PVC composition containing a rare earth additive

Abstract

The PVC compositions disclosed in this specification contain a PVC resin, a rare earth compound, and an inorganic flame retardant. These PVC compositions have improved flame retardancy and have a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm. The rare earth compound can be a rare earth hydroxide, a hydrated rare earth oxide, and mixtures thereof. The inorganic flame retardant can be antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), and mixtures thereof. The combination of the rare earth compound and the inorganic flame retardant forms a synergistic relationship.

Description

Technical Field

[0001] Related Applications This application claims the priority and benefit of U.S. Provisional Application No. 63 / 353,445, filed on June 17, 2022, the content of which is incorporated herein by reference in its entirety. The present invention relates to a PVC composition containing a polyvinyl chloride (PVC) resin, an inorganic flame retardant, and a rare earth compound. This PVC composition has a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm. The rare earth compound improves the performance of the inorganic flame retardant additive and / or the flame retardant properties and thermal stability of the PVC formulation.

Background Art

[0002] Polyvinyl chloride (PVC) resin is a polymer made from vinyl chloride monomer. This resin is mixed with other components to make PVC compositions or formulations, which are often simply referred to as PVC. These PVC compositions require specific properties such as, to name just a few, flame retardancy, color, thermal stability, ductility, and moldability. Other components or additives in this composition can impart the desired properties, and these components / additives can be classified as plasticizers, stabilizers, lubricants, fillers, and other functional additives. Also, by having a certain amount of each of these additional components / additives, the desired properties of the PVC composition can be changed.

[0003] PVC compositions and products made from these PVC compositions generate hydrogen chloride gas during high-shear processing or as a direct result of a combustion event, which can corrode external equipment and initiate further decomposition of the PVC. Antimony trioxide (ATO), magnesium dihydroxide (MDH), and aluminum trihydrate (often also called alumina trihydrate (ATH)) are used as flame retardants in PVC compositions. However, ATO is considered to be highly toxic and produces large amounts of smoke during a combustion event. The usefulness of ATH and MDH can be limited by their compatibility with specific PVC compositions, and ATH and MDH may have relatively limited load-bearing capacity before they adversely affect the physical and aesthetic properties of the PVC composition and the end-use product. Employing "environmentally friendly" additives to reduce the content of these flame retardants or eliminate them is a major advantage but still a challenge.

[0004] Other typical examples of flame retardant additives include halogenated organic compounds such as halogenated paraffins. These additives are not considered "environmentally friendly" and are prohibited from use in some jurisdictions such as within Europe.

[0005] Therefore, there is still a need for additives for PVC compositions that impart a synergistic effect with known flame retardants and / or further thermal stability. It is desirable to provide a synergistic flame retardant additive and / or thermal stabilizer and / or acid scavenger and / or smoke suppressant (which reduces the density, emission, and acidity of smoke) for the PVC composition while reducing the amount of ATO due to its toxicity. This desirable additive must have excellent dispersibility in polymer and thermoplastic resin compositions and can be used to prepare a flame-retardant plasticized PVC composition having excellent flame retardancy and mechanical properties. SUMMARY OF THE INVENTION

[0006] In one embodiment, this specification discloses a polyvinyl chloride (PVC) composition comprising a PVC resin, an inorganic flame retardant selected from the group consisting of antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), and mixtures thereof, and a rare earth compound selected from the group consisting of rare earth hydroxides, hydrated rare earth oxides, and mixtures thereof. This PVC composition contains 100 phr of PVC resin, has a sample thickness of about 0.8 mm, and has a UL94 classification of V-2 or higher. In certain embodiments, this PVC composition has a UL94 classification of V-0 with a sample thickness of 0.8 mm.

[0007] In certain embodiments, the rare earth compound is yttrium hydroxide, lanthanum hydroxide, cerium hydroxide, neodymium hydroxide, praseodymium hydroxide, hydrated yttrium oxide, hydrated lanthanum oxide, hydrated cerium oxide, hydrated neodymium oxide, hydrated praseodymium oxide, or a mixture thereof. In specific embodiments, the rare earth compound is yttrium hydroxide, lanthanum hydroxide, or a mixture thereof.

[0008] The combination of the rare earth compound and the inorganic flame retardant forms a synergistic relationship. Thus, a PVC composition containing a rare earth compound contains a lesser amount of the inorganic flame retardant than would be required in the absence of the rare earth compound to achieve desirable flame retardant properties (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm). As such, a PVC composition containing a rare earth compound contains less of the inorganic flame retardant compared to the same PVC composition without the rare earth compound and can achieve the same UL94 classification (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm, and in some embodiments, a UL94 classification of V-0 with a sample thickness of about 0.8 mm).

[0009] In another embodiment, the PVC composition comprises a PVC resin, ATO, and a rare earth hydroxide comprising Y(OH)3, La(OH)3, or a mixture thereof. This PVC composition comprises 100 phr of PVC and comprises ATO and the rare earth hydroxide in a total amount of from about 3 phr to about 10 phr. This PVC composition has a UL94 classification of V-0, V-1, or V-2 with a sample thickness of 0.8 mm and contains less ATO than the same PVC composition without the rare earth hydroxide to achieve the same UL94 classification. In certain embodiments of these embodiments, this PVC composition has a UL94 classification of V-0 with a sample thickness of 0.8 mm.

[0010] In a specific embodiment of these embodiments, this PVC composition comprises about 0 phr of chlorinated paraffin.

[0011] In yet another embodiment, disclosed herein is a PVC composition comprising 100 phr of a PVC resin, from about 25 phr to about 50 phr of MDH, and from about 3 phr to about 10 phr of a rare earth hydroxide comprising Y(OH)3, La(OH)3, or a mixture thereof. This PVC composition has a UL94 classification of V-0, V-1, or V-2 with a sample thickness of 0.8 mm. In certain embodiments, this PVC composition has a UL94 classification of V-0 with a sample thickness of 0.8 mm.

[0012] Furthermore, in certain embodiments of these embodiments comprising MDH and a rare earth compound, the PVC composition can contain about 0 phr of ATO (i.e., does not contain ATO) and can have a desired UL94 classification (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm and, in some embodiments, a UL94 classification of V-0 with a sample thickness of about 0.8 mm).

Brief Description of the Drawings

[0013]

Figure 1

[0014]

Figure 2

DETAILED DESCRIPTION OF THE INVENTION

[0015] Before the compositions, articles, and methods are disclosed and described, it should be understood that this disclosure is not limited to the specific structures, process steps, or materials disclosed herein, but extends to their equivalents as would be recognized by those of ordinary skill in the art. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a", "an", and "the" are to be noted to include plural referents unless the context clearly dictates otherwise. Thus, for example, references to "rare earth compounds" or "inorganic refractory agents" should not be construed as limiting in quantity or source, references to "steps" may include multiple steps, references to "producing" or "products" of a reaction or process should not be construed as all of the products of the reaction / process, and references to "treating" may include references to one or more of such treatment steps. Thus, the step of treating can include multiple or repeated treatments of the same material / stream to produce a specified treatment product.

[0016] Numerical values having "about" or "approximately" include typical experimental variations. As used herein, the terms "about" and "approximately" are used interchangeably and mean within a statistically significant range of values such as weight percentages, surface areas, concentration ranges, time frames, distances, molecular weights, temperatures, pH, etc. described. Such ranges can be within one digit of the indicated value or range, typically within 10%, and even more typically within 5%. Sometimes, such ranges can be within the typical experimental error of the standard methods used for measuring and / or determining a given value or range. The acceptable variations encompassed by the term "about" depend on the particular system under study and can be readily understood by one of ordinary skill in the art. Whenever a range is recited within this application, at least all of the integers within that range are contemplated as embodiments of the invention.

[0017] Polyvinyl chloride (PVC) resin is a polymer made from vinyl chloride monomer, and this resin is mixed with other components to make PVC compositions or formulations. These PVC compositions or formulations are used in end-use PVC products.

[0018] Note that the terms "flame" and "fire" are used interchangeably herein when describing the properties of PVC compositions and when describing additives that impart these properties to PVC.

[0019] ATH can be referred to interchangeably as alumina trihydrate, aluminum trihydrate, or aluminum hydroxide trihydrate, and these names can be used interchangeably to mean the same thing when describing this additive.

[0020] The present disclosure relates to a polyvinyl chloride (PVC) composition having desirable properties including flame retardancy and good thermal stability. The PVC compositions disclosed herein can be in rigid and flexible forms. The PVC compositions of the present disclosure contain a PVC resin, an inorganic flame retardant, and a rare earth compound. The inorganic flame retardant of these compositions can be antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), or a mixture thereof. The rare earth compound of these compositions can be a rare earth hydroxide, a hydrated rare earth oxide, or a mixture thereof.

[0021] Accordingly, the present PVC composition can include a PVC resin, an inorganic flame retardant selected from the group consisting of antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), and mixtures thereof, and a rare earth compound selected from the group consisting of rare earth hydroxides, hydrated rare earth oxides, and mixtures thereof, and the composition includes 100 phr of the PVC resin.

[0022] Without being bound by theory, the combination of the rare earth compound and the inorganic flame retardant is believed to be a synergistic relationship. Accordingly, a PVC composition containing a rare earth compound contains a lesser amount of the inorganic flame retardant than is required in the absence of the rare earth compound and achieves the desired flame retardant properties (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm). A PVC composition containing a rare earth compound contains less of the inorganic flame retardant compared to the same PVC composition without the rare earth compound and can achieve the same UL94 classification (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm, and in some embodiments, a UL94 classification of V-0 with a sample thickness of about 0.8 mm).

[0023] As described above, the inorganic flame retardants of these compositions are antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), or mixtures thereof. The inorganic flame retardant may be present in an amount of about 1 phr to about 60 phr within the PVC composition. In the PVC industry, there is interest in PVC compositions that achieve desirable flame retardancy and thermal stability while minimizing the amount of these inorganic flame retardants (specifically ATO).

[0024] In certain embodiments, the inorganic flame retardant is antimony trioxide (ATO). Thus, in certain embodiments, the PVC composition contains ATO. By combining a rare earth compound with ATO, the PVC composition contains less ATO than the same PVC composition without the rare earth compound and can achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0). Although ATO is a very effective flame retardant, it is considered to be very toxic and generates a large amount of smoke during a combustion event. Therefore, minimizing the amount of ATO required to achieve a PVC composition with acceptable flame retardancy and thermal stability is an important advantage.

[0025] In the PVC compositions of the present disclosure, when the inorganic refractory is ATO, it is generally present in an amount of about 1 phr to about 6 phr.

[0026] In certain embodiments, the inorganic flame retardant is MDH. Thus, in certain embodiments, the PVC composition contains MDH. When the inorganic fire retardant is MDH, it is generally present in an amount of about 15 phr to about 50 phr. In certain embodiments containing MDH, the PVC composition contains about 25 phr to about 50 phr of MDH. In other embodiments containing MDH, the PVC composition contains about 30 phr to about 50 phr of MDH. The usefulness of MDH may be limited by its compatibility with a particular PVC composition, and MDH may have relatively limited load-bearing capacity before adversely affecting the physical and aesthetic properties of PVC products. By the combination of rare earth compounds and MDH, the PVC composition contains less MDH than the same PVC composition without rare earth compounds and can achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0). Further, in certain of these embodiments containing MDH and rare earth compounds, the PVC composition can contain about 0 phr of ATO (i.e., does not contain ATO) and can have a desirable UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0).

[0027] In other embodiments, the inorganic flame retardant is ATH. Thus, in certain embodiments, the PVC composition contains ATH. When the inorganic flame retardant is ATH, it is generally present in an amount of about 15 phr to about 50 phr. In certain embodiments containing ATH, the PVC composition contains about 25 phr to about 50 phr of MDH. In other embodiments containing ATH, the PVC composition contains about 30 phr to about 50 phr of MDH. The usefulness of ATH may be limited by its compatibility with a particular PVC composition, and ATH may have a relatively limited load-bearing capacity before adversely affecting the physical and aesthetic properties of the PVC product. By combining a rare earth compound with ATH, the PVC composition can contain less ATH than the same PVC composition without the rare earth compound and achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0). Further, in certain of these embodiments containing ATH and a rare earth compound, the PVC composition can contain about 0 phr of ATO (i.e., be free of ATO) and have the desired UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0).

[0028] In other embodiments, the inorganic flame retardant is a mixture of ATO and MDH and / or ATH. When the inorganic flame retardant is a mixture of MDH and / or ATH and ATO, this mixture is present in an amount of about 16 phr to about 56 phr. By combining a rare earth compound with this inorganic flame retardant mixture, the PVC composition can contain less ATO than the same PVC composition without the rare earth compound and achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0).

[0029] While showing desirable and necessary flame retardancy for the end use of the PVC composition, the present PVC composition enables the reduction of the amount of these inorganic flame retardants (specifically ATO) by adding rare earth compounds to the composition. The present PVC composition also enables the reduction of the amount of these inorganic flame retardants while showing desirable and necessary thermal stability for the end use of the PVC composition.

[0030] As disclosed above, the rare earth compounds include rare earth hydroxides, hydrated rare earth oxides, or mixtures thereof. The rare earths of these compounds are yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), cerium (Ce), or mixtures thereof. In certain embodiments, the rare earths are yttrium (Y), lanthanum (La), neodymium (Nd), praseodymium (Pr), samarium (Sm), or mixtures thereof. In specific embodiments, the rare earth compound can include yttrium compounds (hydroxides and / or hydrated rare earth oxides), lanthanum compounds (hydroxides and / or hydrated rare earth oxides), cerium compounds (hydroxides and / or hydrated rare earth oxides), or mixtures thereof.

[0031] In certain embodiments, the rare earth compound is yttrium hydroxide, lanthanum hydroxide, cerium hydroxide, neodymium hydroxide, praseodymium hydroxide, hydrated yttrium oxide (e.g., Y2O3·3H2O), hydrated lanthanum oxide (e.g., La2O3·3H2O), hydrated cerium oxide (e.g., CeO2·2H2O), hydrated neodymium oxide (e.g., Nd2O3·3H2O), hydrated praseodymium oxide (e.g., Pr2O3·3H2O), or a mixture thereof. In specific embodiments, the rare earth compound is yttrium hydroxide, lanthanum hydroxide, cerium hydroxide, hydrated yttrium oxide (Y2O3·3H2O), hydrated lanthanum oxide (La2O3·3H2O), hydrated cerium oxide (CeO2·2H2O), or a mixture thereof. In further additional embodiments, the rare earth compound is Y(OH)3, Y2O3·3H2O, or a mixture thereof. In other additional embodiments, the rare earth compound is Y(OH)3, Y2O3·3H2O, La(OH)3, La2O3·3H2O, or a mixture thereof. In further embodiments, the rare earth compound is yttrium hydroxide, lanthanum hydroxide, or a mixture thereof.

[0032] In these embodiments of the above specifically listed rare earth compounds, the rare earth compound may further contain a small amount of any other rare earth hydroxide or hydrated rare earth oxide. The rare earth compound generally exists as a mixture. In certain embodiments, the above specifically listed rare earth compounds may further contain a small amount of neodymium (Nd) and / or samarium (Sm) or hydrated oxides. When present in small amounts, these small amounts are typically less than 5 wt% or trace amounts.

[0033] In some embodiments, the particle size of the rare earth compound enables these compounds to be more easily incorporated into the PVC composition. In these embodiments, the rare earth compound can have a particle size of less than 10 microns. In certain specific embodiments among these embodiments, the rare earth compound has a particle size of about 0.1 micron to about 10 microns. Optionally, the particle size distribution can be changed by a grinding and separation process to create a more uniform particle size distribution. The particle size described herein is measured using a Malvern Mastersizer 2000. This particle size can be combined with any of the specifically enumerated embodiments of the rare earth compound.

[0034] In the PVC composition disclosed herein, the rare earth compound may be present in an amount of about 1 phr to about 10 phr. In certain specific embodiments, the rare earth compound may be present in an amount of about 1 phr to about 6 phr. These amounts of the rare earth compound can be combined with any of the specifically enumerated embodiments of the rare earth compound.

[0035] As described herein, by adding these rare earth compounds to the PVC composition, the PVC composition can exhibit the desired and necessary flame retardancy, and at the same time, it is possible to reduce the amount of these inorganic flame retardants (specifically ATO). Thus, the PVC composition disclosed herein achieves the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0) as the same PVC composition that does not contain rare earth compounds while containing a small amount of these inorganic flame retardants (specifically ATO).

[0036] In the PVC composition, rare earth compounds containing rare earth hydroxides, hydrated rare earth oxides, or mixtures thereof herein are considered to release coordinated water species at treatment temperatures exceeding 200°C. These rare earth compounds have the ability to retain water at high temperatures. Without being bound by theory, the release of water can cool and dilute the combustion process of the PVC composition and / or the end-use PVC product. Particularly in the case of PVC wiring, the release of water in the temperature range of 200 - 600°C is advantageous. The endothermic reaction results in the formation of an oxide layer that acts as an insulating barrier and inhibits the release of gases that can contribute to the thermal decomposition of PVC. Without being bound by it, the thermal stabilization properties of rare earth compounds in PVC delay the release of corrosive HCl and are an important characteristic for their surprisingly desirable properties in the PVC composition.

[0037] The PVC compositions of the present disclosure exhibit the desirable and necessary flame retardancy as measured and determined by UL94 classification. UL94 is a plastic flammability standard published by Underwriters Laboratories (USA). This standard classifies plastics from the lowest to the highest flame retardancy based on how plastics burn in six different classifications at various orientations and thicknesses. The PVC compositions disclosed herein have a UL94 classification of V - 2 or higher with a sample thickness of approximately 0.8 mm. In some embodiments, the PVC compositions disclosed herein have a UL94 classification of V - 0 with a sample thickness of approximately 0.8 mm.

[0038]

Table 1

[0039] In certain embodiments, the PVC compositions disclosed herein have a UL94 classification of V - 2, V - 1, or V - 0 with a sample thickness of approximately 0.8 mm. In specific embodiments, the PVC compositions disclosed herein have a UL94 classification of V - 0 with a sample thickness of approximately 0.8 mm.

[0040] The PVC composition disclosed herein contains 100 phr of PVC resin. An inorganic flame retardant and a rare earth compound are added as additives to this PVC resin to result in the PVC composition. This PVC composition can be used in various end-use PVC products. As described above, the inorganic flame retardant and the rare earth compound interact synergistically such that the PVC composition contains a lesser amount (phr) of the inorganic flame retardant than is normally required to achieve a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm. In certain embodiments, the PVC composition can also have a Congo Red of about 90 minutes to about 200 minutes at 200 °C.

[0041] Accordingly, the PVC composition containing the rare earth compound achieves the same UL94 classification (i.e., a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm, and in some embodiments, a UL94 classification of V-0 with a sample thickness of about 0.8 mm) as the same PVC composition without the rare earth compound while containing a small amount of these inorganic flame retardants (specifically ATO).

[0042] The polyvinyl chloride (PVC) composition disclosed herein includes a PVC resin, an inorganic flame retardant selected from the group consisting of antimony trioxide (ATO), magnesium dihydroxide (MDH), aluminum trihydrate (ATH), and mixtures thereof, and a rare earth compound selected from the group consisting of rare earth hydroxides, hydrated rare earth oxides, and mixtures thereof. The composition includes 100 phr of PVC resin and has a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm. In certain embodiments, the PVC composition has a UL94 classification of V-0 with a sample thickness of about 0.8 mm.

[0043] Conventional PVC compositions containing ATO as an inorganic fire retardant contain more ATO than the amount of ATO required for this PVC composition to achieve UL94 classification. Since ATO is considered to be highly toxic, it is advantageous to contain less ATO. In the PVC compositions disclosed herein, the same UL94 classification is achieved while reducing the amount of ATO. In embodiments of the PVC composition where the inorganic flame retardant is ATO, the ratio of ATO to the rare earth compound can be from about 1:3 to about 3:1. In certain embodiments of these embodiments, the rare earth compound includes yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In other embodiments, the ratio of ATO to the rare earth compound is about 1:1. In certain embodiments of these embodiments, the rare earth compound includes yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In additional embodiments, the ratio of ATO to the rare earth compound can be from about 1:1 to about 1:3. In certain embodiments of these embodiments, the rare earth compound includes yttrium hydroxide, lanthanum hydroxide, or a mixture thereof.

[0044] In certain embodiments where the inorganic flame retardant is ATO, the PVC composition can generally contain from about 3 phr to about 10 phr of ATO and rare earth compounds. In certain specific embodiments among these embodiments, the rare earth compounds include yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In a specific embodiment, the PVC composition can contain from about 1 to about 3.5 phr of ATO and from about 1 to about 3.5 phr of rare earth compounds. In certain specific embodiments among these embodiments, the rare earth compounds include yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In a further embodiment, the PVC composition can contain from about 1 to about 3 phr of ATO and from about 1 to about 3 phr of rare earth compounds. In certain specific embodiments among these embodiments, the rare earth compounds include yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In an additional embodiment, the PVC composition can contain less than from about 1 to about 3 phr of ATO and from about 1 to about 3 phr of rare earth compounds. In certain specific embodiments among these embodiments, the rare earth compounds include yttrium hydroxide, lanthanum hydroxide, or a mixture thereof. In any of the specific embodiments showing the phr of ATO and rare earth compounds, the amount of rare earth can be approximately equal to or more than the amount of ATO. Any of these embodiments showing the phr of ATO and rare earth compounds can be combined, as appropriate, with the embodiments of the above ratios.

[0045] In other embodiments, the PVC composition contains MDH. In certain specific embodiments among these embodiments, the PVC composition contains from about 25 phr to about 50 phr of MDH and from about 3 phr to about 10 phr of rare earth compounds. In a specific embodiment, the PVC composition contains from about 30 phr to about 50 phr of MDH. In a specific embodiment, the PVC composition contains from about 3 phr to about 6 phr of rare earth compounds. In certain specific embodiments among these embodiments, the rare earth compounds include yttrium hydroxide, lanthanum hydroxide, or a mixture thereof.

[0046] With the combination of the rare earth compound and MDH, the PVC composition contains less MDH than the same PVC composition without the rare earth compound and can achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0). Further, in certain embodiments among these embodiments containing MDH and rare earth compounds, the PVC composition can contain about 0 phr of ATO (i.e., does not contain ATO) and can have a desirable UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0).

[0047] In embodiments containing MDH but not ATO, the PVC composition can contain about 25 phr to about 50 phr of MDH and about 3 phr to about 10 phr of rare earth compounds, or in certain embodiments, about 30 phr to about 50 phr of MDH and / or about 3 phr to about 6 phr of rare earth compounds. In certain embodiments among these embodiments, the rare earth compound includes yttrium hydroxide, lanthanum hydroxide, or a mixture thereof.

[0048] All embodiments of the PVC composition of the present invention have a UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher. In certain embodiments, these PVC compositions have a UL94 classification with a sample thickness of about 0.8 mm and V-0.

[0049] In addition to the inorganic flame retardant and the rare earth compound, the PVC composition can further contain additional additives for imparting desirable properties to the PVC. The selection of the additives used in the PVC composition is controlled by the performance requirements and specifications of the end-use finished product. For example, underground pipes, siding, intravenous tubes, and flooring require various additives to be suitable for the end-use products because their performance requirements vary greatly. Those skilled in the art understand how to select additives based on the desired end use. These additives can be fillers, plasticizers, colorants, stabilizers, lubricants, organic flame retardants, smoke suppressants, and mixtures thereof.

[0050] It should be noted that certain additives can have multiple functions within the PVC composition, and those skilled in the art will recognize these multiple functions. Therefore, the additives having the functions described below are not limited with respect to their functions, and these additives are classified by what the skilled person can consider as the main functions including a particular additive.

[0051] The amount of the additional additives contained in the PVC composition is also controlled by the performance requirements and / or physical characteristics desired for the end-use finished product and its specifications. The PVC compositions disclosed herein can contain these additional additives in amounts such that these additional additives do not change the decomposition enthalpy of the composition by more than about 10%, and thus do not substantially affect the flame retardant / fire resistant properties of the PVC composition imparted by the inorganic flame retardant in combination with the rare earth compound.

[0052] The additives and the amounts of these additives can be readily determined by those skilled in the art.

[0053] Fillers are mainly used for cost reduction, but may also impart desirable properties such as rigidity, flexural modulus, hardness, and density. Non-combustible fillers may further function as flame retardants or smoke suppressants within a limited range. Examples of fillers that can be included in the PVC compositions described herein include, for example, calcium carbonate, silica, silicate, clay, kaolin, magnesium silicate (talc), glass fiber, mica, wollastonite, sodium sulfate (Na2SO4), sodium sulfate decahydrate, barium sulfate (BaSO4), sulfates of alkaline earth metals, and the like. When present, the filler may be in an amount of about 2 phr to about 400 phr.

[0054] Plasticizers can improve processability by softening the PVC composition and reducing viscosity, and can also improve impact resistance. Some plasticizers that are non-combustible may function as flame retardants within a limited range. Examples of plasticizers that can be included in the PVC composition described herein are, for example, ATBC (acetyl tributyl citrate), DIDP (diisodecyl phthalate), DINP (diisononyl phthalate), DOP (dioctyl phthalate or bis(2-ethylhexyl) phthalate), DOTP (dioctyl terephthalate or bis(2-ethylhexyl) terephthalate), and TOTM (trioctyl trimellitate). Commonly used plasticizers generally include phthalates, trimelliates, adipates, adipate diesters, sebacates, benzoates, epoxies, epoxidized soybean oil, organic phosphates, phosphate esters, polyesters, etc. Examples of phosphates include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, 2-ethylhexyl diphenyl phosphate (SANTICIZER 141), isodecyl diphenyl phosphate (SANTICIZER 148), octyl diphenyl phosphate (DISFLAMMOL DPO), 2-isopropylphenyl diphenyl phosphate, 3-isopropylphenyl diphenyl phosphate, 4-isopropylphenyl diphenyl phosphate, di(2-isopropylphenyl) phenyl phosphate, etc. When present, the plasticizer may be in an amount of about 15 phr to about 150 phr. Rigid PVC does not contain plasticizer (about 0 phr).

[0055] In certain embodiments, the PVC compositions described herein include a plasticizer selected from the group consisting of dioctyl terephthalate (DOTP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and mixtures thereof. In specific embodiments among these embodiments, the PVC composition includes from about 35 phr to about 70 phr of the plasticizer. In certain embodiments, the PVC composition includes about 50 phr of dioctyl terephthalate (DOTP). These specific amounts and types of plasticizers may be included in any of the PVC embodiments shown herein.

[0056] In certain embodiments of the rigid PVC composition including any of the embodiments shown herein, the PVC composition includes about 0 phr of the plasticizer.

[0057] The colorant can be a pigment and / or a dye and is selected based on the color stability, strength, specific gravity, transparency, and electrical properties of the PVC composition and the end-use product. Pigments are generally insoluble in the PVC composition and can be inorganic or organic compounds. Pigments are dispersed throughout the PVC composition. Pigments are generally selected based on color stability and compatibility with the PVC composition. Dyes are generally soluble in the PVC composition and can also be inorganic or organic compounds. Examples of pigments that can be included in the PVC compositions described herein include inorganic pigments and organic pigments. Examples of inorganic pigments include titanium dioxide (TiO2), lead chromate, lead sulfochromate, iron oxide, and ultramarine blue (sodium aluminosilicate containing sulfur). Examples of organic pigments include carbon black, copper phthalocyanine, diazo condensation products, diazo compounds, polycyclic compounds such as dioxazine, quinacridone, isoindolinone, and monoazo compounds such as benzimidazolone. When present, the colorant may be in an amount of from about 1 phr to about 10 phr. When present, the pigment may be in an amount of from about 1 phr to about 10 phr. When present, the dye may be in an amount of from about 1 phr to about 10 phr.

[0058] Stabilizers are commonly used PVC additives. Stabilizers help prevent the initial release of hydrogen chloride, the removal of unstable chlorine ions and carbocation ions, auto-oxidation, and the addition of polyene sequences, all of which contribute to the chain reaction of decomposition. Stabilizers can further increase the resistance of PVC compositions to sunlight, weathering, and thermal aging, and can have an important impact on the physical properties and cost of the formulation. Stabilizers can be supplied in the form of blends for specific applications, where the main components can be metal soaps, metal salts, and organometallic compounds. The selection of heat stabilizers depends on many factors including the technical requirements of the PVC product, regulatory approval requirements, and cost.

[0059] Examples of stabilizers that can be included in the PVC compositions described herein include, for example, antioxidants, anti-ozone agents, light stabilizers, matting agents, acid scavengers, and the like.

[0060] Examples of antioxidants include phenolic antioxidants, analogs of phloretic acid, phosphite esters, phosphites, tri(2,4-di-tert-butylphenyl) phosphite, and thioethers.

[0061] Examples of anti-ozone agents include p-phenylenediamine.

[0062] Examples of light stabilizers include hindered amine light stabilizers (HALS), benzotriazoles, benzophenones, organic nickel compounds, and nickel phenolates.

[0063] Examples of acid scavengers include metal soaps, barium stearate, calcium stearate, hydocalumite, calcium oxide, zinc oxide, magnesium oxide, tin, lead, mono- and dialkyltin salts, and thio acid half esters such as thioglycolates, often known as thiotins or mercaptides.

[0064] Examples of common stabilizers that can impart one or more desirable properties are often dicarboxylic acid half-esters, often referred to as maleates or carboxylates, mono- or dialkyltin compounds, dibutyltin dichloride (DBTC), dimethyltin dichloride (DMTC), monobutyltin trichloride (MBT), monomethyltin trichloride (MMT), tribasic lead sulfate, dibasic lead sulfate, dibasic lead phosphite, dibasic lead phthalate, dibasic lead stearate, lead stearate, etc.

[0065] When present, the stabilizer may be in an amount of about 0.5 phr to about 70 phr. In certain embodiments, the stabilizer may be in an amount of about 0.5 phr to about 10 phr.

[0066] Lubricants are added either externally or internally to reduce friction due to the slippage of the polymer chains (internally) or between the PVC composition and the outer surface. Examples of lubricants that may be included in the PVC compositions described herein are, for example, fatty acids, waxes, hydrocarbon waxes, polyethylene waxes, glycerin dioleate, glycerin monostearate, zinc laurate, glycerin diol, calcium hydroxystearate, EBS ethylene bis(stearamide), hydrogenated castor oil, stearyl stearate, sodium stearyl fumarate, magnesium stearate, zinc stearate, etc. When present, the lubricant may be in an amount of about 0.1 phr to about 1 phr.

[0067] Examples of organic flame retardants that may be included in the PVC compositions described herein are, for example, chlorinated paraffins and brominated organic compounds (polybrominated diphenyl ethers, polybrominated biphenyls, brominated cyclic hydrocarbons, etc.). When present, the organic flame retardant may be present in an amount of about 1 phr to about 25 phr.

[0068] In certain embodiments, the PVC compositions described herein, including any of the specific embodiments, contain organic flame retardants, and in certain of these embodiments, the organic flame retardants are one or more chlorinated paraffins. In these embodiments, the chlorinated paraffins may be present in an amount of about 1 phr to about 25 phr.

[0069] However, these halogenated organic flame retardant additives, specifically chlorinated paraffins, are not considered "environmentally friendly". In some jurisdictions such as within Europe, the use of these chlorinated paraffins is prohibited. Thus, in certain embodiments of the PVC compositions disclosed herein, including any of the specific embodiments, the composition contains about 0 phr of chlorinated paraffins (i.e., does not contain chlorinated paraffins). An advantage of these PVC compositions is that they can achieve UL94 classification and do not require these chlorinated paraffins.

[0070] Examples of smoke suppressants that may be included in the PVC compositions described herein include ammonium octamolybdate, molybdenum trioxide, zinc borate (2ZnO 3B2O3·3.5H2O, or ZnO B2O3·2H2O, or 2ZnO 2B2O3·3H2O), barium borate, copper oxalate, zinc stannate (ZnSnO3), zinc hydroxystannate (ZnSn(OH)6), zinc sulfide, etc. Zinc hydroxystannate may also have some flame retardant properties. When present, the smoke suppressant may be present in an amount of about 1 phr to about 20 phr.

[0071] Further optional additives may include one or more of the following.

[0072] Blowing agents or foaming agents used to create a cellular structure or foam by decomposing upon heating to release gas (these blowing agents or foaming agents include, for example, carbonates, ammonium carbonate, sodium carbonate, azo compounds, azodicarbonamide (azobisformamide) in an amount of about 0.3 phr to about 1 phr),

[0073] Microsphere,

[0074] Water repellent,

[0075] Impact modifiers such as chlorinated polyethylene, MBS (methyl acrylate butadiene styrene), MABS (methacrylate acrylonitrile - butadiene - styrene copolymer), and acrylic copolymers such as elastomers other than (NPDE) a predetermined outside that function to increase toughness,

[0076] Matting agents such as methyl methacrylate,

[0077] Process oil / base such as paraffin oil in an amount of about 1 phr to about 2 phr,

[0078] Processing aids, and

[0079] Solvents and intermediates such as methyl ethyl ketone, methyl isobutyl ketone, and volatile oils,

[0080] One skilled in the art understands how to select the appropriate additives and the amounts (phr) of these additives to be included to provide a PVC composition that meets the performance requirements and / or physical characteristics desired for the end - use finished product and its specifications. This end - use PVC product may also be dyed to meet the desired physical characteristics.

[0081] These additional additives should be PVC - formulation - friendly and must exhibit good compatibility with other PVC composition components. Mechanical properties such as the tensile strength and processability of the PVC product may be important.

[0082] The rare earth compounds used in the PVC compositions described herein have several advantageous properties as PVC additives, including: 1) significant endothermic decomposition that releases water to form a refractory oxide layer; 2) halogen-free; 3) non-toxic, stable; 4) non-volatile and chemically neutral; 5) aesthetically colorless; 6) readily available and economically feasible; 7) easily processable into small particle sizes; 8) low solubility and leachability; 9) acid scavenging ability to capture HCl; 10) heat stabilization; and 11) smoke suppression.

[0083] As described above, the PVC compositions of the present disclosure have a UL94 classification of V-2 or higher with a sample thickness of about 0.8 mm. In certain embodiments, these PVC compositions disclosed herein have a UL94 classification of V-2, V-1, or V-0 with a sample thickness of about 0.8 mm. In specific embodiments, these PVC compositions disclosed herein have a UL94 classification of V-0 with a sample thickness of about 0.8 mm.

[0084] The PVC compositions of the present disclosure can also exhibit desirable heat stability as measured by Congo Red at 200°C. The Congo Red test method determines the heat stability of PVC compositions when treated at elevated temperatures. This method is applicable to all PVC compositions, copolymers, and products based thereon. The Congo Red test is conducted at a temperature of 200°C according to the procedure outlined in the international standard ISO 182-1. The time (in minutes) required for the material to decompose, as indicated by the generation of hydrogen chloride, is determined by the change in color of the Congo Red test paper. In certain embodiments, the PVC compositions disclosed herein, including any of the above specific embodiments, have a Congo Red of about 90 minutes to about 200 minutes at 200°C.

[0085] In certain embodiments, the PVC composition containing the rare earth compound achieves the same Congo Red at 200 °C as the same PVC composition without the rare earth compound while containing a small amount of these inorganic flame retardants (specifically ATO). In further embodiments, the PVC composition containing the rare earth compound achieves an improved Congo Red at 200 °C compared to the same PVC composition without the rare earth compound while containing a small amount of these inorganic flame retardants (specifically ATO).

[0086] The PVC compositions of the present disclosure can also exhibit a desirable limiting oxygen index (LOI) indicative of the flammability of the PVC composition, from the perspective of the minimum concentration of oxygen required to enable the maintenance of the PVC composition. The limiting oxygen index (LOI) of the PVC compositions disclosed herein is determined in accordance with ASTM D2863. In certain embodiments, the PVC compositions disclosed herein, including any of the above specific embodiments, have an LOI of from about 20 to about 35.

[0087] Without being bound by theory, the PVC compositions disclosed herein, which include an inorganic flame retardant in combination with a rare earth compound, may be capable of absorbing heat generated during combustion by undergoing an endothermic release upon heating, particularly throughout the temperature range associated with the combustion of the PVC composition / product. For example, the rare earth compounds disclosed herein release water upon heating. This endothermic release absorbs thermal energy from the surrounding materials to delay combustion, and the release of water further weakens combustion by restricting access to oxygen and cooling the surrounding materials. In some embodiments, the PVC compositions disclosed herein can interrupt other self-sustaining combustion cycles of the PVC. As described above, this can be an endothermic process, and thus, the heat can be reduced below the threshold required to maintain the combustion of the PVC. In addition to absorbing heat by the endothermic release, the water released during oxidation can further cool and dilute the oxygen required for the combustion process.

[0088] The rare earth compounds disclosed herein can also act as Lewis acid catalysts that provide an acid scavenging function by producing a chlorinated Lewis acid catalyst. By this action, acidic gases released during the combustion of PVC compositions such as HCl can be absorbed. During combustion, the rare earth compounds can form an insulating carbonaceous char layer by crosslinking, and due to their strong acid scavenging characteristics, they can capture HCl gas from the smoke in the char layer, thereby reducing the acidity of the smoke. Therefore, the rare earth compounds may be able to encapsulate the PVC and inhibit the release of gases from combustible components that contribute to the continuation of thermal decomposition in other respects. In this way, the combustible portion of the PVC can be effectively isolated from the ignition source during the oxidation of the rare earth compounds by heating. In certain embodiments, the strong oxygen-philicity of the lanthanum rare earth compounds can contribute to the reduction of chlorides during combustion by forming chloride intermediates that are stable up to 1000 °C. Therefore, the rare earth compounds are unexpectedly advantageous additives / components for the PVC compositions disclosed herein. For this reason, the rare earth compounds can enable a reduction in the amount of inorganic flame retardant (specifically ATO) and achieve the same UL94 classification (i.e., a UL94 classification with a sample thickness of about 0.8 mm and V-2 or higher, and in some embodiments, a UL94 classification with a sample thickness of about 0.8 mm and V-0) as the same PVC composition without the rare earth compounds.

[0089] In one particular embodiment of the PVC composition, the composition comprises a PVC resin, ATO, and a rare earth hydroxide comprising Y(OH)3, La(OH)3, or a mixture thereof. This PVC composition comprises 100 phr of PVC and contains ATO and the rare earth hydroxide in a total amount of about 3 phr to about 10 phr. This PVC composition has a UL94 classification with a sample thickness of about 0.8 mm and V-0, V-1, or V-2, and contains less ATO than the same PVC composition without the rare earth hydroxide to achieve the same UL94 classification. In certain embodiments, this PVC composition has a UL94 classification with a sample thickness of about 0.8 mm and V-0. Further, this PVC composition may also have a Congo Red of about 90 minutes to about 200 minutes at 200 °C.

[0090] This embodiment can include any of the ratios of ATO and rare earth compounds described herein. Further, in certain embodiments of these, the PVC composition can include from about 1 to about 3.5 phr of ATO and from about 1 to about 3.5 phr of rare earth compound. In further embodiments of these, the PVC composition can include from about 1 to about 3 phr of ATO and from about 1 to about 3 phr of rare earth compound. In additional embodiments of these, the PVC composition can include less than about 1 to 3 phr of ATO and from about 1 to about 3 phr of rare earth compound.

[0091] These specific embodiments can further include one or more of the additives described herein. Thus, these specific PVC compositions can further include an additive selected from the group consisting of a filler, a plasticizer, a colorant, a stabilizer, a lubricant, an organic flame retardant, a smoke suppressant, and mixtures thereof. These additives are as described above.

[0092] In certain embodiments of this specific PVC composition, the composition contains about 0 phr of chlorinated paraffin (i.e., does not contain chlorinated paraffin).

[0093] In another specific embodiment of the PVC composition, the composition includes 100 phr of PVC resin, from about 25 phr to about 50 phr of MDH, and from about 3 phr to about 10 phr of a rare earth hydroxide including Y(OH)3, La(OH)3, or a mixture thereof. This PVC composition has a UL94 classification of V-0, V-1, or V-2 with a sample thickness of about 0.8 mm. In certain embodiments, this PVC composition has a UL94 classification of V-0 with a sample thickness of about 0.8 mm. Further, this PVC composition may also have a Congo red of about 90 minutes to about 200 minutes at 200 °C.

[0094] With the combination of the rare earth compound and MDH, the PVC composition contains less MDH than the same PVC composition without the rare earth compound and can achieve the same UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or above, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0). Further, in certain embodiments among these embodiments containing MDH and rare earth compounds, the PVC composition can contain about 0 phr of ATO (i.e., does not contain ATO) and can have a desirable UL94 classification (i.e., the UL94 classification with a sample thickness of about 0.8 mm and V-2 or above, and in some embodiments, the UL94 classification with a sample thickness of about 0.8 mm and V-0).

[0095] In a specific embodiment containing MDH and about 0 phr of ATO (i.e., does not contain ATO), the PVC composition can contain about 25 phr to about 50 phr of MDH and about 3 phr to about 6 phr of rare earth compounds.

[0096] In other specific embodiments containing MDH and about 0 phr of ATO (i.e., does not contain ATO), the PVC composition can contain about 30 phr to about 50 phr of MDH and about 3 phr to about 6 phr of rare earth compounds.

[0097] These specific embodiments can further include one or more of the additives described herein. Thus, these specific PVC compositions can further include additives selected from the group consisting of fillers, plasticizers, colorants, stabilizers, lubricants, organic flame retardants, smoke suppressants, and mixtures thereof. These additives are as described above.

[0098] Any of the embodiments of the PVC compositions disclosed herein can be used in a variety of end-use products well known to those skilled in the art. These types of products include, for example, window frames, doors and door frames, drain pipes, water pipes, conduit pipes, roofs, siding, residential and automotive trim, and flooring. Additional products include plastic bottles, packages, adhesive films, and credit cards, bank cards, or membership cards. Further products include electrical cable insulators or housings, medical devices, blood storage bags, cable and wire insulators, fashionable clothing and footwear, inflatable products, and vinyl records. The PVC composition can be included in a fabric coated for a protective coating. Further PVC products include shower curtains and signs. Still further PVC products include sports equipment such as tents, kayaks, and mountaineering gear.

[0099] As described herein, those skilled in the art understand how to select additional additives and the amounts of those additives included to provide a PVC composition that meets the performance requirements and / or physical characteristics desired for these end-use finished products and their corresponding specifications.

[0100] Preparation of the PVC Composition The process of preparing the PVC composition is well-known in the art, and the PVC compositions disclosed herein can be prepared by any of these known processes. These processes are not limited by any particular steps or methods and can generally be anything that results in a mixture of a PVC resin, an inorganic flame retardant, and a rare earth compound in a suitable PVC composition. The rare earth compound and the inorganic flame retardant can first be mixed together with any other additives and then added to the PVC resin. Or, the PVC resin, the rare earth compound, the inorganic flame retardant, and any optional additional additives can all be first mixed together and then processed to result in the PVC composition. The resulting mixture can be either homogeneous or heterogeneous. The process of providing the PVC composition typically further includes grinding and heating. This process may optionally further include downstream processing steps (e.g., a drying step). These processes for preparing the PVC composition and then preparing the end-use product can include any processing steps commonly utilized for preparing the PVC composition and the end-use product as long as the desired physical characteristics of the PVC composition and the end-use PVC are provided and maintained.

[0101] The PVC composition can be prepared by compounding equipment, such as injection molding or extrusion technology products, to provide a PVC composition having excellent dispersibility and thermomechanical properties.

Examples

[0102] The thermogravimetric analysis (TGA) data and differential scanning calorimetry (DSC) data for the examples disclosed in this specification were obtained using a TA Instruments® Q600 SDT while operating TGA-DSC simultaneously. Each sample was heated from room temperature to 1000 °C at a rate of 10 °C / min using air as the active gas at a rate of 90 mL / min and an N2 balance gas at a flow rate of 10 mL / min. In some examples, the TGA and DSC data for each sample were normalized to reflect the weight of the sample at 200 °C and to account for the weight loss from the sample expected to occur during the PVC manufacturing process. The DSC data were further normalized to reflect the decomposition enthalpy of each sample relative to a starting point of 200 °C. The weight loss on ignition was measured by heating the weighed sample in a furnace at 1000 °C for 1 hour and weighing the remaining solid. The particle size was measured using a Malvern Mastersizer 2000. X-ray diffraction was performed using a Bruker D2 Phaser X-ray diffractometer. The crystallite size was determined using the full width at half maximum of the peaks. D xx The size is the size of the particles made from individual crystallites and measured by laser diffraction.

[0103] The density of the PVC sample was measured by observing the volume change when the pre-weighed sample was immersed in water. The Shore A hardness measurement was performed according to ASTM D2240.

[0104] The limiting oxygen index (LOI) of each compounding material was determined, and the flame retardancy of each sample was evaluated according to ASTM D2863. The LOI determines the flammability of a material in terms of the minimum concentration of oxygen required to allow the material to sustain a candle-like combustion behavior. The oxygen concentration is expressed as the volume percentage of oxygen in a flowing mixture of oxygen and nitrogen. Rod-shaped samples with dimensions of 12.5 mm × 100 mm and a thickness of 3 mm were used according to the ISO4589 standard. A fire was applied to the top of the sample, and the combustion time of the ignited sample was recorded at various oxygen concentrations to determine the minimum oxygen concentration required to sustain combustion for at least 3 minutes after removal of the ignition flame. In this test, a Fire Testing Technology (FTT) model apparatus equipped with an oxygen analyzer was used. The test was repeated up to 5 times for each formulation until the LOI was determined with acceptable reliability.

[0105] The Congo Red test was conducted at a temperature of 200 °C according to the procedure outlined in the international standard ISO182-1.

[0106] The smoke density test was conducted according to ASTM D2843. The color stability was tested by placing the sample in an oven at 190 °C for 1 hour. The color was then visually compared to the unheated sample.

[0107] UL94, a standard regarding the flammability safety of plastic materials in device and appliance component testing, was conducted according to the 7th edition of the 94 standard. The summary of the UL94 evaluation is shown in Table 1 above, and the evaluations increase in the order of non-classifiable (NC), HB, V-2, V-1, V-0, 5VB, and 5VA.

[0108] The materials used in the following examples include the following. A high molecular weight vinyl chloride homopolymer produced by a suspension process, the PVC resin k70 listed under CAS number 9002-86-2. Examples of plasticizers used in the following examples include dioctyl terephthalate (DOTP) (CAS number 6422-86-2), diisononyl phthalate (DINP) (CAS numbers 28553-12-0 or 68515-48-0), and diisodecyl phthalate (DIDP) (CAS number 26761-40-0), among others, although other ones can also be used. The chlorinated paraffin used is considered both a flame retardant and a plasticizer, CP52 chlorinated paraffin 52% Cl (CAS number 85535-85-9), and a mixture of chlorinated vegetable fatty acid esters, thus Essebiochlor 45 which is a chlorinated paraffin. Chlorinated paraffins result in various carbon chain lengths and various chlorination levels. These are classified under two CAS numbers 85535-85-9 and 63449-39-8. Examples of inorganic flame retardants used include magnesium dihydroxide (MDH) (CAS number 1309-42-8) and antimony trioxide (ATO) (CAS number 1309-64-4). Two different MDHs were used, although any MDH can be used. The two MDHs used are Ecopiren 3.5C produced from ground brucite (naturally occurring mineral), and Ecopiren 5.5C (CAS number 57-11-4) which is MDH coated with stearic acid. Two inorganic fillers / acid scavengers were used. Omyacarb 2T-AV (CAS number 1317-65-3) is ground calcium carbonate (CaCO3). Winnofil® S is ultrafine CaCO3. The smoke suppressant used was zinc borate (CAS 1332-07-6). A calcium zinc stabilizer from Reagens was also used. Calcium zinc stabilizers for PVC are generally a mixture of calcium carboxylate and zinc carboxylate, although they may contain polyols, epoxidized soybean oil, antioxidants, and organic phosphites.

[0109] Example 1. Synthesis of Yttrium Hydroxide Yttrium hydroxide was prepared by first preparing a Y(NO3)3 solution containing 250 mg of yttrium oxide base / L. The Y(NO3)3 solution was then added to a solution of approximately 10 M NaOH or 5.5 M NH4OH with OH and metal added in a ratio of at least about 6 moles to 1 mole. The precipitate was collected by filtration and washed with DI water until the conductivity of the aqueous solution was less than 30 mS / cm. Filtration was continued to dehydrate the resulting cake. The precipitated hydroxide was then dried at 80 °C to 200 °C for 6 hours. The material was then jet milled.

[0110] The resulting solid was analyzed by TGA / DSC. As shown in Figure 1, mass losses corresponding to the release of water were observed at 250, 390, and 460 °C. As shown in Figure 2, endothermic transitions at approximately 450 °C and 510 °C corresponding to enthalpies of approximately 270 J / g and 155 J / g, respectively, were revealed by DSC. When measuring the particle size, it was found that D50 was approximately 2.2 μm, D90 was approximately 4.2 μm, and D100 was approximately 7.3 μm. Since the loss on ignition was found to be 39.37%, it is shown that the % of Y2O3 is 60.63%. Further analysis of this solid by X-ray diffraction showed that the crystallite size was 15.99 nm.

[0111] Example 2 In the following example, PVC formulations containing approximately minimal amounts of additives are compared. The four formulations of Example 2 are PVC without ATO or the yttrium hydroxide of Example 1, PVC containing ATO, PVC containing the yttrium hydroxide of Example 1, and PVC containing both ATO and the yttrium hydroxide of Example 1. These examples show that ATO is required to achieve the UL94 evaluation required herein, and that adding yttrium hydroxide increases the thermal stability and allows for a reduction in the amount of ATO.

[0112] Comparative Example 2A. Preparation of Polyvinyl Chloride Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the stabilizer was 0.05 kg (5 phr), and the resulting PVC compound was 1.55 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.24 g / cm 3 It was found to be. The hardness of the material was measured to be 91. The limiting oxygen index (LOI) was measured to be 23%. The result of the Congo red test was 122 minutes. The UL94 classification was unable to be classified.

[0113] Comparative Example 2B. Preparation of Polyvinyl Chloride Containing Antimony Trioxide (ATO) Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate), and flame retardant (antimony trioxide) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the stabilizer was 0.05 kg (5 phr), the flame retardant was 0.05 kg (5 phr), and the resulting PVC compound was 1.60 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.25 g / cm 3 It was found to be. The hardness of the material was measured to be 91. The limiting oxygen index (LOI) was measured to be 28%. The result of the Congo red test was 124 minutes. The UL94 classification was determined to be V-0.

[0114] Example 2A. Preparation of Polyvinyl Chloride Containing Yttrium Hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate), and yttrium hydroxide of Example 1 were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the stabilizer was 0.05 kg (5 phr), and the yttrium hydroxide of Example 1 was 0.05 kg (5 phr), and the resulting PVC compound was 1.60 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.26 g / cm 3 It was found that it was. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 22%. The result of the Congo red test was 177 minutes. It was determined that the UL94 classification was unclassifiable.

[0115] Example 2B. Preparation of Polyvinyl Chloride Containing Antimony Trioxide and Yttrium Hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate), flame retardant (antimony trioxide), and yttrium hydroxide of Example 1 were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the stabilizer was 0.05 kg (5 phr), the flame retardant was 0.025 kg (2.5 phr), and the yttrium hydroxide of Example 1 was 0.025 kg (2.5 phr), and the resulting PVC compound was 1.60 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was 1.28 g / cm 3It was found to be so. The hardness of the material was measured to be 88. The limiting oxygen index (LOI) was measured to be 27%. The result of the Congo red test was 175 minutes. The UL94 classification was determined to be V-0.

Table 2

[0116] Example 3 The following examples of PVC formulations show that a smoke suppressant such as zinc borate can be added and similar results are observed. As the amount of yttrium hydroxide increases, the amount of ATO can be decreased and the thermal stability increases.

[0117] Comparative Example 3A. Preparation of Polyvinyl Chloride Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (CaCO3 omyacarb 2T-AV), smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.35 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was 1.512 g / cm 3 It was found to be so. The hardness of the material was measured to be 88. The limiting oxygen index (LOI) was measured to be 25%. The result of the Congo red test was 93 minutes. The UL94 classification was unclassifiable. No color change was observed in terms of color stability.

[0118] Comparative Example 3B. Preparation of Polyvinyl Chloride Containing ATO Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (CaCO3omyacarb 2T-AV), flame retardant (antimony trioxide), smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the flame retardant was 0.04 kg (4 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.531 g / cm 3 It was found to be so. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 30%. The result of the Congo red test was 104 minutes. The UL94 classification was determined to be V-0. No color change was observed in terms of color stability.

[0119] Example 3A. Preparation of Polyvinyl Chloride Containing ATO and Yttrium Hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (CaCO3 omyacarb 2T-AV), flame retardant (antimony trioxide), yttrium hydroxide of Example 1, smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the flame retardant was 0.03 kg (3 phr), the yttrium hydroxide of Example 1 was 0.01 kg (1 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.534 g / cm 3 It was found to be. The hardness of the material was measured to be 90. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 128 minutes. The UL94 classification was determined to be V-0. Slight darkening was observed in terms of color stability.

[0120] Preparation of polyvinyl chloride containing ATO and yttrium hydroxide of Example 1 in Example 3B. Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (CaCO3 omyacarb 2T-AV), flame retardant (antimony trioxide), yttrium hydroxide of Example 1, smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the flame retardant was 0.02 kg (2 phr), the yttrium hydroxide of Example 1 was 0.02 kg (2 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.529 g / cm 3 It was found to be so. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 27%. The result of the Congo red test was 156 minutes. The UL94 classification was determined to be V-0. In terms of color stability, darkening was observed and it was slightly darker than Example 3A.

[0121] Preparation of polyvinyl chloride containing ATO of Example 3C and yttrium hydroxide of Example 1 To a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (dioctyl terephthalate (DOTP)), stabilizer (CaCO3omyacarb 2T-AV), flame retardant (antimony trioxide), yttrium hydroxide of Example 1, smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were added. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the flame retardant was 0.01 kg (1 phr), the yttrium hydroxide of Example 1 was 0.03 kg (3 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.529 g / cm 3 It was found that it is. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 26%. The result of the Congo red test was 156 minutes. The UL94 classification was determined to be V-2. In terms of color stability, darkening was observed and it was slightly darker than Example 3B.

Table 3

[0122] Example 4 The following examples relate to PVC formulations containing magnesium dihydroxide (MDH) as a flame retardant additive. As three examples, a sample containing ATO, a sample in which 2 / 3 of ATO was replaced with the smoke suppressant zinc borate, and a sample in which 2 / 3 of ATO was replaced with the yttrium hydroxide of Example 1 were compared. As a result, it was found that the addition of yttrium hydroxide increased the thermal stability, brought about smoke suppression similar to that of zinc borate, and the PVC did not darken much during heating.

[0123] Preparation of Polyvinyl Chloride Containing MDH and ATO in Comparative Example 4A Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), inorganic flame retardant (Ecopiren 3.5C, magnesium hydroxide (MDH)), stabilizer (CaCO3 omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the inorganic flame retardant MDH was 0.3 kg (30 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the inorganic flame retardant ATO was 0.06 kg (6 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.532 g / cm 3 It was found to be as follows. The hardness of the material was measured to be 88. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 60 minutes. The UL94 classification was determined to be V-0. Some darkening was observed in terms of color stability. The smoke density evaluation was determined to be 72%.

[0124] Preparation of Polyvinyl Chloride Containing MDH, ATO, and Zinc Borate in Comparative Example 4B Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), inorganic flame retardant (Ecopiren 3.5C, magnesium dihydroxide (MDH)), stabilizer (CaCO3 omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were added. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the inorganic flame retardant MDH was 0.3 kg (30 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the inorganic flame retardant ATO was 0.02 kg (2 phr), the smoke suppressant zinc borate was 0.04 kg (4 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.518 g / cm 3 It was found to be. The hardness of the material was measured to be 85. The limiting oxygen index (LOI) was measured to be 28%. The result of the Congo red test was 53 minutes. The UL94 classification was determined to be V-0. In terms of color stability, significant darkening and some blackening due to the presence of zinc were observed. The smoke density evaluation was determined to be 59%.

[0125] Example 4A. Preparation of polyvinyl chloride containing MDH, ATO, and yttrium hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), a plasticizer (diisodecyl phthalate (DIDP)), an inorganic flame retardant (Ecopiren 3.5C, magnesium dihydroxide (MDH)), a stabilizer (CaCO3 omyacarb 2T-AV), an inorganic flame retardant (antimony trioxide (ATO)), yttrium hydroxide of Example 1, and a stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.5 kg (50 phr), the inorganic flame retardant MDH was 0.3 kg (30 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the inorganic flame retardant ATO was 0.02 kg (2 phr), the yttrium hydroxide of Example 1 was 0.04 kg (4 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.39 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.519 g / cm 3 It was found to be. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 27%. The result of the Congo red test was 92 minutes. The UL94 classification was determined to be V-0. In terms of color stability, it was found that there was less darkening than in Comparative Examples 4A and 4B. The smoke density evaluation was determined to be 59%.

Table 4

[0126] Example 5 In the following two examples, a PVC formulation containing chlorinated paraffin, ATO, and zinc borate is compared with a similar PVC formulation in which yttrium hydroxide of Example 1 replaces part of the ATO. As a result, an increase in thermal stability and a decrease in the amount of ATO are observed when using yttrium hydroxide.

[0127] Comparative Example 5. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin and ATO Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the chlorinated paraffin was 0.15 kg (15 phr), the inorganic flame retardant ATO was 0.06 kg (6 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.41 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.568 g / cm 3 It was found to be as follows. The hardness of the material was measured to be 88. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 35 minutes. The UL94 classification was determined to be V-0. Some darkening was observed in terms of color stability.

[0128] Example 5. Preparation of polyvinyl chloride containing chlorinated paraffin, ATO, and yttrium hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), yttrium hydroxide of Example 1, smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the chlorinated paraffin was 0.15 kg (15 phr), the inorganic flame retardant ATO was 0.03 kg (3 phr), the CaCO3 stabilizer was 0.8 kg (80 phr), the yttrium hydroxide of Example 1 was 0.03 (3 phr), the smoke suppressant was 0.02 kg (2 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.41 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.561 g / cm 3 It was found to be. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 27%. The result of the Congo red test was 47 minutes. The UL94 classification was determined to be V-0. Some darkening was observed in terms of color stability.

Table 5

[0129] Example 6 In the following example, PVC formulations containing chlorinated paraffin, magnesium hydroxide (MDH), and zinc borate are compared with cases with and without ATO. The formulations containing yttrium hydroxide of Example 1 show an increase in thermal stability and a decrease in the amount of ATO.

[0130] Comparative Example 6A. Preparation of polyvinyl chloride containing chlorinated paraffin, magnesium dihydroxide (MDH), and zinc borate Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisononyl terephthalate (DINP)), chlorinated paraffin (CP52 chlorinated paraffin 52% Cl), inorganic flame retardant (Ecopiren 5.5C, natural MDH), stabilizer (CaCO3omyacarb 2T-AV), smoke suppressant (zinc borate), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.4 kg (40 phr), the chlorinated paraffin was 0.15 kg (15 phr), the MDH inorganic flame retardant was 0.4 kg (40 phr), the CaCO3 stabilizer was 0.4 kg (40 phr), the smoke suppressant was 0.04 kg (4 phr), and the calcium zinc stearate stabilizer was 0.05 kg (5 phr), and the resulting PVC compound was 2.44 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.53 g / cm 3 It was found to be so. The hardness of the material was measured to be 92. The limiting oxygen index (LOI) was measured to be 24%. The result of the Congo red test was 79 minutes. The UL94 classification was determined to be V-2.

[0131] Comparative Example 6B. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin, Magnesium Dihydroxide (MDH), Zinc Borate, and Antimony Trioxide (ATO) Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisononyl terephthalate (DINP)), chlorinated paraffin (CP52 chlorinated paraffin 52% Cl), inorganic flame retardant (Ecopiren 5.5C, natural MDH), stabilizer (CaCO3omyacarb 2T - AV), smoke suppressant (zinc borate), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.4 kg (40 phr), the chlorinated paraffin was 0.15 kg (15 phr), the MDH inorganic flame retardant was 0.4 kg (40 phr), the CaCO3 stabilizer was 0.4 kg (40 phr), the ATO inorganic flame retardant was 0.05 kg (5 phr), the smoke suppressant was 0.04 kg (4 phr), and the calcium zinc stearate stabilizer was 0.05 kg (5 phr), and the resulting PVC compound was 2.49 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.54 g / cm 3 It was found to be so. The hardness of the material was measured to be 92. The limiting oxygen index (LOI) was measured to be 30%. The result of the Congo red test was 82 minutes. The UL94 classification was determined to be V - 0.

[0132] Example 6A. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin, Magnesium Dihydroxide (MDH), Zinc Borate, and Yttrium Hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisononyl terephthalate (DINP)), chlorinated paraffin (CP52 chlorinated paraffin 52% Cl), inorganic flame retardant (Ecopiren 5.5C, natural MDH), stabilizer (CaCO3omyacarb 2T-AV), smoke suppressant (zinc borate), yttrium hydroxide of Example 1, and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.4 kg (40 phr), the chlorinated paraffin was 0.15 kg (15 phr), the MDH inorganic flame retardant was 0.4 kg (40 phr), the CaCO3 stabilizer was 0.4 kg (40 phr), the smoke suppressant was 0.04 kg (4 phr), the calcium zinc stearate stabilizer was 0.05 kg (5 phr), and the yttrium hydroxide of Example 1 was 0.05 (5 phr), and the resulting PVC compound was 2.49 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.54 g / cm 3 It was found to be. The hardness of the material was measured to be 93. The limiting oxygen index (LOI) was measured to be 25%. The result of the Congo red test was 101 minutes. The UL94 classification was determined to be V-2.

[0133] Example 6B. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin, Magnesium Dihydroxide (MDH), Zinc Borate, Antimony Trioxide (ATO), and Yttrium Hydroxide of Example 1 Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisononyl terephthalate (DINP)), chlorinated paraffin (CP52 chlorinated paraffin 52% Cl), inorganic flame retardant (Ecopiren 5.5C, natural MDH), stabilizer (CaCO3omyacarb 2T-AV), smoke suppressant (zinc borate), inorganic flame retardant (antimony trioxide (ATO)), yttrium hydroxide of Example 1, and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were added. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.4 kg (40 phr), the chlorinated paraffin was 0.15 kg (15 phr), the MDH inorganic flame retardant was 0.4 kg (40 phr), the CaCO3 stabilizer was 0.4 kg (40 phr), the ATO inorganic flame retardant was 0.025 kg (2.5 phr), the smoke suppressant was 0.04 kg (4 phr), the calcium zinc stearate stabilizer was 0.05 kg (5 phr), and the yttrium hydroxide of Example 1 was 0.025 kg (2.5 phr), and the resulting PVC compound was 2.49 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.53 g / cm 3 It was found to be so. The hardness of the material was measured to be 91. The limiting oxygen index (LOI) was measured to be 30%. The result of the Congo red test was 102 minutes. The UL94 classification was determined to be V-0.

Table 6

[0134] Comparative Example 7 In the following examples, PVC formulations containing chlorinated paraffin and increasing amounts of ATO are compared. As a result, it is observed that the UL94 evaluation correlates with the increasing amount of ATO present. These examples do not contain rare earth compounds and require an increased amount of ATO compared to examples containing rare earth compounds to have a desirable UL94 evaluation. Chlorinated paraffin may also be considered undesirable as described herein.

[0135] Comparative Example 7A. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were charged. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the chlorinated paraffin was 0.15 kg (15 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.03 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.448 g / cm 3 It was found that it was. The hardness of the material was measured to be 88. The limiting oxygen index (LOI) was measured to be 24%. The result of the Congo red test was 34 minutes. The UL94 classification was unclassifiable. In the color stability test, significant darkening was observed.

[0136] Comparative Example 7B. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the chlorinated paraffin was 0.15 kg (15 phr), the ATO inorganic flame retardant was 0.03 kg (3 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.06 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.469 g / cm 3 It was found to be so. The hardness of the material was measured to be 89. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 38 minutes. The UL94 classification was determined to be V-2. In the color stability test, less darkening was observed compared to Comparative Example 7A.

[0137] Comparative Example 7C. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the chlorinated paraffin was 0.15 kg (15 phr), the ATO inorganic flame retardant was 0.06 kg (6 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.09 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.478 g / cm 3 It was found to be. The hardness of the material was measured to be 90. The limiting oxygen index (LOI) was measured to be 31%. The result of the Congo red test was 38 minutes. The UL94 classification was determined to be V-2. In the color stability test, less darkening was observed compared to Comparative Example 7B.

[0138] Comparative Example 7D. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the chlorinated paraffin was 0.15 kg (15 phr), the ATO inorganic flame retardant was 0.09 kg (9 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.12 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.496 g / cm 3 It was found to be so. The hardness of the material was measured to be 90. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 40 minutes. The UL94 classification was determined to be V-0. In the color stability test, less darkening was observed compared to Comparative Example 7C.

[0139] Comparative Example 7E. Preparation of Polyvinyl Chloride Containing Chlorinated Paraffin Into a two-roll mill, polyvinyl chloride resin (PVC resin k70), plasticizer (diisodecyl phthalate (DIDP)), chlorinated paraffin (Essebiochlor 45), stabilizer (CaCO3omyacarb 2T-AV), inorganic flame retardant (antimony trioxide (ATO)), and stabilizer (Stab Ca / Zn CBS 209 / 7, calcium zinc stearate) were introduced. The amounts of each component can be adjusted according to the desired properties of the resulting PVC. In this example, the polyvinyl chloride content was 1 kg (100 phr), the plasticizer was 0.35 kg (35 phr), the CaCO3 stabilizer was 0.5 kg (50 phr), the chlorinated paraffin was 0.15 kg (15 phr), the ATO inorganic flame retardant was 0.12 kg (12 phr), and the calcium zinc stearate stabilizer was 0.03 kg (3 phr), and the resulting PVC compound was 2.15 kg in total. The rolls were heated to approximately 150 °C. The materials were mixed for 5 minutes to produce a sheet with a thickness of 0.8 mm. The sheet was cooled to room temperature. When testing the density of the obtained PVC compound sheet, it was found to be 1.511 g / cm 3 It was found that it is. The hardness of the material was measured to be 91. The limiting oxygen index (LOI) was measured to be 29%. The result of the Congo red test was 40 minutes. The UL94 classification was determined to be V-0. In the color stability test, less darkening was observed compared to Comparative Example 7D.

Table 7

[0140] Unless otherwise specified, all numbers representing properties such as the amounts of components, molecular weights, and reaction conditions used in this specification and the claims should be understood to be modified by the term "about" in all examples. Therefore, unless the contrary is indicated, the numerical parameters shown in the following specification and the appended claims are approximate values that can vary depending on the desired properties to be obtained.

[0141] Numerical ranges and parameters which indicate the broad scope of the technology, however, are approximations in spite of the fact that the numerical values set forth in specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective test measurements.

[0142] It will be apparent that the compositions and methods described herein are well adapted to attain the ends and advantages mentioned as well as those inherent therein. It will be further recognized by those skilled in the art that the methods and systems within this specification can be implemented in many ways and, accordingly, are not limited by the foregoing exemplary embodiments and examples. In this regard, any number of features of the different embodiments described herein may be combined into a single embodiment, and alternative embodiments having less than, or more than, all of the features described herein are possible.

[0143] Although various embodiments have been described for the purposes of this disclosure, various changes and modifications may be made within the full contemplated scope of the disclosure. Many other changes will be readily apparent to those skilled in the art and may be made within the spirit of the disclosure.

Claims

1. A polyvinyl chloride (PVC) composition, PVC resin and An inorganic flame retardant selected from the group consisting of antimony trioxide (ATO), magnesium dihydrate (MDH), aluminum trihydrate (ATH), and mixtures thereof, It comprises rare earth compounds selected from the group consisting of rare earth hydroxides, hydrated rare earth oxides, and mixtures thereof, A PVC composition comprising 100 phr of PVC resin, with a sample thickness of approximately 0.8 mm and having an UL94 classification of V-2 or higher.

2. The PVC composition according to claim 1, comprising approximately 1 phr to approximately 10 phr of rare earth compounds.

3. The PVC composition according to claim 1, wherein the rare earth compound is yttrium hydroxide, lanthanum hydroxide, cerium hydroxide, neodymium hydroxide, praseodymium hydroxide, hydrated yttrium oxide, hydrated lanthanum oxide, hydrated cerium oxide, hydrated neodymium oxide, hydrated praseodymium oxide, or a mixture thereof.

4. The PVC composition according to claim 1, wherein the inorganic flame retardant is antimony trioxide (ATO), magnesium dihydroxyl (MDH), or a mixture thereof.

5. The PVC composition according to claim 1, wherein the inorganic flame retardant is ATO, and the PVC composition contains less ATO than the PVC composition that does not contain the rare earth compound, thereby achieving the same UL94 classification.

6. The PVC composition according to claim 5, wherein the rare earth compound is yttrium trihydrate, lanthanum hydroxide, or a mixture thereof, and the ratio of ATO to the rare earth compound is about 1:3 to about 3:

1.

7. The PVC composition according to claim 6, wherein the ratio of ATO to the rare earth compound is approximately 1:

1.

8. The PVC composition according to claim 6, wherein the composition comprises ATO and a rare earth compound in a total amount of about 3 phr to about 10 phr.

9. The PVC composition according to claim 8, wherein the composition comprises about 1 to about 3.5 phr of ATO and about 1 to about 3.5 phr of a rare earth compound.

10. The PVC composition according to claim 1, wherein the PVC composition has a sample thickness of 0.8 mm and has an UL94 classification of V-0, V-1, or V-2.

11. The PVC composition according to claim 1, further comprising an additive selected from the group consisting of fillers, plasticizers, colorants, stabilizers, lubricants, organic flame retardants, smoke suppressants, and mixtures thereof.

12. The PVC composition according to claim 5, comprising approximately 0 phr of chlorinated paraffin.

13. The PVC composition according to claim 1, wherein the composition has a Congo Red temperature of approximately 90 minutes to approximately 200 minutes at 200°C.

14. The PVC composition according to claim 1, wherein the PVC composition has a critical oxygen index of about 20 to about 35.

15. A PVC composition, PVC resin, ATO, and Y(OH) ３ , La(OH) ３ , or rare earth hydroxides containing mixtures thereof, The PVC composition comprises 100 phr of PVC resin and contains ATO and rare earth hydroxides in a total amount of about 3 phr to about 10 phr. A PVC composition having a sample thickness of 0.8 mm and a UL94 classification of V-0, V-1, or V-2, and containing less ATO than the PVC composition that does not contain rare earth hydroxides, thereby achieving the same UL94 classification.

16. The PVC composition according to claim 15, comprising approximately 0 phr of chlorinated paraffin.

17. The PVC composition according to claim 15, further comprising an additive selected from the group consisting of fillers, plasticizers, colorants, stabilizers, lubricants, organic flame retardants, smoke suppressants, and mixtures thereof.

18. A PVC composition, 100 phr PVC resin, MDH of approximately 25 phr to approximately 50 phr, Y(OH) ３ , La(OH) ３ , or mixtures thereof, comprising about 3 phr to about 10 phr of rare earth hydroxides, The PVC composition is a PVC composition having a sample thickness of 0.8 mm and having an UL94 classification of V-0, V-1, or V-2.

19. The PVC composition according to claim 18, comprising approximately 0 phr of ATO.

20. The PVC composition according to claim 18, further comprising an additive selected from the group consisting of fillers, plasticizers, colorants, stabilizers, lubricants, organic flame retardants, smoke suppressants, and mixtures thereof.

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