DE1446785A1 - Process for coating carriers made of organic polymers - Google Patents

Description

P 14 46 785. 7 New documents

P. 1. DU POMT DS NEMORS AMO COMPANY loth and Market Streets, Wilmington, Delaware I9898, V.St.A.

Process for coating substrates made from organic materials Polymers

The invention relates to a method for Besehlohten of Carriers made from organic polymers with organic substances.

It has been observed that organic laminates are supported on supports from organic polymers due to the action of energizing ionizing radiation can be attached. However, undesirable side effects such as crosslinking and Impairment of the physical properties of the irradiated polymer.

The present invention is based on the object of a method sun} coating a carrier made of an organic

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To create polymers in which the essential physical Properties of the carrier are not impaired.

This object is achieved according to the present invention.

The invention now relates to a process for coating substrates made from organic polymers, which characterized in that the carrier is exposed to ionizing radiation with an energy of 15 to 50,000 eV at a dosage of at least 0.01 watt seconds / o « treated and coated the carrier with a chemically different organic substance before or during the irradiation.

Ztoeckmäesig one provides the carrier with up to 0.065 g / cm of the laminate and irradiates the laminate thereon with electron irradiation with an overall energy of the 1.0 to 20 times the energy absorbed by the layer. The laminate is preferably electrical conductive and it is earthed during the irradiation. The polymeric carrier can be combined with a different, non-polymeric one organic substance can be coated _o The polymeric carrier can also be coated with a different type of organic polymer. The carrier can also be coated with a different type of polymeric ether.

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The inventive method can be ionized with all Particle radiations are carried out, which have an energy of the volt counts listed above »if they hit the layer. Ee is beneficial that beforehand to expose coated carriers to electron beams. Therefore, this type of radiation is the preferred embodiment according to the invention-specific procedure. What is essential is » that the energy of the radiation is greater than that for them Penetration of the layer down to the adjacent surface of the polymeric carrier necessary radiation »so that the Radiation creates an ohemic bond between the surface of the polymeric carrier and the layer can cause. The electron beams of the energy ranges listed above through Energy absorbed by a layer can be determined from the following equation, where D is the weight of the layer

in g / cm and A the radiation energy absorbed by the layer in millions of electron volts (Mev) means:

A-1.92D ^{0 725}

It is advisable to use an excess of radiation energy of at least 0.000005 Mev over the amount absorbed by the layer. Therefore the value for 1.92O ^ 't ² ^ Meν can be between 1 and about 99 % of the total applied radiation energy. Since the radiation «intensity

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Difficult to regulate within precisely defined limits, the value of 1.92D ⁰ ' ⁷²⁵ Mev of about 5 % is used in practice for the value of 1.92. up to about 95 % of the total radiation energy used and preferably from 20 % to 80 % . This means "that the total energy is about 1.5 to 20 times and preferably I" 25 to 5.0 times the energy absorbed by the layer is, if the value for 1,92D ⁰ '^ ⁷² Mev. makes up about a third of the total radiant energy applied.

The upper limit - an irradiation energy of 0.05 Mev - imposes a limit on the weight of the organic laminate used. In the case of electron irradiation, in which the value for 1.92D ^{O> 725} Mev approaches approximately 0.05 Mev, the permissible weight of the layer reaches a value of approximately 0.00652 g / cm. It has proven to be expedient to use Schlohtgewlohte of up to a maximum of 0.00652 g / cm for all types of ionized particle radiation, because the surface effects achieved are practically independent of the thickness of the layer and the irradiation time.

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It can be seen that the layer is extremely thin can be and that it is therefore a comparatively low one Requires radiation energy to establish a solid connection with the to achieve polymeric carrier. In the case of a monomolecular layer of an organic compound before molecular weight 100 would for example a layer weight of about 5.5 10 g / cm are present. To penetrate such a layer »an electron energy of about 0.000011 Mev would be necessary. Sine Irradiation energy of about 0.000015 Mev therefore represents the practically lower limit of the energy which is expedient for carrying out the method according to the invention, whereby a lower limit of 0.000033 Mev is preferred.

The irradiation temperature can be within wide limits vary. For example, the irradiation can be in a range from -80 ° up to the decomposition temperature of the organic laminate or the carrier material, for example up to. at 300 °. However, such high temperatures offer little benefit and it is useful for reasons the economy to apply room temperatures.

The inventive method can be in the air, in a inert atmosphere, e.g. of nitrogen or helium, or if the reaction system is relatively poorly volatile, im Vacuum can be carried out. Irradiation in a vacuum or

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at least under reduced pressure is often desirable because of this the number of coincidence of the radiation points with existing gases and thus the effectiveness of the Radiation is increased.

In certain cases, especially if this is appropriate Procedure is carried out in air, it is two-way, that the surface to be irradiated is electrically grounded. For this purpose, a carrier device or a Select laminate that is noticeably electrically conductive is. If you ground such a carrier or layer » the effectiveness of the irradiation is improved

Under an organic polymeric carrier in the sense of present invention are natural or synthetic * Usually to understand solid organic polymeric substances, especially those with molecular weights above 500.-The polymer can be oriented or disordered. For example, it can polymeric hydrocarbons, such as polyethylene, polystyrene, polybutadiene, rubber, polyisobutylene, butadiene, styrene melt polymers and the like, polymeric halogenated hydrocarbons, such as Polyvinyl chloride «polyvinylidene chloride» polychloroprene, polytetrafluoroethylene, polyvinyl fluoride «chlorinated and chlorosulphonated it polyethylene and the like« ester-containing polymers »

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such as polyvinyl acetate, polymethyl methacrylate, polyethylene terephthalate and the like; hydroxyl-containing polymers such as polyvinyl alcohol * cellulose, regenerated cellulose and the like; ether containing polymers such as polyethylene oxide, polymeric formaldehyde, solid polytetrahydrofuran and the like; Condensation polymers such as polyamides, phenol formaldehyde polymers, urine formaldehyde polymers, triazine formaldehyde polymers and the like; Polypeptides, silicones, and olefin polysulfones; as well as natural Polymers such as wool, cotton, silk and the like can be used

From a chemical point of view, it is only necessary that the organic material used for the sole according to the present invention is chemically different from the carrier. The organic laminate can be solid or liquid at the time of irradiation. Liquids can to the carrier by conventional means such as dipping, spraying, brushing ₅ Printing and the like. Be applied. Solid substances can be applied to the carrier material by sublimation or from the melt, from the solution or from a dispersion. The liquid or solid laminates can be hydrocarbons, halogenated hydrocarbons, alcohols, amines, aldehydes, ketones, ethers, acids, esters, amides, phenols, sulfonic acids, nitrogen compounds, fats, bi-white substances, synthetic polymers and others

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Be organic compounds that contain at least one CX bond in which X is hydrogen or calogen. The organic layer material is preferably compatible with the carrier material under normal circumstances and also has no dissolving effect on the carrier.

Of the non-polymeric organic compounds "that can be used as laminates according to the invention", the chain-transferring or bridge-building substances "are to be named" for example compounds with active hydrogen or halogen "such as. 'J secondary chloroform, carbon tetrachloride, Tr ipheny line than _"s thiols, alcohols, maleic anhydride and the like., As. these substances are particularly reactive and enter into an intimate connection with the wearer.

Those non-polymeric organic compounds are preferably suitable which are usually not polymerizable _and which are easier to apply to the JScMehteasse to be applied to the carrier.

As Johichtstoffe are also particularly suitable especially the polymer ethers because they have a big game Allow space in terms of surface properties.

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The ionizing particle radiation which is used according to the invention can be used in the form of α-rays or electron beams * and it is only limited with regard to the energy present at the time of impact on the layer mass. The radiation according to the invention is expediently of low energy, as indicated above, and it can be generated by means of the known methods which are not the subject of this invention. Thus, particles of suitable energy can be obtained by means of a suitable potential difference, for example by means of cathode ray tubes, by means of resonance cooling, a Van ds Graaff ¹ «see generator (see" Chemie-Ingenieur-Technik ", 1957» pages 165 to 169) or other suitable radiation sources. The accelerated particles can also be used in a vacuum by placing the reaction system in the vacuum chamber of the accelerator.Also, accelerated electrons or α-particles can emerge in a known manner through a window and be used in air or in a gas atmosphere under the necessary precautions , whereby the particles must have the required energy when they hit the reactor system. According to a preferred embodiment, the beams are obtained from electrons with low energy, which are achieved by means of suitable voltage gradients, such as, for example, an induction coil of a Tesla transformer. This radiation source is particularly useful because the radiation borrows, can be generated at low cost and precisely metered penetration force.

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

A film of polyethylene terephthalate of 0.0254 mm thick is dipped a polyethylene oxides having a molecular weight of 20,000 in a $ 10 aqueous solution containing a small amount of a wetting agent ", for example, a Oetyl-phenyl polyglycol ether, mn can dsia film drip and air dry. The polyethylene oxide on the film weighs Oi 3584? ms / cm . The film seen in this way is placed on a rubber pad and introduced into the radiation chamber, which is evacuated to about 1 mm Hg. The film is exposed to a radiation field * which is generated by a T © sla high-frequency induction rinse. öa® SsfeMsfeisiggende this coil iet IG. « 16 © m over uem film mig & maxstib, whereby an energy of the slektru ^ @ n @ trahlei2bünäels of about 0.010 Mev is achieved. The irradiation is carried out for two hours.

The film is then extracted with ethanol in a Soxhlet extraction apparatus for 50 hours. The extracted film shows a weight increase of IS% compared to the original uncut film. On the irradiated surface it shows a visible layer of polyether · which cannot be rubbed with

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A linen cloth could be removed «Der« pesifische electrical resistance of the coated surface is 10 '^ Oho / cm, while an untreated control film is only a resistivity of 10 '^ ohn / om.

Example 2

Polyäthylenflln 0.0508 nm thick is covered with polyethylene oxide as in Example 1. Öle Sohloht has an Oewloht of 0.2467 ng / on ² . The coated film is irradiated as described in Example 1 and then extracted.

The FlIn treated in this way shows a weight increase of 2.8 % compared to the original thread of the film before the film. Oils irradiated surface shows a visible color of polyether. The wettability of the film with water is determined by determining the angle of inclination at which the rear edge of a water drop of 0.05 ml has a speed of 0 ₉ I aa / seo. Slides over the film. In these "Oleitwlnkel-Yersuoh" the coated surface of the film has a value of 40 °, while the unpolished surface has a value of 34 °, which is also shown by the original film. The contact angle of the upper coated surface against water is 26 to 36 °, while the lower unaffected

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layered surface has a contact angle of 53 to 62 °. The film treated according to the invention has an envelope set temperature of 110 °, which means «that the strength of the film drops to zero at 110 °, while one in the same way with a radiation energy, of 2 Mev treated film has a zero temperature of 160 bie 170 °, oils according to the invention treatment at low, dosed energy thus avoids inner® interconnections «the occurs when exposed to high energy.

Example 3

A polyethylene terephthalate film from Q.025 ^ mm Dieke is immersed in a solution of two parts of polyvinyl chloride in 97.5 parts of tetrahydrofuran and 2.5 parts of dimethyl formamide. The film is allowed to drain off and then dried for two hours at 60 °. The layer of polyvinyl chloride has a Qwlht of 0.305 lug / cm. The film coated on both sides is then irradiated for one hour on each side in the irradiation chamber described in Example 1. After 2 or 3 minutes of exposure, the polyvinyl chloride layer turns brown. The irradiated film is then extracted for 40 hours with dioxane in a SoxJilet extractor and then extracted with tetrahydrofuran for a further 20 hours. After this treatment the film has a visible brown layer of adhering © «! Polyvinyl "

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ohlorid »and he shows a weight gain of 7.2 # versus the »starting film, while a comparative film that only includes Polyvinylohlorld was coated but not irradiated, has no visible layer after extraction and only has a weight gain of 1.6 #. The polyvinyl chloride layer formed according to the invention by irradiating the support cannot be removed by rubbing or scratching.

Example 4

A polyethylene film 0.0508 now thick is coated with polyvinyl chloride as in Example 2. The polyvinyl chloride layer weighs 0.2844 wig / cm. The film coated in this way is then irradiated and extracted as in Example 3. According to this, the film has a visible layer of adhering polyvinyl chloride and shows only a reduction in weight of 16.9 ## during the extraction while a control film that was not irradiated has no visible layer and a weight loss of 2δ.3 % after the extraction. Has.

The radiation energy used according to the preceding examples Gentlgt to penetrate through the layer into the wearer. From the Factor 1.920 * '- * Meν can be seen that the used to penetrate the layer in the various examples « Radiation energy is roughly the following:

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Example Mev (roughly)

1 0.0064

2 0.0045

3 0.0054

4 0.0055

Example β

Sin polyethylene film of 0.0508 now thickness with a solution of 0.5 S palmitic IC (0.1 mC / g;. Wherein rac "1 Mlllicurle 1st, cf. Houben-Weyl-Möller," Methoden der organischen Chemie ¹ * , Volume 3, Part 1, Stuttgart 1955 »Page 758, Paragraph 2) in ether 49.5 B. The ether is allowed to evaporate and the film is then placed in a cathode ray tube that can be dismantled and is arranged in such a way that a stream of electrons can flow The tubing system is evacuated to about 0.03 Miteon © ruok and the coated film then has a lung field of 50 eV at 25 to 50 MiteOampsre at 0 ^ 2 Watts® seconds / öm ² deals the film is. dam with ether for six days in a Soxhlet °> apparatus extracted. the remaining radioactivity of the film as it is angeseigt by a Oeiger-föülle ^ Ziihlrohr (end window counter tube), then 1st with 12 pulses / Min / 2.5 cm (12 impulses or counter tube recesses per minute, measured on an area νου 2.5 cm opposite the Background or background effect Kouteen-Weyl-Müller, page 773 »below) constant. The determination of the activity through combustion by means of elemental analysis ergaο

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• inen Vert of O, O4% of the labeled Palroitinsäure, based on the original Qewloht of the film, or 1,8 γε / cro (1 Yg "β 1) of the nit FilmoberfläOhe fixedly connected Palmi tlnsfture.

Example 6

A polyethylene film is coated and irradiated as in Example 5, except that £ 3,000 electron volts (25 Keν) are used, up to 25 microamps and an office radiation of 0.010 seconds / cm ² . After extraction with ether to the point of consumption according to Example 5, the FHm has a remaining radioactivity of 9-16 pulses / nin. / 2.5 cm ² above the background, which corresponds to 1.4-2.4 yg / om of bound palmitic acid.

Example 7

A polyethylene film is coated and irradiated as described in Example 5, with the exception that the irradiation is carried out with 25 Kev electrons at 25 microamps and a total radiation of 12.35 watts / om. After extraction with ether until the activity is constant, the pel shows a permanent radioactivity of 37-42 pulses / min / 2.5 cm ² above ground, which corresponds to 6 yg / s of bound palmitic acid. In a comparison test carried out with 2 Mev in a gleloher irradiation tent, the remaining activity

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just did Il Imp Above zero. Saraue goes the grusaere Effectiveness of the process according to the invention with irradiation carried out with lower energy.

B e i a ρ 1 e 1 8

Obtained Bin O ₅ 038I mm thick film of regenerated cellulose "aws cellulose xanthate, which has been coated on both side with Vinylidenchlorld ^ Mischpolymerein of about 0,05OS min Cioke 1st, is used in a demountable cathode-ray tube with 25 Kev electrons at 25 microamps to a cumulative exposure of 0.2 cotton-wool seconds / am irradiated, the irradiated film is still tough and flexible, while a similar irradiation with 2 Kev leads to a very stiff and brittle film. The film is extracted with Sloxan in a Soxhlet apparatus for 50 hours. Then the side of the film treated with the radiation source has a vinylidene chloride mixed polymer layer. It is not wetted by water, while the other side of the film, which has not been exposed to the electron irradiation, has a vinylldenuhlorld micropolymer layer that is slightly wetted by water.

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An important advantage of the present invention is that non-polymerizable and polymerizable substances are bonded to the substrate by using inexpensive radiation energy with the lowest possible radiation exposure. Before • lie "aueh unerwUnsehte networks, degradation and other changes in physical properties de · be avoided" organic ^{Folymerentragers.!}

The inventive method is above all suitable Sum coating of organic polymeric substances, from an * Striohmltteln, antistatic soles, i.e. the electric ones Charging-preventing oherasty and coloring substances on -Oewebei as well as lubricants, water-resistant boots etc. on films such as those on regenerated cellulose

The invention is not restricted to the embodiments shown.

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Claims (6)

Claims 1. Process for coating substrates made of organic Polymers «characterized in that the carrier with ionizing radiation with an energy of 15 to 50,000 eV at a dosage of at least 0.01 watt seconds / om treated and the carrier before or during the irradiation with a chemically different organic Fabric coated. 2. The method according to claim 1 «characterized in that one the organic coating on the support in an amount up to at 0.0065 g / cm and the laminate on top electron irradiation with a total energy of 1.0 to Seeing the energy absorbed by the fjfcsrsyg is irradiated. 3. The method according to claim 1 or 2, characterized in that the electrically conductive layer body is grounded during the irradiation « 4. The method according to claim 1 Me>, characterized in that « that for coating a non-polymeric organic compound is used. _ _l8 _ ■ ORIGINAL BATHROOM New Lc-: ^ 3en (Aft 7 § % abs. 2 «r. T CIM647-A U46785 is 5. The method according to claim 1 to 3, characterized by that an organic polymer is used for the coating. 6. The method according to claim 5 »characterized in that a polymeric Xther is used on the coating. . 19 - BATH ORIGINAL 909841/1192