DE1646160A1 - Method for connecting substrates - Google Patents

Description

The present invention relates to methods for joining various substrates ("adherends") with ammonium polymer salts, in particular the use of ammonium salts of aliphatic olefin polymers containing carboxyl groups.

It is known that polymers containing polar groups adhere to various substrates or can be bonded to them. Such polymers containing polar groups have been applied to various substrates, for example by extrusion coating, compression molding, solution coating, etc. However, these processes have some undesirable features due to the large-scale plant lots of work space. the solution coating of organic solvents avoids some of the disadvantages of the Strangpreßüberziehens, but provides its own problems in terms of toxicity, fire _t cost of solvent recovery, etc.

1098287142 2

BATH ORIGINAL

It has now been found that aqueous solutions can be applied AliiDatic ^ -olefin polymers containing carboxyl groups on many different substrates ("substrates, adherends") can be used. The use of cheaper, non-toxic Aqueous solutions were made possible by using the ammonium salts of these carboxyl-containing aliphatic olefin polymers. Since they are soluble in water, the ammonium salts can easily applied to the desired substrate and leave a deposit which, after drying, releases gaseous ammonia into the open air

Carboxyl group-containing, aliphatic (\ -olefin polymer is converted back. This conversion can be accelerated by heating.

This method can be used for many purposes. So is, for example, a large flat, with an amino polymer salt solution treated surface after the reconversion into the polymer containing free carboxyl groups an object before that consists of the substrate plus a continuous coating . consists of a polymer, which either as Lberzuc per se , or as an adhesive surface for further bonding of the coated Object can serve with a further substrate, complex shapes can be coated just as easily as flat surfaces,

The method of the invention provides a means of covering of the substrates listed below and for joining two or more of these substrates in large or finely divided Forms themselves of colloidal dimensions, the present

109828/1432

• BATH

Invention * therefore ranges from joining a relatively small Number of substrates in continuous or integral lOrm up to an infinite number of small epidemics with dimensions a size of colloidal glow. .

"Furthermore, the present invention relates to bonding large substrate structures with substrates in small part chen £ orm. E.g. a powdered material with a be connected to a flat surface. The carboxyl-containing ^ -olefin polymer can be used to bond the pulverized particles together as well as serve to bind to the flat surface.

Substrates such as non-woven fabrics, which are composed of a tangle of i ⁿ ils or thread and which cannot be easily connected by simply extruding or pressing, are easily connected into an integral fabric by the above method. By soaking the non-woven fabric in an aqueous solution of the ammonium salt of the oxyl-containing olefin polymer, the salt solution can easily penetrate not only to the surface of each fiber but, by capillary action, into every fiber. By heating to 20-1 € 5 ° G for at least one minute, the free carboxy-containing o (-olefin polymer is formed in the surfaces which are directly inaccessible to the carboxy-containing polymer itself *

HolzobeiSläclien, which by the aqueous ammonium salt polymeri * - s al; Solutions that are easily penetrated are made waterproof by leaving them for at least one minute at room temperature immersed in the solution and then for at least 20 seconds dries at 20-165 g. The pressure is not critical.

- The method according to the invention is also easily applicable in the Paper industry for the production of paper coated with Von, 'being the' ammonium salt, slurry with the clay; on there paper to be treated is applied, a bond between the clay particles themselves and between the de- 'ion particles and your paper substrate causes ... The reaction conditions necessary for this paper covering correspond to those currently in this field applied. Conditions such as heating to 50-1'75 C. for at least a minute.

The method according to the invention can also be used in the formulation common floor polishes are used and delivers thin Floor polish that is waterproof after the gradual release of ammonia »The aliphatic olefin polymer containing free carboxyl groups which "is formed after the ammonia development"., is water-resistant, but by using a Cleaning solution containing ammonium hydroxide can be "optionally" removed again.

^f 109828 / U22

| ·. - BAD ORIGINAL

The property of being able to be removed again by an aqueous, ammonium hydroxide-containing cleaning solution makes the method according to the invention suitable for applying temporary protective covers to various substrates, such as. Automobile horn bumpers, horns, and other accessories, final machined parts such as gears, etc. ' If necessary, the removability in the deposited polymer can be increased by using a mixed salt which consists of ammonium cations and an alkali metal cation. Therefore, V / xrd the flücliti _r; o ammonia is removed, so the deposited polymer contains not only free carboxyl groups but some Alkalimejtallcarboxylatgruppen which increase the overall solubility of the polymer in the aqueous ammonium hydroxide solution. If the concentration of the remaining alkali metal arboxylate groups in the deposited polymer is actually high enough, the applied polymer can be removed by washing with conventional soap solutions without the use of aqueous ammonium hydroxide. -

Temporary protective coatings, which cannot be removed by peeling off but by peeling off or stripping, can also be made from mixtures of aliphatic olefin polymer salts containing carboxyl groups with up to 10% by weight (based on the polymer salt) of polyvinyl alcohol, ie polyvinyl acetate , which is hydrolyzed to 71 to 9 &'i'j , can be formulated «Purely for this end use, a water sensitivity is undesirable thick film with one

109828 / U2 BAD ORfGiNAU

(Peel strength) *
Exfoliation resistance / of about 180-360 g yro cm forms. Some with greater peeling strengths are not easily removable for all practical purposes, while films with lower peeling strengths are too easy to remove due to unintentional stress and cannot provide a suitable protective coating. "

The process according to the invention can also be used in leather finishing, in the formulation of latex paints, nail polish, hairspray, Thickener !!,. Extrusion base materials, emulsifiers and surfactants are used.

An interpolymer of Od -olefin of the general formula is preferably used as the carboxyl-containing, aliphatic ester olefin polymer according to the invention

H - CH = GH ₂ __ ■■. '■■

in which H stands for hydrogen or an alkyl radical with up to zxv 10 " Carbon atoms, the olefin content of the interpoly- merisates at least 50 mol $ of the total interpolymer makes up that with a fl (, ß-ethyIonic imsaturated carboxylic acid overpolymerized with one or more carboxyl groups where the unsaturated carboxylic acid is up to about ^ O MoI- ^ of the entire interpolymer atiS-makes.

The vox'liegende invention is not limited to Jerteh Interpolymerasate which Ernest from the interpolymerization olefin and a "l ■, ß-unsaturated äbhyleniseh Gax'borisäure derived * The for producing the poly according to the invention

BATH ORIGINAL

The starting polymer used can also be grafted on carboxylic acid-containing monomer based on an olefin polymer base structure according to processes known in graft polymerisation (cf. US Pat. No. 2,970,129, which is hereby incorporated in the present application is incorporated) or by grafting of ionoiiieren, such as carboxylic acid derivatives, i.e. » Esters, anhydrides, Amides and nitriles, on an olefin polymer base structure and subsequent conversion into free carboxylic acid groups after Grafting are made «,

The present invention furthermore halogenated, carboxylhalüigejpC -olefinpolymerisate includes "The process for

Introduction of the Iialogenatoms in these polymers is not critical and can be done, for example, by. first a halogen-free Interpolyraerisat made, for example, from ethylene / acrylic acid and this Interpolymerisat then halogenated by known processes, or by interpolymerizing a halogen-containing vinyl monomer with an α ^ -olefin and an unsaturated.Carboxylic acid. A particular example of this last-mentioned class of interpolymers is obtained by interpolymerizing ethylene, vinyl chloride, and acrylic acid. Further examples are interpolymers of ethylene / vinyl chloride / aerylic acid _? Ethylene / vinyl chloride / methacrylic acid, ethylene / vinylidene chloride / methacrylic acid, ethylene / vinyl bromide / acrylic acid, ethylene / vinyl ■ bromide / methacrylic acid _t ethylene / vinyl fluoride / acrylic acid, ethylene / vinyl fluoride / methacrylic acid, ethylene / vinylidene fluoride / acrylic acid, ethylene / vinylidene fluoride , Ethylene / vinyl iodide / acrylic acid, propylene / vinyl chloride / acrylic acid, propylene / vinyl chloride /

Ϊ09828 / Η22

_ s - ■ 1646180

Acrylic acid, propylene / vinyl chloride / meth ^ acry! Acid, propylene / . Tinylidene chloride / acrylic acid and propylene / yinylidene chloride / Methacrylic acid, "

As stated above, the egg olefins preferably used in the polymers according to the invention have the general formula:

"R CH = CH ₂

in which E stands for a hydrogen atom or an alkyl radical with up to 10 carbon atoms. Thus, more suitable oils include, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, keohexene, octene-1, nonene-1, decene-1, 5-methylbutene-1> 4-methylpentene -i, 3 "-Kethylhexen-1,4-methylpentene-1, 3-methylhexene-1 and ^{/ s} -, 4-dimethylhexene-1. Although polymixesates of higher olefins can be used, they are not as readily available and economical as the lower olefins,

The used in the polymers according to the invention, ^ t, ß-ethylenic Unsaturated carboxylic acids preferably have 3-8 carbon atoms, although those with a greater t number of carbon atoms can also be used if necessary. Special Examples are} acrylic acid, methacrylic acid, methacrylic acid, itaconic acid, Maleic acid, eumaric acid and half esters of the above dicarboxylic acids such as methyl hydrogen maleate, methyl hydrogen fumarate, Ethyl hydrogen maleate and ethyl hydrogen fumarate »

. The starting polymers used to prepare the polymer salts according to the invention are not based on two components limited »Therefore, together with the OH ^ in and carboxylic acid

* comonomers other copolymerizable monomers used

109828 / 1A22

BAD iÄ

'_ ₉ _ 7 1648160

will. Starting polymers that can be used include interpolymers from ethylene / acrylic acid, ethylene / methacrylic acid, iithylene / Ij ^ taconic acid, ethylene / methyl hydrogen maleate, ethylene / Maleic acid, ethylene / acrylic acid / methyl acrylate, ethylene / acrylic acid / Ethyl acrylate, ethylene / methacrylic acid / methyl methacrylate, ethylene / Methacrylic acid / ethyl methacrylate, ethylene / acrylic acid / methacrylic acid, Ethylene / methacrylic acid / methyl acrylate, ethylene / aerylic acid / Methyl methacrylate, ethylene / methyl hydrogen maleate / ethyl acrylate, Ethylene / acrylic acid / finyl acetate, ethylene / I-lethacrylic acid / irinylacetate, Ethylene / propylene / acrylic acid, ethylene / propylene / methacrylic acid, Ethylene / maleic acid / ethyl vinyl ether, ethylene / 3ute.n-1 / Acrylic acid, ethylene / tieohexen / acrylic acid, propylene / aerylic acid and Butene-1 / acrylic acid.

The polymer salts used according to the invention do not need

en to be limited to 2 components, ie one 1-olefin part and one unsaturated carbonic acid salt part. Even if the jkusgarigspolymerisat only consists of 2 components, ie. a ^ -olefin and an unsaturated carboxylic acid, the salt obtained may have 3 or more components. For example, may be partially neutralized an ethylene / Äcrylsäure-interpolymer with sodium hydroxide to a Interpolyrnerisatsalz from ~ $ components, ie, ethylene, "■ .crylsilure UNCT Hatriumacrylat. It is clear to the person skilled in the art that the present invention includes polymer salts with innumerable combinations of carbonic and unsaturated carboxylic acids, salts and acid derivatives.

108128/1422 ORIGINAL BATHROOM

Of the. Carboxyl content of Ausgangsolefinpolymerisates -Vorzugs is in the range of 10-25 mole of the entire $ Polymerrsatdsy although optionally Material en with a content of 1-5 mol ^& © * - ^ can be used. The starting olefin polymer used to prepare the polymer carboxyl salts according to the invention should contain sufficient carboxyl groups to allow the formation of at least water-dispersible salts and preferably water-soluble salts. The solubility -. getting better _? if the content of carboxyl salt parts of the polymerizate is increased. The content of carboxyl salts in the polymer, which is necessary to make the polymer dispersible in water, can be reduced by reducing the molecular weight of the polymer.

The content of carboxyl salt parts of these polymer salts is preferably between 3-25 mol of the total polymer salt, although other ranges can also be used if necessary. The term "carboxyl salt moiety" includes both the carboxyl anion and the monovalent cation. _{s =} "

As stated above, although the carboxyl-containing i4 ~ 01 ^e iinpoiyrä ^{e: r?} Isate salts mainly contain Aminoniumkaüioneii - also includes alkali metal cations, such as Ha ⁺ , K * and Li *

will.

The concentration of the polymer salt in the

Aqueous solutions used as intended is not very critical. An .ITosüstoffgolialt of i-40 Gev.:.-,j, especially ^ -2O .Gew.-fJ is preferred. - '.-.- "-. ~' \

ν; .Η - π - ■ 1046160

To produce the salts, only one for · simple mixing ■ is required and heating methods. Mixing device commonly used be applied. > ■: -

Atmospheric pressure is used to produce the Bolymerisätsalzes preferred, although pressures above and below atmospheric can also be used if necessary. Where atmospheric Prints are applied, temperatures will not exceed 98C. preferred, due to the reversible character of the carboxylic ammonium radical formed ♦ When using over- - Atmospheric pressure can of course use this temperature be crossed, be exceeded, be passed.

5ür the reverse process, ie, the regeneration of carboxyl oC-olefin polymers-from the ammonium salt., A temperature preferably from ⁰ C. between 2Q-IPO, although optionally also temperatures can be applied above or under this range. The time required for the conversion of the Junmoniumimsalzesiiotwenaige is also not very important and depends of course on the temperature. So at elevated 'example can fempe- temperatures over 150 ⁰ G., the time required amount to only a minute or even less. With room service, longer times, up to 90 minutes or more, are necessary to · ζ, Β. z \; ischen ^) orösün substrates to achieve a satisfactory adhesion. In order to achieve satisfactory adhesion between these systems it is not absolutely necessary to release all available ammonia. There is no practical upper limit _t since after conversion, further heating will have no harmful effect, provided that the temperatures are not so high that they cause a thermal cross-oxidative decomposition of the polymer.

From the large number of substrates which can be used according to the invention particularly preferred: polar synthetic polymers, cellulose, Cellulose acetate, regenerated cellulose, proteinaceous materials, natural resins, asphalt, asbestos, "metals, vitreous" materials, natural fibers, building materials and siliceous materials Materials. Combinations are also in accordance with the invention of the above materials, such as "e.g. in the case of Floor slabs in which a vinyl polymer with asphalt or is combined with asbestos or where asphalt and abbest itself are combined to floor panels.

The substrates suitable according to the invention generally have a higher surface energy than those used to connect them, free carboxy-containing ^ olefin polymers. These Substrates can be finely divided, granular, fibrous, in the form of FiIs or ropes are available, they can be woven or non-woven., - = - porous, non-porous, hard or not hard.

Metallsubstalte include ζ "B. ■ aluminum, .Chrom, cobalt, copper, gold, iron, lead _T magnesium, nickel, - PIi.tin, silver, tin, Tijiitan, ViTo-If ram j '. Vanadium, zinc, and alloys such as alloy steel, alnico, brass, bronze, carbon steel, cast iron, chrome steel, nichrome, tin, solder, stainless steel, and sterling silver. These metal substrates can be in the form of powder, grains,

ι -

Chips, sheets, foils, plates, bars and ßuäben are present.

Glass-containing substrates include glass, glassware, ceramic ware, ^l one, enamel materials, porcelain. Cellulosic substrates include wood, plywood, sawdust, sugar cane, bamboo, cane, and paper.

108828 / U22

BAÖ ORIGINAL

Include natural resins. " Asphalt, bitumen, _gums: I <acke, pitch, Naturhazr, rubber, shellac, tar and pickling *!

Polar, synthetic, polymeric substrates include thermosetting ones Polymers, such as phenol-aldehyde condensation polymers, Cuma-ron / indene polymers, phenol urea polymers, epoxy resins etc *, and thermoplastic polymers such as styrofoam polymers , Acrylonitrile polymers, polycarbonates, polyurethanes, Polyacetals, polyamides and synthetic rubbers,

"Protein-containing" materials include hides, skins, furs, tobacco products and gelatine *

Natural fibers include cotton, silk, wool, Flax, hemp, jute, manila and sisal.

Building materials include brick, granite, sanastone, plaster of paris, Tiles, boards and cement blocks. ;

In the practice of the present invention, individual Substrates are separated or connected in a continuous process. In the latter case, e.g. paper should be included Aluminum are connected to form a continuous strip, so an aluminum polisher can be used to continuously feed the Swipe through a bath of the aqueous ammonium polymer salt be used; from there the strip can be passed to a drying ■ oven, where then the carboxyIhaltigee ^ olefin polymer as a coating on the continuous aluminum strip The coated aluminum strip can then be formed from there to a Beschichjzftungswalze where he meets with a continuous strip of paper, the converging strips then occur as a paper / aluminum layer-! material from the coating rollers. f

BA0

The following examples illustrate the present invention without limiting it. Unless otherwise stated, "all!" Parts and percentages are parts by weight and - yes * Example 1

20 g of powdered ethylene / acrylic acid copolymer with a content of acrylic acid mischpolymerisierter of $ 22 and a melt index of 350 dg / ^em were slurried in 200 cc of aqueous ammonia 3- £> iS min. After 20-30 minutes long heating the slurry to 85-100 ⁰ G.-obtained was a clear solution, poured a Piim from and 5 minutes at 12O ⁰ G. dried. According to IR analysis of this film was composed iithylen / Acxylsäure copolymer and showed a typical Acrylsiiureab- soprtion at 5 "85 / U ^u nd the lack of Salzabsoprtion 6.5 Ai. This finding shows that the ammonium salt, after heating, is converted back to the original, water-insoluble ethylene / acrylic acid mixture and NEW
Example 2 .

Example 1 was repeated using 50 g of 80 mesh "pulverized ethylene / acrylic acid mixture polymer with a content of highly polymerized acrylic acid of 22 % and a melt index of 350 dg / min. After heating for 20-30 minutes in a slurry of A slightly cloudy solution was obtained from 450 g of 5% aqueous ammonia to 95H10 G. V, from which a clear film was poured and dried for 5 minutes at 120 ° C. The IR investigation showed that The film was the original lithyler's acrylic acid mixed polymer which was insoluble in water.

BATH

Example 3

Example 1 was prepared using 600 g of an ethylene-acrylic mixed polymer with a content of copolymerized acrylic acid and 21 % and a melt index of 330 dg / min and a solution of 175 g of 28% ammonium hydroxide in 2400 g of water repeated. A slightly cloudy polymer ammonium salt solution was obtained from which a clear film was cast and kept at 120 ° C. for ^ minutes. has been dried; According to the IR investigation, this was originally the water-insoluble ifchylene / acrylic acid copolymer.
Example 4 to 6

A floor polish was formulated by adding 10.6 parts high-density polyethylene wax with terminal succinic acid groups, parts of oleic acid, 1.06 parts of moxpholine, 3.0 parts the ethylene-acrylsiturammonium salt solution prepared in Example 3 and mixed 63.54 parts of water.

This polish was applied to a sheet of glass, asphalt floor tiles, or vinyl asbestos floor tiles and allowed to dry at room temperature; thus a coating excellent in gloss and hardness was obtained. After drying, these coatings got iceine water stains. The formulation described above is also compatible with commercially available polyacrylate / floor polishes,
■ Examples 7 to 9 .

- * The floor polish described in Example 4-6 was

! £ twist of Gardner Wasiibarkeitstests (. Cf. ASTM D-1792-60T) O ₀ to coated with this formulation Aäphaltflie-sen on J3nt- - "evaluated disposability. This test showed - that the polish ^ ⁰ with conventional soap solutions according to Angajibeii in ASTM Ώ-1792-60Τ

could not be removed from the As]> holding tiles. she was 'but under the same conditions when using a 2.0 £ Lgem

BATH

aqueous ammonia solution instead of the usual soap solution · easily removable.
Example IQ

15 x 15 ° ni sized pieces of non-woven cellulose acetate fabric were in a 10- $ aqueous solution of the prepared in Beisvdel 3 Immersed ethylene / acrylic acid ammonium salt solution. the Weight absorption of the fabric after drying at 120 ° C. was on 1-10 $ set. After this treatment, all samples were good connected to the ethylene / acrylic acid mixed polymerisa.t, whereby the stiffness of the treated fabric with the. Polymer content "increased. The material treated in this way could be immersed in Water cannot be wetted.

Example 11

50 g q £ -cellulose were added to 1 liter of water and mixed in a Waring mixer for 10 minutes. After soaking in water overnight, the resulting pulp was hand squeezed to remove excess water and formed into a ball. The pulp was divided into 5 parts. Each part was placed in a separate Waring mixer of 1 liter capacity, which contained a 20% aqueous solution of an ammonium salt of the ethylene / acrylic acid mixed polymer with a content of copolymerized acrylic acid of 18-21 % and a melt index of 200-500 dg / min; this solution contained a 5% excess of ammonium hydroxide over that required for complete neutralization of the ethylene / acrylic acid

. Copolymer required, stahiometric amount. After 10 Stirring in the Waring blender for minutes made the five portions reunited and placed in a shaker with wooden sides of

* 14-, 3 x 15j2 x 3j2 cm and a 35 mesh sieve. That.

109828/1422

SchüttelBieb was previously galvanized in a baking sheet Tin with internal dimensions of 32 by 23 x5 cm has been mounted. AIjS poured the pulp / water slurry onto the shaker frame the cellulose mixture floated on the liquid

surface above the sieve. After gently shaking the These floating cellulose fibers arrange themselves to form a uniform dispersion. After lifting the sieve from the sheet the excess water ran through the sieve into the tray and left a mat of coated cellulose fibers on the screen. Then the sieve was dried by putting the underside on a felt pad was drying. Then the sieve was turned over unu the falling out cellulose mat was 30 minutes in one Drying oven at 85 ° C. held. The dried mat passed

-Cellulose particles formed by an ethylene / acrylic acid copolymer related together, that from the elimination of ammonia in the 'drying oven from the original ammonium polymer salt came from.

A part of this hat was in a Carver press between, 2 Sheets of 2 cm 'polyethylene terephthalate film at one temperature of about 185 ° C. Pressed for 1.5 minutes under a pressure of 0.7 kg / cm. The press was cooled for 6 minutes and the mat removed. After stripping the film from the mat, a sheet with a glossy surface 0.45 ml in thickness was obtained. Samples of the, " cellulose film produced in this way showed after 3 months Immersion in.dest. Water does not lose its hardness or water- J-

,. solid properties, thus providing excellent wet strength

■ indicates.

BATH ORIGINAL

Example 12 «

A waterproof, chemical-resistant filter was made from a> non-woven fabric in the form of a "Masslinn" cloth (trade name of Chicopee Mills Inc.) made by taking out a 30 X 4-3 cm, 6.472 g sample from the above described cloth and immersion ^ same in the example ammonium salt solution described. After a few minutes of immersion, the wet cloth was dried in an oven at 85 ° C for 30 minutes. The dried towel weighed 10.128 g.

P From the approximately 1300 cm area of the original cloth the increase in solids was calculated to be 0.18 g

2 deposited polymer per 6.45 era of the cloth

fraud. ......

The treated cloth was made by pressing in a Caryer press

smoothed according to the conditions described in Example 11. The cloth treated in this way was then cut up and used in a funnel for filtering an aqueous solution showed no harmful effect due to the Wässex'by- " ganges.

Example: 13

A 15 x 15 χ 0.95 ^cm piece of plywood made of Douglas spruce was soaked in a 1Q aqueous solution of the ethylene / acrylic acid polytoerisaianmoniura salt described in Example 11. After soaking for 10 minutes at room temperature, the treated spearwood became at 85 ° C for 30 minutes. in an oven ». dried. * Overall a Spearrholzprobe used as control (1) WUR $ e also without pretreatment for 30 minutes at 85 ⁰ G in Qfen

BAD ORIGINAt

. dries. The treated piece of plywood and the control (1) 'were each coated with a film of an ethylene / acrylic acid copolymer with an acrylic acid content of 19-22% and a melt index of 50-90 dg / min by pressing in a Carver press at 80 ^o G. and 5.81 kg / cm between two sheets of polyethylene terephthalate film for 2 minutes. The press was cooled for 6 minutes and the pressed plywood removed from the press and tested for peel resistance in an Instron tensile tester at a crosshead speed of 5 cm / min. 2.5 cm wide strips are used for this determination, measured in two directions, i.e. in the direction with the grain and perpendicular to the grain. For control

■ if the value in the direction with the grain is 560 g / cm

while the flaking value for the treated sample in the direction with the grain was about 5200 g / cm. The peel value for the control (1) perpendicular to the grain was about 270 g / cm and for the treated plywood was about 1440 g / cm. Example 14

15 x 15 x Oj95 cm plywood plates of Douglas fir were immersed 1Q minutes at room temperature in a solution of the described in Example 5 Aramoniaumsalzes of the ethylene / Acrylsüure-polymer and a half hours in an oven at 85 ⁰ C. dried, then inirden the The dried platelets are placed in a Carver's head covered with films of low-density polyethylene with a melt index of about 2 dg / min

The pressing conditions were such that an initial temperature of about. 188 ⁰ C «in connection with a pressure of about O ₉ 07 kg / em ^c a ί-Iimit ^ v ^ 2? W; ends was * Then the press

.slowly cooled, whereby 'the pressure allnählicli up to about

2 became
5.6 kg / cm increased /. When the press temperature was room temperature, the flakes were left about G Hinuteri in the pressure plates and then removed. The peeling resistance found across the grain was about 1080 g / cm and with the ICorn also about 1080 g / cm. The without the above treatment with the ammonium polymer salt on polyethylene pressed plaques gave values of about 18.0 g / cm or less.

Example ; 1 ^ ■

A 10 × 20 cm aluminum plate, 0.65 ram thick, was immersed in an ammonium polymeric satiyal solution prepared as in Example 3 with a solids concentration of about 10 ° ^C. The plate was removed from the The saline solution was removed and dried in an oven at 85 ° C for 30 minutes. Then the coated plate was placed in a press without the pressure plate being poured, the press temperature being increased to about 220 ° C. This heated the coated plate, which was then removed from the press and brought into contact with a polyurethane foam plate (made from tolylene diisocyanate and propylene ethylene glycol), the polyurethane layer material and the plate being applied

. ■ good

a pressure of about 0.07 kg6m was applied ^ = Die / Adhesion This layer material was shown by the .Polyurethane itself into a coherent bridge: tore when nan tried that Peel the polyurethane from the plate.

109828/1422

BATH

^F - 21 -

B e i s β i e 1 16

1846160

As in Example 1i>, cotton fabric was "coated" onto a -coated "aluminum plate produced according to Example 1>. In this case too, the adhesion between the cotton layer and the metal plate was adhered to. ·". ■ -.-

Example 1? "■ ·;

A 10 20 χ, cm piece of glass-reinforced styrene / acrylonitrile-- .. iiiochpolyrnerisat was coated according to Examples 15 and 16 εχχϊ polyurethane (made from Llylene diisocyanate and piopylene ether glycol). -The layers could not be separated without the polyurethane sheet tearing in a coherent break. B e is ρ each 1 18 to 20 -

Example 1 ^ to 17 was repeated, but instead of the aluminum plate (Example I ^ and 16) and the styrene-acrylonitrile copolymer (Example 17) a steel plate was used. 'ISs a similarly good adhesion between the metal plate, and achieved the other splint * ■ "

B e is ρ ie 1 21 '. . : ■

Beis?) Iel 14 was repeated using high-density polyethylene instead of low-density polyethylene and an aluminum plate instead of plywood, but the coating of the ammonium salt on the aluminum plate was dried for 10 minutes at 90 ° C and then 1 ^s -1> 5 minutes ^ at 195 ° ö. and a pressure of about 4.7 ^ kg / cm on the liqch dense polyethylene. The peeling strength of the layer material obtained was about 800 g / cm,

BAD ORlGHNAl.

B.eiapie "! 2 2 ■

17> ö χ 17> ö χ 0.95 cm Sheets of foamed, high-density polyethylene (density 0.7) were coated with an ammonium salt solution described in Example 1. The coated plates were dried for about 30 minutes at about 50 ^° G *. Then a strip of paper was placed over the coated polyethylene sheet; which in turn was placed in a heated press. The jaws were quickly closed and relaxed after a contact time of about 0.5 seconds. This process simulates a pulse Helßstanzeii, Ss obtained a strong adhesion between the highly dense ψ th polyethylene and paper *
Be is ρ I e 1 25 to 26

An ethylene / Äcrylsäure-Mischpolymerlsat with 2.1 "yes miscopolymerislerter acrylic acid and a melt index of 530 dg / min • neutralized with a mixture of heißem'wässrigem AmmcniumLiydroxyd and • Hatriumhydroxyd in different quantities., So AASS e ₌ ln ethylene / acrylic acid Hischpolynierisatsalz formed v / urde, which after heating to remove ammonia contained different proportions of sodium acrylate in the polymer, n-: Imlich 20% by weight, 12% by weight, 10.5% by weight and 6% by weight Control (2) was made with ammonium hydroxide alone, so that after heating and ammonia removal, the resulting ethylene / acrylic acid polymer did not contain any sodium acrylate Acrylic resin was f inlly coated. This was done by applying a coating of 0.125 ^mi "nasa thickness = Returning a / check rod and subsequent 5 minutes "long the thus treated plates at 120 ⁰ O. i'rocfcnung Then, by the Gardner-Vaydibarkeitstester

BAD OBIGiNAL

determined how easy it was to remove the top coats of the ethylene / acrylocure-1-ash polyacrylate with water and with a soap solution. The / jex ¹ test with the coated panels simulates the results of coating removal using a metal

ßie
e would be achieved, v / ie / z. '£> . in an automobile during

of verse, the situation> un _t; ; and preparation for sale pre-3co; .a: ien. The V / csch results mentioned in -: table 1 are the number of ', .. ashes for removing the coatings with water b ^: v.'. Soif solution. The 1-ate shows that the top coat can be removed more easily with a higher sodium acrylate content than with a lower content. So there is a water: umacrylate content. from ο : '> the Uasch cycle et v / a in the order of magnitude of the control. xJei a iCatriunacrylat-ehalt of 10, 3 ^c / ^s ° i 't a decided Abfc.ll, the sharp continues at 12 and 20 ^c / o Natriumacrylatgehal'ü.

'Jabe-lle 1 ''

Example

24- 2 ^ 26 , control 2 '

Wt .-; j sodium 20 12 20.5 6.0 0

acrylcit in the Dbex 'train

Washing cycles for g ^. _Q ' _{p π} ν

jjintfernung ^d ^ ^u , iy ^> ^ ü ^ 2 ^ 0

(Water)

V / ash cycles for

Distance "24 18 200 S-250

(oeif enlüsung) * '

Example 2? """.'■

A 10 χ 15 χ 0.95 cm Sperruolis slab made of Douglas spruce was made with an aqueous solution of an "ammonium salt of ethylene / Acrylic acid mixed polymer with an acrylic acid gel from

109828 / U22

BATH

about 20 fo and a melt index of about 200 dg / min. The solids content of the solution was about 10% and dex ^v percentage of converted into carboxyl groups Ammoniumacrylatteile about 6Q # .The plate was JO minutes at about 85 ° G. dried and then immersed in a 'sensitizing' solution of the following composition:

η 00 S. 400 ecm 1000 ecm

. Stannous chloride (SnCl ₂ conc. Hydrochloric acid (37 $ HCl)

water

Ss was immersed for about 1 minute and an additional minute P rinsed in running water. This gave a sensitized surface. Then the treated plate was through Immersion in a dilute palladium chloride solution activates and then to an electroless plating bath which Copper sulfate, water, hydrazine sulfate, sodium hydroxide and water contained, transferred. Thus - a wooden board covered with a continuous layer of metallic copper was obtained, the by common procedures due to their imparted conductivity could not be further electroplated,

P Polymeric films with characteristic, paper-like properties can also be produced by means of the polymeric according to the invention ianmonium salts can be combined with other substrates, the corresponding polymeric films include:

(1) a high density polyethylene resin with a melt index from 0.1-2.0 dg / minj

C2) 5-50 parts by weight of an ethylene / vinyl copolymer resin / with a melt index of 0.2-100 dg / min per 100 parts of high density polyethylene resin $ and

(/ + "acconodation resin") -

109828/142 2

BAD OBiGfNAt

(3) 5-75 parts by weight of a finely divided, siliceous filler per 100 parts of high-density polyethylene resin or 3-50 parts of thermoplastic, unmodified polystyrene resin or 5-60 parts of a combination of thermoplastic, unmodified polystyrene resin and finely divided, silicic acid-containing filler per 100 Share, high density polyethylene resin. The above-mentioned high-density Polyäthylenharze usually have a density greater than about 0,94-, generally between E "94 · to about 0.97." These resins are substantially linear and are commonly called "linear polyethylene" described Example 28

A piece of the abovementioned polymeric film, 15 × 20 cm in size, was immersed in the aqueous ammonium polymerizate solution described in Example 1 and then dried for 10 minutes at 85.degree. Then a piece of aluminum of 0.13 mm thickness was mil; the coated, polymeric film for 1 minute at about 5> 6 kg / cm and 110 ⁰ G.in set a Carver press. After cooling, the layer material was removed and showed a peeling strength above the tensile strength of the 0.1 mm thick polymeric film between the polymeric film and the aluminum. Example 29

Example 28 was repeated with cellophane * instead of the aluminum (Gello- plum = regenerated gelulose). A strong layer material was obtained.
Example 50

Example 28 was väederhalted with a piece of hardboard instead of the aluminum. A strong layer material was obtained.

t0982g / 1422 BAD ORIGiNAC

_ ₂₆ . 16A61 60

Examples 31 to 35

The following examples show the effect of the Jithylen / Acrylic acid copolymers present Alkalinietairbeile, the after the evolution of ammonia from ammonium alkali metal salts These carboxyl-containing polymers remain vex ^,;,. uf the physical Properties of the polymer.

Ethylene / acrylic acid mixed polymer with 21 ~ o mixed polymexasized acrylic acid and a melt index of 330 dg / min was dissolved in aqueous solutions which contained different amounts of sodium hydroxide and ammonium hydroxide, at about 98 ° C. was stirred. The ammonium sodium salts obtained from the ethylene / acrylic acid mixed polymer were obtained from the solution by precipitation with acetone. The solid polymer salts were deformed into hard disks that were used for reading; physical properties and water absorption were used. Table 2 gives the data in comparison to a control sample. (3)> those from the untreated, u.ii. Urine-neutralized, ursjvillri iithylen / AcrylSc-ure starting copolymer consisted.

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BATH ORIGINAL

I a · b e 1 le

Example g IaOH g KH

(28 $ ig) sodium acrylate module no phr in the product (wt. ^) kg / cm ^ calculated by I.E.

tensile strenght
Kg / Qior

1o

strain

Water absorption Wt. $ In 7 days

Control ^) .. ■ -

'. '' 3t ■, ■■■ ^; '^; . "'.. I ■

32
3t
34
35

2.7

5.8

20th
18th
16.2

13.6.

9.8

3.0

6.0

• 8.5

12.0

18.0

0 325.5 206.5 4.0 1713.6 196 7.9 3498.2 247.0 9.6 4190.6 275.5 12.1 4223.2 312 15.8 4340.8 316.5

590

415
360

322 '
314
276

■ 0.06 0.15 0.22

0.77 2.0 20.2 J &

cn.

cn -i

CD O

- 2υ -

Table 2 shows that an increase in the amount of sodium hydroxide in the solution increases the sodium acrylate content in the dissolved polymer and thus the modulus, tensile strength and water absorption of the polymer. The solution composition therefore regulates the rigidity, toughness, resistance to surface abrasion and the sensitivity to water of the deposited film. Thus, according to the process according to the invention, both temporary (strippable or soluble in aqueous cleaning solutions) and permanent (non-water sensitive) coatings and adhesives can be used ? be formulated .; Those particular aqueous _L used for Intfernung · temporary coatings are unification solutions, aqueous solutions of ammonia, soap, detergent or surfactant I-iitteln etc. i; unification agents may be anionic, cationic or * non-ionic.

Example- 36

To evaluate the effect of polyvinyl alcohol on the adhesion of the ethylene / acrylic acid mixture to various substrates, a series of mixtures was prepared by adding 50 parts of an aqueous solution with a solids content of 20% of the ethylene / acrylic acid mixture prepared in Beisjdel 3. ) Olymerisatammoniumsalzes with different parts of an aqueous solution of 71- / jigem hydrousierteia polyvinyl alcohol fiber content of 15 y> Pest or 2o-fjigeii solution of 98 - / 'i £;. mixed em hydrolyäertem polyvinyl alcohol. Each JjOrmulierung was applied with a brush on aluminum or Chrouplatten • and dried for about 30 minutes at about 50-60 ⁰ G. to about 0.05 mm thick coatings.

109828/1422

As Kpntrollen (4 to 6) were each 100! 'The aqueous Ammoniumpolymerisatsalzlösung parts (15% solids content) of the aqueous solution of Ji-joigem hydrolyzed polyvinyl alcohol (15 ° / ο hard st off content) and the aqueous solution of 98 / jigem hydrolyzed polyvinyl alcohol (20>'a solids content) used for coating two types of panels in a similar way »

Then, as the hatred of the adhesion, the peeling resistance became each Coating found «Controls 4 and 5 with aluminum slats were unsatisfactory as the peeling strengths were too still, i.e. ^ 2700 g / cm. Control 6 was unsatisfactory, as the peeling resistance of the aluminum plate increases was low, i.e. ^ 180 g / cm,.

(Content 2o # solid.) By Vex'wendung an I-iischung wiissrigem from about 50 parts Aramoniurapolyraerisatsalz and about 1oo ropes wäscrigem, 9ö-; ji £ 's hydrolyzed polyvinyl alcohol (20 ^L yes solid content) of k ^ nntiuf an aluminum plate, a coating with a peel strength of about 360-540 g / cm can be obtained.

The values for Control Sample 4- were for adhesion to chrome plates too high while for controls 5 and 6 too were low, i.e. ^ 90 g / cm or 0 g / cm. The following Mixtures gave peel strengths on chrome plaques of 360-4-50 g / cmi

50 parts aqueous Ammoniumpolymerisatsalzlösung (2o $ Feststoff§) gemiacht with 50 or 40! Hasten aqueous, 71- ^ strength hydrolys.lerter polyvinylaltoholösung. (15 ^ solids) and 40 or 30 I parts of 98 # aqueous polyvinyl alcohol solution (2o fa solids)

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BATH 05P $ fcö GAS

Claims (3)

F ate η ta η a ρ r ü che ■ -,, 1, - "Process cum coating of substrates with an aliphatic ', carboxyI-group-containing ^ -olymex'isat, characterized in that one ... (1) A salt of a carbon-olefin polymer containing carboxy groups with ammonium cations, the olefin in the gel of the polymer salt being at least 0 mole of the total polyhydric salt, from a mixture of water and ammonium salt on the substrate and (2) the substrate containing the deposit dries.2, - Method according to claim 1, characterized in that the substrate is selected from the class of polar synthetic polymers, e.g. vinyl polymer, cellulose-containing materials, e.g. cellulose or wood, cellulose acetate , regenerated cellulose, proteinaceous materials, glashaltii.; er materials, e.g. glass, natural resins, natural fibers, silicic acid-containing building materials, “e.g. from, asphalt, asbestos, and metal. 5 · - Process en "according to claims 1 and 2, characterized in that also i, -olef is used in ethylene. 4. Process according to Claims 1 to 3, characterized in that the olefin polymer salt containing carboxyl groups contains up to. ..!? * - procedural text according to claim 4, characterized in that "the äthyieniscii unsaturated carbonsLuro Aci ^ ylaäux'e and the acrylic acid anions plus the cations about 1-2> mol ->. J, preferably 1-12 mol ^ j, make up the entire olefin polymer range.BAD ORIGINAL ■ 6, - VeX1Xahren to create a temporary coating for objects, characterized in that one 1) a salt of a carboxyl-containing, aliphatic ^ -olefiniiolymerisates with ammonium kai "ions, where" the d , ß-oil content of the salt is at least 50 Hol-jj. of the total polymer salt re. ^ t, tus e .nor mixture of water with the salt is deposited on the object, 2) the substrate containing the deposit to form one 1 ol "merisatüberzu ^: it dries and 3) the, at '^ u,'; away from the object. 7 · - »/ erfahron nacJi claim u, characterized in that uas oC-Ulufinpol ^ mexasatsalz also contains alkali metal cations ... and the 'coating is enL'fei-nt by the Geo; enstaud with an ileiniyi-ü"i; -solution auo der ü-ruppe \; ilssri ^; cr, 3eifenlösuiigen, iaainoniakrei. i! un ^ clösmii-ieii ocer Lc; 3un; .en surfactants at least one minute with a L ^; eH »era-6iir of at least 20 ° C. In contact, whereby the deposited polymer from the no. Env> removes - "./ i 6, - Incidents according to claim 1 and 7> characterized in that the mixture of -water and (j (-Qlefinpol; / inerisatsaLz still hydrolyzed Contains polyvinyl acetate. 9 * - The method of claim 8, characterized in that the PolyvinylaXcetat to about 71-98 ü ^ hydro Siert and in an amount between about 30-100 parts per 50 Gev /.- l'elle ^ -Olefinpolymerisatsalz is present. - 10582 ^ / 1422 1Oc- method for coating paper, characterized in _that: & L d 1) a kishunp: made of clay and some salt. a carboxyl-containing ^ -ülef !!! polymerisates mix- AmM..aiiumkat ion, where the ^ -Ol efin-, celiclt des 1 olymerisatsa.lzes.iiiiiidestehs 50 mol- ^ J of the total Polymorisircsalzes is, on the paper from an isolation of V / ater-u.it separates the Äumoniura salt and clay and 2) onto a ^{r v} l he at least one hiiiute: rieratur heated from about 50-175 ° G ₀ 11, - Vei ^ lead to the production of non-gev / ebter fabrics, dadui'ch Indicates that one :. _____ - _ 1) the non-woven l'uch in a watery lot of salt of a carboxyl-containing gelfin polymer with ammuium cations, v; obei der o (-. 01efinalt des Polfenierisatsaizes miiide-_ is at least 50 mol. 2) the nicely-leveled cloth is removed from the aqueous solution and 3) at least one minute at about 20-165 ° © .- dries. 12, - Method aum waterproofing bolts, characterized in that one. . "_ 1) wood in an aqueous solution of a salt of a carboxylhaluigen J-Olefinpolyme.risates nit ammonium cations, wherein the ß ^ ~ 01efingehalt jrOljnnerisatsalzes of at least 50 mole -j6 constitutes the, entire Polymerisatsalzes in Zimiaerte;. .Vperatur immersed at least one minute ,. ΛΜ2 BAD OflfGJNAL 2) removed the wood from the -'aqueous bath and j5) at least one minute to about 2'O- * to 5 ° C. heated. The patent attorney: 109828 / U22 BATH ORIGINAL