KR20200107131A - Flame-resisting paint and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a flame retardant paint and a manufacturing method thereof and, more specifically, to a flame retardant paint which minimizes effects on the appearance and processability of a coating film coated with the paint by mixing a copolymer of ethene and tetrafluoroethene, a brominated flame retardant and a flame retardant adjuvant, and further improves flame retardancy, and to a manufacturing method thereof.

Description

Flame retardant paint and its manufacturing method {FLAME-RESISTING PAINT AND MANUFACTURING METHOD THEREOF}

The present invention relates to a flame retardant paint and a method of manufacturing the same, and in particular, to a fluororesin flame retardant paint having improved flame retardancy by mixing a copolymer of ethene and tetrafluoroethene, a bromine flame retardant and a flame retardant auxiliary, and a method of manufacturing the same.

The ethylene tetrafluoroethylene (ETFE) resin, a copolymer of ethene and tetrafluoroethene of the present invention, has excellent heat resistance and chemical resistance, and has been widely used to coat the inner surfaces of metal pipes, metal tanks, and metal bottles of chemical plants and semiconductor plants.

The flame retardant level of the currently applied ETFE resin is UL-94V0, and shows flame retardancy in the thickness of the coating ETFE resin 0.3 to 0.4 T. By the way, when ETFE resin is applied to the lining, the thickness of the coating film is increased to 1.6 to 1.8 T, but in this case, ignition occurs. Therefore, in the case of the lining, higher flame retardant performance is required to secure marketability.

On the other hand, in order to increase flame retardancy, a method of adding a flame retardant when manufacturing a polymer is widely adopted, and types of flame retardants include halogen-based flame retardants, phosphorus-based flame retardants and inorganic flame retardants.

Korean Patent Registration No. 1746739 (registered on July 6, 2017) discloses a flame retardant paint with an inorganic flame retardant added and a method for manufacturing the same, but in the case of inorganic flame retardants, the flame retardant effect is low if not added in large quantities, and paints when added in large quantities There is a problem that affects the physical properties of.

Korean Patent Registration No. 1193037 (registered on October 15, 2012) discloses a flame retardant paint with a phosphorus-based flame retardant added, but in the case of phosphorus-based flame retardants, various applications are limited due to the nature of phosphoric acid, which is acidic. However, there is a problem in that phosphine gas, which has an explosion risk, is released in a closed space.

Accordingly, there is considerable demand for a flame retardant paint having high flame retardancy while minimizing the toxic gas discharged during combustion while not damaging the appearance and workability of the paint.

Korean Patent Registration No. 1746739 (registered on July 6, 2017) Korean Registered Patent No. 1193037 (registered on October 15, 2012)

The present invention has been devised to solve the above problems, and an object thereof is to provide a flame retardant paint including a copolymer of ethene and tetrafluoroethene, a bromine-based flame retardant, and a flame retardant aid.

In addition, another object of the present invention is to provide a method of manufacturing the flame retardant paint.

The present invention can also aim to achieve these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification, in addition to the above-described clear objects.

In order to achieve the object as described above, the flame retardant paint of the present invention,

100 parts by weight of a copolymer of ethene and tetrafluoroethene,

1 to 15 parts by weight of a brominated flame retardant, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight, and

It is characterized in that it comprises 0.5 to 6.5 parts by weight of the flame retardant aid, preferably 1 to 4.5 parts by weight, more preferably 1.5 to 3.75 parts by weight.

In addition, the copolymer of ethene and tetrafluoroethene may be a copolymer of 100 mole parts of ethene and 90 to 120 mole parts of tetrafluoroethene, preferably 95 to 110 mole parts.

In addition, the copolymer of ethene and tetrafluoroethene may be an alternating copolymer.

In addition, the weight ratio of the bromine-based flame retardant to the flame retardant auxiliary may be 0.5 to 3, preferably 1 to 2.5, more preferably 1.5 to 2.

In addition, the thickness of the coating film formed by the flame retardant paint may be 0.7 to 2.2 mm, preferably 0.8 to 2.1 mm.

In addition, the bromine-based flame retardant is tetrabromobisphenol-A (tetrabromobisphenol-A. TBBA, TBBPA), tetrabromobisphenol-A ether (tetrabromobisphenol-A ether), 1,2-bis (tribromophenoxy) ethane (1,2-bis(tribromophenoxy)ethane), 2,4,6-tribromophenyl glycidyl ether (2,4,6-tribromophenyl glycidyl ether), tetrabromophthalic anhydride, Dimethyl 4-bromophthalate, tetrabromo phthalic disodium, decabromodiphenyl ether, decabromodiphenyl oxide (DBDPO), decabromo phthalic disodium Bromodiphenyl ethane, 1,4-bis (pentabromophenoxy) tetrabromobenzene (1,4-bis (pentabromophenoxy) tetrabromobenzene), tribromophenoxy ethane, 1, 2-bis (pentabromophenyl) ethane (1,2-bis (pentabromophenyl) ethane), bromo trimethylphenyl indane, pentabromobenzyl acrylate, pentabromodiphenyl benzyl bro Pentabromodiphenyl benzyl bromide, hexabromobenzene, pentabromotoluene, 2,4,6-tribromophenyl maleic imide (2,4,6-tribromophenyl maleic imide), hexa Bromocyclodecane (hexabromocyclodecane. HBCD), hexabromocyclododecane, penta Bromo chlorocyclohexane, bis(2,3-dibromopropyl ether) (bis(2,3-dibromopropyl ether)), tri(2,3-dibromopropyl)iso-melamine ester ( tri(2,3-dibromopropyl)iso-melamine ester), 1,2-bis(tetrabromophthalimido)ethane (1,2-bis(tetrabromophthalimido)ethane), N,N'-ethylene-bis(3 ,4,5,6-tetrabromophthalimide) (N,N'-ethylene-bis(3,4,5,6-tetrabromophthalimide), N,N'-1,2-bis(ethylene-bis( 5,6-dibromonorbornane-2,3-dicarboximide) (N,N'-1,2-bis(ethylene-bis(5,6-dibromonorbornane-2,3-dicarboximide)), Brominated styrene copolymer, tetrabromobisphenol A carbonate oligomer, poly(pentabromobenzyl acrylate) (poly(pentabromobenzyl acrylate)), poly(dibromo It may be selected from the group consisting of phenylene ether) (poly(dibromo phenylene ether)) and mixtures thereof, and preferably 1,2-bis (tetrabromophthalimido) ethane.

In addition, the flame retardant index of the bromine-based flame retardant constituting the present invention may be 0.1 to 2, preferably 0.2 to 1, more preferably 0.3 to 0.7.

In addition, the flame retardant aid may be selected from the group consisting of antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, molybdate, zirconium, and mixtures thereof.

In addition, the average particle diameter of the copolymer of ethene and tetrafluoroethene may be 150 to 400 µm, preferably 200 to 350 µm, more preferably 230 to 330 µm.

And, the method of manufacturing the flame retardant paint of the present invention

(A) 100 parts by weight of a copolymer of ethene and tetrafluoroethene,

1 to 15 parts by weight of a brominated flame retardant, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight, and

Preparing 0.5 to 6.5 parts by weight of a flame retardant aid, preferably 1 to 4.5 parts by weight, more preferably 1.5 to 3.75 parts by weight;

(B) Preparing a mixture by mixing the copolymer of ethene and tetrafluoroethene, a bromine-based flame retardant, and a flame retardant auxiliary;

(C) Sieving the mixture

It characterized in that it comprises a.

In addition, the mixing of step (B) may be performed at a mixing speed of 450 to 600 rpm, preferably 400 to 700 rpm, more preferably 350 to 800 rpm.

And, the mixing of step (B) may be performed for 10 to 40 minutes, preferably 12 to 30 minutes, more preferably 15 to 20 minutes.

In addition, the sieving of step (C) may be made of a sieve of 10 to 70 mesh, preferably 20 to 65 mesh, more preferably 30 to 60 mesh.

The flame retardant paint according to the present invention can significantly increase flame retardancy by mixing a bromine-based flame retardant and a flame retardant auxiliary in ETFE resin, which is a copolymer of ethene and tetrafluoroethene.

The flame retardant paint of the present invention provides a flame retardant effect by reducing the concentration of oxygen and hydroxyl radicals, which are active radicals, and stopping the chain reaction by adding a bromine-based flame retardant as a radical scavenger, and the cleavage of C-Br bonds during combustion is an endothermic reaction. As a result, it has the effect of reducing the heat of combustion of the combustible material, and also has the effect of blocking oxygen by generating a non-combustible gas during decomposition.

In addition, by adding a bromine-based flame retardant, there is no defect in the appearance of the coating film coated with the coating material, and the workability of the coating material may not be deteriorated.

The flame retardant paint of the present invention can maximize the flame retardant effect by adding a flame retardant auxiliary in an appropriate ratio, and minimize the emission of toxic gases during combustion by lowering the bromine-based flame retardant content.

In addition, the flame retardant paint of the present invention contains an antimony compound as a flame retardant auxiliary. The antimony-based compound reacts with a bromine-based flame retardant to generate SbOBr or SbBr ₃ , of which SbOBr exhibits a dehydrocarbonation effect, and SbBr ₃ is a heavy gas, which can increase flame retardancy through the shielding effect of oxygen.

Hereinafter, preferred embodiments of the present invention will be described in detail.

However, the following is only for describing in detail by exemplifying specific embodiments, and since the present invention may be variously changed and may have various forms, the present invention is not limited to the illustrated specific embodiments. It is to be understood that the present invention includes all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

In addition, in the following description, there are many specific matters such as specific elements, etc., which are provided only to help a more general understanding of the present invention, and the present invention can be practiced without these specific matters. It is self-evident to those who have the knowledge of Further, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

In addition, terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

In this application, expressions in the singular include plural expressions unless the context clearly indicates otherwise.

In the present application, terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the present application, terms such as'include','include', or'have' are intended to refer to the presence of features, elements (or constituents), etc. described in the specification, but one or more other features or It does not mean that the component or the like does not exist or cannot be added.

In this application, the'flame retardant index' is defined as follows:

Flame retardant index

= (Number of nitrogen atoms in flame retardant molecule) / (number of oxygen atoms in flame retardant molecule).

The flame retardant paint of the present invention is 100 parts by weight of a copolymer of ethene and tetrafluoroethene, 1 to 15 parts by weight of a bromine-based flame retardant, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight, and a flame retardant auxiliary It is characterized by including 0.5 to 6.5 parts by weight, preferably 1 to 4.5 parts by weight, more preferably 1.5 to 3.75 parts by weight, and does not generate harmful gases during combustion within this range and has excellent flame retardancy.

ETFE (ethylene tetrafluoroethylene) resin, a copolymer of ethene and tetrafluoroethene constituting the flame retardant paint of the present invention, has excellent heat resistance and chemical resistance, and is used for lining processing of chemical plants and semiconductor plant facilities. The lining processing refers to covering the inner surface of plant equipment such as metal pipes, metal tanks, metal bottles, and the like.

The flame retardant level of the currently applied ETFE resin is UL-94V0, and shows flame retardancy in the thickness of the coating ETFE resin 0.3 to 0.4 T. By the way, when ETFE resin is applied to the lining, the thickness of the coating film is increased to 1.6 to 1.8 T, but in this case, ignition occurs. Therefore, in the case of lining, the FM4922 certification level, which is higher flame retardant performance, is required to secure marketability.

The inventors of the present invention have reached the completion of the present invention that exhibits a better flame retardant effect as compared to TL-081 (Asahi Glass, Japan), an ETFE resin certified by FM4922 by adding an appropriate flame retardant and a flame retardant auxiliary to the ETFE resin.

In the present invention, the copolymer of ethene and tetrafluoroethene may be a copolymer of 100 mole parts of ethene and 90 to 120 mole parts of tetrafluoroethene, preferably 95 to 110 mole parts. When the ratio of the tetrafluoroethene is less than the above range, heat resistance is reduced to accelerate aging of the coating film, and chemical properties are weakened. On the contrary, if it exceeds the above range, mechanical strength is lowered, so that adhesion to metal is deteriorated and workability is weakened.

The copolymer of ethene and tetrafluoroethene may be an alternating copolymer. Since the blocking effect by fluorine atoms does not reach more than one C-C bond length, if the copolymer is not an alternating copolymer, oxidation stability due to heat or ultraviolet rays is inferior.

The copolymer of ethene and tetrafluoroethene may have an average particle diameter of 40 to 350 µm, preferably 50 to 330 µm, and more preferably 230 to 330 µm. If the average particle diameter of the copolymer is less than the above range, bubbles are easily generated during the formation of the coating film or defects in the appearance of the coating film are likely to occur. Conversely, when the average particle diameter of the copolymer exceeds the above range, there is a problem that the coating film thickness is formed unevenly during processing.

Halogen flame retardants act competitively with oxygen against radicals generated in the combustion process, and halogenated radicals do not propagate chain reactions, so the fire goes out. Specifically, active radicals OH and H, which play a propelling role of combustion, are trapped and stabilized by HX. HX is non-flammable and has a dilution effect and an effect of blocking oxygen, thereby exhibiting flame retardancy.

Of the halogens, iodine is the most effective flame-retardant element, but it is expensive and lacks heat resistance and light resistance, and chlorine and fluorine are very poor in radical trapping ability or have little effect.

On the other hand, bromine is the second most effective flame retardant element after iodine, and it is the most widely used because it can exert a high flame retardant effect in a small amount that does not affect the physical properties of the polymer. In particular, the phenomenon that only traces of carbonization are visible even after digestion is a distinctive feature from existing flame retardants.

Inorganic flame retardants are inorganic compounds that decompose during combustion to release non-combustible gases such as water, nitrogen, ammonia, or carbon dioxide. Aluminum hydroxide and magnesium hydroxide are representative flame retardants that have a physical action, and they are decomposed through endothermic reactions to produce water. However, in order to exert an effect, the flame retardant must be added in an amount of 50% by weight or more, and thus the physical properties of the resin are deteriorated.

Phosphorus-based flame retardants thermally decompose during combustion to produce phosphoric acid, and dehydration and carbonization by phosphoric acid and hydrogen and hydroxy radical capture of phosphorus-containing radicals contribute to flame retardancy. It facilitates the processing of the flame retardant resin and has good compatibility and weather resistance, but the disadvantage is that heat resistance is lowered.

The flame retardant paint of the present invention contains 1 to 15 parts by weight, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight of a bromine-based flame retardant per 100 parts by weight of the copolymer of ethene and tetrafluoroethene. It is desirable. If the content of the brominated flame retardant is less than the above range, sufficient self-extinguishing properties are not exhibited, and thus it is difficult to secure the expected flame retardant effect. If the content of the brominated flame retardant is exceeded, the melt viscosity increases, making it difficult to secure a uniform coating thickness.

In the present invention, the bromine-based flame retardant is tetrabromobisphenol-A (TBBA, TBBPA), tetrabromobisphenol-A ether, 1,2-bis (tribromophenoxy) ethane (1,2-bis(tribromophenoxy)ethane), 2,4,6-tribromophenyl glycidyl ether (2,4,6-tribromophenyl glycidyl ether), tetrabromophthalic anhydride, Dimethyl 4-bromophthalate, tetrabromo phthalic disodium, decabromodiphenyl ether, decabromodiphenyl oxide (DBDPO), decabromo phthalic disodium Bromodiphenyl ethane, 1,4-bis (pentabromophenoxy) tetrabromobenzene (1,4-bis (pentabromophenoxy) tetrabromobenzene), tribromophenoxy ethane, 1, 2-bis (pentabromophenyl) ethane (1,2-bis (pentabromophenyl) ethane), bromo trimethylphenyl indane, pentabromobenzyl acrylate, pentabromodiphenyl benzyl bro Pentabromodiphenyl benzyl bromide, hexabromobenzene, pentabromotoluene, 2,4,6-tribromophenyl maleic imide (2,4,6-tribromophenyl maleic imide), hexa Bromocyclodecane (hexabromocyclodecane. HBCD), hexabromocyclododecane, penta Bromo chlorocyclohexane, bis(2,3-dibromopropyl ether) (bis(2,3-dibromopropyl ether)), tri(2,3-dibromopropyl)iso-melamine ester ( tri(2,3-dibromopropyl)iso-melamine ester), 1,2-bis(tetrabromophthalimido)ethane (1,2-bis(tetrabromophthalimido)ethane), N,N'-ethylene-bis(3 ,4,5,6-tetrabromophthalimide) (N,N'-ethylene-bis(3,4,5,6-tetrabromophthalimide), N,N'-1,2-bis(ethylene-bis( 5,6-dibromonorbornane-2,3-dicarboximide) (N,N'-1,2-bis(ethylene-bis(5,6-dibromonorbornane-2,3-dicarboximide)), Brominated styrene copolymer, tetrabromobisphenol A carbonate oligomer, poly(pentabromobenzyl acrylate) (poly(pentabromobenzyl acrylate)), poly(dibromo 1,2-bis (tetrabromophthalimido) ethane in that it can be selected from the group consisting of phenylene ether) (poly(dibromo phenylene ether)) and mixtures thereof, and is not easily decomposed at high temperatures and exhibits flame retardancy. This is desirable.

In addition, the flame retardant index of the bromine-based flame retardant constituting the present invention may be 0.1 to 2, preferably 0.2 to 1, more preferably 0.3 to 0.7. In this application, the'flame retardant index' is defined as follows:

Flame retardant index

= (Number of nitrogen atoms in flame retardant molecule) / (number of oxygen atoms in flame retardant molecule).

The flame retardant index is an indirect index for the flame retardant performance of the brominated flame retardant among the flame retardant paints of the present invention.When the value is within the above range, it is optimal while maintaining the physical properties of the coating film for the copolymer of ethene and tetrafluoroethene. It shows the flame retardant performance of

When only the flame retardant is added to the ethene and tetrafluoroethene copolymer, combustion gas is severely generated. Therefore, it is required to maximize the flame retardant properties and reduce the content of the brominated flame retardant by mixing flame retardant aids.

The flame retardant aid of the present invention can be used without limitation, as long as it is a flame retardant aid known in the art, for example, flame retardant compounds such as antimony trioxide and antimony pentoxide, metal antimony such as sodium antimonate, and antimony trichloride, and other hydroxides. It may be selected from the group consisting of aluminum, magnesium hydroxide, zinc borate, zinc stannate, molybdate, zirconium, and mixtures thereof.

The antimony compound itself has extremely limited flame retardancy, but when combined with a halogenated flame retardant, it exhibits a synergism effect that greatly increases the radical trapping effect. Typically, antimony trioxide reacts with halogen to generate SbOCl and SbCl ₃ , and SbCl generates HCl to exhibit a radical trapping effect, SbCl _{3 is} also a heavy gas and exhibits oxygen shielding effect, and SbOCl exhibits dehydrocarbonation. .

The flame retardant aid may be included in an amount of 0.5 to 6.5 parts by weight, preferably 1 to 4.5 parts by weight, more preferably 1.5 to 3.75 parts by weight, per 100 parts by weight of the copolymer of ethene and tetrafluoroethene. If the content of the flame retardant auxiliary is less than the above range, it is difficult to secure the flame retardant effect because the synergistic effect with the brominated flame retardant is insignificant. On the contrary, if it exceeds the above range, it is difficult to secure processability by lowering the flexibility of the coating.

The weight ratio of the bromine-based flame retardant to the flame retardant aid may be 0.5 to 3, preferably 1 to 2.5, more preferably 1.5 to 2. If the weight ratio of the bromine-based flame retardant is less than the above range, it does not exhibit sufficient self-extinguishing properties and thus does not meet the expected flame retardant effect.

The thickness of the coating film formed by the flame retardant paint of the present invention may be 0.7 to 2.2 mm, preferably 0.8 to 2.1 mm. If the thickness of the coating film is less than the above range, when the shape of the object to be coated is complicated, it may be difficult to form a normal coating film, and the chemical properties guaranteed by the lining are inevitably weak. Conversely, when the above range is exceeded, air bubbles in the coating film generated during the formation of the coating film are difficult to be completely removed, resulting in poor appearance.

And, the method of manufacturing the flame retardant paint of the present invention

(A) 100 parts by weight of a copolymer of ethene and tetrafluoroethene,

1 to 15 parts by weight of a brominated flame retardant, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight, and

Preparing 0.5 to 6.5 parts by weight of a flame retardant aid, preferably 1 to 4.5 parts by weight, more preferably 1.5 to 3.75 parts by weight;

(B) Preparing a mixture by mixing the copolymer of ethene and tetrafluoroethene, a bromine-based flame retardant, and a flame retardant auxiliary;

(C) Sieving the mixture

It characterized in that it comprises a.

The mixing of step (B) may be made at a mixing speed of 450 to 600 rpm, preferably 400 to 700 rpm, more preferably 350 to 800 rpm, and if the mixing speed is less than the above range, dispersibility with the flame retardant Since it is insufficient, it is difficult to secure the expected flame retardant effect. Conversely, if it exceeds the above range, the flame retardant and the flame retardant aid may aggregate due to excessive dispersion and impair the appearance.

In addition, the mixing of step (B) may be performed for 10 to 40 minutes, preferably 12 to 30 minutes, more preferably 15 to 20 minutes, and if the mixing time is less than the above range, dispersibility with the flame retardant is insufficient. Therefore, it is difficult to secure the expected flame retardant effect. Conversely, if it exceeds the above range, the flame retardant and the flame retardant aid may aggregate due to excessive dispersion and impair the appearance.

The sieving of step (C) may be made of a sieve of 10 to 70 mesh, preferably 20 to 65 mesh, more preferably 30 to 60 mesh.If the sieve size is less than the above range, ethene and tetrafluoro Since the copolymer of Loethene does not pass through the sieve, the content may vary. Conversely, if it exceeds the above range, foreign matters and the like cannot be filtered out and contamination in the paint cannot be prevented.

Hereinafter, an embodiment of the present invention will be described.

Example

Comparative Examples 1 to 11: No flame retardant auxiliary

As shown in Table 1 below, each component was added and mixed in the corresponding content, and after degreasing with 1.0 T SUS PLATE solvent, a coating film was formed to be 1.2 to 1.5 T, and then 260° C. 30 minutes, 270° C. 30 minutes, 280° C. 30 minutes It was fired step by step.

The compounds used are as follows:

TL-581: ETFE resin (Asahi Glass, Japan), a copolymer of ethene and tetrafluoroethene, with a film thickness of 2002 µm or more, and the molding method is rotational molding method

Brominated flame retardant: 1,2-Bis(Tetrabromophthalimido)Ethane (UNIBROM, USA)

Inorganic flame retardant 1: magnesium hydroxide

Inorganic flame retardant 2: aluminum hydroxide

Inorganic flame retardant 3: Hydrated calcium borate (Sibelco, Belgium)

Phosphorus flame retardant 1: aluminum diethylphosphinate

Phosphorus flame retardant 2: ammonium polyphosphate

Phosphorus flame retardant 3: trifetyl phosphate.

Unit: g Comparative example One 2 3 4 5 6 7 8 9 10 11 TL-581 100 100 100 100 100 100 100 100 100 100 100 Brominated flame retardant 5 7.5 10 Inorganic flame retardant 1 3 Inorganic flame retardant 2 3 Inorganic flame retardant 3 3 5 10 Phosphorus flame retardant 1 5 Phosphorus Flame Retardant 2 5 Phosphorus Flame Retardant 3 5

Test Example 1: Coating property evaluation (1)

In order to compare the flame retardant effect according to the type of flame retardant, the properties of the paints prepared in Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Table 2.

Appearance: The appearance was observed with the naked eye to evaluate whether boiling, air bubbles, or the like occurred.

Workability: The specimen was bent 180° to check the presence or absence of cracks, and the deformability of the material was evaluated.

Flame retardancy: After burning for 60 seconds at 15 cm perpendicular to the lined specimen using Gas Torch, ignition was confirmed by observing the state of the coating film.

Film thickness before fire extinguishing (T): The film thickness before combustion was measured.

Film thickness after fire extinguishing (T): The film thickness after combustion was measured.

division Comparative example One 2 3 4 5 6 7 8 9 10 11 Exterior ○ ○ △ x x ○ △ x △ x x Processability ○ ○ △ x x x x x x Flame retardant △ ○ ○ x x x △ x x Fire hydrant
Film thickness 1.6
~1.8 1.7
~1.8 1.5
~1.7 1.5
~1.8 1.7
~1.8 1.6
~1.7 1.5
~1.8 1.7
~1.8 1.6
~1.7 After digestion
Film thickness 1.0
~1.2 1.4
~1.5 1.4
~1.5 0.2
~0.3 0.2
~0.3 Measure
Impossible 0.7
~0.8 Measure
Impossible Measure
Impossible

As shown in Table 2, Comparative Examples 1 to 11 obtained results in which the effect on the appearance and processability reduction was negligible while securing excellent flame retardancy through a brominated flame retardant. However, it has been confirmed that the combustion gas is severely generated during combustion.

When the inorganic flame retardant 1 (magnesium hydroxide. Comparative Example 4) and the inorganic flame retardant 2 (aluminum hydroxide. Comparative Example 5) are added, the processing temperature of magnesium hydroxide and aluminum hydroxide is higher than that of the ETFE resin at 280 to 305°C. It is low (200 to 250° C.) and appearance defects (boiling, air bubbles) occurred even with small application.

When Hydrated calcium borate, which is an inorganic flame retardant 3, was added (Comparative Examples 6 to 8), it was stable up to 330°C and was not decomposed. However, as the content increased, the appearance was affected and the flame retardant effect was extremely insignificant.

In addition, in the case of the phosphorus-based flame retardant (Comparative Examples 9 to 11), even a small amount of application affects the appearance deterioration, and the flame retardancy tends to be partially improved, but the processability is remarkably decreased.

Control Examples and Examples 1 to 4: Use of flame retardant auxiliary

In order to solve the combustion gas problem shown in Comparative Examples 1 to 3, an experiment was conducted to maximize flame retardant properties and reduce the content of bromine flame retardants by mixing antimony flame retardant aids.

Examples 1 to 4 were mixed for 15 to 20 minutes at 500 rpm by adding each component in the corresponding content as shown in Table 3, and sieved with 30 to 60 mesh to prepare the flame retardant paint of the present invention. 1.0 T SUS PLATE After solvent degreasing, a coating film was formed to be 1.6 to 1.9 T, followed by sintering step by step at 260°C for 30 minutes, 270°C for 30 minutes, and 280°C for 30 minutes.

The compounds used are as follows:

TL-081: ETFE resin (Asahi Glass, Japan), which is a copolymer of ethene and tetrafluoroethene, with a film thickness of 1000 µm or less and the molding method is electrostatic powder coating

Flame retardant aid: Antimony trioxide (Sb ₂ O ₃ ).

Unit: g Example Contrast One 2 3 4 TL-581 100 100 100 100 TL-081 100 Brominated flame retardant 2.5 3.75 5.0 6.25 Flame retardant aid 1.5 2.25 3.0 3.75

Test Example 2: Evaluation of coating properties (2)

In order to compare the properties according to the addition of the flame retardant auxiliary, the physical properties and flame retardancy of the flame retardant paints prepared in Examples 1 to 4 were measured in the same manner as described above, and the results are shown in Table 4.

division Example One 2 3 4 Exterior ○ ○ △ △ Film thickness 1.8~1.9 1.7~1.8 1.7~.1.8 1.6~1.7 Processability ○ ○ △ △ Flame retardant ○ ○ ○ ○ Film thickness after digestion 1.6 1.5~1.6 1.6 1.5

As shown in Table 4, Examples 1 to 4 showed excellent flame retardancy at a level that did not impair appearance and processability by applying a bromine-based flame retardant and antimony trioxide as a flame retardant auxiliary.

Test Example 3: In-depth evaluation of flame retardant effect

A control example is TL-081, an ETFE resin that has obtained FM4922 certification, and is a comparative evaluation standard of Examples 1 to 4.

In order to clearly confirm the flame-retardant effect, a flame propagation test was conducted for the above control examples and Examples 1 to 4, and the average continuous heat, critical heat flux during extinguishing, the total amount of heat released, and the maximum heat release rate were repeatedly measured three times and the average value was derived. And the results are shown in Table 5.

Average sustained combustion heat (MJ/m ² ): This is the product of the time to reach each point as the flame progresses and the amount of radiant heat at that time, and the smaller it is, the more it means that combustion can continue even with a smaller radiant heat source. The larger the value, the better the flame retardant effect.

Critical heat flux during fire extinguishing (kW/m ² ): It is a critical point that appears in boiling heat transfer, and refers to the point at which heat transfer efficiency rapidly decreases. The larger the value, the better the flame retardant effect.

Total heat released (MJ): The smaller the value, the better the flame retardant effect.

Maximum heat release rate (kW): The smaller the value, the better the flame retardant effect.

Flame drop: The smaller the value, the better the flame retardant effect.

Final flame reach distance (mm): The smaller the value, the better the flame retardant effect.

Ignition time: The higher the value, the better the flame retardant effect.

Extinguishing time: The smaller the above value, the better the flame retardant effect.

division Example Contrast One 2 3 4 Average continuous heat of combustion 5.55 5.84 7.73 6.56 5.44 Critical heat flux during digestion 49.5 48.3 49.5 50.4 40 Total calories released 0.18 0.32 0.036 0.19 0.17 Highest heat release rate 1.03 1.05 0.65 0.80 1.36 Fireworks fall none none none none none Final flame reach 100 100 100 50~100 230~300 Ignition time 40-50 seconds 60 seconds 45 seconds 40 seconds 1-2 minutes Digestion time 9-10 minutes 5-10 minutes 5-8 minutes 7-9 minutes 4-10 minutes

As shown in Table 5, as a result of the flame propagation test, Examples 1 to 4 in which the bromine-based flame retardant and antimony trioxide were applied showed excellent flame retardant effects because the maximum heat release rate was low and the ignition time was short.

On the other hand, the control example to which the brominated flame retardant and antimony trioxide were not applied showed relatively high values in the maximum heat release rate, the final flame reach distance, and the ignition time.

In addition, it was confirmed that the best flame retardant effect was exhibited in Example 3 when considering the total amount of heat released and the highest heat release rate.

In the above, preferred embodiments of the present invention have been described, but the present invention is not limited to the specific embodiments described above, and those of ordinary skill in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Therefore, the scope of the present invention should not be construed as limited to the above embodiments, and should be determined by the claims and equivalents to the claims to be described later.

Claims (3)

100 parts by weight of a copolymer of ethene and tetrafluoroethene,
1 to 15 parts by weight of a brominated flame retardant, and
Flame retardant paint containing 0.5 to 6.5 parts by weight of a flame retardant aid. The method according to claim 1,
The bromine-based flame retardant is tetrabromobisphenol-A (tetrabromobisphenol-A. TBBA, TBBPA), tetrabromobisphenol-A ether, 1,2-bis (tribromophenoxy) ethane (1 ,2-bis(tribromophenoxy)ethane), 2,4,6-tribromophenyl glycidyl ether (2,4,6-tribromophenyl glycidyl ether), tetrabromophthalic anhydride, dimethyl 4 -Bromophthalate (dimethyl 4-bromophthalate), tetrabromo phthalic disodium, decabromodiphenyl ether, decabromodiphenyl oxide (DBDPO), decabromodiphenyl Phenyl ethane (decabromodiphenyl ethane), 1,4-bis (pentabromophenoxy) tetrabromobenzene (1,4-bis (pentabromophenoxy) tetrabromobenzene), tribromophenoxy ethane (tribromophenoxy ethane), 1,2- Bis(pentabromophenyl)ethane (1,2-bis(pentabromophenyl)ethane), bromo trimethylphenyl indane, pentabromobenzyl acrylate, pentabromodiphenyl benzyl bromide ( pentabromodiphenyl benzyl bromide), hexabromobenzene, pentabromotoluene, 2,4,6-tribromophenyl maleic imide (2,4,6-tribromophenyl maleic imide), hexabromobenzene Clodecane (hexabromocyclodecane. HBCD), hexabromocyclododecane, pentabromo Chlorocyclohexane (pentabromo chlorocyclohexane), bis (2,3-dibromopropyl ether) (bis (2,3-dibromopropyl ether)), tri (2,3-dibromopropyl) iso-melamine ester (tri( 2,3-dibromopropyl)iso-melamine ester), 1,2-bis(tetrabromophthalimido)ethane (1,2-bis(tetrabromophthalimido)ethane), N,N'-ethylene-bis(3,4) ,5,6-tetrabromophthalimide) (N,N'-ethylene-bis(3,4,5,6-tetrabromophthalimide), N,N'-1,2-bis(ethylene-bis(5, 6-dibromonorbornane-2,3-dicarboximide) (N,N'-1,2-bis(ethylene-bis(5,6-dibromonorbornane-2,3-dicarboximide)), bromine Brominated styrene copolymer, tetrabromobisphenol A carbonate oligomer, poly(pentabromobenzyl acrylate) (poly(pentabromobenzyl acrylate)), poly(dibromo phenylene) Ether) (poly(dibromo phenylene ether)) and a mixture thereof, characterized in that selected from the group consisting of, flame retardant paint. The method according to claim 1,
The flame retardant auxiliary is selected from the group consisting of antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, molybdate, zirconium, and mixtures thereof.