FI67392B - FRAMEWORK FOR FRAMEWORK FOR FASTENING OF A WHEEL - Google Patents

Description

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German Li ittota & avalta-Förbundsrepubliken Tyskland (DE) P 2736499-4 (71) Wacker-Chemie GmbH, Prinzregentenstr. 22, 8000 MUnchen 22, Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Friedrich Hockemeyer, Emmerting, Federal Republic of Germany-Förbundsrepubl iken Tyskland (DE) (74) Lei tz Inger Oy (54) Method for coating adhesive-repellent coatings for the purposes of paragraph 1, the first and second subparagraphs shall apply

The invention relates to a process for preparing adhesion-repellent coatings by applying mixtures consisting of (1) an organopolysiloxane containing Si-linked vinyl groups having a viscosity of at least 40 cP at 25 ° C, (2) an organopolysiloxane containing at least 3 Si-bonded hydrogen atoms, 4 to 150 cP at 25 ° C in an amount of 0.5 to 35 gram equivalents of Si-bonded hydrogen for each Si-bonded vinyl group in the diorganopoly siloxanes (1), (3) a platinum complex that promotes the attachment of Si-bonded hydrogen to an aliphatic multiple bond in an amount of 5 to 100 ppm as elemental platinum based on the total weight of organopolysiloxane (1) and (2), and a substance which retards the incorporation of Si-bonded hydrogen into an aliphatic multiple bond at room temperature in an amount of 0.1 to 0.8% by weight of total organopolysiloxane (1) and (2) , on surfaces made to repel adhesives.

67392

A process for preparing adhesion-repellent coatings by applying mixtures of (1) an organopolysiloxane containing Si-linked vinyl groups, (2) an organopolysiloxane having at least 3 Si-bonded hydrogen atoms per molecule, (3) a platinum complex that promotes Si aliphatic multiple bond, and (4) a substance that slows the incorporation of Si-bonded hydrogen into the multiple bond at room temperature, to surfaces to be made repellent, and by crosslinking organopolysiloxane (1) is already known and (cf. e.g. DOS 22 22 380, published September 21, 1972, filed by Dow Corning Ltd., London). In this known method, the networking is performed by heating in the usual way.

DOS Publication No. 24 17 944, published April 3, 1975 to Dow Corning Corp., relates to an ultraviolet curable preparation consisting essentially of organopolysiloxane containing vinyl groups, organopolysiloxane containing Si-bonded hydrogen and a photosensitizer, and this mixture is also recommended. manufacturing.

Finally, from British Patent Publication No. 13,998,885, published July 2, 1975, to Imperial Chemical Industries Limited, a process is known for preparing adhesion-repellent coatings by applying compositions consisting of (1) dimethylsiloxane units having one Si-bonded unit in each of the terminal units. a hydroxyl group, (2) an organopolysiloxane containing Si-bonded hydrogen, and (3) a platinum catalyst, for surfaces to be made repellent to adhesives, and by crosslinking the organopolysiloxane (1). However, also in this known method, the crosslinking energy of the organopolysiloxane (1) is not crosslinked by attaching a Si-bonded hydrogen to an aliphatic multiple bond but by condensing a Si-bonded hydrogen and a Si-bonded hydroxyl group.

According to the invention, it is provided that at least when the platinum complex (3) is not already a photosensitizer, the mixture used in each case contains at least one photosensitizer (5) in an amount of 67392 0.01 to 5% by weight of the total weight of organopolysiloxane (1) and (2), and that at least part of the network energy comes from ultraviolet light.

In contrast to the methods outlined above for preparing adhesion-repellent coatings, the method of the invention has the particular advantages that it can be performed at lower temperatures, which means lower thermal stress on the substrates to be coated, that it can be performed in a shorter time and / or that crosslinking can be performed. with a lower amount of ultraviolet light and / or that the ready-to-use mixtures are more durable.

Diorganopolysiloxanes (1) containing Si-linked vinyl groups are best compounds of the general formula (CH2 = CH) (CH3) 2SiO (SiR20) nSi (CH3) 2 (CH = CH2), where R represents the same or different, monovalent, optionally substituted hydrocarbon groups, and n is an integer such that the viscosity of the diorganopolysiloxane (1) is at least 40 cP at 25 ° C.

Within the organopolysiloxane chain of the above formula, i.e. along its length, there may be other siloxane units not normally shown in such formulas, in addition to diorganopolysiloxane units, i.e. units of the general formula SiR20. Examples of such other siloxane units, which in most cases appear only as impurities, are those of the formula RSiO3 / 2, R3SiOjy2 and SiO2, in which case R in each case has the same meaning as above. The amount of such other siloxane units is preferably at most 10 mol%, in particular at most 1 mol%.

In addition to vinyl groups, examples of other SiC-bonded hydrocarbon groups in diorganopolysiloxanes (1) and thus also of hydrocarbon groups R of the above formula are alkyl groups having 1 to 18 carbon atoms, 4 67392 such as methyl, ethyl, n-propyl, iopropyl, n-butyl and a sec-butyl group and an octadecyl group and cycloalkyl groups having 5 to 8 carbon atoms such as a cyclohexyl and cycloheptyl group and a methylcyclohexyl group * aryl groups such as a phenyl group and a xenyl group; alkaryl groups such as tolyl group; and aralkyl groups such as benzyl and beta-phenylethyl group.

In addition to the vinyl groups in the terminal units or in the terminal units, the diorganopolysiloxanes may also contain vinyl groups in the diorganosiloxane units. Thus, the hydrocarbon groups R in the above formulas can also be vinyl groups or also other alkenyl groups, such as allyl groups or cycloalkylene groups. However, the total amount of all alkenyl groups and cycloalkenyl groups in diorganopolysiloxanes (1) is preferably not more than 10%, in particular not more than 1% of all organic groups present.

In the SiC-bonded, substituted hydrocarbon groups in diorganopolysiloxanes (1) and thus also in the substituted hydrocarbon groups R of the above formulas, examples are halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl group and o-, p- and m-chlorophenyl groups.

For the sake of its readiness alone, the number of SiC-linked organic groups other than vinyl groups in the diorganopolysiloxanes (1) and thus also in the groups R of the above formulas is preferably at least 50%, in particular at least 90% of the methyl groups.

If the mixtures used according to the invention should be at least practically solvent-free, which is desirable for environmental protection, for example to avoid explosion, to reduce transport and storage costs and also to avoid solvent evaporation costs, the value of n is such that the viscosity of diorganopolysiloxane (1) ° C is not more than 10,000 cP, in particular not more than 5,000 cP. However, if solvents are used in the process of the invention, the viscosities of the diorganopolysiloxane (1) may range from 10,000 cP to 10 ^ cP at 25 ° C, and in a Brabender plastograph at 25 ° C and 60 rpm. specified values can be up to 80 - 500 mpp.

5 67392

The diorganopolysiloxanes (1) may be only a single copolymer or mixtures of different copolymers with a similar degree of polymerization or mixtures of similar or different copolymers with a different degree of polymerization. When diorganopolysiloxanes (1) contain different diorganosiloxane units, these different units may be randomly distributed or may be in the form of polymer segments.

If a particularly high adhesion repellent effect is desired and the associated diorganopolysiloxane (1) should be particularly readily available, especially in food packaging materials, all SiC-linked organic groups other than vinyl groups in diorganopolysiloxanes (1) are methyl groups. If, instead, a slight, tack-repellent effect is desired, for example in the manufacture of self-adhesive label covers or foils, this is best achieved by having 3 to 30 mole percent of the diorganopolysiloxane units (1), preferably 5 to 20 mole percent 1) at least 50% of the SiC-bonded organic groups of the other diorganopolysiloxane units are methyl groups. The higher the proportion of diphenylsiloxane units, the lower the adhesion to the adhering substances.

As organopolysiloxanes (2) containing at least 3 Si-bonded hydrogen atoms per molecule, the same organopolysiloxanes containing at least 3 Si-bonded hydrogen atoms per molecule can also be used in the process according to the invention as in all hitherto known processes for preparing tack-repellent vinyl coatings. a di-crganopolysiloxane, an organopolysiloxane containing at least 3 Si-bonded hydrogen atoms per molecule, and a catalyst that promotes the incorporation of Si-bonded hydrogen into an aliphatic multiple bond.

Organopolysiloxanes (2) containing at least 3 Si-bonded hydrogen atoms per molecule have bivalent unsaturated hydrogen and siloxanoic oxygen atoms, preferably saturated with methyl, ethyl and / or phenyl groups. These organopolysiloxanes (2) are preferably compounds of the general formula 6 67392 R'Si (CH3) 20 (SiR'20) pSi (CH3) 2R 'wherein R' represents hydrogen or a methyl, ethyl and / or phenyl group, provided that only one hydrogen atom is attached to one Si atom, each SiR'20 unit has on average at least 0.2 Si-bonded hydrogen atoms and, of course, at least 3 Si-bonded hydrogen atoms per molecule, and p is an integer such that organopolysiloxanes (2 ) has a viscosity of 4 to 150 cP at 25 ° C.

The amount of Si-bonded hydrogen atoms is preferably 0.2 to 1.6% by weight, especially 1.03 to 1.46% by weight, based on the weight of the organopolysiloxane (2).

Organopolys.iloksaaneista Examples of the above compounds of formula (2) are, in particular dimetyylivetysiioksaani-, methylhydrogensiloxane, dimethylsiloxane, and copolymers of trimetyylisiloksaaniyksiköiden, trimethylsiloxane, dimetyylivetysiioksaani- and methylhydrogensiloxane copolymers, trimethylsiloxane, dimethylsiloxane and methylhydrogensiloxane copolymers, and methylhydrogensiloxane trimetyylisiloksaaniyksiköiden copolymers, methylhydrogensiloxane, and difenyylisiloksaani- trimetyylisiloksaaniyksiköiden copolymers, methylhydrogensiloxane, and dimetyylivetysiioksaani- diphenylsiloxane copolymers, methylhydrogensiloxane, phenyl-methyl, trimethylsiloxane and / or dimetyylivetysiloksaaniyksiköiden copolymers, methylhydrogensiloxane, dimethylsiloxane, diphenyl siloxane, trimethylsiloxane and / or copolymers of dimethylhydrogensiloxane units and dimethylhydrogensiloxane, copolymers of trimethylsiloxane, phenylhydrogeniloxane, dimethylsiloxane and / or phenylmethylsiloxane units.

Also in organopolysiloxanes (2), when it has different SiR'20 units, these are best distributed statistically. However, the SiR'20 units may also be in the form of polymer segments.

Organopolysiloxanes (2) still preferably have all silicon solvents which are not saturated with hydrogen and siloxane oxygen atoms, saturated with methyl groups. This means that in the above formula of organopolysiloxanes (2), each R 'represents a 7 6 7 3 9 2 methyl group when R' is not hydrogen.

The process for the preparation of organopolysiloxanes (2), including the above-mentioned organo-dust siloxanes (2), and the process for the preparation of diorganopolysiloxanes (1) are generally known.

Mixtures of different organopolysiloxanes (2) can also be used. However, a single organopolysiloxane can also be used (2).

Organopolysiloxane (2) is best used in 0.5 to 35, especially 1 to 5, gram equivalents of Si-bonded hydrogen per gram of Si-bonded vinyl groups in diorganopolysiloxanes (1).

As platinum complexes (3) which promote the attachment of Si-bonded hydrogen to an aliphatic multiple bond, the same platinum complexes used to promote crosslinking in hitherto known methods for crosslinking aliphatic multiple bonded or Si-bonded hydroxyl groups can also be used in the process according to the invention. polysiloxanes as compounds containing Si-bonded hydrogen. Examples of such platinum complexes are platinum-olefin complexes, for example complexes with ethylene, propylene or butadiene, and platinum-olefin complex known as dichlorodicyclohexene-my-dichloroplatinum (II), platinum-alcohol complexes, platinum-ether complexes platinum -aldehyde complexes, platinum diacetylacetonate, N, PtCl 2 · 6H 2 O and monoketones, for example cyclohexanone, methyl ethyl ketone, acetone, methyl n-propyl ketone, methyl isobutyl ketone, diisobutyl ketone, methoxyacetone, 2-ethoxyphenone, 2-ethophenone, 2-ethophenone reaction products of phenone, 2-ethoxy-2-phenylacetophenone or mesityl oxide, and platinum-vinylsiloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, with or without detectable organic halogen.

Mixtures of different platinum complexes can also be used, for example the reaction product of H 2 PtCl 2 * 6H 2 O with cyclohexanone and a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex which does not contain detectable inorganic halogen.

8 67392

Platinum complexes (3) can be used as solutions, for example in the complexing agents used for their preparation, such as cyclohexanone.

The platinum complex (3) is preferably used in an amount of 5 to 100 ppm by weight (parts by weight per million parts by weight), especially 30 to 50 ppm, in each case calculated as elemental platinum and organopolysiloxaneE (1) and (2).

As substances (4) which retard the incorporation of Si-bonded hydrogen into an aliphatic multiple bond at room temperature, all substances which retard the incorporation of Si-bound hydrogen into an aliphatic multiple bond at room temperature, which have hitherto been used for a similar purpose, can also be used in the process according to the invention. Examples of substances which retard the incorporation of Si-bonded hydrogen into an aliphatic multiple bond at room temperature include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, benzotriazole, dialkylformamide, alkylthiourea, methylethyl ketoxime and organic or silicon organic compounds with at least 25 ° C at 760 mm Hg (abs.) and at least one aliphatic triple bond compound such as ethynylcyclohexanol and 2-methyl-3-butinol-2.

Mixtures of various substances which retard the incorporation of Si-bonded hydrogen into the aliphatic multiple bond at room temperature can also be used, for example a mixture of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and ethynylcyclohexanol.

The substance (4) which slows down the incorporation of Si-bonded hydrogen into the aliphatic multiple bond at room temperature is best used in an amount of 0.1 to 0.8% by weight, based on the total weight of the organopolysiloxanes (1) and (2).

As already mentioned above, at least when the platinum complex (3) used in each case is not already a photosensitizer, a photosensitizer (5) is to be used in the method according to the invention. Platinum complexes, which are photosensitizers and thus do not require the use of any other photosensitizer, are, for example, the reaction products of the above-mentioned 67392 9 H 2 PtCl 2 * 6 H 2 O and monoketones, as well as the above-mentioned platinum-vinylsiloxane complexes.

The platinum complex is considered a photosensitizer when it has a significant absorption capacity in the ultraviolet range.

Examples of photosensitizers (5) are the above-mentioned ketones as well as propophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-41-benzylbenzophenoline, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone , chloroanthraquinone, MIchler's ketone, cinnamic acid, benzoin ethyl ether, anthracino-1,5-disulfonic acid disodium salt, 2-naphthalenesulfonyl chloride and benzyl.

If photosensitizers (5) are used, they are best used in an amount of 0.01 to 5% by weight based on the total weight of the organopolysiloxanes (1) and (2).

Although the order in which the ingredients (1), (2), (3), (4) and possibly (5) are mixed is not decisive, in practice it has proved best to add ingredient (2) last, i. An organopolysiloxane containing Si-bonded hydrogen in a mixture of other ingredients.

The solvents optionally used in the process of the invention may be the same as those used in the prior art processes for preparing tack repellent coatings, Si-bonded vinyl group-containing di-organopolysiloxane, Si-bonded hydrogen-containing organopolysiloxane and catalyst, the attachment of bound hydrogen to an aliphatic multiple bond. Examples of such solvents are benzene, for example an alkane mixture having a boiling range of 80 to 110 ° C at 760 mm Hg (abs.), Benzene, toluene and xylene, halogenated alkanes having 1 to 6 carbon atoms, such as methylene chloride, trichlorethylene and perchlorethylene, ethers , such as di-n-butyl ether, esters such as ethyl acetate and ketones such as methyl ethyl ketone and cyclohexanone.

10 67392

If organic solvents are used, they are suitably used in an amount of from 100 to 5,000% by weight, based on the weight of the diorganopoly siloxane (1).

A mixture of (1) a diorganopolysiloxane containing Si-linked vinyl groups, (2) an organopolysiloxane containing at least 3 Si-bonded hydrogen atoms per molecule, (3) a platinum complex that promotes the incorporation of Si-linked hydrogen into an aliphatic multiple bond, and (4) which slows the incorporation of Si-bonded hydrogen into the aliphatic multiple bond at room temperature, application to a surface which is made to adhere adhesives can take place by arbitrary and frequently used methods for preparing liquid coatings, e.g. by dipping, brushing, pouring, spraying, rolling, By means of an offsetgravus coating machine, by blade or squeegee coating, including a Meyer rod (in English: Meyer-Rod) or by means of an air brush. If the application takes place with an offset gravur coating device, for example a raster-roll system, then the substrate with its adhesion-repellent surfaces can travel faster than the shaped cylinder.

The fact that the method according to the invention can be carried out in a particularly short time means that the devices with which the mixtures used according to the invention are applied to surfaces to be repelled by adhesives can be used at a particularly high speed.

Adhesion-repellent surfaces that can be treated in accordance with the invention can be surfaces of arbitrary solids at room temperature and pressure of 760 mm Hg (abs.). Examples of such surfaces are surfaces made of paper, wood, cork, plastic foils, for example polyethylene foil or polypropylene foil, woven or nonwoven fabric made of natural or synthetic fibers or fiberglass, ceramics, glass, metals, polyethylene coated and coated with polyethylene . The above-mentioned polyethylene may be high, medium or low pressure polyethylene. Inferior paper grades, such as absorbent papers, including untreated kraft paper, i.e. kraft paper not pre-treated with chemicals and / or polymeric natural substances and weighing 60 to 150 g / m 2, uncoated papers, low grinding papers, wood-containing papers, unsaturated or non-calendered papers, papers, are smooth on the other side, because their production is being used in the drying cylinder without any additional measures, and are therefore referred to as "the other side konesileiksi papers", uncoated papers or papers made of a so-called waste paper. jätepape-vectors. The paper to be treated according to the invention can, of course, also be high-quality paper, such as low absorbency papers, glued papers, papers with a high degree of grinding, paperless papers, calendered or satinized papers, parchment papers, parchment papers or uncoated papers. Cardboard can also be of good or poor quality.

The best ultraviolet light is considered to be light with a wavelength of 253.7 nm (nanometers). Several lamps are commercially available which emit ultraviolet light in the range of 200 to 400 nm and which emit mostly ultraviolet light having a wavelength of 253.7 nm. In addition to ultraviolet light, other energy sources can be used, for example furnaces, heating channels, heated rollers, heated plates or infrared heat radiation. When all the advantages of the invention are to be exploited, temperatures above 120 ° C are avoided.

The process according to the invention can be used, for example, for the production of release, lining and intermediate papers, including intermediate papers used in the production of cast or decorative foils or foams, including polyurethane foams. The method according to the invention is further suitable, for example, for the production of separating, cladding and interleafboard, foils and fabrics, it can be provided on the backs of self-adhesive tapes or self-adhesive films or on the text pages of self-adhesive labels. The method according to the invention is also suitable for the production of packaging materials, such as packaging materials made of paper, cardboard boxes, metal foils and fibers, e.g. cardboard, plastic, wood or iron, for adhesives such as adhesives, sticky foods, e.g. cakes, honey, confectionery and for the storage and / or transport of meat, bitumen, asphalt, greasy metal parts and raw rubber. One example of the use of the method 67392 12 according to the invention is the production of substrates for the transfer of adhesive layers by the so-called "transfer method".

The following information includes all parts and percentages calculated by weight unless otherwise indicated or if this makes sense.

The mixture of platinum-divinyltetramethyldisiloxane complex and diluent used in some of the following examples was prepared as follows:

To a mixture of 10 parts of H 2 PtCl 3 * 6H 2 O, 20 parts of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 50 parts of ethanol were added 20 parts of sodium bicarbonate. The mixture was heated at reflux for 30 minutes with stirring, then allowed to stand for 15 hours at room temperature and filtered. The volatiles were distilled from the filtrate at a pressure of about 12 mm Hg (abs.). The residue was dissolved in benzene. The solution was filtered and benzene was distilled from the filtrate. The residue was mixed with an amount of dimethylpolysiloxane used as a diluent containing vinyldimethylsiloxane units as terminal units and having a viscosity of 1,400 cP at 25 ° C such that the mixture contained 1% of platinum based on the element.

The mixture of platinum-cyclohexanone complex and diluent used in the second of the following examples was prepared as follows:

A solution of so much H 2 PtCl 2 / H 2 O in 200 ml of cyclohexanone that contained 0.2% platinum in the solution was heated at 100 ° C for 1 hour and then dried over anhydrous sodium sulfate.

Example 1 10 parts of dimethylpolysiloxane containing vinyldimethylsiloxane units as terminal units and having a viscosity of about 1,000 cP at 25 ° C are mixed with 0.03 parts by weight of methyl ethyl ketoxime and dissolved in 10 parts of toluene (so that in the laboratory test without the use of a solvent). Mix together the solution thus obtained, 0.3 part of a mixture of the platinum-cyclohexanone complex and the diluent containing 60 ppm of platinum, calculated on the element and weight of the organo-polysiloxane containing vinyl groups, and 0.3 part of the methylhydrogensiloxane and trimethylsiloxane , having a viscosity of 60 cP at 25 ° C.

2 The mixture thus obtained is applied by means of a Rake to about 1.5-2 g / m of satin-coated and sparingly water-absorbing parchment paper weighing 67 g / m 2. In this case, a stainless steel rod is used as the raw material, around which a 0.2 mm thick stainless steel wire is wound. After most of the toluene has evaporated, the paper is placed in the form of a ring at a distance of 2 cm around a finger-shaped ultraviolet lamp with a lighting section of 2.5 cm. The coated side of the paper is then naturally inside the ring. The power of the ultraviolet lamp is 150 Watts, i.e. 60 Watts per cm of lighting unit. The maximum power is at 253.7 nm. As long as the ultraviolet lamp is on, the temperature of the lamp and the paper is maintained at about 90 ° C by means of a fresh air blower. Table 1 below shows the on-time of the ultraviolet lamp.

Then, a 2 cm wide adhesive tape ("Tesafilm rot", No. 154, Beiersdorf AG, Hamburg, Germany-BRD; the word "Tesa" is a registered trademark) is applied to the coated side of the paper and is pressed with a rubber roller with a force of 15 kp. Heat for 24 hours at 70 ° C under a load of 20 rpm, after which the adhesive tape is pulled off the paper at 20 ° C at an angle of 180 ° at a rate of 30 cm / minute. The force required for this release is measured and is referred to in the following tables as the "separation force". Residual sizing force means the sizing force of an adhesive tape obtained before this tape was printed on the coated paper, the basic value of which is set to 100%.

Comparative test a

The procedure described in Example 1 is repeated with the change that 0.3 part of pure cyclohexanone is used instead of the mixture of platinum-cyclohexanone complex and diluent.

The procedure described in Example 1 is repeated with the change that the temperature between the lamp and the paper is maintained at 45 to 50 ° C while the ultraviolet lamp is on.

14 67392

Example 2

Examples 1 and 2 and Comparative Experiment a give the following results:

Table 1 UV lamp top- Temperature lam- Separation- Residual soak time, soap and paper strength seasoning force between municipalities, ° C w / cm%

Eg 1 30 about 90 3 69

Eg 1 60 to about 90 1 80

Eg 2 120 45-50 3 75

Comparative test a 300 90 3 8

Comparative test b

The procedure described in Example 2 is repeated with the change that the paper is kept for 10 minutes in a convection oven at 45 ° C without the use of ultraviolet light. In this case, no formation of a crosslinked coating is observed. After at least 5 minutes at 90 ° C, the separation force is 2 p / cm and the residual gluing force is 71%.

Example 3

First, 100 parts of dimethylpolysiloxane containing vinyldimethylsiloxane units as terminal units and having a viscosity of 118 cP at 25 ° C and 0.3 parts of ethinyl-cyclohexanol are mixed, followed by 0.6 parts of platinum-divinyl-jalanisiloxytetramethyldimethyl finally, 3 parts of a copolymer of methylhydrogensiloxane and trimethylsiloxane units having a viscosity of 60 cP at 25 ° C.

67392 The mixture thus obtained is applied by means of the Rake 2 described in Example 1 to about 4-5 g / m of parchment paper of the type described in Example 1. The paper is then placed in the form of a ring at a distance of 2 cm around an ultraviolet lamp of the type described in Example 1. As long as the ultraviolet lamp is on, the temperature between the lamp and the paper is maintained at 45 or 90 ° C by means of a fresh air fan.

The properties of the coatings obtained are reported in the same way as in Example 1.

Comparative test c

The procedure described in Example 3 is repeated with the change that the paper is kept in the recirculating air oven at 45 ° C or 90 ° C for the times shown in Table 2 below without the use of ultraviolet light.

In Example 3 and Comparative Experiment c, the following results are obtained:

Table 2 UV lamp top- Treatment at 45 ° C Treatment at 90 ° C residence time when- Separation- Residual- Separation- Residual- in the drying cabinet, force gluing force gluing sec. w / w force,% w / w force,%

Eg 3 15 4 76 1 90 same 30 4 70 1 99 same 45 192 same 60 3 84

Comparative 15 No networking No networking experiment c same 30 same same same 45 same same 60 same same 120 5 86 same 1800 1 88

Example 4 16.5 parts of dimethylpolysiloxane containing vinylmethylsiloxane units as terminal units and having 67392 16

Brabender plastograph at 25 ° C and 60 rpm. the value determined is 400, dissolved in 83.5 parts of toluene. The solution thus obtained is mixed with so much 2-methyl-3-butinol-2 that the solution contains 0.25% of alkynol by weight of the organopolysiloxane, followed by mixing with a mixture of platinum-cyclohexanone complex and diluent such that the mixture contains 24 ppm platinum based on the element and the weight of the organopolysiloxane, and finally 0.2 parts of a copolymer of methylhydrogensiloxane and trimethylsiloxane units having a viscosity of 60 cP at 25 ° C are mixed.

The mixture thus obtained is applied by means of the Rake described in Example 1 to a kraft paper glued with polyvinyl alcohol weighing 2 75 g / m 2. The paper is then placed in the form of a ring at a distance of 2 cm around an ultraviolet lamp of the type described in Example 1. As long as the ultraviolet lamp is on, the temperature between the lamp and the paper is maintained at 45 ° C or 90 ° C by means of a fresh air fan.

The properties of the coating are reported as described in Example 1. Comparative test d

The procedure described in Example 4 is repeated with the change that the paper is kept in the recirculating air oven at 45 ° C or 90 ° C for the times given in Table 3 below without the use of ultraviolet light.

Comparative test e

The procedure described in Example 4 is repeated with the change that 0.2 parts of pure cyclohexanone are used instead of the mixture of platinum-cyclohexanone complex and diluent.

In Example 4 and Comparative Experiments d and e, the following results are obtained:

Table 3 UV lamp treatment at 45 ° C Treatment at 90 ° C residence time or Separation- Residual- Separation- Residual time drying force gluing force in gluing cabinet, sec. w / w force,% w / w force,%

Eg 4 30 8 77 same 15 10 67

Comparative test d 600 No networking same 60 14 49

Comparative test e 60 14 66

Comparative Experiment f (referring to English Patent Publication 13,998,885)

First, 10 parts of dimethylpolysiloxane containing one Si-linked hydroxyl group in each of the units in the main theme and having a viscosity of 443 cP at 25 ° C and 0.06 parts of a mixture of platinum-divinyltetramethyldisiloxane complex and diluent are mixed and then .3 parts of a copolymer of methylhydrogensiloxane and trimethylsiloxane units having a viscosity of 60 cP at 25 ° C.

The mixture thus obtained is applied to the parchment paper of the type described in Example 1 on a granule 2 described in Example 1. The paper is then placed in the form of a ring at a distance of 2 cm around the ultraviolet lamp described in Example 1.

As long as the ultraviolet lamp is on, the temperature between the lamp and the paper is maintained at 45 ° C or 90 ° C by means of a fresh air fan. The operating times of the ultraviolet lamp are shown in Table 4 below.

The properties of the coating are reported in the same way as in Example 1.

67392 18

Table 4 On top of the UV lamp- Treatment at 45 ° C Treatment at 90 ° C residence time, sec. Separation- Residual- Separation- Residual- force gluing force gluing p / cm force,% p / cm force,% 30 3 64 60 3 52 3 72 90 3 59

Example 5

First mix 100 parts of diraethylpolysiloxane containing vinyldimethylsiloxane units as terminal units and having a viscosity of 550 cP at 25 ° C, and 0.3 part of ethinyl-cyclohexanol, then 0.4 parts of platinum-divinyltinamethane-disinomethane-disiloxane finally, 3 parts of a copolymer of methylhydrogensiloxane and trimethylsiloxane units having a viscosity of 60 cP at 25 ° C.

The mixture thus obtained is continuously applied in a plant using a Flexo press (cf., for example, Ullmanns Enxyklopädie der technischen Chemie, 4th edition, volume 10, Weinheim, 1975) on a 100 cm wide kraft paper web glued with polyvinyl alcohol and 2 weighing 75 g / m . Immediately after this application, the paper is passed under 6 consecutive ultraviolet lamps spaced 7.5 cm apart in each case. The power of each of these ultraviolet lamps is 8 kilowatts per 100 cm of width, or 80 watts / cm. The distance between the paper and the ultraviolet lamps is about 8-9 cm. The temperature between the paper and the ultraviolet lamp is given in Table 5 below.

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Eh I H E »_ H N -¾1 20 67392

To demonstrate that cyclohexanone is also a photosensitizer, the following experiments were performed which are not included in the invention because no platinum complex is present:

20 parts of a solution of 10 parts of a copolymer blocked with trimethylsiloxane groups at the terminal position, prepared using 99.5 mol% of dimethylsiloxane units and 0.5 mol% of vinylmethylsiloxane units and having in a Brabender plastograph and 60 ° C plastograph, are mixed. the value determined is 400 mcp, 10 parts of methyl ethyl ketone, and 0.2 parts of a copolymer of methylhydrogensiloxane and trimethylsiloxane units having a viscosity of 60 cP at 25 ° C, followed by 0.5 parts of each of the compounds given in the following table.

The mixture thus obtained is applied to parchment paper of the type described in Example 1 by means of the Rachel described in Example 1. The coating is crosslinked in a manner known from Example 1. The times required for networking are shown in Table 6 below. The properties of the coating are reported in the same manner as in Example 1.

Table 6

Time Difference Force Residual gluing-___ sec .__ p / cm__force, p / cm_

Benzophenone 30 9 141

Michler's ketone 90 2 98

Cyclohexanone 90 5 95

Chloroanthraquinone 60 13 113

Claims (1)

2i 67392 Claim A process for preparing adhesion-repellent coatings by applying compositions consisting of (1) an organopolysiloxane having Si-linked vinyl groups having a viscosity of at least 40 cP at 25 ° C, (2) an organopolysilicon having at least 3 Si-bonded hydrogen atoms having a viscosity 4 to 150 cP at 25 ° C in an amount of 0.5 to 35 gram equivalents of Si-bonded hydrogen for each Si-bonded vinyl group in diorganopolysiloxanes (1), (3) a platinum complex that promotes the incorporation of Si-bonded hydrogen into an aliphatic multiple bond in an amount of 5 to 100 ppm as elemental platinum based on the total weight of organopolysiloxane (1) and (2), and (4) a substance which retards the incorporation of Si-bonded hydrogen into an aliphatic multiple bond at room temperature in an amount of 0.1 to 0.8% by weight of organopolysiloxane ( 1) and (2) of the total weight, on surfaces made of adhesives repellent characterized in that at least when the platinum complex (3) is not already a photosensitizer, the mixture used in each case contains at least one photosensitizer (5) in an amount of 0.01 to 5% by weight of the total weight of the organopolysiloxane (1) and (2), and that at least some of the network energy comes from ultraviolet light.