KR101977818B1 - Flame retardant master batch composition for extruded polystyrene foam and extruded polystyrene foam using the same - Google Patents

Abstract

The present invention relates to a flame retardant masterbatch composition for extruded polystyrene foam, more specifically 30 to 50% by weight of a base resin consisting of polystyrene and / or low density polyethylene; Bis (2,3-dibromo-2-methylpropoxy) benzene], or a mixture of these compounds, such as BDDP (Tetrabromobisphenol A bis 40 to 60% by weight of a flame retardant composed of a mixture; 1 to 5% by weight of a filler; And 1% to 5% by weight of ascending agent. The extruded polystyrene foam produced using the flame retardant masterbatch composition according to the present invention has sufficient flame retardancy to satisfy the KS M 3808 flammability standard without using the existing HBCD and at the same time satisfies the environmental certification standards for human harmfulness and environment friendliness There is an effect that the foaming property is not lowered during the extrusion foaming process of the polystyrene.

Description

FIELD OF THE INVENTION The present invention relates to a flame retardant masterbatch composition for extruded polystyrene foam and an extruded polystyrene foam using the extruded polystyrene foam,

The present invention relates to a flame retardant masterbatch composition for extruded polystyrene foam having excellent flame retardancy and at the same time minimizing human harmfulness.

Polystyrene (PS) materials can be divided into expandable polystyrene foam (EPS) or extruded polystyrene foam (XPS) depending on the type of foam, which can be used to modernize old buildings or to prevent the cold of new buildings Not only is the line the best in terms of efficient insulation. However, since the polystyrene (PS) resin is excellent in foaming property, it is made of a material that is easy to burn, so that a high level of flame retardancy is required, which can minimize the damage to human life and property from a flame when a fire occurs. Currently, HBCD (Hexabromocyclododecane) flame retardants have been used for decades in the destruction of polystyrene (PS) foams. This is because HBCD has the most excellent properties in consideration of proper viscosity, pressure, crosslinking and foaming speed of the mixture, which are important factors in the formation of polystyrene foam.

 EPS in polystyrene foam is a effervescent resin impregnated with a foaming agent in polystyrene resin, and is an eco-friendly product with little residual volatile matter in the product. It is used for construction and civil engineering because of its heat insulation, high heat resistance and convenience of construction, but it has a property of absorbing water, but construction on base part should be avoided. XPS, on the other hand, is a preferred material for load-bearing thermal insulation in civil engineering fields such as flat roof, perimeter, and facade because it has superior compression strength in the vertical direction and boasts not only elasticity but also airtightness. The XPS seems to be rapidly increasing in use due to the need for sustainable climate change and energy conservation in the coming years.

On the other hand, the brominated flame retardants such as HBCD have occupied the greatest proportion in the world, but recently, from the environmental argument, the behavior of the dehalogenous compounds such as the specific bromine compound is suspected of dioxin generation, The European RoHS 1.0 regulation limited the use of some halogen-based flame retardants (PBBs, PBDEs) in all electrical and electronic products. In particular, the HBCD has been found to interfere with the hormonal system and have harmful effects on the human body such as the nervous system and the immune system. Due to the danger of accumulation of ecological properties due to the degradation, the "POPs of the persistent organic pollutants" It has been designated as a prohibited substance worldwide. Currently, the production and use of HBCD as foamed polystyrene for construction purposes is prohibited as a production prohibited item except for the application, but since 2021, the ban on the construction materials excluded from the application is also prohibited. Therefore, it is urgent to develop a flame retardant that satisfies environmental certification standards for human health and environmental friendliness, while having flame retardancy (flame retardancy sufficient to satisfy the KS M 3808 flammability standard) to replace the existing HBCD.

Meanwhile, EBPBB (tetrabromobisphenol A) and TBBPA (ethylenebis (penta-bromobenzene)) have been developed as substitutes for HBCD according to the needs as described above. However, 3808, but when used for extruded polystyrene foam, there is a problem that the substitute materials cause interferences during the extrusion foaming process, so that the foamability is remarkably deteriorated and it is difficult to commercialize them.

1. Korean Published Patent Application No. 2007-0098862 (Oct. 05, 2007) 2. Korean Registered Patent No. 750626 (Aug. 13, 2007)

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned needs, and it is an object of the present invention to provide a flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant flame retardant It is an object of the present invention to provide a flame retardant masterbatch composition for extruded polystyrene foam that meets environmental certification standards.

It is another object of the present invention to provide a flame-retardant masterbatch composition which does not deteriorate foaming properties during extrusion foaming even when it is used for extruded polystyrene foam while having flame retardancy and environment friendliness as described above.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. will be.

One aspect of the present invention is to provide a flame retardant masterbatch composition for extruded polystyrene foam comprising 30 to 50% by weight of a base resin made of polystyrene and / or low density polyethylene; Bis (2,3-dibromo-2-methylpropoxy) benzene], or a mixture of these compounds, such as BDDP (Tetrabromobisphenol A bis 40 to 60% by weight of a flame retardant composed of a mixture; 1 to 5% by weight of a filler; And 1% to 5% by weight of ascending agent.

Another aspect of the present invention relates to a flame retardant masterbatch composition for extruded polystyrene foam, more specifically 30 to 50 wt% of a base resin made of polystyrene and / or low density polyethylene; Bis (2,3-dibromo-2-methylpropoxy) benzene], or a mixture of these compounds, such as BDDP (Tetrabromobisphenol A bis 40 to 60% by weight of a flame retardant formed by mixing a biphenyl derivative in the mixture; 1 to 5% by weight of a filler; And 1% to 5% by weight of ascending agent.

The extruded polystyrene foam produced using the flame retardant masterbatch composition according to the present invention has sufficient flame retardancy to satisfy the KS M 3808 flammability standard without using the existing HBCD and at the same time satisfies the environmental certification standards for human harmfulness and environment friendliness There is an effect that the foaming property is not lowered during the extrusion foaming process of the polystyrene.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a test report showing the results of the KS M 3808: 2011 Combustibility Test for Examples 6-10 according to the present invention.
2 to 3 relate to a test report showing the results of UL 94 horizontal flammability test for Example 9 according to the present invention.
Figs. 4 to 5 relate to a test report showing the UL 94 horizontal flammability test result for Example 10 according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

The present invention relates to a flame retardant masterbatch composition for extruded polystyrene foam, more specifically 30 to 50% by weight of a base resin consisting of polystyrene and / or low density polyethylene; 40 to 60% by weight of a flame retardant; 1 to 5% by weight of a filler; And 1 to 5 wt% of ascending.

In the present invention, the base resin contributes to the stabilization of feeding of the flame retardant as a base material or a carrier of the flame-retardant master batch. In the present invention, the base resin may be made of polystyrene alone, but may be made of low-density polyethylene alone, or may be made of polystyrene and low-density polyethylene in a range that does not impair various foaming factors of the polystyrene extrusion foaming process. have.

The content of the base resin is preferably 30 to 50% by weight based on the total weight of the flame-retardant masterbatch composition. If the content of the base resin is less than 30% by weight, the base resin and the flame retardant are uniformly mixed to form a kneading dough having an appropriate viscosity, and the kneading workability is significantly reduced. When the content of the base resin exceeds 50% , There is a problem that the foaming workability during the extrusion foaming process of polystyrene is lowered and the flame retardancy of the final polystyrene foam is lowered.

In the present invention, the flame retardant is included in the master batch composition to impart flame retardancy to the extruded polystyrene foam. In the present invention, the flame retardant is BDDP (Tetrabromobisphenol A bis (2,3-dibromopropyl ether)) instead of the conventional HBCD, 1,1 '- (isopropylidene) bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene] or a mixture thereof.

The BDDP has a molecular formula C ₂₁ H ₂₀ Br ₈ O ₂ (molecular weight of 943.6) having a molecular structure shown in the following structural formula 1, having a white powder form and melting point of 105 to 115 ° C.

[Structural formula 1]

Also, the 1,1 '- (isopropylidene) bis [3,5-dibromo-4- (2,3-dibromo-2- methylpropoxy) benzene] is a molecular formula C ₂₃ H ₂₄ Br ₈ O ₂ (molecular weight: 971.667) And has the molecular structure shown in the following structural formula 2.

[Structural formula 2]

In the present invention, by using BDDP, 1,1 '- (isopropylidene) bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene] or a mixture thereof as a flame retardant, It has flame retardancy enough to replace flame retardants and at the same time satisfies the environmental certification standards for human hazards and environmental friendliness and does not deteriorate foaming properties even during the extrusion foaming process of polystyrene A flame retardant masterbatch composition for extruded polystyrene foam can be provided.

In order to further reduce the difference between the flame retardancy and the flame retardancy of the conventional HBCD and to further reduce the degradation of the foaming property during the extrusion foaming process of polystyrene, the present invention provides BDDP, 1,1 '- (isopropylidene) bis [ 5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene] or a mixture thereof may be more preferably a mixture of biphenyl derivatives. Examples of the biphenyl derivatives include 2,3-diphenyl-1,3-butadiene, 1,1-diphenylethylene, 3,3-diphenylpentane, and 1,3-diphenylpropane. Wherein the biphenyl derivative is selected from the group consisting of BDDP, 1,1 '- (isopropylidene) bis [3,5-dibromo-4- (2,3-dibromo-2-methyl propoxy) benzene] 9 by weight.

In addition, the content of the flame retardant in the present invention is preferably 40 to 60% by weight based on the total weight of the master batch composition. If the content of the flame retardant is less than the above range, there is a problem that the flame retardancy of the polystyrene foam is excessively low. If the content of the flame retardant is higher than the above range, the base resin and the flame retardant are uniformly mixed, the kneading workability is significantly lowered.

The masterbatch composition according to the present invention comprises from 1 to 5% by weight of a filler. The type of the filler is not particularly limited, but it is preferable to use any inorganic compound selected from the group consisting of talc, calcium carbonate and silica in order to prevent the foaming power from lowering during the extrusion foaming process of polystyrene.

In the present invention, the synergist is added to the flame retardant together with the flame retardant to enhance the flame retardancy, and the content thereof is preferably 1 to 5% by weight. Although the type of the elevating agent is not particularly limited, it is preferable to use antimony pentoxide (Sb ₂ O ₅ ) in order to enhance the flame retardancy in harmony with the flame retardant and minimize the decrease of the foaming power during the foaming process .

The flame retardant masterbatch composition for extruded polystyrene foam according to the present invention may further comprise at least one selected from the group consisting of zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and the like in order to increase the melting point of the flame retardant to be evenly mixed with the base resin, It may be preferable to further include a metal stearate. Of these, it may be most preferable to further include zinc stearate in order to minimize the deterioration of the foaming power during the extrusion foaming process of polystyrene.

Another aspect of the present invention relates to an extruded polystyrene foam formed by extrusion foaming after a raw material composition comprising a polystyrene resin, the above-mentioned flame retardant masterbatch composition and a nucleating agent is melted and a foaming agent is charged.

The extruded polystyrene foam prepared using the flame retardant masterbatch composition according to the present invention may have a degree of flame retardancy sufficient to satisfy the KS M 3808 flammability standard It has a sufficient flame retardancy, at the same time can meet environmental certification standards for human health and environmental friendliness, and further, the foaming property is not lowered during the extrusion foaming process of polystyrene.

Hereinafter, the present invention will be described by way of examples. The following examples are only illustrative of the present invention, and the scope of the present invention is not limited thereby.

<Examples>

Preparation of Flame Retardant Masterbatch Composition

The flame retardant master batch composition (Example) and the comparative master batch composition (Comparative Example) according to the present invention were prepared by mixing the base resin, the flame retardant, the filler and the synergist in the composition shown in Table 1 below.

Example 1
(weight%) Example 2
(weight%) Example 3
(weight%) Example 4
(weight%) Example 5
(weight%) Comparative Example 1
(weight%) GPPS
(General purpose polystyrene) 45 45 30 45 - 45 LDPE
(Low density polyethylene) - - 15 - 45 - BDDP 50 - 50 42 - - 1,1 '- (isopropylidene) bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropoxy) benzene]
-
50
-
-
42
- 2,3-Diphenyl-1,3-butadiene - - - 8 8 - HBCD - - - - - 50 Talc 2 2 2 2 2 2 Sb ₂ O ₅ 3 3 3 3 3 3

Extruded polystyrene ( XPS ) Foam  Produce

According to the composition shown in the following Table 2, a raw material composition was formed by mixing a general-purpose polystyrene resin, a flame-retardant masterbatch composition of Examples and Comparative Examples and a nucleating agent, heating the material composition to 240 ° C and melting, And extruded and foamed in an extruder to prepare an extruded polystyrene foam.

Example 6
(weight%) Example 7
(weight%) Example 8
(weight%) Example 9
(weight%) Example 10
(weight%) Comparative Example 2
(weight%) GPPS
(General purpose polystyrene)
94
94
94
94
94
94


Flame Retardant
Master batch
Composition Example 1 4 - - - - - Example 2 - 4 - - - - Example 3 - - 4 - - - Example 4 - - - 4 - - Example 5 - - - - 4 - Comparative Example 1 - - - - - 4 Nucleating agent
(Talc) 2 2 2 2 2 2

<Experimental Example>

1. Flammability Test (KS M 3808 Flammability Test)

The flammability test was conducted on the above Examples 6 to 10 based on the flammability test method prescribed in KS M 3808: 2011 (submitted to the FITI test institute), and the test results are shown in FIG.

1 (Example 1), Example 7 (Specimen 2), Example 8 (Specimen 3), Example 9 (Specimen 4), and Examples (Examples 1 to 6), which are extruded polystyrene (XPS) foams according to the present invention 10 (Psalm 5) has flame retardancy sufficient to meet the criteria specified in KS M 3808: 2011.

2. Flammability Test (UL 94 Horizontal Flammability Test)

The above Examples 9 and 10 were further subjected to a combustion test according to UL 94 Horizontal Flammability Test (HBF) (submitted to the FITI Test Research Institute), and the test results are shown in FIGS. 2 to 5.

2 to 3, it can be seen that the extruded polystyrene foam of Example 9 (sample name: XPS 5000) has an excellent flame retardancy that satisfies the highest grade of HF-1 grade.

4 to 5, it can be seen that the extruded polystyrene foam of the example 10 (sample name: XPS 5005) also has excellent flame retardancy to satisfy the highest grade HF-1 grade.

3. Harmfulness and environment-friendliness: Satisfies EL243

Insulation of Notification No. 2015-5 of the Ministry of the Environment (Jan. 21, 2015). ㅇ Considering the environmental label certification standard EL243 for insulation, Examples 1 to 5 of the present invention were obtained by analyzing components through a mass spectrometer EL243's four major flame retardants are polybrominated biphenyls (PBBs), polybromodiphenyl ethers (PBDEs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) , hexabromocyclododecane) were not detected. In the case of Comparative Example 1, the HBCD detection amount was 268000 mg / kg as a result of analyzing the components through a mass spectrometer, and the flame retardant of EL243 (See Table 3 below).

Environmental sign
Certification Criteria
EL243
(Ministry of the Environment Notice
No. 2015-5) regulation
Flame retardant Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 PBBs
(mg / kg) Not detected Not detected Not detected Not detected Not detected Not detected PBDEs
(mg / kg) Not detected Not detected Not detected Not detected Not detected Not detected TBBPA
(mg / kg) Not detected Not detected Not detected Not detected Not detected Not detected HBCD
(mg / kg) Not detected Not detected Not detected Not detected Not detected 268000

4. Foaming

For Examples 6 to 10 and Comparative Example 2, the magnifications of foaming for 3 minutes were measured, and the results are shown in Table 4 below. According to Table 4, it was confirmed that Examples 6 to 10 maintained the same level of foamability as Comparative Example 2.

Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 3 minutes foaming
(ship) 75.3 71.7 73.5 78.1 77.8 77

As described above, those skilled in the art will understand that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It will be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention as defined by the appended claims and their equivalents. .

Claims (10)

30 to 50% by weight of a base resin made of polystyrene and / or low density polyethylene;
Bis (2,3-dibromo-2-methylpropoxy) benzene], or a mixture of these compounds, such as BDDP (Tetrabromobisphenol A bis 40 to 60% by weight of a flame retardant formed by mixing 2,3-Diphenyl-1,3-butadiene (b) in the mixture (a) so that the weight ratio of b: a is from 1: 4 to 1: 9;
1 to 5% by weight of a filler; And
1 to 5% by weight of antimony pentoxide (Sb ₂ O ₅ ).
The method of claim 1,
Wherein the filler is any inorganic compound selected from the group consisting of talc, calcium carbonate and silica.
delete The method of claim 1,
Stearic acid metal salt. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;
Polystyrene resin; A flame retardant masterbatch composition according to any one of claims 1, 2 and 4; And a crude nucleating agent is melted and then a foaming agent is added thereto to be extruded and foamed to form an extruded polystyrene foam. delete delete delete delete delete

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