Multilayer structure suitable for floor

Abstract

Disclosed is a multilayer structure comprising: (1) a printed porous substrate layer having first and second faces; (2) a polyvinyl chloride clear wear-resistant layer arranged on the first surface of the printed porous base material layer; and (3) a polyvinyl chloride backing layer disposed on the second layer of the printed porous substrate layer; and wherein the printed porous substrate layer comprises: (i) a polyolefin, a polyester, or a mixture thereof; and (ii) an ink comprising a pigment dispersion; and wherein the pigment dispersion comprises a pigment and a poly (vinyl chloride-vinyl acetate) copolymer binder. A method for producing the multilayer structure and a floor comprising the multilayer structure is also disclosed.

Description

TECHNICAL FIELD

[0001] The present invention relates to a multilayer structure suitable for flooring, a method of manufacturing a multilayer structure, and a flooring article comprising a multilayer structure. BACKGROUND

[0002] Inkjet printing is used for a variety of printing applications and can provide high resolution images on a range of substrates.

[0003] In recent years, inkjet printing has been used in the production of flooring components. US11014394 describes an existing system for the production of vinyl tiles using plastisol. WO2017 / 017472 describes an existing system for the production of vinyl tiles using plastisol. Such tiles require the ink to be printed onto a plastisol and subsequently cured at high temperature. A carrier substrate is used during printing and curing which increases the weight of the tile and can only be used a limited number of times before it must be replaced. The printed plastisol sheet is then fused to a clear PVC layer and a backing PVC layer at temperatures of 150 to 190°C.

[0004] [CITATION LIST]

[0005] [PATENT LITERATURE]

[0006] [PATENT LITERATURE 1]

[0007] US11014394

[0008] [PATENT LITERATURE 2]

[0009] WO2017 / 017472 SUMMARY

[0010] [TECHNICAL PROBLEM]

[0011] The production of a multilayer structure suitable for flooring which can be prepared without adding unnecessary weight to the structure, which does not require the use of a carrier substrate, and which requires less energy to be used in its production, while maintaining the image quality throughout the heating and curing phase and meeting the target adhesion strength between the printed layer and the PVC layer, remains a particular problem.

[0012] Therefore, there is a need for a new multilayer structure which addresses the above problems.

[0013] [SOLUTION TO THE PROBLEM]

[0014] The present invention provides a multilayer structure comprising:

[0015] (1) a printed porous substrate layer having a first and a second side;

[0016] (2) a polyvinyl chloride clear wear layer disposed on the first side of the printed porous substrate layer; and

[0017] (3) a polyvinyl chloride backing layer disposed on the second layer of the printed porous substrate layer; and

[0018] wherein the printed porous substrate layer comprises: (i) a polyolefin, a polyester, or a mixture thereof; and (ii) an ink comprising a pigment dispersion;

[0019] and wherein the pigment dispersion comprises a pigment and a poly(vinyl chloride-co-vinyl acetate) copolymer binder.

[0020] The present invention also provides a method of manufacturing the multilayer structure of the present invention, comprising:

[0021] - providing a printed porous substrate layer having first and second sides, providing a polyvinyl chloride clear wear layer on the first side of the printed porous substrate layer, and providing a polyvinyl chloride backing layer on the second layer of the printed porous substrate layer to form an intermediate multilayer structure; wherein the printed porous substrate layer, polyvinyl chloride clear wear layer, and polyvinyl chloride backing layer are as described herein with reference to the multilayer structure of the present invention; and

[0022] - heating the intermediate multilayer structure to a temperature in the range of 130 °C to 150 °C;

[0023] to form the multilayer structure of the present invention.

[0024] The present invention also provides a flooring article comprising the multilayer structure of the present invention.

[0025] The multilayer structure, method, and flooring of the present invention have advantages including:

[0026] - a reduction in the overall weight of the multilayer structure compared to prior art plastisol-based systems;

[0027] - no need for curing of the printed layer, and the option of omitting the curing step is an advantage compared to prior art plastisol-based systems;

[0028] - no need for a carrier substrate, and the option of omitting the carrier substrate is an advantage compared to prior art plastisol-based systems;

[0029] - good adhesion between the layers of the multilayer system of the present invention;

[0030] - the multilayer system of the present invention can be laminated at lower temperatures than prior art plastisol-based systems;

[0031] - When the multilayer system of the present invention is laminated, image quality is maintained;

[0032] - Adhesion strength in the multilayer system of the present invention is improved even at high ink levels compared to prior art systems based on plastisol. BRIEF DESCRIPTION OF DRAWINGS

[0033] [ Figure 1 ]

[0034] Figure 1 is a schematic illustration that illustrates the difference between the multilayer structure of the present invention and prior art systems based on plastisol. DETAILED DESCRIPTION

[0035] The present invention provides a multilayer structure comprising:

[0036] (1) a printed porous substrate layer having first and second sides;

[0037] (2) a polyvinyl chloride clear wear resistant layer disposed on the first side of the printed porous substrate layer; and

[0038] (3) a polyvinyl chloride backing layer disposed on the second layer of the printed porous substrate layer; and

[0039] wherein the printed porous substrate layer comprises: (i) a polyolefin, a polyester, or a mixture thereof; and (ii) an ink comprising a pigment dispersion;

[0040] and wherein the pigment dispersion comprises a pigment and a poly(vinyl chloride-co-vinyl acetate) copolymer binder.

[0041] Printed Porous Substrate Layer

[0042] The printed porous substrate layer typically has a weight of 90 gsm to 250 gsm. Preferably, the printed porous substrate layer has a weight of 110 gsm to 230 gsm. More preferably, the printed porous substrate layer has a weight of 130 gsm to 210 gsm. Still more preferably, the printed porous substrate layer has a weight of 150 gsm to 190 gsm. Most preferably, the printed porous substrate layer has a weight of 160 gsm to 180 gsm or about 170 gsm. The weight of the printed porous substrate layer can be determined according to ASTM D-3776.

[0043] The printed porous substrate layer typically has a thickness of 145 to 365 pm. Preferably, the printed porous substrate layer has a thickness of 175 to 335 pm. More preferably, the printed porous substrate layer has a thickness of 205 to 305 pm. Still more preferably, the printed porous substrate layer has a thickness of 225 to 325 pm. Most preferably, the printed porous substrate layer has a thickness of 245 to 265 pm, or 250 to 260 pm. The thickness of the printed porous substrate layer can be determined according to ASTM D-374.

[0044] The printed porous substrate layer typically has good temperature resistance. Typically, the printed porous substrate layer has a melting point of 135 °C or more (e.g., 135 °C to 200 °C or 135 °C to 180 °C). Preferably, the printed porous substrate layer has a melting point of 145 °C or more (e.g., 145 °C to 200 °C or 140 °C to 180 °C). More preferably, the printed porous substrate layer has a melting point of 150 °C or more (e.g., 150 °C to 200 °C or 150 °C to 180 °C). Still more preferably, the printed porous substrate layer has a melting point of 155 °C or more (e.g., 155 °C to 200 °C or 155 °C to 180 °C). Most preferably, the printed porous substrate layer has a melting point of 160 °C or more (e.g., 160 °C to 200 °C or 160 °C to 180 °C). The melting point can be determined by differential scanning calorimetry (e.g., at a rate of 10 °C / minute).

[0045] Typically, the printed porous substrate layer has a high temperature shrinkage of 10% or less (e.g., 1% to 10% or 2% to 10%). Preferably, the printed porous substrate layer has a high temperature shrinkage of 8% or less (e.g., 1% to 8% or 2% to 8%). More preferably, the printed porous substrate layer has a high temperature shrinkage of 6% or less (e.g., 1% to 6% or 2% to 6%). Still more preferably, the printed porous substrate layer has a high temperature shrinkage of 5% or less (e.g., 1% to 5% or 2% to 5%). Most preferably, the printed porous substrate layer has a high temperature shrinkage of 4% or less (e.g., 1% to 4% or 2% to 4%). The high temperature shrinkage can be measured as the shrinkage after heating in a forced air oven at 135 °C for 15 minutes.

[0046] Typically, the printed porous substrate layer has a porosity of 45% to 85%. Preferably, the printed porous substrate layer has a porosity of 50% to 80%. More preferably, the printed porous substrate layer has a porosity of 55% to 75%. Still more preferably, the printed porous substrate layer has a porosity of 60% to 70%. Most preferably, the printed porous substrate layer has a porosity of 63% to 67% or about 65%.

[0047] As used herein, porosity is the volume of pore space in the printed porous substrate layer expressed as a percentage of the total volume of the printed porous substrate layer, and can be determined according to ISO 15901-2:2022.

[0048] The printed porous substrate layer comprises a polyolefin, a polyester, or a mixture thereof. Suitable polyolefins include polyethylene, polypropylene, polybutylene, and mixtures thereof. Suitable polyesters include polyethylene terephthalate (PET). The polyolefin and / or polyester typically has a molecular weight (Mw) of about 20,000 to 2,000,000 gmol -1

[0049] The printed porous substrate layer can further comprise a filler, for example an inorganic filler or a non-abrasive inorganic filler. The filler is preferably silica. The filler can be present in the printed porous substrate layer in an amount of up to 80 wt% based on the total weight of the printed porous substrate layer, for example, 1 to 80 wt% based on the total weight of the printed porous substrate layer. Typically, the filler is present in an amount of 40 wt% to 80 wt% based on the total weight of the printed porous substrate layer. Preferably, the filler is present in an amount of 45 wt% to 75 wt% based on the total weight of the printed porous substrate layer. More preferably, the filler is present in an amount of 50 wt% to 70 wt% based on the total weight of the printed porous substrate layer. Still more preferably, the printed porous substrate layer has a filler present in an amount of 55 wt% to 65 wt% based on the total weight of the printed porous substrate layer. Most preferably, the filler is present in an amount of 58 wt% to 62 wt%, or about 60 wt% based on the total weight of the printed porous substrate layer.

[0050] The printed porous substrate layer has a first face and a second face. Typically, the first face is opposite the second face.

[0051] The printed porous substrate layer can comprise a coating. The coating, if present, can be located on either face of the printed porous substrate layer. Thus, the coating, if present, typically forms the first face and / or the second face of the printed porous substrate layer.

[0052] The printed porous substrate layer comprises an ink. The ink is typically present in the printed porous layer such that the ink is visible when viewed from the first face of the printed porous layer. The ink may, for example, be present at the first face of the printed porous layer, and / or, can be present in the pores of the printed porous layer so as to be visible when viewed from the first face of the printed porous layer.

[0053] ​The ink can form a printed image, for example a decorative image. The image can be an inkjet printed image. The inkjet printed image can be identifiable by a characteristic pattern of printed dots. Thus, the ink can form a printed image (such as a decorative image) comprising dots.

[0054] The ink comprises a pigment dispersion. The pigment dispersion comprises a pigment and a poly(vinyl chloride-co-vinyl acetate) copolymer binder. Unless otherwise stated, the term binder used herein typically refers to a poly(vinyl chloride-co-vinyl acetate) copolymer binder. Unless otherwise stated, the term pigment dispersion used herein typically refers to a pigment and a binder. However, it will be appreciated that the pigment is typically present in the form of a dispersion throughout the ink.

[0055] The pigment typically has a number average particle size (Dn50) of 0.020 pm to 0.150 pm, as measured by disc centrifugation, for example as measured using a CPS DC24000 disc centrifuge particle size analyser.

[0056] The pigment typically has a volume average particle size characterised by:

[0057] (a) a Dv50 of 110 to 120 nm; and / or

[0058] (b) a Dv90 of less than 350 nm;

[0059] as measured by dynamic light scattering, for example as measured using a Malvern Zetasizer Nano-ZS dynamic light scattering particle size analyser.

[0060] The binder used in the pigment dispersion is also not particularly limited. The binder comprises a poly(vinyl chloride-co-vinyl acetate) copolymer. The poly(vinyl chloride-co-vinyl acetate) copolymer can have a random copolymer structure. The poly(vinyl chloride-co-vinyl acetate) copolymer can have an alternating copolymer structure. The poly(vinyl chloride-co-vinyl acetate) copolymer can have a block copolymer structure. The poly(vinyl chloride-co-vinyl acetate) copolymer can have a graft copolymer structure. The poly(vinyl chloride-co-vinyl acetate) copolymer can have a vinyl chloride: vinyl acetate monomer ratio of 80:20 to 90:10 (typically weight:weight). The poly(vinyl chloride-co-vinyl acetate) copolymer can have a molecular weight (Mw) of 40000 gmol -1 to 50000 gmol -1 The molecular weight (Mw) can be measured by methods well known to those skilled in the art, for example in accordance with ISO 16014-3:2019.

[0061] The ratio of binder (e.g. the above poly(vinyl chloride-vinyl acetate) copolymer) to pigment can be 30:70 to 80:20 (typically weight:weight), for example 40:60 to 60:40 (typically weight:weight), 50:50 to 70:30 (typically weight:weight), 40:60 to 55:45 (typically weight:weight), 58:42 to 68:32 (typically weight:weight), 60:40 to 66:34 (typically weight:weight), about 50:50 (typically weight:weight), about 48:52 (typically weight:weight), about 49:51 (typically weight:weight), about 44:56 (typically weight:weight), or about 63:37 (typically weight:weight).

[0062] The ink typically further comprises a solvent composition.

[0063] The ink typically does not comprise a volatile, hazardous, or environmentally hazardous solvent.

[0064] The ink typically does not comprise a solvent classified as flammable, corrosive, or hazardous. As part of the common general knowledge of a person skilled in the art, they will understand which substances are classified as flammable, corrosive, or hazardous, and suitable solvent classifications include those in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) (4th Revision, United Nations New York and Geneva, 2011).

[0065] Preferably, the ink does not comprise one or more solvents selected from cyclohexanone, butyl glycol acetate, and methoxy propanol acetate.

[0066] The ink typically has desirable evaporation properties. The ink typically does not comprise a solvent that shows 1% or more by weight evaporation over 16 hours at 30°C, for example as determined by the following method:

[0067] - Weigh 2g of test material into an open container (50mm diameter);

[0068] - Place into an oven set to 30°C for a period of 16 hours; and

[0069] - At the end of this 16 hour period, assess the weight loss.

[0070] The ink typically does not comprise a solvent that shows 1% or more by weight evaporation at 150°C, for example as determined by the following method:

[0071] - using a humidity analyser (e.g. Ohaus MB45), set the temperature to 150°C;

[0072] - weigh 2g of test material into a dish on a balance,

[0073] - close the lid

[0074] - terminate the test when the amount of change over 60 seconds is within 0.001 g.

[0075] Preferably, the ink does not comprise one or more solvents selected from cyclohexanone, butyl glycol acetate, methoxy propanol acetate, propylene glycol diacetate, and dimethyl adipate.

[0076] The solvent composition can comprise a soy methyl ester. The soy methyl ester is derived from an acid (hereinafter referred to as the acid component of the soy methyl ester) and an alcohol (hereinafter referred to as the alcohol component of the soy methyl ester).

[0077] The acid component of the soy methyl ester is an unsaturated fatty acid. Preferably, the acid component of the soy methyl ester is a di-unsaturated fatty acid. The di-unsaturated fatty acid can be obtained, for example, by hydrolysis of a vegetable oil (e.g. soybean oil). Examples of suitable di-unsaturated fatty acids include linoleic acid, eicosadienoic acid, and docosadienoic acid. Linoleic acid is preferred as the acid component of the first ester. Linoleic acid can be obtained by hydrolysis of soybean oil.

[0078] The alcohol component of the first ester is a monohydric alcohol. Examples of suitable monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol. Methanol is the alcohol component of the soy methyl ester.

[0079] The soy methyl ester can be an ester of a di-unsaturated fatty acid and a monohydric alcohol, and examples of the soy methyl ester include methyl esters such as linoleic acid methyl ester, eicosadienoic acid methyl ester, docosadienoic acid methyl ester, and elaidic acid. Linoleic acid methyl ester is preferred as the soy methyl ester.

[0080] The solvent composition can further comprise an ester, a diol ester, a diol ester acetate, a diol ether, a diol ether acetate, a lactone, an adipate ester, a succinate ester, a glutarate ester, or a mixture thereof.

[0081] The ink of the present application typically has a desirable viscosity for inkjet printing. Preferably, the viscosity of the ink is from 7 to 20 cP at 25°C. More preferably, the viscosity of the ink is from 8 to 14 cP at 25°C. The viscosity can be determined using a cone and plate viscometer, for example, a Brookfield DV3T viscometer with a CPA-40Z cone operating at 10 rpm.

[0082] In a first set of embodiments of the ink, the solvent composition comprises soy methyl ester, diisobutyl succinate, diisobutyl glutarate, and diisobutyl adipate, and the soy methyl ester is present in an amount of 30 to 75 weight % based on the total weight of the ink.

[0083] The pigment used in the pigment dispersion in the ink of the first set of embodiments is not particularly limited. Typically, the pigment dispersion comprises a black pigment, a blue pigment, a green pigment, a violet pigment, a red pigment, a brown pigment, a yellow pigment, or a white pigment, or a mixture thereof. The pigment can be a black pigment. The pigment can be a white pigment. The pigment can be a coloured pigment (i.e. a pigment that is not black or white, such as cyan, red or yellow). The pigment dispersion can comprise a mixture of pigments. Preferably, the pigment dispersion comprises a pigment selected from Pigment Black 7, Pigment Blue 15:3, Pigment Blue 60, Pigment Green 7, Pigment Violet 37, Pigment Red 144, Pigment Red 166, Pigment Red 185, Pigment Red 254, Pigment Brown 23, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 110, Pigment Yellow 151, Pigment White 7, or a mixture thereof.

[0084] The pigment dispersion in the ink of the first set of embodiments can be a commercially available pigment dispersion. Examples of commercially available pigment dispersions that can be used in the ink of the first set of embodiments include the Microlith (registered trademark) - K series (e.g. Yellow 1040 K, Yellow 1061 K, Yellow 1550 K, Yellow 2040 K, Brown 3001 K, Scarlet 3430 K, Red 3630 K, Red 3890 K, Red 4410 K, Violet 5700 K, Blue 6480 K, Blue 7080 K, Green 8750 K, Black 0066 K, and White 0022 K) available from BASF SE.

[0085] The pigment dispersion in the ink of the first set of embodiments can be present in an amount of 1 to 40 weight % based on the total weight of the ink, for example, when the pigment dispersion comprises a white pigment. The pigment dispersion can be present in the ink of the first set of embodiments in an amount of 1 to 20 weight % based on the total weight of the ink, for example, when the pigment dispersion comprises a coloured pigment.

[0086] Preferably, the pigment dispersion is present in an amount of 1 to 10 weight % based on the total weight of the ink, for example, 1 to 6 %, 1 to 4 weight %, 2 to 6 %, 3 to 5 %, or about 4 % based on the total weight of the ink. As noted above, the amount of the pigment dispersion described above is typically the total amount of pigment and binder.

[0087] Typically, the soy methyl ester is present in the ink of the first group of embodiments in an amount of 30 to 68% by weight, based on the total weight of the ink. Preferably, the soy methyl ester is present in an amount of 40 to 68% by weight, based on the total weight of the ink. More preferably, the soy methyl ester is present in an amount of 50 to 68% by weight, based on the total weight of the ink.

[0088] Typical inks of the first group of embodiments include inks wherein:

[0089] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 20 to 65% by weight, based on the total weight of the ink;

[0090] - the soy methyl ester is present in an amount of 30 to 75% by weight, based on the total weight of the ink; and

[0091] - the pigment dispersion is present in an amount of 3 to 5% by weight, based on the total weight of the ink.

[0092] Further typical inks of the first group of embodiments include inks wherein:

[0093] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 28 to 59% by weight, based on the total weight of the ink;

[0094] - the soy methyl ester is present in an amount of 30 to 68% by weight, based on the total weight of the ink; and

[0095] - the pigment dispersion is present in an amount of 3 to 5% by weight, based on the total weight of the ink.

[0096] Preferred inks of the first group of embodiments include inks wherein:

[0097] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 28 to 56% by weight, based on the total weight of the ink;

[0098] - the soy methyl ester is present in an amount of 40 to 68% by weight, based on the total weight of the ink;

[0099] - the pigment dispersion is present in an amount of 3 to 5% by weight, based on the total weight of the ink.

[0100] Particularly preferred inks of the first group of embodiments include inks wherein:

[0101] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 28 to 46% by weight, based on the total weight of the ink;

[0102] - the soy methyl ester is present in an amount of 50 to 68 weight % based on the total weight of the ink;

[0103] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0104] Preferred cyan inks of the first group of embodiments include those wherein the pigment is Pigment Blue 15:3, and wherein:

[0105] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 27 to 57 weight % based on the total weight of the ink;

[0106] - the soy methyl ester is present in an amount of 39 to 69 weight % based on the total weight of the ink; and

[0107] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0108] Preferred cyan inks of the first group of embodiments include those wherein the pigment is Pigment Blue 15:3, and wherein:

[0109] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 36 to 47 weight % based on the total weight of the ink;

[0110] - the soy methyl ester is present in an amount of 49 to 60 weight % based on the total weight of the ink;

[0111] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0112] Preferred cyan inks of the first group of embodiments include those wherein the pigment is Pigment Blue 15:3, and wherein:

[0113] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 33 to 47 weight % based on the total weight of the ink;

[0114] - the soy methyl ester is present in an amount of 49 to 63 weight % based on the total weight of the ink; and

[0115] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0116] Preferred cyan inks of the first group of embodiments include those wherein the pigment is Pigment Blue 15:3, and wherein:

[0117] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 33 to 44 weight % based on the total weight of the ink;

[0118] - soy methyl ester is present in an amount of 52 to 63 weight % based on the total weight of the ink;

[0119] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0120] Preferred yellow inks of the first group of embodiments include those in which the pigment is Pigment Yellow 110, and in which:

[0121] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 21 to 47 weight % based on the total weight of the ink;

[0122] - soy methyl ester is present in an amount of 49 to 75 weight % based on the total weight of the ink; and

[0123] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0124] Particularly preferred yellow inks of the first group of embodiments include those in which the pigment is Pigment Yellow 110, and in which:

[0125] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 36 to 47 weight % based on the total weight of the ink;

[0126] - soy methyl ester is present in an amount of 49 to 60 weight % based on the total weight of the ink;

[0127] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0128] Preferred black inks of the first group of embodiments include those in which the pigment is Pigment Black 7, and in which:

[0129] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is 21 to 66 weight % based on the total weight of the ink;

[0130] - soy methyl ester is present in an amount of 30 to 75 weight % based on the total weight of the ink; and

[0131] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0132] Particularly preferred black inks of the first group of embodiments include those in which the pigment is Pigment Black 7, and in which:

[0133] - the total amount of diisobutyl succinate, diisobutyl glutarate, and diisobutyl adipate present in the ink is 24 to 34 weight % based on the total weight of the ink;

[0134] - the soy methyl ester is present in an amount of 62 to 72 weight % based on the total weight of the ink;

[0135] - the pigment dispersion is present in an amount of 3 to 5 weight % based on the total weight of the ink.

[0136] In a second group of embodiments of the ink, the solvent composition comprises diisobutyl succinate, diisobutyl glutarate, and diisobutyl adipate, wherein the total amount of the diisobutyl succinate, diisobutyl glutarate, and diisobutyl adipate is 50 weight % or more based on the total weight of the ink.

[0137] The pigment used in the pigment dispersion in the ink of the second group of embodiments is not particularly limited. Typically, the pigment dispersion comprises a red pigment, a blue pigment, or a black pigment, or a mixture thereof. The pigment can be a magenta pigment or a cyan pigment. Preferably, the pigment dispersion comprises a pigment selected from the group consisting of Pigment Red 202, Pigment Red 144, Pigment Red 166, Pigment Red 185, Pigment Red 254, Pigment Blue 15:3, Pigment Blue 60, and Pigment Black 7, or a mixture thereof. More preferably, the pigment dispersion comprises Pigment Red 202. Still more preferably, the pigment dispersion comprises a mixture of Pigment Red 202 and one or more additional pigments selected from the group consisting of Pigment Red 144, Pigment Red 166, Pigment Red 185, and Pigment Red 254.

[0138] The pigment dispersion in the ink of the second group of embodiments can be a commercially available pigment dispersion. Examples of commercially available pigment dispersions that can be used in the ink of the present application include the Microlith (Registered Trademark) - K series (e.g., Magenta 4330 K, Magenta 4535 K, Blue 7080 K, Blue 6480 K, and Black 0066 K) available from BASF SE.

[0139] The pigment dispersion can be present in the ink of the second group of embodiments in an amount of 1 to 20 weight % based on the total weight of the ink. Preferably, the pigment dispersion is present in an amount of 1 to 10 weight % based on the total weight of the ink, for example, 1 to 6 %, 1 to 4 weight %, 2 to 6 %, 3 to 5 %, or about 4 % based on the total weight of the ink. As noted above, the amount of the pigment dispersion described above is typically the total amount of pigment and binder.

[0140] Soy methyl ester can be present in the ink of the second group of embodiments. Typically, if present, soy methyl ester is present in the ink of the second group of embodiments in an amount of 47 wt% or less based on the total weight of the ink, for example from 1 wt% to 47 wt% based on the total weight of the ink. Preferably, if present, soy methyl ester is present in an amount of 37 wt% or less based on the total weight of the ink, for example from 1 wt% to 37 wt% based on the total weight of the ink. More preferably, if present, soy methyl ester is present in an amount of 27 wt% or less based on the total weight of the ink, for example from 1 wt% to 27 wt% based on the total weight of the ink. Still more preferably, if present, soy methyl ester is present in an amount of 19 wt% or less based on the total weight of the ink, for example from 1 wt% to 19 wt% based on the total weight of the ink. Most preferably, soy methyl ester is not present in the ink of the second group of embodiments.

[0141] Preferred inks of the second group of embodiments include inks in which:

[0142] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is from 50 wt% to 97 wt% based on the total weight of the ink;

[0143] - soy methyl ester is optionally present in the ink in an amount of 46 wt% or less based on the total weight of the ink;

[0144] - the pigment dispersion is present in an amount of from 3 to 5 wt% based on the total weight of the ink.

[0145] More preferred inks of the second group of embodiments include inks in which:

[0146] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is from 70 wt% to 97 wt% based on the total weight of the ink;

[0147] - soy methyl ester is optionally present in the ink in an amount of 26 wt% or less based on the total weight of the ink;

[0148] - the pigment dispersion is present in an amount of from 3 to 5 wt% based on the total weight of the ink.

[0149] Particularly preferred inks of the second group of embodiments include inks in which:

[0150] - the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate present in the ink is from 95 wt% to 97 wt% based on the total weight of the ink;

[0151] - soy methyl ester is not present in the ink; and

[0152] - the pigment dispersion is present in an amount of from 3 to 5 wt% based on the total weight of the ink.

[0153] The inks of the first and second groups of embodiments can provide desirable viscosity stability and evaporation characteristics, and can exhibit good nozzle recovery in inkjet printing, and typically do not use volatile, hazardous, or environmentally harmful solvents.

[0154] The printed porous substrate layer can be prepared by providing a porous substrate comprising a polyolefin, a polyester, or a mixture thereof and applying an ink as described above thereto (e.g., by inkjet printing). The porous substrate suitable for producing a printed porous substrate layer in this manner is typically as described above with reference to a printed porous substrate layer, but does not comprise an ink. Suitable porous substrates are commercially available and include synthetic papers such as the Teslin series of synthetic papers from PPG (e.g., Teslin IJWP Substrate Grade 600, 700, 800, 1000, 1200, and 1400), the Synplas series of synthetic papers from DEP (e.g., Synplas SPQ, Synplas SPG, Synplas SPH, Synplas SPC, Synplas SPCD, Synplas SPCT, Synplas SPA, and Synplas SYPH), and the NeverTear series of synthetic papers from Xerox.

[0155] Polyvinyl chloride clear wear layer

[0156] The polyvinyl chloride clear wear layer is disposed on the first face of the printed porous substrate layer. Typically, the polyvinyl chloride clear wear layer is adhered to the first face of the printed porous substrate layer. The polyvinyl chloride clear wear layer can be adhered directly to the first face of the printed porous substrate layer, or, can be adhered to the first face of the printed porous substrate layer via one or more intermediate layers.

[0157] The polyvinyl chloride clear wear layer typically has a thickness of 0.1 mm to 1.0 mm. Preferably, the polyvinyl chloride clear wear layer has a thickness of 0.2 mm to 0.8 mm. More preferably, the polyvinyl chloride clear wear layer has a thickness of 0.3 mm to 0.7 mm. Still more preferably, the polyvinyl chloride clear wear layer has a thickness of 0.4 mm to 0.6 mm or about 0.5 mm.

[0158] The polyvinyl chloride clear wear layer is typically transparent, and typically has a light transmission of 70% or more (e.g., 70% to 99%, or 70% to 95%, or 70% to 90%). Preferably, the polyvinyl chloride clear wear layer has a light transmission of 80% or more (e.g., 80% to 99%, or 80% to 95%, or 80% to 90%). More preferably, the polyvinyl chloride clear wear layer has a light transmission of 85% or more (e.g., 85% to 99%, or 85% to 95%, or 85% to 90%). Light transmission can be measured as per ASTM D1003.

[0159] The polyvinyl chloride clear wear layer typically has a haze of 30% or less (e.g., 1% to 30%, or 5% to 30%, or 10% to 30%). Preferably, the polyvinyl chloride clear wear layer has a haze of 20% or less (e.g., 1% to 20%, or 5% to 20%, or 10% to 20%). More preferably, the polyvinyl chloride clear wear layer has a haze of 15% or less (e.g., 1% to 15%, or 5% to 15%, or 10% to 15%). Haze can be measured as per ASTM D1003.

[0160] The polyvinyl chloride clear wear layer typically provides good wear resistance. The polyvinyl chloride clear wear layer typically has a hardness (Shore A) of 70 or more (e.g., 70 to 99, or 70 to 95, or 70 to 90). Preferably, the polyvinyl chloride clear wear layer has a hardness (Shore A) of 80% or more (e.g., 80 to 99, or 80 to 95, or 80 to 90). More preferably, the polyvinyl chloride clear wear layer has a hardness (Shore A) of 85 or more (e.g., 85 to 99, or 85 to 95, or 85 to 90). Shore A hardness can be measured as per BS 2782.

[0161] The polyvinyl chloride clear wear layer comprises polyvinyl chloride.

[0162] Suitable polyvinyl chloride clear wear layers are commercially available, and include products that will be familiar to the skilled person, for example, as generic “PVC clear wear layers”.

[0163] Polyvinyl chloride backing layer

[0164] The polyvinyl chloride backing layer is disposed on the second face of the printed porous substrate layer. Typically, the polyvinyl chloride backing layer adheres to the second face of the printed porous substrate layer. The polyvinyl chloride backing layer can adhere directly to the second face of the printed porous substrate layer, or, can adhere to the second face of the printed porous substrate layer via one or more intermediate layers.

[0165] The polyvinyl chloride backing layer typically has a thickness of 0.5 mm to 5.0 mm. Preferably, the polyvinyl chloride clear wear layer has a thickness of 1.0 mm to 3.0 mm. More preferably, the polyvinyl chloride clear wear layer has a thickness of 1.5 mm to 2.5 mm. Still more preferably, the polyvinyl chloride clear wear layer has a thickness of 1.8 mm to 2.2 mm or about 2.0 mm.

[0166] The polyvinyl chloride backing layer comprises polyvinyl chloride. Typically, the polyvinyl chloride backing layer comprises polyvinyl chloride in the form of a PVC foam, and / or, further comprises glass fibers.

[0167] When the polyvinyl chloride backing layer further comprises glass fibers, the glass fibers can be present in an amount of 80% or less (e.g., 5% to 80% or 15% to 80%), 70% or less (e.g., 5% to 70% or 15% to 70%), 60% or less (e.g., 5% to 60% or 15% to 60%), 50% or less (e.g., 5% to 50% or 15% to 50%), 40% or less (e.g., 5% to 40% or 15% to 40%), 30% or less (e.g., 5% to 30% or 15% to 30%), or 20% or less (e.g., 5% to 20% or 15% to 20%), by weight, based on the total weight of the polyvinyl chloride backing layer. When the polyvinyl chloride backing layer further comprises glass fibers, the glass fibers can be present in an amount of 5% or more (e.g., 5% to 80% or 5% to 50%), 10% or more (e.g., 10% to 80% or 10% to 50%), 15% or more (e.g., 15% to 80% or 15% to 50%), 20% or more (e.g., 20% to 80% or 20% to 50%), 25% or more (e.g., 25% to 80% or 25% to 50%), 30% or more (e.g., 30% to 80% or 30% to 50%), or 35% or more (e.g., 35% to 80% or 35% to 50%), by weight, based on the total weight of the polyvinyl chloride backing layer.

[0168] The polyvinyl chloride clear backing typically has a hardness (Shore A) of 70 or more (e.g., 70 to 99, or 70 to 95, or 70 to 90). Preferably, the polyvinyl chloride backing layer has a hardness (Shore A) of 80% or more (e.g., 80 to 99, or 80 to 95, or 80 to 90). More preferably, the polyvinyl chloride backing layer has a hardness (Shore A) of 85 or more (e.g., 85 to 99, or 85 to 95, or 85 to 90).

[0169] Method for forming a multilayer structure

[0170] The present invention provides a method of manufacturing the multilayer structure of the present invention as described above, comprising:

[0171] - providing a printed porous substrate layer having first and second faces, providing a polyvinyl chloride clear wear layer on the first face of the printed porous substrate layer, and providing a polyvinyl chloride backing layer on the second layer of the printed porous substrate layer to form an intermediate multi-layer structure; wherein the printed porous substrate layer, the polyvinyl chloride clear wear layer, and the polyvinyl chloride backing layer are as described above with reference to the multi-layer structure of the present invention; and

[0172] - heating the intermediate multi-layer structure to a temperature in the range of 130 °C to 150 °C;

[0173] to form the multi-layer structure of the present invention.

[0174] The step of heating the intermediate multi-layer structure to a temperature in the range of 130 °C to 150 °C can for example comprise heating the intermediate multi-layer structure to a temperature in the range of 130 °C to 140 °C, 135 °C to 145 °C, 140 °C to 150 °C, 130 °C to 135 °C, 135 °C to 140 °C, 140 °C to 145 °C, or 145 °C to 150 °C.

[0175] The step of heating the intermediate multi-layer structure can cause the polyvinyl chloride clear wear layer to adhere (e.g. directly adhere) to the first face of the printed porous substrate layer, and / or, can cause the polyvinyl chloride backing layer to adhere (e.g. directly adhere) to the second face of the printed porous substrate layer.

[0176] In the method of the present invention, providing a printed porous substrate layer can comprise providing a porous substrate comprising a polyolefin, a polyester, or a mixture thereof, and applying an ink thereto by inkjet printing, wherein the ink is as described above with reference to the multi-layer structure of the present invention.

[0177] Flooring article

[0178] The present invention provides a flooring article comprising the multi-layer structure of the present invention. The flooring article of the present invention can be in the form of a tile, a board or a sheet.

[0179] The present invention is illustrated below by the following non-limiting examples.

[0180] Example

[0181] Example 1

[0182] An ink comprising a Microlith pigment dispersion was inkjet printed onto a TESLIN (registered trademark) IJWP 1000 porous polymeric substrate layer. The ink level was 100%. The printed polymeric substrate layer thus obtained was laminated with a PVC wear layer and a vinyl backing layer at a temperature between 130 °C and 150 °C to obtain a multi-layer structure.

[0183] Example 2

[0184] A multilayer structure was prepared in the same way as Example 1, except that the ink level was 200%.

[0185] Comparative Example 1

[0186] A liquid plastisol coat was applied to a carrier substrate and an oil-based ink was inkjet printed onto the liquid plastisol (wet-on-wet printing). The ink level was 100%. The printed liquid coat was cured at a temperature of 130°C to 200°C. The carrier substrate was removed and the cured printed plastisol layer was laminated with a PVC wear layer and a PVC backing layer at a temperature of between 150°C to 190°C to obtain a multilayer structure.

[0187] Comparative Example 2

[0188] A multilayer structure was prepared in the same way as Comparative Example 1, except that the ink level was 200%.

[0189] Peel Test

[0190] The multilayer structures of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to a peel test using the following procedure.

[0191] The peel test was performed on a Testometric μ350 tensile tester. A 25mm sample was pulled between two jaws of the tester (PVC wear layer and printed substrate in one jaw and PVC backing layer in the other jaw, at a 180° angle) at 100mm / minute. The force was measured in Newtons (N). The unit of the peel result was N / cm. The target for adequate bond strength in a laminated flooring article was 10 N / cm or higher.

[0192] The results are given in the table below.

[0193] [Table 1]

[0194]

[0195] From the test results above, it can be seen that the multilayer structures of Examples 1 and 2 provided a bond strength higher than the target and were superior in both cases to the compared plastisol-based structures.

[0196] This application is based on and claims priority to United Kingdom Patent Application No. 2314902.4, filed September 28, 2023, United Kingdom Patent Application No. 2314905.7, filed September 28, 2023, and United Kingdom Patent Application No. 2314906.5, filed September 28, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. A multi-layered structure, comprising: (1) A printed porous substrate layer having first and second surfaces; (2) A clear, abrasion-resistant polyvinyl chloride layer disposed on the first surface of the printed porous substrate layer; and (3) A polyvinyl chloride backing layer disposed on the second layer of the printed porous substrate layer; and The printed porous substrate layer comprises: (i) a polyolefin, a polyester, or a mixture thereof; and (ii) an ink comprising a pigment dispersion; The pigment dispersion comprises a pigment and a poly(vinyl chloride-vinyl acetate) copolymer binder.

2. The multilayer structure according to claim 1, wherein the printed porous substrate layer has a melting point of 135°C or higher.

3. The multilayer structure according to claim 1 or claim 2, wherein the printed porous substrate layer comprises silica filler.

4. The multilayer structure according to any one of claims 1-3, wherein the printed porous substrate layer has a porosity of 45% to 85%.

5. The multilayer structure according to any one of claims 1-4, wherein the ink further comprises a solvent composition, wherein the solvent composition comprises soy methyl ester, diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate, wherein the soy methyl ester is present in an amount of 30% to 75% by weight based on the total weight of the ink.

6. The multilayer structure according to any one of claims 1-4, wherein the ink further comprises a solvent composition, wherein the solvent composition comprises diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate, and wherein the total amount of diisobutyl succinate, diisobutyl glutarate and diisobutyl adipate is 50% by weight or higher based on the total weight of the ink.

7. The multilayer structure according to any one of claims 1-6, wherein the polyvinyl chloride clear abrasion-resistant layer is adhered to a first side of the printed porous substrate layer, and the polyvinyl chloride backing layer is adhered to a second layer of the printed porous substrate layer.

8. The multilayer structure according to any one of claims 1-7, wherein the polyvinyl chloride clear abrasion-resistant layer has a thickness of 0.1 mm to 1.0 mm.

9. The multilayer structure according to any one of claims 1-8, wherein the polyvinyl chloride backing layer has a thickness of 0.5 mm to 5.0 mm.

10. The multilayer structure according to any one of claims 1-9, wherein the polyvinyl chloride backing layer comprises polyvinyl chloride in the form of polyvinyl chloride foam, and / or further comprises glass fiber.

11. A method for producing a multilayer structure according to any one of claims 1-10, comprising: - A printed porous substrate layer having first and second sides is provided, a polyvinyl chloride clear abrasion-resistant layer is provided on the first side of the printed porous substrate layer, and a polyvinyl chloride backing layer is provided on the second layer of the printed porous substrate layer to form an intermediate multilayer structure; The printed porous substrate layer, the PVC clear abrasion-resistant layer, and the PVC backing layer are defined as in any one of claims 1-10; and - Heat the intermediate multilayer structure to a temperature in the range of 130℃-150℃; To form a multi-layered structure as defined in any one of claims 1-10.

12. The method of claim 11, wherein providing the printed porous substrate layer comprises: A porous substrate comprising a polyolefin, a polyester, or a mixture thereof is provided, and ink is applied thereto by inkjet printing, wherein the ink is as defined in any one of claims 1-10.

13. A flooring article comprising a multi-layer structure as defined in any one of claims 1-10.

14. The flooring article as defined in claim 13, wherein it is in the form of brick, board or sheet.

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