composition that has a surface-active Contains agent which has a hydrophilic group and a perfluorocarbon fgruppe with mindecterie 3 carbon atoms having. 2. Anti-bash pad composition that sioh sum apply on solid surfaces, characterized in that they a surface active agent comprising a hydrophilic group and a perfluorocarbon group having at least 3 carbon atoms has, in a mixture with a hydrophobic substance, which is not wetted by water, contains. 3. Composition according to claim 2, characterized in that that the hydrophobic substance consists of a polysiloxane or a hydrocarbon. 4 »Composition according to claim 2 or 3 or like them has been specified for the method according to claim 1, characterized in that it is also a water-soluble hydrophilic Contains compound that is not a fluorocarbon compound, 5. Composition according to claim 4 »characterized in that that the water-soluble hydrophilic compound that käine Is fluorocarbon compound, an alkali metal salt of a Sulfosuccinataaters is. 6 »Combination according to -Snßpir.ch 5, characterized by that egg sulfosucoinate ester is an alkyl ester, BATH ORIGINAL 309810/0958 7 · Supplementary payment according to claim ^! j, characterized in that the hydrophilic compound is the liatriuraealii of the octyl ester of üuifo "berneteii: 9äurö. 8. Composition according to claim 4, characterized in that d? it is the water soluble compound that is not a fluorocarbon it consists of a glycol, glycerine or polyglycol " 9. Composition according to claim 4, characterized in that deas the water-soluble compound, the koin Pluorokohlenetoff let, consists of eir-am polyailoxane, which is sulfonated with Phenyl groups or Üxyäthylenkatten is substituted. 10. SussLTinenBetzung according to one of the preceding claims, characterized in that the perfluorocarbon group alt at least 3 carbon atoms one ending continuously · aliphatic Perflttorokcbienetoffgruppe is » 11. Composition according to Anapruoh 10, characterized in that the Perfluorokohlenetoffgruppe a Terevelgte ö9jbt straight-chain perfluoroalkyl *. or perfluoroalkenyl group which has 6 to 12 carbon atoms. 12. Zueamraenoetch according to claim 11, characterized thereby, gekennaeicrust, that the perfluorocarbon group is a highly refused group is where et? is a residue of an oligomeric compound of tetrafluoroethylene or hexafluoropropene. 13. ZuearameDBetEung according to claim 12, dedux'oh gekennaeichnet that -jiβ rerflv>ro.kohlenstoffg; 7up »fe the Porael C ^ P._, ^g q ^» c * C ^ _n P ₁ . oiler C ₁₀ P- cries. 309810/0958 BADORIGfNAt 14 »zucainme; seCZUHf-; iiiah a ä-s-r VOi'liergcner.döi? Expectations, known'jhne-b, because ^ .j she aut Ί a "relieni.i tt] ent 15 ZuuamflienaetKUii, ^ ne3h Claim 3 4, d ^ that then oiling agent "" .ass agar-agar Oier u-elatiae bc. -ht. 16. Sueaityneneetziuig iiaah an aspräcLa preceding it, d ^ duroh konz.3ichnet ,. that be also one contains. (ML-MO. H. HKCXt DlPt. IMG rl · Ο »ι» OMd-IMG 309810/0958 BAD ORSGINM.