Light-activated coating composition

FIELD: protective coatings.

SUBSTANCE: invention relates to composition to form coatings with quick-setting surface at ambient temperature for use in re-finishing industry, in manufacture of clear coating, and as primer layer in multilayer coating. Composition contains at least one latent base-type photoactivator and base-catalyzed polymerizable or hardenable organic material including isocyanate-reactive groups bearing at least one thiol group.

EFFECT: enabled preparation of compositions, which can be UV hardened and are characterized by acceptable setting velocity at ambient temperature in locations not easily accessible for UV emission.

15 cl, 11 tbl, 10 ex

 

The invention relates to photoactivated composition coating comprising at least one photoinitiator and base catalyzed curable or curable organic material, comprising at least one polyisocyanate and at least one compound having groups reactive toward isocyanate, and its application to obtain coatings with surface quickly suitable for processing at ambient temperature.

Photoactivated composition of the coating of the type specified above is known for example from US-A-4369206. This paper proposes the use of ammonium salts α-ketocarboxylic acids as photoinitiator, and photoactivated composition coatings include polyurethane precursors or epoxy resins, curable in the presence of amines. A disadvantage of the known compositions is that they otverzhdajutsja only in places that are easily accessible to UV light. In the case of three-dimensional surfaces or where the presence of pigments does not allow UV radiation to penetrate into the lower layers, the curing speed is too low.

EP-A-0898202 discloses education in the light of amines from α-aminoacetophenone as latent primary catalyst catalyzed by base composition of the coating. Curable systems contain only organic is their connection, who are able to participate in a base catalyzed reaction or the condensation reaction. Specifically mentioned (poly)alcohol and (poly)isocyanate. In order to increase the curing speed in places that are not readily available for UV-light, made reference to the possible use of additional non-blocked primary catalyst, which, however, requires the use of additional stages of heating.

This invention relates to coating compositions which can be solidified by UV radiation and have an acceptable rate of curing at ambient temperatures in areas that are not easily accessible to UV light, the composition includes at least one photoinitiator and base catalyzed curable or curable organic material, comprising at least one polyisocyanate and at least one compound containing groups reactive toward isocyanate.

Photoactivated composition of the coating according to the invention differs in that group reactive towards isocyanate include at least one Tilney group and photoinitiation is votolatino base.

It should be added that photoactivated composition of the coating, including photoinitiator and polymerized and the and-curable organic material, includes (poly)isocyanate and a compound containing tirinya group known from, for example, EP-A-0188880. Coatings obtained from coating compositions, disclosed there may be solidified first UV radiation, and then, finally, in the usual manner at ambient temperature. The main disadvantage of the known coating compositions is the simultaneous presence of at least two different curing mechanisms. One mechanism is based on the interaction between multifunctional alkene and a multifunctional thiol, which requires UV radiation, while the secondary curing includes significantly more mechanisms, such as interaction of free isocyanate with water and the interaction of free isocyanate with a thiol component. One effect of the so-called system dual-cure is that of unirradiated places will be solidified only in part, the result of which will be unreacted amount of alkene in the unexposed areas. Therefore, in order still to achieve a minimum degree of cure in such places, it is necessary to use compounds having a higher functionality. The use of such compounds has the effect of increasing the viscosity, which leads to the necessity of using a larger amount of solvent to achieve the od is orodno viscosity when spraying, what causes the problems associated with the increase of volatile organic compounds.

An additional advantage of photoactivated composition of the coating according to the invention is that, when used votolatino basis, it remains active even after the end of exposure.

Suitable focoltone bases include N-substituted 4-(o-nitrophenyl)dihydropyridines, optionally substituted groups simple and/or complex Olkiluoto ether, and photoinitiator based on Quaternary boron compound. Example of N-substituted 4-(o-nitrophenyl)dihydropyridines is N-methyl-nifedipine (Macromolecules 1998, 31, 4798), N-butyl nifedipine, diethyl ether N-butyl-2,6-dimethyl-4(2-nitrophenyl)-1,4-dihydropyridines-3,5-dicarboxylic acid and nifedipine, the following formula:

i.e. diethyl ether N-methyl-2,6-dimethyl-4(4,5-dimethoxy-2-nitrophenyl)-1,4-dihydropyridines-3,5-dicarboxylic acid. Examples of photoinitiators based on Quaternary boron compounds disclosed in GB-A-2307473, such as

So, quite optimal results were obtained with photolents base belonging to the group α-aminoacetophenone. Examples α-aminoacetophenone, which can be used in photoactivated compositions coverage on this from the bretania, are: 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure® 907 from Ciba Specialty Chemicals) and 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure® 369 from Ciba Specialty Chemicals), disclosed in EP-A-0898202. It is preferable α-aminoacetophenone, the following formula

Votolatino base can be used in amounts of from 0.01 to 10 wt.% in the calculation of the solid curable material, preferably from 0.05 to 5 wt.%, more preferably from 0.05 to 3 wt.%.

For most coating compositions using votolatino base, an acceptable balance between viability and the rate of curing can be achieved by the introduction into the composition of a certain number of organic acids. Preference is given in this case, the organic acid, which is compatible with other parts of the composition. So, quite optimal results were obtained with dodecylbenzenesulfonic acid. Used, its amount varies from 0.01 to 20 wt.% based on the total weight of the coating composition, preferably from 0.05 to 10 wt.%, more preferably from 0.1 to 5 wt.%.

Although the irradiation of the majority α-aminoacetophenone known from the literature, leads to the formation of the active catalyst, for some of them unirradiated places make them unattractive to perfo the operating quality because of too long time curing. This problem may be overcome by the introduction into the composition a very weak base and/or compounds of the metal.

Generally, good results are obtained with metal complexes and/or salts of the metals, which are known as such as catalysts for isocyanate-hydroxyl reaction. Preference is given in this case, the metal complexes or metal salts where the metal is selected from the group of aluminum, titanium, zirconium and hafnium. These metals form complexes with carboxylate groups and/or diketones or alkylacrylate. Examples of satisfactory catalysts are disclosed in US-A-5846897. So, quite optimal results were obtained with aluminum complex-CAT® HS (from King Industries) and with organic titanates, such as bis-2,4(pentagonal) diisopropoxide titanium (Tyzor® AA from DuPont). These catalysts can be used in amounts of from 0.01 to 10 wt.% in the calculation of the solid curable material, preferably from 1 to 5 wt.%.

Composition for coating according to the invention is capable of curing under the action of radiation after application and, optionally, solvent evaporation. In particular, they are suitable for curing by irradiation of UV light. Combination IR/UV radiation are also suitable. Radiation sources which can be used are the conventional sources of UV, such as mercury lamps, high and medium pressure. To avoid any risk when handling UV light of very short wavelength (UV and/or With UV light), is preferred, especially for use in repair shops for the painting of cars, fluorescent lamps, which emit less of harmful UV And light. However, the low intensity of the light emitted by these lamps, as it was discovered, has a deleterious effect on the curing of known radiation curable systems dual-cure, as a result of oxygen inhibition.

It has been unexpectedly discovered that, when used votolatino basis as photoinitiator more specifically, when using sensibilization, there are no problems that are the result of oxygen inhibition during exposure to UV light from fluorescent lamps.

Suitable sensitizers are thioxanthone, such as isopropylthioxanthone the following formula

(Quantacure® ITX from G.Lakes), oxazine and rhodamine. Colorless surface can be obtained with benzophenone and its derivatives. Examples of suitable derivatives of benzophenone are:

where R1, R2and R3may be the same or different and denote SN3 or N (Speedcure® BEM from Lambson),

(Quantacure® ITX from G.Lakes) and

where R1, R2and R3may be the same or different and denote SN3or N (Esacure® TZT from Lamberti).

The sensitizer can be present in amounts of from 0.1 to 5 wt.% from the solid curable material, preferably from 0.5 to 2.5 wt.%.

Examples of reactive towards isocyanate compounds containing at least one Tilney group include tilne functional compound containing at least two tirinya functional group, and a compound containing at least one Tilney functional group and one hydroxyl functional group. Also mixtures of these compounds can be used in the compositions of this invention.

Suitable compounds containing tirinya group, usually obtained by the interaction of the compounds containing hydroxyl groups, with acids containing tirinya group, such as 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiosalicylic acid, mercaptoethane acid, mercaptoacetate acid or cysteine. Examples of suitable compounds containing hydroxyl groups, are diols, trioli and tetraol, such as 1,4-butanediol, 1,6-exand the ol, 2,2-dimethyl-1,3-propandiol, 2-ethyl-2-propyl-1,3-propandiol, 1,2-, 1,3 - and 1,4-cyclohexanediol, and the corresponding cyclohexane-dimethanol, 1,1,1-trimethylolpropane, 1,2,3-trimethylolpropane and pentaerythritol. Examples of the compounds obtained according to the method include pentaerythritol-tetrakis(3-mercaptopropionate), pentaerythritol-tetrakis(2-mercaptoacetate), trimethylolpropane-Tris(3-mercaptopropionate), trimethylolpropane-Tris(2-mercaptopropionate) and trimethylolpropane-Tris(2-mercaptoacetate). Good results were obtained with trimethylolpropane-Tris(3-mercaptopropionate) and pentaerythritol-tetrakis (3-mercaptopropionate).

Additional example compounds obtained according to the method specified, contains the kernel of hyperbranched polyol based on the original polyol, such as trimethylolpropane, and dimethylolpropionic acid. This polyol then atrificial 3-mercaptopropionic acid and isononanoic acid. These methods are described in European patent application EP-A-0448224 and international patent application WO 93/17060.

Other synthesis for compounds containing at least two tirinya functional groups include:

- the reaction of aryl - or alkylhalogenide with NaHS to introduce side tylenol groups in the alkyl - or allseeingeye, respectively;

reaction of Grignard reagent with sulfur for the introduction of side-thiol the Noah group in the structure;

response of polymercaptan with polyolefin according to the reaction joining Michael, nucleophilic reactions, electrophilic reaction or a radical reaction;

- the reaction of the thiol-functional alcohol and isocyanate-functional compounds; and

- restoration of disulfides.

The compound containing at least one Tilney functional group and one hydroxyl functional group can be, for example, a structure of the following formula: T[(C2H6O)nCH2SNONCE2SH]3where T means triol, such as trimethylolpropane or glycerin. An example of such a compound is commercially available from Henkel under the trademark of Henkel Capcure® 3/800.

Alternative reactive towards isocyanate compound containing at least one Tilney group, is a resin having, for example, as the base resin of the complex polyester, polyurethane resin, polyacrylate resin or resin from a polyether. These reactive towards isocyanate compounds can also contain hydroxyl groups.

Reactive towards isocyanate compound containing at least one Tilney group, can be a complex polyester derived from (a) at least one polycarboxylic acid or its reacciones is capable of derivatives, (b) at least one polyol, and (C) at least one thiol-functional carboxylic acid. Polyesters preferably have a branched structure. Branched polyesters are usually obtained by condensation of polycarboxylic acids or their reactive derivatives such as corresponding anhydrides or lower complex alkalemia esters, polyalcohol, when at least one of the reagents has a functionality of at least 3.

Examples of suitable polycarboxylic acids or their reactive derivatives are tetrahydrophtalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyl-hexahydrophthalic acid, methyl-hexahydrophthalic anhydride, dimethylcyclohexane, in primary forms, 1,4-cyclohexane-dicarboxylic acid, 1,3-cyclohexane-dicarboxylic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 5-trebuil-isophthalic acid, trimellitic anhydride, maleic acid, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, dodecenyl-succinic anhydride, dimethylsuccinic, glutaric acid, adipic acid, dimethyladipate, azelaic acid and mixtures thereof.

Examples of suitable polyols include trimethylolpropane, trimethylol the Tang, glycerin, 1,2,6-hexanetriol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methylpropane-1,3-diol, neopentylglycol, 2-butyl-2-ethyl-1,3-propandiol, cyclohexane-1,4-Dimethylol, complex monoether neopentyl glycol and hydroxypivalic acid, hydrogenated bisphenol a, 1,5-pentanediol, 3-methylpentanediol, 1,6-hexanediol, 2,2,4-trimethylpentane-1,3-diol, dimethylolpropionic acid, pentaerythritol, di-trimethylolpropane, dipentaerythritol and mixtures thereof.

Examples of suitable thiol-functional organic acids include 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiosalicylic acid, mercaptoethanol acid, mercaptohexanol acid, cysteine, and mixtures thereof.

Optional, monocarboxylic acids and monoparty can be used to produce polyesters. Preferably use C4-C18monocarboxylic acid and With6-C18monosperma. Examples of C4-C18monocarboxylic acids include Pavlinov acid, hexanoic acid, heptane acid, octanoic acid, nonanoyl acid, 2-ethylhexanoyl acid, isononanoic acid, dekanovu acid, lauric acid, myristic acid, palmitic acid, isostearoyl acid, stearic acid, hydroxystearic acid, benzoic acid, 4-trebovaniya acid and sm is si. Examples of C6-C18monospitovo include cyclohexanol, 2-ethylhexanol, stearyl alcohol and 4-trebuetsyasya.

Good results can be obtained with water thiol-functional polyurethane dispersion, which can be prepared first by obtaining the isocyanate-functional polyurethane of diols, diisocyanates and elementary units containing groups, which facilitate the stabilization of the resins in water dispersion, followed by the interaction of the isocyanate-functional polyurethane with the polyfunctional thiol in the base catalyzed reaction of accession and subsequent dispersion in water.

Reactive towards isocyanate compound containing at least one Tilney group may be a thiol-functional polyacrylate. Such polyacrylate can be derived from (meth)acrylic monomers such as (meth)acrylic acid, methyl(meth)acrylate, butyl(meth)acrylate, vinyl derivative such as styrene, and optionally hydroxy-functional acrylic monomers such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate and the like, or mixtures thereof, where the terms (meth)acrylate and (meth)acrylic acid refers to methacrylate and acrylate, as well as methacrylic acid and acrylic acid matched with the public. Tilney group introducing reaction product of dimethyl-m-isopropylbenzylamine and mercaptoethanol. Alternatively, glycidylmethacrylate injected into the polymer to obtain epoxy-functional polyacrylate. Epoxypropyl then subjected to interaction with a suitable thiol-functional organic acids, such as those listed above. Polyacrylate receive conventional methods, for example by slow addition of suitable monomers to the solution of a suitable polymerization initiator, such as azo - or peroxidization.

In the composition of the coating according to the invention can also be introduced di-, tri - or higher thiol-functional diluents, such as acondition or bis-beta-mercaptoethylamine. Preference is given to using more high-molecular thiol-functional compounds which can be obtained by the interaction politial-functional compound with a polyisocyanate.

The most preferred thiol-functional compound is pentaerythritol-tetrakis(3-mercaptopropionate).

The organic polyisocyanate comprises a polyfunctional preferably free polyisocyanates with an average NCO-functionality of from 2.5 to 5 and can be (cyclo) aliphatic, aliphatic or aromatic in character. The organic polyisocyanate may be blocked. Polyisocyanate to include derivatives biureta, urethane, uretdione and isocyanurate. Examples of such organic polyisocyanates include 1,6-diisocyanatohexane, isophorone-diisocyanate, 2,4-toluene-diisocyanate, 2,6-toluene-diisocyanate, diphenyl-methane-diisocyanate, 4,4'-bis(isocyanato-cyclohexyl)methane, 1,4-diisocyanatobutane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatohexane, 4,4-diisocyanato-cyclohexane, 2,4-exagerately-diisocyanate, 2,6-exagerately-diisocyanate, norbornane-diisocyanate, 1,3-xylylene-diisocyanate, 1,4-xylylene-diisocyanate, 1-isocyanato-C-(isocyanatomethyl)-1-methyl-cyclohexane, m-α,α-α',α'-tetramethyl-xylylene-diisocyanate, above their derivatives and their mixtures. Typically, these products are liquid at ambient temperature and commercially available in a wide range. Particularly preferred isocyanate hardeners are triisocyanate and adducts. Their examples are 1/8-diisocyanato-4-(isocyanatomethyl)octane, the adduct of 3 moles colordistance and 1 mole of trimethylolpropane, which is the trimer of 1,6-diisocyanatohexane, which is a trimer of isophorondiisocyanate, writtenby the trimer of 1,6-diisocyanatohexane, the biuret trimer of 1,6-diisocyanatohexane, the adduct of 3 moles of m-α,α-α',α'-tetramethyldisilane and 1 mole of trimethylolpropane and mixtures thereof. Predpochtitel who are cyclic trimers (isocyanurates) and uretdione 1,6-exanguination and isophorondiisocyanate. Usually these compounds contain small amounts of their higher homologues.

Optionally, the coating composition water based on this invention can also contain hydrophilic organic compound MDI, substituted non-ionic groups, such as groups C1-C4alkoxy-polyalkylene. Preferably, when there is 30 wt.% non-ionic groups from all solid connections MDI, more preferably 20 wt.%, most preferably 15 wt.%. Preferred isocyanurate 1,6-hexane-diisocyanate and isophorone-diisocyanate, substituted methoxy-polyethylene glycol.

Optional hydroxyl-functional compound containing at least two hydroxyl functional groups may be present in the curable material. The hydroxyl-functional compound containing at least two hydroxyl functional groups may be selected from polyols and polyesters, polyether polyols, polyacrylate polyols, poliuretanovuyu, acetobutyrate cellulose, hydroxyl-functional epoxy resins, alkido and dendrimeric polyols such as described in WO 93/17060. Can also be included in the hydroxyl-functional oligomers and monomers, such as castor oil and trimethylolpropane. Preferred is entrusted by the polyol is acrylicpaint. More preferred is acrylicpaint, available from Akzo Nobel Resins having a trademark Setalux® 1157.

The polyisocyanate and the compound containing reactive towards isocyanate groups should be mixed so that the ratio of isocyanate groups to groups reactive toward isocyanate, were in the range of 0.5-3:1, preferably 0.75 to 2.5 to 1 and more preferably 1-2:1.

If the hydroxyl-functional compounds present in the coating composition, there can be catalysts for the crosslinking of isocyanate groups with hydroxyl groups. Their examples include catalysts based on Sn, such as dilaurate dibutylamine and diacetate dibutylamine.

The polyisocyanate may be mixed with a compound reactive towards isocyanate, any suitable method. However, it is usually quite simple mixing agitator. Sometimes it may be useful to dilute the polyisocyanate with an organic solvent such as ethyl acetate or 1-methoxy-2-propyl, in order to reduce its viscosity.

The viability of the coating composition at ambient temperature is usually more than 1 day, depending on the catalysts and their number.

The composition of this invention can be a composition of a water-based composition based solution is a dye or a composition without solvent. Since the composition may be prepared from liquid oligomers, it is particularly suitable for use as a composition with a high solids content or composition without solvent. Alternatively, the coating composition according to this invention may be aqueous dispersion of a powder coating, where reactive towards isocyanate compound containing at least one Tilney group has a Tg above 20°C. the Composition of the coating can also be used in powder coating compositions and coating compositions melting when heated surfaces. Preferably theoretical content of volatile organic compounds (VOC) in the composition is less than about 450 g/l, more preferably less than about 350 g/l, most preferably less than about 250 g/l

The coating composition can optionally contain other ingredients, additives or auxiliary substances, such as pigments, dyes, emulsifiers (surfactants), substances that contribute to the dispersion of pigments, leveling agents, agents against defects (pock marks) surface, prepodavatel, agents against education flows, thermal stabilizers, UV absorbents, antioxidants and fillers.

The coating composition according to this invention can be of NAS is sung on any substrate. The substrate may be, for example, metal, plastic, wood, glass, ceramics or a layer of any other coverage. Layer another layer may consist of a coating composition according to this invention or may be a different composition of the coating. The coating composition according to this invention show particular applicability as a transparent cover, main cover, pigmented top coating, primer and putty. Preferably, the coating composition according to this invention can be used as a clear coating or as a primer. When applying a clear coating preferably use α-aminoacetophenone as votolatino Foundation. When applying primer, preferably the use of N-substituted 4-(o-nitrophenyl)dihydropyridines as votolatino Foundation.

The coating composition can be applied by conventional means such as spray, brush or roller, spraying is preferred. Temperature curing is preferably between 0 and 100°and more preferably between 20 and 60°C. the Compositions are particularly suitable for the preparation of coated metal substrates, such as in the repair industry, in particular in workshops on repair of cars and vehicles, and in the decoration of large transport among the STV, such as trains, track transport, buses and airplanes.

When the coating composition is a transparent coating, the primary coating may be a conventional primary coating, known in the art of coating. Examples are basic coatings solvent-based, for example Autobase® from Akzo Nobel Coatings BV, based acetobutyrate cellulose, acrylic resins and melamine resins, and the main cover is water-based, for example Autowave® from Akzo Nobel Coatings BV on the basis of a dispersion of acrylic resin and the resin of the complex polyester. Moreover, the primary coating may contain pigments (coloured pigments, metal and/or mother-of-pearl), paraffin, solvents, fluid additives, neutralizing agent and prepodavatel. Can also be used basic coating with high solids content. They can be, for example, based polyols, Iminov and isocyanates. A composition for a transparent coating applied to the surface of the primary coating and then utverjdayut. Can be entered intermediate stage of curing the primary coating.

The invention is further illustrated by the following examples. Of course, these examples are submitted only for a better understanding of the invention, they should not be construed as limiting in any way its volume.

Examples

In the following examples disclosed at the time of curing some of the coating compositions according to the invention.

The coating is cured when the label from the hard pressing your finger leaves no imprint.

The time periods referred to under "viability", correspond to the length of time until, when the viscosity is doubled.

Hardness by pendulum device Persona was determined in accordance with French industrial standard method NF T30-016, the results are presented in seconds.

Resistance to solvent was measured by exposing the film to the exposure to methyl ethyl ketone in air for one minute. The test results of 0 means that the film is completely dissolved, and 5 means that the film was not damaged at all.

Resistance to water was measured by exposing the film to the action of water within one hour. The test results of 0 means that the film is completely dissolved, and 5 means that the film was not damaged at all.

Example 1

Prepare five photoactivated coating compositions, each of which contains votolatino base selected from the group consisting of N-methyl-nifedipine (base 1), diethyl ether N-butyl-2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridines-3,5-dicarboxylic acid (base 2) and diethyl ether N-methyl-2,6-dimethyl-4-(4,5-dimethoxy-2-nitrophenyl)-1,4-dihydropyridines-3,5-dicarboxylic acid (base 3).

Photoactivated composition a, b, C, D and E contain 56 h the capacity by weight (parts by weight) Desmodur® N3390 (aliphatic trimer hexamethylene-diisocyanate from Voeg) and 27 parts by weight of trimethylol-propane-Tris(3-mercaptopropionate).

Mass percentage votolatino base varies from 0.1 to 0.4. The film thickness of 50 microns stretch on the glass plate and act on it UV And light (fluorescent lamp, the type of Cleo® from Philips) at a distance of 10 cm (7 mW/cm2). The results of experiments conducted at ambient temperature in the dark, and after a 10-minute exposure, are given in table 1. The percentages in the examples mean weight percents and parts are by mass parts.

Table 1
CompositionAndInDE
The base 10,40,20,1
The base 20,4
Basis 30,4
curing after exposure (minutes)251021
curing in the laboratory (minutes) 60701007525
curing in the dark>1 day>1 day>1 day>1 day>1 day
viable4 days4 days4 days4 days<1 day

According to the results listed in table 1, the curing time increases with decreasing concentration of nifedipine. Viability is always acceptable, but curing in the dark reduces performance. However, it was found that if, instead of curing in the dark the whole film is exposed to light, at least in laboratory conditions, the curing time of the parts, only open for access of light available in laboratory conditions, it was quite acceptable and ranged from 25 to 100 minutes depending on the type votolatino the substrate and its concentration.

Example 2

Example 1 is repeated under the condition that used photolents is Borat tetrabutylammonium in the amount of 2 parts by weight (parts by weight) of the following formula:

Fototerapia compositions a and b contain 50 parts by weight of Tolonate® HDT-LV (aliphatic trimer hexamethylene-diisocyanate from Rhone-Poulenc) and 27 parts by weight of trimethylolpropane-Tr is(3-mercaptopropionate). Composition And contains 1 parts by weight of sensitizer Quantacure® ITX (G.Lakes). The results are shown in table 2.

Table 2
Composition (parts by weight)AndIn
Tolonate® HDT-LV5050
trimethylolpropane-Tris(3-mercaptopropionate))2727
22
Quantacure® ITX1-
the curing time after UV exposure And2 minutes>1 day
the curing time in the lab3-4 hours>1 day
viable>1 day>1 day

According to the results indicated in the table, in this case, the presence of the sensitizer leads to satisfactory results.

Example 3

Example 1 is repeated under the condition that used photolents is based on α-aminoacetophenone, ie (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure® 369 from Ciba Specialty Chemicals) in the quantity of 0.4 or of 1.8 parts by weight (parts by weight).

Fototerapia compositions a, b and C, each contain 50 parts by weight of Toonate® HDT-LV (aliphatic trimer hexamethylene-diisocyanate from Rhone-Poulenc) and 27 parts by weight of trimethylolpropane-Tris(3-mercaptopropionate). Composition And contains 1.8 parts by weight of Irgacure® 369, composition contains a 0.4 parts by weight, and the composition contains a 0.4 parts by weight and 0.1 parts by weight of dodecylbenzenesulfonic acid.

The results are shown in table 3.

Table 3
Composition (parts by weight)AndIn
Tolonate® HDT-LV505050
trimethylolpropane-Tris(3-mercaptopropionate)272727
dodecylbenzensulfonate acid--0,1
Irgacure® 3691,80,40,4
the curing time after UV exposure (min)111,5
the curing time in the laboratory (minutes)454560
viable1.5 hours1.5 hours>5 days

According to the results listed in table 3, in this case, the presence of sulfonic acid gives a significant improvement in viability, that is how the cure time after UV exposure And / or available in the laboratory light is almost not affected.

Example 4

Prepare two photoactivated composition of the coating, each of which contains as votolatino base of 1.1 parts by weight (parts by weight) α-aminoacetophenone corresponding to the formula:

Composition as shown in table 4

Table 4
Composition (parts by weight)AndIn
The pentaerythritol-tetrakis(3-mercaptopropionate)1010
Tolonate® HDT-LV17,917,9
Byk 306 (10% in butyl acetate)0,630,63
α-aminoacetophenone (10% in butyl acetate)1,11,1
Tyzor® AA (75 wt.% bis-2,4-(pentagonal) diisopropoxide titanium isopropanol from Dupont-1,16

The viability of the composition And is 6 hours, whereas the composition, which contains more complex metal as a catalyst, 2 hours.

The film thickness of 75 microns stretch on the glass plate and act on it UV And light (fluorescent lamp, the type of Cleo® from Philips) at a distance of 20 cm (3 mW/cm2). The non-irradiated film utverjdayut after UV exposure And light in accordance with the s 1 and 2 minutes, respectively, or without radiation.

Data on the curing time of irradiated or non-irradiated films are given in table 5.

Table 5
The curing time film
The irradiation time of UV-a001 minute2 minutes
storage conditionsdarknesslaboratorylaboratorylaboratory
composition And330 minutes90 minutes1.5 minutes<2 minutes
composition75 minutes60 minutes1.5 minutes<2 minutes

According to the results listed in table 5, in this case, the presence of additional catalyst does not have or has a negligible effect on the curing time of the film irradiated with UV-a light. However, the curing in the dark is accelerated to a considerable extent from 330 to 75 minutes by introducing into the composition an additional catalyst.

The films obtained are examined for their resistance to methyl ethyl ketone and water. After 7 days measure hardness by pendulum device Persona. Resistance to methyl ethyl ketone obtained coating layers is given in table 6.

Table 6
resistance to methyl ethyl ketone after a drying time of 24 h(I)/7 days(II)
The irradiation time of UV-a001 minute2 minutes
storage conditionsdarknesslaboratorylaboratorylaboratory
composition And(l)2/(II)5(I)3/(II)5(I)5/(II)5(I)5/(II)5
composition(l)5/(II)5(I)5/(II)5(I)5/(II)5(I)5/(II)5

The resistance to water of the obtained coating layers is given in table 7.

(I)5/(II)5
Table 7
resistance to water after a drying time of 24 h(I) /7 days(II)
The exposure time001 minute2 minutes
UV-a
storage conditionsdarknesslaboratorylaboratorylaboratory
composition And(I)2/(II)5(I)3/(II)5(I)5/(II)5
composition(I)5/(II)5(I)5/(II)5(I)5/(II)5(I)5/(II)5

Hardness by pendulum device Persona obtained of the coating layers is given in table 8.

Table 8
the hardness of Perozo after a drying time of 7 days
The irradiation time of UV-a001 minute2 minutes
Storage conditionsdarknesslaboratorylaboratorylaboratory
composition And235"223"305"305"
composition286"308"288"298"

Example 5

Example 1 is repeated, provided that as votolatino base use 2,22 parts by weight (parts by weight) α-aminoacetophenone formula:

This example shows that not only the choice of photoinitiator and, depending on the type of photoinitiator, additional use of acids and/or bases, but also the type of MDI can be an important parameter to achieve good ball the sa between viability and drying or curing in the darkness.

Viability and curing conditions 6 compositions are given in table 9.

Table 9
Composition (parts by weight)246
Comparative composition (parts by weight)135
Pentaerithrityl (3-mercaptopropionate)202020202020
Tolonate® HDT-LV--26,9026,9035,8635,86
Desmodur® N3400 (from Bayer)38,9338,939,739,73--
α-aminoacetophenone (10% in butyl acetate)-2,22-2,22-2,22
Byk 306 (10% in butyl acetate)2,602,602,602,602,602,60
viability (minutes)15155024>480130
With the Cabinet in the dark (minutes) 40355045>1260990
drying UV-a (min)401501,5>2602

From the results shown in table 9, it follows that the use Desmodur® N3400 leads to too short viability, which may be renewed by the Union of the specified isocyanate with Tolonate® HDT-LV.

Example 6

Example 1 is repeated under the condition that the applied coating composition containing a physical mixture of a hydroxyl-functional resin and a thiol-functional resin.

The hydroxyl-functional acrylate, Setalux 1157 XS-54 from Akzo Nobel Resins (Ew(OH)=693 g, St. = 54%), mixed with pentaerythritol-tetrakis(3-mercaptopropionate). Dilaurate dibutyrate (DBTL) is added as catalyst for the reaction of NCO/OH. The results are shown in table 10.

Table 10
Composition (parts by weight)
The pentaerythritol-tetrakis(3-mercaptopropionate)12,5
Setalux 1157 XS-5471
Tolonate HDT-LV33
Byk 306 (10% in butyl acetate)a 3.9
α-aminoacetophenone (10% in butyl acetate) as in other 4 3,3
DBTL (10% butylacetate)8,2
the time for drying after UV-a irradiation (fluorescent lamps, type Cleo® from Philips, a distance of 10 cm, 7 mW/cm2)10 min
the drying time in the dark>6 hours
viable>6 hours

Example 7

Example 1 is repeated under the condition that the applied resin having both hydroxyl and thiol-functionality prepared as follows.

In the first stage get complicated polyester from 31,05 parts by weight of pentaerythritol, of 1.55 parts by weight of dipentaerythritol, a 27.4 parts by weight of hexahydrophthalic anhydride and 10 parts by weight of isononanoic acid at 230°C in nitrogen atmosphere at the boiling xylene under reflux until the acid value of 14 to 18 mg KOH/g solids. Then the reaction mixture is cooled to 180°C.

In the second stage, 30 parts by weight of 3-mercaptopropionic acid is introduced into the reaction mixture at 180°C in nitrogen atmosphere at the boiling xylene under reflux. After turning more than 75% of doses add a solution of Tetra-isopropylmalate in xylene (1.0 wt.% Tetra-isopropylidene calculated on solid). The esterification reaction continued under reduced pressure until such time as displaying the spruce acidity will not be from 8 to 11 mg KOH/g solids. Thereafter, the xylene is distilled off under reduced pressure. The variance of the complex polyester is diluted with n-butyl acetate until a solids content of 75%. The resin solution is filtered through a pressure filter at 70°C. the Resin on the basis of complex polyester having hydroxyl and tirinya functional groups, is obtained solids content 77,8% in butyl acetate, Ew(OH)=344, Ew(SH)=320 and Av=9,9.

The results are shown in table 11.

Table 11
Composition (parts by weight)
resin A (g)50,0
Tolonate® HDT-LV (g)48,18
Byk 306 (10% in butyl acetate)4,35
DBTL (10% butylacetate)8,71
α-aminoacetophenone (10% in butyl acetate), as other 48,71
butyl acetate14,0
the drying time after UV-a irradiation (fluorescent lamps, type Cleo® from Philips, a distance of 10 cm, 7 mW/cm2)10 min
the drying time in the dark8 h
viable2 hours

Example 8

In this example, prepare the primer.

Composition (parts by weight)
the pentaerythritol-tetrakis(3-mercaptopropionate)60
Disperbyk 1107,048
add with stirring mixer
zinc sulfate45,271
barium sulphate180,90

Silicon dioxide (Aeropsil 380)0,60
butyl acetate6,75
mixer at maximum speed to the dispersion of <25 μm
Tolonate HDT-LV (g)86
α-aminoacetophenone (10% in butyl acetate), as other 414,62
Byk 306 (10% in butyl acetate)14,62
Xylene16,11
butyl acetate16,11

The composition of the primer sprayed on the steel plate to a dry film thickness of 50 microns. Immediately after deposition, the film is irradiated with UV-a light (fluorescent lamp, the type of Cleo® from Philips, a distance of 50 cm, 1 mW/cm2). The film dries and is ready for processing sand after 5 minutes. In the darkness drying takes 2 hours. Two hours after mixing, the results are still the same.

Example 9

The composition is water-based and is finding prepared as follows.

Composition (parts by weight)
Bayhydur LS2032 from Bayer32
Acetate simple nanometrology ether of propylene glycol8
dodecylbenzensulfonate acid (70%)0,64
Byk 3460,7
the pentaerythritol-tetrakis(3-mercaptopropionate)the 13.4
α-aminoacetophenone as in the other 4 (24.9% in acetate simple nanometrology ether propylene glycol)3,6
Water20,3

The composition of the water-based applied tensile strap on a tin plate with a dry film thickness of 70 microns. After 1 hour setting time the film is irradiated with UV-a light (fluorescent lamp, the type of Cleo® from Philips, a distance of 10 cm, 7 mW/cm2). The film dries in 2 minutes. In the darkness drying takes another 6 hours. Two hours after mixing, the results are still the same.

Example 10

The composition of example 3 is applied to two metal plates covered with a commercially available basic coatings, i.e. Autowave and Autobase from Akzo Nobel Coatings BV. The panel is irradiated with UV-a light (fluorescent lamp, the type of Cleo® from Philips) at a distance of 10 cm (7 mW/cm2). The clear coat dries in 1 minute.

1. Photo is kivirauma composition of the coating, including at least one photoinitiator and base catalyzed curable or curable organic material, comprising at least one polyisocyanate and at least one compound containing groups reactive toward isocyanate, wherein the reactive toward isocyanate groups comprise at least one Tilney group, and photoinitiation is votolatino base.

2. Photoactivated composition of the coating according to claim 1, characterized in that photolents base is 4-(ortho-nitrophenyl)dihydropyridines, optionally substituted groups simple Olkiluoto ether and/or complex Olkiluoto ether.

3. Photoactivated composition of the coating according to claim 1, characterized in that photolents base is a Quaternary boron compound-photoinitiator.

4. Photoactivated composition of the coating according to claim 1, characterized in that photolents is based on α-aminoacetophenone.

5. Photoactivated composition of the coating according to claim 4, characterized in that photolents is based on α-aminoacetophenone the following formula:

6. Photoactivated composition of the coating according to any one of the preceding paragraphs, characterized in that the composition further what about the contains organic acid.

7. Photoactivated composition of the coating according to any one of the preceding paragraphs, characterized in that the composition additionally contains a complex of metal and/or metal salt as socializaton.

8. Photoactivated composition of the coating according to claim 7, where the metal socializaton selected from the group of compounds of aluminum, titanium, zirconium and hafnium.

9. Photoactivated composition of the coating according to any one of the preceding paragraphs, characterized in that the composition further comprises a sensitizer selected from the group thioxanthones, oxazines, rodinov, benzophenone and derivatives thereof.

10. A method of obtaining a coating layer, comprising applying the coating composition according to any one of the preceding paragraphs on the substrate, which must be covered, curing the surface of the obtained film by UV light and exposure to full curing deeper or non-irradiated layers at room temperature or with heating.

11. The coating composition defined in any one of claims 1 to 9, to produce coatings with bystrootverdevayuschey surface.

12. The coating composition defined in any one of claims 1 to 9, for use as a layer of putty in multi-layer lacquer coating.

13. The coating composition defined in any one of claims 1 to 9, for use as a transparent cover.

14. The coating composition according to item 13 on the I application as a transparent coating multi-layer lacquer coating.

15. The coating composition defined in any one of claims 1 to 9, for use in industry re-finishing and finishing of large vehicles.



 

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Polymer composition // 2263695

FIELD: polymerizing mixtures for making water-repellent and anticorrosive coats.

SUBSTANCE: proposed polymer composition contains polyester resins, styrene, hardening agent-peroxide compounds and accelerating agent, inert substances, gel-type binder, paraffins and poly-urethanes. Proposed composition increases service life of coat due to reduction of effect of aggressive factors of outside medium on characteristics of coat.

EFFECT: increased rate of polymerization without considerable stresses in coat; facilitated procedure of applying coats on base of this composition.

23 cl, 80 ex

FIELD: spray compositions for coating.

SUBSTANCE: the invention is pertaining to a composition used for coating including at least one isocyanate- reactive compound containing: a) at least one thiol group; b) at least one polyisocyanate-functional compound; and c) a catalytic agent containing at least one organometallic compound, in which as a metal is used a metal from groups 3-13 of Mendeleyev's periodic system of elements. The invention is also pertaining to usage of the composition for spray coating in the form of the transparent coating layer, to its use in the form of the transparent coating layer in a multilayer lacquer coating and to its use for a repeated finishing and for refinishing of the large-scale transportation means.

EFFECT: the invention ensures production of transparent coating layers used in multilayer lacquer coatings and refinishing of the large-scale transportation means.

11 cl, 17 ex

FIELD: polymer materials.

SUBSTANCE: composition contains 5-95% of alkali-swelled polymer prepared by stepped nucleus/shell-type polymerization and 95-5% of at least one polyurethane. Composition is suitable as priming in priming/transparent layer system, which is characterized by high mechanical properties, high "flop", good brightness, essentially lack of "penetration", and good waterproofness.

EFFECT: reduced coating drying time and number of layers.

8 cl, 3 tbl, 17 ex

FIELD: varnish-and-paint industry.

SUBSTANCE: invention relates to polyurethane coatings intended to be applied on a variety of surfaces (metal, wood, etc.). Composition comprises toluene solution of hydroxyl-containing component and toluene solution of polyisocyanate. Hydroxyl-containing component is oligoether obtained by in-melt reaction of tall oil with triethanolamine at 170-200°C and characterized by viscosity at most 10000 mPa·s, acid number at most 5.0 mg KOH/g and hydroxyl number 125-138 mg KOH/g. Oligoether-to-polyisocyanate ratio is 1:1.

EFFECT: enabled preparation of two-component lacquer with elevated light resistance, water resistance, and stability, which is suitable for anticorrosive coatings on metal products.

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FIELD: corrosion prevention technologies.

SUBSTANCE: method includes serial application of layers of polymer compositions to metallic surface, while serial layers of polymer compositions are made with various thermal expansion coefficients. As said polymer composition polyurethane compound is used with special admixtures and filling agent, influencing thermal expansion coefficient of covering layer, and content of said filling agent in each following layer is set less than content of said filling agent in previous layer.

EFFECT: higher efficiency.

2 cl, 9 ex

FIELD: building materials, in particular polymer composition for sealing adhesive, coats, filling floors, etc.

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EFFECT: composition of increased strength, flexibility and alternated characteristics.

4 ex

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FIELD: building industry, in particular polymer composition for sealing adhesives.

SUBSTANCE: claimed composition contains polyisocyanate oligomer comprising 1.9-8.9 mass % of isocyanate groups, water, polymethylsiloxane, dioctylphtalate, chloroparaffin, glycerol, and inorganic powder. Composition of present invention is useful in manufacturing of floor, roof cladding, etc.

EFFECT: composition if increased flexibility, strength, uniform surface flowing, improved wettability, adhesion, homogeneity, radiation resistance, and increased curing time.

4 ex

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EFFECT: increased rupture strength and reduced light loss.

2 cl, 1 tbl, 8 ex

The invention relates to methods for producing polyisocyanates used for various polymeric materials, as well as to compositions based on polyisocyanates

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FIELD: optical engineering.

SUBSTANCE: invention, in particular, relates to UV solidifying composition based on urethane acrylates and containing 6.0-19.3 wt parts of hydroxyalkylacrylate and 1-5 wt parts of light initiator, said urethane acrylate base being mixture of 30.0-82.0 wt parts of interaction product of poly(oxypropylene glycol), 2,4-tolylenediisocyanate, hydroxypropyl acrylate, and 1,2-propylene glycol [molar ratio (1-2):(2-3):(2-2.1):(0.003-0.33)] with 4.7-60.0 wt parts of interaction product of 2,4-tolylenediisocyanate, hydroxypropyl acrylate, and 1,2-propylene glycol [molar ratio 1:(2.5:(0.004-0.065)]. Fiber light guide consisting of quartz optical fiber enrobed by above-defined composition is further described. Loss of light in light guide is thus lowered to 0.42-0.23 dB/km. Rupture strength is thus increased by 7.0 GPa.

EFFECT: increased rupture strength and reduced light loss.

2 cl, 1 tbl, 8 ex

Resin composition // 2247087

FIELD: building industry, in particular polymer composition for sealing adhesives.

SUBSTANCE: claimed composition contains polyisocyanate oligomer comprising 1.9-8.9 mass % of isocyanate groups, water, polymethylsiloxane, dioctylphtalate, chloroparaffin, glycerol, and inorganic powder. Composition of present invention is useful in manufacturing of floor, roof cladding, etc.

EFFECT: composition if increased flexibility, strength, uniform surface flowing, improved wettability, adhesion, homogeneity, radiation resistance, and increased curing time.

4 ex

FIELD: building materials, in particular polymer composition for sealing adhesive, coats, filling floors, etc.

SUBSTANCE: method includes blending at pH 7.5-13.0 of inorganic powder, water and technological additives: polymethylsiloxane, dioctylphtalate, chloroparaffin, followed by addition of polyisocyanate oligomer comprising 1.9-8.9 mass % of isocyanate groups. Method makes it possible to create fastness mode for carbolinic acid and its involvement in chain-elongation reaction without releasing of carbon dioxide.

EFFECT: composition of increased strength, flexibility and alternated characteristics.

4 ex

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SUBSTANCE: method includes serial application of layers of polymer compositions to metallic surface, while serial layers of polymer compositions are made with various thermal expansion coefficients. As said polymer composition polyurethane compound is used with special admixtures and filling agent, influencing thermal expansion coefficient of covering layer, and content of said filling agent in each following layer is set less than content of said filling agent in previous layer.

EFFECT: higher efficiency.

2 cl, 9 ex

FIELD: varnish-and-paint industry.

SUBSTANCE: invention relates to polyurethane coatings intended to be applied on a variety of surfaces (metal, wood, etc.). Composition comprises toluene solution of hydroxyl-containing component and toluene solution of polyisocyanate. Hydroxyl-containing component is oligoether obtained by in-melt reaction of tall oil with triethanolamine at 170-200°C and characterized by viscosity at most 10000 mPa·s, acid number at most 5.0 mg KOH/g and hydroxyl number 125-138 mg KOH/g. Oligoether-to-polyisocyanate ratio is 1:1.

EFFECT: enabled preparation of two-component lacquer with elevated light resistance, water resistance, and stability, which is suitable for anticorrosive coatings on metal products.

3 cl, 1 tbl

FIELD: polymer materials.

SUBSTANCE: composition contains 5-95% of alkali-swelled polymer prepared by stepped nucleus/shell-type polymerization and 95-5% of at least one polyurethane. Composition is suitable as priming in priming/transparent layer system, which is characterized by high mechanical properties, high "flop", good brightness, essentially lack of "penetration", and good waterproofness.

EFFECT: reduced coating drying time and number of layers.

8 cl, 3 tbl, 17 ex

FIELD: spray compositions for coating.

SUBSTANCE: the invention is pertaining to a composition used for coating including at least one isocyanate- reactive compound containing: a) at least one thiol group; b) at least one polyisocyanate-functional compound; and c) a catalytic agent containing at least one organometallic compound, in which as a metal is used a metal from groups 3-13 of Mendeleyev's periodic system of elements. The invention is also pertaining to usage of the composition for spray coating in the form of the transparent coating layer, to its use in the form of the transparent coating layer in a multilayer lacquer coating and to its use for a repeated finishing and for refinishing of the large-scale transportation means.

EFFECT: the invention ensures production of transparent coating layers used in multilayer lacquer coatings and refinishing of the large-scale transportation means.

11 cl, 17 ex

Polymer composition // 2263695

FIELD: polymerizing mixtures for making water-repellent and anticorrosive coats.

SUBSTANCE: proposed polymer composition contains polyester resins, styrene, hardening agent-peroxide compounds and accelerating agent, inert substances, gel-type binder, paraffins and poly-urethanes. Proposed composition increases service life of coat due to reduction of effect of aggressive factors of outside medium on characteristics of coat.

EFFECT: increased rate of polymerization without considerable stresses in coat; facilitated procedure of applying coats on base of this composition.

23 cl, 80 ex

FIELD: protective coatings.

SUBSTANCE: invention relates to composition to form coatings with quick-setting surface at ambient temperature for use in re-finishing industry, in manufacture of clear coating, and as primer layer in multilayer coating. Composition contains at least one latent base-type photoactivator and base-catalyzed polymerizable or hardenable organic material including isocyanate-reactive groups bearing at least one thiol group.

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15 cl, 11 tbl, 10 ex

FIELD: polymer production.

SUBSTANCE: coating composition comprising at least one compound with at least two isocyanate functional groups; at least one compound reactive to isocyanate and having at least two groups reactive to isocyanate groups, which are selected from mercapto groups, hydroxyl groups and combinations thereof; and cocatalyst consisting of phosphine and Michael acceptor, amount of catalyst constituting from 0.05 to 20% of the weight of dry residue. Invention also describes a method for coating substance with indicated composition as well as coated substrate, and adhesive containing at least one compound with at least two isocyanate functional groups and at least one compound containing at least two above defined groups reactive to isocyanate groups. Moreover, invention discloses employment of composition for finishing of great vehicles and refinishing of motor cars. Composition is characterized by drying time at a level of 20 min, modulus of elasticity 1904, Persose hardness 303, and brightness (85°C) at a level of 100.

EFFECT: expanded coating assortment.

16 cl, 16 tbl, 48 ex

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