One]The present invention relates to a method for producing a flame-retardant aid, and a flame-retardant resin composition comprising the flame-retardant aid produced by the method.
background
[2]
[Correction with related applications]
[3]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0120027, filed on September 27, 2019 and Korean Patent Application No. 10-2020-0118225, filed on September 15, 2020, , all contents disclosed in the Korean patent application documents are incorporated as a part of this specification.
[4]
[5]
[Technical field]
[6]
Thermoplastic resin compositions are being applied to various fields from daily necessities to automobile interior materials, office equipment, and electrical and electronic products such as displays. In addition, flame-retardant thermoplastic resins to which flame retardancy is imparted by injecting a flame retardant into a thermoplastic resin composition for application to heat generating products or high voltage products have been used in various fields.
[7]
Flame retardants are usually divided into halogen-based and non-halogen-based flame retardants, and brominated flame retardants are representative halogen-based flame retardants. Bromine-based flame retardants have excellent flame retardancy even in thin films, and when mixed with antimony trioxide, a flame retardant aid, have an excellent flame retardant effect even when a small amount is added.
[8]
However, in the case of antimony trioxide used as a flame-retardant aid, since it is classified as a first-class carcinogen, the development of a new flame-retardant aid to replace it is required. Accordingly, attempts have been made to use other metal oxides such as Fe 2 O 3 , MoO 2 , and Bi 2 O 3 as flame retardant aids. However, in the case of these metal oxides, the flame retardant efficiency is low and the application is limited due to the unique color of inorganic materials. .
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[9]
The present invention is to solve the above problems, does not contain carcinogens, and is applied to a thermoplastic resin composition together with a halogen-based flame retardant to show excellent flame retardant efficiency, and a flame retardant manufactured through the method An object of the present invention is to provide a flame-retardant resin composition comprising an adjuvant.
[10]
means of solving the problem
[11]
According to one embodiment, the present invention, by adding a zinc precursor and a precursor including a M 1 metal to a solvent to prepare a metal precursor solution; and adding an acid or a base to the metal precursor solution to perform a sol-gel reaction to prepare a multi-component metal hydroxide represented by Formula 1 below.
[12]
[Formula 1]
[13]
Zn x M 1 y (OH) z
[14]
In Formula 1, M 1 is at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, and x and y mean the atomic ratio of Zn and M 1 , respectively, x : y is 0.5 to 2.0: 0.1 to 3.0, and 2≤z≤6.
[15]
[16]
According to another embodiment, the present invention provides a flame-retardant resin composition comprising a base resin, a halogen-based flame retardant, and a flame-retardant auxiliary, wherein the flame-retardant auxiliary is a multi-component metal hydroxide represented by Formula 1 above.
[17]
Effects of the Invention
[18]
The method for manufacturing a flame retardant aid according to the present invention is a method of forming a flame retardant aid in the form of a hydroxide including two or more metal components through a sol-gel process. When manufacturing a flame retardant aid through the sol-gel process as in the present invention, the metal component and content in the flame retardant aid can be variously controlled, and a flame retardant aid having excellent particle size uniformity can be manufactured.
[19]
In addition, although mass production was not possible in conventional methods such as hydrothermal synthesis used for preparing metal hydroxides, according to the manufacturing method of the present invention, mass production is possible and thus economical efficiency is excellent.
[20]
The flame-retardant aid prepared according to the method of the present invention has high particle size uniformity, excellent dispersibility when mixed with a thermoplastic resin, and excellent flame retardancy and thermal stability improvement effect.
[21]
In addition, the flame-retardant resin composition comprising a flame-retardant aid prepared according to the method of the present invention does not use an antimony-based flame-retardant aid that generates carcinogens, so it is environmentally friendly, safe, and exhibits excellent flame-retardant performance. In addition, when using the flame retardant aid prepared according to the method of the present invention, it is possible to obtain the effect of improving the thermal stability degradation due to the decomposition of the halogen-based flame retardant.
[22]
Brief description of the drawing
[23]
1 is a SEM photograph of the Zn-Sn hydroxide particles prepared in Example 1.
[24]
FIG. 2 is a photograph showing the distribution of Zn in the Zn—Sn hydroxide particles prepared in Example 1. FIG.
[25]
3 is a photograph showing the distribution of Sn in the Zn—Sn hydroxide particles prepared in Example 1. FIG.
[26]
4 is a graph showing the composition ratio of Zn and Sn in the Zn-Sn hydroxide particles prepared in Example 1 measured through EDS mapping.
[27]
5 is a SEM photograph of the Zn-Al hydroxide particles prepared in Example 2.
[28]
6 is a photograph showing the distribution of Zn and Al in the Zn-Al hydroxide particles prepared in Example 2.
[29]
7 is a graph showing the composition ratio of Zn and Al in the Zn-Al hydroxide particles prepared in Example 2 measured through EDS mapping.
[30]
Best mode for carrying out the invention
[31]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[32]
The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise.
[33]
In the present specification, terms such as “comprise” or “have” are intended to designate the existence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or number, step, configuration It should be understood that it does not preclude the possibility of the presence or addition of elements, or combinations thereof.
[34]
[35]
Hereinafter, the present invention will be described in detail.
[36]
[37]
Manufacturing method of flame retardant aid
[38]
The present invention relates to a method for producing a flame retardant aid that can replace an antimony-based flame retardant aid, and specifically, a method of forming a flame retardant aid in the form of a multi-component metal hydroxide including two or more metal components through a sol-gel process is about
[39]
[40]
The manufacturing method of the flame retardant auxiliary of the present invention comprises the steps of (1) adding a zinc precursor and a precursor containing M 1 metal to a solvent to prepare a metal precursor solution; and (2) adding an acid or a base to the metal precursor solution to perform a sol-gel reaction to prepare a multi-component metal hydroxide represented by the following Chemical Formula 1.
[41]
[Formula 1]
[42]
Zn x M 1 y (OH) z
[43]
In Formula 1, M 1 is at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, and x and y mean the atomic ratio of Zn and M 1 , respectively, x : y is 0.5 ~ 2.0 : 0.1 ~ 3.0, 2≤z≤6.
[44]
[45]
First, a metal precursor solution is prepared by adding a zinc precursor and a precursor including a M 1 metal to a solvent. The M 1 metal may be at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, and specifically, Sn, Al, Ti, Nb, Fe, Co, Ni, Cu , Zr, Mo, Pd, Sc, Cd, Ca, Sr, may be at least one selected from the group consisting of Si and Sb.
[46]
In this case , the solvent may dissolve the zinc precursor and the precursor including the M 1 metal, and the type thereof is not particularly limited. For example, the solvent may be deionized water, ethanol, methanol, isopropanol, acetonitrile, dimethylamine borane, or a mixture thereof, but is not limited thereto.
[47]
The zinc precursor may be, for example, zinc chloride, zinc sulfate, zinc acetate, zinc nitrate, zinc sulfide, or a mixture thereof, and the precursor including the M 1 metal is a chloride, sulfur oxide, or nitrogen of the M 1 metal. products, sulfides, acetates, or mixtures thereof, and the like. Specifically, the precursor containing the M 1 metal is Sn, Al, Ti, Nb, Fe, Co, Ni, Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, Si or Sb chloride. , sulfur oxides, nitric products, sulfides, acetates, or mixtures thereof.
[48]
Meanwhile, in the metal precursor solution, the zinc precursor and the precursor containing the M 1 metal have an atomic ratio of zinc:M 1 metal of 0.5 to 2.0: 0.1 to 3.0, preferably 0.5 to 2.0: 0.1 to 2.0, more preferably Preferably, it is included in an amount such that it is 0.7 to 1.3: 0.2 to 1.3. When the addition amount of the precursor containing the zinc precursor and M 1 metal in the metal precursor solution satisfies the above range, it is possible to prepare a flame-retardant aid having excellent effects of improving flame retardancy efficiency and thermal stability.
[49]
After the zinc precursor and the precursor including the M 1 metal are added to a solvent, the metal precursor solution is prepared by mixing with stirring to be well dissolved in the solvent.
[50]
[51]
Next, the sol-gel reaction proceeds by adjusting the pH by adding an acid or a base to the metal precursor solution.
[52]
The acid or base is added to adjust the pH of the metal precursor solution, and acids or bases well known in the art may be used, for example, acetic acid, sodium hydroxide, ammonium hydroxide, calcium hydroxide, etc. may be used. , but is not limited thereto.
[53]
Meanwhile, when an acid is applied to adjust the pH, the acid may be added in an amount such that the pH of the metal precursor solution is 2 to 4. When a base is applied to adjust the pH, the base may be added in an amount such that the pH of the metal precursor solution is 8 to 10.
[54]
After adjusting the pH of the metal precursor solution through the addition of an acid or base, when stirred, hydrolysis occurs and a sol-gel reaction proceeds, and as a result of the reaction, zinc and M 1 containing zinc and M 1 metals represented by the following Chemical Formula 1 Multi-component hydroxide particles are formed.
[55]
[Formula 1]
[56]
Zn x M 1 y (OH) z
[57]
In Formula 1, M 1 is at least one selected from the group consisting of transition metals other than Zn, alkaline earth metals, and Groups 13 to 16 metals, preferably Sn, Al, Ti, Nb, Fe, Co, Ni , Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, may be at least one selected from the group consisting of Si and Sb.
[58]
Wherein x and y mean the atomic ratio of Zn and M 1 , respectively , x: y is 0.5 to 2.0: 0.1 to 3.0, preferably 0.5 to 2.0: 0.1 to 2.0, more preferably x: y is 0.7 ~ 1.3: may be 0.2 ~ 1.3.
[59]
The z means the molar ratio of OH, 2≤z≤6.
[60]
[61]
Specifically, the multi-component metal hydroxide may be represented by the following [Formula 2].
[62]
[Formula 2]
[63]
Zn x M 2 y1 M 3 y2 (OH) z
[64]
In Formula 2, M 2 is at least one selected from the group consisting of Sn and Al, and M 3 is one selected from the group consisting of transition metals, alkaline earth metals, and Groups 13 to 16 metals except Zn, Sn and Al. or more, and preferably, it may be at least one selected from the group consisting of Ti, Nb, Fe, Co, Ni, Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, Si and Sb.
[65]
Wherein x, y1, y2 means an atomic ratio of Zn, M 2 and M 3 , respectively , x: y1: y2 is 0.5 to 2.0: 0.1 to 3.0: 0 to 2.9, preferably, 0.5 to 2.0: 0.1 to 2.0: 0 to 1.9, more preferably 0.7 to 1.3: 0.2 to 1.3: may be 0 to 1.1.
[66]
The z means the molar ratio of OH, 2≤z≤6.
[67]
[68]
More specifically, the multi-component metal hydroxide may be a metal hydroxide including two or three kinds of metal elements, for example, Zn x Sn y (OH) z, Zn x Al y (OH) z , Zn x Sn y1 Al y2 (OH) z, Zn x Sn y1 Ti y2 (OH) z, Zn x Sn y1 Fe y2 (OH) z, Zn x Sn y1 Fe y2(OH) z, Zn x Sn y1 Ti y2 (OH) z, Zn x Sn y1 Co y2 (OH) z, Zn x Sn y1 Ni y2 (OH) z, Zn x Sn y1 Zr y2 (OH) z, Zn x Sn y1 Mo y2 (OH) z, Zn x Sn y1Pd y2 (OH) z, Zn x Sn y1 Sc y2 (OH) z, Zn x Sn y1 Cd y2 (OH) z, Zn x Sn y1 Mg y2 (OH) z, Zn x Sn y1 Ca y2 (OH) z , Zn x Sn y1 Sr y2 (OH) z, Zn xSn y1 Si y2 (OH) z, Zn x Sn y1 Sb y2 (OH) z, Zn x Al y1 Ti y2 (OH) z, Zn x Al y1 Fe y2 (OH) z, Zn x Al y1 Fe y2 (OH ) ) z, Zn x Al y1 Ti y2 (OH) z,Zn x Al y1 Co y2 (OH) z, Zn x Al y1 Ni y2 (OH) z, Zn x Al y1 Zr y2 (OH) z, Zn x Al y1 Mo y2 (OH) z, Zn x Al y1 Pd y2 (OH) z, Zn x Al y1 Sc y2(OH) z, Zn x Al y1 Cd y2 (OH) z, Zn x Al y1 Mg y2 (OH) z, Zn x Al y1 Ca y2 (OH) z, Zn x Al y1 Sr y2 (OH) z, Zn x Al y1 Si y2 (OH) z, Zn x Al y1Sb y2 (OH) z (wherein x, y, y1, y2, and z are the same as defined in Formula 1 or Formula 2), and the like, but is not limited thereto.
[69]
[70]
When multi-component metal hydroxide particles are formed through the above process, the formed multi-component metal hydroxide particles are precipitated, a supernatant is removed, washed and dried to obtain a multi-component metal hydroxide.
[71]
[72]
The multi-component metal hydroxide prepared according to the present invention is used together with a flame retardant to improve the flame retardancy and thermal stability of the thermoplastic resin, and thus can be usefully used as a flame retardant aid.
[73]
[74]
Meanwhile, in the prior art, it has been common to prepare multi-component metal hydroxides through hydrothermal synthesis. However, the hydrothermal synthesis method has a problem in that it is difficult to mass-produce and thus economical. In addition, when the hydrothermal synthesis method is used, the composition of the metal components in the multi-component metal hydroxide is formed to satisfy the stoichiometry, and it is difficult to prepare a metal hydroxide of various composition ratios because a non-stoichiometric compound cannot be prepared.
[75]
In contrast, when a multi-component metal hydroxide is prepared through the sol-gel process as in the present invention, mass production is possible, and compounds having a non-stoichiometric metal composition are also formed by controlling the input amount and/or reaction conditions of the precursor. can do. Therefore, by adjusting the metal composition in the multi-component metal hydroxide in consideration of the applied thermoplastic resin or use, it is possible to provide a flame-retardant aid having optimized desired performance.
[76]
In addition, the multi-component metal hydroxide prepared according to the method of the present invention has a uniform particle size distribution compared to the multi-component metal hydroxide prepared by the hydrothermal synthesis method, and since additives such as surfactants are not used in the manufacturing process, the thermoplastic resin It has excellent dispersibility when mixed with, thereby maximizing the flame retardant synergistic effect and thermal stability improvement effect when the flame retardant resin composition is applied.
[77]
[78]
flame retardant resin composition
[79]
Next, the flame retardant resin composition according to the present invention will be described. The flame retardant resin composition of the present invention contains (1) a base resin, (2) a flame retardant, and (3) a flame retardant auxiliary.
[80]
[81]
(1) base resin
[82]
In the present invention, the base resin is various thermoplastic resins applied to the flame-retardant resin composition in the art, for example, a rubbery polymer resin, an aromatic vinyl-based resin, a polycarbonate resin, a polyolefin resin, an acrylic resin, or a mixture thereof. It can be used without limitation, and the type is not particularly limited.
[83]
Specifically, the flame retardant resin composition of the present invention may include a base resin including a conjugated diene-based graft copolymer and a matrix copolymer in which the conjugated diene-based graft copolymer is dispersed.
[84]
In this case, the graft copolymer may be a copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a conjugated diene-based polymer.
[85]
The graft copolymer may be prepared through a conventional graft polymerization method generally known in the art, and specifically, emulsion polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in the presence of a conjugated diene-based polymer. , can be prepared by a method of suspension polymerization or bulk polymerization.
[86]
In this case, the conjugated diene-based polymer refers to a polymer prepared by polymerization of a conjugated diene-based monomer, and the conjugated diene-based monomer may be at least one selected from the group consisting of butadiene, isoprene and chloroisoprene, among them, butadiene is may be desirable.
[87]
The conjugated diene-based polymer used in the present invention may have an average particle diameter of 0.1 to 1.0 μm, 0.1 to 0.5 μm, or 0.1 to 0.3 μm, of which 0.1 to 0.3 μm is preferable. When the average particle diameter of the conjugated diene-based polymer satisfies the above-mentioned range, the mechanical properties, glossiness, and colorability of the graft copolymer can be further improved.
[88]
Meanwhile, the conjugated diene-based polymer may be used by mixing two or more types having different average particle diameters within the aforementioned particle diameters.
[89]
Meanwhile, in the present invention, the average particle size may be defined as a particle size corresponding to 50% or more of the cumulative volume in the particle size distribution curve of the particles. In the present invention, the average particle diameter of the conjugated diene-based polymer can be measured after dissolving a certain amount of the conjugated diene-based polymer in a solvent. Specifically, 0.5 g of the conjugated diene-based polymer is dissolved in 100 ml of methyl ethyl ketone, and the measurement can be performed using a Coulter counter (trade name: LS230, manufacturer: Beckman Coulter).
[90]
The aromatic vinyl monomer is one selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene and 4-ethylstyrene. or more, and among these, styrene is particularly preferable.
[91]
The vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and among them, acrylonitrile is preferable.
[92]
The graft copolymer of the present invention may include 50 to 65 wt% of a conjugated diene-based polymer, 25 to 35 wt% of an aromatic vinyl-based monomer-derived unit, and 5 to 20 wt% of a vinyl cyan-based monomer-derived unit. When the above ranges are satisfied, the mechanical properties, glossiness and colorability of the graft copolymer may be improved, and the rigidity, processability, surface gloss, chemical resistance and weather resistance of the flame-retardant resin composition may be further improved.
[93]
The graft copolymer may have a graft rate of 30 to 70%, 40 to 60%, or 40 to 50%, of which 40 to 50% is preferable. If the above-mentioned range is satisfied, it is possible to achieve a balance between thermal stability and mechanical properties of the graft copolymer.
[94]
Here, the graft rate can be calculated using the following formula after adding a certain amount of the graft copolymer to a solvent, dissolving it using a vibrator, centrifuging with a centrifugal separator, and drying to obtain an insoluble content. In detail, a certain amount of the graft copolymer is added to acetone and vibrated with a vibrator (trade name: SI-600R, manufacturer: Lab. companion) for 24 hours to dissolve the free graft copolymer, and 14,000 rpm with a centrifugal separator. After centrifugation for a period of time and dried at 140° C. for 2 hours with a vacuum dryer (trade name: DRV320DB, manufacturer: ADVANTEC) to obtain an insoluble content, it can be calculated using the following formula.
[95]
Graft rate (%)=[(Y-(X × R))/(X × R)] × 100
[96]
Y: weight of insoluble matter
[97]
X: weight of graft copolymer added when obtaining insoluble matter
[98]
R: Fraction of conjugated diene-based polymer in graft copolymer added when obtaining insoluble matter
[99]
[100]
Meanwhile, the matrix copolymer may be a copolymer of an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[101]
In this case, the aromatic vinyl monomer is selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene and 4-ethylstyrene. It may be one or more types, and among these, styrene is especially preferable.
[102]
The vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and among them, acrylonitrile is preferable.
[103]
The aromatic vinyl-based monomer and the vinyl cyanide-based monomer included in the matrix copolymer of the present invention are preferably included in a weight ratio of 6:4 to 9:1. If the above-mentioned range is satisfied, color, rigidity, processability, productivity, chemical resistance, and weather resistance may be excellent.
[104]
[105]
On the other hand, the base resin is a graft copolymer and a matrix copolymer in a weight ratio of 1:9 to 9:1, preferably in a weight ratio of 1:9 to 6:4, more preferably in a weight ratio of 1:9 to 4:6. It may be included by weight ratio. When the graft copolymer is included in less than this, the impact strength is lowered and may be broken during the injection and assembly process of the product.
[106]
[107]
(2) flame retardant
[108]
The flame retardant is to provide flame retardancy to the flame retardant resin composition, and may be a halogen-based flame retardant generally used in the art.
[109]
Specific examples of the halogen-based flame retardant include hexabromocyclododecane, tetrabromocyclooctane, monochloro pentabromocyclohexane, and decabromodiphenyl oxide. , octabromodiphenyl oxide, decabromodiphenyl ethane, ethylene bis (tetrabromophthalimide), tetrabromobisphenol A (tetrabromobisphenyl A), bro Brominated epoxy oligomers, bis(tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1, 3,5-triazine (2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine), tetrabromobisphenol A bis(allyl ether) )) and the like, but is not limited thereto.
[110]
[111]
The flame retardant may be included in an amount of 10 to 30 parts by weight, preferably 10 to 30 parts by weight, more preferably 10 to 25 parts by weight based on 100 parts by weight of the base resin. When the content of the flame retardant satisfies the above range, it is possible to effectively improve the flame retardancy without adversely affecting the physical properties of the base resin.
[112]
[113]
(3) flame retardant preparation
[114]
The flame retardant aid acts to increase the flame retardant effect of the flame retardant, and in the present invention, a multi-component metal hydroxide represented by the following Chemical Formula 1 prepared according to the method of the present invention as described above is used as the flame retardant aid.
[115]
[Formula 1]
[116]
Zn x M 1 y (OH) z
[117]
In Formula 1, M 1 is at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, and x and y mean the atomic ratio of Zn and M 1 , respectively, x : y is 0.5 to 2.0: 0.1 to 3.0, and 2≤z≤6.
[118]
Preferably, the M 1 is one selected from the group consisting of Sn, Al, Ti, Nb, Fe, Co, Ni, Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, Si and Sb It may be more than one species, and x: y may be 0.5 to 2.0: 0.1 to 2.0, more preferably, 0.7 to 1.3: 0.2 to 1.3.
[119]
[120]
Specifically, the multi-component metal hydroxide may be represented by the following [Formula 2].
[121]
[Formula 2]
[122]
Zn x M 2 y1 M 3 y2 (OH) z
[123]
In Formula 2, M 2 is at least one selected from the group consisting of Sn and Al, and M 3 is one selected from the group consisting of transition metals, alkaline earth metals, and Groups 13 to 16 metals except Zn, Sn and Al. or more, and preferably, it may be at least one selected from the group consisting of Ti, Nb, Fe, Co, Ni, Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, Si and Sb.
[124]
Wherein x, y1, y2 means atomic ratios of Zn, M 2 and M 3 , respectively , x: y1: y2 is 0.5 to 2.0: 0.1 to 3.0: 0 to 2.9, preferably 0.5 to 2.0: 0.1 to 2.0: 0 to 1.9, more preferably, 0.7 to 1.3: 0.2 to 1.3: 0 to 1.1.
[125]
The z means the molar ratio of OH, 2≤z≤6.
[126]
[127]
More specifically, the multi-component metal hydroxide may be a metal hydroxide including two or three kinds of metal elements, for example, Zn x Sn y (OH) z, Zn x Al y (OH) z , Zn x Sn y1 Al y2 (OH) z, Zn x Sn y1 Ti y2 (OH) z, Zn x Sn y1 Fe y2 (OH) z, Zn x Sn y1 Fe y2(OH) z, Zn x Sn y1 Ti y2 (OH) z, Zn x Sn y1 Co y2 (OH) z, Zn x Sn y1 Ni y2 (OH) z, Zn x Sn y1 Zr y2 (OH) z, Zn x Sn y1 Mo y2 (OH) z, Zn x Sn y1Pd y2 (OH) z, Zn x Sn y1 Sc y2 (OH) z, Zn x Sn y1 Cd y2 (OH) z, Zn x Sn y1 Mg y2 (OH) z, Zn x Sn y1 Ca y2 (OH) z , Zn x Sn y1 Sr y2 (OH) z, Zn xSn y1 Si y2 (OH) z, Zn x Sn y1 Sb y2 (OH) z, Zn x Al y1 Ti y2 (OH) z, Zn x Al y1 Fe y2 (OH) z, Zn x Al y1 Fe y2 (OH ) ) z, Zn x Al y1 Ti y2 (OH) z,Zn x Al y1 Co y2 (OH) z, Zn x Al y1 Ni y2 (OH) z, Zn x Al y1 Zr y2 (OH) z, Zn x Al y1 Mo y2 (OH) z, Zn x Al y1 Pd y2 (OH) z, Zn x Al y1 Sc y2(OH) z, Zn x Al y1 Cd y2 (OH) z, Zn x Al y1 Mg y2 (OH) z, Zn x Al y1 Ca y2 (OH) z, Zn x Al y1 Sr y2 (OH) z, Zn x Al y1 Si y2 (OH) z, Zn x Al y1Sb y2 (OH) z (wherein x, y, y1, y2, and z are the same as defined in Formula 1 or Formula 2), and the like, but is not limited thereto.
[128]
[129]
The multi-component metal hydroxide prepared according to the method of the present invention has high particle size uniformity, and thus has excellent dispersibility when mixed with a thermoplastic resin. In addition, the multi-component metal hydroxide has excellent flame retardant synergistic effect when used together with a halogen-based flame retardant, and prevents discoloration due to decomposition of the flame retardant during high temperature residence, thereby implementing excellent flame retardancy and thermal stability.
[130]
[131]
The flame retardant auxiliary may be included in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the base resin. When the content of the flame retardant aid satisfies the above range, flame retardancy and thermal stability can be effectively improved without adversely affecting the physical properties of the base resin.
[132]
[133]
As described above, the flame-retardant resin composition comprising the flame-retardant aid of the present invention does not use an antimony-based flame-retardant agent that generates carcinogens, so it is environmentally friendly, safe, and exhibits excellent flame-retardant performance, and has excellent thermal stability, so discoloration even after high temperature residence this is less
[134]
[135]
(4) additives
[136]
The flame-retardant resin composition according to the present invention may further include one or more additives selected from the group consisting of an impact modifier, a lubricant, an anti-drip agent, an antioxidant, a light stabilizer, a sunscreen, a pigment, and an inorganic filler, if necessary. there is.
[137]
The specific material of the additive may be used without particular limitation as long as it is used in the thermoplastic flame-retardant resin composition. For example, as the anti-drip agent, one or more selected from the group consisting of Teflon, polyamide, polysilicon, PTFE (polytetrafluoroethylene) and TFE-HFP (tetrafluoroethylene-hexafluoropropylene) copolymers can be used in terms of additional flame retardancy improvement. , As the inorganic filler, at least one selected from the group consisting of barium sulfate, barium glass filler, and barium oxide may be used.
[138]
Modes for carrying out the invention
[139]
Hereinafter, the present invention will be described in detail through specific examples.
[140]
[141]
Example 1
[142]

[143]
0.5M ZnCl 2 and 0.25M SnCl 2 were added to 750 mL ethanol, stirred with a magnetic bar to dissolve until transparent, and then 750 mL 3.2 M NaOH aqueous solution was slowly injected for 15 minutes to induce a sol-gel reaction. . When a hydrolysis reaction occurred according to the addition of NaOH aqueous solution and white particles were formed, the mixture was stirred rapidly for 1 hour, and then precipitated without stirring for 12 hours. After decanting the upper reaction solution from the precipitated reactant, the remaining reactant was washed thoroughly with water and ethanol for 10 minutes at 10000 rpm through a centrifugal separator, and dried in an oven at 80° C. for 12 hours to obtain Zn-Sn hydroxide particles.
[144]
[145]

[146]
ABS copolymer (product name: DP270, LG Chem) and SAN resin (product name: 90HR, LG Chem) were mixed in a weight ratio of 3:7 to prepare a base resin. With respect to 100 parts by weight of the prepared base resin, 16 parts by weight of tetrabromobisphenol A (TBBA) as a flame retardant and 3 parts by weight of the Zn-Sn hydroxide particles prepared above as a flame retardant were mixed to prepare a flame retardant resin composition.
[147]
[148]
Example 2
[149]

[150]
1M ZnCl 2 and 0.6M AlCl 3 were added to 300 mL distilled water and 700 mL ethanol, stirred with a magnetic bar to dissolve until transparent, and then 750 mL of 3.5 M NaOH aqueous solution was slowly injected for 20 minutes for sol-gel reaction. was induced. When a hydrolysis reaction occurred according to the addition of NaOH aqueous solution and white particles were formed, the mixture was stirred rapidly for 30 minutes, and then precipitated without stirring for 4 hours. After decanting the upper reaction solution from the precipitated reactant, the remaining reactant was washed thoroughly with water and ethanol at 10000 rpm for 10 minutes through a centrifugal separator, and dried in an oven at 80° C. for 12 hours to obtain Zn-Al hydroxide particles.
[151]
[152]

[153]
ABS copolymer (product name: DP270, LG Chem) and SAN resin (product name: 90HR, LG Chem) were mixed in a weight ratio of 3:7 to prepare a base resin. With respect to 100 parts by weight of the prepared base resin, 16 parts by weight of tetrabromobisphenol A (TBBA) as a flame retardant and 3 parts by weight of the Zn-Al hydroxide particles prepared above as a flame retardant were mixed to prepare a flame retardant resin composition.
[154]
[155]
Comparative Example 1
[156]
ABS copolymer (product name: DP270, LG Chem) and SAN resin (product name: 90HR, LG Chem) were mixed in a weight ratio of 3:7 to prepare a base resin. Based on 100 parts by weight of the prepared base resin, 16 parts by weight of tetrabromobisphenol A (TBBA) as a flame retardant and 3 parts by weight of Sb 2 O 3 as a flame retardant were mixed to prepare a flame retardant resin composition.
[157]
[158]
Comparative Example 2
[159]
ABS copolymer (product name: DP270, LG Chem) and SAN resin (product name: 90HR, LG Chem) were mixed in a weight ratio of 3:7 to prepare a base resin. Based on 100 parts by weight of the prepared base resin, 16 parts by weight of tetrabromobisphenol A (TBBA) as a flame retardant, 3 parts by weight of Sb 2 O 3 as a flame retardant aid, and 0.2 parts by weight of a stabilizer were mixed to prepare a flame retardant resin composition.
[160]
[161]
Experimental Example 1
[162]
The shapes of the Zn-Sn hydroxide particles prepared in Example 1 and the Zn-Al hydroxide particles prepared in Example 2 were observed through a scanning electron microscope (SEM).
[163]
In addition, through EDS (Energy Dispersive X-ray spectroscopy) component analysis, the component distribution and composition ratio of the Zn-Sn hydroxide particles prepared in Example 1 1 and the Zn-Al hydroxide particles prepared in Example 2 were confirmed.
[164]
[165]
1 is a SEM photograph of the Zn-Sn hydroxide particles prepared in Example 1. As shown in FIG. 1 , the Zn—Sn hydroxide particles prepared in Example 1 were cubic particles having a particle diameter of about 2 μm, and were found to have a relatively uniform particle size distribution.
[166]
FIG. 2 is a photograph showing the distribution of Zn in the Zn-Sn hydroxide particles prepared in Example 1, and FIG. 3 is a photograph showing the distribution of Sn in the Zn-Sn hydroxide particles prepared in Example 1. FIG. 4 is a graph showing the composition ratio of Zn and Sn in the Zn-Sn hydroxide particles prepared in Example 1 measured through EDS mapping.
[167]
As shown in FIGS. 2 and 3 , in the Zn—Sn hydroxide particles prepared in Example 1, Zn and Sn were found to be evenly distributed throughout the particles.
[168]
In addition, the composition ratio of Zn and Sn in the Zn-Sn hydroxide particles was calculated using the graph of FIG. 4 . As a result of the calculation, the atomic ratio of Zn:Sn was about 1.25:1.
[169]
[170]
5 is a SEM photograph of the Zn-Al hydroxide particles prepared in Example 2. As shown in FIG. 5 , the Zn-Al hydroxide particles prepared in Example 2 were plate-shaped particles having a thickness of about 20 nm and an area of ​​about 250 nm×250 nm, and were found to have a relatively uniform particle size distribution.
[171]
6 is a photograph showing the distribution of Zn and Al in the Zn-Al hydroxide particles prepared in Example 2. As shown in FIG. 6 , in the Zn-Al hydroxide particles prepared in Example 2, Zn and Al were found to be evenly distributed throughout the particles.
[172]
7 is a graph showing the composition ratio of Zn and Al in the Zn-Al hydroxide particles prepared in Example 2 measured through EDS mapping. The composition ratio of Zn, Sn and Al in the Zn-Al hydroxide particles was calculated using the graph of FIG. 7 , and as a result of the calculation, the Zn-Al hydroxide of Example 2 had an atomic ratio of Zn:Al of about 1.9:0.1, and typical zinc - It was found to have a higher Zn content than aluminum dihydroxide (Zn-Al Layered Double Hydroxide). The higher the ratio of Zn, the better the performance as a flame retardant aid is due to excellent reactivity with Br of the flame retardant. Also, when the Al content is high, when blended with a resin, it is changed to an oxide form of Al 2 O 3 and lowered the physical properties of the resin. may cause
[173]
[174]
Experimental Example 2
[175]
After uniformly mixing the thermoplastic flame-retardant resin composition of Examples and Comparative Examples using a Henschel mixer, it was put into a twin-screw extruder set at 220° C. and extruded to prepare pellets. Then, the pellets were injected through an injection machine to prepare a specimen, and physical properties were measured according to the following method for measuring physical properties. The physical property measurement results are shown in [Table 1] below.
[176]
[177]

[178]
(1) Thermal stability: During injection molding using an injection machine, the processing temperature was set to 230° C., and the resin was allowed to stay for 15 minutes, and then a specimen was prepared, and CIE Lab color coordinate values ​​were measured. The ΔE value was measured by substituting the CIE Lab color coordinate value measured in the specimen and the CIE Lab color coordinate value of the reference specimen prepared without retention into the following equation.
[179]

[180]
In the above formula, L', a', and b' are L, a, and b values ​​measured by the CIE Lab color coordinate system of the specimen prepared after the resin was retained at 230°C for 15 minutes, and L 0 , a 0 , b 0 are retention These are the L, a, and b values ​​measured by the CIE Lab color coordinate system for the reference specimen prepared without it.
[181]
[182]
(2) Flame retardancy: Based on the UL 94 measurement method, the flame retardancy was evaluated for a 1/10 inch thick specimen as follows.
[183]
First, after contacting the specimen with a flame of 20 mm in height for 10 seconds, the combustion time t1 of the specimen was measured. Then, when the combustion was finished after the first contact, the combustion time t2 of the specimen after contacting for 10 seconds was measured again, and when the sum of t1 and t2 was 50 seconds or less, it was evaluated as a V-0 grade.
[184]
[Table 1]
Thermal stability (ΔE) Flame retardancy
Example 1 4.12 V-0
Example 2 5.04 V-0
Comparative Example 1 7.97 V-0
Comparative Example 2 11.85 V-0
[185]
As shown in [Table 1], the flame-retardant resin composition to which the flame-retardant aids of Examples 1 and 2 prepared according to the method of the present invention were applied had a flame retardancy equivalent to those of Comparative Examples 1 and 2 using the antimony trioxide flame-retardant aid. It was shown that, compared to Comparative Examples 1 and 2 using antimony trioxide, the color deterioration after high temperature retention was less, and the thermal stability was more excellent.

WE CLAIMS

preparing a metal precursor solution by adding a zinc precursor and a precursor including a M 1 metal to a solvent; And by adding an acid or base to the metal precursor solution to proceed with a sol-gel reaction to prepare a multi-component metal hydroxide represented by the following Chemical Formula 1: [Formula 1] Zn x M 1 y (OH) z In Formula 1, M 1 is at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, and x and y are the atomic ratios of Zn and M 1 , respectively means, x : y is 0.5 ~ 2.0 : 0.1 ~ 3.0, and 2≤z≤6.
[Claim 2]
According to claim 1, wherein M 1 is Sn, Al, Ti, Nb, Fe, Co, Ni, Cu, Zr, Mo, Pd, Sc, Cd, Mg, Ca, Sr, Si and Sb selected from the group consisting of A method for producing one or more flame-retardant auxiliary agents.
[Claim 3]
The method of claim 1, wherein the zinc precursor is zinc chloride, zinc sulfate, zinc acetate, zinc nitrate, zinc sulfide, or a mixture thereof.
[Claim 4]
The method of claim 1, wherein the M 1 metal precursor containing the M 1 metal is a chloride, a sulfur oxide, a nitrate sulfide, an acetic acid, or a mixture thereof.
[Claim 5]
The flame retardant of claim 1, wherein the metal precursor solution includes the zinc precursor and the precursor including the M 1 metal in an amount such that the atomic ratio of zinc: M 1 metal is 0.5 to 2.0: 0.1 to 3.0. A method for preparing the preparation.
[Claim 6]
The method of claim 1, wherein the multi-component metal hydroxide is represented by the following [Formula 2]. [Formula 2] Zn x M 2 y1 M 3 y2 (OH) z In Formula 2, M 2 is at least one selected from the group consisting of Sn and Al, and M 3 is a transition metal other than Zn, Sn and Al, at least one selected from the group consisting of alkaline earth metals and Groups 13 to 16 metals, wherein x, y1, and y2 are Zn, M 2 and M 3 , respectively , meaning an atomic ratio, x: y1: y2 is 0.5 to 2.0 : 0.1 ~ 3.0 : 0 ~ 2.9, 2≤z≤6.
[Claim 7]
The method of claim 1, wherein the solvent is deionized water, ethanol, methanol, isopropanol, acetonitrile, dimethylamine borane, or a mixture thereof.
[Claim 8]
A flame-retardant resin composition comprising a base resin, a halogen-based flame retardant, and a flame-retardant auxiliary, wherein the flame-retardant auxiliary is a multi-component metal hydroxide represented by Formula 1: [Formula 1] Zn x M 1 y (OH) z In Formula 1 , M 1 is at least one selected from the group consisting of transition metals other than zinc, alkaline earth metals, and Groups 13 to 16 metals, x and y mean atomic ratios of Zn and M 1 , respectively, x: y is 0.5 ~ 2.0: 0.1 ~ 3.0, 2≤z≤6.
[Claim 9]
The flame retardant resin composition according to claim 8, wherein the base resin comprises a conjugated diene-based graft copolymer and a matrix copolymer that is a copolymer of an aromatic vinyl-based monomer and a vinyl cyan-based monomer.
[Claim 10]
According to claim 8, wherein the halogen-based flame retardant hexabromocyclododecane (hexabromocyclododecane), tetrabromocyclooctane (tetrabromocyclooctane), monochloro pentabromocyclohexane (monochloro petabromocyclohexane), decabromodiphenyl oxide (decabromodiphenyl oxide) ), octabromodiphenyl oxide, decabromodiphenyl ethane, ethylene bis (tetrabromophthalimide), tetrabromobisphenol A (tetrabromobisphenyl A), Brominated epoxy oligomers, bis(tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1 ,3,5-triazine (2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine), and tetrabromobisphenol A bis (allyl ether) (tetrabromobisphenol A bis ( ally ether))) at least one flame-retardant resin composition selected from the group consisting of.
[Claim 11]
The flame-retardant resin composition of claim 8, wherein the flame-retardant auxiliary is a multi-component metal hydroxide represented by the following [Formula 2]: [Formula 2] Zn x M 2 y1 M 3 y2 (OH) z In Formula 2, M 2 is at least one selected from the group consisting of Sn and Al, and M 3 is at least one selected from the group consisting of transition metals other than Zn, Sn and Al, alkaline earth metals, and group 13 to 16 metals, wherein x, y1 , y2 means atomic ratios of Zn, M 2 and M 3 , respectively, and x : y1 : y2 is 0.5 to 2.0 : 0.1 to 3.0 : 0 to 2.9, and 2≤z≤6.
[Claim 12]
The flame-retardant resin composition according to claim 8, wherein the flame-retardant resin composition comprises 100 parts by weight of the base resin, 10 to 30 parts by weight of the halogen-based flame retardant, and 1 to 10 parts by weight of the flame-retardant auxiliary.
[Claim 13]
The flame-retardant resin composition according to claim 8, wherein the flame-retardant resin composition further comprises at least one selected from the group consisting of impact modifiers, lubricants, anti-drip agents, antioxidants, stabilizers, sunscreens, pigments and inorganic fillers.