KR102280245B1 - Complex flame retardant with inorganic flame retardant and method for preparing of the same - Google Patents

Abstract

The present invention relates to a composite flame retardant and a method for manufacturing the same, and more particularly, an organic-inorganic composite flame retardant capable of exhibiting improved flame retardancy and excellent physical properties by mixing a phosphorus-nitrogen flame retardant and an inorganic flame retardant with a silane surface treatment, and manufacturing the same it's about how

Description

Composite flame retardant containing inorganic flame retardant and manufacturing method thereof {COMPLEX FLAME RETARDANT WITH INORGANIC FLAME RETARDANT AND METHOD FOR PREPARING OF THE SAME}

The present invention relates to a composite flame retardant and a method for manufacturing the same, and more particularly, to an organic-inorganic composite flame retardant prepared by mixing a phosphorus-nitrogen-based flame retardant and an inorganic flame retardant, and a method for manufacturing the same.

A fire causes a lot of property damage and casualties. The main cause of toxic gas generated in a fire is the combustion of synthetic resins used for interior and exterior materials in buildings, vehicles, and furniture. To solve this problem, flame retardancy is given to synthetic resins to prevent the rapid spread of fire. At the same time, the development of technology has been carried out to minimize the damage to human life by reducing the generation of toxic gas.

In general, a method of adding bromine (Br), which is a flame-retardant material, or the like, as a flame retardant material by a chemical reaction, or adding a flame retardant is made in order to make a synthetic resin flame retardant. At this time, the added flame retardant is classified into halogen-based, phosphorus-based, nitrogen-based, complex-based, inorganic-based, and the like, depending on the composition it contains. Among conventional flame retardants, organic halogen-based compounds have been widely used, and in particular, when a bromine-based flame retardant and an antimony-based flame retardant are used together, it is known that the flame retardant effect is further improved. However, halogen-based flame retardants generate toxic gas when burned, causing suffocation, and antimony-based flame retardants are also carcinogenic. In addition, when a flame retardant containing chlorine (Cl) in a high content among halogen elements is applied to solvent-free urethane, there is a problem in that a difference in physical properties occurs due to a difference in reaction rate. In the weather resistance measurement for confirmation, corrosion of the PCB substrate causes fatal problems such as product leakage, which lowers stability, making its application difficult.

Halogen-based flame retardants are the most widely used in Korea due to their excellent flame retardancy and economical efficiency. However, due to the aforementioned problems and international concerns about the impact of halogen-containing materials on the environment and stability, the demand for the development of non-halogen-based flame retardants is increasing. is a growing trend. In general, halogen-free products require that the sum of bromine and chlorine (Cl) content be 1500 ppm or less, and chlorine alone is 1000 ppm or less.

Non-halogen flame retardants have significantly lower flame retardant performance than brominated flame retardants or have high manufacturing costs. Therefore, many efforts are being made to develop new flame retardants with excellent flame retardant performance and excellent economic feasibility. Such non-halogen flame retardants include, for example, phosphorus-based, nitrogen-based, silicon-based, boron-based, and the like, and among them, research and development for phosphorus-based flame retardants is being actively conducted. However, when the organic phosphoric acid flame retardant, which is a representative phosphorus flame retardant, is applied to a polymer product, there is a problem in that the quality of the product is deteriorated due to volatile components.

The phosphorus-nitrogen-based flame retardant exhibits a flame retardant effect by controlling combustion by thermal decomposition by making nitrogen gas porous to char generated by heat operation. It is widely known as an intumescent flame retardant with excellent flame retardancy and hydrolysis resistance, and is mainly used as an additive type. It is known that the most excellent structure for constituting such a foaming layer forms the most excellent foaming layer in a structure (Perstorp, sweden) in which the carbon source:polyphosphoric acid:N ratio is 1:2:1.

Nano-sized materials are being used in various industrial fields. Various methods are used for the preparation of nanoparticles, and a sol-gel method, an electric explosion method, and the like are used. Among them, when the electric explosion method heats a metal or ceramic material to a temperature slightly higher than the melting point, the atoms leave the surface of the material to form vapor, and when these high-temperature atoms meet cold atoms in the reaction vessel, they are cooled and condensed to form a nano-sized solid material. It is a principle that can form

KR 1020150082359 A

An object of the present invention is to provide a method for manufacturing a halogen-free organic-inorganic composite flame retardant that can be applied to polymer materials, artificial leather, textile materials and electronic components requiring flame retardancy to excellently improve flame retardancy.

In addition, another object of the present invention is to provide a method for manufacturing a ceramic flame retardant that can be used in combination with a phosphorus-nitrogen-based flame retardant, and can significantly improve flame retardancy when used in combination.

Another object of the present invention is to provide a flame retardant prepared by the above manufacturing method.

In addition, it is another object of the present invention to provide a polymer material, artificial leather, textile material or electronic component that is processed with the flame retardant and has excellent flame retardancy.

According to an aspect of the present invention, a flame retardant preparation step of preparing a phosphorus-nitrogen-based flame retardant and a ceramic-based flame retardant, respectively; a surface treatment step of surface-treating the ceramic-based flame retardant with a silane-based compound; and a complexing step of mixing and compounding the ceramic-based flame retardant surface-treated with a silane-based compound and the phosphorus-nitrogen-based flame retardant.

In addition, in the complexing step, the ceramic-based flame retardant surface-treated with a silane-based compound and the phosphorus-nitrogen-based flame retardant may be mixed in a weight ratio of 1:4 to 8.

In addition, the phosphorus-nitrogen-based flame retardant, a first step of reacting by adding a bis-cyclic phosphate (bis-cyclic phosphate), phosphorus oxide _{chloride (POCl 3 ) and a catalyst to a hydrophilic solvent;} a second step of synthesizing a bis-type flame retardant by adding and reacting a nitrogen compound; a third step of atomizing the bis-type flame retardant synthesized in the second step; and a fourth step of washing the bis-type flame retardant atomized in the third step with a water-soluble solvent.

According to another aspect of the present invention, a first step of reacting by adding _{bis-cyclic phosphate, phosphorus oxide chloride (POCl 3 ) and a catalyst to a hydrophilic solvent;} a second step of synthesizing a bis-type flame retardant by adding and reacting a nitrogen compound; A third step of complexing by solvent replacement with a ceramic-based flame retardant slurry surface-treated with a silane-based compound; and a fourth step of washing with a water-soluble solvent; including, a method for producing a composite flame retardant is provided.

In addition, the step of atomizing between the third step and the fourth step; may be further performed.

In addition, the bis-cyclic phosphate may be neopentyl glycol, ethylbutyl glycol, or a mixture thereof.

In addition, the catalyst may be anhydrous magnesium chloride (anhydride MgCl ₂ ) or anhydrous aluminum chloride (anhydride AlCl ₃ ).

In addition, in the first step, biscyclic phosphate and a catalyst are first added to a hydrophilic solvent, and phosphorus oxide chloride is added dropwise for 1 to 2 hours while stirring at 45 to 55° C., and then the temperature is raised to 70 to 80° C. for 2 to 4 It can be carried out by aging for a period of time.

In addition, the catalyst may be added in an amount of 0.05 to 0.2 moles based on 1 mole of the biscyclic phosphoric acid.

In addition, the second step may be performed at 20 to 30 ℃ for 4 to 6 hours.

In addition, the ceramic-based flame retardant and the bis-type flame retardant surface-treated with the silane-based compound in the third step may be mixed in a weight ratio of 1:4 to 8.

According to another aspect of the present invention, a first step of preparing a ceramic comprising at least one selected from the group consisting of Zn-based, Al-based, Sn-Cu-based, Mg-based and Si-based ceramics; a second step of synthesizing a ceramic flame retardant whose particle size is controlled by a sol-gel method or an electric explosion method; and a third step of surface treatment with a silane-based compound; including, in the second step, selected from the group consisting of water, hydrogen peroxide, 1,4-dioxane, ethanol, IPA, MEK and DMF A method for producing a surface-treated ceramic-based flame retardant is provided in which a solvent containing at least one is used and a dispersant is added.

In addition, the silane-based compound is vinyl (vinyl), epoxy (epoxy), styryl (styryl), methacryloxy (methacryloxy), acryloxy (acryloxy), amino (amino), ureide (ureide), mercapto ( mercapto) and may include at least one functional group selected from the group consisting of isocyanate.

According to the manufacturing method according to an aspect of the present invention, by accelerating the char of the flame retardant mechanism through the complexing of the amide phosphoric acid-based flame retardant and the nano-ceramic-based flame retardant to maximize the synergistic effect, a halogen-free organic-inorganic composite flame retardant with remarkably excellent flame retardancy is prepared can be manufactured.

In addition, organic-inorganic flame retardants can be manufactured with high productivity through an eco-friendly and simplified manufacturing process.

In addition, it is possible to prepare an organic-inorganic flame retardant with improved compatibility, flame retardancy, economic feasibility and physical properties while reducing harmfulness.

1 shows a schematic diagram of the surface treatment of a ceramic-based flame retardant according to an embodiment of the present invention;
Figure 2 shows a schematic diagram of a ceramic flame retardant of one embodiment,
3 is a result of analyzing the physical properties of the synthesized phosphorus-nitrogen-based flame retardant;
Figure 4 is a result of analyzing the particle size distribution by solvent replacement of the synthesized phosphorus-nitrogen-based flame retardant,
5 is a result of analyzing the particle size distribution of the synthesized phosphorus-nitrogen-based flame retardant;
^{6 is a 1} H-NMR analysis result of the synthesized phosphorus-nitrogen-based flame retardant;
7 is a FT-IR analysis result of the synthesized phosphorus-nitrogen-based flame retardant;
8 is a TGA analysis result of the synthesized phosphorus-nitrogen-based flame retardant;
9 is an HPLC analysis result of the synthesized phosphorus-nitrogen-based flame retardant;
10 is a result of confirming the flame retardant performance after processing the synthesized phosphorus-nitrogen-based flame retardant to the fiber material,
11 is a view confirming the result of dispersing agent input during the preparation of nano-type slurry;
12 is a result of measuring the solubility of the synthesized nano ceramic;
13 is to confirm the flame retardant synergistic effect of the synthesized ceramic flame retardant,
14 and 15 are FT-IR analysis results of amino silane used as a surface treatment agent and a surface-treated Al ceramic-based flame retardant;
16 and 17 are SEM-EDS analysis results of the synthesized Al ceramic-based flame retardant;
18 is a SEM analysis result of the synthesized Al ceramic-based flame retardant;
19 is a TEM analysis result of the synthesized ceramic-based flame retardant;
20 and 21 are SEM analysis results of the prepared composite flame retardant,
22 is a result of SEM-EDS analysis of the prepared composite flame retardant;
23 is to confirm the synergistic effect in the composite flame retardant according to the flame retardant mixing ratio,
24 is a measurement result of the manufactured composite flame retardant toxic substance.

The present invention provides a method for producing a ceramic flame retardant that can be added to an amide phosphoric acid flame retardant to improve flame retardancy and physical properties, and a composite flame retardant prepared by compounding the ceramic flame retardant, amide phosphoric acid flame retardant and ceramic flame retardant produced thereby It relates to a method and a composite flame retardant prepared thereby.

Hereinafter, the present invention will be described in detail.

According to one aspect of the present invention, there is provided a method for manufacturing a ceramic-based flame retardant.

The ceramic-based flame retardant according to an aspect of the present invention is for manufacturing a composite flame retardant, and when compositely treated with an amide phosphoric acid flame retardant, flame retardancy and physical properties can be improved.

The ceramic for manufacturing the ceramic-based flame retardant may be selected in consideration of the properties of the product to which the final manufactured flame retardant will be applied and the physical properties harmonization with the amide phosphoric acid-based flame retardant. For example, a ceramic including at least one selected from the group consisting of Zn-based, Al-based, Sn-Cu-based, Mg-based and Si-based ceramics may be selected, but is not limited thereto. Preferably, the ceramic may include at least one selected from the group consisting _{of MgO, SiO 2} , Al(OH) _{3 and ZnO.} It is better to select a ceramic with excellent flame retardant synergy with the urethane resin used for artificial leather.

The ceramic may be prepared by synthesizing a flame retardant in the form of a slurry having a controlled particle size. The ceramic-based flame retardant may be synthesized using a sol-gel method or an electric explosion method, and the ceramic-based flame retardant slurry prepared through this may have a nano-sized particle size. The ceramics whose particle size is controlled may have a particle size of 500 nm or less, and preferably have a particle size of 100 nm or less. In the case of using the electric explosion method, the ceramic may be evaporated and condensed to solidify in a new form. Through this evaporation-condensation process, the ceramic material may be reconstituted from a coarse particle form to a fine powder composed of nano-sized particles.

Nanoparticles of nano-ceramic slurries prepared by the electro-explosion method may have a problem in that they cannot properly exhibit the intrinsic functions and properties of nanoparticles due to cohesion between particles due to their large surface area. Therefore, it is preferable to increase the dispersibility of the nanoparticles by applying a dispersing agent to control the nano size and to prepare a nano-type slurry at a high concentration.

The solvent used in synthesizing the ceramic-based flame retardant may be selected in consideration of cohesion between nanoparticles, a surface treatment process to be described later, and environmental friendliness. Specifically, in the case of preparing the nano-ceramic slurry by the electric explosion method, since the cohesive force between the nanoparticles may vary depending on the solvent selection, a solvent in consideration of the cohesive force may be used. In addition, in consideration of the surface treatment process to be described later, hydrolysis of the silane coupling agent needs to be performed, and water or a solvent having a hydroxyl group may be selected as the solvent to dissolve the solvent. In addition, it is preferable that an environmentally friendly solvent is selected in consideration of the wastewater to be generated after the completion of the reaction.

The prepared nano-ceramic slurry may be added in the solvent replacement step during the manufacturing process of the amide phosphoric acid-based flame retardant to be described later to form a composite flame retardant. In order to use the prepared nano-ceramic slurry for solvent replacement, the inorganic nano-sol nano-ceramic is dispersed in the solvent replacement solvent used in the last step of solvent replacement of the nano-sol. Milling, washing, and solvent replacement can be easy. Therefore, when the compounding of the amide phosphoric acid flame retardant and the nano ceramic slurry is performed in the solvent replacement step of the amide phosphoric acid flame retardant, the solvent may be selected in consideration of this.

The solvent may include at least one selected from the group consisting of water, hydrogen peroxide (oxide production), 1,4-Dioxane, Ethanol, IPA, MEK, and DMF. In this case, the last solvent to be substituted is water or DMF. can be used. The final solvent may be selected in consideration of the formulation of the final product. For example, in the case of a powder form, solidification and nano-composite are advantageous when substituted with water. When applied to leather, it may be advantageous to apply to DMF.

If necessary, for complexation with the amide phosphoric acid-based flame retardant, the prepared nano-ceramic-based flame retardant may be surface-treated with a silane-based compound.

The surface of the ceramic-based flame retardant is oxidized with -OH, and by using a silane compound having organic functional groups as a coupling agent, the ceramic surface can be surface-treated with silane having a desired functional group. The silane compound is preferably selected to have excellent compatibility with the amide phosphoric acid flame retardant, for example, vinyl (vinyl), epoxy (epoxy), styryl (styryl), methacryloxy (methacryloxy), acryloxy (acryloxy) ), amino (amino), ureide (ureide), mercapto (mercapto) and may include at least one functional group selected from the group consisting of isocyanate (isocyanate), but is not limited thereto. The silane compound is preferably an amino silane compound.

The silane coupling agent may be hydrolyzed prior to being treated with the ceramic. The hydrolysis may be performed using water or a solvent having a hydroxyl group, and preferably, alcohol or ethanol is used for stability. The hydrolysis time is preferably 1 hour or more, and preferably, may be 1 to 3 hours.

The aqueous solution of the silane coupling agent is very unstable in a hydrolyzed state and has a pot life. After the pot life, the hydrolyzed silane coupling agent is condensed and changed to an oligomeric state. Depending on the organic functional groups, this pot life may vary, for example amino silanes may be as high as 30 days.

The surface treatment may be performed by a dry method or a wet method. Preferably, it is preferably carried out by a wet method in order to improve process efficiency. The dry method may be performed by dropping or spraying a hydrolyzed silane coupling agent to the powder. The wet method may be performed by immersing the powder in a hydrolyzed silane coupling agent, filtering, and drying the powder. The concentration of the silane aqueous solution may be adjusted according to the surface treatment method, for example, when a dry method is applied, a 20-50 wt% aqueous solution of silane, and when a wet method is applied, a 0.5-2 wt% aqueous solution of silane may be used. Surface treatment may be performed by adding 0.5-1wt% of powder (filler) to both the dry method and the wet method. In order to surface-treat the hydrolyzed silane coupling agent to the oxidized inorganic material, a condensation process in which water is removed by applying heat may be performed. A schematic diagram of the surface treatment of a ceramic flame retardant for amide phosphoric acid/inorganic composite is shown in FIG. 1 , and a schematic diagram of a ceramic flame retardant having a particle size of 100 nm or less to which a flame retardant functional group is applied is shown in FIG. 2 .

According to another aspect of the present invention, there is provided a method for manufacturing a composite flame retardant prepared by compounding an amide phosphoric acid flame retardant and a ceramic flame retardant.

The amide phosphoric acid-based flame retardant is a bis-cyclic phosphate (bis-cyclic phosphate) and a primary esterification reaction of phosphorus chloride; synthesizing a bis-type flame retardant by adding a nitrogen compound to the product synthesized by the esterification reaction and performing a secondary amination reaction; And it may be a phosphorus-nitrogen-based flame retardant prepared by a manufacturing method comprising the step of washing with a water-soluble solvent.

The phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention may include a step (S1) of primary reaction by adding a catalyst to the biscyclic phosphate and phosphorus chloride.

As the biscyclic phosphate, a glycol-based compound may be selected and used. A branch capable of producing a cyclic primary phosphate ester compound in order to produce a compound with a high melting point because a problem of generating a low-melting-point compound that cannot be used as a final product may occur when linear glycol and triol-type glycol are used (Branch) type, in particular, branched diol (branched diol) type glycol compound is preferably selected. Preferably, neopentyl glycol, ethylbutyl glycol, or a mixture thereof is selected as the bis-cyclic phosphate salt. More preferably, neopentyl glycol having excellent solubility in various solvents such as alcohol-based, ketone-based, ester-based and hydrophilic solvents, excellent usability, and easy reaction control is selected. In the case of using a compound that does not form a structurally symmetric structure, for example, ethylbutylpentanediol, there may be problems in that the reaction does not occur or it is difficult to control the reaction. In addition, when an ester compound is used, a problem of reducing the phosphorus content may occur.

The phosphorus chloride is preferably a compound capable of a stable room temperature reaction is selected and used. Preferably, phosphorus oxide chloride (POCl ₃ ) having a high boiling point of 105.8° C. is preferably selected.

The catalyst may be added to reduce the reaction time and improve the yield. As the catalyst, at least one selected from the group consisting of metal chloride anhydride, triethanolamine, EDA (ethylenediamine), pyridine, piperazine, and platinum (Pt) may be selected, but is limited thereto it is not Preferably, a metal chloride anhydride having excellent product yield improvement in the first reaction is selected. More preferably, aluminum chloride anhydride (AlCl ₃ anhydride) or magnesium chloride anhydride (MgCl ₂ anhydride) is selected.

This step (S1) is performed to produce a primary phosphoric acid ester compound, and may be performed by adding the biscyclic phosphate salt, the phosphorus chloride, and the catalyst to a hydrophilic solvent for an esterification reaction. Specifically, the step of first adding and dissolving the bis-cyclic phosphate and the catalyst in a hydrophilic solvent; adding the phosphorus chloride dropwise while stirring; And it may be carried out including the step of aging by raising the temperature. The step of first adding and dissolving the biscyclic phosphate salt and the catalyst in a hydrophilic solvent may be performed by dissolving the solution until completely transparent, and may be performed at 50 to 70°C. The dropping is preferably performed within 2 hours with stirring at 45 to 55° C., preferably for 1 to 2 hours. By adding reactants as described above, the reaction can be optimized to reduce side reactions and improve the primary reaction yield. The aging by raising the temperature is preferably performed for 2 to 4 hours by raising the temperature to 70 to 80 ℃. The biscyclic phosphate and the phosphorus chloride may be used in a molar ratio of 1:0.8 to 1.2, preferably 1:1. The biscyclic phosphate salt and the catalyst may be used in a molar ratio of 1:0.05 to 0.2. An example of a preferred chemical reaction carried out in this step (S1) is shown in Scheme 1 below.

[Scheme 1]

The hydrophilic solvent may be selected in consideration of the physical properties of the bis-cyclic phosphate, ease of reflux, reaction yield, and the target of application of the prepared flame retardant. For example, at least one selected from the group consisting of 1,4-dioxane, THF, MEK, DMF, acetone, and IPA may be used. Preferably, 1,4-dioxane or DMF, not a low-boiling solvent, is preferably used in consideration of the boiling point to facilitate solvent reflux during the reaction.

The phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention may include a step (S2) of adding a nitrogen compound to the product synthesized through the first reaction to perform a secondary reaction.

The nitrogen compound may be added to provide a nitrogen component to the synthesized flame retardant. The nitrogen compound has a structure for bridging the primary phosphate ester compound, and is preferably selected in consideration of unit cost and flame retardancy. For example, ethylenediamine or piperazine may be used, but is not limited thereto. Preferably, ethylenediamine having an ideal symmetric structure among diamines containing nitrogen is used.

This step (S2) may be performed in order to synthesize a phosphoric acid amide-based flame retardant compound through an amine reaction in which the reaction product synthesized in the first reaction, which is the previous step, is connected with diamine. A bis-type flame retardant is synthesized by adding and reacting the nitrogen compound to the reaction product synthesized in the first reaction. The amount of the nitrogen compound can be adjusted in consideration of the number of moles of the reactant reacted in the previous step and the reaction product produced, preferably 1:0.8 to 1.2, preferably 1: based on the biscyclic phosphate reacted in the previous step. A molar ratio of 1 may be used. This step (S2) may be performed at 20 to 30 ℃ for 4 to 6 hours. An example of a preferred chemical reaction carried out in this step (S2) is shown in Scheme 2 below.

[Scheme 2]

Hydrochloric acid (HCl) gas generated during the first reaction and the second reaction is to be removed by collecting it using at least one selected from the group consisting _{of nitrogen (N 2 ) gas, potassium hydroxide (KOH) and sodium hydroxide (NaOH).} can For example, neutralization can be performed by continuously adding sodium hydroxide using a pickling bottle throughout the reaction.

If necessary, the phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention comprises a step (S3) of solvent replacing the flame retardant synthesized through the primary and secondary reactions with water or DMF (N,Ndimethylformamide) may include more.

This step (S3) may be performed to improve the conventional flame retardant slurry solidification method, which is economical by reducing the number of manufacturing process steps, and to adjust the particle size of the manufactured flame retardant. By solidifying the flame retardant slurry by using a solvent replacement method that proceeds in the direction of washing, atomization, and reducing harmfulness and risk, stability and economic feasibility can be improved during flame retardant manufacturing. In the case of applying the solvent replacement method, the solidification method of the flame retardant may be performed by first performing purification and atomization, and then finally solidification using spray drying or the like.

This step (S3) is prepared by preparing a concentrated flame retardant slurry by concentrating the flame retardant slurry synthesized through the first and second reactions with a concentrator, and adding a micelle auxiliary to water or DMF solvent to the concentrated solution It can be carried out by dispersing the used flame retardant slurry. The micelle adjuvant added to the mixed solution may be a dispersant or a surfactant. When preparing the mixed solution, it is preferable to use 1 to 3% (w/w) of the micellar adjuvant. The concentrated flame retardant slurry may be 30 to 60% (w/w), but is not limited thereto. The concentrated flame retardant slurry is preferably used after slowly cooling to room temperature. The room temperature is 15 to 25 ℃ in a conventional sense.

The phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention may further include atomizing the flame retardant synthesized through the primary and secondary reactions (S4). When the phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention includes the step of solvent replacement, this step (S4) may be performed after the solvent replacement step is performed.

This step (S4) is performed in order to nanosize by controlling the particle size of the flame retardant to be manufactured, and is preferably performed by a wet milling method in order to reduce manufacturing cost and simplify the process. The wet milling may be performed by a known method, for example, atomization of the flame retardant slurry may be performed using a ball mill.

The phosphorus-nitrogen-based flame retardant manufacturing method according to an aspect of the present invention includes washing (S5) the flame retardant synthesized through the primary and secondary reactions with a water-soluble solvent. When the phosphorus-nitrogen-based flame retardant manufacturing process according to an aspect of the present invention includes the step of atomizing, this step (S5) may be performed after the atomizing step is performed.

This step (S5) may be performed to remove residual chlorine (Cl). It can be carried out by adding a water-soluble solvent to the flame retardant slurry and dispersion washing. The dispersion washing may be performed by adjusting the number of times in consideration of the residual chlorine removal rate and process productivity, and is preferably performed 3 to 5 times.

If necessary, solidification of the washed flame retardant slurry may be performed. The solidification may be performed using a known method, for example, spray drying, atmospheric drying, or reduced pressure drying may be performed. It is preferably carried out by spray drying.

The manufacturing method according to one aspect of the present invention shortens the reaction time for synthesizing the flame retardant, and after pulverizing the synthesized flame retardant slurry to have a particle size of 1 μm or less, it is possible to remove the residual chlorine concentration to 50 ppm or less by washing with an aqueous solvent. there is. The phosphorus-nitrogen-based flame retardant prepared by the manufacturing method according to an aspect of the present invention is a bis-type compound and includes 17% or more of P and 13% or more of N, and may have an N-P complex structure of Formula 1 below.

The flame retardant of Formula 1 has a structure capable of imparting flame retardancy with a small amount of use by forming an intumescent layer by thermal decomposition, which is the best of the phosphorus-nitrogen-based flame retardant. In order to form an intumescent layer, it is most advantageous to have a carbon source, polyphosphoric acid, and a foaming agent in one body. As mentioned above, the phosphorus-nitrogen flame retardant is thermally decomposed and neopentyl glycol is converted into a carbon source. ), PO ₂ polyphosphoric acid (condensation reaction), and N foaming agent. In addition, from the phosphorus-nitrogen-based flame retardant structure, it can be confirmed that the polyhydric alcohol 2, N 2, PO2 4.2 structure is at a level very close to the ideal structure for forming an intumescent layer.

The bis-type flame retardant prepared according to the manufacturing method according to an aspect of the present invention has an average particle size of 300 to 500 nm, and is a halogen-free flame retardant from which chlorine has been removed and has excellent flame retardancy. Since the residual chlorine concentration is less than 50 ppm, it does not affect urethane reactivity and does not cause corrosion problems due to chlorine even when applied to electronic parts, so it can be applied to reactive urethane resins and electronic parts.

The ceramic-based flame retardant may be a ceramic-based flame retardant prepared by the manufacturing method according to an aspect of the present invention described above. The ceramic-based flame retardant may be surface-treated with a silane compound.

An organic-inorganic composite flame retardant in the form of a nano-composite may be manufactured by complexing the amide phosphoric acid flame retardant and the ceramic flame retardant. The compounding may be performed by simply mixing the amide phosphoric acid-based flame retardant and the ceramic-based flame retardant, respectively, and then simply mixing them. Alternatively, in the step of performing solvent replacement during the process of preparing the amide phosphoric acid flame retardant, solvent replacement may be performed using a solvent including the ceramic flame retardant.

For compounding, the ceramic flame retardant and the amide phosphoric acid flame retardant may be mixed in a weight ratio of 1:2 to 10, preferably 1:4 to 8. When the content of each flame retardant is added within the above range, the flame retardancy of the composite flame retardant to be manufactured and the flame retardancy and physical properties of the product to which it is applied can be maximized.

The silane surface treatment of the ceramic flame retardant may be performed before or after mixing with the amide phosphoric acid flame retardant. The silane coupling agent can be treated by internally adding to an organic material or directly surface-treating an inorganic material, or by applying both, and when internally added, the productivity is excellent, and when surface-treated, the flame retardant and physical properties of the manufactured flame retardant are better It can be improved so that the effect of surface treatment can be maximized. The surface treatment may be performed by the method described above in the method for manufacturing a ceramic-based flame retardant according to an aspect of the present invention. When an amino silane coupling agent capable of ion bonding with an amide phosphoric acid flame retardant is used, the hydrolysis rate is fast and the hydrogen bonding rate with -OH groups on the surface of the oxidized inorganic material is also fast, so that the production time can be shortened. The pH of a suitable aqueous solution of the amino silane coupling agent is 9 to 11, more preferably 10, and at this pH, it can be maintained in a monomeric state. The pH of the appropriate aqueous solution may vary depending on the organic functional group.

In terms of increasing productivity and eco-friendliness in the manufacturing process, the compounding is performed by applying a solvent containing the ceramic flame retardant in the step of slurrying using a solvent replacement method in the process of preparing the amide phosphoric acid flame retardant. it's good to be At this time, when describing a preferred embodiment of manufacturing the composite flame retardant, the silane coupling agent is first mixed with the ceramic-based flame retardant slurry and surface-treated by a wet method, and then is internally added to the amide phosphoric acid-based flame retardant slurry to increase productivity, and then An amide phosphoric acid-based/inorganic composite flame retardant can be obtained by applying heat to and performing solidification. Nanoparticles can be nanosized through the solvent replacement step in which the optimum solvent and process are grafted, and the ball mill process in the subsequent atomization step, which improves the tendency to function as a catalyst rather than the intrinsic inorganic properties and flame retardancy. And it can increase the synergistic effect with the amide phosphoric acid-based flame retardant. In addition, it is possible to secure the diversity of application fields of the composite flame retardant to be finally manufactured. The particle size of the composite flame retardant to be prepared may be 500 nm or less.

After synthesizing the ceramic flame retardant using a solvent for solvent replacement of the amide phosphoric acid flame retardant, the nano-sized ceramic flame retardant is compounded on the surface of the amide phosphoric acid flame retardant to obtain a composite composite flame retardant. When compounding is performed through solvent replacement, the amount of solvent used can be reduced, thereby reducing overall production cost and alleviating environmental problems. In addition, since the solvent replacement method has little loss, no dust generation, and an environment-friendly method for recycling the solvent, the environmental friendliness of the process can be improved when the solvent replacement method is applied.

The flame retardant prepared according to the manufacturing method according to an aspect of the present invention may be applied to the product in the form of a dry powder or may be applied to the product in the form of a slurry dispersed in a solvent without drying. For example, in the form of dry powder, it can be applied to the manufacture of eco-friendly solvent-free adhesives, polymer products, or flame-retardant yarns. When applied in the form of a slurry, it can be applied to solvent-based (DMF) or water-based products, depending on the dispersion solvent, and can be applied to artificial leather, textile products, or furniture.

The powdering of the complexed complex flame retardant may be performed using a known method. For example, it may be solidified by using a spray dryer or a thin film evaporator, or by drying under reduced pressure after concentration processing using a palmetary mixer. In terms of reducing the amount of solvent used and powder agglomeration, it is preferable to perform concentration processing and drying under reduced pressure using a mixer rather than a spray dryer. If necessary, the solidified composite flame retardant may be prepared in a form mixed with other materials. For example, in order to have excellent dispersibility even when applied to high viscosity solvent-free urethane, it may be prepared in a form dispersed in a high concentration in solvent-free urethane.

The composite flame retardant prepared by the manufacturing method according to an aspect of the present invention has excellent compatibility, flame retardancy and physical properties. In addition, since it is manufactured by a manufacturing method to which excellent productivity and eco-friendly processes are applied, economic efficiency can be improved. In addition, the harmfulness can be reduced.

The amide phosphoric acid-based flame retardant prepared by the manufacturing method according to an aspect of the present invention can rapidly form char, has improved hydrolysis, and improves flame retardancy when nanoing it, so it can be applied to flame retardant of polymers. In this case, it is possible to reduce the amount of flame retardant used and reduce the physical properties of the polymer. In addition, when the ceramic flame retardant manufactured by the manufacturing method according to an aspect of the present invention is applied in a composite manner by accelerating the char of the flame retardant mechanism, a synergistic effect with the amide phosphoric acid flame retardant is generated to further improve the flame retardancy and polymer properties can promote

The composite flame retardant manufactured by the manufacturing method according to an aspect of the present invention has excellent flame retardancy, and thus can exhibit excellent flame retardant effect even with a small amount of use. Through this, it is possible to reduce the generation of waste and reduce the environmental impact. In addition, since the polymer product to which it is applied has excellent hydrolysis resistance and alkali resistance while exhibiting excellent flame retardancy, it can be applied to fields requiring high physical properties. For example, it can be applied to artificial leather for automobile interior materials.

Hereinafter, the present invention will be described in more detail based on the following Examples and Comparative Examples in order to help the understanding of the present invention. However, these examples only illustrate the present invention and do not limit the appended claims, and it is obvious to those skilled in the art that various changes and modifications to the examples are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims.

Example

<Catalytic reaction design to improve the yield of the primary reaction in the manufacture of phosphorus-nitrogen-based flame retardants>

In the first-step ester reaction, an experiment was performed to confirm the reaction and yield of glycol and phosphorus oxychloride by the catalyst. In 1000 ml of a 4-neck vertical separation reactor equipped with a reflux condenser, thermometer, stirrer, and pressure equalization funnel, 208.4 g (2 mol) of neopentyl glycol and 73 g of 1,4-dioxane are added and heated to 50° C. After complete dissolution, the catalyst was added. 307 g (2 mol) of phosphorus oxychloride was dropped over 1 hour through a pressure-equilibrated dropping funnel under stirring at a temperature of 70 to 80° C. in the separation reactor. After the dropwise addition was completed, the temperature was raised to 80° C. and the reaction was further performed for 2 hours, and HCl was recovered using a pickling bottle in the reaction. In order to select a catalyst for the first reaction, _{synthesis was performed using AlCl 3} anhydride, MgCl ₂ anhydride, and platinum (Pt) as catalysts, respectively. The type of catalyst used, the content of the catalyst used, and the reaction results are shown in Table 1 below. showed In Table 1 below, the yield results show the results of measuring the nonvolatile matter of water after drying the liquid after the additional reaction and washing it twice with water. All reagents performed in the experiment were purchased from DAEJUNG CHEMICALS and used.

No. POCl ₃
(mole) Neopentyl
glycol
(mole) catalyst loading time
(70℃) menstruum transference number
(%) B 2 2 - 1hr 1,4-dioxane 27.3 A-1 2 2 0.05 1hr 1,4-dioxane 44.1 A-2 2 2 0.1 1hr 1,4-dioxane 50.1 A-3 2 2 0.2 1hr 1,4-dioxane 73.2 M-1 2 2 0.05 1hr 1,4-dioxane 42.1 M-2 2 2 0.1 1hr 1,4-dioxane 60.1 M-3 2 2 0.2 1hr 1,4-dioxane 75.1 P-1 2 2 0.05 1hr 1,4-dioxane 38.1 P-2 2 2 0.1 1hr 1,4-dioxane 49.1 P-3 2 2 0.2 1hr 1,4-dioxane 58.2

* B : Blank, A : AlCl ₃ Anhydrous, M : MgCl ₂ Anhydrous, P : Pt catalyst

Referring to Table 1, it can be seen that the reaction rate is very slow in the case where the catalyst is not used (B), and it can be confirmed that the results are excellent when the reaction is performed using _{AlCl 3} anhydride and MgCl _{2 anhydride as catalysts.} In addition, it can be confirmed that the reaction proceeds differently even with the same catalyst depending on the amount of catalyst used.

<Experiment for selecting the optimal solvent for the manufacture of phosphorus-nitrogen-based flame retardants>

An experiment was performed to evaluate the efficiency performance according to the synthesis of a phosphorus-nitrogen-based flame retardant using a representative hydrophilic solvent. In 1000 ml of a 4-neck vertical separation reactor equipped with a reflux condenser, thermometer, stirrer, and pressure equalization funnel, 208.4 g (2 mol) of neopentyl glycol, 100 ml of solvent and catalyst were dissolved at 50 ° C. 307 g (2 mol) of phosphorus oxychloride was dropped over 1 hour through a pressure equalization dropping funnel under stirring. After the dropwise addition was completed, the temperature was raised to 80° C. and the reaction was further carried out for 2 hours. HCl was recovered using a pickling bottle in the reaction and the solvent was refluxed with a reflux condenser to proceed with the reaction. The experiment was performed by changing the solvent under the conditions shown in Table 2 below.

No. POCl ₃
(mole) Neopentyl glycol (mole) catalyst
(MgCl ₂ ) loading time
(70℃) menstruum transference number
(%) S-1 2 2 0.2 1hr 1,4-dioxane 75.4 S-2 2 2 0.2 1hr THF 68 S-3 2 2 0.2 1hr MEK 72.5 S-4 2 2 0.2 1hr DMF 78

There was no problem in the reaction rate or product formation by the hydrophilic solvent when measuring the yield result, but it was found that reflux was not easy when using a low boiling point solvent such as Acetone, THF, or MEK. The boiling point of 1,4-Dioxane is similar to that of water, so it is easy to wash with water and replace the solvent at the same time, so it has the advantage of reducing the risk of accidents caused by organic solvents during drying. In addition, it seems to be easy to use because water is easily applied to the nano-sol synthesis or dispersion of nano materials used for the application of the composite flame retardant, and since the solvent applied to the impregnation process of artificial leather is DMF, it is a nano-composite 1,4-dioxane is selected as the optimal solvent for the flame retardant synthesis process because it is judged to be easy for the preparation of the composite phosphoric acid amide-based flame retardant slurry, and solvent replacement due to the difference in boiling point with 1,4-dioxane is easy. became

<Selection of optimal synthesis conditions for phosphorus-nitrogen flame retardants>

208.4 g (2 mol) of neopentyl glycol, 73 g of 1,4-dioxane and 73 g of catalyst were completely dissolved at a temperature of 50 to 70 ° C. 307 g (2 mol) of phosphorus oxychloride was slowly added dropwise through a pressure-equilibrated dropping funnel under stirring at a temperature of 45-55° C. in the reactor. After the dropwise addition was completed, the temperature was raised to 80° C. to evaluate the reactivity according to the additional reaction time. HCl was recovered using a pickling bottle throughout the reaction, and the reaction was carried out by refluxing the solvent with a reflux condenser. At this time, a pressure reducing device using water was used to facilitate recovery of HCl. As a result of the reaction product analysis, the dropping time was adjusted to 2 hours, the reaction temperature was lowered by 10° C., and HCl recovery was facilitated using an aspirator. As a result, it was found that the yield of the compound due to the first-step reaction was slightly increased. The one-step reaction conditions and results are shown in Table 3 below.

No. POCl ₃
(mole) Neopentyl
glycol
(mole) EthylButyl pentane
diol
(mole) catalyst
(MgCl ₂ ) loading time
(45-55℃) menstruum reaction time yield APT07 2 2 - 0.2 2hr 1,4-dioxane 2hr 88% APT07-1 2 - 2 0.2 2hr 1,4-dioxane 2hr 60%

Next, a two-step reaction was performed on the product of the first step. After the amount of HCl generated in the washing bottle became invisible, EDA was added over about 2 hours, the temperature was raised, and the reaction was continued for 4 hours until the HCl was not detected, and the results are shown in Table 4 below. In the case of pickling, neutralization was continued by continuously adding 24% (w/v) NaOH to the washing bottle.

No. primary product loading time
(30℃) menstruum reaction time yield APT07 421g 2hr 1,4-dioxane 4hr 72.5% APT07-1 370g 3hr 1,4-dioxane 4hr 53%

After filtering the sample obtained in step 2 with a filter, the solid content: water = 1: 1 ratio was stirred for 30 minutes and a water washing process of filtration was performed 7 times or more, and after final filtration, 189 g of a flame retardant compound was obtained by drying at 120 ° C. obtained.

The reaction for the synthesis of phosphorus-nitrogen compounds was divided into primary and secondary, and sufficient time and temperature conditions were changed for each stage, and OH-peak was measured using FT-IR in the reaction slurry state at each stage to measure OH It was synthesized by minimizing errors occurring during the drying process. The properties of the synthesized flame retardant were evaluated using IR (Thermo scientific iD5), DSC (Scinco DSC N-650), NMR, TGA and ICP, and the results are shown in Table 5 and FIG. 3 below. The LOI (limiting oxygen index) index was evaluated according to JIS-K-7210 standard, and the LOI was measured three times in the form of a film by adding a flame retardant (APT07) synthesized to the existing adhesive layer resin in a weight ratio of 20%, and the average value was used. marked. For hydrolysis, the flame retardant is quantified, exposed to 121℃/0.2MPa, 100% RH, 96 hr conditions, dispersed in water for 10 minutes, filtered with a 0.1 μm glass filter under reduced pressure, and dried to determine the degree of dissolution in percent (%) was measured with For alkali solubility, 10 g of the prepared flame retardant was added to 100 ml of an aqueous solution having a pH of 10 using ammonia water, and after forced stirring for 10 minutes, filtered under reduced pressure with a 0.1 μm glass filter and dried to measure solubility (%). . The fogging test was performed by the MS 300-54 test method after placing 2 g of the sample on the specimen. 3, (A) is an FT-IR analysis result, (B) is a differential scanning calorimetry (DSC) analysis result, (C) is a TGA (thermal gravitational analysis) analysis result, (D) is an H-NMR analysis result .

No. yield hydrolysis resistance 90℃ Solubility alkali
Solubility LOI Index APT07 72.5% 1.72% 0.62% 0.6% 26.5 APT07-1 53% 1.28% 0.32% 0.4% 25.3

It was possible to synthesize a flame retardant having a melting point of 270 ~ 280 ℃ according to the product design by the manufacturing method as described above. Looking at the results of the evaluation of the properties of the synthesized flame retardant, it can be seen that impurities were not analyzed on FT-IR and DSC, and about 5% of impurities appeared during NMR analysis. It was analyzed that impurities not appearing in TGA, DSC, and FT-IR were excessively melted by dissolving it in DMSO during analysis pre-treatment. In the case of APT07-1 than APT07, the hydrophobic Alkyl group was higher, so water resistance, alkali solubility, and hydrolysis resistance were better. appeared not to be high. Therefore, it was confirmed that APT07 was more excellent in product mass productivity.

Residual chlorine was detected more than 2000 ppm by washing with an existing solvent or by volatilizing through a reduced pressure process, making it difficult to apply to urethane resins or electronic parts, so an experiment was performed to remove halogen elements by changing post-process conditions. .

Samples were prepared by different post-processing for the synthesized flame retardant, and the presence or absence of halogen elements was analyzed. The post-process conditions were divided into three categories: heat treatment for 15 hours, heat treatment for 24 hours, and heat treatment for 1 hour at 120°C after 5 times (1 time/30 minutes) of general water washing, and the results are shown in Table 6 below. Halogen-containing analysis was performed using a combustion ion chromatography (Combustion-Ion Chromatography) test method.

Sample name element Measurement result (mg/kg) LOQ (mg/kg) APTO7
(15 hours heat treatment) Cl 6,472 0.5 Br Below LOQ 0.5 APTO7
(24 hours heat treatment) Cl 7,030 0.5 Br Below LOQ 0.5 APTO7
(Water wash 5 times, heat treatment at 120℃ for 1 hour) Cl Below LOQ 0.5 Br Below LOQ 0.5

*LOQ: Limit of quantification Cl detected in the synthesized flame retardant was analyzed to be due to Cl of hydrochloric acid, a synthetic by-product. Referring to Table 6 above, the sample subjected to only heat treatment does not remove Cl regardless of the treatment time. , it was found that Cl was not detected only in dry samples after washing with water.

<Solidification of nano-type phosphorus-nitrogen-based flame retardant slurry using solvent substitution method>

100 g of a 50% flame retardant slurry was prepared by concentrating the solvent using a concentrator for the synthesized flame retardant (APT07). As a solvent, 100 g of a mixture solution in which a surfactant is mixed with DMF or water was added and dispersed by adding a concentrated flame retardant slurry while stirring, and particle size and viscosity were measured. For surfactant, LA-2, LA-7, LA-15, and LA-30 with different hydrophile-lipophile-balance (HLB) for each solvent were applied, respectively, and the results of substituting with DMF as the solvent are shown in Table 7 , the results of substitution using water as the solvent are shown in Table 8. Viscosity was measured under Brookfield RVT 4# 20rpm condition, and particle size was measured with Particle size Analyzer (Marvern, USA).

ITEM LA-2 (HLB:6.2) LA-7 (HLB:12.3) LA-15 (HLB:15.4) LA-30(HLB:17.6) granularity 200㎛ or more 150㎛ or more 200㎛ 200㎛ or more Viscosity
(cps) 2000 1500 1800 1200

ITEM LA-2 (HLB:6.2) LA-7 (HLB:12.3) LA-15 (HLB:15.4) LA-30(HLB:17.6) granularity 150㎛ or more 200㎛ or more 200㎛ 300㎛ or more Viscosity
(cps) 1200 1000 1120 900

When the first dispersant was added, it was found to be helpful in dispersibility but not effective in controlling particle size and viscosity, so a BYK (Germany) dispersant, a polymer-type dispersant, was secondarily added. BYK A (102) and BYK B (182) were used to proceed to solvent type, aqueous and amphoteric, and the results are shown in Table 9 below. In addition, in order to confirm the difference in the particle size distribution according to the presence or absence of a dispersant during solvent replacement, an experiment was performed by varying the application of BYK B using water as a solvent, and the results are shown in FIG. 4 . In FIG. 4, (A) is a flame retardant that is solvent-substituted without applying a dispersant and the D50 value is 150 μm, and (B) is a flame retardant that is solvent-substituted by applying BYK B as a dispersant. The D50 value is 9 μm.

ITEM BYK A (DMF) BYK B (DMF) BYK A (Water) BYK B(Water) granularity 10㎛ 15㎛ 12㎛ 9㎛ Viscosity 300 200 250 300 slurry concentration 55% 60% 35% 33%

Referring to Table 9 and FIG. 4, it was found that the average particle size after solvent replacement was significantly reduced in the case of using the dispersant compared to the case of not using it. Through this, the applicability of particle size control at the same time as solvent replacement by the addition of micellar adjuvant can be confirmed.

<Wet milling for nano-type phosphorus-nitrogen flame retardant slurry>

There is a limit to the control of particle size by solvent replacement alone, so atomization of the flame retardant slurry using a ball mill was performed after solvent replacement. With respect to the slurry prepared by applying the solvent replacement process to water to which BYK B was applied as a dispersing agent, after applying the solvent replacement process, processing was performed for 24 hours using a ball mill (zirconia beads 0.5 μm) to prepare a nano-type flame retardant slurry . The atomized flame retardant slurry was solidified by spray-drying after dispersion washing 3 to 5 times with water. After wet milling, the particle size of the nano-type flame retardant slurry was analyzed with a particle size analyzer (NanoPlus, USA) according to the ISO-13320 standard, and the results are shown in FIG. 5, and the results of analyzing the presence or absence of halogen compounds are shown in Table 10 below. As a result of the analysis in FIG. 5, the particle size (mean size) was analyzed to be 322.2 nm.

element Measurement result (mg/kg) L.O.Q. (mg/kg) Cl L.O.Q. Below 0.5 Br L.O.Q. Below 0.5 S L.O.Q. Below 0.5

Referring to FIG. 5 , as a result of the particle size analysis, the particle size (mean size) was analyzed to be 322.2 nm, confirming that the particle size was nano-sized. In addition, looking at Table 10, all halogen elements are L.O.Q. It can be confirmed that Cl is removed by measuring the following.

<Structure and physical properties analysis according to the post-processing conditions of the synthesized phosphorus-nitrogen flame retardant>

¹ H-NMR and FT-IR analysis of the structure of each compound for the flame retardant synthesized by performing a two-step reaction, a flame retardant that has undergone a water washing process through solvent substitution and milling, and a flame retardant further recrystallized using methanol through and the results are shown in FIGS. 6 and 7 . In addition, in order to confirm the physical properties of the flame retardant, heat resistance was checked by TGA analysis, and the results are shown in FIG. 8 . In addition, HPLC (ACHE 9000, Younglin Instrument) analysis was performed for the purity analysis of the flame retardant, and the results are shown in FIG. 9 . HPLC conditions were a flow rate of 0.5 ml/min, an injection volume of 80 μl, a concentration of 100 ppm, and a C18 reversed-phase column as a stationary phase, and the developing solution was methanol: water = 40: 60. 6 to 9, (A) is a flame retardant immediately after synthesis (APT07), (B) is a flame retardant that is solvent-substituted and milled, (C) is a flame retardant that is further recrystallized with methanol with respect to (B) it means.

6 to 9 , it can be seen that impurities are removed through solvent replacement, milling, and purification by methanol recrystallization, and the purity of the flame retardant is gradually increased. Referring to FIG. 8 , it can be seen that the heat resistance of the flame retardant is improved as the purity is increased. Referring to FIG. 9 , the flame retardant immediately after synthesis can confirm a broad impurity peak after a main peak of 3 minutes of retention time, but the impurity peak is significantly reduced through subsequent post-processing. It can be confirmed that atomization is possible by controlling the average particle size by solvent replacement and wet milling post-processing in the synthesized flame retardant, improving purity and reducing Cl.

<Check the flame retardant performance of the synthesized phosphorus-nitrogen-based flame retardant>

After synthesis, the flame retardant performance was measured by applying it to the fiber material for the wet milling and water washing treatment. Cotton (ISO ADJ COTTON, standard white fabric from Testfabrics), nylon (ISO ADJ POLYAMIDE, standard white fabric from Testfabrics), and polyester (Polyester Adjacent Fabric, standard white fabric from SDC Enterprises Limited) were selected as the fiber materials used, and the flame retardant concentration was determined for each material. 3, 5, and 7% ows respectively treated with A flame retardant and polyurethane-based binder 2PGN-pi were used in a ratio of 1:1, padded at a pressure of 0.4 MPa and a speed of 7, and dried at 180° C. for 2 minutes to process. The amount of pickup (pick-up) of the flame retardant processing agent for each fiber material is shown in Table 11 below.

Flame Retardant Concentration Pick-up (%) Cotton nylon Polyester 3% ows 91.13 87.12 80.61 5% ows 94.40 112.89 85.40 7% ows 90.91 98.16 85.39

After the synthesis, the flame retardant performance was measured by applying it to the fiber material for the flame retardant treated with wet milling and water washing, and the results are shown in FIG. 10 . The flame-retardant test for each of the flame-retardant-processed fibers was performed by MS 300-08, the horizontal method.

Referring to FIG. 10, it can be seen that the flame retardant performance of the flame retardant when applied to a fiber material is excellent. When applied to polyester fiber material, it showed very good flame retardant performance even when the flame retardant was treated with a small amount of 3% o.w.s.

<Optimization of nano-sol synthesis process for solvent replacement>

An experiment was performed to confirm the optimization conditions in synthesizing the nano-ceramic flame retardant slurry for application to the solvent replacement step in the manufacturing process of the amide phosphoric acid flame retardant. The nano-ceramic slurry was prepared using the electro-explosive method, and the concentration and particle size distribution (based on 4 hours) according to the solvent were checked by changing the solvent to select the optimal solvent, and the results are shown in Table 12 below. In Table 12, the particle size was measured using a particle size analyzer (Marvern, USA).

water H ₂ O ₂ (2%) 1,4-Dioxane Ethanol IPA MEK DMF granularity
(nm) 350 310 120 170 210 180 110 slurry concentration
(%) 0.72 0.58 1.18 0.54 0.42 0.61 1.11

Referring to Table 12, it was found that the particle size and concentration of the slurry greatly changed depending on the type of polar solvent, and it was determined that it would be preferable to add an auxiliary agent as it was found that nanoization was not performed well in a solvent with a large polarity similar to water. became

The particle size distribution in the case where the dispersant was added and the case in which the dispersant was not added during the preparation of the nano-type slurry by the electric explosion method was confirmed, and the results are shown in FIG. 11 . In FIG. 11, (A) shows the result when the dispersant is not added and applied, and (B) shows the result when the dispersant is added and applied. 11 , it can be seen that the particle size distribution of the dispersant-treated group is superior to that of the dispersant-treated group.

An experiment was conducted again to compare the particle size according to the input dispersant by changing the type of dispersant to be added, and the results are shown in Table 13 below. In Table 13, the viscosity was obtained under Brookfield RVT 3# 50rpm condition, and the particle size was measured using a particle size analyzer (Marvern, USA).

ITEM BYK A BYK B BYK C BYK D granularity 89nm 14nm 154nm 91nm Viscosity 19 15 23 18 slurry concentration 1.02% 1.22% 0.86% 1.05%

<Confirmation of flame retardant synergistic effect of amide phosphoric acid flame retardant and ceramic flame retardant>

An experiment was conducted to select a ceramic with excellent flame retardant synergistic effect with the amide phosphoric acid flame retardant and the urethane resin used for artificial leather. Three types of Zn, Al, and Sn-Cu were selected, and solubility at 90°C and solubility in alkali were measured for each type of ceramic. The solubility of nano-colloidal ceramics was difficult to filter, so the solubility was measured with bulk size (metal wire). In order to apply to artificial leather, solubility and alkali solubility at 90 ° C in consideration of the weight loss condition of artificial leather were measured, and the results are shown in Table 14 below, and the results of measuring the surface of the metal wire with a microscope after measuring the solubility are shown in FIG. did.

Sample name 90℃ Solubility alkali solubility Zn 0.009% 0.086% Al 0.019% 0.106% Sn-Cu 0.028% 0.120%

Referring to Table 14, it can be seen that all three types of ceramics have very low solubility. Referring to FIG. 12 , it can be seen that Zn and Al exhibit little surface corrosion after dissolution at 90° C. and alkali, and surface corrosion of Sn—Cu occurs most frequently.

In order to confirm the flame retardant synergistic effect of the amide phosphoric acid-based flame retardant and the ceramic flame retardant, 20 parts of the phosphorus-nitrogen flame retardant (APT07) and 2.5 parts of the ceramic flame retardant prepared in an embodiment of the present invention were applied to the urethane for impregnation. were compared, and the results are shown in Table 15.

Urethane for impregnation 100 100 100 100 100 Amide Phosphoric Acid Flame Retardant 20part 20part 20part 20part Zn 2.5part Al 2.5part Sn-Cu 2.5part LOI value 23.1 25.6 26.5 26.8 26.0

Referring to Table 15, when only 20 parts of the phosphorus-nitrogen-based flame retardant was added, the LOI was 25.6, and when 20 parts of the phosphorus-nitrogen-based flame retardant and 2.5 parts of Al were added, the LOI was 26.8, compared to the addition of the phosphorus-nitrogen-based flame retardant alone, the ceramic flame retardant It was found that the LOI value was increased by 1.2 times when added together. Compared to Zn and Sn-Cu, Al showed the greatest flame retardant synergy effect, so the ceramic flame retardant to be used later was selected as an Al-based ceramic.

In order to confirm the flame retardant synergistic effect of the ceramic flame retardant, the sample in which only the phosphorus-nitrogen flame retardant (APT07) content was increased to 20 parts, 22.5 parts, and 25 parts, and the sample in which the content of Al was increased to 2.5 parts and 5 parts in 20 parts of the phosphorus-nitrogen flame retardant The results of graphing the LOI values are shown in FIG. 13 .

Referring to FIG. 13 , it can be seen that the latter treatment results in a higher LOI value compared to the former treatment in which only the amide phosphoric acid-based flame retardant content is increased.

<Surface treatment of ceramic flame retardant>

As a surface treatment agent for surface treatment of the Al ceramic flame retardant, an amino silane coupling agent among silane coupling agents was selected and applied. As the amino silane coupling agent, N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane (KBM602), N-2-(Aminoethyl)-3-aminopropyltrimethoxysilane (KBM603) and 3-Aminopropyltriethoxysilane (KBM903) were used, respectively.

In order to increase the nano-composite property considering compatibility and complexation with the amide phosphoric acid-based flame retardant, surface modification was performed on the nano-sized Al product in 1,4-Dioxane as a solvent before processing with a surface treatment agent. In the first step, an Al product (particle size of 14 nm) nanosized in 1,4-Dioxane as a solvent was used. In step 2, for the hydrolysis of silane, make a volume of 300 ml with a ratio of 95% ethanol and purified water 80 : 20 (V%), and then prepare 500 ml of a solvent adjusted to pH 6.0 ~ 6.5 by adding acetic acid. After transferring this to a round flask, it was closed with a glass stopper and mixed at 300 rpm for 30 minutes using a magnetic stirrer. After mixing, 20 g of an amino silane coupling agent was added and hydrolysis was performed while stirring at 300 rpm. At this time, the hydrolysis time was carried out at intervals of 20 minutes, 40 minutes, and 1 hr. In step 3, after the hydrolysis reaction, 200 ml of the Al 1.18% 1,4-Dioxane solution prepared in step 1 was put into a round flask, stirred at 300 rpm, 10 ml of the solution hydrolyzed in step 2 was added, and the surface was treated at room temperature for 1 hour. proceeded. After the reaction was completed, the solution was centrifuged at 3,000 rpm for 30 minutes using a centrifuge, the supernatant was discarded, washed 3 times using the solvent before hydrolysis prepared in step 2, and then washed 2 more times using pure ethanol. . It was dried in an oven condition of 50° C. for 30 minutes to allow condensation polymerization to take place on the surface, and then dried in a vacuum oven at room temperature for 24 hours to obtain Al powder with a modified surface. The yield of surface-treated Al for each amino silane coupling agent was 2.8 g in the sample using KBM602 hydrolyzate, 2.7 g in the sample using KBM603 hydrolyzate, and 2.9 g in the sample using KBM903 hydrolyzate.

FT-IR analysis and SEM-EDS component analysis were performed on the surface-treated Al product to confirm the compositional change according to the surface treatment. First, as a result of checking whether the condensation reaction was sufficiently performed on the surface after surface treatment according to the hydrolysis time of the silane, if the time for hydrolysis of the silane is less than 1 hour, sufficient hydrolysis does not occur and the reaction site does not open and the reaction site does not open on the Al surface. It appeared that the reaction did not take place. Considering these results, it can be confirmed that a hydrolysis time of 1 hour or more is required.

The FT-IR confirmation results are shown in FIGS. 14 and 15 . 14 is FT-IR of amino silane used as a surface treatment agent, FIG. 15 (A) is FT-IR of Al without surface treatment, (B) is FT-IR after hydrolysis surface treatment for 20 minutes, (C) ) is FT-IR after hydrolysis surface treatment for 40 minutes, and (D) is FT-IR after hydrolysis surface treatment for 1 hour.

14 and 15, since a small amount of silane is used, it is difficult to measure the peak during analysis. However, in the case of silane hydrolyzed for 1 hour or more, a peak in the CH portion was observed at 2900 cm -1 , and the Si-O peak is about A peak was also confirmed near 1200 cm -1 . Referring to this, it was confirmed that the surface treatment of the ceramic-based flame retardant was made.

The results of surface inspection through additional SEM-EDS are shown in FIGS. 16 and 17 . Fig. 16 is Al without surface treatment, and Fig. 17 is Al after surface treatment with amino silane and washing with ethanol.

Referring to FIGS. 16 and 17 , it was found that the Si peak was confirmed in the AI of FIG. 8, and it was confirmed that the surface treatment of the ceramic-based flame retardant was made.

The appearance of the inorganic flame retardant before and after surface treatment was confirmed through SEM, and the results are shown in FIG. 18 .

<Evaluation of environmental friendliness and particle size of surface-treated inorganic flame retardants>

Eco-friendliness evaluation was performed on two types of surface-treated ZnO and Al ceramic flame retardants. As, Hg, Sb, Pb, Co, Cd, Ni, Cr, Cr(VI) and Cu were tested for a total of 10 hazardous substances, and the test analysis method was ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometer) analysis method. was used, and the measurement results are shown in Table 16 below.

element/
flame retardant ZnO ceramic Al ceramic LOQ (mg/kg) Measurement result ( mg/kg ) Measurement result ( mg/kg ) As Below LOQ Below LOQ 0.01 Hg Below LOQ Below LOQ 0.01 Sb Below LOQ Below LOQ 0.1 Pb Below LOQ Below LOQ 0.02 Co Below LOQ Below LOQ 0.05 CD Below LOQ Below LOQ 0.05 Ni Below LOQ Below LOQ 0.1 Cr Below LOQ Below LOQ 0.1 Cr(VI) Below LOQ Below LOQ 0.5 Cu Below LOQ Below LOQ 0.1

* LOQ : Limit of quantification, LOD : Limit of detection, LOQ = LOD × 3

Referring to Table 16, it was found that the regulated substances were not detected, and it was confirmed that the inorganic flame retardant manufactured by the manufacturing method according to an aspect of the present invention was excellent in environmental friendliness.

The result of confirming the ceramic particle size of the surface-treated Al, Zn, and ZnO ceramic-based flame retardants using TEM is shown in FIG. 19 .

<Composite of surface-treated ceramic flame retardant and amide phosphoric acid flame retardant>

First, the surface modification was performed on the Al inorganic flame retardant nanoized in the solvent DMF. A nano-sized Al product (NV 2%) was used in the solvent DMF. For the hydrolysis of silane, 95% ethanol and purified water were mixed in a ratio of 80:20 (V%) to make 150ml, and then acetic acid was added to adjust the pH. The solvent adjusted to be 6.0 to 6.5 was mixed at 300 rpm for 30 minutes using a stirrer. After mixing, 3 g of an amino silane coupling agent was added, followed by hydrolysis for 1 hour while stirring at 300 rpm, and then the hydrolyzed silane coupling agent was added to the Al slurry over 1 hour to prepare a surface-treated ceramic flame retardant. .

The composite of the surface-treated ceramic flame retardant and the amide phosphoric acid flame retardant was carried out in two ways. In one case, complexing was performed by simply mixing the surface-treated ceramic flame retardant and the amide phosphoric acid flame retardant, and in the other, the surface-treated ceramic flame retardant was added to the solvent of the last step of the solvent replacement process of the amide phosphoric acid flame retardant to be compounded. was performed. The composite result was confirmed using SEM and is shown in FIG. 20 .

<Manufacture of composite flame retardant with different types of silane compound and mixing ratio of organic/inorganic flame retardants>

By using the silane coupling agent of Table 17 below, the ratio of the organic and inorganic flame retardants was varied in the ratio of Table 18 to be complexed.

functional group (X) division compound name Epoxy Epoxy-A 3-Glycidoxypropyl methyldimethoxysilane Epoxy-B 3-Glycidoxypropyl trimethoxysilane Amino Amino-A N-2-(Aminoethyl)-3-aminopropylmethyl
dimethoxysilane Amino-B 3-Aminopropyltrimethoxysilane

division Al Organic-inorganic composite flame retardant ratio Type of surface treatment agent Al flame retardant solid content
Silane surface treatment agent content (amide phosphoric acid type: ceramic type) 1st-1 Amino-A 30% 8:1 1st-2 4:1 2nd-1 Amino-B 30% 8:1 2nd-2 4:1 3rd-1 Epoxy-A 30% 8:1 3rd-2 4:1 4th-1 Epoxy-B 30% 8:1 4th-2 4:1

First, for the hydrolysis of silane, 187.5 ml of ethanol and purified water were made in a ratio of 80: 20 (V%), and then a solvent adjusted to pH 6.0-6.5 by adding acetic acid was mixed for 30 minutes. Then, 3.75 g of a silane coupling agent was added, diluted with NV 2%, and hydrolysis was performed for 1 hour. Next, hydrolyzed silane was added to 625 g of Al slurry (2%) dispersed in DMF, and surface treatment was performed at room temperature for 1 hour. Then, the amide phosphoric acid-based flame retardant and the ceramic-based flame retardant were mixed in a specified weight ratio. When preparing at 8:1, the surface-treated Al slurry was added to 200 g of an amide phosphoric acid flame retardant (NV 50%) dispersed in 1,4-Dioxane, stirred for 1 hour, and dried, followed by amide phosphoric acid flame retardant When preparing at a ratio of 4:1, the surface-treated Al slurry was added to 100 g of an amide phosphoric acid flame retardant (NV 50%), stirred for 1 hour, and dried to prepare a composite flame retardant. When performing drying for powdering of the complex flame retardant, it was concentrated using a palmetary mixer, dried under reduced pressure to solidify the product, and then the physical properties of each complex type flame retardant were evaluated.

In order to confirm the flame retardant synergistic effect, 20 parts of a composite flame retardant was applied to the urethane for impregnation and the LOI values were compared after the film was prepared, and the results are shown in Table 19 below.

1st-1 1st-2 2nd-1 2nd-2 3rd-1 3rd-2 4th-1 4th-2 LOI value 26.5 26.7 26.7 26.7 26.8 26.9 27.2 27.1

Referring to Table 19, it was confirmed that good results were obtained when comparing the LOI values after film production by applying 20 parts of a composite flame retardant (based on flame retardant content) to the urethane for impregnation in order to confirm the flame retardant synergistic effect. It was found to have a more effective LOI index value when evaluating the flame retardancy depending on the degree of complexation of the ceramic flame retardant and the amide phosphoric acid flame retardant, which acts on a large area when the amide phosphoric acid flame retardant is involved in the process of forming the foaming layer and acts on a Char film It is judged to be a phenomenon that occurs by facilitating formation. It is judged that if the amide phosphoric acid (N-P) flame retardant forms a foaming layer and the ceramic flame retardant accelerates the char speed simultaneously, the char film is formed more evenly and faster.

The result of confirming the composite result using SEM is shown in FIG. 21 . Referring to FIG. 21 , the aggregation phenomenon of the surface-treated inorganic flame retardant was improved.

The results of performing the SEM-EDS analysis of the composite results are shown in FIG. 22 . Referring to FIG. 22 , the C, N, O, and P content of the amide phosphoric acid flame retardant, the Al content of the ceramic flame retardant, and Si used for surface treatment were detected, confirming that the complexation was well performed.

In order to check the flame retardant synergistic effect according to the mixing ratio of the composite flame retardant, the LOI value for each sample in which the content of only amide phosphoric acid flame retardants was increased to 20 parts, 22.5 parts, and 25 parts and Al was increased to 2.5 parts and 5 parts was graphed and the The results are shown in FIG. 23 . In FIG. 23, the phosphoric acid-based flame retardant was denoted as APT.

Referring to FIG. 23, as a result of evaluating the LOI index according to the ratio of the amide phosphoric acid flame retardant to the ceramic flame retardant when manufacturing the composite flame retardant, the graph obtained by compounding the ceramic flame retardant with 2.5 and 5 parts based on the amide phosphoric acid flame retardant 20 and 22.5 parts is a ceramic-based flame retardant. Depending on the flame retardant content, the LOI index graph has a secondary function type, whereas the compounding by increasing the ceramic flame retardant content at 25 parts with an amide phosphoric acid flame retardant content shows a graph of the primary function type, not the secondary function, in which the LOI value is not a secondary function. From this, it can be confirmed that the ratio of compounding a high flame retardant content is more effective.

<Evaluation of eco-friendliness of organic-inorganic composite flame retardants>

Eco-friendliness evaluation was performed on the compounded flame retardant. As, Hg, Sb, Pb, Co, Cd, Ni, Cr, Cr(VI) and Cu were tested for a total of 10 hazardous substances, and the test analysis method was ICP-OES (Inductively Coupled Plasma - Optical Emission Spectrometer) analysis method. was used. The measurement results are shown in Table 20 below.

element/flame retardant Measurement result ( mg/kg ) LOQ (mg/kg) As Below LOQ 0.01 Hg Below LOQ 0.01 Sb Below LOQ 0.1 Pb Below LOQ 0.02 Co Below LOQ 0.05 CD Below LOQ 0.05 Ni Below LOQ 0.1 Cr Below LOQ 0.1 Cr(VI) Below LOQ 0.5 Cu Below LOQ 0.1

Referring to Table 20, it can be confirmed that the regulated substance is not detected as a result of the measurement.

Next, Br detection was performed through CIC (Combustion Ion Chromatography) analysis. The equipment is Mitsubishi anal. AQF-2100H (Comb.), Thermo Scientific ICS-1100 (IC) were used, and the column was measured under IonPac AS19 analytical (4*250 mm), mobile phase 45 mM KOH / Dionex EGC (Eluent Generator Cartridge) Ⅲ KOH conditions. The measurement results are shown in FIG. 24 .

<Evaluation of eco-friendliness of artificial leather with organic-inorganic composite flame retardant>

After 25 parts of the composite flame retardant was applied to the solvent-free binder layer, 20 parts of the composite flame retardant was mixed with the impregnated resin, and the artificial leather specimen to which the impregnated fabric was applied was analyzed for regulated hazardous substances and halogen elements. For the analysis method, ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer) was used for the analysis of halogen elements, and Combustion-Ion Chromatography was used for the analysis of regulated hazardous substances. The analysis results are shown in Table 21 below.

test method element Measurement result ( mg/kg ) LOQ (mg/kg) ICP As Below LOQ 0.01 Hg Below LOQ 0.01 Sb 32 0.1 Pb Below LOQ 0.02 Co Below LOQ 0.05 CD Below LOQ 0.05 Ni Below LOQ 0.1 Cr Below LOQ 0.1 Cr(VI) Below LOQ 0.5 Cu Below LOQ 0.1 C-IC Cl Below LOQ 0.5 Br Below LOQ 0.5

Referring to Table 21, halogen elements were not detected, and as a result of analysis of regulated hazardous substances, it appears that all but Sb (antimony) were not detected. The amount of Sb element detected was 32 mg/kg. Sb element is not detected in the flame retardant component, but is detected in the polyester fabric used as the base material for artificial leather. Considering that the Sb regulation limit in Ecotex 100 is 300 mg/kg for polyester fiber, it is safe product was confirmed.

It was confirmed that the organic-inorganic composite flame retardant prepared according to one aspect of the present invention is an environmentally friendly and safe flame retardant because it has excellent flame retardancy and physical properties, and no regulated substances are detected.

Claims (13)

A flame retardant preparation step of preparing a phosphorus-nitrogen-based flame retardant and a ceramic-based flame retardant, respectively;
a surface treatment step of surface-treating the ceramic-based flame retardant with a silane-based compound; and
A method for producing a composite flame retardant comprising a; a complexing step of mixing the ceramic-based flame retardant surface-treated with a silane-based compound and the phosphorus-nitrogen-based flame retardant.
According to claim 1,
A method for producing a composite flame retardant, wherein the ceramic-based flame retardant surface-treated with a silane-based compound and the phosphorus-nitrogen-based flame retardant are mixed in a weight ratio of 1:4 to 8 in the complexing step.
According to claim 1,
The phosphorus-nitrogen-based flame retardant,
A first step of reacting by adding bis-cyclic phosphate, phosphorus oxide _{chloride (POCl 3 ) and a catalyst to a hydrophilic solvent;}
a second step of synthesizing a bis-type flame retardant by adding and reacting a nitrogen compound;
a third step of atomizing the bis-type flame retardant synthesized in the second step; and
The method for manufacturing a composite flame retardant, which is prepared by a manufacturing method comprising a fourth step of washing the bis-type flame retardant atomized in the third step with a water-soluble solvent.
A first step of reacting by adding bis-cyclic phosphate, phosphorus oxide _{chloride (POCl 3 ) and a catalyst to a hydrophilic solvent;}
a second step of synthesizing a bis-type flame retardant by adding and reacting a nitrogen compound;
A third step of complexing by solvent replacement with a ceramic-based flame retardant slurry surface-treated with a silane-based compound; and
A fourth step of washing with a water-soluble solvent; comprising, a method for producing a composite flame retardant.
5. The method of claim 4,
The third step and the step of atomizing between the fourth step; is further performed, the method for producing a composite flame retardant.
5. The method of claim 3 or 4,
The biscyclic phosphate is neopentyl glycol, ethylbutyl glycol, or a mixture thereof, a method for producing a composite flame retardant.
5. The method of claim 3 or 4,
The catalyst is anhydrous magnesium chloride (anhydride MgCl ₂ ) or anhydrous aluminum chloride (anhydride AlCl ₃ ).
5. The method of claim 3 or 4,
In the first step, a biscyclic phosphate salt and a catalyst are first added to a hydrophilic solvent, and phosphorus oxide chloride is added dropwise for 1 to 2 hours while stirring at 45 to 55° C., and then the temperature is raised to 70 to 80° C. for 2 to 4 hours. A method for producing a composite flame retardant, which is carried out by aging.
5. The method of claim 3 or 4,
The catalyst is added in an amount of 0.05 to 0.2 moles based on 1 mole of the biscyclic phosphoric acid, the method for producing a composite flame retardant.
5. The method of claim 3 or 4,
The second step is carried out at 20 to 30 ℃ for 4 to 6 hours, the method for producing a composite flame retardant.
5. The method of claim 4,
The method for producing a composite flame retardant, wherein the ceramic-based flame retardant and the bis-type flame retardant surface-treated with the silane-based compound in the third step are mixed in a weight ratio of 1:4 to 8.
A first step of preparing a ceramic containing at least one selected from the group consisting of Zn-based, Al-based, Sn-Cu-based, Mg-based and Si-based ceramics;
a second step of synthesizing a ceramic flame retardant whose particle size is controlled by a sol-gel method or an electric explosion method; and
A third step of surface treatment with a silane-based compound; including,
In the second step, a solvent containing at least one selected from the group consisting of water, hydrogen peroxide, 1,4-dioxane, ethanol, IPA, MEK and DMF is used, and a dispersant is added, the surface A method for producing a treated ceramic-based flame retardant.
13. The method of claim 12,
The silane-based compound is vinyl (vinyl), epoxy (epoxy), styryl (styryl), methacryloxy (methacryloxy), acryloxy (acryloxy), amino (amino), ureide (ureide), mercapto (mercapto) and at least one functional group selected from the group consisting of isocyanate.

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