Inherently flame retardant varnish / paint formulation

Abstract

The invention relates to an itaconic acid or maleic anhydride functional DOPO based inherently flame retardant vamish / paint formulation developed for use in vamish / paint application.

Description

[0001] INHERENTLY FLAME RETARDANT VARNISH / PAINT FORMULATION

[0002] Technical Field

[0003] The invention relates to a varnish / paint formulation developed for use in vamish / paint application, comprising an itaconic acid or maleic anhydride functional DOPO based inherently flame retardant polyester binder.

[0004] Prior Art

[0005] There are a wide variety and a large number of flame retardant components in the world. However, among these flame retardant components, there are also halogen-based ones, but their use is prohibited due to their toxicity. Inorganic flame retardants and organic flame retardants are commonly used as flame retardants. Among these, inorganic flame retardants include aluminum trihydroxide (ATH), magnesium dihydroxide, antimony, boron, aluminum, tin, zinc and molybdenum, zinc borate. . .etc. Organic flame retardants include 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetrabromobisphenol A (TBBPA), BBMP 2,2-bis(bromomethyl)-l,3-propanediol, triphenyl phosphate (TPP), tris(l,3-dichloro-2-propyl) phosphate (TDCPP), tris(2-chloroethyl) phosphate (TCEP), 2- ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2)-ethylhexyl) 3, 4,5,6- tetrabromophthalate (TBPH). . .etc. The polymer obtained by incorporating said organic and inorganic flame retardants as additives into the formulation at high levels leaches out (release) from the matrix over time due to various reasons (e.g., ambient humidity, rain, wind, surface washing, or cleaning processes), and this leads to the material losing its flameretardant properties over time. Said leaching occurs as a result of the direct addition of organic and inorganic flame retardants as additives to the polymer. Therefore, when commercial products are examined, they generally comprise inorganic and organic additives, and it is observed that these additives gradually leach out (release) from the matrix over time.

[0006] Besides, transparency is a desired property especially in varnish applications. Inorganic flame retardants negatively affect the transparency of the varnish, causing it to appear cloudy. The random scattering of light caused by the disruption of the resin's (or binder's) crystalline structure (such as becoming amorphous) may lead to the varnish appearing cloudy. Additionally, the presence of direct inorganic additives in the material may also cause the material to appear cloudy. Furthermore, to impart flame-retardant properties, many additive materials on the market need to be incorporated into the formulation in high amounts, which leads to undesired outcomes obtained in the mechanical and physical properties of the varnish. Today, various restrictions are being imposed on inorganic-based flame retardants as well as flame retardants comprising organic groups such as Br and Cl. It is anticipated that in the coming years, regulations will change, and flame retardants that do not leach out (release), thereby not harming the ecosystem, will be used. In addition, another problem of the state of the art is the difficulty in dispersion of especially inorganic flame retardants in the production process. In order to clearly present this disadvantage, the process steps traditionally used in varnish production can be summarized as follows:

[0007] 1. A pre-grinding process is carried out with the mixture of resin, wetting and rheology agents,

[0008] 2. A dispersion and grinding process is performed to reduce the particle size of powder materials, fillers (to grind them), making them suitable for use in varnish,

[0009] 3. The production of varnish is completed with the final finishing and adjustment process, which involves adding viscosity modifiers and some additive materials to the mixture.

[0010] When additional flame retardant powder materials and additives are added to the materials used in the formulation, it may require the addition of a large amount of wetting agents to the formulation, thereby prolonging the grinding process. Furthermore, sometimes, the grinding process may be insufficient, and particles may remain in the varnish. This may require additional filtering processes. This further complicates dispersion.

[0011] In a state of the art, the patent document numbered W02008150157A1 mentions a flameresistant composition comprising a water-soluble flame extinguishing agent, an intumescent agent, and a charring agent. Said document states that the additive used for flame resistance is ammonium dihydrogen phosphate.

[0012] In a state of the art, the patent document numbered US3925137A describes a method for forming a coating that is non-flammable and has a flame-retardant effect on the coated material. The flame retardant additives used in said patent are ammonium phosphate, pentaerythritol, tris(2-chloroethyl)-phosphate, and tris(2-bromoethyl)-phosphite.

[0013] In another state of the art, the patent document numbered US20060079612A1 describes a flame-retardant coating comprising a hydroxylamine and nitroxyl compound, and a flame retardant. In this patent as well, the flame-retardant components, i.e., additives, are halogenbased (pcBs) and phosphorus-based (triphenyl phosphate).

[0014] In another state of the art, the patent document numbered CN105085926A includes the synthesis method of a transparent phosphorus-nitrogen polymeric flame retardant and its application in varnish. In this study, resorcinol, urea, and polyphosphoric acid were used as flame-retardant additives.

[0015] In another state of the art, the patent document numbered CN115260852B relates to EB flame-retardant spray varnish and its preparation method. In this patent, a phosphorus-based diol is used as a flame-retardant additive.

[0016] In another state of the art, the patent document numbered CN1076208A relates to flameretardant materials and antistatic paint. In this patent, commercially available ammonium polyphosphate (APP) is used as a flame retardant.

[0017] In another state of the art, the patent document numbered CN108864922B relates to the preparation method of a flame-retardant, waterproof, and light-resistant water-based polyurethane coating and adhesive. The flame-retardant additive developed in this study is based on aminopropyl triethoxysilane and phosphoric acid.

[0018] In another state of the art, the patent document numbered JP6338681B2 describes a formulation developed using commercial additives (melamine), a charring agent, a phosphating agent (phosphoric acid), and a hydroxyl-containing cross-linking agent (ethylene glycol / pentaerythritol). These additives were added to a formulation such as paint, varnish, applied to a surface, and the flame-retardant properties were examined.

[0019] In another state of the art, the patent document numbered MXPA06002054A describes a flame-retardant coating composed of flame-retardant filler particles coated with metallic stannate. In this study, inorganic additives such as aluminum trihydroxide were used as flame retardants.

[0020] In another state of the art, the patent document numbered CH214614A relates to a flameresistant paint film. In this patent, inorganic additives were used as flame retardants.

[0021] In another state of the art, the patent document numbered RU2726730C1 also uses an inorganic additive-based flame retardant (aluminum hydroxide and zinc borate). In another state of the art, the patent document numbered CN102702875A relates to a halogen-free flame-resistant coating. In this patent, silicone-based resins were used as flame retardants.

[0022] In another state of the art, the patent document numbered EP1630203A1 aims to produce a flame-retardant polyester resin without using phosphorus-based or halogen-based flameretardant components.

[0023] In another state of the art, the patent document numbered CN108912928B achieved flameretardant properties by developing a shell on acrylic resin surfaces. Said patent also does not refer to phosphorus-based organic polymers.

[0024] In another state of the art, the patent document numbered US3131071A examines the flameretardant properties of boron-based additives. Said patent also does not refer to phosphorus- based organic polymers.

[0025] In another state of the art, the patent document numbered CN113292910B mentions that diethyl phosphoacetic acid was used in an epoxy-based coating formulation, providing the coating with flame-retardant properties. In this study, itaconic acid was also used to achieve a bio-based formulation. However, said itaconic acid is not covalently bonded to DOPO.

[0026] In another state of the art, the patent document numbered CN102428091B relates to flameretardant additives, DOPO derivatives. In this study, phosphorus-based DOPO was reacted with ethylene glycol, and the resulting epoxy was used in the system.

[0027] In another state of the art, the patent document numbered KR20190134760A provides information about itaconic acid and DOPO-based flame retardants. However, there is no application and experimental formula within the scope of a varnish / paint formulation. Additionally, said itaconic acid is not covalently bonded to DOPO.

[0028] Similar to the previous technique, the patent document numbered US20120095140A1 in another state of the art provides information about DOPO-based polyester and other DOPO- based compounds. The document does not include an itaconic acid based DOPO compound. Furthermore, there is no application and experimental formula within the scope of a varnish / paint formulation.

[0029] Similarly, the patent document numbered CN103833947B, which is in another state of the art, provides information about itaconic acid and DOPO-based flame retardants. It is stated that they can be used in the synthesis of polyurethane-based materials. However, there is no application and experimental formula within the scope of a varnish / paint formulation.

[0030] Similarly, the patent document numbered US10633591B2, which is in another state of the art, provides information about itaconic acid and phosphorus-based flame retardants. However, there is no application and experimental formula within the scope of a varnish / paint formulation.

[0031] Similarly, the patent document numbered EP2190903, which is in another state of the art, describes a method for reducing the flammability of organic material by using specific cyclic aryl phosphines as flame retardants and incorporating these specific cyclic phosphines into the material. Also, in said document, there is no application and experimental formula within the scope of a varnish / paint formulation. This study is also not polyester-based. For this reason, it prevents the desired level of flame resistance and has minimal impact on mechanical properties (such as surface scratch tests).

[0032] Similarly, the invention in the patent document numbered EP2284208, which is in another state of the art, relates to a phosphorus-containing flame retardant and its use in curable synthetic resins and polymerizable compositions. Additionally, the document provides information about itaconic acid and DOPO-based flame retardants. However, there is no application and experimental formula within the scope of a varnish / paint formulation. Also, said itaconic acid is not covalently bonded to DOPO.

[0033] In another state of the art, the invention numbered CN101880395A relates to polymer-type phosphorus-containing flame retardants comprising 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide and their preparation method. The document describes and protects the preparation method of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified with aromatic diphenol or aromatic radical glycol and pentaerythritol diphosphate diphosphoryl chloride, phenyl phosphate dichloride, or 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide modified with phenylphosphonyl dichloride. Phenol-based aromatic groups are used in the mentioned document.

[0034] The additives used as flame retardants are mostly inorganic additives, which can cause cloudiness on the coating surface. Additionally, since they are not covalently bonded to the polymer structure, they may leach out, reducing their flame-retardant properties. This deficiency should be addressed by obtaining organic-based polymers where at least one functional group is covalently bonded to DOPO, allowing the polymer to have inherently flame-retardant properties. Particularly, when examining the state of the art, there is no polyester resin formulation that is itaconic acid or maleic anhydride functional DOPO based inherently flame-retardant, where aromatic groups, specifically phthalic anhydride and / or terephthalic acid are used in the prior art. The functionality here arises because they are used as functional group and attached to the binder through a reaction.

[0035] It should also be noted that many flame-retardant varnishes are produced in the sector for various surfaces (such as metal, wall, wood, plastic). Varnishes are classified into many categories not only based on surface differences but also according to their chemical structure, such as cellulose-based, polyurethane-based, UV (ultraviolet) systems, waterbased systems, and polyester systems. The differences between these systems are the differences in types of binders they comprise and the differences in their drying mechanisms.

[0036] As mentioned above, in the production of existing flame-retardant varnishes, an ordinary polyester binder is used, and flame-retardant varnishes are obtained by using many flameretardant additives, mostly in the form of powder additives and very few in liquid form, to impart flame-retardant properties. However, the issue here is that a very large amount of flame-retardant additives are added to achieve the desired flame-retardant properties. Since the additives are generally in powder form, this leads to cloudiness in the varnish. Additionally, as mentioned, powder materials make grinding / dispersion in varnish production difficult. At the same time, since these are not covalently bonded to the structure of the binder chemically, leaching may occur on the surface. Developments to prevent this need to be implemented.

[0037] Besides, there are many and a wide variety of varnish / paint formulations comprising polyesters in the state of the art. It should be noted that each formulation exhibits unique mechanical and physical properties.

[0038] Therefore, a varnish formulation should be developed that does not leach from the applied surface, creates a transparency effect on the surface, is environmentally friendly, inherently flame-retardant, eliminates the need for using additional flame-retardant additives, and in this sense, comprises itaconic acid or maleic anhydride functional DOPO-based polyester.

[0039] Summary of the Invention The invention relates to a varnish / paint formulation developed for use in varnish / paint application, comprising an itaconic acid or maleic anhydride functional DOPO based inherently flame retardant polyester binder.

[0040] No incompatibility has been observed in fire-resistant materials within the scope of the polymeric binder proposed / developed in the patent. Because the produced binder (resin) itself is flame-resistant, and no cloudiness is observed in the material where it is used. Furthermore, while migration (leaching) is observed in flame-retardant products made with existing additive materials in the long term, this issue is not encountered in formulations (e.g., varnish and paint formulations) made with the polymeric binder (or resin) that is the subject-matter of the patent.

[0041] Accordingly, the invention aims to provide the polymer with an organic, inherently flameretardant a covalently bonded to the polymer that does not leach (migrate) from the matrix instead of inorganic and / or organic flame-retardant additive materials. The itaconic acid or maleic anhydride functional groups in the formulation of the invention are covalently bonded to DOPO. The thermal properties of the flame-retardant polymer synthesized in the invention are high due to the abundance of phosphorus groups and aromatic groups in its structure. Aromatic groups will contribute to the formation of a carbon layer (graphitization) by the polyester during combustion. Phosphorus groups will enhance the flame resistance of the material by forming both radical scavenger in the gas phase and polyphosphoric acid layer in the solid phase. In an exemplary embodiment of the invention, the varnish obtained with these polymers was applied to MDF (Medium Density Fiberboard) and tested in TSE (Turkish Standards Institute). Standard tests of EN13823 were conducted within the scope of EN13501-1 in TSE. The most important parameter, FIGRA0,4 MJ (W / s), which is the fire growth rate index at the 0.4 MJ total heat release threshold, was determined to be 158,2. The result for the material that is not polymeric but supported only by additives was determined to be 231,2. Therefore, the material coated with the polyester formulation of the invention is more resistant to flame.

[0042] In the invention, an inherently flame-retardant bio-based polyester resin formulation was developed using phosphorus-based itaconic acid or maleic anhydride. With the use of itaconic acid, the incorporation of a renewable raw material into the formulation was also achieved. In other words, the use of natural resources like itaconic acid was ensured. The originality of the molecules developed / targeted within the scope of this patent lies in the fact that the polymeric binder (DOPO-based polyester binder) used in the formulation or the functional group covalently bonded to DOPO (maleic anhydride or itaconic acid) is inherently flame-resistant. The originality of the patent lies in the development of a polymeric structure that does not release into the environment, is not inorganic (organic), and is covalently bonded to the polymer chain. The synthesis of an inherently flameretardant polyester binder has been achieved within the scope of the patent. Since phosphorus functional polyester resins - the functional groups within the polyester (DOPO- functional group) - are inherently flame-retardant, they eliminate the need to add any extra flame-retardant additives to the formulation. In addition, the formulation provides long- lasting flame-retardant properties to the applied matrix. Since it does not contain halogen or halogen-based additives / flame retardants, there will be no toxic gas emission. In varnish applications, by not using flame-retardant inorganic additives, a more transparent varnish film can be obtained compared to the existing system, which will visualize all the details of the surface without altering its nature.

[0043] In the invention, since the flame-retardant property comes from the DOPO-function, binding it to the polyester structure ensures that the polyester also possesses flame-retardant characteristics. As a result, using this polymeric product in the final varnish / paint formulation is sufficient for flame retardancy. Moreover, aromatic groups specifically from phthalic anhydride and / or terephthalic acid have been used in the invention.

[0044] In paint or varnish formulations, a polymer-based additive called binder is already used. This is an essential component of all paints or varnishes. However, the binder processed in the invention is a polyester binder. The polymeric binder (DOPO based polyester) used / developed within the scope of this patent is inherently flame retardant. There is no need for using an additional flame-retardant additive. The DOPO additive is not new; however, the DOPO-Polyester binder developed with the invention is unique, and its application in paint / varnish is innovative. Using the polyester binder, varnish or paint is obtained.

[0045] In one embodiment of the invention, DOPO-Maleic anhydride (MAH) was obtained as a result of the reaction of DOPO with Maleic anhydride under specific conditions. The obtained DOPO-MAH is used to modify the polyester resin. In other words, the DOPO- MAH component is considered as an acid equivalent, and as a result of the reaction, a polyester resin is obtained. This obtained resin is now referred to as DOPO-MAH modified polyester resin. Then, varnish is prepared using the obtained DOPO-MAH modified polyester resin. This produced varnish inherently possesses flame-retardant properties. Another embodiment can be similarly considered for DOPO-Itaconic acid. The modification refers to the attachment of the obtained intermediates (DOPO-MAH and DOPO-Itaconic acid) to the chemical backbone of the polyester structure. In other words, when DOPO, which is a phosphorus-containing material, is bonded to the binder structure via a chemical reaction and used in varnish, flame-retardant properties are achieved without the need for additional additives.

[0046] Additionally, it should be noted that properly wetting the filler materials in the formulation is important. Wetting agents are often used in the formulation to establish a homogeneous network. In the synthesized polyester binder, this feature has been achieved without the need for an external additive. Additionally, in the varnish application, which is one of the embodiments of the invention, it prevents potential sedimentation problems in varnish after varnish is kept in an oven at 50°C for 1 week and then removed after 1 week in stock-stability tests. Because the inability to properly grind and wet the filler materials used causes sedimentation problems, this issue has been solved with the polymer. Therefore, in the varnish production process described in the prior art, dispersion is facilitated with the polymer of the invention without using flame-retardant powder materials that are difficult to grind. Therefore, the varnish formulation comprising DOPO based polyester of the invention exhibits different mechanical and physical properties compared to the prior art. Additionally, the presence of DOPO in the polyester resin both increases resistance to burning and enhances mechanical properties (such as surface scratch tests).

[0047] In one embodiment of the invention, the flame-retardant varnish for wooden surfaces is a two-component polyurethane varnish. The first component forms the varnish part comprising the binder. The second component forms the isocyanate part, referred to as the hardener. When these two components are mixed and applied as a film, urethane bonds form as a result of a chemical reaction, producing a polyurethane varnish film (coating). The main advantage of the invention is the opacity in the varnish and the ease of dispersion. Another difference of the invention from other documents in the known state of the art is that it is a two-component polyurethane varnish. In summary, the flame retardants used in the invention of the patent application are phosphorus based polymers. Therefore, the polymers used as flame retardants, for example, due to comprising phosphorus groups in their structures (DOPO comprises phosphorus groups), are inherently flame retardant organic based polymers. Besides, with itaconic acid or maleic anhydride functional DOPO based inherently flame-retardant saturated polyesters the formulation of the invention comprises, the formulation can be used in paint / varnish applications. In order to make it suitable for use in paint / varnish formulations, R&D and product development activities have been carried out on how itaconic acid or maleic anhydride functional DOPO based inherently flame-retardant polyesters can be applied in this field, and related plans and studies have been conducted.

[0048] With the production of paint / varnish with the polyester binder which is subject-matter of the invention, a varnish formulation comprising itaconic acid or maleic anhydride functional DOPO based polyester has been developed to ensure properties such as being non-leaching from the applied surface, inherently flame-retardant or flame-resistant, creating a transparency effect on the surface, being environmentally friendly, allowing easy dispersion in the production process, and providing strong mechanical and UV resistance.

[0049] In order to ensure properties such as being non-leaching from the applied surface, inherently flame-retardant or flame-resistant, creating a transparency effect on the surface, being environmentally friendly, allowing easy dispersion in the production process, and providing strong mechanical and UV resistance for varnish (or paint) applications, the wet varnish / paint formulation of the invention, in one embodiment, comprises predetermined amounts of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier, at least one natural wax or synthetic wax, at least one solvent, and additionally at least one polyester, a phosphorus-based monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and said polyester covalently bonded to said DOPO-maleic anhydride (MAH) structure (Figure-2), and a polyester comprising phthalic anhydride and / or terephthalic acid.

[0050] The wet varnish / paint formulation of the invention, in another embodiment, comprises predetermined amounts of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier, at least one natural wax or synthetic wax, at least one solvent, and additionally at least one polyester, a phosphorus- based monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), said polyester covalently bonded to said DOPO-itaconic acid structure, and a polyester comprising phthalic anhydride and / or terephthalic acid.

[0051] Description of the Figures

[0052] Figure-1. It is a schematic representation of the DOPO-MAH chemical structure in one embodiment of the invention.

[0053] Figure-2. It is a schematic representation of the DOPO-MAH modified polyester chemical structure in one embodiment of the invention.

[0054] Figure-3. It is a schematic representation of the DOPO-itaconic acid modified polyester chemical structure in another embodiment of the invention.

[0055] Figure-4. It is a schematic representation of the polyurethane film obtained by the reaction of the hardener di-isocyanate with the varnish / paint formulation of the invention.

[0056] Detailed Description of the Invention

[0057] The formulation obtained for varnish in the document is also applicable for paint. Wherever varnish application is mentioned, paint application should also be considered. The polyester binder synthesized within the scope of the invention is also used for the paint formulation.

[0058] To achieve properties such as not leaching from the applied surface, being inherently flameretardant and / or non-flammable, creating a transparency effect on the surface, being environmentally friendly, enabling easy dispersion during the production process, and providing strong mechanical and UV resistance; in one embodiment, the varnish formulation of the invention comprises a predetermined amount of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier, at least one natural wax or synthetic wax, at least one defoamer, at least one solvent, and a phosphorus-based monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), maleic anhydride covalently bonded to said DOPO (raw material 1, HM1) and phthalic anhydride and / or terephthalic acid. The polyester resin (or binder) of the invention in said embodiment comprises 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) which is a phosphorus-based monomer and maleic anhydride (raw material 1, HM1) covalently bonded to the said DOPO, as well as phthalic anhydride.

[0059] In another embodiment of the invention, the varnish formulation of the invention comprises predetermined amounts of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier additive, at least one natural wax or synthetic wax, at least one defoamer, at least one solvent, and a phosphorus- based monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), itaconic acid (raw material 2, HM2), and phthalic anhydride and / or terephthalic acid. In said embodiment, the polyester resin (or binder) of the invention comprises the phosphorus-based monomer 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), itaconic acid (raw material 2, HM2), and phthalic anhydride and / or terephthalic acid.

[0060] The formulation comprises the matting additive in the range of 0.2% to 4%. In the preferred embodiment of the invention, this ratio is 2%. The reason for using it with this ratio is to produce a varnish with the desired gloss level.

[0061] In the varnish formulation of the invention, the mentioned wetting additive is a solution of a salt of unsaturated polyamine amides and acidic polyesters; the rheology additive is an oxidized polyolefin-based thixotropic agent; the matting agent is synthetic amorphous silica; the surface modifier is a silicone-based surface agent; the wax is micronized polyethylene wax, and the defoamer is silicone defoamers.

[0062] Within the scope of the invention, an inherently flame-retardant polyester resin (or polyester binder) comprising phosphorus was synthesized firstly. In the invention, varnish (or paint) application was carried out with polyester resins obtained from raw materials (HM1 or HM2). In the varnish (or paint) formulation, DOPO-based HM1 and HM2 were added to the formulation based on the amount of phthalic anhydride and / or terephthalic acid according to the embodiments of the invention, and polyester resin synthesis was carried out in different formulations (Scheme 1).

[0063] Raw material 1 Raw material 2

[0064] Scheme 1. Phosphorus based monomers used in the formulation of the polyester binder The mole ratios below were determined using the phosphorus-based polymer obtained from the DOPO-Maleic anhydride embodiment which is one embodiment of the invention, and three polyesters, which are POLYESTER-1, POLYESTER-2, and POLYESTER-3, were synthesized firstly. The standard polyester (STD POLYESTER) was synthesized without using a phosphorus-based polymer. Varnish formulations specific to the invention were created using these synthesized polyesters.

[0065] THE FIRST EMBODIMENT OF THE INVENTION

[0066] Therefore, in one embodiment, the mentioned polyesters comprise predetermined ratios of DOPO-MAH / phthalic anhydride or DOPO -itaconic acid / phthalic anhydride. In the preferred embodiment of the invention, the mole ratios of the mentioned polyesters for both DOPO-

[0067] MAH / Phthalic Anhydride and DOPO-Itaconic Acid / Phthalic Anhydride are as follows:

[0068] POLYESTER-1 ; Mole ratio of Phthalic Anhydride / Dopo-MAH (or itaconic acid): 0,5 / 1, 5

[0069] POLYESTER-2 ; Mole ratio of Phthalic Anhydride / Dopo-MAH (or itaconic acid): 1,5 / 0, 5

[0070] POLYESTER-3 ; Mole ratio of Phthalic Anhydride / Dopo-MAH (or itaconic acid): 1 / 1 In this embodiment, the phthalic anhydride value in the non-flame-retardant polyester is 0,1470. This ratio was obtained as a result of calculations required for the polyester resin to provide the best performance in a varnish. Based on this, the ratios mentioned above were adjusted. Based on this, the ratios mentioned above were adjusted.

[0071] The materials used in the DOPO-MAH / phthalic anhydride embodiment of the DOPO-based polyester used in the varnish formulation of the invention are given in Table-1.

[0072] Table 1. Mole values of polyester for the DOPO-MAH / phthalic anhydride embodiment of the invention Flame retardancy is controlled by the Limiting Oxygen Index (LOI). LOI tests determine the amount of oxygen required for the sample to burn. Oxygen is necessary for fire to start. The higher the LOI, the more difficult it is to ignite.

[0073] 1. While the LOI test result for Standard Polyester was 26, the LOI (ASTM D 2863-00) values for POLYESTER-1, POLYESTER-2, and POLYESTER-3 were determined to be 28, 27, and 27.6, respectively. Varnish formulations given in Table 2 were prepared with the obtained polyesters. The usage ratio of the polyester binder in the varnish formulation ranges between 35% and 75%. In the preferred embodiment of the invention, the usage ratio of the polyester binder in the formulation is 65%. When used at these ratios in the formulation, the invention exhibits the desired technical effect. When used at these ratios in the formulation, the invention exhibits the desired technical effect.

[0074] Table 2. The prepared varnish formulations.

[0075] As can be seen from Table-2, the varnish formulation at the state of the art comprises predetermined standard amounts of wetting additive, rheology additive, matting additive, surface modifier, wax, defoamer, and solvent.

[0076] 5 THE SECOND EMBODIMENT OF THE INVENTION

[0077] The aforementioned polyesters, in another embodiment, comprise DOPO-MAH / terephthalic acid in predetermined ratios. In the preferred embodiment of the invention, the mol ratios of the mentioned polyesters are as follows for both Terephthalic acid / DOPO-MAH and Terephthalic acid / DOPO-Itaconic acid:

[0078] 10 DOPO-Itaconic acid and terephthalic acid

[0079] POLYESTER-1.1 ; Mole ratio of terephthalic acid / DOPO-MAH: 0,5 / 1, 5

[0080] POLYESTER-2.1 ; Mole ratio of terephthalic acid / DOPO-MAH: 1,5 / 0, 5

[0081] POLYESTER-3.1 ; Mole ratio of terephthalic acid / DOPO-MAH: 1 / 1

[0082] In Table-3, the mole values of the synthesized polyesters are provided in comparison with 15 the standard polyester. The materials used in the second embodiment of the polyester formulation of the invention are given in Table-3.

[0083] Table 3. Mole values of polyesters for the DOPO-MAH / Terephthalic acid embodiment of the invention

[0084] 20 While the LOI test result for the Standard Polyester is 26, the LOI (ASTM D 2863-00) values for Polyester- 1.1, Polyester-2.1, and Polyester-3.1 were determined as 28, 27, and 27.5, respectively. Varnish formulations given in Table 4 were prepared with the obtained polyesters.

[0085] Table 4. The prepared varnish formulations Using the phosphorus-based polymer in the DOPO + itaconic acid embodiment of the invention, the mole ratios below were determined, and three POLYESTERS, namely POLYESTER-IO, POLYESTER-20, and POLYESTER-30, were synthesized. The standard polyester was synthesized without using a phosphorus-based polymer. Varnish formulations were created using these synthesized POLYESTERS. Therefore, the mentioned polyesters in this embodiment comprise predetermined ratios of DOPO-Itaconic acid and phthalic anhydride (or terephthalic acid). In the preferred embodiment of the invention, the mole ratios of the mentioned polyesters are as follows for both Phthalic Anhydride / DOPO- Itaconic Acid and Terephthalic Acid / DOPO-Itaconic Acid: POLYESTER-IO ; Mole ratio of Phthalic Anhydride / DOPO-Itaconic Acid: 0,5 / 1, 5

[0086] POLYESTER-20 ; Mole ratio of Phthalic Anhydride / DOPO-Itaconic Acid: 1,5 / 0, 5

[0087] POLYESTER-30 ; Mole ratio of Phthalic Anhydride / DOPO-Itaconic Acid: 1 / 1

[0088] The materials used in the DOPO-Itaconic acid and phthalic anhydride embodiment of the polyester formulation of the invention are given in Table-5. The mole ratios for the example embodiments of the mentioned polyester are provided in Table-5.

[0089] Table 5. The mole values of the polyester formulations

[0090] The LOI test result for Standard Polyester was 26, whereas the LOI (ASTM D 2863-00) values for Polyester-10, Polyester-20, and Polyester-30 were determined to be 27.5, 27, and 27.2, respectively.

[0091] Varnish formulations given in Table 6 were prepared with the obtained polyesters.

[0092] Table 6. The prepared varnish formulations.

[0093] The flame-retardant property of the polymer of the invention has been imparted through functional groups. In the preferred embodiment of the invention, the functional groups providing the flame-retardant property are phosphorus and aromatic groups. The majority of the flame-retardant property comes from phosphorus groups. Although itaconic acid or

[0094] MAH comprises aromatic groups, they are not sufficient on their own to provide flameretardant properties. The reason for binding MAH (Maleic anhydride) or itaconic acid is to attach the functional group to the polyester structure.

[0095] The mentioned polyester, in another application, comprises predetermined ratios of DOPO- Itaconic acid and terephthalic acid. In the preferred embodiment of the invention, the mole ratios of the mentioned polyesters for Terephthalic Acid / DOPO-Itaconic Acid are as follows: POLYESTER-lO.l ; Mole ratio of Terephthalic Acid / DOPO-Itaconic Acid: 0,5 / 1, 5

[0096] POLYESTER-20.1 ; Mole ratio of Terephthalic Acid / DOPO-Itaconic Acid: 1,5 / 0, 5

[0097] POLYESTER-30.1 ; Mole ratio of Terephthalic Acid / DOPO-Itaconic Acid: 1 / 1

[0098] In Table-7, the mole ratios of the synthesized polyesters are presented in comparison with the standard polyester. The materials used in the first alternative embodiment of the second embodiment of the polyester formulation of the invention are provided in Table-7.

[0099] Table 7. Mole values of the polyester formulations.

[0100] While the LOI test result for Standard Polyester was 26, the LOI (ASTM D 2863-00) values for Polyester-10, Polyester-20, and Polyester-30 were determined to be 28,2, 27,5, and 27,6, respectively.

[0101] Varnish formulations given in Table 8 were prepared with the obtained polyesters.

[0102] Table 8. The prepared varnish formulations.

[0103] In the invention, varnishes are produced with the obtained polyesters. The produced varnishes are then mixed with hardeners and, after their application, a dry film is obtained. Therefore, in the varnish formulation studies, varnishes produced with the polyester sample comprising phosphorus were cured with hardeners comprising aromatic and aliphatic isocyanates to obtain a polyurethane film.

[0104] THE FIRST STAGE STUDIES:

[0105] The first stage studies are valid for polyesters obtained from both DOPO + maleic anhydride and DOPO + itaconic acid. The prepared varnish (first component) and hardener (second component) were mixed in a 100 / 50 (by weight %) ratio. Within the scope of the application, films were created on glass and filled wooden panel surfaces with an applicator for a 90-micron film thickness. After mixing the varnish and hardener, the samples that reached the application viscosity were applied to filled wooden panels using a spray gun. The application weight is 150 g / m2The varnish formulation was then applied to glass and wooden surfaces, and surface tests of said application (such as glass hardness, gloss test, adhesion test, UV aging test, Erichsen test) were performed. As mentioned above, varnish is obtained by using a polyester binder. This varnish is mixed with a hardener and applied to obtain a dry film. Flame tests are conducted on the dry film. Gloss is the property that causes surfaces to appear glossy or polished, metallic or matte. Gloss was measured with a glossmeter device. The 20° acute measurement angle provides enhanced resolution for highly glossy surfaces. Surfaces measured at 70 GU and above, with a standard angle value of 60°, are generally measured with this geometry. The device performs measurements using its 60° geometry (a universal application angle for all surfaces), and the 60° angle is used as the reference angle for all products. Measurements using 85° and 60° geometry contribute to the examination of the MATTE property, while measurements using 20° and 60° geometry contribute to the examination of the GLOSS property. According to the standard 60° measurement angle, values above 90 gloss are considered ideal for the study. The results obtained are shown in Table 9.

[0106] Adhesion Test (TS 4313 EN ISO 2409): This standard defines a test method for evaluating the resistance of a paint coating to separation from the base material when the coating is cut through the base material with a lattice pattern at a right angle. As a result of the varnish formulation studies, no issues were observed in adhesion strength.

[0107] Erichsen Test: A gradually increasing weight starting from 1 Newton is applied from the outside to the inside on panels cut to specific dimensions.

[0108] Pendulum hardness test (ASTM D 4366-95): Hardness measurements of films applied to glass plates with a 90-micron applicator were conducted using a Pendulum device.

[0109] THE SECOND STAGE STUDIES:

[0110] 1. DOPO-Maleic Anhydride MODIFIED POLYESTER

[0111] The wet product tests shown in Table 9 were applied to the varnishes prepared with the invention's DOPO-MAH modified polyester (with phthalic anhydride) embodiment.

[0112] Table 9. Varnish wet product tests

[0113] The varnish flame test results are provided in Table 10, and the dry film test results are presented in Table 11.

[0114] Table 10. Varnish coating flame tests.

[0115] Table 11. Varnish dry film tests. 2. DOPO-ITACONIC ACID MODIFIED POLYESTER

[0116] The wet product tests shown in Table 12 were performed on the varnishes prepared with the DOPO-ITACONIC ACID modified polyester (with phthalic anhydride) embodiment of the invention.

[0117] Table 12. Varnish wet product tests

[0118] Similar to the first embodiment, the varnish dry film test results are presented in Table 13, and the varnish coating flame test results are presented in Table 14.

[0119] Table 13. Varnish dry film tests.

[0120] Table 14. Varnish coating flame tests.

[0121] 3. DOPO-ITACONIC ACID MODIFIED POLYESTER The wet product tests shown in Table 15 were carried out on the varnishes prepared with the DOPO-Itaconic acid / Terephthalic acid modified polyester embodiment of the invention.

[0122] Table 15. Varnish wet product tests Similarly, the varnish dry film test results are presented in Table 16, and the varnish coating flame tests are presented in Table 17.

[0123] Table 16. Varnish dry film tests.

[0124] Table 17. Varnish coating flame tests.

[0125] For the varnishes produced with the varnish formulation of the invention; varnish wet product tests, varnish dry film tests, and varnish coating flame tests were also conducted for the DOPO-MAH / Terephthalic Acid Modified Polyester, similar to the DOPO-Itaconic Acid / Terephthalic Acid Modified Polyester, and results similar to those in Tables 10, 11, and 12 were obtained.

[0126] The functional groups of itaconic acid or maleic anhydride in all formulations of the polyester resin of the invention are covalently bonded to DOPO, and by using phosphorus- based DOPO, an inherently flame-retardant material has been produced. The issue of cloudiness, which is one of the problems at the prior art, has been eliminated in the invention's formulation by using a polyester covalently bonded to the DOPO-maleic anhydride (MAH) structure and a polyester comprising phthalic anhydride and / or terephthalic acid, or a polyester covalently bonded to the DOPO-itaconic acid structure and a polyester comprising phthalic anhydride and / or terephthalic acid, instead of additional powder additives. Similarly, inherently flame-retardant properties are imparted to the produced varnish or paint through a structure designed in this manner. With the polyester formulation of the invention, an inherently flame-retardant polymer has been obtained. Thus, the desired transparency has also been achieved. This transparency can be achieved through a more homogeneously aligned crystal structure. Obtaining a homogeneous crystal structure (due to the equal or nearly equal distance between atoms) will prevent light scattering and thus result in the production of a more transparent material. Additionally, the absence of inorganic particles in the material also contributes to achieving a transparent material.

[0127] Industrial Applicability of the Invention

[0128] The invention is a varnish / paint formulation developed for use in varnish / paint application, in coating industry, comprising itaconic acid or maleic anhydride functional DOPO based inherently flame retardant polyester binder, and it is industrially applicable.

[0129] The invention is not limited to the descriptions above, a skilled person in the art can perform different embodiments of the invention easily. These should be interpreted within the protection scope of the invention claimed with the claims.

Claims

CLAIMS1. To ensure properties such as being non-leaching from the applied surface, inherently flame-retardant or flame-resistant, creating a transparency effect on the surface, being environmentally friendly, allowing easy dispersion in the production process, and providing strong mechanical and UV resistance for varnish (or paint) applications; a wet varnish / paint formulation comprising predetermined amounts of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier, at least one natural wax or synthetic wax, at least one solvent, and additionally at least one polyester; characterized by comprising a phosphorus-based monomer 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and said polyester covalently bonded to said DOPO-maleic anhydride (MAH) structure, and a polyester comprising phthalic anhydride and / or terephthalic acid.

2. To ensure properties such as being non-leaching from the applied surface, inherently flame-retardant or flame-resistant, creating a transparency effect on the surface, being environmentally friendly, allowing easy dispersion in the production process, and providing strong mechanical and UV resistance for varnish (or paint), coating applications; a wet varnish / paint formulation comprising predetermined amounts of solvent and at least one wetting additive, at least one rheology additive, at least one matting additive, at least one surface modifier, at least one natural wax or synthetic wax, at least one solvent, and additionally at least one polyester; characterized by comprising a phosphorus-based monomer 9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), and said polyester covalently bonded to said DOPO-itaconic acid structure, and a polyester comprising phthalic anhydride and / or terephthalic acid.

3. A formulation according to claim 1 or 2, characterized by comprising Phthalic Anhydride / DOPO-MAH (or itaconic acid) wherein its mole ratio is 0,5 / 1, 5.

4. A formulation according to claim 1 or 2, characterized by comprising Phthalic Anhydride / DOPO-MAH (or itaconic acid) wherein its mole ratio is 1,5 / 1.

5. A formulation according to claim 1 or 2, characterized by comprising Phthalic Anhydride / DOPO-MAH (or itaconic acid) wherein its mole ratio is 1 / 1.

6. A formulation according to claim 1 or 2, characterized by comprising Terephthalic acid / DOPO-MAH (or itaconic acid) wherein its mole ratio is 0,5 / 1, 5.

7. A formulation according to claim 1 or 2, characterized by comprising Terephthalic acid / DOPO-MAH (or itaconic acid) wherein its mole ratio is 1,5 / 0, 5.

8. A formulation according to claim 1 or 2, characterized by comprising Terephthalic acid / DOPO-MAH (or itaconic acid) wherein its mole ratio is 1 / 1.

9. A formulation according to claim 8, characterized by comprising the wetting additive which is a solution of a salt of unsaturated polyamine amides and acidic polyesters; the rheology additive which is an oxidized polyolefin-based thixotropic agent; the matting additive which is synthetic amorphous silica; the surface modifier which is a silicone- based surface agent; the wax which is micronized polyethylene wax, and the defoamer which is silicone defoamers.

10. A formulation according to any of claims above, characterized by comprising the matting additive between 0.2% to 4%.

11. A formulation according to any of claims above, characterized by comprising the polyester binder with a usage ratio between 35% to 75%.

12. A formulation according to any of claims above, characterized by comprising the polyester binder with a usage ratio of 65%.

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