KR102295204B1 - Flame-resisting paint and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a flame retardant paint and a method for producing the same, and in particular, by mixing a copolymer of ethene and tetrafluoroethene, a brominated flame retardant and a flame retardant auxiliary agent to minimize the effect on the appearance and processability of the coating film applied with the paint, It relates to a flame retardant paint with improved flame retardancy and a method for manufacturing the same.

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 for producing the same, and more particularly, to a fluororesin flame retardant paint having improved flame retardancy by mixing a copolymer of ethene and tetrafluoroethene, a brominated flame retardant and a flame retardant auxiliary agent, and a method for producing the same.

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

The currently applied ETFE resin has a flame retardancy level of UL-94V0, showing flame retardancy at 0.3 to 0.4 T coating thickness of ETFE resin for coating. However, when ETFE resin is applied to the lining, the coating film thickness increases to 1.6 to 1.8 T, and in this case, ignition occurs. Therefore, in the case of linings, higher flame retardancy performance is required to secure marketability.

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

Korea Patent No. 1746739 (registered on June 7, 2017) discloses a flame retardant paint with an inorganic flame retardant added thereto and a method for manufacturing the same. There is a problem that affects the physical properties of

Korea Patent No. 1193037 (registered on October 15, 2012) discloses a flame retardant paint with phosphorus-based flame retardant added, but phosphorus-based flame retardants have limitations in various applications due to the acidic phosphoric acid characteristics, and are highly toxic when in contact with water. , there is a problem of emitting phosphine gas with a risk of explosion in an enclosed space.

Accordingly, there is a significant demand for a flame retardant paint having a high flame retardancy while minimizing the toxic gas emitted during combustion while not impairing the appearance and processability of the paint.

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

The present invention has been devised to solve the above problems, and an object of the present invention is to provide a flame retardant paint comprising a copolymer of ethene and tetrafluoroethene, a brominated flame retardant and a flame retardant auxiliary agent.

Another object of the present invention is to provide a method for manufacturing the flame retardant paint.

The present invention may also have as its object 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 clear objects.

In order to achieve the above object, 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 the bromine-based flame retardant, preferably 2 to 12 parts by weight, more preferably 2.5 to 10 parts by weight, and

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.

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

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

And, the weight ratio of the brominated flame retardant to the flame retardant auxiliary agent may be 0.5 to 3, preferably 1 to 2.5, more preferably 1.5 to 2.

And, 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), deca 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 bromine Mide (pentabromodiphenyl benzyl bromide), hexabromobenzene (hexabromobenzene), pentabromotoluene (pentabromotoluene), 2,4,6-tribromophenyl maleic imide (2,4,6-tribromophenyl maleic imide), hexa Bromocyclodecane (hexabromocyclodecane. HBCD), hexabromocyclododecane (hexabromocyclododecane), penta Bromo 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), 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(dibromo) phenylene ether) (poly(dibromo phenylene ether)) and mixtures thereof, preferably 1,2-bis(tetrabromophthalimido)ethane.

And, the flame retardant index of the brominated 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 auxiliary agent may be selected from the group consisting of antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, molybdate, zirconium, and mixtures thereof.

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

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

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

1 to 15 parts by weight of the bromine-based 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 is characterized in that it includes.

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

And, 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 brominated flame retardant and a flame retardant auxiliary in ETFE resin, which is a copolymer of ethene and tetrafluoroethene.

In the flame retardant paint of the present invention, by adding a bromine-based flame retardant as a radical scavenger, the concentration of active radicals, oxygen and hydroxyl radicals, is reduced and the chain reaction is stopped to give a flame retardant effect, and the cleavage of the C-Br bond during combustion is an endothermic reaction. This has the effect of reducing the heat of combustion of combustible materials, and also has the effect of blocking oxygen by generating incombustible gas during decomposition.

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

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

In addition, in the flame retardant paint of the present invention, an antimony compound is added as a flame retardant auxiliary. The antimony-based compound reacts with the bromine-based flame retardant _{to generate SbOBr or SbBr 3} . Among them, SbOBr exhibits dehydration carbonization, and SbBr ₃ is a heavy gas, and flame retardancy can be increased through the shielding effect of oxygen.

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

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

In addition, in the following description, many specific details such as specific components are described, which are provided to help a more general understanding of the present invention, and it is common in the art that the present invention can be practiced without these specific details. It will be self-evident to those who have the knowledge of And, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

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

In this application, the singular expression includes the plural expression unless the context clearly dictates otherwise.

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

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

In the present application, 'flame retardancy 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 contains 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 agent. 0.5 to 6.5 parts by weight, preferably 1 to 4.5 parts by weight, and more preferably 1.5 to 3.75 parts by weight.

The copolymer ETFE (ethylene tetrafluoroethylene) resin of ethene and tetrafluoroethene constituting the flame retardant paint of the present invention has excellent heat resistance and chemical resistance, and is a resin used for lining processing of chemical plants and semiconductor plant facilities. The said lining process refers to coating|covering the inner surface of plant equipment, for example, a metal pipe, a metal tank, a metal bottle, etc.

The currently applied ETFE resin has a flame retardancy level of UL-94V0, showing flame retardancy at 0.3 to 0.4 T coating thickness of ETFE resin for coating. However, when ETFE resin is applied to the lining, the coating film thickness increases to 1.6 to 1.8 T, and in this case, ignition occurs. Therefore, in the case of lining, FM4922 certification level, which is a higher flame retardant performance, is required to secure marketability.

The present inventors have completed the present invention by adding an appropriate flame retardant and a flame retardant auxiliary to the ETFE resin to achieve a better flame retardant effect compared to TL-081 (Asahi Glass, Japan), which is an ETFE resin certified FM4922.

In the present invention, the copolymer of ethene and tetrafluoroethene may be a copolymer of 100 parts by mole of ethene and 90 to 120 parts by mole of tetrafluoroethene, preferably 95 to 110 parts by mole. When the ratio of the tetrafluoroethene is less than the above range, the thermal stability is reduced to accelerate the aging of the coating film, and the chemical properties are weak. Conversely, when it exceeds the above range, there is a problem in that mechanical strength is lowered, 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 the fluorine atom 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 deteriorated.

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 in the process of forming the coating film or defects in the appearance of the coating film are easily generated.

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

On the other hand, bromine is the second most effective flame retardant element after iodine and is most widely used because it can produce 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 after extinguishing is a distinctive feature from existing flame retardants.

Inorganic flame retardants are inorganic compounds that decompose during combustion to release non-flammable gases such as water, nitrogen, ammonia, or carbon dioxide. Aluminum hydroxide and magnesium hydroxide are representative flame retardants that act physically, and they decompose in an endothermic reaction to produce water. However, 50% by weight or more of the flame retardant must be added in order to exhibit the effect, and this has a disadvantage in that the physical properties of the resin are deteriorated.

Phosphorus-based flame retardants are thermally decomposed during combustion to produce phosphoric acid, and dehydration and carbonization by phosphoric acid and hydrogen and hydroxy radical trapping action of phosphorus-containing radicals contribute to flame retardancy. It facilitates the processing of flame-retardant resins 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 the brominated flame retardant per 100 parts by weight of the copolymer of ethene and tetrafluoroethene. it is preferable When the content of the brominated flame retardant is less than the above range, it is difficult to secure the expected flame retardant effect because it does not exhibit sufficient self-extinguishing properties.

In the present invention, 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), deca 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 bromine Mide (pentabromodiphenyl benzyl bromide), hexabromobenzene (hexabromobenzene), pentabromotoluene (pentabromotoluene), 2,4,6-tribromophenyl maleic imide (2,4,6-tribromophenyl maleic imide), hexa Bromocyclodecane (hexabromocyclodecane. HBCD), hexabromocyclododecane (hexabromocyclododecane), penta Bromo 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), 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(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 preferable.

And, the flame retardant index of the brominated 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 the present application, 'flame retardancy 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 in the flame retardant paint of the present invention, and 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. of flame retardant performance.

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

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 to which the present invention belongs, for example, flame retardant compounds such as antimony trioxide and antimony pentoxide, metal antimony and antimony trichloride such as sodium antimonate, 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 exhibits a synergism effect that greatly increases the radical trapping effect when combined with a halogenated flame retardant. Typically, antimony trioxide reacts with halogen _{to generate SbOCl and SbCl 3} , 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. When the content of the flame retardant auxiliary agent is less than the above range, the synergistic effect with the brominated flame retardant is insignificant, so it is difficult to secure the flame retardant effect.

The weight ratio of the brominated flame retardant to the flame retardant auxiliary may be 0.5 to 3, preferably 1 to 2.5, more preferably 1.5 to 2. When the weight ratio of the bromine-based flame retardant is less than the above range, it does not exhibit sufficient self-extinguishing properties and does not reach 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, if 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, there is a problem in that it is difficult to completely remove air bubbles in the coating film that are generated in the process of forming the coating film, resulting in poor appearance.

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

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

1 to 15 parts by weight of the bromine-based 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 is characterized in that it includes.

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. If the mixing speed is less than the above range, dispersibility with the flame retardant is It is difficult to secure the expected flame retardant effect because it is insufficient, and on the contrary, if it exceeds the above range, the flame retardant and the flame retardant auxiliary may agglomerate due to excessive dispersion, thereby impairing the appearance.

And, the mixing of the step (B) can be made for 10 to 40 minutes, preferably 12 to 30 minutes, more preferably 15 to 20 minutes, if the mixing time is less than the above range, the dispersibility with the flame retardant is insufficient. Therefore, it is difficult to secure the expected flame retardant effect, and on the contrary, if it exceeds the above range, the flame retardant and the flame retardant auxiliary may agglomerate due to excessive dispersion, thereby impairing the appearance.

The sieving of step (C) may consist 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 copolymer, the content may vary, and on the contrary, if it exceeds the above range, foreign substances and the like cannot be filtered, so that contamination in the paint cannot be prevented.

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

Example

Comparative Examples 1 to 11: No use of flame retardant aids

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

The compounds used were as follows:

TL-581: A copolymer of ethene and tetrafluoroethene, ETFE resin (Asahi Glass, Japan) with a film thickness of 2002 μm or more and a rotation 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-based flame retardant 1: aluminum diethyl phosphinate

Phosphorus-based flame retardant 2: Ammonium polyphosphate

Phosphorus-based flame retardant 3: Triethylphosphate.

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: Evaluation of paint properties (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: It was evaluated whether boiling, bubbles, etc. occurred by visually observing the appearance.

Processability: 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 at 15 cm perpendicular to the lined specimen for 60 seconds using a gas torch, the state of the coating film was observed to confirm ignition.

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

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

division comparative example One 2 3 4 5 6 7 8 9 10 11 Exterior ○ ○ △ x x ○ △ x △ x x machinability ○ ○ △ x x x x x x flame retardant △ ○ ○ x x x △ x x before fire extinguishing
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 measurement
impossible 0.7
~0.8 measurement
impossible measurement
impossible

As shown in Table 2, Comparative Examples 1 to 11 obtained results with insignificant effect on appearance and workability deterioration while ensuring excellent flame retardancy through the bromine-based flame retardant. However, a problem in that combustion gas is severely generated during combustion has been confirmed.

When the inorganic flame retardant 1 (magnesium hydroxide. Comparative Example 4) and the inorganic flame retardant 2 (aluminum hydroxide. Comparative Example 5) were added, the processing temperature of magnesium hydroxide and aluminum hydroxide was higher than that of the ETFE resin was 280 to 305 ° C. Low (200 to 250 ° C.), even with a small amount of application, poor appearance (boiling, bubbles) occurred.

When hydrated calcium borate, which is inorganic flame retardant 3, was added (Comparative Examples 6 to 8), it was stable up to 330 ℃ and did not decompose, but in actual application results, 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, and the flame retardancy tends to be partially improved, but the workability tends to be significantly reduced.

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

In order to solve the combustion gas problem shown in Comparative Examples 1 to 3, an experiment was conducted to maximize the flame retardant properties and reduce the content of the brominated flame retardant by mixing the antimony-based flame retardant auxiliary agent.

In Examples 1 to 4, each component was added in the corresponding content as described in Table 3 below, mixed at 500 rpm for 15 to 20 minutes, and sieved to 30 to 60 mesh to prepare a flame retardant paint of the present invention. After degreasing the 1.0 T SUS PLATE solvent, a coating film was formed so as to be 1.6 to 1.9 T, and calcined in stages at 260 ° C. for 30 minutes, 270 ° C. for 30 minutes, and 280 ° C. for 30 minutes.

The compounds used were as follows:

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

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

Unit: g Example contrast example 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 Supplement 1.5 2.25 3.0 3.75

Test Example 2: Evaluation of paint 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 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 machinability ○ ○ △ △ 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 does not impair appearance and processability by application of a bromine-based flame retardant and a flame retardant aid, antimony trioxide.

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 performed on the control examples and Examples 1 to 4, and the average continuous heat, critical heat flux during extinguishing, total heat emitted, and maximum heat release rate were measured three times repeatedly and the average value was derived. and the results are shown in Table 5.

Average heat of sustained combustion (MJ/m ² ): As the flame progresses, it is the product of the time reached at each point and the amount of radiant heat flow at that time. The larger the value, the better the flame retardant effect.

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

Total amount of heat emitted (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 reaching distance (mm): The smaller the value, the better the flame retardant effect.

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

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

division Example contrast example One 2 3 4 average heat of sustained 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 amount of heat emitted 0.18 0.32 0.036 0.19 0.17 highest heat release rate 1.03 1.05 0.65 0.80 1.36 flame fall does not exist does not exist does not exist does not exist does not exist Final Flame Reach 100 100 100 50 to 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 above, as a result of the flame propagation test, Examples 1 to 4 to which a bromine-based flame retardant and antimony trioxide were applied exhibited excellent flame retardant effects due to a low maximum heat release rate and a short ignition time.

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

In addition, when considering the total amount of heat emitted and the maximum heat release rate, it was confirmed that Example 3 exhibits the most excellent flame retardant effect.

Although preferred embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments described above, and those skilled in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Accordingly, the scope of the present invention should not be construed as being limited to the above embodiments, and should be defined by the claims described below as well as the claims and equivalents.

Claims (3)

A method for manufacturing a flame-retardant paint for linings having a thickness of 0.8 to 2.1 mm,
(A) 100 parts by weight of a copolymer of ethene and tetrafluoroethene,
2.5 to 10 parts by weight of a brominated flame retardant, and
Preparing 1.5 to 3.75 parts by weight of a flame retardant aid;
(B) preparing a mixture by mixing the copolymer of ethene and tetrafluoroethene, a brominated flame retardant and a flame retardant auxiliary;
(C) sieving the mixture.
including,
The mixing of step (B) is made at a mixing speed of 350 to 800 rpm,
The mixing of step (B) is made for 15 to 20 minutes,
The sieving of step (C) consists of a sieve of 30 to 60 mesh,
The copolymer of ethene and tetrafluoroethene is an alternating copolymer,
The average particle diameter of the copolymer of ethene and tetrafluoroethene is 230 to 330 μm,
The thickness of the coating film formed by the flame-retardant paint is 0.8 to 2.1 mm,
The bromine-based flame retardant is 1,2-bis (tetrabromophthalimido) ethane (1,2-bis (tetrabromophthalimido) ethane),
The flame retardant aid is antimony trioxide,
The flame retardancy index defined by the following formula is 0.3 to 0.7,
A method of manufacturing a flame-retardant paint for lining with a thickness of 0.8 to 2.1 mm:
Flame retardant index
= (Number of nitrogen atoms in flame retardant molecule) / (Number of oxygen atoms in flame retardant molecule).
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