RU2578146C2 - Surface covering comprising a citrate-based plasticizer - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: invention relates to a multilayer floor covering comprising layers selected from the group consisting of the carrier layer, the wear layer, the saturation layer of the lower foam layer and an upper foam layer, at least one of said layers comprises PVC-containing layer made from a composition comprising at least one PVC resin, at least one naphthalate plasticizer generating VOC and/or at least one additive generating VOC, the said composition further comprises at least one citrate-based plasticizer. Invention also relates to a method for producing a multilayer flooring.

EFFECT: invention provides a floor covering with a suitable degree of rigidity and very low VOC emissions.

10 cl, 1 dwg, 9 tbl

Description

Technical field

[0001] The present invention relates to a composition for creating a surface coating layer, said composition comprising a citrate based plasticizer, and the present invention relates to a method for producing a surface coating containing such a layer.

The prior art and related techniques

[0002] Surface coatings, in particular PVC (polyvinyl chloride) -containing surface coatings, are widely used for surface finishing of buildings or houses. However, PVC-containing surface coatings have a drawback, namely, they release VOCs (volatile organic substances) due to the presence of plasticizers, especially plasticizers based on phthalate.

[0003] To solve this problem, it was proposed to replace phthalate plasticizers with alternative plasticizers. However, this replacement negatively affects the stiffness of the surface coatings, while at the same time, suitable stiffness is an important requirement when creating elastic surface coatings, especially floor coverings. In addition, these alternative plasticizers do not solve the problem of the release of VOCs from other PVC-containing layers that are part of the surface coating.

[0004] Indeed, other plasticizers, such as dibenzoate-based plasticizers, thermal stabilizers, viscosity reducing agents, and other additives commonly used in surface coating compositions also have VOC emissions.

[0005] It has also been proposed to use a barrier layer inside a surface coating or a varnish coating, typically based on polyurethane (PU), applied on top of the surface coating. However, even if the polyurethane layer reliably protects against emission, it is difficult to apply it evenly on finished products having a relief surface with recesses or sharp protrusions.

In addition, if the product experiences intense loads for a long time, the barrier layer or polyurethane layer may be worn out, which again leads to emission.

OBJECTS OF THE INVENTION

[0006] An object of the present invention is to provide a composition for creating a surface coating layer, a surface coating containing such a layer, and a method for producing such a surface coating without the disadvantages of the prior art.

[0007) An object of the present invention is also to provide a surface coating layer and a surface coating itself with a suitable degree of rigidity and a very low level of VOC emission.

SUMMARY OF THE INVENTION

[0008] The present invention relates to a PVC-containing composition for creating a surface coating layer, wherein the above composition contains at least one PVC resin, at least one oil-based plasticizer generating VOC, and / or at least one additive generating VOC, as well as the above composition contains at least one citrate based plasticizer.

[0009] According to one embodiment, a PVC-containing composition may have one or more characteristics, such as:

a citrate based plasticizer is selected from the group consisting of triethyl citrate (TEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), acetyl triethyl citrate (ATEC) and acetyl tri-2-ethylhexyl citrate (ATEHC),

- the proportion of plasticizer based on citrate is from 8 to 72 phr (parts per hundred of resin - mass parts per 100 mass parts of resin),

- the proportion of non-phthalic plasticizer is from 0 to 36 phr,

- the proportion of additives is from 0 to 15 phr,

- the oil phthalic plasticizer is selected from the group consisting of adipates, benzoates, monobenzoates and dibenzoates, trimellitates, FAME (fatty acid methyl ester - methyl esters of fatty acids) terephthalates and cyclohexanoates,

- additives are selected from the group consisting of liquid stabilizers, viscosity reducing agents, blowing agents, liquid ejectors, antistatic agents and fire retardants,

- citrate-based plasticizer is acetyl tributyl citrate (ATBC), oil-based plasticizer is diisononyl adipate (DINA) and isononyl benzoate (INB).

[0010] The proportion of each component is given in phr, as a percentage of the mass of PVC.

[0011] The present invention relates to the use of a PVC-containing composition of the present invention for producing a surface coating having reduced VOC emission.

[0012] In preferred embodiments, the surface coating layer is a carrier layer, a wear resistant layer, a saturation layer, lower or upper foam layers included in the multilayer surface coating.

[0013] The present invention relates to the use of a PVC-containing composition of the present invention to obtain a surface coating having reduced VOC emissions.

[0014] The present invention relates to a method for producing a surface coating, comprising the steps of preparing a composition of the present invention, gelling the composition at a temperature that varies between 130 ° C and 200 ° C to form a film or layer, attaching the above first film or layer at least at least to the second layer to obtain the above multilayer surface coating.

[0015] According to a preferred embodiment of the method of the present invention, at least one of the layers comprises a composition of the present invention.

[0016] The present invention relates to a surface coating comprising at least one layer, which consists of a composition of the present invention.

[0017] According to one embodiment, the surface coating is a floor covering.

A brief description of the graphic materials

[0018] Figure 1 shows a surface coating according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The surface coating according to the present invention is a PVC-based multilayer surface coating having at least one layer comprising a PVC-based composition comprising at least one PVC resin and at least one citrate based plasticizer.

[0020] This composition makes it possible to obtain a layer of elastic surface coating having a stable reduced emission of VOCs (in accordance with ISO 19000-9), even if volatile plasticizers or VOCs generating VOCs, such as liquid stabilizers or substances that reduce viscosity, are used to obtaining a layer with suitable properties, such as, for example, stiffness.

[0021] The layer composition of the present invention contains at least one oil phthalic plasticizer, preferably a plurality of phthalate plasticizers. These non-phthalic plasticizers can be both volatile and non-volatile, and can both generate VOCs and not generate VOCs.

[0022] "Non-phthalate plasticizers" are plasticizers that are not orthophthalate esters.

[0023] The nephthalate plasticizers are selected from the group consisting of adipates, benzoates, monobenzoates and dibenzoates, cyclohexanoates, pyrrolidones, trimellitates, FAME (methyl esters of fatty acids) terephthalates and cyclohexanoates and mixtures of these compounds.

[0024] The proportion of non-phthalic plasticizers is from 0 to 36 phr.

[0025] The adipate-based plasticizer may be diisononyl adipate (DINA), dioctyl adipate (DOA), di- (2-ethylhexyl) adipate (DEHA), or benzyloctyl adipate (BOA).

[0026] The benzoate-based plasticizer may be isononyl benzoate (INB) or isodecyl benzoate (Jayflex MB 10).

[0027] A citrate based plasticizer is an ester of citric acid and primary alcohols comprising from two to eight carbon atoms.

[0028] The citrate based plasticizer is selected from the group consisting of triethyl citrate (TEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), acetyl triethyl citrate (ATEC) and acetyl tri-2-ethylhexyl citrate (ATEHC).

[0029] The concentration of the citrate based plasticizer is from 8 to 72 phr.

[0030] Preferably, the proportion of citrate based plasticizer is at least 20 mass. % of the total number of plasticizers in the composition, and the proportion of non-phthalic plasticizer is a maximum of 80 mass. % of the total number of plasticizers in the composition.

[0031] In a preferred embodiment, the composition comprises 20 to 30 phr of diisononyl adipate (DINA) and 20 to 30 phr of acetyl tributyl citrate (ATBC).

[0032] In a preferred embodiment, the composition comprises 13 to 17 phr diisononyl adipate (DINA), 8 to 13 phr acetyl tributyl citrate (ATBC), and 13 to 17 isononyl benzoate (INB).

[0033] The composition may also consist of one or more additives, such as a liquid stabilizer, a viscosity reducing agent, a foaming agent, a liquid ejector, an antistatic agent, a fire retardant, or a mixture of these compounds. These additives can be both volatile and non-volatile and can both generate VOCs and not generate VOCs.

[0034] The proportion of additives may be from 0 to 15 phr.

[0035] The liquid stabilizer may be, for example, a Ca / Zn stabilizer or a Ba / Zn stabilizer.

[0036] The viscosity reducing agent may, for example, be either linear or branched paraffin, or a fatty acid methyl ester.

[0037] The foaming agent can be made, for example, based on azodicarbonamide or baking soda.

[0038] The liquid ejectors can be, for example, a mixed metal soap based on, for example, potassium or zinc.

[0039] The antistatic agent can be made on the basis of a polyethylene glycol ether, for example Markstat from Artek Surfin Chemicals.

[0040] The coating of the present invention is obtained from the composition of the present invention by gelling the composition at a temperature of 130 ° C to 200 ° C using gel drums or a furnace.

[0041] The coating of the present invention may be a film or foam.

[0042] In the case of a foam coating according to one embodiment, the composition includes zinc oxide as a foaming catalyst, and an increase in viscosity occurs, which can be balanced by adipate plasticizers and citrate plasticizers. Using this approach, the degree of foaming and the structure of the cells does not change compared to a coating consisting of phthalate-based plasticizers.

[0043] The coating can be used as a carrier layer, a wear-resistant layer, a saturation layer, a foam layer on the back and front surfaces of a multilayer surface coating.

[0044] In general, VOC emissions are defined as the sum of WOC (very volatile organic compound - very volatile organic compounds), TVOC (total volatile organic compound - all volatile organic compounds) and SVOC (semi volatile organic compound - semi-volatile organic compounds). The measurements were carried out on day 3 in accordance with the method based on ISO 16000, and were performed by Eurofins using a micro camera, or on day 28 in accordance with ISO 16000-9 or ISO 16000-10.

[0045] When using the composition of the present invention, the VOC emission from the layer and from the surface coating containing this layer is less than 10 μg / m ³ .

[0046] A very low level of VOCs emission from the layer containing volatile material or VOCs-generating material was ensured by the use of a citrate-based plasticizer, which allows a surface coating with a specific gel structure to be produced.

[0047] In addition, the use of a PVC-containing composition comprising citrate-based plasticizer made it possible to obtain a layer and surface coating that met the basic requirements of traditional PVC-containing flooring, including phthalate-based plasticizers, such as viscosity, aging of PVC pastes , exudation, thermal stability, aging.

[0048] The surface coating of the present invention is either a monolayer surface coating or a multilayer surface coating (Fig. 1). An implementation option has been developed for a multilayer surface coating, which provides for a surface coating, which may consist of one or more layers having a composition comprising a citrate based plasticizer together with oil-based plasticizers and / or additives, while all plasticizers can generate VOCs. Many layers can be assembled by calendering or spreading layer by layer.

Examples

Monolayer surface coatings

[0049] Comparative examples (CE1 and CE2) illustrate monolayer surface coatings made from a composition containing a phthalate-based plasticizer.

[0050] The composition of compositions CE1 and CE2 are shown in table 1.

[0051] Lacovyl PB 1704H from Arkema or Vestolit B6021 Ultra from Vestolit is used as PVC. As the filler, Omya BL 20 from Omya is used. As phthalate-based plasticizer, DINP is used, for example Vestinol 9 from Evonik. As a benzoate-based plasticizer, Vestinol INB from Evonik or Benzoflex 9-88 from Eastman are used. A fatty acid methyl ester, for example Byk-LP R 21151 from Byk-Chemie, is used as a viscosity reducing agent. As a stabilizer, Lankromark LZC 393 from Akcros is used.

[0052] The composition of the surface coating compositions is illustrated in the examples of the present invention (S1-S3), which are shown in table 2.

[0053] As PVC, Lacovyl PB 1704H from Arkema or Vestolit B6021 Ultra from Vestolit is used. As the filler, Omya BL 20 from Omya is used. As citrate based plasticizer, ATBC is used, for example, Patech Pacizer 6412. As an adipate-based plasticizer, DOA is used, for example Plastomoll DOA from BASF, or DINA, for example Plastomoll DNA from BASF. As a stabilizer, Lankromark LZC 393 from Akcros is used.

[0054] The level of VOCs emission from comparative samples and samples of the present invention is shown in Table 3. VOCs are measured on day 3 according to a method based on ISO 16000 by Eurofins using a micro camera. Samples S3 and S4 are analyzed in accordance with ISO 16000-10.

[0055] As expected, coatings containing a phthalate-based plasticizer release a large amount of VOC, especially TVOC and SVOC.

[0056] Coatings made from a composition comprising a citrate based plasticizer exhibit reduced VOC emissions.

Multilayer surface coatings

[0057] Comparative Example CE3 illustrates a surface coating comprising a dense layer 1, on the surface of which a lower foam layer 2 is applied, on the surface of which a saturation layer 3 is applied, on the surface of which an upper foam layer 4 is applied, on the surface of which a wear-resistant layer 5. is applied. Composition each of the layers is shown in table 4 in phr units. CE3 specifications are given in table 5.

[0058] Comparative Example CE4 illustrates a surface coating having the same layer structure and composition as CE3, except that an oil-based plasticizer is used as a plasticizer, i.e. a plasticizer based on castor oil, and also instead of DIBP, a wear-resistant layer that contains 12 phr INB is used. CE3 specifications are given in table 6.

[0059] The multilayer surface coating of the present invention (S5) has the same structure as CE3 (FIG. 1), however, the layers have a composition as in Table 7 and characteristics as in Table 8.

[0060] In all examples (comparative and the present invention), either Pevikon P682 from Ineos, Vinnolit EP 6953 from Vinnolit, Solvin 266 SF from Solvin, Solvin 372 NA from Solvin, EP 6602 C from Vinnolit, Vinnolit E 80 are used as PVC TT or Vestolit B 7021 Ultra from Vestolit, Solvin 372 NA from Solvin, Vinnolit E 68 FO from Vinnolit, LG PB 1202 or a mixture of these compounds.

[0061] In comparative examples, DOP, for example Eastman OK from Eastman, is used as a phthalate 1 plasticizer. As phthalate 2-based plasticizer, DINP is used, for example Vestinol 9 from Evonik. As phthalate 3-based plasticizer, DINP is used, for example, Palatinol IC from BASF.

[0062] INB (isononyl monobenzoate), for example Vestinol INB from Evonik, is used as a benzoate plasticizer in the sample of the present invention. As citrate-based plasticizer, ATBCs are used, for example Citrofol BII from Jungbunzlauer, or Pacizer 6412 from Patech. As castor oil, Danisco Soft-N-Safe is used.

[0063] In all examples, Mikhart 40 from Provencale was used as calcium carbonate. As a viscosity reducing agent, Vegalon PB 0505 from Vega-him or Atepas 5316 from Byk-Chemie are used. As a blowing agent, azodicarbonamide, for example, Unifoam VI 40 from Hebron, is used. As a stabilizer, Lankromark LZC 393 from Akcros is used. ESBO is an epoxy oil of soybeans, for example Drapex 39 from Chemtura.

[0064] Measurements of VOC emissions from comparative examples and examples of the present invention are carried out in accordance with ISO 16000-10. The results are shown in table 9.

[0065] The data in table 9 indicate that comparative example CE3, which describes phthalate-based plasticizers, has a high level of VOC emission. The use of a phthalate analogue, such as castor oil (CE4), reduces VOC emissions, however, the emission level remains high. At the same time, S5 has a low level of VOC emissions. This decrease is not only due to the replacement of phthalate-based plasticizers with oil-based plasticizers, since the emission level of CE4 is not much lower than that of CE3. The use of citrate-based plasticizer provides an additional effect, since S5 contains the same additives as CE3 and CE4, such as viscosity reducing agents, such as Vegalon PB 0505, and the Lankromark LZC 393 stabilizer, which are known to have VOC emissions . Thus, it can be expected that S5 will have an average VOC emission between CE4 and CE3, or that the S5 emission level will be substantially the same as CE3, since S5 contains an oil phthalic plasticizer that is volatile and may have VOC emission. However, it should be noted that this does not happen. The level of VOC emissions in Example S5 is significantly reduced. This can occur due to the structure of the layer obtained from the composition, which includes a citrate based plasticizer.

Claims (10)

1. A multilayer floor covering comprising layers selected from the group consisting of a carrier layer, a wear-resistant layer, a saturation layer, a lower foam layer and an upper foam layer, at least one of these layers includes a PVC-containing layer made from a composition comprising at least one PVC resin, at least one non-phthalate plasticizer generating volatile organic substances (VOC) and / or at least one additive generating VOC, the above composition further comprises at least one citrate based plasticizer. 2. A multilayer floor covering according to claim 1, wherein the citrate-based plasticizer is selected from the group consisting of triethyl citrate (TEC), tributyl citrate (TBS), acetyl tributyl citrate (ATBC), acetyl triethyl citrate (ATEC) and acetyl tri-2-ethyl hexyl citrate (hex) . 3. A multilayer flooring according to claim 1 or 2, in which the proportion of citrate-based plasticizer is from 8 to 72 phr (parts by weight per 100 parts by weight of resin). 4. A multilayer flooring according to claim 1, in which the proportion of non-phthalic plasticizer is from 0 to 36 phr. 5. A multilayer flooring according to claim 1, in which the proportion of additives is from 0 to 15 phr. 6. The multilayer floor covering of claim 1, wherein the oil phthalic plasticizer is selected from the group consisting of adipates, benzoates, monobenzoates and dibenzoates, trimellitates, methyl fatty acid esters (FAME), terephthalates and cyclohexanoates. 7. The multilayer flooring according to claim 1, wherein the additives are selected from the group consisting of liquid stabilizers, viscosity reducing agents, blowing agents, liquid ejectors, antistatic agents and fire retardants. 8. The multilayer flooring of claim 1, wherein the citrate based plasticizer is acetyl tributyl citrate (ATBC) and the oil-free plasticizer is diisononyl adipate (DINA) and isononyl benzoate (INB). 9. A method of obtaining a multilayer flooring according to any one of paragraphs. 1-8, comprising the following stages:
providing a PVC-containing composition comprising at least one PVC resin, at least one oil-based plasticizer generating VOC, and / or at least one additive generating VOC, the above composition comprising at least one citrate-based plasticizer,
gelling the above PVC-containing composition at a temperature that is from 130 ° C to 200 ° C, to obtain the first film or first layer,
joining the aforementioned first film or layer to at least a second layer to obtain the aforementioned multilayer floor covering, in which the above layers are selected from the group consisting of a carrier layer, a wear resistant layer, a saturation layer, a lower foam layer or an upper foam layer, and at least at least one of these layers includes a PVC-containing composition comprising at least one PVC resin, at least one oil-based plasticizer generating VOC, and / or at least one additive BW generating VOC, the above composition comprising at least one citrate based plasticizer. 10. The method according to p. 9, in which at least the second layer has the same composition as the first layer.

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