KR102342103B1 - Flame retardant resin composition - Google Patents

Abstract

The present invention relates to a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; halogen-based organic compounds; And it relates to a flame-retardant resin composition comprising a halogen-based metal compound.

Description

Flame-retardant resin composition {FLAME RETARDANT RESIN COMPOSITION}

The present invention relates to a flame-retardant resin composition, and more particularly, to a flame-retardant resin composition comprising a halogen-based metal compound.

The acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as 'ABS copolymer') has good processability, excellent physical properties, especially impact strength, and excellent appearance. It is widely used for various purposes such as electronic products. However, the ABS copolymer has a disadvantage in that it can be burned when heat is generated or used in high-voltage products such as computers and fax machines. Therefore, methods for imparting flame retardancy to the ABS copolymer have been developed.

There is a method of injecting a flame retardant in order to impart flame retardancy to the ABS copolymer. Flame retardants are usually divided into halogen-based and non-halogen-based, and bromine-based flame retardants are representative of 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 auxiliary, have excellent flame retardant effects even when a small amount is added.

However, despite the high performance of antimony trioxide, it must be replaced as it is a suspected carcinogen, and if antimony trioxide is not used, an excessive amount of brominated flame retardant must be added. can

KR2004-0063415A

It is an object of the present invention to provide a flame-retardant resin composition that is harmless to the human body and can implement excellent flame retardancy.

In order to solve the above problems, the present invention provides a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; halogen-based organic compounds; And it provides a flame-retardant resin composition comprising a halogen-based metal compound.

Since the flame-retardant resin composition according to the present invention contains a metal halide, it is harmless to the human body and can achieve excellent flame retardancy equivalent to that of the flame-retardant resin composition containing antimony trioxide.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

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.

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 graft copolymer in a solvent. Specifically, after dissolving 0.5 g of the graft copolymer in 100 ml of methyl ethyl ketone, it can be measured using a Coulter counter (trade name: LS230, manufacturer: Beckman Coulter).

In the present invention, the weight average molecular weight can be measured as a relative value with respect to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent.

A flame-retardant resin composition according to an embodiment of the present invention comprises: 1. a graft copolymer comprising a conjugated diene-based polymer, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; 2. halogen-based organic compounds; and 3. a halogen-based metal compound.

Hereinafter, each component of the flame-retardant resin composition according to an embodiment of the present invention will be described in detail.

One. graft copolymer

The graft copolymer includes a unit derived from a conjugated diene-based polymer, an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer.

The graft copolymer may impart excellent chemical resistance, impact resistance, thermal stability, colorability, fatigue resistance, rigidity and processability to the flame-retardant resin composition.

The conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to a conjugated diene-based polymer prepared by polymerization of a conjugated diene-based monomer.

The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene may be preferable.

The conjugated diene-based polymer may be included in an amount of 10 to 40 wt%, 10 to 30 wt%, or 15 to 25 wt%, based on the total weight of the graft copolymer, of which 15 to 25 wt% is preferable. do. If the above-described range is satisfied, the mechanical properties, heat resistance and processability of the graft copolymer may be further improved.

The conjugated diene-based polymer 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 above-mentioned range is satisfied, the mechanical properties, glossiness, and colorability of the graft copolymer can be further improved.

Two or more types of the conjugated diene-based polymer having different average particle diameters within the aforementioned particle diameter may be used.

The aromatic vinyl-based monomer-derived unit may be at least one derived unit selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and among these, a styrene-derived unit is preferable.

The aromatic vinyl-based monomer-derived unit may be included in 40 to 80 wt%, 50 to 70 wt%, or 55 to 65 wt%, based on the total weight of the graft copolymer, of which 55 to 65 wt% it is preferable When the above-described range is satisfied, the rigidity, processability and surface gloss of the flame-retardant resin composition may be further improved.

The vinyl cyan-based monomer-derived unit may be at least one derived unit selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile is derived from units are preferred.

The vinyl cyan-based monomer-derived unit may be included in an amount of 10 to 40 wt%, 10 to 30 wt%, or 15 to 25 wt%, based on the total weight of the graft copolymer, of which 15 to 25 wt% it is preferable When the above-described range is satisfied, the chemical resistance and weather resistance of the flame-retardant resin composition may be further improved.

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.

The graft copolymer may have a weight average molecular weight of 70,000 to 200,000 g/mol, 90,000 to 150,000 g/mol, or 90,000 to 130,000 g/mol, of which 90,000 to 130,000 g/mol is preferable. When the above-mentioned range is satisfied, there is an advantage in that polymerization reaction control is easy and the balance between processability and mechanical properties is good.

The first copolymer may be prepared by polymerization of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in one or more methods selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization in the presence of a conjugated diene-based polymer, It is preferably prepared by heavy emulsion polymerization.

2. Halogen-based organic compounds

Halogen-based organic compounds are flame retardants.

The halogen-based organic compound may be a bromine-based organic compound. The bromine-based organic compound can implement excellent flame retardancy even when the flame-retardant resin composition is processed into a thin film, and can provide excellent fluidity to the flame-retardant resin composition.

The halogen-based organic compound is tetrabromobisphenol A (tetrabromoBisphenol A), decabromodiphenyl oxide, decabromodiphenyl ethane, 1,2-bis(2,4,6- Tribromophenyl) ethane ((1,2-Bis (2,4,6-tribromophenyl) ethane), octabromo-1,3,3-trimethyl-1-phenylindane (octabromo-1,3,3-trimethyl) -1-phenylindane), tetrabromo bisphenol A-bis (2,3-dibromopropyl ether) (tetrabromo Bisphenol A-Bis (2,3-dibromopropyl ether)) and 2,4,6-tris (2, Selected from the group consisting of 4,6-tribromophenoxy)-1,3,5-triazine (2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine) It may be at least one type, and among them, tetrabromobisphenol A is preferable.

The halogen-based organic compound may be included in an amount of 10 to 35 parts by weight or 15 to 30 parts by weight based on 100 parts by weight of the graft copolymer, of which 15 to 30 parts by weight is preferable. When the above-described range is satisfied, excellent flame retardancy and fluidity can be imparted to the flame-retardant resin composition without deterioration of other physical properties.

The content of the halogen-based organic compound may be affected by the thickness of the injection product made of the flame-retardant resin composition.

3. Halogen-based metal compounds

The halogen-based metal compound is a metal halide, and is a flame retardant auxiliary agent.

Antimony trioxide, which is generally used as a flame retardant auxiliary agent, is a suspected carcinogen and needs to be replaced despite its excellent flame retardancy as a flame retardant.

Accordingly, when the halogen-based metal compound is included as a flame retardant auxiliary agent in the flame retardant resin composition, unlike antimony trioxide, it is harmless to the human body, environmentally friendly and excellent flame retardancy can be realized. In addition, it is possible to reduce the content of the halogen-based organic compound as a flame retardant.

The halogen-based metal compound may include at least one selected from the group consisting of Mo, W, and Bi, and preferably includes Mo.

The halogen-based metal compound may be at least one selected from the group consisting of _{molybdenum chloride (MoCl 5} ), tungsten chloride (WCl ₆ ), and bismuth chloride (BiCl _{5 ), of which molybdenum chloride (MoCl 5 )} ) is preferred.

The average particle diameter of the halogen-based metal compound may be 0.1 μm to 10 μm, 0.1 μm to 5 μm, or 0.1 μm to 1.5 μm, of which 0.1 μm to 1.5 μm is preferable. When the above-described range is satisfied, there is an advantage in that deterioration of mechanical properties is minimized.

The halogen-based metal compound may be included in an amount of 3 to 10 parts by weight or 4 to 9 parts by weight based on 100 parts by weight of the graft copolymer, of which 4 to 7 parts by weight is preferable. When the above-described range is satisfied, it is possible to help realize excellent flame retardancy while reducing the amount of halogen-based organic compound used as the flame retardant.

Since the flame-retardant resin composition according to an embodiment of the present invention does not contain an antimony-based compound, which is a suspected carcinogen, it may be harmless to the human body and environmentally friendly.

The injection product made of the flame-retardant resin composition according to an embodiment of the present invention is a V-O grade based on the UL-94 vertical combustion evaluation method, and thus has excellent flame retardancy.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

<Preparation of flame-retardant resin composition>

Example One

ABS graft copolymer (product name: HI-121H, manufacturer: LG Chem) 100 parts by weight, tetrabromobisphenol A 24 parts by weight as a halogen-based organic compound, and molybdenum chloride (MoCl _{5 ,} average particle size) as a halogen-based metal compound by weight : 0.7㎛) 5 parts by weight of a twin-screw extruder (trade name: ZSE27MAXX-HP, manufacturer: Leistritz) set at 220 ℃ and extruded to prepare a flame-retardant resin composition in the form of pellets.

Example 2

A flame retardant resin composition was prepared in the same manner as in Example 1, except that tungsten chloride (WCl _{6 , average particle diameter: 1.2 μm) was added instead of molybdenum chloride.}

Example 3

A flame retardant resin composition was prepared in the same manner as in Example 1, except that bismuth chloride (BiCl _{3 , average particle diameter: 0.5 μm) was added instead of molybdenum chloride.}

The configurations of the examples are summarized in Table 1 below.

division Example 1
(parts by weight) Example 2
(parts by weight) Example 3
(parts by weight) ABS Graft
copolymer 100 100 100 tetrabromo
bisphenol 24 24 24 MoCl ₅ 5 - - WCl ₆ - 5 - BiCl ₃ - - 5

comparative example One

A flame retardant resin composition was prepared in the same manner as in Example 1, except that antimony trioxide (Sb ₂ O _{3 ) was added instead of molybdenum chloride.}

comparative example 2

100 parts by weight of ABS graft copolymer (brand name: HI-121H, manufacturer: LG Chem) and 24 parts by weight of tetrabromobisphenol A were put into a twin-screw extruder (product name: ZSE27MAXX-HP, manufacturer: Leistritz) set at 220°C and extruded To prepare a flame-retardant resin composition in the form of pellets.

comparative example 3

A flame retardant resin composition was prepared in the same manner as in Comparative Example 2, except that 35 parts by weight of tetrabromobisphenol A was added.

comparative example 4

A flame retardant resin composition was prepared in the same manner as in Comparative Example 2, except that 40 parts by weight of tetrabromobisphenol A was added.

The composition of Comparative Examples is summarized in Table 2 below.

division Comparative Example 1
(parts by weight) Comparative Example 2
(parts by weight) Comparative Example 3
(parts by weight) Comparative Example 4
(parts by weight) ABS Graft
copolymer 100 100 100 100 tetrabromo
bisphenol 24 24 35 40 Sb ₂ O ₃ 5 - - -

Experimental example

Specimens were prepared by injecting the flame-retardant resin compositions of Examples and Comparative Examples, and physical properties were evaluated by the method described below, and the results are shown in Table 3 below.

1) Flame retardancy: In accordance with the UL-94 vertical combustion evaluation method, a specimen having a thickness of 2.5mm, a width of 12.7mm, and a length of 127mm was injection-manufactured and flame retardancy was evaluated.

2) Izod impact strength (kg·cm/cm): According to ASTM D256, 1/4" specimen was injection-manufactured and then the notch impact strength was measured.

3) Heat deflection temperature (℃): According to ASTM D648, 1/4" specimen was injection-manufactured, and the heat deformation temperature was measured at a load of 18.6 kg and a temperature increase rate of 120 ° C./min without prior heat treatment.

division flame retardant Izod impact strength heat deflection temperature Example 1 PASS 19 76 Example 2 PASS 17 77 Example 3 PASS 18 76 Comparative Example 1 PASS 19 77 Comparative Example 2 FAIL 20 76 Comparative Example 3 FAIL 12 69 Comparative Example 4 PASS 10 67

Referring to Table 3, it can be seen that Examples 1 to 3 implement the same level of flame retardancy, impact resistance and heat resistance as Comparative Example 1. From these results, it could be predicted that metal halide could replace antimony trioxide.

And, as in Comparative Example 4, in order to improve the flame retardancy only with the bromine-based compound without the input of a metal halide, an excess of the bromine-based compound should be added, and thus it was confirmed that the impact resistance and the thermal deformation temperature were significantly reduced.

As in Comparative Example 2 and Comparative Example 3, even if the halogen-based organic compound is added, if the flame retardant auxiliary is not added, it can be confirmed that the flame retardancy improvement effect is not realized even if the bromine-based compound is added.

Claims (9)

ABS graft copolymer;
halogen-based organic compounds; and
containing a halogen-based metal compound,
The halogen-based metal compound is at least one flame-retardant resin composition selected from the group consisting of _{molybdenum chloride (MoCl 5} ) and tungsten chloride (WCl _{6 ).}
delete delete The method according to claim 1,
The average particle diameter of the halogen-based metal compound is a flame-retardant resin composition of 0.1 μm to 10 μm.
The method according to claim 1,
The halogen-based organic compound is a flame-retardant resin composition that is a bromine-based organic compound.
The method according to claim 1,
The halogen-based organic compound is tetrabromobisphenol A (tetrabromoBisphenol A), decabromodiphenyl oxide, decabromodiphenyl ethane, 1,2-bis(2,4,6- Tribromophenyl) ethane ((1,2-Bis (2,4,6-tribromophenyl) ethane), octabromo-1,3,3-trimethyl-1-phenylindane (octabromo-1,3,3-trimethyl) -1-phenylindane), tetrabromo bisphenol A-bis (2,3-dibromopropyl ether) (tetrabromo Bisphenol A-Bis (2,3-dibromopropyl ether)) and 2,4,6-tris (2, Selected from the group consisting of 4,6-tribromophenoxy)-1,3,5-triazine (2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine) A flame-retardant resin composition that is one or more of the following.
The method according to claim 1,
The flame-retardant resin composition is a flame-retardant resin composition that does not include an antimony-based compound.
The method according to claim 1,
Based on 100 parts by weight of the ABS graft copolymer,
10 to 35 parts by weight of the halogen-based organic compound; and
The flame-retardant resin composition comprising 3 to 10 parts by weight of the halogen-based metal compound.
It is prepared from the flame-retardant resin composition according to any one of claims 1, 4 to 8,
Based on the UL-94 vertical combustion evaluation method, the flame retardant resin injection product is VO grade.