KR102665698B1 - Flame retardant composition - Google Patents

Abstract

The present invention relates to a flame retardant composition used in the production of a flame retardant that is added to a resin and provides flame retardancy. More specifically, it not only provides flame retardancy, but also reduces physical properties due to agglomeration and yellowing phenomenon that occurs due to the use of the flame retardant. It is about a flame retardant composition that can improve performance by minimizing and providing additional functions.

Description

Flame retardant composition {Flame retardant composition}

The present invention relates to a flame retardant composition used in the production of a flame retardant that is added to a resin and provides flame retardancy. More specifically, it not only provides flame retardancy, but also reduces physical properties due to agglomeration and yellowing phenomenon that occurs due to the use of the flame retardant. It is about a flame retardant composition that can improve performance by minimizing and providing additional functions.

Plastic products are used in a variety of fields, and the properties required for them vary depending on their use, and various additives are used to improve the performance of the final manufactured plastic product. For example, in the case of plastic products that require flame retardancy, additives such as flame retardants are essentially used in the resin that serves as the raw material during their manufacture. The following patent document shows an example of a flame retardant added to a resin to provide flame retardancy.

<Patent Document>

Registered Patent No. 10-1186962 (registered on September 24, 2012) “Transparent flame-retardant plastic additive, resin composition thereof, and method for manufacturing the same”

Flame retardancy can be improved by using conventional flame retardants, but other physical properties may deteriorate due to the use of flame retardants, and when various additives are mixed into the resin to provide functions other than flame retardancy, the manufacturing process is complicated when manufacturing the product. And there is the problem of poor economic feasibility.

The present invention is intended to solve the above problems,

The purpose of the present invention is to provide a flame retardant composition that not only provides flame retardancy, but also minimizes deterioration of physical properties due to agglomeration and yellowing phenomenon that occurs due to the use of flame retardants, and improves performance by providing additional functions. .

In order to achieve the above-described object, the present invention is implemented by an embodiment having the following configuration.

According to one embodiment of the present invention, the flame retardant composition according to the present invention includes tris (2-ethylhexyl) phosphate, pervinyloctasilsesquioxane, and thecahydro-3,5,1,7-(1,2,3 ,4) Butanetetraylnaphthalene, 2-[2-hydroxyethyl(octadecyl)amino]ethyl octatecanoate, 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3 , 10-disiladodecane, dodecyl 2-methyl-2-propenoate, ethylphthalyl ethyl glycolate, poly(vinylidene fluoride-co-hexafluoropropylene, decanedioic acid, didodecyl ester) and ethyl 4-(dimethylamino)benzoate.

According to another embodiment of the present invention, the flame retardant according to the present invention includes 20 to 40 parts by weight of tris (2-ethylhexyl) phosphate, 20 to 40 parts by weight of pervinyloctasilsesquioxane, and Tecahydro-3,5,1 , 10 to 20 parts by weight of 7-(1,2,3,4)butanetetriylnaphthalene, 10 to 20 parts by weight of 2-[2-hydroxyethyl(octadecyl)amino]ethyl octatecanoate, 3, 10 to 20 parts by weight of 10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane, 10 to 20 parts by weight of dodecyl 2-methyl-2-propenoate, ethyl 15 to 25 parts by weight of phthalyl ethyl glycolate, 15 to 25 parts by weight of poly(vinylidene fluoride-co-hexafluoropropylene), decanedioic acid, 15 to 25 parts by weight of didodecyl ester, and ethyl 4-(dimethyl It is characterized in that it is manufactured by reacting 0.1 to 1 part by weight of amino) benzoate.

According to another embodiment of the present invention, the flame retardant according to the present invention is characterized in that it has a particle form.

The present invention can achieve the following effects by combining the above-mentioned embodiment with the configuration, combination, and use relationship described below.

The present invention not only provides flame retardancy, but also minimizes the deterioration of physical properties due to agglomeration and yellowing phenomenon that occurs due to the use of flame retardants, and improves performance by providing additional functions.

Hereinafter, preferred embodiments of the flame retardant composition according to the present invention will be described in detail. Unless otherwise specified, all terms in this specification have the same general meaning as understood by a person skilled in the art to which the present invention pertains, and if there is a conflict with the meaning of the terms used in this specification, this specification Follow the definitions used in the specification. Additionally, detailed descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted. Throughout the specification, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

One embodiment of the present invention relates to a flame retardant composition used in the production of a flame retardant to improve flame retardancy by adding to a resin, the flame retardant composition comprising 20 to 40 parts by weight of tris(2-ethylhexyl) phosphate, pervinyloctacil 20 to 40 parts by weight of sesquioxane, 10 to 20 parts by weight of tecahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene, 2-[2-hydroxyethyl (octa) 10 to 20 parts by weight of decyl) amino] ethyl octatecanoate, 10 to 20 parts by weight of 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane, dode 10 to 20 parts by weight of 2-methyl-2-propenoate, 15 to 25 parts by weight of ethylphthalyl ethyl glycolate, 15 to 25 parts by weight of poly(vinylidene fluoride-co-hexafluoropropylene), decanedio It is characterized in that it contains 15 to 25 parts by weight of acid acid and didodecyl ester, and 0.1 to 1 part by weight of a reaction accelerator.

The tris(2-ethylhexyl) phosphate (Cas N0.: 78-42-2) is added to improve flame retardancy, and is preferably used in the range of 20 to 40 parts by weight. do. The tris(2-ethylhexyl) phosphate produces phosphoric acid and polyphosphoric acid through thermal decomposition, which is then esterified and dehydrogenated to form char, which blocks oxygen and heat. The flame retardant prepared from the above flame retardant composition can be used by adding it to various resins. Tris(2-ethylhexyl) phosphate has excellent flame retardant performance but has poor water resistance performance, especially polyurethane produced during the production of polyurethane foam. Since it has the disadvantage of promoting foam resistance, it is manufactured as a composite to compensate for the above disadvantages.

Pervinyloctasilsesquioxane (Cas No.: 69655-76-1) is used to improve flame retardancy and lower dielectric constant, and is preferably used in the range of 20 to 40 parts by weight. The pervinyloctasilsesquioxane, unlike the phosphorus-based flame retardant component, has low solubility in water and low toxicity, and improves flame retardancy by generating a complex inorganic layer of white residue and carbonized layer upon combustion, that is, the tris (2 -Ethylhexyl) phosphate and pervinyloctasilsesquioxane provide flame retardant effects through different mechanisms, thereby further improving the flame retardant effect of plastic products. Most synthetic resins have a low dielectric constant, but in some products (e.g., wires, cables, etc.), some polar polyolefin resins can be mixed to improve mechanical properties, and the pervinyloctasilsesquioxane provides flame retardancy while maintaining a low dielectric constant. By lowering the frequency, the effect of frequency changes can be reduced and the electrical characteristics can be improved.

The decahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene (decahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene, Cas No . : 2292-79-7) is a flame retardant that improves the water resistance of manufactured plastic products and prevents oxidation, and is preferably used in the range of 10 to 20 parts by weight. If water resistance and oxidation resistance are poor, the performance of the manufactured flame retardant will deteriorate and the electrical and mechanical properties of the plastic product to which the flame retardant is added will deteriorate. Therefore, Tecahydro-3,5,1,7-(1,2, 3,4) Buteintetriylnaphthalene is used.

The 2-[2-hydroxyethyl(octadecyl)amino]ethyl octadecanoate (2-[2-hydroxyethyl(octadecyl)amino]ethyl octadecanoate, Cas No.: 52497-24-2) suppresses the generation of static electricity. As a composition used for this purpose, it is preferably used in the range of 10 to 20 parts by weight. When static electricity is generated in a plastic product, the electrical properties and mechanical properties deteriorate, so the 2-[2-hydroethyl(octadecyl)amino]ethyl octatecanoate is used to suppress the generation of static electricity in products manufactured. I do it.

The 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane (3,10-dimethoxy-3,10-dimethyl-2,11-Dioxa-3, 10-disiladodecane, Cas No.: 191917-78-9) is used to increase the bonding strength of the components constituting the flame retardant composition, and is preferably used in the range of 10 to 20 parts by weight.

The dodecyl 2-methyl-2-propenoate (Cas No.: 142-90-5) is used to improve miscibility with the resin, 10 to 20 It is preferable to use it in the range of parts by weight.

The ethylphthalyl ethylglycolate (Cas No.: 84-72-0) is used to prevent agglomeration of flame retardant particles, and is preferably used in the range of 15 to 25 parts by weight.

The poly(vinylidene fluoride-co-hexafluoropropylene, Cas No.: 9011-17-0) is a composition used to improve the processability of the resin, and has 15 to 25 It is preferable to use it in the range of parts by weight.

The decanedioic acid, didodecyl ester (Cas No.: 2432-88-4) is used to improve the processability of the resin, and is used in the range of 15 to 25 parts by weight. desirable.

The reaction accelerator is used to promote the reaction, and is preferably used in the range of 0.1 to 1 part by weight. The reaction promoter may be a conventional reaction promoter, such as ethyl 4-(dimethylamino)benzoate (CAS No.: 10287-53-3), dimethyl 2, 2'-azo. Bis(2-methylpropionate) (Dimethyl 2,2'-azobis(2-methylpropionate), Cas No.: 2589-57-3) may be used.

Another embodiment of the present invention relates to a flame retardant that is added to a resin to provide flame retardancy, and the flame retardant includes 20 to 40 parts by weight of tris(2-ethylhexyl) phosphate, 20 to 40 parts by weight of pervinyloctasilsesquioxane, Tecahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene 10 to 20 parts by weight, 2-[2-hydroxyethyl(octadecyl)amino]ethyl octatecanoate 10 to 20 parts by weight, 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane 10 to 20 parts by weight, dodecyl 2-methyl-2-propeno 10 to 20 parts by weight of ate, 15 to 25 parts by weight of ethylphthalyl ethyl glycolate, 15 to 25 parts by weight of poly(vinylidene fluoride-co-hexafluoropropylene), decanedioic acid, 15 to 25 parts by weight of didodecyl ester. The flame retardant is manufactured by reacting 0.1 to 1 part by weight of a reaction accelerator in the form of particles and has a certain size, but preferably has an average particle size of 0.001 to 1 mm.

Hereinafter, the present invention will be described in more detail through examples. However, these are only for explaining the present invention in more detail and the scope of the present invention is not limited thereto.

<Example 1> Preparation of flame retardant

1. Flame retardant 1

A first solution was prepared by mixing 30 parts by weight of tris(2-ethylhexyl) phosphate in water, a second solution was prepared by mixing 30 parts by weight of pervinyloctasilsesquioxane in toluene, and thecahydro-3 in ether. Prepare a third solution by mixing 15 parts by weight of 5,1,7-(1,2,3,4)butanetetriylnaphthalene, and add 2-[2-hydroxyethyl(octadecyl)amino]ethyl octa to water. A fourth solution was prepared by mixing 15 parts by weight of tecanoate, a fifth solution was prepared by mixing 20 parts by weight of poly(vinylidene fluoride-co-hexafluoropropylene) in hexane, decanedioic acid in ethanol, Prepare a sixth solution by mixing 20 parts by weight of didodecyl ester, add 10 parts by weight of fatty acid and 2 parts by weight of sodium hydroxide to the reactor (A) containing 1000 parts by weight of water, stir, and heat to 90°C to form fatty acid salt. Then, the first to sixth solutions and 0.2 parts by weight of ethyl 4-(dimethylamino)benzoate were mixed in the reactor (A). 15 parts by weight of 2,11-dioxa-3,10-disiladodecane, 15 parts by weight of dodecyl 2-methyl-2-propenoate, and 20 parts by weight of ethylphthalyl ethyl glycolate were further mixed and heated to 90°C. After the reaction was performed by increasing the temperature, sulfuric acid was added to form aggregates, dried in a dryer, and pulverized to obtain particulate flame retardant 1.

2. Flame retardant 2

Flame retardant 2 was obtained under the same conditions as Example 1, except that 60 parts by weight of tris(2-ethylhexyl) phosphate was used instead of pervinyloctasilsesquioxane.

3. Flame retardant 3

Flame retardant 3 was obtained under the same conditions as in Example 1, except that 60 parts by weight of pervinyloctasilsesquioxane was used instead of tris(2-ethylhexyl) phosphate.

4. Flame retardant 4

Flame retardant 4 was obtained under the same conditions as in Example 1, except that thecahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene was not used.

5. Flame retardant 5

Flame retardant 5 was obtained under the same conditions as Example 1, except that 2-[2-hydroxyethyl(octadecyl)amino]ethyl octatecanoate was not used.

6. Flame retardant 6

Flame retardant 6, except that 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane was not used, and other conditions were the same as in Example 1. got it

7. Flame retardant 7

Flame retardant 7 was obtained under the same conditions as Example 1, except that dodecyl 2-methyl-2-propenoate was not used.

8. Flame retardants 8

Flame retardant 8 was obtained under the same conditions as Example 1, except that ethylphthalyl ethyl glycolate was not used.

9. Flame retardants 9

Flame retardant 9 was obtained under the same conditions as in Example 1, except that poly(vinylidene fluoride-co-hexafluoropropylene, decanedioic acid, and didodecyl ester were not used.

<Example 2> Dispersibility evaluation

1. Masterbatches 1 to 9 were prepared using 90% by weight of LDPE and 10 parts by weight of flame retardant. Masterbatches 1 to 9 used flame retardants 1 to 9, respectively. For masterbatches 1 to 9, the dispersion form and dispersed particle size were confirmed using SEM, and the dispersibility was evaluated. Dispersibility was evaluated as poor when the particles were aggregated by checking the SEM image and there were approximately 20% or more of particles larger than 100 μm.

2. As a result of the dispersibility evaluation, masterbatches 6 to 8 were evaluated as having poor dispersibility, and masterbatches 1 to 5 and 9 were evaluated as having good dispersibility, indicating that the component that increases the bonding power of the components and the formed flame retardant were properly used. If it is not coated and has poor miscibility with the resin, it can be seen that the dispersibility is poor.

<Example 3> Flame retardancy evaluation

1. Flame retardancy evaluation 1

(1) Mix 70 parts by weight of low-density polyethylene, 30 parts by weight of ethylene ethyl acrylate, 30 parts by weight of flame retardant, 5 parts by weight of flame retardant auxiliary (commercially available from Pacific Interchem), and 2 parts by weight of dicumyl peroxide to make a 1/16 inch thick film. Samples 1 to 9 having thickness were prepared. The samples 1 to 9 used flame retardants 1 to 9, respectively.

(2) Samples 1 to 9 were evaluated for combustion rate and flame resistance according to UL94, and the results are shown in Table 1. Looking at Table 1, it can be seen that Samples 2, 3, and 6 to 8 have lower flame retardancy than Samples 1, 4, 5, and 9, so tris(2-ethylhexyl) phosphate and pervinyloctasilsesquioxane were used together. It can be seen that flame retardancy can be improved when used and dispersibility is improved.

sample One 2 3 4 5 6 7 8 9 Flame retardant V0 V0 V0 V0 V0 V0 V0 V0 V0 Burning rate (seconds) 3 5 6 3 2 12 15 13 3

2. Flame retardancy evaluation 2

(1) A solution was prepared by mixing 40 parts by weight of polyester polyol, 60 parts by weight of polyether polyol, 30 parts by weight of blowing agent, 30 parts by weight of flame retardant, and 1 part by weight of catalyst, followed by 100 parts by weight of methylene diphenyl diisocyanate and 5 parts by weight of water. Samples 1 to 9 in the form of polyurethane foam were prepared by mixing additional parts by weight and reacting in a container. The samples 1 to 9 used flame retardants 1 to 9, respectively.

(2) For samples 1 to 9, the carbonized length was measured according to DIN 4102-1, and the relative values were calculated based on sample 1 and shown in Table 2. For sample 1, the flame resistance was evaluated according to UL94. . Looking at Table 2, it can be seen that Samples 1, 4, 5, and 9 have excellent flame retardancy because the carbonized length is less than Samples 2, 3, and 6 to 8, and in the UL94 test, Sample 1 was confirmed to be V0.

sample One 2 3 4 5 6 7 8 9 carbonized
length One 1.6 1.8 1.1 0.9 1.5 1.6 1.5 1.0

<Example 4> Processability evaluation

1. For masterbatches 1 and 6 to 9 prepared in Example 2, specimens were extruded at a constant shear rate (~400s ^-1 ) using a rheodrove7 single screw from Thermofisher (die diameter is 1.5mm, L=20d). It was tested. As a test evaluation item, check the melt crack removal time (melt crack phenomenon can be visually detected in the state of the strand discharged at the beginning of extrusion, and this phenomenon is eliminated over time) and calculate the relative value based on masterbatch 1. This is shown in Table 3. In addition, the time at which the extruded plastic accumulates at the die exit surface was confirmed to confirm the order in which build-up occurs first for masterbatch samples 1 and 6 to 9.

2. Looking at Table 3, it can be seen that masterbatch 1 has a shorter melt crack removal time than masterbatch 9, resulting in the use of poly(vinylidene fluoride-co-hexafluoropropylene, decanedioic acid, and didodecyl ester) In addition, it can be seen that processability can be improved, if the build-up is displayed in the order in which it occurred first, the build-up appears in the following order: masterbatch 9, masterbatch 8, masterbatch 7, masterbatch 6, and masterbatch 1. It can be seen that the results are similar to the evaluation results for melt crack removal time.

masterbatch One 6 7 8 9 Melt crack removal time 1.0 1.5 1.7 1.8 2.7

<Example 5> Confirmation of physical properties

1. After placing each of the samples 1, 4, and 5 prepared in Example 3-2 in a humid indoor environment, a dusty indoor environment, and an outdoor environment exposed to the sun for 3 weeks, the change in yellowness index was measured using a colorimeter. Measurements were made, and the relative values of Samples 4 and 5 were calculated based on the change in yellow index of Sample 1 and are shown in Table 4.

2. Looking at Table 4, it can be seen that Sample 1 shows less yellowing than Samples 4 and 5, Sample 4 shows a lot of yellowing in humid indoor environments and outdoor environments exposed to the sun, and Sample 5 shows less yellowing than Samples 4 and 5. In this case, it can be seen that yellowing occurs especially often in indoor environments with a lot of dust.

sample One 4 5 High humidity indoor environment 1.0 1.3 1.1 dusty indoor environment 1.0 1.0 1.4 sun exposure outdoor environment 1.0 1.1 1.0

<Example 6> Confirmation of electrical characteristics

1. Samples 1 to 5 in the form of a film were prepared by mixing 70 parts by weight of low-density polyethylene, 30 parts by weight of ethylene ethyl acrylate, 20 parts by weight of a flame retardant, and 2 parts by weight of dicumyl peroxide and then molding them. Samples 1 to 5 used flame retardants 1 to 5, respectively.

2. After each of Samples 1 to 5 prepared in Example 6-1 was exposed to an environment in which dust was artificially suspended, the amount of dust attached to each of Samples 1 to 5 was visually evaluated. As a result of the experiment, it was confirmed that Sample 5 had a significantly greater amount of dust than Samples 1 to 4. In addition, each of Samples 1, 4, and 5 prepared in Example 3-2 was exposed to an environment in which dust was artificially suspended, and then the amount of dust attached to each of Samples 1, 4, and 5 was visually evaluated. As a result of the experiment, it was confirmed that Sample 5 contained significantly more dust than Samples 1 and 4.

3. The dielectric constant was measured at 8 GHz for each of samples 1 to 3 prepared in Example 6-1 using a dielectric analyzer. Looking at the dielectric constant measurement results, it was confirmed that the dielectric constant was higher for Sample 3, Sample 1, and Sample 2.

4. Samples 1 and 4 prepared in 1 of Example 6 were treated for 15 days at a temperature of 70°C and constant temperature and humidity conditions of 95%, and then static electricity generation was evaluated in the same manner as above using dried samples 1 and 4. did. After the experiment of Example 6-2, there was no significant difference in the amount of dust attached to Samples 1 and 4, but after the experiment of Example 6-4, it was confirmed that Sample 4 had significantly more dust attached to it than Sample 1. I was able to.

In the above, the applicant has described preferred embodiments of the present invention, but such embodiments are only embodiments that implement the technical idea of the present invention, and no changes or modifications can be made to the present invention as long as the technical idea of the present invention is implemented. It should be interpreted as falling within the scope.

Claims (3)

Tris(2-ethylhexyl) phosphate, pervinyloctasilsesquioxane, thecahydro-3,5,1,7-(1,2,3,4)butanetetraylnaphthalene, 2-[2-hydroxy Ethyl(octadecyl)amino]ethyl octatecanoate, 3,10-dimethoxy-3,10-dimethyl-2,11-dioxa-3,10-disiladodecane, dodecyl 2-methyl-2- Characterized by comprising propenoate, ethylphthalyl ethyl glycolate, poly(vinylidene fluoride-co-hexafluoropropylene, decanedioic acid, didodecyl ester and ethyl 4-(dimethylamino)benzoate. A flame retardant composition. 20 to 40 parts by weight of tris(2-ethylhexyl) phosphate, 20 to 40 parts by weight of pervinyloctasilsesquioxane, thecahydro-3,5,1,7-(1,2,3,4)butane tetra 10 to 20 parts by weight of ylnaphthalene, 10 to 20 parts by weight of 2-[2-hydroxyethyl(octadecyl)amino]ethyl octatecanoate, 3,10-dimethoxy-3,10-dimethyl-2,11- 10 to 20 parts by weight of dioxa-3,10-disiladodecane, 10 to 20 parts by weight of dodecyl 2-methyl-2-propenoate, 15 to 25 parts by weight of ethylphthalyl ethyl glycolate, poly(vinylidene) It is manufactured by reacting 15 to 25 parts by weight of fluoride-co-hexafluoropropylene, decanedioic acid, 15 to 25 parts by weight of didodecyl ester, and 0.1 to 1 part by weight of ethyl 4-(dimethylamino)benzoate. Flame retardant. According to paragraph 2,
The flame retardant is characterized in that the flame retardant has a particle form.