Coated articles and coating formulations

Abstract

Articles for use in food contact applications. The articles comprise a substrate having at least one surface and a coating disposed on at least one surface. The coating comprises a polymer material (A) and at least one non-stick additive, the polymer material having repeating units of formula: -O-Ph-O-Ph-CO-Ph- I and repeating units of formula: -O-Ph-Ph-O-Ph-CO-Ph- II, where Ph represents the phenylene portion. The coating provides a non-stick coating to the article. Coating formulations, methods for forming a non-stick coating on an article for use in food contact applications, and related uses are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to articles intended for food contact having a non-stick coating. The present invention also relates to coating formulations, coating compositions, methods for forming such non-stick coatings on articles, and related uses of polymer materials for forming such non-stick coatings. In particular, the present invention relates to non-stick coatings that do not contain per / polyfluoroalkyl substances. [Background technology]

[0002] Non-stick coatings are available for many items intended for food contact, including consumer, professional, and industrial cookware and heat-resistant dishes, such as cookware (e.g., frying pans and rice cookers) and heat-resistant dishes (e.g., baking trays and tins). Articles with such non-stick coatings are less likely to react with food and / or more likely to release food during and after cooking / baking, compared to uncoated articles. This is advantageous in use, and particularly in the subsequent cleaning of the cookware or heat-resistant dishes.

[0003] The majority of such non-stick coatings for cookware and heat-resistant dishes are currently formed using per- and polyfluoroalkyl substances (PFAS). The PFAS group of chemicals includes perfluorosulfonic acids such as perfluorooctanesulfonic acid (PFOS) and perfluorocarboxylic acids such as perfluorooctanoic acid (PFOA). PFAS have found widespread utility in industry and have proven to possess excellent properties for use in non-stick coatings. Polytetrafluoroethylene (PTFE) is a PFAS that is widely used in forming such non-stick coatings on cookware and heat-resistant dishes.

[0004] However, concerns about the public health impacts of PFAS have grown over time with the increasing use of these chemicals in industry. PFAS, particularly PFOS and PFOA, are called “perpetual chemicals” due to their resistance to degradation in the environment and their tendency to accumulate in groundwater, plants, animals, and humans. High levels of exposure to and accumulation of PFAS in humans are strongly associated with dyslipidemia, reduced infant and fetal growth, and serious medical conditions such as kidney cancer.

[0005] Regulatory authorities are seeking to restrict the use of PFAS and reduce the accumulation of these chemicals in the environment. In particular, such authorities are considering banning the use of PFAS, such as PTFE, in non-stick coatings in order to reduce PFAS contamination from the manufacture, use, and disposal of non-stick articles and to reduce the exposure of users of such articles to PFAS.

[0006] For these reasons, researchers are seeking to develop alternative non-stick coatings that do not contain PFAS and do not require such chemicals in the manufacture of non-stick coated articles. Progress toward this goal has been made using high-performance polymer (HPP) based coatings. HPP coatings can be applied by techniques similar to those of PFAS-based non-stick coatings, for example, by coil coating, roller coating, curtain coating, flame spray coating, electrostatic powder coating, or spray coating. All of these coating techniques require that HPP particles be heated above their melting or fusion point in order to form a continuous HPP film coating on the substrate.

[0007] HPP coatings do not necessarily provide inherent non-stick properties, and therefore, the use of non-stick enhancing additives may be necessary to achieve non-stick properties equivalent to or suitable for specific use cases of PFAS-based coatings.

[0008] Such non-stick properties enhancing additives include silica-based or alumina-based metal alkoxides, waxes, oils, fats, talc, ceramics, boron nitride, graphite, carbon black, siloxane / silicone, nanoparticles, or glass fibers. However, to date, it has proven difficult to provide PFAS-free non-stick coatings that have properties equivalent to PFAS-based non-stick coatings and can be formed reliably and efficiently. Therefore, the need for alternative high-performance PFAS-free non-stick coatings remains. [Overview of the project]

[0009] Polyaryl ether ketone (PAEK) polymers are a well-known group of high-performance thermoplastic polymers, many of which possess excellent chemical and mechanical properties, such as polyether ether ketone (PEEK) polymers. PEEK polymers can form coatings with long-term durability due to their abrasion resistance, scratch resistance, friction resistance, chemical resistance, and heat disintegration resistance. However, PEEK polymer-based non-stick coatings often rely on PFAS non-stick additives to achieve the properties required for non-stick coatings for cookware and heat-resistant dishes. Therefore, such coatings are not necessarily PFAS-free.

[0010] One object of the present invention is, in particular, to provide non-stick coating compositions, formulations, and methods that address at least one drawback of the prior art, whether or not specified herein or elsewhere, or to provide alternatives to existing non-stick coating compositions, formulations, and methods. For example, an object of the present invention may be to provide cookware or heat-resistant dish articles having a non-stick, PFAS-free PAEK-type polymer coating.

[0011] According to an aspect of the present invention, there are provided an article, a coating formulation, a coating, a method and a use as described in the appended claims. Other features of the invention will become apparent from the dependent claims and the following description.

[0012] According to the present invention, there is provided an article for use in food contact applications, wherein the article comprises a substrate having at least one surface and a coating disposed on the at least one surface, and the coating is Formula: -O-Ph-O-Ph-CO-Ph- I a repeating unit of and a repeating unit of formula -O-Ph-Ph-O-Ph-CO-Ph- II wherein Ph represents a phenylene moiety, and the article comprises a polymer material (A).

[0013] According to a first aspect of the present invention, there is provided an article for use in food contact applications, which comprises a substrate having at least one surface and a coating disposed on the at least one surface, the coating comprises a polymer material (A) and at least one non-stick enhancing additive, and the polymer material has Formula: -O-Ph-O-Ph-CO-Ph- I a repeating unit of and a repeating unit of formula -O-Ph-Ph-O-Ph-CO-Ph- II wherein Ph represents a phenylene moiety.

[0014] Articles of this first embodiment are intended for use in food contact applications. Preferably, articles are intended for use in food preparation and / or serving. In particular, articles may be intended for use in heating or cooking food. For example, articles of this first embodiment may be cookware and / or heat-resistant dishes. At least one surface of the article on which the coating is applied is a surface intended to come into contact with food during use. Thus, the coating is intended to come into contact with food through its outer surface during use. Preferably, the coating is intended to come into contact with food while the food is being heated. Heat can be transferred from the article to the food through the surface. The coating preferably has a “non-stick” outer surface and therefore provides a “non-stick” outer surface of the article. A non-stick surface is intended to come into contact with food during use and preferably while the food is being heated. Such a non-stick surface can be described as having an improved tendency to detach food items in contact with the surface and a lower tendency to react with food during heating.

[0015] A non-stick coating is a coating that aims to reduce adhesion between the surface of a first material to which it is coated and a second material or surface that the first material is intended to come into contact with during use. In the case of non-stick cookware or heat-resistant dish articles, the non-stick coating is applied to the cookware or heat-resistant dish article to reduce food adhesion to the surface of the cookware or heat-resistant dish article.

[0016] Polymer material (A) is a polyaryl ether ketone (PAEK) polymer. More specifically, polymer material (A) is a copolymer of poly(ether ether ketone) (PEEK) and poly(ether diphenyl ether ketone) (PEDEK), where the repeating unit of formula I (which may be called EEK) provides the PEEK polymer component, and the repeating unit of formula II (which may be called EDEK) provides PEDEK. Therefore, polymer material (A) may be called a PEEK / PEDEK copolymer.

[0017] The inventors have found that the use of PEEK polymers to produce PFAS-free non-stick coatings limits the non-stick enhancing additives that can be used to provide the required properties of the coated surface due to the relatively high temperature processing window for these polymers. Such relatively high temperatures can decompose many of the preferred types of non-stick enhancing additives, reducing their usefulness in providing non-stick properties or adding complexity to the coating process. A typical processing temperature window for PEEK polymers is 380–420°C. Processing PEEK polymers and non-stick enhancing additives such as siloxane / silicone compositions at this temperature has been found to partially decompose the siloxane / silicone compositions, thereby significantly reducing the non-stick enhancing effect of the additives and compromising the overall reliability of the coating process.

[0018] The inventors have surprisingly found that an effective non-stick coating can be produced on articles according to this first embodiment using a polymer material (A) defined herein, which is a PEEK / PEDEK copolymer. Such a coating can advantageously provide thermomechanical durability, hydrophobicity, abrasion resistance, chemical resistance, and scratch resistance that are at least equivalent to those of PFAS-based non-stick coatings such as PTFE, without the problematic PFAS being included in the coating or used in the manufacture of the coating.

[0019] In some embodiments, the coating of the article according to this first embodiment includes a non-stickiness enhancing additive. The inventors have found that a non-PFAS non-stickiness enhancing additive used in combination with a polymer material (A) can provide a PFAS-free non-stick coating on an article having enhanced non-stick properties compared to a coating of the article with the polymer material (A) in the absence of any non-stickiness enhancing additive. Forming such a non-stick coating can advantageously avoid the degradation of non-stickiness enhancing additives such as siloxanes or silicones, because the processing temperature window of the polymer material (A) is lower than the temperature that induces substantial degradation of such suitable non-stickiness enhancing additives. For example, the polymer material (A) may be processable into a coating at a temperature below 380°C. Preferably, the polymer material (A) may be processable into a coating at a temperature below 360°C, or below 350°C, or below 340°C. The polymer material (A) preferably has a processing temperature window of 200 to 600°C, a preferred processing temperature window of 300 to 550°C, and a particularly preferred processing temperature window of 300 to 380°C or 340 to 380°C. At such temperatures, a coating containing the polymer material (A) and non-stick-enhancing additives, such as siloxane / silicone, can be formed on an article without decomposing the non-stick-enhancing additives, thus providing an effective non-stick coating in which the additives retain their non-stick-enhancing properties.

[0020] Furthermore, the use of the polymer material (A) disclosed herein may enable the application of a non-stick coating in a single layer, and a single layer of the non-stick coating has sufficient durability and substrate adhesion due to the favorable physical properties of the polymer material (A). The application of a single layer may provide an efficient manufacturing process for articles intended for food contact applications, such as cookware and heat-resistant dishes. However, the non-stick coating may also be applied in two or more layers.

[0021] Polymer material (A) The coating on an article according to this first embodiment comprises a polymer material (A). The polymer material (A) is preferably crystalline and generally has a crystalline melting point lower than that of a homopolymer of repeating unit I or a homopolymer of repeating unit II. However, the glass transition temperature of the polymer material (A) is generally the same as or slightly higher than that of a homopolymer of repeating unit I. More specifically, the polymer material (A) preferably has a glass transition temperature of over 143°C to a maximum of 160°C and a crystalline melting temperature of 300°C to a maximum of 330°C. For example, a polymer containing repeating units I and II in a relative ratio of 80:20 has a glass transition temperature of about 149°C and a crystalline melting temperature of about 309°C.

[0022] Preferably, the polymer material (A) has a processing temperature in the range of 200 to 600°C, a preferred processing temperature in the range of 250 to 550°C, and a particularly preferred processing temperature in the range of 300 to 380°C or 340 to 380°C. Processing temperature is understood to mean the temperature at which the polymer material is at least partially melted and / or is sufficiently fluid to be molded into a desired form, such as a substantially continuous coating on the surface of an article described herein.

[0023] Each repeating unit's phenylene moiety (Ph) may independently have 1,4-para linkages or 1,3-meta linkages to the atoms to which they bond. When the phenylene moiety contains 1,3-linkages, the moiety will be in the amorphous phase of the polymer. The crystalline phase will contain phenylene moieties having 1,4-linkages. In many applications, it is preferable that the polymer material be highly crystalline, and therefore, the polymer material preferably contains a high level of phenylene moieties having 1,4-linkages.

[0024] Preferably, at least 95% or at least 99% of the phenylene moieties (Ph) in the repeating unit of formula I have 1,4-linkages at the moieties to which they bind. It is particularly preferable that each phenylene moiety in the repeating unit of formula I has 1,4-linkages at the moieties to which it binds.

[0025] Preferably, at least 95% or at least 99% of the phenylene moieties (Ph) in the repeating unit of formula II have 1,4-linkages at the moieties to which they bind. It is particularly preferable that each phenylene moiety in the repeating unit of formula II has 1,4-linkages at the moieties to which it binds.

[0026] Preferably, the phenylene portion in the repeating unit of formula I is unsubstituted. Preferably, the phenylene portion in the repeating unit of formula II is unsubstituted. The repeating unit of formula I is preferably structure Ia:

[0027] [ka]

[0028] It has Ia. The repeating unit of formula II is preferably structure IIa:

[0029] [ka]

[0030] IIa. Preferably, in the polymer material (A) of the coating, The repeating unit of formula I is structure Ia:

[0031] [ka]

[0032] Having Ia, The repeating unit of formula II is structure IIa:

[0033] [ka]

[0034] IIa. The polymer material (A) preferably contains at least 10 mol%, at least 20 mol%, or preferably at least 30 mol% of repeating units of formula I. The polymer material (A) preferably contains up to 95 mol%, up to 90 mol%, or preferably up to 85 mol% of repeating units of formula I. The polymer material (A) preferably contains 10 to 95 mol%, preferably 20 to 90 mol%, of units of formula I.

[0035] The polymer material (A) preferably contains at least 10 mol%, at least 20 mol%, or preferably at least 30 mol% of repeating units of formula II. The polymer material (A) preferably contains up to 95 mol%, up to 90 mol%, or preferably up to 80 mol% of repeating units of formula II. The polymer material (A) preferably contains 5 to 95 mol%, preferably 10 to 80 mol% of units of formula II.

[0036] The total mol% of the units of formulas I and II in polymer material (A) is preferably at least 95 mol%, preferably at least 98 mol%, more preferably at least 99 mol%, and in particular, about 100 mol%.

[0037] Preferably, the coating polymer material (A) comprises repeating units I and II in a relative molar ratio I:II of 10:90 to 95:5, preferably 40:60 to 90:10, or 20:80 to 90:10.

[0038] In some embodiments, the polymer material (A) of the coating comprises repeating units I and II in a relative molar ratio I:II of 65:35 to 95:5. In some embodiments, the polymer material (A) of the coating comprises repeating units I and II in a relative molar ratio I:II of 20:80 to 45:55.

[0039] In some embodiments, the polymer material (A) may contain at least 10 mol%, at least 20 mol%, or preferably at least 30 mol% of repeating units of formula I. The polymer material (A) may contain up to 55 mol%, up to 45 mol%, or preferably up to 40 mol% of repeating units of formula I. The polymer material (A) may contain 15 to 50 mol%, preferably 20 to 45 mol%, and more preferably 25 to 40 mol% of units of formula I.

[0040] In such embodiments, the polymer material (A) may contain at least 40 mol%, preferably at least 50 mol%, or at least 55 mol% of the repeating units of formula II. The polymer material (A) may contain less than 90 mol%, preferably less than 80 mol% of the repeating units of formula II. The polymer material (A) may contain 40 to 90 mol%, preferably 50 to 85 mol%, more preferably 55 to 80 mol% of the units of formula II.

[0041] In such embodiments, the total mol% of the units of formulas I and II in the polymer material (A) is preferably at least 95 mol%, preferably at least 98 mol%, more preferably at least 99 mol%, and in particular about 100 mol%.

[0042] In such embodiments, the polymer material (A) preferably contains repeating units I and II in a molar ratio I:II of 15:85 to 50:50 or 20:80 to 45:55.

[0043] Such polymer material (A) may be formed by a method described in WO19215304A1, which is incorporated herein by reference. In some embodiments, the polymer material (A) may contain at least 68 mol%, preferably at least 71 mol%, of repeating units of formula I. Particularly advantageous polymer material (A) may contain at least 72 mol%, or more specifically, at least 74 mol%, of repeating units of formula I. The polymer material (A) may contain up to 95 mol%, up to 90 mol%, or preferably up to 82 mol%, of repeating units of formula I. The polymer material (A) may contain 68-82 mol%, preferably 70-80 mol%, more preferably 72-77 mol%, of units of formula I.

[0044] In such embodiments, the polymer material (A) may contain at least 10 mol%, preferably at least 18 mol%, of the repeating units of formula II. The polymer material (A) may contain less than 32 mol%, preferably less than 29 mol%, of the repeating units of formula II. Particularly advantageous polymer material (A) may contain 28 mol% or less, or 26 mol% or less, of the repeating units of formula II. The polymer material (A) may contain 18 to 32 mol%, preferably 20 to 30 mol%, more preferably 23 to 28 mol%, of the units of formula II.

[0045] In such embodiments, the total mol% of the units of formulas I and II in the polymer material (A) is preferably at least 95 mol%, preferably at least 98 mol%, more preferably at least 99 mol%, and in particular about 100 mol%.

[0046] In such embodiments, the polymer material (A) preferably contains return units I and II in a molar ratio I:II of 70:30 to 90:10 or 70:30 to 80:20. Typically, the polymeric material (A) according to this first aspect of the present invention may have terminal units that are the same as the repeating units, but will have terminal units of the polymer with terminal OH or F groups. However, the process for forming the polymer may comprise a separate end-capping step upon completion of polymerization, in which case a separate monomer or reagent may be added as an end-capping agent, with the result that the terminal units may be different from the repeating units of the polymer. Such end-capping is well known in the field of nucleophilic polycondensation reactions.

[0047] In some embodiments, the polymeric material of formula (A) has at least 0.06kN.s.m -2 , and more preferably at least 0.10kN.s.m -2 melt viscosity (MV). Suitably, the polymeric material (A) has at least 0.20kN.s.m -2 MV.

[0048] Suitably, the polymeric material has a maximum of 1.80kN.s.m -2 , a maximum of 1.50kN.s.m -2 , or a maximum of 1.00kN.s.m -2 MV. Suitably, the polymeric material (A) has 0.06 to 1.80kN.s.m -2 , 0.10 to 1.50kN.s.m -2 , or 0.20 to 1.00kN.s.m -2 MV.

[0049] In some embodiments, the polymeric material (A) has 0.20 to 0.50kNsm -2 , or 0.25 to 0.40kNsm -2 MV. Melt viscosity (MV), unless otherwise specified herein, may be measured by extrusion through a tungsten carbide capillary die having a diameter of 0.5 mm and a length of 8.0 mm, using capillary rheometry at 400°C at a shear rate of 1000s -1

[0050] ​ The melt viscosity of the polymer material can be measured by capillary rheometry using an RH10 capillary rheometer (Malvern Instruments Rosand RH10 capillary rheometer) fitted with a tungsten carbide die, 0.5 mm (capillary diameter) × 8.0 mm (capillary length). Approximately 5 grams of polymer material is dried in an air-circulating oven at 150°C for 3 hours. The extruder is equilibrated at 400°C. The dried polymer material is filled into the heated barrel of the extruder, a brass tip (12 mm long × 9.92 + 0.01 mm diameter) is placed on top of the polymer, followed by the piston, and the screw is manually turned until the pressure gauge proof ring engages with the piston to help remove any trapped air. The column of polymer material is heated and melted for a period of at least 5 minutes. After the preheating stage, the molten polymer material is extruded through a die for 1000 seconds, while recording the pressure (P) required to extrude the polymer material. -1 The screw is operated to form thin fibers at a shear rate. The melt viscosity is given by the following formula.

[0051] [ka]

[0052] In the formula, P = pressure / kN m -2 L = Die length / m S = Ram velocity / ms -1 A = barrel cross-sectional area / m 2 r = die radius / m The relationship between shear rate and other parameters is given by the following equation: Apparent wall shear rate = 4Q / πr 3 In the formula, Q = volumetric flow rate / m³ 3 s -1 =SA.

[0053] A suitable polymer material (A) can be prepared by polycondensation of monomers containing a carbonyl chloride group in the presence of a Friedel Crafts reagent, or by polycondensation of a phenol compound with a halo compound in the presence of an alkaline reagent.

[0054] More specifically, a suitable polymer material (A) can be obtained by polycondensation of a mixture of at least one dihydroxybenzene compound and at least one dihydroxybiphenyl compound with at least one dihalobenzophenone. Preferably, hydroquinone; 4,4'-dihydroxybiphenyl and 4,4'-difluorobenzophenone are used as monomers. The polycondensation is preferably carried out in the presence of an alkali metal carbonate or bicarbonate, or a mixture thereof. Polymerization is preferably carried out in the presence of a polymerization solvent such as an aryl sulfone.

[0055] Further preferred polymer materials (A) (PEEK / PEDEK copolymers) and methods for preparing them are as described in US4717761, WO2014 / 207458A1, and WO2015 / 124903A1, the contents of which are incorporated herein by reference.

[0056] WO2014 / 207458A1 has repeating units of formulas I and II in molar ratios of 55:45 to 95:5, and is suitable for heating at 340°C and 1000s. -1 At least 0.25 kNsm measured at a shear rate of -2 and 1.2kNsm -2 The document discloses a PEEK / PEDEK copolymer having an MV of less than 5.

[0057] WO2015 / 124903A1 is a repeating unit of formulas I and II in molar ratios of 55:45 to 95:5, and is specified at 340°C and 1000s. -1 The present invention discloses PEEK / PEDEK copolymers having MV values ​​of at least 0.25 and less than 1.2 as measured at shear rates.

[0058] In some embodiments, the polymer material (A) may be as described in WO2020 / 141329A1, the details of which are incorporated herein by reference. In such embodiments, the polymer material (A) is of formula Ia:

[0059] [ka]

[0060] Ia repeating unit, and Formula IIa:

[0061] [ka]

[0062] It may have a repeating unit of IIa, At least 95 mol% of the repeating units are the repeating units of formulas Ia and IIa. Repeating units Ia and IIa have molar ratios Ia:IIa of 65:35 to 95:5 or 55:45 to 80:20.

[0063] In other words, in polymer material (A), 95 mol% of all existing repeating units are units of formulas Ia and IIa in the specified molar ratio Ia:IIa of 55:45 to 80:20. This can be established by knowledge of the number of moles of monomers used in the preparation of the polymer.

[0064] The phenylene moieties in each repeating unit Ia and IIa have 1,4-para linkages with the atoms to which they are bonded. This results in a polymer material that is inherently crystalline. Preferably, in such embodiments, the polymer material (A) is extruded through a tungsten carbide capillary die with a diameter of 0.5 mm and a length of 8.0 mm for 1000 seconds. -1 When measured using capillary rheometry at 400°C with a shear rate of 0.35~0.55 kNsm-2 It has a music video.

[0065] Preferably, the 1000s described above -1 The MV of polymer material (A) measured at 400°C was 0.40~0.50 kNsm -2 That is the case. Preferably, the molar ratio Ia:IIa is 60:40 to 75:25.

[0066] Preferably, at least 98 mol% of the repeating units are repeating units of formulas Ia and IIa, and more preferably 99 mol%. Most preferably, the polymer material consists essentially of repeating units of formulas Ia and IIa.

[0067] In some embodiments, the polymer material (A) may be as described in WO2022 / 013520A1, the details of which are incorporated herein by reference. In such embodiments, the polymer material (A) is formula I: -O-Ph-O-Ph-CO-Ph- I Repeating unit, formula IIa:

[0068] [ka]

[0069] The repeating unit of IIa, and can essentially be derived from terminal units, The molar ratio of the repeating units of Equation I to the repeating units of Equation IIa is 55:45 to 95:5. The repeating unit of formula I is formula Ia in 50-90 mol%:

[0070] [ka]

[0071] Ia repeating unit, and essentially consisting of repeating units of formula Ib, formula Ic, or mixtures thereof in 10-50 mol%. The repeating unit of formula Ib is,

[0072] [ka]

[0073] Ib, The repeating unit of formula Ic is,

[0074] [ka]

[0075] It is Ic. Preferably, the molar ratio of the repeating units of formula I to the repeating units of formula IIa is 60:40 to 90:10, preferably 70:30 to 90:10, and more preferably 80:20 to 90:10.

[0076] The repeating units of formula I essentially consist of, or preferably consist of, 50 to 90 mol% of repeating units of formula Ia in combination with 10 to 50 mol% of repeating units of formula Ib and / or formula Ic. Preferably, the repeating units of formula I essentially consist of, or preferably consist of, 65 to 90 mol% of repeating units of formula Ia in combination with repeating units of formula Ib, formula Ic, or mixtures thereof in combination with 10 to 35 mol% of repeating units of formula Ib, formula Ic, or mixtures thereof. More preferably, the repeating units of formula I essentially consist of, or preferably consist of, 80 to 90 mol% of repeating units of formula Ia in combination with repeating units of formula Ib, formula Ic, or mixtures thereof in combination with 10 to 20 mol% of repeating units of formula Ib, formula Ic, or mixtures thereof.

[0077] The repeating unit Ia is R PEEK It is called, and the repeating unit Ib is R mPEEK It is called, and the repeating unit Ic is R oPEEK It is called that. Therefore, in other words, the repeating unit of equation I, when expressed as a mole ratio, R 90:10~50:50, preferably 90:10~65:35, more preferably 90:10~80:20 PEEK :(R mPEEK +R oPEEK ) has.

[0078] In a preferred embodiment, the polymer material (A) is the copolymer described above, the molar ratio of repeating units of formula I to repeating units of formula II is 90:10 to 80:20, and the repeating units of formula I essentially consist of, or preferably consist of, 80 to 90 mol% of repeating units of formula Ia in combination with 10 to 20 mol% of repeating units of formula IIb, formula Ic, or a mixture thereof.

[0079] Formula I:-O-Ph-O-Ph-CO-Ph- does not provide information as to whether the ether linkage on the -O-Ph-O- part is in a para-, meta-, or ortho- configuration, however, this would be understood to be specified for formulas Ia, Ib, and Ic as well as for all other configurations within the repeating unit.

[0080] In one embodiment, the copolymer according to the first aspect of the present invention may be a copolymer that does not contain repeating units of formula Ib. In another embodiment, the copolymer according to the first aspect of the present invention may be a copolymer that does not contain repeating units of formula Ic.

[0081] coating The coating of the article according to this first embodiment preferably has a thickness of 300 nm to 6,000 μm, and preferably 3 to 600 μm.

[0082] The coating is preferably provided as at least one layer on at least one surface of the substrate. In some embodiments, the coating is provided in two or more layers, for example, two layers, on at least one surface of the substrate. Preferably, the coating is provided as one layer on at least one surface of the substrate, preferably with the thickness described above.

[0083] Preferably, at least one layer has a thickness of 3 to 200 μm, preferably 5 to 150 μm, more preferably 15 to 100 μm, and more preferably 25 to 75 μm. Preferably, the overall combined thickness of the coating layer is 3 to 200 μm, preferably 5 to 150 μm, for example, 45 to 150 μm. Preferably, the combined thickness of the layers is 125 μm.

[0084] In a preferred configuration, the coating comprises at least a first layer and a second layer. Preferably, the first layer is adjacent to the substrate. Preferably, the second layer is adjacent to the first layer and preferably away from the substrate. Preferably, the first layer comprises the polymer material (A) described above. The polymer material (A) may have any of the preferred characteristics described herein. Most preferably, the first layer consists of the polymer material (A) and is preferably adjacent to the substrate. Preferably, the first layer has a thickness of 3 to 100 μm, preferably 25 to 75 μm, and most preferably substantially 50 μm. Preferably, the second layer comprises the polymer material (A) and at least one non-stick-enhancing additive. Preferably, the second layer comprises at least 90% by weight of the polymer material (A). Most preferably, the second layer comprises at least 95% by weight of polymer material (A), for example, 97% by weight of polymer material (A), and at least 2% by weight of non-stick-enhancing additives, preferably silicone oil and / or fumed silica. In the most preferred configuration, the second layer comprises substantially 97.6% by weight of polymer material (A), substantially 2% by weight of silicone oil, and 0.4% by weight of fumed silica. Preferably, the second layer has a thickness of 3 to 100 μm, preferably 25 to 75 μm, most preferably substantially 75 μm, and preferably the combined thickness of the first and second layers is 100 to 200 μm, preferably 75 μm to 150 μm, preferably 125 μm. The coating preferably comprises at least 1.0% by weight, at least 50% by weight, or at least 80% by weight, most preferably at least 90% by weight of polymer material (A).

[0085] Preferably, the coating comprises up to 100% by weight of polymer material (A), preferably up to 95% by weight, or up to 80% by weight of polymer material (A). As discussed above, articles and coatings preferably do not contain PFAS. Coatings preferably contain less than 1% by weight, less than 0.1% by weight, or less than 0.01% by weight of PFAS, based on the total weight of the coating. Preferably, coatings do not contain either perfluoroalkyl substances. Preferably, coatings do not contain PTFE. Preferably, articles do not contain either perfluoroalkyl substances. Preferably, articles do not contain PTFE.

[0086] The coating is preferably a non-stick coating. The coating preferably has equal or better non-stick properties compared to similar coatings formed from PEEK polymer materials. Such non-stick properties can be measured by the water contact angle or forward and backward contact angles at different sliding angles.

[0087] The coating preferably has a hydrophobic outer surface. Hydrophobicity can be evaluated by measuring the water contact of the surface. The outer surface of the coating preferably has a water contact angle of at least 80°, preferably at least 90°, more preferably at least 92°, and particularly at least 94°. The water contact angle may be 120°, 110°, or less than 100°. The water contact angle is preferably 80° to 160°, for example, 80° to 120°. The water contact angle can be evaluated as described in Example 3 of WO2012 / 175965A1, which is incorporated herein by reference.

[0088] Hydrophobicity may also be determined using contact angle measurement with ethylene glycol as the test fluid. The receding contact angle of a 30 μl droplet of ethylene glycol may be measured on the test surface. Satisfactory non-stick properties may be demonstrated by a test surface having a receding contact angle greater than 60°. Preferably, the coating of the article of this first embodiment has such a receding contact angle greater than 60°.

[0089] Satisfactory non-stick properties may be further demonstrated by a test surface having a roll-off angle of less than 20° (a plane inclination angle sufficient to cause droplet displacement). Preferably, the coating of the article of this first embodiment has such a roll-off angle of less than 20°.

[0090] Furthermore, satisfactory non-stick properties may include sufficient cohesive force, absence of surface cracking, thermal inertia in cooking temperature environments, and lack of reactivity with food. The latter may be demonstrated in burnt milk and fried egg tests, as described in WO2022 / 241019A1, which is incorporated herein by reference. Preferably, coatings of articles of this first embodiment provide satisfactory performance in such tests.

[0091] The desired non-stick properties of the coating containing polymer material (A) may be achieved in the present invention in several ways, as further described below. In some embodiments, the coating comprises at least one non-stick additive. Such a non-stick additive is a substance that can improve the non-stick properties of a polymer coating, such as a coating comprising the polymer material (A) of the present invention. The non-stick additive may improve the non-stick properties of the coating by increasing the hydrophobicity of the coating / polymer material (A) and / or by reducing the tendency of the coating to react with food during heating, and / or in particular by increasing the tendency of the coating to detach food that comes into contact with the coating during heating.

[0092] At least one non-stick-enhancing additive is preferably not a PFAS. Preferably, the article, and specifically the coating, does not contain any PFAS as discussed above.

[0093] Preferably, at least one non-stick-enhancing additive is selected from silica- or alumina-based metal alkoxides, waxes, oils, fats, talc, ceramics, boron nitride, graphite, carbon black, silicone resins, silicone oils, siloxanes / silicones including fumed silica, nanoparticles, or glass fibers. In some preferred embodiments, at least one non-stick-enhancing additive is a polysiloxane. Preferred polysiloxanes (silicones) may be selected from the group consisting of linear or branched polydimethylsiloxanes, linear or branched polydiphenylsiloxanes, linear or branched polymethylphenylsiloxanes, copolymers and mixtures thereof. In some embodiments, such polysiloxanes may contain or be mixed with polysiloxanes that may contain reactive groups such as hydroxy-, alkoxy-, acetoxy-, vinyl-, silane-, amino-silazane-, or others. Preferably, at least one non-stickiness enhancing additive is selected from polydimethylsiloxane (PDMS), polydiphenylsiloxane (PDPS), and polydimethyldiphenylsiloxane (PDMDPS, i.e., PDMS / PDPS copolymer).

[0094] Suitable siloxane / silicone non-stick enhancement additives may be provided by polydimethylsiloxanes sold under the trademark names SILBIONE FLD 70047V350 by ELKEM and WACKER AK200 by WACKER, as well as polysiloxanes having methyl and phenyl groups sold under the trademark names WACKER AP 150, WACKER AP200, WACKER AR200 by WACKER, and DOWSIL 550 Fluid by DOW.

[0095] In such embodiments, the article has the advantage that the polymer material (A) provides sufficient non-stick properties for the coating to function effectively in food contact applications without the use of PFAS such as PTFE. Furthermore, the polymer material (A) allows for the formation of a coating at a temperature that does not decompose non-stick-enhancing additives, particularly the siloxane / silicone discussed above.

[0096] At least one non-stickiness enhancing additive may be present in the coating in an amount of 0.1% to 90% by weight based on the total weight of the coating, in a preferred embodiment, in an amount of 0.1% to 50% by weight based on the total weight of the coating, and in a particularly preferred embodiment, in an amount of 1.0% to 30% by weight based on the total weight of the coating.

[0097] In a further preferred embodiment, at least one non-stickiness enhancing additive may be present in the coating in an amount of 0.001% to 50% by weight, most preferably 0.1% to 40% by weight, based on the total weight of the coating.

[0098] Preferably, if two or more non-stick-enhancing additives are present in the coating, the combined amount of such additives is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, and most preferably 0.6 to 36% by weight. Preferably, the combination of additives includes a silicone resin, a silicone oil, fumed silica, and boron nitride. In a preferred configuration, the coating preferably contains 0.1 to 30% by weight of silicone resin, preferably 0.1 to 30% by weight of silicone oil, 0.1 to 10% by weight of fumed silica, and 0.5 to 20% by weight of boron nitride.

[0099] In the most preferred combination, the coating comprises a polymer material (A), a silicone oil, and fumed silica. Preferably, the silicone oil is present in an amount of 1 to 2.5% by weight, preferably substantially 2% by weight, and the fumed silica is present in an amount of 0.2 to 0.5% by weight, preferably substantially 0.4% by weight of the coating composition.

[0100] If two or more non-stick properties enhancing additives are present in the coating, the total amount of non-stick properties enhancing additives present is preferably as defined above. The coating is preferably a substantially uniform and continuous layer placed on the surface of the substrate of the article. In some embodiments, the coating has a relatively smooth and continuous outer surface, i.e., the outer surface of the coating does not have prominent pores or topographic features. In such embodiments, the coating may be non-porous. Such a substantially uniform and non-porous coating can be formed by applying a suitable coating formulation in the form of a liquid dispersion and drying / curing the coating formulation. Alternatively, such coatings can be formed by dry powder coating, coil coating, roller coating, curtain coating, flame spray coating, and electrostatic powder coating. Spray coating and electrostatic powder coating are preferred methods.

[0101] In such embodiments, the coating preferably comprises at least one non-stickiness enhancing additive as discussed above, and the required non-stick properties of the coating are preferably achieved or improved by the use of the non-stickiness enhancing additive. In such embodiments, the at least one non-stickiness enhancing additive is preferably dispersed within and throughout the polymer material (A) of the coating, but not necessarily evenly dispersed, and therefore at least some of the non-stickiness enhancing additive are present on the outer surface of the coating, but not always.

[0102] In some embodiments, the coating has a porous structure and / or includes prominent surface topographic features on the outer surface of the coating. In such embodiments, the polymer material (A) forms the porous structure and / or topographic features. In such embodiments, the desired non-stick properties of the coating may be provided by the porous structure and / or topographic features of the coating. The non-stick properties of the porous structure and / or topographic features of the coating may be enhanced by the presence of non-stick enhancing additives as discussed above.

[0103] In embodiments where the coating has a porous structure, the coating preferably has pore sizes of 300 nm to 6000 μm, and more preferably 1 μm to 10 μm. The porous structure of the coating preferably provides pores that allow non-stickiness enhancing additives to be impregnated into the coating. Therefore, in such embodiments, the coating preferably includes non-stickiness enhancing additives as defined above.

[0104] Alternatively, at least one non-stick additive may be retained within the pores of a porous structure. In such embodiments, the non-stick additive may be a liquid, such as an oil, such as silicone oil. Therefore, in such embodiments, the non-stick additive is preferably a non-stick additive oil. In such embodiments, the non-stick additive oil is preferably impregnated into the pores of the coating. The pores of the coating preferably retain and substantially fix the non-stick additive oil within the coating, including the outer surface of the coating, to provide non-stick properties to the outer surface of the coating. During use, the non-stick additive oil may be removed from the outer surface of the coating over time, for example, due to abrasion and leaching. Preferably, the non-stick additive oil is replaced on the outer surface of the coating by migration of the non-stick additive oil from the pores in the bulk of the coating to the outer surface of the coating. Therefore, coatings of such embodiments may provide long-lasting non-stick properties to articles, maintained despite some expected loss of the non-stick additive oil from the outer surface of the coating.

[0105] Such porous coatings may be formed by any suitable method including additive manufacturing, filament fusion, laser sintering, pologen leaching, laser puncture, film cavitation, fiber printing / weaving, or amorphous particle sintering of polymer material (A), or by using a foaming agent within polymer material (A).

[0106] In embodiments in which the coating includes topographic features on the outer surface of the coating, the coating preferably has an outer surface having an array of topographic features formed by a polymer material (A), the array of topographic features including spaced-out protrusions and / or depressions, the protrusions and / or depressions having a maximum dimension of less than 3 μm, and the topographic features being separated by a distance of less than 10 μm.

[0107] In such embodiments, the coating may preferably be described as having a textured outer surface that includes the topographic features. Advantageously, the provision of such topographic features has been found to affect the hydrophobicity and / or hydrophilicity of the surface, and by selecting appropriate topographic features, the hydrophobicity and / or hydrophilicity can be controlled in a reproducible and predictable manner. The topographic features are preferably arranged and configured to increase the hydrophobicity of the polymer material (A) and to increase the non-stick properties of the outer surface of the coating of polymer material (A) compared to a substantially uniform and smooth coating of the polymer material (A).

[0108] The outer surface of the coating containing the arrangement of topographic features preferably has a water contact angle of at least 80°, preferably at least 90°, more preferably at least 92°, and particularly at least 94°. The water contact angle may be 120°, 110°, or less than 100°. The water contact angle may be evaluated as described in Example 3 of WO2012 / 175965A1, which is incorporated herein by reference.

[0109] The arrangement of the topographic features may include at least 100, preferably at least 1,000, and more preferably at least 10,000 of the topographic features. The arrangement is preferably 1 mm 2 At least 100,000 such topographic features per unit, preferably 1 mm 2 At least 3,000,000, more preferably 1 mm per unit area. 2 Each contains at least 6,000,000.

[0110] If the topographic feature includes a protrusion, the maximum height of the protrusion is less than 3 μm, preferably less than 500 nm, and more preferably less than 200 nm. The protrusion may have a height of at least 10 nm.

[0111] If the topographic feature includes a depression, the maximum depth of the depression is less than 3 μm, preferably less than 500 nm, and more preferably less than 200 nm. The depression may have a depth of at least 10 nm.

[0112] The arrangement of the topographic features preferably includes protrusions or depressions, but does not include both protrusions and depressions. Preferably, the topographic features include protrusions, preferably only protrusions.

[0113] The topographic feature may be circular, triangular, or square in the plan view. Preferably, the topographic feature is circular in the plan view. Preferably, at least 50%, preferably at least 90%, and more preferably substantially all, of the topographic features (e.g., protrusions) associated with the surface have the maximum dimensions specified herein. The surface preferably contains less than 10% (preferably substantially 0%) of the topographic features (e.g., protrusions) having a maximum dimension greater than 3 μm.

[0114] The topographic feature (e.g., a protrusion) may have a maximum dimension (e.g., diameter in the case of a circular protrusion) of less than 0.5 μm, preferably less than 0.25 μm, and more preferably less than 0.2 μm.

[0115] These topographic features can be separated by a distance of less than 5 μm, preferably less than 1 μm, more preferably less than 750 nm, and particularly less than 500 nm (i.e., the shortest distance between the edges of adjacent features).

[0116] These topographic features are individually 20 μm 2 Less than 0.8 μm, preferably 0.8 μm 2 Less than 0.2 μm, preferably 0.2 μm 2 Less than 0.14 μm, especially 0.14 μm 2It may have a maximum area of ​​less than 200 nm. Preferably, at least 50%, 80%, 90%, 95%, or 99% of the topographic features provided on the surface have the aforementioned maximum area. The minimum area of ​​the topographic features (preferably at least 50%, 80%, 90%, 95%, or 99% of the topographic features provided on the surface) is at least 200 nm. 2 or at least 7,000 nm 2 That's fine.

[0117] The arrangement of the topographic features preferably has at least 1,000, preferably at least 10,000, and particularly at least 10,000, all having substantially the same maximum dimension (e.g., diameter). 6 The sequence includes topographic features, which have substantially the same height, or substantially the same depth in the case of depressions, at least 1,000, preferably at least 10,000, particularly at least 10 6 The topographic features may include the following: The arrangement of these topographic features is at least 1,000, preferably at least 10,000, and particularly at least 10 6 The topographic features may include the following: The arrangement of the topographic features preferably consists of at least 1,000, preferably at least 10,000, and particularly at least 10,000 of substantially the same size and shape. 6 It includes topographic features (preferably protrusions).

[0118] The outer surface of the coating preferably has an arrangement of topographic features arranged in a pattern based on a conceptual symmetric lattice, where the distance between the nearest neighbor conceptual lattice points is C, which is 10 nm to 10 μm, and the topographic features are locally unordered such that the center of each topographic feature is at a distance of up to half C from its respective conceptual lattice point.

[0119] Preferably, C is at least 20 nm, at least 30 nm, at least 40 nm, at least 50 nm, at least 60 nm, at least 70 nm, at least 80 nm, at least 90 nm, at least 100 nm, at least 110 nm, at least 120 nm, at least 130 nm, at least 140 nm, at least 150 nm, at least 160 nm, at least 170 nm, at least 180 nm, at least 190 nm, at least 200 nm, at least 210 nm, at least 220 nm, at least 230 nm, at least 240 nm, at least 250 nm, at least 260 nm, at least 270 nm, at least 280 nm, at least 290 nm, or about 300 nm.

[0120] Preferably, C has a maximum diameter of 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, 3 μm, 2 μm, 1 μm, 900 nm, 800 nm, 700 nm, 600 nm, 500 nm, and 400 nm.

[0121] The most preferred range for C is 30 nm to 3 μm. Preferably, the height or depth of the topographic feature (e.g., average height or depth) is at least 5%, more preferably at least 10%, of the remaining portion of the device surface. For example, the height or depth of the topographic feature may be at least 10 nm.

[0122] Preferably, each topographic feature has the same shape. The topographic features may be cylindrical pits or protrusions, rectangular pits or protrusions, hemispherical pits or protrusions, partially spherical pits or protrusions, or other regular shapes.

[0123] Preferably, the diameter of the topographic feature is at least 10%, more preferably at least 20%, at least 30%, at least 40%, or at least 50% of C. For example, the diameter of the topographic feature may be at least 20 nm.

[0124] Preferably, the center of each topographic feature is at a maximum of 45%, more preferably at a maximum of 40%, 35%, 1 / 3, 30%, 25%, 20%, 15%, 10%, or 5% of C from its respective conceptual grid point.

[0125] Preferably, for at least 50% of the topographic features, the center of each topographic feature is 1 / 10 to 1 / 4 of C from its respective conceptual grid point. More preferably, at least 60%, at least 70%, at least 80%, or at least 90% of the topographic features satisfy this criterion. The lower limit for the distance of the center of each topographic feature from its respective conceptual grid point is preferably at least 12%, at least 14%, or at least 16% of C. The upper limit for the distance of the center of each topographic feature from its respective conceptual grid point is preferably up to 22%, up to 20%, or at least 18% of C.

[0126] The symmetry properties on which the conceptual lattice is based can be selected from parallelogram lattices, rectangular lattices, square lattices, rhombic lattices, triangular lattices, and hexagonal lattices. Preferably, the conceptual lattice is either a rectangular lattice or a square lattice.

[0127] In one embodiment, topographic features can be defined to mimic the lotus effect exhibited by the leaves of a lotus flower. Such topographic features on the outer surface of the coating may be formed as described in WO2012 / 175965A1, which is incorporated herein by reference.

[0128] Such topographic features on the outer surface of the coating may be achieved by forming the coating by laser sintering, filament fusion, pologen leaching, laser puncture, and fiber weaving.

[0129] The coating may also include further additives such as pigments, stabilizers, lubricants, and fillers. Preferably, additives for these purposes are known in the art. Goods Preferably, the article of this first embodiment is a heat-resistant dish or cooking utensil article. Preferably, the article is intended to come into contact with the food while the article and / or food is being heated. For example, the article may be a frying pan, saucepan, griddle, skillet, rice cooker, baking tray or sheet, or baking tin.

[0130] The base material of the article may be made of metal, enamel, or glass fiber reinforced material. The base material of the article is preferably made of metal. Such heat-resistant dishes or cookware articles, mainly made of metal, tend to require and benefit most from a non-stick coating.

[0131] The base material of the article may be made of stainless steel, aluminum, electrochromium-coated steel, or carbon steel. Preferably, the coating is provided on the base material to coat the surface of the base material that is intended to come into contact with food during use. In some embodiments, the coating is provided only on such surfaces. In some embodiments, the coating is provided on substantially the entire outer surface of the base material.

[0132] The coating preferably provides an article with a non-stick surface as defined above. Therefore, the article may be referred to as a non-stick article, preferably a non-stick cookware or heat-resistant dish article.

[0133] The coating may be applied directly to the substrate, or it may be applied on top of a primer or a previously applied coating layer on the substrate. According to a second aspect of the present invention, a solid composition comprising a polymer material (A) and at least one non-stick-enhancing additive, wherein the polymer material (A) is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A solid composition is provided having repeating units, wherein Ph represents the phenylene moiety.

[0134] The polymer material (A) and at least one non-stick-enhancing additive may have any of the preferred features and advantages described in relation to the first embodiment. The solid composition of this second embodiment may have any of the preferred features and advantages of the coating described in relation to the first embodiment.

[0135] The solid composition of this second embodiment preferably has a non-stick outer surface as described in relation to the first embodiment. A solid composition of this second embodiment, preferably disposed on an article such as those described in relation to the first embodiment.

[0136] Coating formulations According to a third aspect of the present invention, a coating formulation comprising a polymer material (A) and at least one non-stick-enhancing additive, wherein the polymer material (A) is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A coating formulation is provided having a repeating unit, wherein Ph represents the phenylene moiety in the formula.

[0137] The polymer material (A) and at least one non-stick-enhancing additive may have any of the preferred features and advantages described in relation to the first embodiment. For example, the polymer material (A) may be such as that described in WO2020 / 141329A1, the details of which are incorporated herein by reference. In such embodiments, the polymer material (A) is of formula Ia:

[0138] [ka]

[0139] Ia repeating unit, and Formula IIa:

[0140] [ka]

[0141] It may have a repeating unit of IIa, At least 95 mol% of the repeating units are the repeating units of formulas Ia and IIa. Repeating units Ia and IIa have molar ratios Ia:IIa of 65:35 to 95:5 or 55:45 to 80:20.

[0142] The coating polymer material (A) contains repeating units I and II in a relative molar ratio I:II of 65:35 to 95:5. Preferably, at least one non-stickiness enhancing additive is a siloxane / silicone. A suitable siloxane / silicone is one such as those described in relation to the first embodiment.

[0143] The coating formulation preferably comprises 10 to 99.9% by weight of polymer material (A) and 0.001 to 90% by weight, preferably 0.1 to 90% by weight of at least one non-sticking enhancer.

[0144] The coating formulation preferably contains 10 to 99.9% by weight of polymer material (A), preferably 50 to 99.9% by weight, or 70 to 99% by weight. The coating formulation preferably contains 0.001% to 50% by weight, preferably 0.1 to 50% by weight, of at least one non-stickiness enhancing additive, preferably 1 to 30% by weight, wherein the at least one non-stickiness enhancing additive is a siloxane / silicone.

[0145] In some embodiments, the polymer material (A) of the coating formulation is provided as a dry powder. The polymer material (A) may have a particle size d50 of 100 nm to 2,000 μm, preferably 1 μm to 200 μm, or 1 to 50 μm.

[0146] In some embodiments, the coating formulation is provided in powder form. Preferably, the powder comprises a polymer material (A) and a non-stickiness enhancing additive in the amounts and forms discussed above.

[0147] In such embodiments, the coating formulation can be applied to an article to form a coating on the article using any suitable method known in the art, for example, by using electrostatic powder coating.

[0148] Coating formulations in powder form can be formed by grinding a polymer material (A) to the required particle size in the presence of a non-stickiness enhancing additive. In some embodiments, the coating formulation is provided in liquid form. In such embodiments, the coating formulation preferably contains a solvent. Preferably, the solvent is water, and therefore the coating formulation may be an aqueous coating formulation. In such an aqueous coating formulation, the polymer material (A) and the non-stickiness enhancing additive are preferably dispersed in water. Dispersants may be present in such formulation to facilitate the formation and stabilization of such dispersions.

[0149] In such embodiments, the coating formulation can be applied to an article to form a coating on the article using any suitable method known in the art for applying liquid coating formulations, for example, spray coating.

[0150] In this third embodiment of the coating formulation, at least one non-stickiness enhancing additive is preferably a siloxane, and the coating formulation does not contain any per / polyfluoroalkyl substances.

[0151] Coating method According to a fourth aspect of the present invention, a method for forming a non-stick coating on an article for use in food contact applications, a) A step of providing an article for use in food contact applications, wherein the article includes a base material, and the base material has a surface, b) The surface of the substrate formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A step of treating with a polymer material (A) having repeating units, wherein Ph represents the phenylene moiety in the formula, c) A method is provided which includes the step of treating the surface of a substrate with a non-stick-enhancing additive.

[0152] The polymer material (A), at least one non-stick-enhancing additive, articles, substrates, and coatings may have any of the preferred features and advantages described in relation to the first embodiment. Preferably, at least one non-stickiness enhancing additive is a siloxane / silicone. A suitable siloxane / silicone is one such as those described in relation to the first embodiment.

[0153] Preferably, the method of this fourth embodiment provides an article according to the first embodiment and / or a solid composition according to the second embodiment. In some embodiments, the steps of the method are carried out in the order of step a), followed by step b), followed by step c).

[0154] In some embodiments, steps b) and c) are performed simultaneously after step a). In embodiments in which steps b) and c) are performed simultaneously after step a), steps b) and c) preferably involve treating the surface of the substrate with a coating formulation comprising polymer material (A) and at least one non-stick-enhancing additive. Preferably, such a coating formulation is a coating formulation according to the third embodiment. Thus, the coating formulation may have any of the preferred features and advantages described in relation to the coating formulation of the third embodiment.

[0155] In such embodiments, the coating formulation comprising the polymer material (A) and at least one non-stick-enhancing additive may preferably be a powder, as described in relation to the third embodiment, and may be applied by an electrostatic powder coating technique. Such a coating technique preferably involves spraying the coating formulation powder onto a substrate, and then heating the substrate to form a coating upon cooling.

[0156] Alternatively, coating formulations in powder form can be applied by a thermal spray technique. Such a coating technique may involve spraying the coating formulation powder onto the surface of a substrate through a flame that melts a polymer material (A). The molten coating formulation then impacts and adheres to the surface of the substrate, which is also preferably heated to form a coating and solidified upon cooling.

[0157] In some embodiments, a coating formulation comprising a polymer material (A) and at least one non-stick-enhancing additive can be extruded onto a substrate. In some embodiments, the coating formulation comprising the polymer material (A) and at least one non-stickiness enhancing additive may preferably be a liquid, as described in relation to a third embodiment, which can be applied to the surface of a substrate using a liquid spray coating technique. Such a coating technique may involve spraying the coating formulation, in the form of a liquid dispersion of the polymer material (A) and at least one non-stickiness enhancing additive, onto the surface of the substrate, and then heating the substrate to form a coating on the substrate. When the substrate is heated, preferably the solvent evaporates from the coating formulation, thereby solidifying the polymer material (A) on the surface of the substrate and forming a coating containing the non-stickiness enhancing additive dispersed within the polymer material (A).

[0158] In further embodiments, the coating formulation comprising the polymer material (A) and at least one non-stick-enhancing additive may preferably be a liquid, as described in relation to the third embodiment, which can be applied to the surface of a substrate using a liquid spray coating technique. Such a coating technique may involve spraying the coating formulation, in the form of a liquid dispersion of the polymer material (A) and at least one non-stick-enhancing additive, onto the surface of the substrate, and then heating the substrate to form a coating on the substrate. When the substrate is heated, the solvent evaporates from the coating formulation, and if heating continues, the polymer material (A) melts and forms a homogeneous film on the surface of the substrate. By cooling, the polymer material (A) solidifies on the surface of the substrate to form a coating containing the non-stick-enhancing additive dispersed within the polymer material (A).

[0159] In embodiments in which the steps of the present method are carried out in the order of step a), followed by step b), followed by step c), step b) preferably involves forming a coating containing polymer material (A) on the surface of a substrate, and step c) preferably involves treating the polymer material (A) coating with a non-stickiness enhancing additive.

[0160] In such embodiments, step b) preferably involves forming a coating comprising a polymer material (A) having a porous structure and / or prominent surface topographic features on the outer surface of the coating, as described in relation to the first embodiment. Preferably, step b) involves forming a coating comprising a polymer material (A) having a porous structure. Such a porous structure of the polymer material (A) can be formed by one of the techniques described below.

[0161] The porous structure of polymer material (A) can be formed by a pologen leaching technique, where pologens (e.g., salts) are dispersed within the polymer material (A) by a mixing process such as an extrusion process, and subsequently processed into a coating. The coating can then be treated with a solvent to dissolve the pologens. This solvent is removed from the coating to preserve the porous structure of polymer material (A).

[0162] The porous structure of polymer material (A) can be formed by laser puncture of a film of polymer material (A) to create a thin film that supports the porous structure. The film can then be applied to the surface of a substrate to form a porous coating.

[0163] The porous structure of polymer material (A) can be formed by film cavitation through uniaxial or biaxial orientation of a mineral-filled film of polymer material (A). By adding a suitable additive, such as CaCO3, and subsequently stretching / orienting the semi-crystalline film, a voided / cavitated / porous film can be obtained.

[0164] The porous structure of polymer material (A) can be formed by printing / weaving fibers of polymer material (A) onto the surface of a substrate. The porous structure of polymer material (A) can be formed by using a special foaming agent. For example, polymer material (A) may be expanded by filling it with pressurized CO2, then reducing the pressure and rapidly evaporating the CO2, in order to create pores in polymer material (A).

[0165] The porous structure of polymer material (A) can be formed by amorphous particle sintering. In such a technique, a porous sintered structure can be provided by inducing controlled diffusion and recrystallization of polymer material (A) powder in an amorphous state.

[0166] In such embodiments, the coating comprising a polymer material (A) having a porous structure formed in step b) is preferably then treated with a non-stick additive in step c). The non-stick additive is preferably a non-stick additive oil, such as a silicone oil, as described in relation to the first embodiment. Preferably, step c) impregnates the pores of the porous coating with the non-stick additive oil so that the non-stick additive oil is present on the outer surface of the coating, thereby providing a non-stick outer surface of the coating as described in relation to the first embodiment.

[0167] The non-stick-enhancing additive used to treat the surface of the substrate in step c) may be provided in a solution containing a solvent. In such embodiments, the solvent is preferably subsequently removed. Alternatively, the non-stick-enhancing additive may be added purely to a coating comprising a polymer material (A) having a porous structure. For example, the non-stick-enhancing additive used in step c) may be a pure non-stick-enhancing additive oil such as a silicone oil.

[0168] A non-stick coating formed by the method of this fourth embodiment described above may have any of the preferred features and advantages described in relation to the first embodiment, for example, the non-stick properties described therein.

[0169] A further aspect of the present invention relates to a method for forming a non-stick coating on an article for use in food contact applications, a) A step of providing an article for use in food contact applications, wherein the article includes a base material, and the base material has a surface, b) A step of treating the surface of a substrate with polymer material (A) to form a coating having an outer surface containing an array of topographic features of polymer material (A), wherein the array of topographic features includes spaced projections and / or depressions, the projections and / or depressions having a maximum dimension of less than 3 μm, and the topographic features are separated by a distance of less than 10 μm, and the polymer material (A) formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A method is provided which has a repeating unit of the formula, wherein Ph represents the phenylene moiety, and comprises a processing step; In such embodiments, step b) may be performed by injection molding a polymer material (A) in a mold configured to define the topographic features. In other embodiments, step b) may be performed by techniques of additive manufacturing practices or subtractive manufacturing practices. Such practices include direct 3D laser texturing methods, particularly laser-induced periodic surface structures (LIPSS), direct laser interference patterning (DLIP), or direct laser writing (DLW).

[0170] In such embodiments, a non-stick coating including topographic features may have any of the preferred features and advantages described in relation to the first embodiment. Such topographic features on the outer surface of the coating may be formed as described in WO2012 / 175965A1, which is incorporated herein by reference.

[0171] According to a fifth aspect of the present invention, the use of a composition comprising a polymer material (A) for providing a non-stick surface to an article for use in food contact applications, wherein the polymer material (A) is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A formula is provided which has repeating units, where Ph represents the phenylene moiety.

[0172] Preferably, in the use of this fifth embodiment, the composition comprises at least one non-stickiness enhancing additive. The polymer material (A), articles, non-stick surfaces, and non-stick-enhancing additives used in this fifth embodiment may have any of the preferred features and advantages described in relation to the first embodiment.

[0173] Use of this fifth embodiment may involve method steps described in relation to the fourth embodiment. Any feature of any invention or any aspect of any embodiment described herein may be combined with any feature of any other invention described herein, with necessary modifications.

[0174] Here, specific embodiments of the present invention are described by the following examples of evaluations. Example 1: Evaluation of the non-stick behavior of the coating Both polymer materials (A) described above, with and without non-stickiness enhancing additives, were tested against PTFE and sol-gel (ceramic) as shown in Table 1.

[0175] Comparative Coating 1: PTFE (PFAS): Pan used for testing - KitchenCraft PFOA-free Eco Non-stick Frying Pan 20cm - Aluminum base Comparative Coating 2: Sol-Gel (Ceramic): Pan used for testing - Salter BW09277 Earth 24cm frying pan - Aluminum base Polymer material (A) (PEEK / PEDEK copolymer) and methods for preparation are as described in US4717761, WO2014 / 207458A1, and WO2015 / 124903A1, the contents of which are incorporated herein by reference. In the example in the table below, polymer material (A) is as described in WO2020 / 141329A1, the contents of which are incorporated herein by reference, and polymer material (A) is of formula Ia:

[0176] [ka]

[0177] Ia repeating unit, and Formula IIa:

[0178] [ka]

[0179] Having a repeating unit of IIa, At least 95 mol% of the repeating units are the repeating units of formulas Ia and IIa. The repeating units Ia and IIa have a molar ratio of 75:25 (Ia:IIa).

[0180] The polymer material (A) blend was prepared in powder form by first adding the dry material and then an optional wetting additive, such as silicone oil. This mixture was blended in a Henschel mixer for a maximum of 2 minutes at approximately 38,000 rpm to obtain a homogeneous composition.

[0181] Coatings 2-14 containing polymer material (A) were tested against PTFE (comparative coating 1), a current cookware coating, and a commercially available PFAS-free solution known as a sol-gel (ceramic) (comparative coating 2). In addition, comparative coatings 1 and 2 were also tested against PEEK (coating 1). In all cases, the substrate was aluminum.

[0182] All coatings in Table 1 were single-layer coatings deposited on an aluminum substrate. The water contact angle was measured according to DIN EN 828 using a drop-shape analyzer DAS100S from Kruess GmbH, and the dynamic contact angle of water was determined. The droplet application setting was 0.2 μL / s, and the total volume was 6.0 μL.

[0183] [Table 1]

[0184] Table 1 shows the substantial increase in contact angle for coatings (3-14) containing blends of polymer material (A) with at least one non-stick-enhancing additive. For example, tests show that low levels of silicon resin and boron nitride result in coatings with superior quality in contact angle compared to existing PTFE cookware coating solutions or currently available PFAS-free sol-gel ceramic solutions.

[0185] Example 2: Evaluation of polymer material (A) non-stick coating against comparative coatings Both polymer materials (A) described above, with and without non-stickiness enhancing additives, were tested against PTFE and sol-gel (ceramic) against several standards related to the use of cookware, as shown in Table 2. The polymer material (A) (PEEK / PEDEK copolymer 75:25) and the method of preparation are described above and are similar to those described in US4717761, WO2014 / 207458A1, and WO2015 / 124903A1, the contents of which are incorporated herein by reference.

[0186] Comparative coating 1: PTFE (PFAS): Pan used for testing - KitchenCraft PFOA-free Eco Non-Stick frying pan 20cm - aluminum base.

[0187] Comparative Coating 2: Sol-Gel (Ceramic): Pan used for testing - Salter BW09277 Earth 24cm frying pan - Aluminum base Coating 5 was prepared as a single-layer coating as shown in Table 1. However, in the example shown in Table 2 below, Coating 5 was prepared as a double polymer layer as follows: A first layer of polymer material (A) was deposited on an aluminum substrate. The first layer consisted of the polymer material (A) described above and contained no additives. A second layer containing polymer material (A) Coating 5 was deposited on top of the first layer. The second layer contained both a non-stickiness enhancing additive and polymer material (A). The two-layer coating (Coating 5) was evaluated for its performance in applications regarding non-stickiness and mechanical behavior. Table 2 shows the findings compared to current cookware coating systems of comparative coatings 1 and 2, which are PFAS (PTFE) and sol-gel ceramic, respectively.

[0188] The thickness of the dry coating was measured using a BYK Gardner amplitude-sensitive eddy current instrument, the BYK-Test 8500, in accordance with ISO 2808 for determining the thickness of film coatings, and ISO 2360 in particular for non-magnetic substrates.

[0189] [Table 2]

[0190] In both Tables 1 and 2, the substrate was first cleaned with IPA and then grit-blasted with Corundum K100-300 to achieve a roughness (Rz) of 13-20 μm. Coating 5 was applied by spray application using an OptiFlex 2 GM03 manual gun combined with an OptiFlex 2 CG09 control unit from GEMA. The powder d50 was approximately 25 μm. The egg test was conducted according to the Cookware and Bakeware Alliance (CBA), Engineering Standards for Cookware and Bakeware (CBA 21.3.1 Egg Test (adapted from British Standard 7069:1988), revised October 2022). This test evaluates the cleanliness of the product by heating the cookware to approximately 150-180°C (160°C in Table 2) and then cooking an egg until firm without fat or lubricant. The ability to remove the egg using a plastic or nylon spatula is recorded. "Pass" indicates that no solid material is recorded when wiping the surface of the cookware. "Fail" indicates that a small amount of solid material remains on the cookware.

[0191] As shown in Table 2, coating 5 (97.6% polymer material (A), 2% silicone oil, 0.4% fumed silica) exhibited similar performance to that of the PFAS (PTFE) coating. Advantageously, this formulation outperformed the sol-gel ceramic alternative. This test demonstrates that a PFAS-free polymer material (A) blend is at least equivalent to the PTFE (PFAS) solution in the test.

[0192] A polymer material (A) coating may be applied using electrostatic powder deposition and hot flocking to accumulate the desired thickness. For example, polymer material (A) powder is sprayed directly onto a substrate and then heated to a temperature in the range of 340°C to 360°C. As soon as the powder melts, the part is cooled, or another coat of the same material or blend is hot-flocked onto the top of the first coating. Subsequent coats can be applied by the hot-flocking technique to accumulate the thickness of the coating.

[0193] An alternative method for applying the coating is by liquid dispersion coating with an aqueous polymer material (A) dispersion. For example, the polymer material (A) may be sprayed onto a cleaned and grit-blasted substrate, which is then heated to form a thin film on the substrate. In particular, the substrate is grit-blasted to achieve a profile of 20-25% of the total coating DFT (Dry Film Thickness). Further solvent cleaning of the substrate is preferable, and the aqueous dispersion is applied (using an HVLP gun with a tip size of 0.7 mm to 1.8 mm) until a uniform wet surface is achieved. After maintaining the coated surface at ambient air temperature for approximately 5 minutes, it is heated in an oven at 120°C for approximately 5 minutes. The oven temperature is then increased to 340°C to 360°C. Once the polymer melting temperature is reached, the part is left for a further 5-10 minutes to allow the coating to melt and flow. The part is then removed from the oven and allowed to cool to ambient temperature. Further coatings can be applied to build up the thickness.

[0194] In some embodiments, the polymer material (A) coating includes a porous structure that provides pores into which non-stick-enhancing additives (such as silicone oil) can be impregnated. Such polymer material (A) porous coatings can be fabricated through additive manufacturing processes (e.g., selective laser sintering or filament fusion).

[0195] One example of achieving a porous coating of polymer material (A) and additive (e.g., silicone oil) is by a 3D printing filament fusion process, following the conditions described in Table 3 below.

[0196] [Table 3]

[0197] [Table 4]

[0198] In further embodiments, the polymer material (A) coating includes topographic features designed to influence the hydrophobic and / or hydrophilic (non-sticky behavior of the coating) surface.

[0199] Such topographic features, including protrusions or depressions, are generated by utilizing the different melting temperatures of the polymer material (A) and the PEEK (or polyetherketone (PEK)) blend. A more or less significant effect of the topographic features can also be obtained by varying the particle size gradient between the polymer material (A) and the PEEK (or PEK) powder, particularly its d50, d90, and d99. The polymer material (A) and the PEEK (or PEK) powder may be deposited on a substrate to provide a coating. Such a final dried film coating may include at least one layer of the polymer material (A) coating and the PEEK (or PEK) blend, or at least two layers: a lower layer containing the polymer material (A) and the PEEK (or PEK) blend to provide the topographic features, followed by an upper layer containing the polymer material (A) coating.

[0200] By heating polymer material (A) powder to a temperature in the range of 340-360°C (e.g., in an oven), the polymer material (A) polymer is allowed to melt, leading to the flow and embedding of partially melted and glassy PEEK (or PEK) particles, and generating topographic features that bond together upon cooling (e.g., by removing from the oven).

[0201] Upon cooling to ambient temperature, the combined polymer material (A) and PEEK (or PEK) coating provide a coated surface with topographic characteristics, which leads to improved non-stick properties, as well as durability, abrasion resistance, and scratch resistance.

[0202] Alternatively, such polymer material (A) coatings with topographic features may be fabricated using other exothermic manufacturing processes, such as selective laser sintering (SLS) or laser-based directed energy deposition (DED).

[0203] While several preferred embodiments have been shown and described, those skilled in the art will understand that various changes and modifications can be made without departing from the scope of the invention as defined in the appended claims.

[0204] Throughout this specification, the terms “comprising” or “comprises” mean that the specified components are included, but the presence of other components is not excluded. The terms “consisting essentially of” or “consists essentially of” mean that the specified components are included, but other components are excluded, except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for purposes other than achieving the technical effects of the present invention. Typically, when referring to a composition, a composition essentially consisting of a set of components will contain less than 5% by weight, typically less than 3% by weight, and more typically less than 1% by weight of unspecified components.

[0205] The terms "consisting of" or "consists of" mean that the specified components are included, but the addition of other components is excluded.

[0206] Wherever appropriate, depending on the context, the use of the terms “comprises” or “comprising” may be interpreted as encompassing or including the meaning of “consists essentially of” or “consisting essentially of,” or it may be interpreted as including the meaning of “consists of” or “consisting of.”

[0207] To avoid misunderstanding, when the amount of a component in a composition is stated in weight percent, this means the weight percentage of the specified component relative to the entire composition being referred to.

[0208] The optional features shown herein may be used individually, in combination with each other as appropriate, and in particular in combinations as shown in the appended claims. The optional features for each aspect or exemplary embodiment of the Invention as shown herein should also be read as applicable to any other aspect or exemplary embodiment of the Invention as appropriate. In other words, a person skilled in the art reading this specification should consider the optional features for each exemplary embodiment of the Invention to be interchangeable and combinable between different exemplary embodiments.

[0209] Attention is directed to all papers and documents filed concurrently with or prior to this specification in connection with this application and made available to the public together with this specification, the contents of all such papers and documents are incorporated herein by reference.

[0210] All of the features disclosed herein (including any appended claims and drawings), and / or all of the steps of any method or process disclosed herein, may be combined in any combination, except for any combination in which at least some of such features and / or steps are mutually exclusive.

[0211] Each feature disclosed herein (including any appended claims and drawings) may be replaced by alternative features serving the same, equivalent, or similar purpose unless expressly stated otherwise. Thus, unless expressly stated otherwise, each disclosed feature is merely an example of a general set of equivalent or similar features.

[0212] The present invention is not limited to the details of the embodiments described above. The present invention extends to any novel one or any novel combination of features disclosed herein (including any appended claims and drawings), or any novel one or any novel combination of any method or step of a process so disclosed herein.

Claims

1. An article for use in food contact applications, the article comprising a substrate having at least one surface and a coating disposed on the at least one surface, wherein the coating comprises a polymer material (A) and at least one non-stick-enhancing additive, and the polymer material is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II An article having repeating units, wherein Ph represents the phenylene moiety in the formula.

2. The article according to claim 1, wherein the coating is a non-stick coating.

3. The article according to claim 1 or 2, wherein the article is a heat-resistant dish or cooking utensil article.

4. The article according to any one of claims 1 to 3, wherein the base material of the article is formed of a metal, enamel, or glass fiber reinforced material.

5. The article according to any one of claims 1 to 4, wherein the coating does not contain any per / polyfluoroalkyl substances.

6. The article according to any one of claims 1 to 5, wherein in the polymer material (A) of the coating, repeating units I and II are within a relative molar ratio I:II of 65:35 to 95:

5.

7. In the polymer material (A) of the coating, The repeating unit of the above formula I is structure Ia: 【Chemistry 1】 Having Ia, The repeating unit of formula II is structure IIa: 【Chemistry 2】 An article according to any one of claims 1 to 6, having IIa.

8. The article according to any one of claims 1 to 7, wherein at least one non-stickiness enhancing additive is selected from silica-based or alumina-based metal alkoxides, waxes, oils, fats, talc, ceramics, boron nitride, graphite, carbon black, siloxane / silicone, nanoparticles, or glass fibers.

9. The article according to any one of claims 1 to 8, wherein at least one non-stick additive is present in an amount of 0.001% to 40% by weight.

10. The article according to any one of claims 1 to 9, wherein at least one non-stickiness enhancing additive is a siloxane / silicone.

11. The article according to any one of claims 1 to 10, wherein the coating has a porous structure and / or the outer surface of the coating includes prominent surface topographic features.

12. The article according to claim 11, wherein the coating has a porous structure, and at least one non-stickiness enhancing additive is held within the pores of the porous structure.

13. An article for use in food contact applications, comprising a substrate having at least one surface and a coating disposed on the at least one surface, wherein the coating is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II The polymer material (A) has repeating units and in the formula, Ph represents the phenylene moiety, An article wherein the coating has an outer surface having an array of topographic features formed by the polymer material (A), the array of topographic features including spaced projections and / or depressions, the projections and / or depressions having a maximum dimension of less than 3 μm, and the topographic features are separated by a distance of less than 10 μm.

14. A coating formulation comprising a polymer material (A) and at least one non-stick-enhancing additive, wherein the polymer material (A) is formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A coating compound having repeating units, wherein Ph represents the phenylene moiety in the formula.

15. The coating formulation according to claim 14, wherein the at least one non-stickiness enhancing additive is a siloxane / silicone.

16. A method for forming a non-stick coating on an article for use in food contact applications, a) A step of providing an article for use in food contact applications, wherein the article includes a base material, and the base material has a surface, b) The surface of the substrate, formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II A step of treating with a polymer material (A) having repeating units, wherein Ph represents the phenylene moiety in the formula, c) A method comprising the step of treating the surface of the substrate with a non-stickiness enhancing additive.

17. Use of a composition comprising a polymer material (A) for providing a non-stick surface to an article for use in food contact applications, wherein the polymer material (A) formula: -O-Ph-O-Ph-CO-Ph- I The repeating unit and formula -O-Ph-Ph-O-Ph-CO-Ph- II It has repeating units, and in the formula, Ph represents the phenylene moiety.

18. The use according to claim 17, wherein the composition comprises at least one non-stickiness enhancing additive.

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