UA119862C2 - Improved phtalate-free polyvinyl chloride plastisol compositions - Google Patents

Abstract

The present invention is related to improved phthalate-free polyvinyl chloride plastisol compositions for the production of decorative surface coverings, in particular floor and wall coverings with low emission of volatile organic compounds, to a method for the preparation of said phthalate-free PVC plastisols and to a process for the production of said surface coverings.

Description

Field of the invention 0001) This invention relates to improved phthalate-free polyvinyl chloride (PVC) plastisol compositions for the production of decorative surface coatings, in particular floors and walls with low emission of volatile organic compounds. The invention additionally relates to the method of obtaining the specified phthalate-free PVC plastisols and to the method of obtaining the specified surface coatings.

Prior art

І0002| Plasticizers have been used to process polyvinyl chloride for decades. Plasticizers are additives used in the processing of polymers to improve processability, flexibility, and extensibility. Plasticizers for the flexible production of polyvinyl chloride are mainly phthalic acid esters, such as the universal products di-2-ethylhexyl phthalate (OENR), diisononyl phthalate (DIMR) and diisodecyl phthalate (DIOR).

ИО003| Recently, the requirements for plasticizers have become stricter in terms of performance and non-toxicity for humans and the environment.

Restrictions on the use of phthalates are constantly increasing due to legislative requirements. Thus, there is a need for a phthalate-free replacement of plasticizers based on phthalic ethers. The replacement of phthalate-based plasticizers with phthalate-free plasticizers is forced and is already the subject of a number of technical publications and patent literature. (0004) In the European patent application EP 1983024 A1, plasticizing mixtures with a low dissolution temperature and low volatility are proposed for the processing of plastics such as polyvinyl chloride. The plasticizing mixture consists of a mixture of ethers, which includes benzyl-alkyl esters of aromatic tri- and tetra-carboxylic acids.

I0005)| European patent application EP 2039718 AT describes plasticizing mixtures based on aryl alkylsulfonates and diol dibenzoates. A special property of these plasticizing mixtures is low volatility.

II0006| In the European patent application EP 2404962 A1, a phthalate-free plasticizing mixture for processing plastics, such as polyvinyl chloride, containing from 5 to 95 wt. 96 arylalkylsulfonate and from 95 to 5 wt. 95 SU or C10 monoatomic benzoic ether

From alcohol. The plasticizing mixture provides a shorter gelation time than individual components used separately.

I0007| European patent application EP 2145914 A1 describes a plasticizing mixture for polyvinyl chloride containing from 5 to 50 wt. 95 triacetin and from 50 to 95 wt. 95 one or more plasticizers having a melting point in polyvinyl chloride of less than 180 "C, which is a phthalate-free plasticizer that is selected from the group consisting of alkyl esters of benzoic acid, dialkyl ethers of aliphatic dicarboxylic acids, polyesters of aliphatic dicarboxylic acids and aliphatic dicarboxylic acids , tri- and tetrols, trialkyl esters of citric acid, acetylated trialkyl esters of citric acid, esters of glycerol, benzoic diesters of mono-, di-, tri- or polyalkylene glycol, trimethylolpropane ethers, dialkyl ethers of cyclohexanedicarboxylic acid, dialkyl ethers of terephthalic acid, trialkyl esters of trimellite acid, triaryl esters of phosphoric acid, diarylalkyl esters of phosphoric acid, trialkyl esters of phosphoric acid and/or aryl esters of alkyl teulfonic acids.

I0008| European patent applications EP 1415978 Ai and EP 1354867 Ai describe the use of plasticizing mixtures, respectively, of isomeric decylbenzoates and isomeric nonylbenzoates with dialkyl phthalate, dialkyl adipate or cyclohexanedicarbon ether.

ИО009| US Patent Application 2007/0027242 describes a plasticizing composition for polyvinyl chloride containing at least one ester of an aliphatic or aromatic di- or tricarboxylic acid having a C10 alcohol component and containing at least one ester of an aliphatic or aromatic di- or tricarboxylic acid, having a C7 alcohol component, where the aliphatic or aromatic di- or tricarboxylic acid is selected from the group consisting of citric acid, phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid.

ИЙ0О010| European patent application EP 2231763 AT describes a composition that contains a plasticizing polymer, such as polyvinyl chloride, at least one low-melting plasticizer selected from cyclohexanecarboxylic acid esters, and at least one high-melting plasticizer selected from the group consisting of isodecyl benzoate, isononyl benzoate, 2-ethylhexylbenzoate, isooctylbenzoate, di-2-propylheptylbenzoate, dibutyl terephthalate, dibenzoate esters of dipropylene glycol, dibenzoate esters of diethylene glycol, esters of C4-C7-aliphatic alcohols ("

cyclohexanoates, acetyl tributyl citrate, acetyl trihexyl citrate, butyryl tributyl citrate and their mixtures. Also described is a plasticizing mixture for polyvinyl chloride, which includes cyclohexanecarbon ester and other nephthalate plasticizers. 0011) German patent application OE 1962500 describes a plasticizing mixture based on alkylbenzoate and succinate complex diesters. The final flexible polyvinyl chloride product containing the plasticizer compound exhibits excellent color fastness values. 0012) US patent application 7973194 describes a highly soluble plasticizing mixture for polyvinyl chloride plastisols containing a mixture of dibutyl ethers, dibenzyl ethers and butylbenzyl ethers of 1,4-cyclohexanedicarboxylic acid.

I0013| US Patent Application 2009/0281220 relates to plasticizers containing esters of monobasic carboxylic acids (mono- and/or diesters) of poly(trimethylene ether) glycol, as well as their use in the plasticization of various base polymers, such as polyvinyl chloride. Poly (trimethylene ether) glycol ethers can be mixed with other known ether plasticizers, such as, for example, synthetic and natural esters.

II0014| US Patent Application 2008/0242895 relates to polyketone compounds and their at least partially hydrogenated products as plasticizers for polymers such as polyvinyl chloride. The polymer additionally contains at least one plasticizing compound selected from phthalic acid esters, adipic acid esters, trimellitic acid esters, cyclohexatonates, cyclohexanedicarboxylic esters and benzoates.

ІІ0015| The international patent application UMO 2013/048775 describes the method of obtaining a composition of a dry mixture of polyvinyl chloride, which includes mixing polyvinyl chloride, a phthalate-free plasticizer on a biological basis and a filler. The biologically based plasticizer contains a mixture of epoxidized triglyceride liquid and epoxidized ether

C1-C14 fatty acids.

І0016| US Patent 7,071,252 describes a non-aqueous plastisol composition containing at least one organic polymer, at least one primary plasticizer and at least one secondary plasticizer selected from the group consisting of monoesters derived from dihydric alcohol and aromatic monocarboxylic acid; wherein said primary plasticizer is selected from the group consisting of diethylene glycol dibenzoate, triethylene glycol dibenzoate, and dipropylene glycol dibenzoate, and at least a portion of said secondary plasticizer is a suitable monoester, and the sum of all monoesters is from 5 to 20 95 by weight of the total weight of said primary and secondary plasticizers . The concentration of the specified secondary plasticizer is sufficient to reduce the viscosity demonstrated by the specified plastisol in the presence of only the specified primary plasticizer, while maintaining compatibility with the specified plastisol.

I0017| European patent EP 2045286 B1 describes improved polyvinyl chloride compositions containing a mixture of cyclohexanepolycarboxylic acid ester and one or more than one other plasticizer, where the other plasticizer is a fast-melting plasticizer selected from diethylene glycol dibenzoate, butyl benzyl phthalate, dipropylene glycol dibenzoate, esters of aromatic sulfonic acids such as pentadecyl sulfonic acid phenyl or cresyl ester, citrates, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, 2-ethylhexyl isodecyl phosphate, and 2-di-ethylhexylphenyl phosphate.

ІІ0018| International patent application UMO 2013/004265 describes a polyvinyl chloride composition containing at least one non-phthalate-based plasticizer and at least one citrate-based plasticizer selected from the group consisting of triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, and acetyl tri-2g- ethylhexylcitrate.

I0019| Until now, the phthalate-free polyvinyl chloride compositions described in the prior art do not meet the requirements of fast processing and/or reduced energy consumption during processing, which is specially adapted for the production of decorative surface coatings, and in particular floors or walls. In addition, the products obtained as a result of the processing of these phthalate-free plastisols do not provide a sufficiently reduced release of volatile organic compounds (VOCs). 0020) The advantages associated with the prior art systems are undeniable, but it is nevertheless apparent that there is still a need for improved phthalate-free PVC plastisols, particularly phthalate-free PVC plastisols that do not exhibit any of the existing shortcomings

Purpose of the invention 00211) This invention is directed to providing phthalate-free plasticizing mixtures for PVC plastisols that do not have the disadvantages of the prior art, in other words, to create phthalate-free plasticizing mixtures for polyvinyl chloride plastisols with good gelling properties, for which the compositions allow rapid processing and/ or reducing energy consumption during processing.

I0022| Another object of this invention is to provide phthalate-free plastisol compositions for decorative surface coatings with low emission of volatile organic compounds (VOCs), and a method of producing such surface coatings.

Brief Description of the Invention 0023) As is commonly practiced in the art, the proportions of the various components of the compositions are given in parts by weight, hereinafter referred to simply as "parts" for brevity. The present invention discloses a phthalate-free plastisol composition based on PVC for decorative surface coatings, which has a low (reduced) emission of VOCs, and this composition contains from 10 to 200 parts, preferably from 20 to 150 parts per 100 parts of polyvinyl chloride of a plasticizing mixture, which includes: - from 5 to 190 parts, preferably from 10 to 160 parts, more preferably from 15 to 130 parts, most preferably from 15 to 75 parts of one or more phthalate-free primary plasticizers, characterized by a dissolution temperature at the point of transparency from 130 to 200 "C, preferably from 130 to 160 "C, and the vapor pressure at 25 "C, which is less than 5x103 mm Hg; - from 1 to 100 parts, preferably from 3 to 80 parts, more preferably from 5 to 60 parts, most preferably from 5 to 50 parts of one or more than one phthalate-free secondary plasticizer, characterized by a melting temperature at the point of transparency of less than 130 "C, preferably from 70 to 129 "C, and a vapor pressure at 25 "C , which are less than 10 mm Hg. art.; and the dissolution temperatures of the specified one or more than one primary and secondary plasticizer are measured in accordance with IM 53408 for suspension PVC with a value of K 71; the vapor pressure of one or more than one primary and secondary plasticizer is measured in accordance with ABTM E1194-07, and the vapor pressure of one or more than one primary and secondary plasticizer is measured in accordance with AZTM E1194-07, and the ratio (by mass) of the content of the specified one or more than one

From the phthalate-free primary plasticizer to the content (by weight) of one or more phthalate-free secondary plasticizers is from 0.1 to 10, preferably from 0.5 to 7.5, to reduce the gelation temperature demonstrated by said plastisol in the presence of only one or more than one primary plasticizer, at least by 5". (0024) Preferred embodiments of the invention reveal one or more of the following features: - the specified one or more than one phthalate-free primary plasticizer is characterized by a molecular weight ranging from 200 to 1000 g/mol ", preferably from 350 to 800 g/mol"; - specified one or more than one phthalate-free secondary plasticizer is characterized by a molecular weight of from 150 to 600 g/mol", preferably from 200 to 450 g/mol"; - specified one or more than one phthalate-free primary plasticizer is characterized by a dynamic viscosity at 20 "С, which is from 5 to 200 mPag"s, preferably from 10 to 150 mPa-"s; - vka the one or more than one phthalate-free secondary plasticizer is characterized by a dynamic viscosity at 20 "С, which is from 1 to 150 mPa"s, preferably from 5 to 120 mPa"s; - specified one or more than one phthalate-free primary plasticizer is characterized by a vapor pressure at 25 "C of less than 107 mm of mercury column (Hg), preferably

BO is less than 5x105 mm Hg. art.; - specified one or more than one phthalate-free secondary plasticizer is characterized by a vapor pressure at 25 "C of less than 102 mm Hg, preferably less than 103 mm Hg, more preferably less than 107 mm Hg; - specified one or more than one phthalate-free primary plasticizer selected from the group consisting of alkyl esters of cyclohexane dicarboxylic acids, dialkyl esters of aliphatic dicarboxylic acids and alkyl esters of aromatic di-, tri- or tetra-carboxylic acids, excluding orthophthalic acid; - specified one or more than one non-phthalate secondary plasticizer selected from the group consisting of lower alkyl esters of aromatic dicarboxylic acids such as benzoates, citrates, phosphates and sulfonates;

- phthalate-free PVC plastisol composition contains 100 parts of polyvinyl chloride, from 5 to 190 parts of one or more than one phthalate-free primary plasticizer, from 1 to 100 parts of one or more than one phthalate-free secondary plasticizer, up to 250 parts of filler, up to 7 parts of stabilizer, up to 5 parts of epoxidized vegetable oil and up to 100 parts of other components selected from the group consisting of viscosity reducers, foaming agents, liquid catalysts, antistatic agents, flame retardants, dyes, pigments, lubricants and technological additives; 0025) This invention additionally describes a method of obtaining phthalate-free PVC plastisols, which includes the stages of: a) mixing 100 parts of polyvinyl chloride, from 5 to 190 parts of one or more than one phthalate-free plasticizer to form a plastisol; p) determination of the difference between the gelation/melting profiles of the phthalate-free plastisol from stage a) and the phthalate-based plastisol, taken as a reference, using a rheometer in dynamic oscillating mode with a controlled heating rate; c) adjusting the gelation/melting profile of the phthalate-free plastisol from stage a) according to the gelation/melting profile of the phthalate-based plastisol, taken as a reference, by gradually adding from 1 to 100 parts of one or more than one phthalate-free secondary plasticizer to the plastisol from stage a);

I0026| In the preferred embodiment of the method of obtaining plastisol according to the invention: - plastisol from stage a) additionally contains up to 250 parts of filler, up to 7 parts of stabilizer, up to 5 parts of epoxidized vegetable oil and up to 100 parts of other components, which are selected from the group consisting of viscosity reducers, foaming agents, liquid catalysts, antistatic agents, flame retardants, dyes, pigments, lubricants and technological additives.

I0027| This invention additionally describes a method of obtaining a decorative surface coating using phthalate-free PVC plastisol according to the invention, which includes the following stages: a. providing a substrate layer; r. bringing the substrate layer into contact with the composition according to any of the paragraphs 1-7,

From the village gel formation of the specified composition at a temperature in the range from 130 "C to 200 "C.

I0028| In the preferred embodiment of the invention, the method of obtaining a decorative surface coating includes additional stages: a. printing the pattern on the gel-like layer at stage c) e. bringing the PVC gel-like layer into contact with the printed pattern obtained at stage 4) with the wear protection layer.

I0029| Preferred variants of the method of obtaining a decorative surface coating reveal one or more of the following features: - the protective anti-wear layer is a layer of polyvinyl chloride, a layer of polyurethane or a layer of polyvinyl chloride with a polyurethane layer on top; - a decorative surface coating, in particular a floor or wall coating, obtained after processing a phthalate-free PVC plastisol composition, has a total emission of volatile organic compounds (VOCs) below 100 mg"mU, mainly the emission of volatile organic compounds (VOCs), which is the sum of the emission of VOCs , emissions of highly volatile organic compounds (VOCs) and emissions of formaldehyde below 10 µgemU, when measured after 28 days according to the test method based on IZO 16000-6, IBO 16000-9 or IZO 16000-10.

A brief description of the figures

I0OOZ0| In Fig. 1 shows the viscoelastic profile of gelation and melting of plastisol obtained with PVC/diisononyl phthalate (solid line), PVC/phthalate-free primary plasticizer (dashed line), and PVC/phthalate-free primary and secondary plasticizer (dashed line).

Detailed description of the invention

ЙОО31| The object of this invention is to provide improved phthalate-free polyvinyl chloride plastisol compositions that are intended for decorative surface coatings, in particular floor and wall coatings, with gelation/melting properties comparable or better than the gelation/melting properties of modern optimized phthalate-based plastisols, allowing decorative surface coatings, which are obtained as a result of treatment with the specified plastisols, have a reduced emission of volatile organic compounds, and the specified emission of VOCs is preferably less than 100 μgm-, more preferably below 10 μgm when measured according to standardized conditions.

II0032| We have found that this task is accomplished by PVC plastisols containing from 10 to 200 parts of plasticizer mixture per 100 parts of PVC, said mixture containing from 5 to 190 parts of one or more than one particular primary plasticizer and from 1 to 100 parts one or more than one specific secondary plasticizer.

Y0033| Plastisol is a liquid or paste consisting of a mixture of polyvinyl chloride and a plasticizer, possibly containing various additives. Plastisol is used to obtain layers of polyvinyl chloride, which are then fused with flexible polyvinyl chloride products. Plastisols usually contain 15 to 200 parts of plasticizer per 100 parts of polyvinyl chloride.

I0034| Plastisols are usually made from polyvinyl chloride, which is obtained by emulsion polymerization or microsuspension polymerization. Plastisol can be obtained by the manufacturer of polyvinyl chloride or an intermediary and supplied to the user in liquid form. As an alternative, the plastisol can be obtained by the user.

I0035| For PVC produced by suspension polymerization, vinyl chloride monomer is suspended in water under agitation at carefully controlled temperature and pressure.

The batch will also contain suspending agents and initiators. After complete polymerization, the batch is unloaded into a desorber, where unreacted monomer is removed. Finally, the suspension is washed and dried to obtain a suspension of polyvinyl chloride. A typical suspension of polymerized polyvinyl chloride consists of agglomerated particles ranging in size from 80 to 200 μm. Polyvinyl chloride with a particle size of 1 to 40 μm can be obtained using microsuspension polymerization. 0036) For PVC obtained by emulsion polymerization, vinyl chloride monomers are emulsified in water so that latex particles are formed as a result of polymerization.

The ratio of water and vinyl chloride monomer in emulsion polymerization is greater than the ratio of water and vinyl chloride monomer in suspension polymerization. Polyvinyl chloride obtained by emulsion polymerization also consists of agglomerated particles, but the particles, as a rule, are smaller than those of polyvinyl chloride obtained by suspension polymerization. Usually agglomerated particles of emulsion polyvinyl chloride have a particle size in the range of 15 to 20 microns. Polyvinyl chloride obtained by

Emulsion polymerization is commonly used in the production of plastisols used in coating operations where the plastisol is applied to a substrate layer and then fused by heating.

I0037| Different forms of polyvinyl chloride are used in different ways. An important property is the average molecular weight of the polymer. A factor known as the "K value" is used to refer to the average molecular weight of polyvinyl chloride. The value of K is a viscosity of 0.005 wt. 96 of a solution of polyvinyl chloride in cyclohexanone at a temperature of 25 "С, which is measured using an OBBreiIpode viscometer. The value of K is the German standard IM 53726.

ИЙОО38| The value of K of polyvinyl chloride affects the melting temperature and the rate of gelation from the plasticized composition of polyvinyl chloride. Of course, the higher the K value, the better the mechanical properties, but the less flowability. 0039) Emulsion and microsuspension of polymerized polyvinyl chloride are preferred for those purposes where a good flow of polyvinyl chloride is required, such as spreading used in the production of floor or wall coverings. For spreading size

K from 65 to 90 is preferable.

I0040| One or more than one phthalate-free primary plasticizer is characterized by a melting temperature at the transparency point of from 130 "C to 200 "C, preferably from 130 C to 160 76. 00411) One or more than one phthalate-free secondary plasticizer is characterized by a melting temperature at the transparency point of less than 130 "C, mostly from 70 "C to 129 76.

I0042| The dissolution temperature is the temperature at which a homogeneous phase will form in the plasticizer from the dispersion of polyvinyl chloride (I. Meieg: "M/eisptaspeg" (Riaviisigege), in K.

Saspieg, N. Miyyeg (Ea.): Tazspeprisy deg KypvivIoyMaaayme (Riaziesvz adayime5 Naparook|u, 3

Eaiyop, pp. 361-362, Napseg Mepad, Mypispy 1990). Plasticizers with a low melting point allow faster processing, which saves energy.

I0043| The dissolution temperatures of one or more than one primary and secondary plasticizers were measured according to SIM 53408 (1967) in suspension PVC with a K value of 71. (0044) Phthalate-free primary plasticizers are additionally characterized by a vapor pressure at 25 "C of less than 52103 mm Hg, preferably less than 105 mm Hg, more preferably less than 5106 mm Hg, dynamic viscosity at 20 "C in the range from 5 to 200 mPa"s, preferably from

10 to 150 mPags, and a molecular weight of 200 to 1000 hemols, preferably between 350 and 800 hemols. (0045) Phthalate-free secondary plasticizers are additionally characterized by a vapor pressure at 25"C that is less than 107 mm Hg, preferably less than 102 mm Hg, more preferably less than 103 mm Hg, most preferably 107 mm Hg, with a dynamic viscosity at 20 °C of from 1 to 150 mPas, preferably from 5 to 120 mPas, and a molecular weight of from 150 to 600 hemols, preferably between 200 and 450 hemol".

II0046| Steam pressure is the pressure exerted by steam in thermodynamic equilibrium with its condensed phase at a given temperature in a closed system; measured according to

ATM E1194-07 and refers to the tendency of particles to leave a given condensed phase.

Low vapor pressure is related to low VOC emissions.

I0047| Dynamic viscosity was measured according to ATM 02983 using a Brookfield rotary viscometer (Vgookte!ia). (0048) Primary plasticizers are preferably selected from the group consisting of alkyl esters of cyclohexane dicarboxylic acids, dialkyl esters of aliphatic dicarboxylic acids, and alkyl esters of aromatic di-, tri-, or tetracarboxylic acids, excluding orthophthalic acid.

I0049| Examples of alkyl esters of cyclohexane dicarboxylic acids are diisobutyl-, diisopentyl-, diisohexyl-, di-2-ethylhexyl-, dicyclohexyl-, di-n-heptyl-, diisoheptyl-, di-n-octyl-, diisooctyl-, di-n -nonyl-, diisononyl-, di-(3,5,5-trimethylhexyl)-, di-(2,6-dimethyl-4-heptyl)-, di-n-decyl, diisodecyl-, di-2-propylheptyl, di-n-undecyl, diisoundecyl-, di-n-dodecyl, diisododecyl-, di-n-tridecyl-, diisotridecyl-, di-n-tetradecyl, di-n-hexadecyl-, di-n-octadecyl-, diisooctodecyl compounds esters of 1,2-cyclohexanedicarboxylic acids, 3-methyl-1,2-cyclohexanedicarboxylic acids, 4-methyl-1,2-cyclohexanedicarboxylic acids, 1,4-cyclohexanedicarboxylic acids and /3-methyl-1,4-cyclohexanedicarboxylic acids.

II0050| Examples of dialkyl esters of aliphatic dicarboxylic acids are digeptyl, dioctyl, dinonyl, dodecyl, diundecyl, didodecyl, ditridecyl, ditetradecyl, dihexadecyl, dioctodecyl, dicyclohexyl, diisoheptyl, di-(3,5,5 -trimethylhexyl)-, di-(2,6-dimethylheptyl)-, diisooctyl-, diisononyl-, diisodecyl-, diisoundecyl-, diisododecyl, diisotridecyl-, di-2-ethylhexyl-, di-2-propylheptyl-, diisooctadecyl esters adipic and azelaic acid. 0051) Examples of alkyl esters of aromatic di-, tri- or tetracarboxylic acids, with the exception of orthophthalic acid, are dicyclohexyl-, di-n-octyl-, diisooctyl-, di-2-ethylhexyl-, di-n-nonyl-, diisononyl-, di-n-decyl-, diisodecyl-, di-n-undecyl-, diisoundecyl-, di-n-dodecyl-, diisododecyl-, di-n-octadecyl-, diisooctadecyl-, di-n-eicosyl esters of isophthalic and terephthalic acid , tricyclohexyl-, tri-2-ethylhexyl-, tri-n-octyl-, triisooctyl-, tri-n-nonyl-, triisononyl-, tri-n-decyl-, triisodecyl-, tri-n-undecyl, triisodecyl-, tri-n-dodecyl, triisododecyl-, tri-n-octadecyl-, triisooctadecyl-, tri-n-eicosyl esters of trimellitic acid or its anhydride, tetracyclohexyl-, tetra-2-ethylhexyl-, tetra-n-octyl-, tetraisooctyl- , tetra-n-nonyl-, tetraisononyl-, tetra-n-decyl-, tetraisodecylae, tetra-n-undecyl-, tetraisoundecyl-, tetra-n-dodecyl, tetraisododecyl-, tetra-n-octadecyl, tetraisooctadecyl-, tetra- n-eicosyl esters of pyromellitic acid or its anhydride. 0052) Diisononyl cyclohexanoate, diisooctyl adipate, dioctyl adipate, dioctyl terephthalate and mixtures thereof are preferred primary plasticizers according to this invention. 0053) Secondary plasticizers are preferably selected from the group consisting of lower alkyl esters of aromatic dicarboxylic acids, benzoates, citrates, phosphates and sulfonates.

I0054| Examples of lower alkyl esters of aromatic diacids are dimethyl-, diethyl-, di-n-propyl-, di-n-butyl, di-tert-butyl, diisobutyl, diglycol esters of isophthalic acid and terephthalic acid. 0055) Examples of benzoates are diethylene glycol dibenzoate, triethylene glycol dibenzoate and tripropylene glycol dibenzoate, cyclohexyl-, n-heptyl-, isoheptyl-, n-octyl, isooctyl-, 2-ethylhexyl-, n-nonyl-, isononyl-, Z,5,5 -trimethylhexyl-, 2,6b-dimethyl-4-heptyl, n-decyl-, isodecyl-, 2-propylheptyl, n-undecyl-, isoundecyl-, n-dodecyl, isododecyl-, n-tridecyl-, isotridecyl-, n -tetradecyl-, n-hexadecyl-, n-octadecyl-, isooctadecyl esters of benzoic acid.

II0056| Examples of citrates are triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate and acetyl tri-2-ethylhexyl citrate.

(00571 Examples of phosphates are tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, 2-ethylhexylisodecyl phosphate and 2-di-ethylhexylphenyl phosphate. 0058) Examples of sulfonates are phenyl or cresyl esters of pentadecyl sulfonic acid. (0059) Isononyl benzoate, dibutyl terephthalate, diethylene glycol dibenzoate, acetyl tributyl citrate and mixtures thereof are preferred secondary plasticizers according to the present invention.

I0060| The phthalate-free plastisol according to the present invention preferably contains from 10 to 160 parts, more preferably from 15 to 130 parts, most preferably from 15 to 75 parts of one or more than one phthalate-free primary plasticizer, and from 3 to 80 parts, more preferably from 5 to 60 parts, most preferably from 10 to 50 parts of one or more phthalate-free secondary plasticizers per 100 parts of polyvinyl chloride.

I0061)| Phthalate-free plastisol according to this invention additionally contains up to 250 parts of fillers, up to 7 parts of stabilizers, up to 5 parts of epoxidized vegetable oils and up to 100 parts of other components selected from the group consisting of viscosity reducers, foaming agents, liquid catalysts , antistatic agents, flame retardants, dyes, pigments, lubricants and technological additives.

I0062| Illustrative examples of fillers are calcium carbonate, clays, calcium silicate, talc, calcium sulfate, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminosilicates, dolomite, bauxite and silicon dioxide, diatomite, and molecular sieves. 0063) Examples of stabilizers are benzotriazole and benzophenone compounds, which are necessary to reduce degradation under the influence of sunlight, and stabilizers to ensure stability during heat treatment, which are usually metal compounds, in particular, lead salts, organotin compounds, barium, cadmium and zinc salts and calcium/zinc stabilizers.

I0064| Examples of epoxidized vegetable oils are epoxidized soybean oil, sunflower oil, linseed oil, corn oil, rubber tree seed oil, melia oil, and maduca oil. These epoxidized vegetable oils can be added to the plastisol composition as a plasticizer that provides heat resistance and light resistance.

From 0065) Examples of viscosity reducers are aliphatic hydrocarbons such as Mizsoruk? 4010, 4013, 4015 and 4040, derivatives of carboxylic acids such as Mizsoruk? 5025, 5125 and 5050, dauyeh? 615 or Eckhzoi? 0100, dodecylbenzene, such as dauyeh? 602, in particular esters based on oleates and laurates, 2,2,4-trimethylpentanediol diisobutyrate, C3-C17 esters of 1,2,4-trimethyl-1,3-pentanediol, C3-C17 esters of 1,2,4-trimethyl -1,3-pentadiol monoisobutyrate and mixtures thereof, such as those described in US patent 7,741,395.

IOO6b) Examples of foaming agents include azodicarbonamide, oxybisbenzenesulfonylhydrazide, azobisisobutyronitrile, toluenesulfonylhydrazide, sodium bicarbonate, and citric acid, which release, for example, nitrogen and carbon dioxide, and water upon heating.

I0067| Examples of catalysts include lead compounds such as dibasic lead phthalate, zinc oxide, or a barium/cadmium compound. Catalysts control and reduce the decomposition temperature of the foaming agent. (0068) Examples of antistatic agents are cationic, nonionic or anionic in nature agents, usually selected from the group consisting of amides and amines, quaternary ammonium compounds, polyalkylene glycol derivatives, sulfates and sulfonates, and other ethers and esters. 0069) Typical examples of antistatic agents are lauramidopropyltrimethylammonium methosulfate, myristamidopropyltrimethylammonium methosulfate, stearamidopropyltrimethylammonium methosulfate and stearamidopropyldimethyl-beta-hydroxyethylammonium dihydrophosphate. Antistatic agents reduce the accumulation of static charges and contribute to the dissipation of the charge in their products.

I0070| Examples of flame retardants that can be used in phthalate-free plastisol compositions according to this invention include halogen-containing compounds and phosphorus-containing organic compounds such as triaryl, trialkylamine or alkyldiaryl phosphate esters. Other materials that can be used include chloroparaffins, aluminum trihydrate, or antimony oxides.

Flame retardants are added to the composition according to this invention in order to increase the ignition time, reduce the flame spread and burning speed.

II0071| A variety of dyes and pigments can be used in the phthalate-free plastisol compositions of this invention. Examples of useful pigments and 60 dyes are: metal oxides such as iron oxide, metal hydroxides, metal powders,

sulfides, sulfates, carbonates, silicates such as ammonium silicate, carbon black, white clay, barytes, iron sorghum, lead sorghum, organic red, organic maroon, and the like.

I0072| Examples of lubricants and processing additives that can be used in the phthalate-free plastisol compositions of this invention include stearic acid, metal stearates, petroleum waxes, silicone oil, mineral oil, synthetic oils, and polyethylene waxes.

I0073| Phthalate-free plastisol compositions according to this invention are obtained using any convenient method known to specialists in this field of technology.

In general, finely dispersed PVC polymer and possibly other finely divided solids are dispersed in a liquid plasticizer mixture to form a paste. When the dispersion is heated to a temperature above 100 "C, the polymer becomes soluble in the plasticizer, after which the two dispersion phases are transformed into a single phase system. Usually, PVC plastisols are obtained in batch processes using high-shear mixing equipment. Mixing is mainly carried out over a period of about 15 up to about 60 minutes, after which the mixture is cooled.In general, this method is used for the production of plastisols that are immediately subjected to further processing, since the high frictional level of mixing of elements in plastisols leads to a high local temperature increase, which usually leads to low viscosity stability plastisol during storage.

I0074| On the other hand, storage-resistant plastisols can be obtained by mixing finely dispersed PVC polymer, possibly other finely dispersed solid materials, a liquid plasticizer mixture, and possibly other liquid materials in a mixing tank with low shear forces. The pre-homogenized plastisol is recirculated from the mixing tank through the dynamic mixer back into the mixing tank.

This recirculation is carried out up to 10 times before obtaining the final plastisol.

I0075| The present invention relates to a method of obtaining a composition of an optimized composition of phthalate-free PVC plastisol with low VOC emission.

I0076| Regarding optimized phthalate-containing PVC plastisols, currently, in general, a plastisol composition containing diisononyl phthalate is used as a reference.

Optimized diisononyl phthalate containing PVC plastisol forms decorative surface coatings with low VOC emission, total VOC emission equal to or lower than 100 mgem3, measured after 28 days according to the test method based on ISO 16000-6, I5O 16000-9 or ISO 16000-10.

I0077| Diisononyl phthalate-containing PVC plastisol is then subjected to viscosity-elasticity measurement.

Rheometric mechanical spectrometer KM5-605 was used in dynamic oscillatory mode with controlled heating rate. The frequency of oscillations was maintained at the level of 1 Hz; heating started from room temperature to 200 °C with a programmed rate of increase of 5 °C per minute. After a few minutes to equilibrate to the desired temperature, measurements were taken (Fig. 1, solid line).

I0078| The gelation/melting profile of diisononyl phthalate-containing PVC plastisol is preferably obtained from a plastisol composition that contains filler, plasticizer, epoxidized vegetable oil and other auxiliary components.

I0079| Diisononyl phthalate is then replaced with a phthalate-free primary plasticizer that meets the physical characteristics claimed in this invention, where the melting temperature at the clear point and the vapor pressure at 25"C are key in selecting the most suitable primary plasticizer. 0080 The replacement is preferably carried out in a plastisol composition that includes filler, stabilizer, epoxidized vegetable oil and other auxiliary components.

The composition of phthalate-free PVC plastisol is therefore identical to the composition of diisononyl-based PVC plastisol, except for the plasticizer.

I0081| The gelation/melting profile is then determined for the phthalate-free PVC plastisol using the identical measurement conditions used for the diisononyl phthalate-containing PVC plastisol described in paragraph 77 (Figure 1, dashed line). (0082) At the next stage, a phthalate-free secondary plasticizer corresponding to the physical characteristics claimed in this invention is gradually added until the curve, which is the modulus of elasticity depending on the temperature (gelation/melting profile) does not coincide with the gelation/ melting of PVC plasticizer based on diisononyl phthalate (Figure 1, dashed line). 0083) The type and amount of one or more than one secondary plasticizer is chosen so that said one or more than one secondary plasticizer remains compatible with the plastisol; thus, with a ratio of primary to secondary plasticizer that is from 0.1 to 10, preferably from 0.5 to 7.5, the plastisol should remain homogeneous and after transformation into a PVC layer, the secondary plasticizer may not appear on the surface of said layer .

I0084| Phthalate-free PVC plastisols are intended for decorative surface coatings, more specifically for covering floors and walls.

I0085)| Accordingly, the present invention provides decorative surface coatings comprising one or more than one layer comprising a phthalate-free PVC plastisol.

I0086| According to the second preferred embodiment, the present invention relates to a multi-layer decorative surface coating of one or more than one contiguous phthalate-free plasticized polyvinyl chloride layer obtained from phthalate-free PVC plastisol according to the present invention. As a rule, these layers include a foam layer, a decorative layer and a transparent protective layer against wear. (0087) In another embodiment, the present invention relates to a method of obtaining a decorative surface coating, which includes the distribution of at least one layer of phthalate-free PVC plastisol in accordance with the present invention on the substrate layer and the formation of a gel from said at least one layer of phthalate-free PVC plastisol at a temperature in the range from 130 "C to 200 7C. Also, at least one phthalate-free PVC plastisol according to the present invention is distributed on the substrate layer while moving at a speed of approximately 15 to 25 meters per minute. (0088) To obtain multilayer decorative surface coatings, phthalate-free

PVC plastisol is distributed over the substrate layer in several layers so that the floor covering is literally built.

I0089| The multi-layered product first turns into a gel when brought into contact with one or more than one heated shaft, and then it is passed into an oven for gelation and melting at a temperature of 130 "C to 200 "C.

I0090)| Gelation is often performed after the distribution of each individual layer, starting with the base layer. After gelation, the next layer can be distributed. 0091) After the gel formation of the decorative layer, the image can be printed before

With the application of a protective layer against wear.

I0092| The wear protection layer generally contains the PVC layer obtained after the gelation/melting of the PVC plastisol. 0093) After the distribution of all layers and gelation at a temperature in the range from 130 "C to 200 "C, the product is placed in an oven for complete fusion of all layers together and adequate expansion of the foamed layers.

Y0094| After gelation and melting of at least one phthalate-free PVC plastisol composition according to this invention, the decorative surface coating is cooled and possibly supplied with a coating, preferably a polyurethane coating, in order to improve resistance to wear and contamination. Preferably, the polyurethane coating is a water-based coating; more preferably, the coating is obtained by actinic irradiation of polyurethane dispersions hardened by irradiation. In general, the thickness of the polymer coating is from 5 to 50 μm, preferably from 15 to 40 μm.

I0095| Decorative surface coatings according to the present invention, which do not have a coating, preferably polyurethane coatings, are subjected to measurement of VOC emissions according to ISO 16000, IBO 16000-6, IBO 16000-9 or IZO 16000-10. The total emission of volatile organic compounds (VOCs) and low-volatile organic compounds (VOCs) is measured after 28 days.

EXAMPLES

(0096) The following illustrative examples are intended to illustrate the invention only, but are not intended to limit or otherwise define the scope of the invention.

II0097| Table 1 describes the compositions of optimized phthalate-containing (column 3) and phthalate-free (column 4) polyvinyl chloride plastisol, which after gelation turns into a regular layer of polyvinyl chloride.

ЙО098| Table 2 defines the composition of the optimized phthalate-containing (column 3) and phthalate-free (column 4) polyvinyl chloride plastisol, which after gelation turns into a regular foamed layer of polyvinyl chloride.

І0099| Table 3 defines the composition of the optimized phthalate-containing (column 3) and phthalate-free (column 4) polyvinyl chloride plastisol, which after gelation turns into an ordinary wear-resistant layer of polyvinyl chloride.

Optimization of the composition of phthalate-free plastisol was carried out on the basis of such criteria as the gelation/melting profile of plastisol and hardness, flexibility, rigidity, heat resistance,

UV stability and VOC emission of the derived layer.

IO100| Phthalate-free PVC plastisol compositions are prepared from the corresponding phthalate-based compositions by applying the procedure as described in paragraphs 75 through 83.

Table 1

POD Component Phthalato- Phthalate-free and contained

Microsuspension of PVC paste 100.00 | 100.00

Primary diisononyl phthalate | 75.00 plasticizer Diisononyl cyclohexanoate 65.00

Secondary fatty acids! !

Calcium carbonate 5200 152.00

Rheological additive | 2.90 | 2.90

ИО1О1| In Table 1, the microsuspension of PVC resin is Mevzioi? RI415 K80 from Mezioia; diiiisononyl phthalate is Meziipo!? 9 from Emopik; Is diisononylcyclohexane Nehatoi? BIMSN from VABE; Acetyl Tributyl Citrate is a Cytoglycan from Didippliaceg; fatty acid methyl ester is Mizsoruke-| Р-В-21151 from VUUK Spetiye; calcium carbonate is Micpagie 10 from Rhomepsaiie and the rheological additive consists of 0.40 parts of Aegobvia? 200 from Emopik and 2.50 pieces of Vuk? 8070

Computer from Spetiev University of Applied Sciences.

I0102| Polyvinyl chloride layers, obtained after gelation/melting at a temperature of 170 "C for 30 seconds, with a thickness of about 200 microns, are characterized by: - phthalate-based composition: emission of ZLOS after 28 days is less than 100 μgm', - phthalate-free composition: emission of ZLOS, VLOS and of formaldehyde after 28 days, which is equal to or less than 10 μg.

Table 2 and ! contained PVC Microsuspension of PVC | 100.00 | 100.00 / Primary diisononyl phthalate | 53.00 and

I. plasticizer 55.00 / Secondary isononyl benzoate! 11.00 10.00 plasticizer

Solvent Complex methyl ether) 9.00 shi ! fatty acid and

Filler | Calcium carbonate 160.00 160.00

Other components Foaming agent | 2.90

Catalyst | 1.70

ИО103) In table 2, the microsuspension of PVC resin is a mixture of 59 parts of Mevisia? P1357 K from

Mevioii and 41 parts of I asomui? RV 1156 from Agket, diisononyl phthalate is Mebziipo!? 9 from Emopik, diisononyl cyclohexane is Nehatoi? BIMSN from VABE, isononyl benzoate is Meziiipoi!? IMV from Emopik, diethylene glycol dibenzoate is Veployekh 9 9-88 from Eazitap, complex methyl ester of fatty acid is Mizsoruke-I| R-B-21151 from Vuk Spetieye, calcium carbonate is Mmikpagi? 40 from Rhomepsaie, foaming agent, azodicarbonamide, is Opibat? Oiga 1035 from Nebgop and the catalyst, zinc oxide, are Naggziedei!? 1001 from Moglipso. (0104) Polyvinyl chloride layers obtained after gelation/melting at a temperature of 180 "C for 60 seconds, with a thickness of about 2000 microns, are characterized by:

Zo - a phthalate-based composition: the emission of GHG after 28 days, which is equal to or less than 100

MKM,

- phthalate-free composition: emission of VOCs after 28 days, which is equal to or less than 100 μgemWith its VOC emission after 28 days, equal to or less than 0.1 mgem, which is in accordance with the regulation of AO9VV.

Table C is included

PVC resin expander

More» spenonenit in the plasticizer Diisononyl cyclohexanoate 11800

Secondary | Isononyl benzoate

software SHIN: ZI NI

And acids

Epoxidized soybean oil (components | Air-emission additive | 060 | 060 ДЖ КЯюй- 01051) In table C, the microsuspension of PVC resin is a mixture of 60.00 parts of I asomuiye РВ 1704 H, 10 parts of Gasomuiye РВ 1202 from Agket and 30.00 parts of Mippoi? EHT from Mippoi, diisononyl phthalate is

Mesiipoi? 9 from Emopik, diisononylcyclohexane Nekhatoi? OIMSN from VABE, isononyl benzoate is

Mesiipoi? IMV from Emopik, complex methyl ester of fatty acid is Mizsoruk?-I R K 21151 from

Vuk Spetiye, liquid Ca/2n stabilizer is IGapkgotagk? 17 393 from AKsgo5, epoxidized soybean oil is Ogareh? H5E from Saiaia Spetisai!5 and the air-emission additive is Vuk? 3160 from Vuk

Spnetov (0106) Polyvinyl chloride layers, obtained after gelation/melting at a temperature of 170 "C for 40 seconds, with a thickness of about 300 microns, are characterized by: - phthalate-based composition: emission of hazardous substances after 28 days of less than 100 μge"m; - phthalate-free composition: by emission of hazardous substances after 28 days, which is equal to or less than 100 μgeMm 3,

I0107| The examples clearly show that currently optimized phthalate-based PVC plastisols can be replaced by phthalate-free plastisols that can be converted into PVC layers using identical processing conditions, with said PVC layer having VOC emissions comparable to those of PVC layers that contain phthalate.

IO108| The correct choice and appropriate combination of phthalate-free primary and secondary plasticizers is the key rule for matching the gelation/melting profile of the phthalate-free plastisol with the gelation/melting profile of the phthalate-based reference plastisol.

IO109| As has been unexpectedly discovered in the present invention, the correct selection of appropriate primary and secondary plasticizers to form a plastisol having a gel/melt profile identical to that of a reference phthalate-based plastisol and to produce polyvinyl chloride layers that

Zo demonstrate comparable emissions of VOCs, dictated by a number of certain physical and chemical characteristics.

ИО110) As can be seen from Table 4, the physicochemical characteristics of interest are the dissolution temperature at the transparency point, the vapor pressure at 25 "C in the first place and the viscosity at 20 7C and the molecular weight in the second place.

Table 4! dissolution at 2576 at 2070 mass / Diisononyl cyclohexanoate / Acetyl tributyl citrate

Isononyl benzoate

Diethylene glycol dibenzoate

(0111) Phthalate-free plastisols according to this invention allow decorative surface coatings, in particular, floors and walls, to have such properties as hardness, flexibility,

hardness, heat resistance, UV stability and VOC emission similar to those obtained after gelation and melting of phthalate equivalents.

Claims (13)

FORMULA OF THE INVENTION 1. Phthalate-free plastisol composition based on PVC (polyvinyl chloride) for decorative surface coatings, containing from 10 to 200 parts per 100 parts of polyvinyl chloride plasticizing mixture, including the following ingredients in parts by weight: - from 5 to 190 parts of one or more than one phthalate-free primary plasticizers, characterized by a dissolution temperature at the point of transparency from 130 to 200 "C and a vapor pressure at 25 "C of less than 5-103 mm of mercury column (Hg); - from 1 to 100 parts of one or more phthalate-free secondary plasticizers, characterized by a melting temperature at the point of transparency of less than 130 "C and a vapor pressure at 25 "C of less than 107 mm Hg. art.; and the dissolution temperatures of one or more than one primary and secondary plasticizers are measured in accordance with IM 53408 in a PVC suspension with a value of K 71; and the vapor pressure of one or more than one primary and secondary plasticizers is measured in accordance with ATM E1194-07, where the ratio of the content of the specified one or more than one phthalate-free primary plasticizers and the content of one or more than one phthalate-free secondary plasticizers is from 0.1 to 10, as a result of which the gelation temperature exhibited by said plastisol in the presence of only one or more than one primary plasticizer is reduced by at least 5 "C. 2. The composition according to claim 1, which is characterized by the fact that the specified one or more than one phthalate-free primary plasticizer is characterized by a molecular weight of from 200 to 1000 g-mol", preferably from 350 to 800 g.mol", and in which the specified one or more phthalate-free secondary plasticizers are characterized by a molecular weight of from 150 to 600 g.mol", preferably from 200 to 450 g.mol". 3. The composition according to claim 1 or claim 2, which is characterized by the fact that the indicated one or more than one phthalate-free primary plasticizer is characterized by a dynamic viscosity at 20 "С, which is from 5 to 200 mPa-s, preferably from 10 to 150 mPa -s, and in which the indicated one or more than one phthalate-free secondary plasticizer is characterized by a dynamic viscosity at 20 "С, which is from 1 to 150 mPa-s, preferably from 5 to 120 mPa. 4. The composition according to any of claims 1-3, which is characterized by the fact that one or more than one phthalate-free primary plasticizer is characterized by a vapor pressure at 25"C that is less than 105 mm Hg, preferably less than 5- 10 mm Hg, and in which one or more of the specified non-phthalate secondary plasticizers is characterized by a vapor pressure at 25 "C of less than 102 mm Hg. art., preferably less than 103 mm Hg. art., more preferably less than 107 mm Hg. Art. 5. The composition according to any of claims 1-4, which is characterized in that the specified one or more than one phthalate-free primary plasticizer is selected from the group consisting of alkyl esters of cyclohexanedicarboxylic acids, dialkyl esters of aliphatic dicarboxylic acids and alkyl esters aromatic di-, tri- or tetracarboxylic acids, with the exception of orthophthalic acid. 6. The composition according to any one of claims 1-5, which is characterized by the fact that one or more phthalate-free secondary plasticizers are specified, selected from the group consisting of lower alkyl esters of aromatic diacids, benzoates, citrates, phosphates and sulfonates. 7. The composition according to any of claims 1-6, which is characterized by the fact that it contains 100 parts of polyvinyl chloride, from 5 to 190 parts of one or more than one phthalate-free primary plasticizer, from 1 to 100 parts of one or more than one phthalate-free secondary plasticizer , up to 250 parts of filler, up to 7 parts of stabilizer, up to 5 parts of epoxidized vegetable oil and up to 100 parts of other components selected from the group consisting of viscosity reducers, foaming agents, liquid catalysts, antistatics, flame retardants, dyes, pigments , lubricants and technological additives. 8. The method of obtaining phthalate-free PVC plastisols according to any of claims 1-7, which is characterized by the fact that it contains stages: a) mixing 100 parts of polyvinyl chloride, from 5 to 190 parts of one or more phthalate-free primary plasticizers to form a plastisol; p) determination of the difference between the gelation/melting profile of the phthalate-free plastisol from stage a) and the phthalate-based plastisol, taken as a reference, using a rheometer in an oscillating dynamic mode with a controlled heating rate; c) adjusting the gelation/melting profile of the phthalate-free plastisol from stage a) according to the gelation/melting profile of the phthalate-based plastisol, taken as a reference, by gradually adding from 1 to 100 parts of one or more phthalate-free secondary plasticizers to the plastisol from stage a) , while maintaining the ratio of the content of the specified one or more than one phthalate-free primary plasticizers to the content of one or more than one phthalate-free secondary plasticizers equal to 0.1 to 10. 9. The method according to claim 8, which is characterized by the fact that the plastisol from stage a) additionally contains up to 250 parts of filler, up to 7 parts of stabilizer, up to 5 parts of epoxidized vegetable oil and up to 100 parts of other components selected from the group consisting of viscosity reducers, foaming agents, liquid catalysts, antistatic agents, flame retardants, dyes, pigments, lubricants and technological additives. 10. The method of obtaining a decorative surface coating with a composition of phthalate-free PVC plastisol according to claims 1-7, which is distinguished by the fact that it includes the following stages: a) applying the substrate layer; p) bringing the substrate layer into contact with the composition according to any of claims 1-7, c) gelation of the specified composition at a temperature from 130 "С to 200 76. 11. The method according to claim 10, which is characterized by the fact that it includes additional stages: a) printing a drawing on a gel-like layer from stage c); e) bringing the gel-like layer of PVC with the printed pattern obtained in stage a) into contact with the wear protection layer. 12. The method according to claim 11, which is characterized by the fact that the wear protection layer is a layer of polyvinyl chloride, a polyurethane layer or a layer of polyvinyl chloride with a polyurethane layer on top. Zo 13. Decorative surface coating, in particular floor or wall coating, obtained by the method according to any of claims 10-12, which is characterized by the fact that the specified surface coating has a VOC (total volatile organic compounds) emission lower than 100 μg-m7U, preferably emission of VOCs (volatile organic compounds) lower than 10 μg-mU, measured after 28 days in accordance with the test method based on IZO 16000-6, I5O 16000-9 or IBO 16000-10, where the emission of VOCs is equal to the sum of the emission of VOCs, the emission of VLOCs ( volatile organic compounds) and formaldehyde emissions.