Liquid hardening

FIELD: chemistry.

SUBSTANCE: invention relates to curing agents for air-drying alkyd-based resins, coating compositions, such as paint, varnish, wood stain, inks and linoleum floor coverings. Described is a curable liquid medium containing a) from 1 to 90 wt % of an alkyd-based resin and b) from 0.0001 to 0.1 wt % of a siccative in form of an iron or manganese complex with a tetradentate, pentadentate or hexadentate nitrogen donor ligand.

EFFECT: said siccative has high activity and enables hardening of compositions at relatively low concentration in a curable liquid medium.

19 cl, 8 tbl, 5 ex

 

The technical field to which the invention relates.

The present invention relates to fixation and solidification of liquids. In particular, the present invention relates to the consolidation and curing of printing inks and paints.

The level of technology

Recent reviews describe the various alternatives, particularly based connection Mn and Fe (Bieleman, in J.H. Additives in Plastics and Paints, Chimia, 56, 184 (2002); Bieleman, J.H., Marcomol. Symp., 187, 811 (2002); van Gorkum R, Bouwman E, Coord. Chem. Rev., 249, 1709 (2005)).

WO 03/093384 describes the use of salts of transition metals on the basis of pyrazoles, aliphatic and aromatic amines, 2,2'-bipyridine, 1,10'-phenanthroline, 1,4,7-trimethyl-1,4,7-triazacyclononane in combination with regenerating agent as a drying agent. Especially preferred are salts of Fe and Mn in combination with ascorbic acid and its derivatives. WO 03/093384 shows that the iron compounds show a much weaker activity and, therefore, require large quantities to achieve a satisfactory drying activity. The disadvantage of using iron compounds in large quantities is that the mixture is given excessive yellowish/brownish color.

The invention

The present invention relates to the curable liquid compositions that contain a desiccant and alkyd resin. Desiccant, not only is em a component of the liquid composition, which promotes drying, consolidation, solidification or hardening of the composition.

The fluid may be any curable liquid, such as paint, printing ink and paint. The term paint includes varnishes. The term alkyd resin mainly relates to polyesters, modified fatty acids. Alkyd resin is predominantly obtained through reaction of a polymerization condensation of three types of monomers: polyalcohol, polybasic acids and fatty acids or triglyceriderich oils.

The inventors have discovered active compounds of iron and manganese, that are active drying agent at relatively low concentrations.

In one embodiment, the present invention provides a capable of curing a liquid environment, including:

a) from 1 to 90 wt.%, preferably from 20 to 70 wt.% alkyd resins, and

b) from 0.0001 to 0.1 wt.% dryers where the desiccant is a complex of iron or manganese with tetradentate, pentadentate or hexadentate astonomy ligand; tetradentate, pentadentate or hexadentate azotaemia ligands, are described below.

Preferably, the complex of iron or manganese is a tetradentate or pentadentate astonomy ligand.

Most preferably the compound contains iron of mentadent the hydrated astonomy ligand, and the connection manganese tetradentate astonomy ligand.

In another embodiment, the present invention provides a composition of the present invention after fixing.

Detailed description of the invention

The present invention relates to a drier for alkyd resins, coatings, printing inks and linoleum floor coverings, including complex iron or manganese containing tetradentate, pentadentate or hexadentate astonomy ligand. At the same time, some paints/printing inks contain unsaturated oil/acid as cross-linking agents, most of them contain alkyd resins with unsaturated groups. Drying in air coatings based on alkyd resins, to which may be added to the desiccant of the present invention include coatings such as paint, varnish or stain, and include printing inks and linoleum floor coverings and the like. Desiccant equally suitable for ink/printing ink/printing paper, which do not contain alkyd resins, but contain at least 2% of unsaturated compounds with double or triple bond.

Coatings, printing ink and linoleum flooring can also include compositions which in addition to binders based on alkyd resin so the e contain other binder, for example, compositions comprising 1) a binder based on alkyd resin and 2) a polyacrylate and/or a polyurethane binder. Typical drying in air alkyd resins can be obtained by polycondensation reaction of one or more polyhydric alcohols, one or more polycarboxylic acids or the corresponding anhydrides, and long-chain polyunsaturated fatty acids or oils.

Glycerin is a common polyatomic alcohol, thanks to its content of natural oils. Other examples of suitable polyhydric alcohols include pentaerythritol, dipentaerythritol, ethylene glycol, diethylene glycol, propylene glycol, neopentylglycol, trimethylolpropane, trimethylacetyl, di-trimethylolpropane and 1,6-hexanediol. Polycarboxylic acid and the corresponding anhydrides used for the synthesis of alkyd resins include aromatic, aliphatic and cycloaliphatic compounds, which are mainly derived from petrochemical products. Typical examples of such PolicyKit include phthalic acid and its Regio-isomeric analogues, trimellitic acid, pyromellitic acid, timelineview acid, adipic acid, azelaic acid, sabotinova acid, maleic acid, fumaric acid and tetrahydrophthalic acid.

Suitable unsaturated the fatty acid and polonisation fatty acids or their mixture, used in this invention are ethylene unsaturated conjugated or unconjugated With2-C24carboxylic acids, such as oleic, ricinoleate, linoleic, linolenic, lisanova acid and eleostearic acid or their mixture, are generally used as mixtures of fatty acids obtained from natural or synthetic oils. Under polinenasyschennami fatty acids and unsaturated fatty acids involve fatty acids, which have a similar fatty acid composition of oils from which they are derived. Classification of oils based on the iodine number; for drying oils iodine value >140; for semidrying oils iodine value is between 125 and 140, and non-drying oils iodine value <125 ("Surface Coatings", Swaraj Paul, John Wiley and Sons; str). Suitable organic solvents for dilution drying in air alkyd resins of the present invention include aliphatic, cycloaliphatic and aromatic hydrocarbons, ethers, ethers, and N-organic. However, it is also possible aqueous media containing alkyd resin in the form of an emulsion and a suitable emulsifier, widely known from the prior art.

Printing ink of the present invention, containing varnish based on alkyd resin, modified unsaturated girn the mi acids, which, as defined above, are used as a binder component of printing inks, but are not limited to metal printing form, the printing ink for offset printing, printing ink for relief printing, ink for screen printing or ink to print with an intermediate surface on top of the text.

The desiccant is preferably partially or completely dissolved in the alkyd resin, emulsion, etc. Catalytic activity of transition metal ion depends on the ion and the type of ligands disclosed in this document. The desiccant can also be added to the composition only when the use composition.

The composition of the present invention may, if it is necessary, also include other additives such as other dryers.

The invention is also a drying air coating based on alkyd resins, rosin, printing ink, or a floor covering, comprising a drier in accordance with the present invention, for example, containing from 0.00001 to 0.1 wt.% (in terms of the amount of the binder; it is generally from 5 to 50 times higher than that of the metallic base, depending on the molecular weight of the compounds described herein) of iron complex or is organza, containing tetradentate, pentadentate or hexadentate donor nitrogen. Drying in air coating based on alkyd resins, rosin, printing ink, or the floor may additionally include polyacrylate and/or a polyurethane binder.

The composition of the present invention may contain dyes, pigment, anti-corrosive pigment and/or filler and/or a dye. It may additionally contain, if necessary, a plasticizer, a surface-controlling additives, additives that protect against loss of gloss, protivovspenivayushchie additive rheological additive and/or absorber of ultraviolet rays.

Adding the desiccant is usual technique known to a person skilled in the art. Desiccant is added either during the manufacture of alkyd resins, coatings, printing inks and linoleum flooring or added under stirring with them before using.

The composition according to the present invention preferably is stored in an inert atmosphere, e.g. nitrogen or carbon dioxide. In a preferred embodiment, in an inert atmosphere using nitrogen or argon.

Stabilizing additives

The composition according to the present invention preferably includes an antioxidant quantitatively in the range from 0.001% to 0.1%, most preferably from 0.002 to 0.05%. Suitable antioxidants are disclosed in US 6586383. The most suitable antioxidants are selected from the group consisting of di-tert-butylhydroxytoluene, ethoxyquin, α-tocopherol and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.

Capable of curing liquid medium preferably contains between 0.001 and 90% of ethylene glycol, diethylene glycol, dipropyleneglycol, glycerin, pentaerythrol, dipentaerythritol, neopentyl glycol, trimethylolpropane, trimethanolamine, di-trimethylolpropane and 1,6-hexandiol.

The composition according to the present invention preferably includes ethylene glycol and/or glycerol in the quantitative range from 0.1 to 50 wt.%, preferably 0.3 to 5 wt.%.

Capable of curing liquid medium preferably contains from 0.001 to 2.5% of lead, zirconium, bismuth, barium, vanadium, cerium, calcium, lithium, strontium and zinc.

DESICCANT

Preferably the desiccant contained in the curable liquid medium from 0.0001 and 0.1% in weight ratio, more preferably between 0.001 and 0.1% in weight ratio, and most preferably from 0.002 and 0.05% in weight ratio.

Tetradentate, pentadentate or hexadentate astonomy ligand can be embedded in any organic structure, which may contact the coordinating nitrogen atoms. For example, you can take simple is th tridentate ligand, such as 1,4,7-triazacyclononane and additional coordination group, for example, -CH2-CH2-NH2, -CH2-Roux, covalently linking one or more cyclic nitrogen or aliphatic groups.

Preferably, iron ion selected from Fe(II)n Fe(III), and mn ion selected from Mn(II) and Mn(III) and Mn(IV).

Preferably the ligand is present in one or more forms [MnLCl2]; [FeLCl2]; [FeLCl]Cl; [FeL(H2O)](PF6)2; [FeL]Cl2; [FeLCl]PF6and [FeL(H2O)](BF4)2.

These preferred classes of desiccant are complexes of iron or manganese and tetradentate, pentadentate or hexadentate astonomy ligands.

If not defined the length of any alkyl chain, preferably an alkyl chain C1-C8and preferably linear. Unless otherwise specified, the aryl group is a phenyl group.

BIBIGON

Type basedon often exists in the form of a catalyst with iron as the transition metal.

The ligand of bispinosa preferably has the form

where each R is independently selected from hydrogen, F, Cl, Br, hydroxyl, C1-C4-alkyla-, -NH-CO-Cl-C4-alkyl, -NH2, -NH-C1-C4-alkyl and C1-C4-alkyl;

R1and R2independently selected from

C1-sub> 24-alkyl,

With6-C10-aryl, and a group containing a heteroatom capable of coordinating to the transition metal;

R3and R4independently selected from hydrogen, C1-C8-alkyl, C1-C8-alkyl-O-C1-C8-alkyl, C1-C8-alkyl-O-C6-C10-aryl, C6-C10-aryl, C1-C8-hydroxyalkyl and -(CH2)nC(O)OR5where R5independently selected from hydrogen, C1-C4-alkyl, n has a value from 0 to 4, and mixtures thereof; and X is selected from C=O, -[C(R6)2]y-, where y has a value from 0 to 3, each R6independently selected from hydrogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkyl.

Preferably R3=R4and selected from-C(O)-O-CH3-C(O)-O-CH2CH3-C(O)-O-CH2With6H5and CH2HE.

Preferably a group containing a heteroatom capable coordinated with the transition metal, a is a pyridine-2-yl-methyl optionally substituted-CO-C4-alkyl.

Preferably X represents C=O or C(OH)2.

Preferred groups for R1and R2CH3- 2H5- 3H7, benzyl, -C4H9- 6H13- 8H17- 12H25and-C18H37and pyridine-2-yl. Preferred so the grade of bispinosa, in which at least one of R1or R2represents pyridin-2-yl-methyl or benzyl, preferably pyridine-2-yl-methyl.

Preferably basedon represents dimethyl-2,4-di-(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diazo-bicyclo [3.3.1]nonan-9-one-1,5, in primary forms (N2py3O-Cl) and its complex with iron FeN2py3O-Cl, which is obtained as described in WO 02/48301. Other preferred buspidone are those in which in place of a methyl group (C1) in the third position contains a longer alkyl chain, namely isobutylene, (n-hexoloy)6, (n-aktiline)8, (n-dodecyloxy)12, (n-tetradecyl) C14, (n-octadecyl)18obtained in the same way.

Preferred tetradentate bispinosa also disclosed in WO 00/60045 and preferred pentadentate bispinosa disclosed in WO 02/48301 and WO 03/104379.

N4py type

Type N4py is preferably a catalyst containing iron as the transition metal.

N4py ligands preferably have the form

where each R1and R2independently represents-R4-R5,

R3represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or R4-R5,

each R4independently before the hat is a simple bond or optionally substituted alkylene, albaniles, oxyalkylene, aminoalkyl, alkalinity ether, ether carboxylic acids or carboxylic acid amide and

each R5independently represents an optionally N-substituted aminoalkyl group or optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.

Preferably R1represents pyridin-2-yl, or R2represents pyridine-2-ylmethyl. Preferably R2or R1represent 2-amino-ethyl, 2-(N-(m)ethyl)aminoethyl or 2-(N,N-di(m)ethyl)aminoethyl. Substituted R5preferably represents 3-methylpyridin-2-yl. R3preferably represents hydrogen, benzyl or methyl.

Preferred ligands are N4py (i.e. N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine), which is disclosed in WO 95/34628 MeN4py (i.e. N,N-bis(pyridin-2-yl-methyl-1,1-bis(pyridin-2-yl)-1-aminoethane, as disclosed in EP 0909809.

TACN-Nx

Type TACN-Nx is preferably a catalyst containing iron as the transition metal.

The basic structure of the ligands is a 1,4,7-triazacyclononane, but may additionally contain one or more side groups of the nitrogen, which form a complex with a transition metal to ensure tetradentate, PE is talenttrove or hexadentate ligand. Preferably the main 1,4,7-triazacyclononane structure has two side nitrogen groups, which form a complex with a transition metal (TACN-N2).

TACN-Nx preferably has the form

where each R20selected from alkyl, cycloalkyl, heteroaryl, aryl and arylalkyl group, optionally substituted by a Deputy selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, sulfonate, amine, alkylamine and N+(R21)3where R21selected from hydrogen, alkenyl, alkenyl, arylalkyl, oxyalkyl, aminoalkyl, aminoalkyl, alonelove ether, alkenilovyh ether and-CY2-R22in which Y is independently selected from H, CH3With2H5With3H7and R22independently selected from optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and in which at least one of R20represents-CY2-R22.

Preferably R22selected from optionally substituted groups pyridine-2-yl, imidazol-4-yl, pyrazole-1-yl, quinoline-2-yl. Most preferably R22represents or pyridine-2-yl or quinoline-2-yl.

CYCLE AND POPERECHNOPOLOSATYE LIGANDS

Cycles and the ligands are preferably the catalyst manganese as a transition metal. The ligand preferably has the form

where Q is independently selected from

and

R is 4.

R is independently selected from hydrogen, C1-C6-alkyl, CH2CH2HE pyridine-2-yl-methyl and CH2COOH, or one of R is linked to N or another Q via ethylene bridge; R1, R2, R3, R4, R5and R6independently selected from H, C1-C4-alkyl and C1-C4-alkylperoxy.

Preferably poperechnopolosatye ligands are 1,4,8,11-tetraazacyclotetradecane(cycles), 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane(Mezcla), 1,4,7,10-tetraazacyclododecane(cyclen),1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane(Mericle) and 1,4,7,10-tetrakis(pyridin-2-yl-methyl)-1,4,7,10-tetraazacyclododecane (Rosicler).

The preferred complex of iron with Rosilina.

Preferably poperechnyy ligand is of the form

where R1independently selected from H, linear or branched, substituted or unsubstituted from C1to C20of alkyl, alkylaryl, alkenyl or quinil, and all nitrogen atoms in the macrocyclic rings coordinated to go to denim metal.

Preferably R1=Me, which is a ligand 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane, from which the complex [Mn(Cyclam)Cl2] can be synthesized according to WO 98/39098.

Other suitable Poperechnaya ligands can also be found in WO 98/39098.

TYPE TROPICANA

Tropicana preferred are catalysts containing iron as the transition metal.

Ligands Tropicana preferably are in the form

where X is selected from-CH2CH2, -CH2CH2CH2-, -CH2S(HE) HCH2and

R17independently represents a group selected from R17and alkyl, cycloalkyl, geteroseksualnoe, heteroaryl, aryl and arylalkyl group optionally substituted by a Deputy selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, sulfonate, amine, alkylamine and N+(R19)3where R19selected from hydrogen, alkenyl, alkenyl, arylalkyl, arylalkyl, oxyalkyl, oxyalkyl, aminoalkyl, aminoalkyl, alonelove ether, alkenilovyh ether and-CY2-R18in which Y is independently selected from hydrogen, CH3With2H5With3H7, a R18independently selected from optionally substituted GE is erealloc group, selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and where at least two of R17represent-CY2-R18.

Heteroatomic donor group preferably represents a pyridinyl optionally substituted-C0-C4-alkyl.

Other preferred heteroatomic donor groups represent imidazol-2-yl, 1-Mei-2-yl, 4-Mei-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1-Mei-4-yl, benzimidazole-2-yl and 1-methylbenzimidazole-2-yl.

Preferably three R17represent-CY2-R18.

Ligand Tpen (i.e. N,N,N',N'-Tetra(pyridin-2-yl-methyl)Ethylenediamine) disclosed in WO 97/48787.

Following tristepin are preferred: N-methyl-Tris(pyridine-2-yl-methyl)ethylene-1,2-diamine; N-octyl-Tris(pyridine-2-yl-methyl)ethylene-1,2-diamine; N-octadecyl-Tris(pyridine-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-butyl-N,N',N'-Tris(pyridin-2-yl-m is Teal)ethylene-1,2-diamine; N-octyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-dodecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-octadecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-ethyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propan-2-ol)-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propane-2-ol)-N,N',N'-Tris(1-methyl-imidazol-2-yl-methyl)-Ethylenediamine; N,N-diethyl-N',N",N"-Tris(5-methyl-imidazol-4-yl-methyl)-Diethylenetriamine; N-(3-propan-1-ol)-N,N',N'-Tris(1-methyl-imidazol-2-yl-methyl)-Ethylenediamine; N-hexyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-methyl-N,N',N'-Tris(benzimidazole-2-yl-methyl)-Ethylenediamine and N-(3-propan-1-ol)methyl-N,N',N'-Tris(benzimidazole-2-yl-methyl)-Ethylenediamine.

Other suitable Tropicana disclosed in WO 02/077145.

In a series nbspeconomic types of driers, the following are preferred: 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane,1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10-Tetra-azocyclotin, 1,4,7,10-tetramethyl-1,4,7,10-tetraaza-cyclododecane, and 1,4,7,10-tetrakis(pyridin-2-yl-methyl)-1,4,7,10-tetraazacyclododecane, N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine, N,N-bis(pyridin-2-yl-methyl-1,1-bis(pyridin-2-yl)-1-aminoethane, N,N,N',N'-tetr the(pyridin-2-yl-methyl)Ethylenediamine, N-methyl-Tris(pyridine-2-yl-methyl)ethylene-1,2-diamine; N-butyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-octyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-dodecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene 1,2-diamine; N-octadecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(3-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(3-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(5-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(5-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(3-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(5-methylpyridin-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-ethyl-N,N',N'-Tris(imidazol-2-yl-methyl)-ethylene-diamine; N,N'-dimethyl-N,N'-bis(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propan-2-ol)-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propan-2-ol)-N,N',N'-Tris(1-Mei-2-yl-methyl)-Ethylenediamine; N,N-diethyl-N',N",N"-Tris(5-Mei-4-yl-methyl)-Diethylenetriamine; N-(3-propan-1-ol)-N,N',N'-Tris(1-Mei-2-yl-methyl)-Ethylenediamine; N-hexyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-methyl-N,N',N'-Tris(benzimidazole-2-yl-methyl)-Ethylenediamine; N-(3-propan-1-ol)methyl-N,N',N'-Tris(benzimidazole-2-yl-methyl)-Ethylenediamine; 1,4-bis(quinoline-2-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(quinoline-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(quinoline-2-yl-methyl)-methyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(pyrazole-1-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(pyrazole-1-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyrazole-1-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4,7-Tris(quinoline-2-yl-methyl)-1,4,7-triazacyclononane and 1,4,7-Tris(pyridine-2-yl-methyl)-1,4,7-triazacyclononane.

EXAMPLES

The cobalt(II)2-ethylhexanoate (65 wt.% solution in white spirit) was purchased from Aldrich.

Dimethyl-2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-yl-methyl)was 3.7-diazo-bicyclo [3.3.1] nonan-9-one-1,5, in primary forms (N2py3O-C1) and its complex with iron (II) [Fe(N2py3O-C1)Cl]Cl were obtained as described in WO 0248301.

Dimethyl-2,4-di-(2-pyridyl)-3-octyl-7-(pyridin-2-yl-methyl)was 3.7-diazo-bicyclo[3.3.1]nonan-9-one-1,5, in primary forms(N2py3O-C8) and dimethyl-2,4-di-(2-pyridyl)-3-octadecyl-7-(pyridin-2-yl-methyl)was 3.7-diazo-bicyclo[3.3.1]nonan-9-the Dean of 1.5, in primary forms (N 2py3O-C18) and the corresponding iron complexes [Fe(N2py3O-C8)Cl]Cl and [Fe (N2py3O-C18) Cl]Cl were obtained as described in WO 2005042532.

N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine, hereinafter referred to as the N4py and the corresponding complex of iron (II), [Fe(N4py)Cl]Cl were obtained as described in EP 0765381.

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane, hereinafter referred to as MeN4py and the corresponding complex of iron (II), [Fe(MeN4py)Cl]Cl were obtained as described in EP 0909809.

4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane, hereinafter referred to as Cyclam, and the corresponding complex of manganese (II), [Mn(Cyclam)Cl2] were obtained as described in WO 98/39098 and SOC., 122, 2512 (2000)).

N-methyl-crispian (Matrisian), N-octyl-crispian(C8-Tris-pizen), N-octadecyl-crispian(C18-crispian) were synthesized in accordance with methods (Bernal, J. and others, J.Chem.Soc., Dalton Trans. 1995, 3667) and GE 2386615. The corresponding complexes of iron(II) [Fe(Matrisian)Cl]Cl, [Fe (C8-crispian)Cl]Cl and [Fe(C18-crispian)Cl]Cl was obtained according to a similar method described in EP 0909809 for similar MeN4py.

1,4-bis(quinoline-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane (Quin2TACN) and the corresponding compound [Fe(Quin2TACN)C1]ClO4were obtained as described in EP 1259522. Mn2([mu]-O)3(1,4,7-trimethyl-1,4,7-triaza cloneen) 2]PF6)2were obtained as described in J. Chem. Soc. Dalton Trans, 353 (1996).

Experiment 1

Homogeneous bleaching of β-carotene in hexane with merlinoite

This experiment was conducted to show that (β-carotene can be destroyed between the different iron and manganese catalysts with mecillinam, which is an indicator of radical reactions (which in turn increase the degree of drying paint/ink).

UV/VIEW study (spectrophotometric analysis in the visible and ultraviolet regions of the world) was carried out on the equipment Hewlett Packard 8453. All studies were conducted at 35°C and the measurements were carried out for 1 hour in the UV/visible region. The samples were placed in a quartz cuvette, pre shaking them before measurements. The valve was pushed out of the ditch during the measurement.

Solutions of hexane contained 85,6 μm β-carotene, 6,0 mm merlinoite, approximately 5 μm of the catalyst and 3.1% vol. of ethanol. The initial absorbance at 452 nm was about 0.45 A.U. the Difference between the initial absorption rate and absorption through 600 seconds in each case was entered into table 1. The highest value indicates high decolorizing activity of β-carotene.

Table 1
Experiments on homogeneous discoloration with the use of β-carotene and merlinoite in combination with 5 μm of each catalyst
Δ452 nm (600 c)
Blank solution (without added catalyst)0,01
[Fe(N2py3o-C1)Cl]Cl0,08
[Fe(N2py3o-C8)Cl]Cl0,11
[Fe(N2py3o-C18)Cl]Cl0,10
[Fe(MeN4py)Cl]Cl0,06
[Mn(Bcyclam)Cl2]0,07
[Fe(Matrisian)Cl]Cl0,03
[Fe(C8-crispian)Cl]Cl0,06
[Fe(C18-crispian)Cl]Cl0,08
[Fe(Quin2TACN)Cl]ClO40,06
Cobalt(II)-(2-ethylhexanoate)20,01

The result is s, presented in table 1 clearly show that the compounds of iron and manganese disclosed in the present invention, have a significant increase in the bleaching of β-carotene with merlinoite.

Experiment 2

The drying time of oil paint on the varnish

Model seasoned solvent (oil paint in n-heptane) is used in systems based on alkyd resins. All experiments were performed at room temperature, and the film formed on the Petri dish. The initial concentration of the catalyst were between 0,016 mm and 0.32 mm, as illustrated in table 2. With(II)2-ethylhexanoate (1,63 mm) and a blank sample (oil paint/heptane 50/50 vol.%) were also included for comparison.

Film on the Petri dish consisted of 100 ál (50/50 vol.% linseed oil/n-heptane) and 25 μl of the catalyst in a solution of ethanol (see above for final concentrations of the solutions oil paint/n-heptane).

The results of the investigated complexes of iron and manganese are shown in table 2. In all cases, the time required for drying "up tack-free", is given in the table. Films are classified as neoplasia, when they form a straight line, when the roller passes over the film, but the fingerprints are still visible on the film. Unhindered drying indicates that coverage has been strong and has not left any visible OTP is Katkov. A low level indicates a faster drying time. Were applied in various concentrations of driers to establish the lowest level that can still be achieved on an equal or greater level of drying than the salt of cobalt.

Table 2
The drying time required for drying "up tack-free or complete drying of oil paints with different compounds and levels
Initial concentrationConcentration in the film, µg/100 µl of linseed oilDrying time "until tack-free" (h)
Blank sample-->120
Cobalt(II)-(2-ethylhexanoate)21,63 mm2228
[Fe(N2py3o-C1)Cl]Cl0,064 mm1,020
[Fe(N2py3o-C1)Cl]Cl0,016 mm 0,2628
[Fe(N2py3o-C8)Cl]Cl0,064 mm1,220
[Fe(N2py3o-C8)Cl]Clto 0.032 mm0,6128
[Fe(N2py3o-C18)Cl]Cl0,064 mm1,420
[Fe(N2py3o-C18)Cl]Clto 0.032 mm0,728
[Fe(N4py)C1]Cl0.32 mm422 (complete drying)
[Fe(MeN4py)Cl]Cl0,064 mm0,820
[Fe(MeN4py)Cl]Cl0,016 mm0,227
[Mn(Bcyclam)Cl2]0.32 mm3,120 (complete drying)

The results presented in table 2, yasnovidyaschey about these compounds of iron and manganese are much more active in terms of molar ratio than the corresponding cobalt(II)-(2-ethylhexanoate)2. Especially [Fe(N2py3o-C1)Cl]Cl and [Fe(MeN4py)Cl]Cl showed an improvement factor of 100 times in terms of molar ratio, which is comparable with the desiccant Co-ethylhexanoate.

Table 3
The drying time required for drying "up tack-free or complete drying of oil paints with [Mn(Cyclam)Cl2] and Mn2(µ-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2]PF6)2(abbr. as Mn-Me3TACN)
Initial concentrationDrying time "until tack-free" (h)
Blank sample->120
Cobalt(II)-(2-ethylhexanoate)21,63 mm28
[Mn(Cyclam)Cl2]2.5 mm6 (non sticky)
[Mn(Cyclam)Cl2]0,5 mm 10 (non sticky)
Mn-Me3TACN0,5 mm20 (non sticky)
[Mn(Cyclam)Cl2]0.2 mm20 (non sticky)
Mn-Me3TACN0.2 mm23 (non sticky)

The data shown in table 3, indicate that [Mn(Cyclam)Cl2] shows a significantly higher activity than the Mn-Me3TACN, confirming that the manganese complex with tetradentate astonomy ligand exhibits a faster drying activity paint than the manganese complex containing a tridentate triazacyclononane ligand.

Experiment 3

The storage stability of the catalysts in oil paint on drying oil in the presence of (+)-α-tocopherol (vitamin E), purchased from the company Sigma.

Drying activity [Fe(MeN4py)Cl]Cl and [Fe(N2py3o-C18)Cl]Cl were investigated in the presence of (+)-α-tocopherol (vitamin E).

A sample of oil-based paint flax was obtained when the content of 4 ml of linseed oil, 3820 μl of n-heptane, 80 μl (10 mm (+)-α-tocopherol in heptane) and 100 μl of a solution of catalyst in ethanol. As the standard used the sample of oil paint without (+)-α-tocopherol, sod is rasego 4 ml of linseed oil, of 3.9 ml of n-heptane and 100 μl of a solution of catalyst in ethanol. Samples of oil paints were stored in closed glass containers at ambient conditions. The films were painted, each individual brush on a wooden Board after some interval-keeping. The drying time was determined and the results are summarized in tables 4 and 5.

Not defined
Table 4
Drying activity of 0.004 wt.% [Fe(MeN4py)Cl]Cl (0,0004% metal Fe) in the absence and presence 0,009 wt.% α-tocopherol to determine the various periods of storage at room temperature. The catalyst was added in a quantity of calculate the amount of linseed oil (not a mixture of linseed oil/heptane)
Storage time (days)Drying time without α-tocopherolDrying time with α-tocopherol
0<20 h<19 h
3<20 hNot defined
525 hNot defined
6<22 h
10>30 h;<46 hNot defined
11Not defined>24 h; <28 h

Table 5
Drying activity 0,006 wt.% [Fe(N2py3o-C18)Cl]Cl (0,0004% metal Fe) in the absence and presence 0.009 wt.% α-tocopherol to determine the various periods of storage at room temperature. The catalyst was added at the rate of linseed oil (not a mixture of linseed oil/heptane)
Storage time (days)Drying time without α-tocopherolDrying time with α-tocopherol
022 h22 h
324 hoursNot defined
525 hNot defined
6Not defined 22 h
1030 hNot defined
11Not defined22 h

The results given in tables 3 and 4 show that the presence of α-tocopherol also slows down the decrease in drying the catalyst activity of linseed oil.

Experiment 4

The stability of the catalyst during storage in oil paint in a nitrogen atmosphere compared to atmospheric conditions

Samples of oil paints in terms of raw linseed oil and n-heptane were prepared in glass containers (50/50 vol.%) and kept in a nitrogen atmosphere. [Fe(MeN4py)Cl]Cl was present in the amount of 0.004 wt.% (at the rate of 0.0004% metal Fe) (was added in a solution of ethanol) and α-tocopherol was present in the amount 0,009 wt.% (added to a solution of n-heptane). The number of added [Fe (MeN4py)Cl]Cl was calculated based on the weight of the connection. Similarly, experiments were carried out using [Fe(N2py3o-C1)Cl]Cl (0,0004% metal Fe) (was added in a solution of ethanol). The amount of added catalyst depended on the amount of linseed oil (not a mixture of linseed oil/heptane). Samples of oil paint was purged with nitrogen each time were open glass amasteel some time of storage the samples were painted on a wooden Board, and it was determined drying time. The drying time for [Fe(MeN4py)Cl]Cl and [Fe(N2py3o-Cl)Cl]Cl are presented in tables 6 and 7, respectively.

Table 6
Drying activity of 0.004 wt.% [Fe(MeN4py)Cl]Cl (at the rate of 0.0004% of Fe metal) storage in the atmosphere of nitrogen and at atmospheric conditions. The catalyst was added in a quantity of calculate the amount of linseed oil (not a mixture of linseed oil/heptane). Tabular data 2 and 4 show the time required to achieve drying in the presence 0,009% α-tocopherol in the composition
Storage time (days)The drying time during storage in ambient conditionsThe drying time when stored in nitrogen atmosphere
0 (no tocopherol)<20 hNot defined
0 (tocopherol)<19 hNot defined
30 (without tocopherol)More than 32 hours, but less than 4729 h
30 (tocopherol)Over the 30 h, but less than 4629 h

Table 7
The storage stability 0, 005% [Fe(N2py3o-C1)Cl]Cl (at the rate of 0.0004% of Fe metal) storage in the atmosphere of nitrogen and at atmospheric conditions. The catalyst was added in a quantity of calculate the amount of linseed oil (not a mixture of linseed oil/heptane). Tabular data 2 and 4 show the time required to achieve drying in the presence 0,009% α-tocopherol in the composition
Storage time (days)The drying time during storage in ambient conditionsThe drying time when stored in nitrogen atmosphere
0 (no tocopherol)<19 hNot defined
0 (tocopherol)<19 hNot defined
30 (without tocopherol)32 h24 hours
30 (tocopherol)28 h26 h

The results given in table 5 and 6 show that AZ is t also slows down the decrease in drying the catalyst activity of linseed oil.

Experiment 5

The stability of the catalyst during storage in oil paint in the presence of ethylene glycol

Samples of oil paints in terms of linseed oil and n-heptane (700 l; 50/50 vol.%) were prepared with a content of 0.005% [Fe (MeN4py)Cl]Cl (0,0005% of Fe metal)added to a solution of ethylene glycol (100 ml). Drying time "until tack-free in this sample was comparable with drying time "until tack-free" 0.005% of the [Fe(MeN4py)Cl]Cl (0,0005% metal Fe)is added to ethanol (table 7). The catalyst was added in a quantity of calculate the amount of linseed oil (not a mixture of linseed oil/heptane). After some time of storage of the samples were painted on a wooden Board, and it was determined drying time (table 8).

Table 8
The storage stability [Fe(MeN4py)Cl]Cl (0,0005% metal Fe), dissolved in ethanol (left) and ethylene glycol (right) and added to oil paint after some time of storage at room temperature
Storage time (days)The catalyst was dissolved in ethanol
Drying time "until tack-free"
The catalyst dissolved in ethane is Les
Drying time "until tack-free"
0<20 h<16 h
3129 h<20 h

Data in table 7 clearly show that the presence of ethylene glycol in addition to the ethanol much slows down the decrease of the drying activity of oil paint.

1. Capable of curing a liquid medium, including:
a) from 1 to 90 wt.% alkyd resins; and
b) from 0.0001 to 0.1 wt.% dryers where the desiccant is a complex of iron or manganese with tetradentate, pentadentate or hexadentate astonomy ligand, where the ligand is selected from the group consisting of:

where each R is independently selected from:
hydrogen, F, Cl, Br, hydroxyl, C1-C4-alkyla-, -NH-CO-H, -NH-CO-C1-C4-alkyl, -NH2, -NH-C1-C4-alkyl and C1-C4-alkyl;
R1and R2independently chosen from:
With1-C24-alkyl,
With6-C10-aryl, and
group containing a heteroatom capable of coordinating to the transition metal;
R3and R4independently selected from: hydrogen, C1-C8-alkyl, C1-C8-alkyl-O-C1-C8-alkyl, C1-C8-alkyl-O-C6-C10-aryl, C6-C 10-aryl, C1-C8-hydroxyalkyl and
-(CH2)nC(O)OR5,
where R5independently selected from: hydrogen, C1-C4-alkyl, n has a value from 0 to 4, and mixtures thereof, and
X is selected from C=O, -[C(R6)2]y-where y has a value from 0 to 3, each R6independently selected from hydrogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkyl;

where each R1and R2independently represent-R4-R5,
R3represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or R4-R5,
each R4independently represents a simple bond or optionally substituted alkylene, albaniles, oxyalkylene, aminoalkyl, alkalinity ether, ether carboxylic acids or carboxylic acid amide, and
each R5independently represents an optionally N-substituted aminoalkyl group or optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;

where each R20selected from: alkyl, cycloalkyl, geteroseksualnoe, heteroaryl, aryl and arylalkyl group, optionally substituted by a Deputy, you have the security of hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, sulfonate, amine, alkylamine and N+(R21)3where R21selected from hydrogen, alkenyl, alkenyl, arylalkyl, oxyalkyl, oxyalkyl, aminoalkyl, aminoalkyl, alonelove ether, alkenilovyh ether and-CY2-R22in which Y is independently selected from H, CH3With2H5With3H7and R22independently selected from optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; and where at least one of R20represents-CY2-R22;

where Q is independently selected from:
and

R equals 4;
R is independently selected from: hydrogen, C1-C6-alkyl, CH2CH2HE pyridine-2-yl-methyl and CH2COOH;
R1, R2, R3, R4, R5and R6independently selected from: H, C1-C4-alkyl and C1-C4-alkylperoxy;

where R1independently selected from: H, linear or branched, substituted or unsubstituted from C2to C20of alkyl, alkylaryl, alkenyl or quinil; and any nitrogen atoms in the poppy is acyclically rings can be coordinated with the transition metal;

where X is selected from-CH2CH2, -CH2CH2CH2-, -CH2S(HE)HCH2-; and
R17independently represents a group selected from: R17and alkyl, cycloalkyl, geteroseksualnoe, heteroaryl, aryl and arylalkyl group, optionally substituted by a Deputy selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, sulfonate, amine, alkylamine and N+(R19)3where R19selected from hydrogen, alkenyl, alkenyl, arylalkyl, arylalkyl, oxyalkyl, oxyalkyl, aminoalkyl, aminoalkyl, alonelove ether, alkenilovyh ether and-CY2-R18in which Y is independently selected from hydrogen, CH3With2H5With3H7and R18independently selected from optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl featlil; and
where at least two of R17represent-CY2-R18.

2. Capable of curing a liquid medium according to claim 1, where in formula (I) group containing a heteroatom capable coordinated with the transition metal, a is a pyridine-2-ylmethyl, optionally substituted-C0-C4-al the mud.

3. Capable of curing a liquid medium according to claim 2 wherein the group containing a heteroatom capable coordinated with the transition metal, a is an unsubstituted pyridine-2-ylmethyl.

4. Capable of curing a liquid medium according to claims 1 to 3, where in the formula (I) X represents C=O or C(OH)2.

5. Capable of curing a liquid medium according to any one of claims 1 to 3, where in the formula (I): R3=R4and selected from-C(O)-O-CH3-C(O)-O-CH2CH3-C(O)-O-CH2With6H5and CH2HE.

6. Capable of curing a liquid medium according to any one of claims 1 to 3, where in the formula (I) at least one of R1or R2represents pyridin-2-yl-methyl, and the other is selected from-CH3- 2H5- 3H7- 4H9, -C6H13, -C8H17, -C12H25and
-C18H37.

7. Capable of curing a liquid medium according to claim 1, where the ligand is selected from the group consisting of 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane; 5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane; 1,4,8,11-tetraazacyclotetradecane; 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; 1,4,7,10-tetraazacyclododecane; 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 1,4,7,10-tetrakis(pyridin-2-yl-methyl)-1,4,7,10-tetraazacyclododecane; N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine; N,N-bis(pyridine-2-what-methyl-1,1-bis(pyridin-2-yl)-1-aminoethane; N,N,N',N'-Tetra(pyridin-2-yl-methyl)Ethylenediamine; N-methyl-Tris(pyridine-2-yl-methyl)ethylene-1,2-diamine; N-butyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-octyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-dodecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-octadecyl-N,N',N'-Tris(pyridin-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-ethyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(3-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-benzyl-N,N',N'-Tris(5-methyl-pyridine-2-yl-methyl)ethylene-1,2-diamine; N-methyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-ethyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N,N'-dimethyl-N,N'-bis(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propan-2-ol)-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-(1-propan-2-ol)-N,N',N'-Tris(1-methyl-imidazol-2-yl-methyl)-Ethylenediamine; N,N-diethyl-N',N",N"-Tris(5-methyl-imidazol-4-yl-methyl)-Diethylenetriamine; N-(3-propan-1-ol)-N,N',N'-Tris(1-methyl-imidazol-2-yl-methyl)-Ethylenediamine; N-hexyl-N,N',N'-Tris(imidazol-2-yl-methyl)-Ethylenediamine; N-methyl-N,N',N'-Tris(the benzimidazole-2-yl-methyl)-Ethylenediamine; N-(3-propan-1-ol)methyl-N,N',N'-Tris(benzimidazole-2-yl-methyl)-Ethylenediamine; 1,4-bis(quinoline-2-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-b is C(quinoline-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(quinoline-2-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyridyl-2-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(pyrazole-1-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4 bis(pyrazole-1-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(pyrazole-1-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 3,5-(dimethylpyrazol-1-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-octyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-ethyl-1,4,7-triazacyclononane; 1,4-bis(1-Mei-2-yl-methyl)-7-methyl-1,4,7-triazacyclononane; 1,4,7-Tris(quinoline-2-yl-methyl)-1,4,7-triazacyclononane; and 1,4,7-Tris(pyridine-2-yl-methyl)-1,4,7 triazacyclononane.

8. Capable of curing a liquid medium according to any one of claims 1 to 3, where iron ion selected from Fe(II) and Fe(III), and mn ion selected from Mn(II), Mn(III) and Mn(IV).

9. Capable of curing a liquid medium according to any one of claims 1 to 3, where the concentration of the desiccant is between 0,0001 and 0.5 wt.%.

10. Capable of curing a liquid medium according to any one of claims 1 to 3, additionally containing between about 0.001% and 0.1% of the following antioxidants: di-tert-butyl-hydroxytoluene, ethoxyquin, α-tocopherol and 6-hydroxy-2,5,7,8-t the tra-methylchromone-2-carboxylic acid.

11. Capable of curing a liquid medium of claim 10, where the content of the antioxidant is between 0,002 and 0.05%.

12. Capable of curing a liquid medium of claim 10, where the antioxidant is selected from α-tocopherol.

13. Capable of curing a liquid medium according to any one of claims 1 to 3, which is stored in the atmosphere of nitrogen or argon.

14. Capable of curing a liquid medium according to any one of claims 1 to 3, containing between 0.001 and 90% of ethylene glycol, diethylene glycol, dipropyleneglycol, glycerin, pentaerythrol, dipentaerythritol, neopentyl glycol, trimethylolpropane, trimethanolamine, di-trimethylolpropane and 1,6-hexandiol.

15. Capable of curing a liquid medium 14 containing from 0.1 to 50% of ethylene glycol or glycerin.

16. Capable of curing a liquid medium according to § 15 containing from 0.3 to 5% of ethylene glycol or glycerin.

17. Capable of curing a liquid medium according to any one of claims 1 to 3, containing from 0.001 to 2.5% of lead, zirconium, bismuth, barium, vanadium, cerium, calcium, lithium, strontium and zinc.

18. Capable of curing a liquid medium according to any one of claims 1 to 17 after drying.

19. Capable of curing a liquid environment p after drying, where the desiccant is a complex of iron with dimethyl-2,4-di-(2-pyridyl)-3-methyl-7-(pyridine-2-ylmethyl)was 3.7-diazo-bicyclo [3.3.1]nonan-9-one-1,5- - in primary forms.



 

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EFFECT: production of new product of floor covering in the form of PVC web with homogeneous coating and high consumer properties.

FIELD: construction.

SUBSTANCE: said utility invention relates to floor coverings and may be used by individuals or in industry for floor covering in residential flats and industrial premises. The floor covering manufacture method involves operations of the application of PVC coatings using the air cushion for the preservation of the printed layer(s), levelling of the web edges, creation of stock of the floor covering rolled in the process of its coating, tensioning, drying, and cooling; along with a number of auxiliary operations related to the collection of excessive covering mass. The invention ensures cost effectiveness of the process, consisting in the selection of the most optimal operations of manufacture and inspection of the web proper, in the process of application of the coatings and the ultraviolet lacquer, the process of web tension synchronisation in various periods of its processing, the operations of linoleum web cooling, and other operations related to careful treatment of the covering, for example, during web rotation using the air cushion.

EFFECT: increased cost effectiveness of floor covering manufacture process.

1 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to filled polyvinylchloride composition intended for use in manufacture of linoleum having utilization as floor toppings in industrial and civil construction. Composition contains suspended polyvinylchloride, dioctyl phthalate, calcium stearate, and filler in the form of swollen sand, namely exhausted insulating filling from cryogenic plants.

EFFECT: improved performance characteristics and reduced cost due to utilized waste.

2 tbl

FIELD: filled plasticized polyvinyl chloride compositions for linoleum production.

SUBSTANCE: claimed composition contains suspended polyvinyl chloride as film-forming agent; di-(2-ethylhexyl)-phthalate as plasticizer; stearic acid and complex stabilizer as stabilizers; chalk and pigments as filler. Additionally composition contains mixture of crezyldiphenyl phosphate and liquid chlorinated paraffin in ratio of 3:1 as plasticizer and three-based lead sulphate as stabilizer and aluminum hydroxide and antimony trioxide as fire-retardant additives. Obtained rolled material has the next burning quality: smoke gases temperature of 120-135°C; damage ration in sample length of 60-65 %; damage ration in sample mass of 17-20 % and duration of spontaneous burning of 0 seconds.

EFFECT: improved fire retardant material.

2 tbl

FIELD: construction industry, in particular, laminated materials, such as rolled polymeric floor coverings, in particular, linoleum.

SUBSTANCE: multilayer rolled polymeric 2.7 mm thick floor covering has base comprising lower layer of nonwoven needle-stitched material of polyester or polypropylene filaments or mixture of filaments having thickness of 1.3-2.0 mm, density of 200-360 g/m2, and upper polymeric layer composed of at least two polyvinyl chloride layers. Lower polyvinyl chloride layer has glass fabric or mineral paper used as reinforcement material and having thickness of 0.6-1.0 mm. Thickness of transparent face layer is 0.12-0.50 mm. Middle polyvinyl chloride layer of polymeric layer may foamed and provided with decorative relief pattern.

EFFECT: increased decorative effect, improved wear resistance, heat and sound isolating properties and sanitary and hygienic qualities of rolled covering.

2 cl, 3 dwg, 1 tbl, 2 ex

The invention relates to the field of layered materials, in particular to a roll of plastic coatings in construction, usually called “linoleum”

FIELD: chemistry.

SUBSTANCE: invention relates to a cleaning, bleaching or disinfecting composition which is a stabilised oxidase composition containing said oxidase and a stabiliser and at least one substrate for said oxidase, where said stabiliser contains at least one oxidase inhibitor, where said stabiliser is selected from thiosulphate and 2-amino-2-methyl-1-propanol. In certain especially preferable versions of the invention, said oxidase is selected from glucose oxidase, sorbitol oxidase, choline oxidase, hexose oxidase and alcohol oxidase. The invention also relates to a method of forming a bleaching product in a detergent solution, involving a step for adding said composition to said detergent solution, wherein the preferred version, said bleaching product is a peroxide or a bleaching system which can be activated using peroxide.

EFFECT: ensuring stability a H2O2-generating system during storage and production of bleaching agents when diluting a detergent in a detergent solution.

15 cl, 8 tbl, 9 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a biocidal composition containing hydrogen peroxide in concentration of 0.05-50% (wt/wt) and a compound of formula 1: (OH)(2-m)(X)(O)P-[(O)p-(R')q-(CH(Y)-CH2-O)n-R]m, where X is H or OH; each Y is independently H or CH3; m equals 1 and/or 2; each p and q is independently equal to 0 or 1, provided that if p equals 0, q equals 1; each n is independently equal to 2-10; each R' is independently an alkylene radical containing 1-18 carbon atoms; each R is independently H or an alkyl radical containing 1-18 carbon atoms; and R'+R≤20; in concentration of 0.01-60% (wt/wt), as a biocidal composition. The invention also relates to use of the disclosed composition as a biocidal composition, as well as for purposes where there is need for disinfection and/or sanitation activity.

EFFECT: composition has excellent biocidal activity.

25 cl, 9 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: aqueous composition has pH equal to or less than 3, and contains the following ingredients (per total weight of the composition) : a) 0.05-20 wt % polymer thickener containing 20-100000 monomer links and an average of at least 0.8-COOR groups per monomer link, where for each separate -COOR group, R is independently selected from H, OH, and a carbon-containing group, b) 0.05-30 wt % hydrogen peroxide in terms of H2O2, c) 0.5-60 wt % one or more aliphatic carboxylic acids containing 1-8 carbon atoms, their alkyl esters, anhydrides and/or peroxy acids. Content of active oxygen, which is ensured by presence of ingredients a) and c) is equal to at least 0.02 wt % (per total weight of the composition).

EFFECT: obtaining a stable aqueous composition with low pH for cleaning different surfaces and for bleaching textile materials or paper.

15 cl, 10 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: sodium percarbonate particles covered by a cladding have a core of sodium percarbonate obtained via fluidised bed granulation. The cladding contains sodium sulphate and sodium carbonate in weight ratio ranging from 95:5 to 75:25 in relative amount of at least 80 wt %.

EFFECT: improved detergent action of sodium percarbonate when used as detergent component with simultaneous increase in stability when stored with detergents.

12 cl, 5 tbl

FIELD: chemistry.

SUBSTANCE: sodium percarbonate particles are covered by a cladding which contains sodium sulphate in form of a high-temperature phase of sodium sulphate and/or in form of a high-temperature phase of a double salt of formula Na4(SO4)1+n(CO3)1-n, where n is a number ranging from 0 to 0.5.

EFFECT: high stability during storage.

8 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: sodium percarbonate particles are covered by a cladding which contains anhydrous sodium sulphate in amount of 70-99.8 wt % and sodium borate in amount of 0.2-20 wt % and where said cladding accounts for 1-10% of the total weight of one particle of sodium percarbonate.

EFFECT: high stability during storage when using sodium percarbonate particles as a component of detergent and cleaning agents.

9 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a bleaching system for household textile items containing at least one bleaching agent, where the bleaching system is selected from peroxybenzoic acid, peroxy-6-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimido peroxycaproic acid, 6-phthalimido peroxyhexanoic acid, nonylimido peroxyamber acid, nonylimido peroxyadipic acid, 1,12-diperoxydodecanoic acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid and 2-decyldiperoxybutane-1,4-diacid and coated by a shell in form of a layer of a polymer with urethane and urea groups, where a prepolymer with terminal NCO groups is obtained from macrools, ionic or potentially ionic polyols and polyisocyanates used in excess, said prepolymer being subjected to reaction with compounds which contain at least two amine groups which are reactive towards isocyanate with ratio of NCO groups to NH groups less than or equal to 1:1, after which said polymer is obtained via neutralisation.

EFFECT: obtaining a novel bleaching system.

11 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: cleaning compositions contain organic catalysts having improved enzyme compatibility and having the following formulae: where each R1 independently denotes a branched alkyl group selected from a group comprising 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, isodecyl, isotridecyl and isopentadecyl, or a linear alkyl group containing 11-18 carbon atoms. The composition also contains one or more auxiliary ingredients.

EFFECT: cleaning compositions with efficient bleaching at low water temperature.

15 cl, 16 ex

FIELD: chemistry.

SUBSTANCE: synthetic detergent with low environmental hazard contains sodium tripolyphosphate, anionic surfactant - sodium soap based on high fatty acids, carboxymethyl cellulose, sodium silicate, optical bleaching agent, fragrance component, sodium sulphate and water. The detergent also contains a nonionic surfactant - oxyethylated fatty alcohols, collagen dissolution products obtained by using leather production wastes (leather cuttings), sodium perborate and sodium carbonate. All components are taken in a defined ratio.

EFFECT: invention enables production of a synthetic detergent with low environmental hazard, good detergent action and low foaming capacity.

3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to pellets which contain diacyl peroxide particles inside a matrix, a method of preparing such pellets and detergents containing such pellets. The pellets contain a matrix made from at least one metal ion-cross-liked polysaccharide and diacyl peroxide particles put inside the said matrix. The pellets are obtained through drop-wise addition of an aqueous suspension in which diacyl peroxide particles are suspended and in which at least one metal ion-cross-linked polysaccharide is dissolved to a solution which contains polysaccharide cross-linking metal ions.

EFFECT: obtaining pellets in which diacyl peroxide is in a form which ensures its reliable production and storage.

11 cl, 1 ex

FIELD: household chemical goods.

SUBSTANCE: invention provides composition for applying self-oxidizing architectural coating, which is suitable for handling by inexperienced users having no personal respiratory protection devices at ambient temperatures and natural day light. Composition contains self-oxidizing polymeric binder and promoter system to promote self-oxidation of the binder, which promoter contains from 0 to 0.01 wt % cobalt ions and metal ions other than cobalt ions promoting surface self-oxidation in amount 0.001 to 0.04 wt % and those promoting bulk self-oxidation in amount 0.5 to 2 wt %, and also at least one photoinitiator in amount 0.3 to 2 wt %, all based on the weight of binder. This composition is applied onto surface to obtain dried architectural coating irradiated by low-energy radiation in the form of light with wavelength between 350 and 650 nm. Composition removes need of utilizing larger than trace amounts of cobalt ions, which are considered to be carcinogenic, and ensures achievement of suitably high self-oxidation rates. No cobalt utilization is preffered. Utilization of low concentrations of other metal ions leads to reduction in composition color variation, often al levels lower than those achieved when utilizing common cobalt promoters.

EFFECT: avoided need of high-energy irradiation and accurately controlled conditions, and improved luster of coating.

7 cl, 4 dwg, 7 tbl, 9 ex

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