HU209873B - Method for making strippable coating film - Google Patents

Abstract

A paint system (I) comprises (a) monomers and/or oligomers and/or synthetic resins and pref. also linear polymers as film-formers (II), (b) up to 50 wt.% alkali and/or alkaline earth salt of (un)satd. 2-24C aliphatic acid and/or synthetic satd. 6-18C aliphatic monocarboxylic acid and/or alkyd resins and/or 6-12C prim. aliphatic alcohols obtd. from these cpds. as adhesion-reducing agent, and (c) 0-100 wt.% paint plasticiser (w.r.t. amt. of polymer from II); the mixed, ready-for-use system has dry substance content (DS) = 30-100 wt.% (the rest being inert organic solvent) and is in the form of a sprayable, essentially homogeneous soln. or dispersion. (II) are commercial paint prods. and/or liq. mono- and/or di- and/or poly-vinyl monomers with viscosity below 200 mPa.s and/or synthetic resins with viscosity below 500 mPa.s, or ethyl and/or 2-hydroxypropyl and/or isopropyl and/or butyl methacrylate and/or ethylcellosolve methacrylate and/or PEG monomethacrylate, or unsatd. esters of polyhydric alcohols, pref. diethylene glycol dimethacrylate and/or unsatd. esters of vinyl alcohols and/or triallyl cyanurate and/or triacrylyl-triazine, or (un)satd. polyesters, opt. modified with natural resins and/or oils and/or epoxy resins, etc.. USE/ADVANTAGE - (I) is useful for providing articles, esp. motor vehicles, with a temporary protective coating (for transport, etc.) which can be easily stripped off by hand when requried without damaging the original surface, and which can be disposed of without adverse environmental effects.

Description

FIELD OF THE INVENTION The present invention relates to the production of a film-like release liner on a varnished vehicle surface.

Vehicle manufacturers usually apply an exterior protective coating to the lacquer coating of new vehicles, which can be easily and quickly removed from the vehicle with hot water or steam. These transition barrier layers are predominantly low softening point materials made from natural and / or synthetic resins and / or waxes which can be removed from the surface by hot water or steam at temperatures above 60-80 ° C in the form of small particles, droplets or aqueous suspensions. An essential requirement for temporary protective coating materials is that they do not attack the original enamel layer of the vehicle, the rubber and chrome surfaces, and provide a temporary corrosion and mechanical protection of the surface so that the appearance of the vehicle after the removal of the protective material a.

Polymer films that are only soluble in warm water or alkaline water are also used to temporarily protect vehicle lacquer coatings. These include polyvinyl alcohols having a high degree of hydrolysis, polyacrylic acids, polymers containing various vinyl carboxylic acids.

These substances cause significant amounts of poorly decomposing organic matter in the wastewater and the environment, which makes them increasingly difficult to protect from the environment.

Ullmann Encyclopedia of Chemistry, Volume 19, Fourth Edition, pages 386-387 and Encyclopedia of Polymer Sci. And Techn. 14. Polyvinyl butyral dispersions containing a plasticizer according to page 233 are used as strip coating for valuable articles and products against corrosion.

Coatings made of polyvinyl butyral dispersions do not mechanically exert sufficient protection against vehicle surfaces, and it is cumbersome and costly to produce such coatings.

U.S. Patent No. 1,960,817 discloses a peelable, water-soluble protective coating for metallic objects comprising polyethylene oxide, polyvinyl alcohol, carboxymethylcellulose and / or hydroxymethylcellulose. The organic matter load in wastewater is also a significant problem in this process.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a protective coating for vehicle coatings that is easily removable by hand and is environmentally friendly, has a controlled adhesion to the lacquer coating layer and provides an external mechanical strength to protect the lacquered metal surface during transport and storage.

A further object of the present invention was to provide a coating with good weather resistance and adhesive strength using environmentally friendly film-forming agents and anti-tacking aids, which are non-toxic in themselves and after biological or thermal degradation and do not damage the lacquered surface to be protected.

The invention thus relates to a process for producing a film-like release liner of 10-100 µm thick on a freshly lacquered vehicle surface having a rubber and / or plastic surface, such that the vehicle surface is homogeneous with a solvent solution or dispersion containing polymerizable film-forming agent. spraying a composition comprising at least 50% by weight, based on dry matter, of a monomer having a viscosity of 100-5000, less than 200 mPas and / or a liquid resin having a viscosity of less than 500 mPas, optionally 20 000 and 500 000 a linear polymer having a molecular weight between the film-forming components with from 0.1 to 50% by weight of C ₂ -C ₂₄ aliphatic saturated or unsaturated fatty acid (s) of alkali or alkaline earth metal salt and / or _Cg-C18 aliphatic saturated synthetic monocarboxylic acid ( and / or previous term alkyd resin (s) and / or C6-C12 aliphatic primary alcohol (s) made from crystals and dicarboxylic acids, and lacquer softeners with a boiling point greater than 200 ° C at atmospheric pressure of 0-100 tr and It consists of lacquerous solvents having a boiling point higher than ° C and a flash point higher than 21 ° C and heating the composition at temperatures between 50 ° C and 90 ° C and / or high energy radiation, preferably UV light and / or X-ray radiation and / or accelerated electrons. polymerized.

Thus, according to the invention, a film-forming device is formed which, in a highly controllable manner, produces a film which has a limited adhesion, so that the film coating can be completely and completely stripped off the original vehicle lacquer surface once its protective role has ceased. The peeled foil can be folded to a small volume and then stored or disposed of with normal municipal waste. Therefore, we use only film-makers that are non-toxic, as such, and are not environmentally hazardous, either by themselves or by biological or thermal degradation.

The release liner according to the present invention is provided as a self-adhesive film formed in situ on a vehicle's conventional lacquer layer which is in direct contact with the metal surface. The film is completely removable on the one hand due to its mechanical properties (such as sufficiently high tensile strength and film thickness) and on the other hand to the adhesive reducing agent (s).

Some commercially solvent-free or solvent-free automotive enamels and lacquer resins can be used to produce protective films of sufficiently high tensile strength.

Adding the required amount and quality of anti-tack additive (s) to some commercially available lacquer products can provide a high quality protective film forming system. The cases

Most other additives (plasticizer, comonomer (s), initiator (s), etc.) are also required.

Of course, many high quality lacquers can be formulated for commercial purposes from commercially available monomers and / or resins and excipients, the composition and application of which provide economic and / or operational advantages. Thus, for example, the film-forming layer is formed by radical polymerization and / or polyaddition and / or polycondensation starting from low viscosity liquid mono and / or polyvinyl monomers, low or medium viscosity resins (η - up to 50,000 mPa.s). Occasionally, the film-forming liquid also contains 010% linear polymer, preferably 0.5-5%.

The monomeric and / or oligomeric and polymeric film formers are selected so as to dissolve each other and to form solutions homogeneous by conventional varnish operations.

From this homogeneous solution, the additives, after spraying and subsequent heat treatment and / or irradiation, form a special film which has a limited adhesion (peeling force min. 0.5, max. 10.0 N / cm, preferably 1-6, 0 N / cm).

The adhesion of the film release liner according to the invention, i.e. adhesion at the interface of the vehicle lacquer to the release film, can be controlled by appropriately selecting the film forming components of the inner layer and by selecting the most suitable plasticizer from the plurality of plasticizers.

Amongst the vinyl monomers, preference is given to materials having a lower vapor density, a boiling point greater than 100 ° C and a high LD ₅₀ (LD ₅₀ > 5.0 g / kg), such as: isopropyl methacrylate, 2-hydroxypropyl methacrylate, isopropyl monoesters of methacrylate, butyl methacrylate, ethyl cellulose solvate of methacrylic acid, methacrylic acid and PEGs.

With the help of di- or polyvinyl compounds, the resulting material can be converted into a cross-linked insoluble polymer, which may be advantageous for example in terms of heat resistance. Preferred di- or polyvinyl compounds are di- or polyesters of polyhydric alcohols with vinyl carboxylic acids, such as diethylene glycol dimethacrylate, vinyl esters with vinyl carboxylic acids such as allyl methacrylate, maleic acid diallyl, ester, furthermore triallyl cyanurate, triacryltriazine.

The monomers and monomer mixtures in question can be converted into linear or crosslinked polymers using known radical initiators and redox systems.

When using photoinitiation, known photoinitiators, photoactivators, are added to the monomers. A detailed summary of these can be found in HoubenWeyl: Methoden dér Organischen Chemie, E 20, 89-94.

Synthetic resins crosslinked at room temperature or higher by radical or ionic polymerization, polycondensation, or polyaddition mechanism can be advantageously used in the film coatings of the present invention.

Of the conventional lacquer resins, saturated and unsaturated polyesters, saturated and unsaturated polyesters modified with natural resins and / or oils and / or epoxy resins, aliphatic polyurethane prepolymers, aliphatic isocyanates containing other groups (e.g. biuret, allophanate, urethane, etc.) are particularly preferred. .) prepolymers, aliphatic, cycloaliphatic and aromatic epoxy resins together with crosslinkers. Of the above resins, particularly low viscosity (η = max. 500 mPas) resins are highlighted. They are used in monomers, plasticizers, so-called film-forming agents, and so on. They generally have good or satisfactory solubility in active diluents and thus significantly reduce their viscosity.

Recently, systems working with accelerated electron irradiation have become increasingly important in industrial practice. For this purpose, solvent-free synthetic resins, which are also used in UV irradiation, are usually most preferred.

Preparing peelable reduce adhesion films are particularly useful for the various carbon atoms, more particularly C ₂ -C ₂₄ aliphatic monocarboxylic acids, Na, K and Ca salts and / or C ₆ -C ₁₈ aliphatic saturated synthetic monocarboxylic acids and / or made using the latter alkyd resins and / or ^C 6 to C ₁₂ aliphatic primary alcohols. Their amount is selected from 0.1 to 50% by weight, preferably from 1 to 20% by weight, based on the weight of the polymer formed.

The ever stricter environmental and occupational health regulations are currently being met with solvent-free, low-viscosity resins.

Spray application requirements can sometimes be met economically by the moderate use of inactive solvents.

The amount of the solvents used should preferably not exceed 50% by weight in the film-forming fluids, and may have a boiling point higher than 50 ° C, but lower than 200 ° C. Aliphatic and cycloaliphatic esters, ketones, ethers, ether alcohols and alcohols are preferred. In addition, aliphatic, cycloaliphatic, aromatic hydrocarbons may sometimes be used.

One or more plasticizers having a boiling point greater than 200 ° C may be used in the protective film-forming lacquers. These are predominantly esters and / or oligo esters and / or epoxy esters of inorganic and organic acids. Epoxidized derivatives of certain vegetable oils and polyester resins which are inactive or reactive only above 100 ° C may also be used as plasticizers in the resulting film coating.

In addition to the film-forming components, the film-forming fluid may contain, in addition to anti-caking agents, plasticizers and inactive solvents, pigments, dyes, light and heat agents known per se.

GB 209 873 Stabilizers, antistatic agents and other lacquer auxiliaries as required. Granular solids (e.g. pigments) have a particle size of not more than 30 µm, preferably less than 10 µm.

Example 7

A homogeneous solution is first prepared in a known varnish equipment and method by the following formula:

Component A:

kg Metallux Coating Lacquer, Λ ”001 (BUDALAKK, Hungary) 441% colorless liquid containing non-volatile matter

0.5 kg of dihexyl adipate

0.3 kg GAA-2 (Galiko BT, Hungary) alkyd resin

0.5 kg soy fatty acid, 3 ”component:

kg Metallux Coating Lacquer "B" 001 (BUDALAKK, Hungary) Yellow liquid containing 73% non-volatile material

0.3 kg Metallux Coating Varnish Thinner (BUDALAKK, Hungary) solvent mixture containing glycol ester, other esters and aromatic hydrocarbons

The two components were used after one to two minutes of homogenization.

From the solution, a film drawing frame is used to make a film of 30 µm slit size on silicone paper used in the synthetic leather industry. After drying, and after heat treatment at 80 ° C for 30 minutes, the film is peeled off and the film's tensile strength and elongation at break are measured. Similarly, we also make a protective film coating on an automotive enamel coated aluminum sheet. The peeling force is measured at an angle of 180 ° to the film as is customary for self-adhesive films. The values obtained are shown in Table 1.

The rest of the solution is sprayed with 2 new Lada 1300 cars after favorable laboratory results. After applying the liquid film, the cars are stored in an 80 ° C chamber for 30 minutes.

From one car, the protective film (cut into pieces about 10 cm below) was pulled from the bottom up by hand while using a jet of water to help pull and release the film. In this way, the film could be removed from the entire surface of the vehicle in about 10 minutes. Underneath, the original coat of paint remained intact.

The film of the other car was washed after several months, hand washed in the usual way, etc. after 1 month of use. similarly, it can be easily removed completely.

Example 2

Example 1 was performed and the results obtained are shown in Table 1. Composition of the protective film forming liquid in contact with the lacquered vehicle surface:

Component A:

2.0 kg of butyl methacrylate

2.0 kg of 2-hydroxypropyl methacrylate

2.0 kg of dipropylene glycol dimethacrylate

0.5 kg AH-3 (MÜKI, Hungary) ethylene glycol diglycidyl ether

0.2 kg Κ-2-ethylbutyrate Component B:

2.0 kg tributyl citrate

0.2 kg Butaflex film (Fatra Napajedla, Czechoslovakia) polyvinyl butyrate

0.1 kg of azo-bis-isobutyronitrile

The preparation, homogenization, and application of the two components are as described in Example 1.

As shown in Table 1, the protective layer of Example 2 has advantageous properties and can be completely removed from the vehicles.

Example 3

The protective film layer was prepared and the resulting liquid tested as described in Example 1. Its formula is as follows:

Component A:

kg AH-14 (MÜKI, Hungary) neopentyl glycol diglycidyl ether

0.2 kg VIALKID EF 935 (VIANOVA Kunstharz AG, Austria) Epoxy ester of castor fatty acid and soy fatty acid

0.2 kg K-acetate Component B:

1.5 kg T-54 (MÜKI Hungary) isophorone diamine adduct

1.0 kg of dioctyl phthalate

0.2 kg Ca stearate

The preparation, homogenization, and application of the two components are as described in Example 1.

The protective film of Example 3 can also be peeled off the lacquered vehicle surface perfectly.

Example 4

The following components are carefully homogenized and stored away from light until sampling or spraying begins. Composition of the film-forming liquid:

2.0 kg of butyl methacrylate

2.0 kg VIAKTINVTE 5955/265 (VIANOVA Kunstharz AG, Austria) acrylate and urethane modified polyester

0.9 kg butyl acetate

0.6 kg of neopentyl glycol bis (2-ethylbutyryl) ester

0.3 kg of Na acetate

0.05 kg isopropyl thioxanthone

0.15 kg N-methyl diethanolamine

The film samples were prepared as in Example 1, except that the crosslinking was done by illumination with a high-pressure mercury vapor lamp of 80 W / cm for 3 minutes.

For the spraying experiment, body elements (bonnets) were used, in which case the spray paint was irradiated with 3 mercury vapor lamps of 80 W / cm for 3 minutes. The protective film is 1 day and

GB 209 873 At the age of one month, we removed it completely by hand, leaving the original lacquer intact. The protective film test results are shown in Table 1.

Example 5

Homogenization of the components used followed by storage and testing of the resulting liquid was as described in Example 4.

recipe:

kg V1AKTIN VTE 5956 (VIANOVA Kunstharz AG, Austria) Melamine acrylate kg (2-hydroxypropyl) methacrylate

0.5 kg AH-14 (MÜKI, Hungary) neopentyl glycol diglycidyl ether

0.2 kg GAA-2 (Galiko BT, Hungary) alkyd resin

0.04 kg isopropyl thioxanthone

0.2 kg of [2- (dimethylamino) ethyl] benzoate

0.1 kg VeoVa-10-acid-K salt (Shell, England)

The resulting protective film had favorable properties and was well removable, as shown in Table 1.

Example 6

The homogenization of the components and testing of the resulting lacquer was carried out similarly to Example 4, except that the lacquer film was crosslinked by accelerated electrons. The irradiation was performed using the EBC system source from FALCO (Hungary) using 5 MRad radiation doses.

recipe:

5 kg VIAKTINVTE 5961 (VIANOVA Kunstharz AG, Austria) Epoxyester Melamine Acrylate 1 kg n-butyl acetate 1 kg tributyl phosphate 0.3 kg GAA-3 (Galiko BT, Hungary) alkyd resin 0.2 kg soybean fatty acid The results are reported in Table 1. The protective film a he lived up to expectations. Example 7 In each case, we followed Example 6, according to the recipe: 3 kg VIAKTINVTE 5961 (VIANOVA Kunstharz AG, Austria) glycidic ester-melamine acrylate 1 kg dipropylene glycol diacrylate LKG PEG 200 dimethacrylate 0.5 kg GAA-3 alkyd resin 0.2 kg oleic 0.2 kg BUDATONER color paste blue 700 (BUDALAKK, Hungary)

The properties of the protective film are detailed in Table 1, the coating was easily removed and the original lacquer coat remained intact.

Table 1

Test results of film layers

Example Film forming content of solution (%) Dry film thickness (μπι) Tensile strength (N / mm ² ) Elongation at break (%) Peeling strength of film (N / cm) First 58 ~ 18 15 300 4.8 Second 100 30 12 700 2.2 Third 100 30 18 100 5.1 4th 85 25 8 600 1.4 5th 100 30 21 80 6.0 6th 86.7 26 10 400 3.1 7th 99 ~ 30 14 200 3.9

PATENT CLAIMS

Claims (3)

PATIENT INDIVIDUAL POINTS A method for producing a film-like film-coating of a film thickness of 10-100 μιη in freshly lacquered vehicle surfaces including rubber and / or plastic surfaces, characterized in that a polymerizable film-forming, optionally admixture-containing, lacquer composition is sprayed onto the surface of the vehicle to be protected. containing at least 50% by weight of a monomer with a viscosity of less than 200 mPas, and / or a liquid resin having a viscosity of less than 500 mPas and a viscosity of less than 500 mPas, less than 200 mPas, optionally from a linear polymer of between 20 000 and 500 000 \ t , from 0.1 to 50% by weight of the alkali or earth alkali metal salt of C ₂ -C ₂₄ aliphatic saturated or unsaturated fatty acid (s) per film-forming component and / or C ₆ -C ₈ aliphatic saturated monocarboxylic acid (s) and / or from the above products and dicarboxylic acids alkyd resin (s) from and / or Cg-C _{12 of} aliphatic, primary alcohol (s) and the weight of the film-forming calculated 0-1001% atmospheric pressure higher CNAL boiling varnish industrial plasticizers 200 ° C and higher CNAL boiling 050% by weight 50 ° and a lacquer solvent having a flash point of more than 21 ° C and the composition is polymerized by heating at 50 ° to 90 ° C and / or high energy radiation, preferably UV light and / or X-rays and / or accelerated electrons. 2. The process according to claim 1, wherein the film-forming plasticizer is esters and / or oligesters and / or epoxy esters and / or aliphatic esters of mono- or polyvalent inorganic and / or organic acids having a boiling point of more than 200 ° C. epoxidated derivatives, preferably benzyl butyl phthalate, dibutyl phthalate, triallyl phosphate, tributyl citrate, glycerol monoleate, Versatic acid glycidyl ester, or epoxidized soybean oil. Method according to claim 1 or 2, characterized in that colorants, light and heat stabilizers and other lacquer auxiliaries are used as additives to the film-forming agents, with the restriction that the particle size of the insoluble solids in the medium is not more than 30 μπι, preferably less than 10 μπι. .