DE1811812A1 - Inorganic layer carriers with organic coating - Google Patents

Description

concerning
Inorganic substrates with an organic coating

The invention relates to inorganic layer supports with an organic coating, in particular layer supports made of inorganic. Oxides treated with certain organic substances that facilitate coating with olefin polymers »

According to the invention, inorganic layer supports such as Inorganic oxides and metals, an organosiloxane and certain copolymers of ethylene are applied. The organic groups of the siloxane are attached to the silicon atom via a carbon-silicon bond bound and contain at least one functional group which is condensable with a carboxylic acid group. The copolymeric ethylene contains units of the formula

R «

-Οι

O = C-OH

in which R is a hydrogen atom or an alkyl group with 1 to means about 4 carbon atoms.

The inorganic support according to the invention with a layer of the organosiloxane mentioned and a layer of the ethylene co-polymer also includes such support

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which the coating binds a further layer support to the first layer support, which can be organic or inorganic in nature. In this case, several layers do not need to be separate layers, but for the purposes according to the invention can consist of a single layer composed of the siloxane and the ethylene copolymer _e

The ethylene copolymers which can be used according to the invention are macromolecular substances with repeating ethylene units - or "-CH- and units of the general formula

in which R has the meaning mentioned. Vorzugsweise'bestehen these polymers to Venigstens φ 40 ~ from Äthyle'aiein-units and ■ ■ at least about 1 fo of units containing the group -GOOH. . ., Most preferred are polymers that are at least $ 50 from ^:. Ethylene units and at least about 2 $ from units with the group -COOH.

The ethylene copolymers can be prepared by copolymerizing ethylene with at least one α, ß-ethylene isoh, unsaturated fermentation acid, such as acrylic acid, methacrylic acid, maleic acid, fum &is>. acid, crotonic acid, 2-Heptencarbonsäure, ^{2-Äthyl'-2-i} propeiiQarboa acid, 2-butyl-2-propencarbonsäure, 3-phenyl-2-propencarboTisäure be obtained and the like *. So that is present under the condition that Äthylfem and the carboxylic acid in sufficient Molverhal1 present Aissen? In the copolymer the desired content of the entsprechendea · structural units also may in the copolymer, other units from ethylenically unsaturated monomers vorlie- _φ gene, together with ethylene and of the unsaturated carboxylic acid ° are copolymerized, such as propylene, 1-butylene, 2-butyl, 1,3 "<» butadiene, 2,5- or 2,6-iiorbornadiene, 2 * -horbornene, dicyclopentadiene, vinyl acetate (as well as the vinyl alcohol derived therefrom) ^ vinyl chloride, isoprene, 2 * -chloroprene, alkyl acrylate or methacrylate (where the alkyl groups contain 1 to about 12 carbon atoms, e.g. methyl, 2-ethylhexyl or dodecyl groups), styrene »ö ^ -Methylstyrene , ß-chlorostyrene, acrylamide, methacrylamide _{,: ΐΐ;.}

Dimethylolacrylamide, dimethylol methacrylamide, N-vinyl-2-pyrrolidone, Acrylonitrile, methacrylonitrile, alkyl vinyl ethers (e.g. with Alkyl groups with 1 to about 6 carbon atoms), alkyl vinyl ketones (e.g. having alkyl groups of 1 to 6 carbon atoms) and the like.

The ethylene copolymers usually have a molecular weight of at least about 1,000, preferably at least about 6,000, and more preferably at least 15,000 to a molecular weight of about 200,000 and above. The molecular weight should be high enough so that the copolymer is solid and has a λ consistency ranging from a waxy substance to a tough horny resinous substance »

The siloxanes provided on the inorganic substrate are repeating units of general formula

characterized in which R ^{1 is} a divalent saturated hydrocarbon residue with at least three bonded carbon atoms, which separates the group X from the silicon atom and X denotes a functional group that is condensable with a carboxylic acid group, e.g. a functional group such as

-CH-CK-, HH-, HS-, HO- or O = C = Ii-, these siloxanes are made by Hydrolysis and condensation of silanes such as those of general formula

obtained, where Y is a hydrolyzable group such as "an alkoxy or aroxy group, a halogen atom, an amino group or the like. It should be noted that in the case of a silane with Xs = O = Cs = N- this functional group in the siloxane is not occurs more because the isocyanate group is unstable to hydrolysis · However, the reaction product of an isocyanate group with water forms t t which is a functional group that

is usable according to the invention. The isocyanate group can through

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Reaction of a siloxane substituted by amino groups with phosgene and subsequent dehydrohalogenation into the siloxane to be introduced. The siloxane is then still to another Implementation enables and "binds itself firmly to the inorganic substrate.

Examples of the silanes mentioned which can be used according to the invention are as follows:

CH ₂ -OHOH ₂ O (CH ₂ ) ₃ Si (OCH

H ₂ OH ₂ Si (OCH-

H ₂ Nf GE ^ fl { OCH ₂ CH ₃ ) H ₂ IT - ("OH ₃ - ^ S i (OCH ₃ ) ₃

HSCH ₂ CH ₂ OH ₂ Si 0

Il.

H ₂ NO BH (CH ₂ ) ₃ Si (OCH ₃ ) (HOCH ₂

It

HH ₂ NC ^ ^ tMOH ₂ - ^ Si (OCH ₂ CH ₃ ),

90985Ϊ) / 1

-. ■ ■ * - ORiGiWAL 1! MSPICTED "

W «. ti

(HOCHg) ₂ -NC CN- KiHg) ₃ -Si (OCHgCH ₃ ;

N (CHgOH) ₂

CH ₃ CO (<3H ₂ 4 ^ Si (OOH ₃ > ₃

HIGH
CH ₃ GH ₂ ^ NCN - - fCHg - t - S i (OCH ₂ CH ₃ ).

0
CH, C-1 fGHo-frß 1 (OCH ₀ CH,),

CH ₃ C-OH-H ₂ N (OH ₂ ) ₃ Si (OGHgGH ₃ ) ₃

H
HGl · HgNGHg CHgN - (- CHg ^ i (OCH ₃ ) ₃

The inorganic support, according to the invention with the siloxane and the ethylene copolymer are coated, metals such as iron, steel, copper, nickel, alloys of these Metals, aluminum and the like, or inorganic particulate Fillers and pigments including inorganic oxide fillers and pigments, e.g. based on silica and Aluminum silicate fillers, e.g. silicon dioxide, sand, Clays and the like. Other inorganic layer supports are metal pigments, such as iron chromates, lead oxide, zinc oxide and titanium dioxide and the like, as well as inorganic fibers such as graphite fibers, glass fibers or tungsten fibers.

It has been found that 'an organic coating consists of the said siloxane and the ethylene copolymer on the substrate gives a substrate unique properties · In the case of the metal substrate, a tough weatherproof coating is used which are usually at least as resistant

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i 1. f J »4» Ϊ «*

capable of more elaborate coatings based on such Backings in combination with silicones / have been used up to now. In addition, such coatings can be excellent adhesives or primers for another coating be that is applied about it. Everyone becomes very general inorganic or organic coating better bound to the layers of the ethylene copolymer and the siloxane. That Ethylene copolymers according to the invention is characterized by excellent adhesive properties and a polymeric material or a metal or an inorganic oxide applied thereon becomes solid through the layer of the ethylene copolymer and the siloxane bound to the underlying metal substrate.

It has also been found to be made of extremely thin layers the siloxane and the ethylene copolymer can be applied to pigments to their properties / and their compatibility to improve with other plastics. This is particularly the case when these pigments are converted into bleophilic polymers v / ie polyolefins, e.g. polyethylene, polypropylene and the like can be introduced. The rate of dispersion of a pigment or filler is increased by the coating according to the invention and the obtained The product is due to a better tolerance of the filler or pigments in the plastic.

The invention is particularly fruitful when the support is a crude silica product, such as glass in torrn of disks, Pearls, fibers or any other shape, it has been found that the layers applied to the glass, e.g. in the case of glass panes, can be used in the manufacture of safety glass. A laminate can therefore be produced which contains the said layer embedded between two layers of glass panes and it becomes a very effective bond that / is extremely solid.

In the case of glass that is then to be processed, e.g. glass fibers, glass beads and the like.

carrier applied layer to protect against damage that

- 909850/1413 _ .ORIGINAL WSPiCTED--

can usually occur during processing. The inorganic support according to the invention with an organic coating develops particularly desirable properties when the support consists of glass fibers which are to be used to reinforce olefin polymers. Embedding glass fibers in such plastics is very difficult because wetting problems occur when the two components are mixed. The glass does not mix easily with the plastic, and the plastic does not immediately accept the glass. Considerable shear forces are therefore required to achieve good mixing, and these shear forces often destroy the glass fibers by breaking them. It has been found that these difficulties can be reduced to a minimum if the glass is coated with the organic layer according to the invention before it is mixed with the plastic and the treated glass fibers are fed to the plastic in the form of chopped rovings. It was found that the plastic absorbs the fibers more easily, shows better compatibility and that. _; · Glass fibers that withstand the shear forces, stresses and forces that occur during mixing and processing during shaping, for example during injection molding and during shrinkage extrusion.

The substrate can first be treated with the siloxane and then the surface of the support be coated with the ethylene copolymer »It can also be a

Mixture of the genuine silane and the ethylene copolymer

placed and applied to the surface of the substrate » will. The siloxane units characterized by formula I. of the surface of the support can be more frequent than the molar concentration of the carboxylic acid groups present in the copolymer. Generally kgb in an equivalent amount of siloxane units of the formula I, based on the equivalent amount of carboxylic acid units used in ethylene copolymers. The term "equivalent denominations" or "equivalent units" means that at least one functional group X according to formula I for every carboxylic acid group in the ethylene copolymer. In. In some cases it may be desirable to have less than an equivalent Amount to use. Usually more than one equiva- '

ORIGINAL INSPECTED

lent amount of the siloxane units do not offer sufficient benefits, but neither do they have disadvantages. In some cases, no more than about 60 wt _e »$ Slloxan, based on the ethylene copolymer, can be used.

The amount of copolymer used depends on the intended use of the coated substrate. If the copolymer is used to laminate two pieces of glass in the manufacture of safety glass, the amount of ethyl copolymer used is usually very high, for example up to 25% by weight, based on the glass. Otherwise, the amount of, Ithylencopolymeren on the support, "based on the weight of the support very small and usually not more than about 10 washed ^ j, based on the support © Usually does not exceed this amount 5 wt _e - $ and can even only 0 ₅ 1 G-ew _o - $, in order to ensure still advantageous results for certain uses. jS, based on the glass fibers ^ use »

Is polymeric of applying the siloxanes, and Xthylene ©, _s applied to the layer support -a two stage process it is usually a first-aqueous solution or dispersion _s which is obtained by hydrolysis of the silanes of the formula II.-Siloxane or siloxanol, on the Schichtträger'gebracht and anscfaliessend dried, usually at a! ^Λ ■ temperature above 50 ⁰ C, preferably above 100 ° 0th Temperatures that cause the siloxane to degrade should not be used. A layer of the ethylene copolymer is applied to the coated substrate. The ethylene polymer can be in the form of a film, an emulsion, a solution, a dispersion and the like.

After the organic layer has been applied to the "layer carrier", the whole is heated sufficiently, usually above the transition temperature of the second degree, namely above 50 ⁰ O

9 G 9 8 S 07 H 2 3 .. f - ~ v * i c ^ _£: - : <^ .

* 4

• and 'in particular above 100 ⁰ C, so that a reaction occurs between the copolymer and the siloxane.

The silane can be mixed with the ethylene co-polymer prior to addition or the coating of both substances can be premixed on the substrate. The silane can be in the molten copolymer before extrusion in the form of an elm or a solution of the copolymer or an emulsion of the copolymer in a solvent be admitted. If an emulsion is used, the silane will hydrolyze before it is applied to the substrate. In other cases the silane will hydrolyze when placed on the surface of the substrate, only through the reaction with the moisture on the substrate surface and the atmosphere,

After the mixed coating of the copolymer and the silane or siloxane has been applied to the layer support surface, it is ^{heated to a temperature usually above 75 ° C., preferably above 100 °} C., this temperature, however, being below the temperature at which the copolymer and / or the silane or siloxane is damaged. It is assumed that this heat treatment causes a reaction between the carboxyl groups of the copolymer and the functional groups of the siloxane or silane to occur and a stronger bond of the copolymer to the substrate surface is achieved. The siloxane structure enables closer and more effective bonding to the substrate surface. Theoretical considerations state that the siloxane bonds chemically with the substrate surface, while others attribute the good bond to the increase in the wettability of the surface.

Regardless of these theoretical considerations, it is assumed that the siloxane structure represents that part of the organic layer which contributes to the improvement of the adhesion. The organofunctional residue of the siloxane couples, as assumed is, with the carboxyl groups of Äthylencοpolymeren and allows the highest possible binding force to be achieved between the copolymer and the substrate.

909850/1413

181-1912 - ίο -

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

Example · '

The binder resins used in this example are as follows marked.

A latex made from a copolymer of ethylene and acrylic acid, which has 5.2% by weight of structural units of acrylic acid, based on the solids of the polymer, and has a melt index below 0.01. The latex has a solids content of 53.1% by weight, an average particle size of 0.36 microns and a pH of 5.0.

A latex made from a copolymer of ethylene and acrylic acid which has 9.9% by weight, based on polymer solids, units of acrylic acid and a copolymer melt index of less than O ₁ Oi. The latex has a pesticide content of 52.2% by weight, an average particle size of 0.36 microns and a pH value of 2.5 »

A latex made from a copolymer of ethylene and acrylic acid, the 17.5% by weight, based on polymer solids, units of acrylic acid and has a melt index of the copolymer of less than 0.01. The latex has a pesticide content of 50.4 Gew »- $, an average particle size of 0.36 microns and a pH of 2.6. .

Binder ^

A latex made from a copolymer of ethylene and acrylic acid, the 8.9 wt .- ^, based on polymer solids, has units of acrylic acid and has a melt index of the copolymer of 133 * The latex has an average solids content of 51.3% by weight Particle size of 0.38 microns and one. pH 2.4.

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A latex made from a copolymer of ethylene and acrylic acid, the 16 | 8% by weight, based on polymer solids, units of acrylic acid and has a melt index of the copolymer of less than 0.01. The latex has a solids content of 16.2% by weight an average particle size of 0.33 microns and a pH of 3.

An aqueous dispersion of an ammonium salt from a copolymer from ethylene and acrylic acid with a content of 19j8 wt .- ^, based on polymer solids, structural units from acrylic acid and a melt index of the copolymer of 44 · The dispersion has a solids content of 19 »6 wt # - $, an average Rope size less than 0.1 micron and a pH of 9.9.

The silane used is T »aminopropyl (triethoxy) silane and is given in the following table ± n öew, - $, based on the weight of the pesticide in the resin binder.

The binders, which are used according to the table with or without the silane contained therein, are applied by dipping a rope (or Kcvings) made of water-sized glass fibers (water being the only sizing agent on the glass fiber), each glass fiber having a diameter of 0 , 0132 mm, has -and- the wet Tau (or roving) is carried out at 26O ⁰ C at a transit speed of 10.7 to 12.1 m / min, dried, and 1 percent of the binder based _e -53 (with or without silane) applied to the weight of the glass. The dried, treated glass fibers are cut to a length of 6.3 mm and mechanically mixed with polypropylene molding resin having a particle size of about 200 microns to obtain a mixture comprising 40% by weight of the treated chopped glass fibers and 60% by weight. - $ Polypropylene contains · A thorough mixture of glass fibers and polypropylene is poured into a vertical screw press and a thread 9f 5 mm in diameter is pressed · The thread is placed in a mold of 20 cm 20 cm 3.1 mm, with the counterpart

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represents a flat cover plate and the thread is under pressure to a board of size 20 cm χ 20 cm χ 3.1 mm under pressure

forms samples of the size 10 cm χ 12.7 mm χ from the plate 3.1 mm cut out for flexural strength tests. The samples were tested for flexural strength using a Balwin testing machine P.T.E, tested according to ASTM D-790.

The results are shown in the following table:

Resin Binding Silane Content, Weight - Flexural Strength, Medium - kg / cnr

1 562

1 16.0 910

2 - 598

2 30.4 834

3 - 623

3 53.7 705

4 - 574

4 27.4 705

5-537

5 51.7 922

6 - 600 6 60.8 910

As can be seen from the example, glass fibers can be mixed with the mixture of the organofunctional siloxane and the ethylene copolymer and the treated glass fibers can be coated with olefin polymers such as polypropylene, polyethylene, polybutadiene-1,3, poly-1-butene and the like. Are mixed and result in mixtures that are deformed on the screw press or by injection molding can be and result in reinforced moldings in which the glass fibers are not destroyed, as would be the case if the glass fibers would not be coated with the siloxane and the ethylene polymer. In addition, "this example shows that the Presence of the siloxane that by hydrolysis of the ΙΓ-aminopropyl (triäthoxy) silane is formed in the aqueous latices or their aqueous dispersion, the reinforcement of the polypropylene with

9 0 9 8 5 0 / 14-23 ^BAD original

will

Glass fibers improved / The siloxane as such without the use of the ethylene copolymers does not give as good results as that Combination of the siloxane and the ethylene copolymer. Thus, the substrate is made of glass fibers with the organic coating according to the invention not only better protection the glass fiber during deformation, but also a molded product of greater strength.

Claims

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Claims (5)

DR.ING. F. WUESTIIOFF λ rs λ λ η λ r ^ 8 MUNICH OO DIPL. ING, G. PtTLS DR.E.V.PECHMANN DR. ING. D. BEHRENS PATENTANWÄLTE 18118 / if12SCHWEIOERSTRASSE 2TELCroV 32 06 91TELKOnAMMADnKSSK: PItOTECTPATEXT MÜNCH KXη s1A-35 371 November 30, 1968Patentaρ r üehe 1. Inorganic substrate with organic coating, characterized by an organic coating from a mixture of an organosiloxane, the organic group of which is bonded to the silicon atom by a carbon-silicon bond and contains at least one functional group which is condensable with a carboxylic acid group with an ethylene copolymer, the units of the general formula -C- O = C-OH wherein R is hydrogen or an alkyl group having 1 to about 4 carbon atoms. 2. Layer support according to claim 1, characterized in that the ethylene copolymer contains ethylene units in an amount of at least 40 ^c / o of the total units and at least 1 ^c ß> of the units contain the group -COOH. . 3. Layer support according to claim 1 to 2, characterized in that that the siloxane repeating units of the general formula "XR ¹ SiO _5/2 _7 contains, in which R ^{1 contains} a divalent saturated hydrocarbon radical with at least three carbon atoms bonded to one another, which separates the group X from the silicon atom and X is a functional group which can be condensed with a carboxylic acid group. 4. Layer support according to claim 3, characterized in that the group X in the siloxane is a group Λ, -CH-CH-, HIf-, HS-, HO- or O = C = IT-, with at least one 909850/1423 ■: "."! ¹ UiUiIi ¹¹ IlIi! ΐ '' ■. '''"!-" ¹ IiJ " free valence at R ^! is bound and the remaining free valences are bound to hydrogen. 5. sight wearer according to claim 1 to 4, characterized in that that the substrate is mixed with a polyolefin 6, layer support according to claim 5, characterized in that it is present in a mixture with polypropylene. 78XXVI 9Q9850 / U2 3