KR20050034893A - Fire-proof resin composition - Google Patents

Abstract

The present invention relates to a flame-retardant resin composition, halogen compounds, phosphorus compounds and epoxy compounds with respect to 100 parts by weight of the basic mixed resin consisting of 10 to 70 parts by weight of rubber-modified styrene-containing graft copolymer and 10 to 60 parts by weight of styrene-containing copolymer 1 to 30 parts by weight of one or more flame retardants selected from the group consisting of; 1 to 25 parts by weight of at least one flame retardant adjuvant selected from the group consisting of antimony oxide, zinc compound, barium borate, zirconium oxide, talc and mica; And 1 to 10 parts by weight of polyethylene chloride; It is made to include and has an excellent flame retardant effect.

Description

Fire-proof resin composition {Fire-proof Resin Composition}

The present invention relates to a flame retardant resin composition. More specifically, the present invention relates to a flame retardant resin composition comprising rubber-modified styrene-containing graft copolymers, styrene-containing copolymers and high molecular weight styrene-containing copolymers, flame retardants, flame retardants and polyethylene chloride, and having excellent flame retardancy.

Flame retardant product means a product made of flame-retardant material or made of flame-retardant material in addition to the flame retardant article prescribed in Article 11, Paragraph 2 of the Fire Act. Plastic sheets, which are used for doors instead of wood, are widely used in general homes and commercial buildings, and there is a risk of fire. Therefore, the plastic door is also required as a flame retardant product together with the interior decoration classified into plywood, wood, furniture, synthetic resin products, etc. installed inside the building.

When plastic is mixed with a large amount of flame retardant and flame retardant, it is possible to achieve the flame retardancy required by electric and electronic products (the performance of printing, but self extinguishing occurs when the fire source is removed). However, to date, no product has achieved the flame retardancy required for building materials (a material or surface condition that no longer propagates when the external flame source is removed). In particular, the performance is important in the door, the development of a plastic material that delays or prevents the spread of sparks due to the expansion of combustion during the fire is an urgent reality.

This performance can be assessed by measuring the carbonization length and the surface area of the surface of the material when contacting the plastic sheet. The plastic sheet melts to a high temperature by the flame and flows downward to increase the contact area, which increases the carbonization length and the carbonization area. . The disadvantage that can not physically prevent the propagation of the flame can be reinforced by strengthening the melt strength of the plastic material at high temperatures.

The present inventors have thus developed a flame retardant resin composition excellent in flame retardancy.

In order to solve the above problems, it is an object of the present invention to provide a composition exhibiting excellent flame retardant performance by increasing the melt strength at a high temperature of the resin.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a rubber modified styrene-containing graft copolymer 10 to 70 parts by weight, 10 to 60 parts by weight of a styrene-containing copolymer having a weight average molecular weight of 50,000 to 150,000, and a weight average molecular weight of 500,000 to 6,000,000 To 100 parts by weight of the basic mixed resin consisting of 0.6 to 30 parts by weight of phosphorus high molecular weight styrene-containing copolymer; Flame retardant 1 to 30 parts by weight; 1 to 25 parts by weight of flame retardant; And it provides a flame-resistant resin composition comprising 1 to 10 parts by weight of polyethylene chloride.

The rubber-modified styrene-containing graft copolymer may be a copolymer obtained by grafting 30 to 65 wt% of a styrene compound and 10 to 30 wt% of an acryl or vinyl cyan compound based on 10 to 60 wt% of a diene rubber.

The styrene-containing copolymer and the high molecular weight styrene-containing copolymer may be an acrylonitrile-styrene copolymer composed of 50 to 80 parts by weight of styrene monomer and 20 to 50 parts by weight of acrylonitrile monomer.

The flame retardant may be one or more selected from the group consisting of halogen compounds, phosphorus compounds and epoxy compounds.

The halogen compound is tetra bromo bisphenol A (TBBA), TBBA-based phenoxy resin, TBBA-based carbonate oligomer, brominated epoxy oligomer (BEO), octabromodiphenyloxide , Decabromodiphenyloxide, tribromophenoxyethane, tribromophenoxyethane, hexabromodiphenoxyethane, decabromodiphenylethane, ethylenebis (tetrabromophthalimide) {ethylenebis (tetrabromophthalimide)}, and 2,4,6, -tris (2,4,6, -tribromophenoxy) 1,3,5-triazine {2,4,6, -tris (2, 4,6, -tribromophenoxy) 1,3,5-triazine}.

The phosphorus compound may be selected from the group consisting of triphenylphosphate, tri (hydroxyphenyly) phosphate and tricresylphosphate.

The epoxy compound may be a brominated epoxy oligomer in which an epoxy end is substituted with tribromophenol.

The epoxy compound has a molecular weight of 500 to 4000, it may be an epoxy oligomer of the formula (1):

[Formula 1]

Wherein X is Br or Cl, a, b, c and d are natural numbers of 1 to 4, and n is one or more natural numbers.

The flame retardant auxiliary agent may be at least one selected from the group consisting of antimony oxide, zinc compound, barium borate, zirconium oxide, talc and mica.

The antimony oxide may be selected from the group consisting of antimony trioxide, antimony tetraoxide and antimony pentoxide.

The zinc compound may be selected from the group consisting of zinc borate, molybdenum zinc and zinc sulfide.

The flame retardant styrene-based thermoplastic resin composition may further comprise one or more additives selected from the group consisting of lubricants, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers.

Hereinafter, the present invention will be described in detail.

The flame retardant resin composition according to the present invention has a high molecular weight of 10 to 70 parts by weight of a rubber-modified styrene-containing graft copolymer, 10 to 60 parts by weight of a styrene-containing copolymer having a weight average molecular weight of 50,000 to 150,000, and a weight average molecular weight of 500,000 to 6,000,000. With respect to 100 parts by weight of the base mixed resin consisting of 0.6 to 30 parts by weight of the styrene-containing copolymer (1 to 50 parts by weight based on 100 parts by weight of the total styrene-containing copolymer); 1 to 30 parts by weight of one or more flame retardants selected from the group consisting of halogen compounds, phosphorus compounds and epoxy compounds; 1 to 25 parts by weight of at least one flame retardant adjuvant selected from the group consisting of antimony oxide, zinc compound, barium borate, zirconium oxide, talc and mica; And 1 to 10 parts by weight of polyethylene chloride.

Hereinafter, the properties, functions, and composition ratios of the components of the present invention will be described in detail.

(1) rubber-modified styrene-containing graft copolymer

The base resin of the flame retardant resin composition of the present invention is a mixed resin of a rubber-modified styrene-containing graft copolymer and a styrene-containing copolymer. Among them, the rubber-modified styrene-containing graft copolymer is a copolymer obtained by grafting 30 to 65 wt% of a styrene compound and 10 to 30 wt% of an acryl or vinyl cyan compound in 10 to 60 wt% of a diene rubber.

Examples of the styrene-based compound include styrene, alpha-methylstyrene, and nuclear substituted styrene such as paramethyl styrene, and one or more of these may be selected and used.

The acrylic compound may include butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, and the like, and may be used by selecting one or more of them. .

As the vinyl cyan compound, acrylonitrile is preferable.

A rubber modified styrene-containing graft copolymer may be prepared by grafting the aromatic vinyl compound and the acrylic or vinyl cyanide compound to a diene rubber by a conventional polymerization method, but emulsion polymerization or bulk polymerization is preferable as the polymerization method. Do. The emulsion polymerization may be used alone or a method of appropriately mixing the bulk polymerization and the emulsion polymerization. Also in the method of adding a monomer at the time of polymer manufacture, the batch addition method or the method of mixing a batch addition method and a continuous addition method can be used.

More preferred as the rubber-modified styrene-containing graft copolymer is acrylonitrile-butadiene-styrene (ABS) resin in which acrylonitrile and styrene are grafted to butadiene rubber.

(2) styrene-containing copolymer

Another component of the basic resin of the present invention, the styrene-containing copolymer has a weight average molecular weight of 50,000 to 150,000, 50 to 80 parts by weight of styrene and 20 to 50 parts by weight of acrylonitrile monomer content of acrylonitrile-styrene air. One or more copolymer resins may be mixed and used. The high molecular weight styrene-containing copolymer having a weight average molecular weight of 500,000 to 6,000,000 used in the present invention serves to increase the melt strength of the resin when the flame and the resin contact in implementing flame retardant performance. The resin melts due to the thermal energy of the flame and flows downward by gravity. This deflection of the specimen widens the area in contact with the flame and may also cause holes. As high molecular weight styrene-containing copolymers are added, they form abundant entanglements between the polymer chains and act as a physical network throughout the resin, increasing the melt strength. As a result, the downward deflection of the resin due to the flame is significantly reduced, which serves to reduce the burn screen area.

A typical method for preparing a high molecular weight styrene-containing copolymer is emulsion polymerization. In the reaction of the acrylonitrile monomer and the styrene copolymer of the high molecular weight styrene-containing copolymer, 50 to 80 parts by weight of styrene and acryl 20 to 50 parts by weight of nitrile is used, and 0 to 20 parts by weight of these mixtures can be administered once or several times, respectively, in batch or continuous administration, with 0.5 to 3.0 weight of emulsifier to induce stability of emulsion polymerization and initiation reaction. Parts, 0.05 to 1.0 parts by weight of a polymerization initiator and the like can be used.

In the present invention, the content of the high molecular weight styrene-containing copolymer is preferably 1 to 50 parts by weight, preferably less than 1 part by weight, when the total styrene-containing copolymer is 100 parts by weight, and 50 parts by weight. In the above case, the fluidity of the flame retardant resin is reduced, so that extrusion, sheet extrusion, and injection molding are impossible under general processing conditions. In addition, even if the molding at high temperature, over-injection pressure conditions, the residual stress in the resin is not desirable in terms of processing performance and flame retardant performance.

(3) flame retardant

In the present invention, a flame retardant is added at a predetermined ratio in order to impart flame retardancy to the resin, and the flame retardant may be selected from the group consisting of a halogen compound, a phosphorus compound and an epoxy compound.

Examples of the halogen compound include tetra bromo bisphenol A (TBBA), TBBA phenoxy resin, TBBA carbonate oligomer, brominated epoxy oligomer (BEO), and octabromodiphenyloxide. ), Decabromodiphenyloxide, tribromophenoxyethane, hexabromodiphenoxyethane, hexabromodiphenoxyethane, decabromodiphenylethane, ethylenebis (tetrabromophthalimide) {ethylenebis (tetrabromophthalimide)}, and 2,4,6, -tris (2,4,6, -tribromophenoxy) 1,3,5-triazine {2,4,6, -tris (2 , 4,6, -tribromophenoxy) 1,3,5-triazine}.

The phosphorus compounds include triphenylphosphate, tri (hydroxypheny) phosphate, and tricresylphosphate.

Moreover, as said epoxy compound, the brominated epoxy oligomer by which the epoxy terminal was substituted by tribromophenol is preferable. More preferably, it is an epoxy oligomer of the following general formula (1) which has a molecular weight of 500-4000.

[Formula 1]

Wherein X is Br or Cl, a, b, c and d are natural numbers of 1 to 4, and n is one or more natural numbers.

(4) Flame retardant

The present invention adopts a flame retardant aid, the flame retardant aid may be selected from the group consisting of antimony oxide, zinc compounds, barium borate, zirconium oxide, talc and mica.

The antimony oxide includes antimony trioxide, antimony tetraoxide, antimony pentoxide, and the like.

The zinc compound includes zinc borate, molybdenum zinc, zinc sulfide and the like.

Among the flame retardant aids described above, antimony trioxide is particularly preferable for ABS resin.

(5) polyethylene chloride

The polyethylene chloride is a chlorinated high-density polyethylene through a substitution reaction by bulk polymerization. The polyethylene chloride suitable for the present invention contains 20 to 65% of chlorine, more preferably 35 to 40%.

(6) additive

In addition to the above components, the flame retardant resin composition of the present invention may further include one or more additives selected from the group consisting of lubricants, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments, and inorganic fillers, depending on the use.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Example 1

40 parts by weight of ABS resin as a rubber-modified styrene-containing graft copolymer, 59.4 parts by weight of acrylonitrile-styrene copolymer resin (SAN resin) having a weight average molecular weight of 100,000 by weight and 30 parts by weight of acrylonitrile monomer as a styrene-containing copolymer. , 0.6 parts by weight of high molecular weight acrylonitrile-styrene copolymer resin (HMSAN resin) having a weight average molecular weight of 2,300,000 and an acrylonitrile monomer content of 30 parts by weight as a high molecular weight styrene-containing copolymer (100 parts by weight of the total styrene-containing copolymer) 1 part by weight), 20 parts by weight of tetrabromo bisphenol A (TBBA) as a flame retardant, 20 parts by weight of antimony trioxide (Sb ₂ O ₃ ) as a flame retardant, 4 parts by weight of polyethylene chloride (CPE), 1 part by weight of lubricant After mixing 1 part by weight of antioxidant and 1 part by weight of light stabilizer uniformly with a mixer, a resin composition in pellet form was prepared using a twin screw extruder. All.

The pellets were prepared by injection molding to prepare the specimens for evaluation of physical properties, and after the specimens were prepared for the evaluation of flame resistance of 20ⅹ30cm through the sheet making extruder, their physical properties and flame resistance were evaluated as follows.

Impact strength: evaluated for 1/8 inch thickness by ASTM D256 test method.

* Fluidity: It was evaluated under the condition of 220 ℃, 10kg load by ASTM D1238 test method.

* Flame retardant: According to KOFEIS1001 which is a criterion for flame retardancy, a sheet having a size of 20 mm 30 cm and a sheet thickness of 1.5 mm were evaluated according to the manufacturing condition of the door sheet. In flame retardant, afterflame time was measured from the removal of burner's flame to the time of burning up, and the remaining time was burning from the removal of burner's flame without burning the flame. The time until was measured. The carbonization length measured the length of the carbonized portion by the flame, and the carbonization area measured the area of the carbonized portion by the flame. The burner used in this example was mekel and contacted for 2 minutes in a flame of 65 mm.

Thus, the composition, physical properties, and flame resistance evaluation results of the components used in Example 1 are shown in Table 1.

[Examples 2 to 4]

In the same manner as in Example 1 with the composition as shown in Table 1, after the addition of 10, 20, 30 parts by weight of a high molecular weight styrene-containing copolymer, respectively, to prepare a resin, their physical properties and flame retardancy was evaluated as a result Is shown in Table 1.

[Examples 5 to 13]

High molecular weight styrene with high molecular weight styrene-containing copolymer (HMSAN1) each having a weight average molecular weight of 900,000 and a weight average molecular weight of 4,000,000, in the same manner as in Example 1, as shown in Table 2. The resins were prepared by adding 0.6, 1.0 and 1.5 parts by weight of the high molecular weight styrene-containing copolymers (HMSAN3) having 3, 7, 10 parts by weight and 5,000,000 parts by weight, respectively, of the containing copolymers (HMSAN2). And the flame resistance was evaluated and the results are shown in Table 2.

[Comparative Examples 1 to 3]

With the composition as shown in Table 1, in Comparative Example 1, the high molecular weight styrene-containing copolymer was removed, and in Comparative Examples 2 and 3, 40 and 60 parts by weight were added, respectively. The physical properties and flame retardancy of were evaluated and the results are shown in Table 1.

division Example Comparative example One 2 3 4 One 2 3 Ingredient ABS 40 40 40 40 40 40 40 SAN 59.4 50 40 30 60 20 HMSAN 0.6 10 20 30 40 60 TBBA 20 20 20 20 20 20 20 Sb ₂ O ₃ 20 20 20 20 20 20 20 CPE 4 4 4 4 4 4 4 Other additives 3 3 3 3 3 3 3 Properties Impact strength (kgcm / cm) 24.8 26.4 28.6 30.3 24.5 31.6 30.7 Fluidity (g / 10min) 14.8 5.2 0.8 0.09 20 Inability to measure Inability to measure Flameproof Afterflaming time (sec) One One One One One One One Remaining time (sec) One One One One One One One Carbonization Length (cm) 8.5 8.0 7.8 7.8 8.2 7.8 - Bullet area (㎠) 35.8 32.1 29.5 29.4 36.6 29.6 -

As shown in Table 1, Comparative Example 1 prepared in the same manner as in Example 1, except that the high molecular weight styrene-containing copolymer is not included, when the resin is in contact with the flame, the melt strength of the resin is low Deflection phenomenon occurred. As a result, the contact area with the flame was widened, and the carbon screen area also increased. In Comparative Examples 2 and 3, the content of the high molecular weight styrene-containing copolymer was excessive, and as a result, it was not possible to secure the fluidity enough to be molded under general injection molding conditions. The impact strengths of Comparative Examples 2 and 3 were measured by molding under high temperature and over injection pressure conditions, and the flowability was not measured. However, it can be seen that the moldability is poor compared to other embodiments.

On the other hand, according to the present invention, 0.6 to 30 parts by weight of a styrene-containing copolymer including a flame retardant, flame retardant, polyethylene chloride, and a weight average molecular weight of 100,000 and a high molecular weight styrene-containing copolymer of 2,300,000 (100 parts by weight of the total styrene copolymer Examples 1 to 4 in which 1 to 50 parts by weight) was added, the melt strength was increased by the high molecular weight styrene-containing copolymer and the downward deflection of the resin was reduced. As a result, the carbonization length did not decrease significantly as the content increased, but the width of the contact area decreased, indicating that the carbon screen area decreased.

On the other hand, manufactured in the same composition as in Example 1, but looking at Comparative Example 3 prepared by being present in the composition ratio range of the present invention, when containing 60 parts by weight of a high molecular weight styrene-containing copolymer, the self-extinguishing properties but the residual stress during molding Since this hole is not removed, it can be seen that the carbonization length and the carbon screen are meaningless.

division Example 5 6 7 8 9 10 11 12 13 Ingredient ABS 40 40 40 40 40 40 40 40 40 SAN 50 40 30 57 53 50 59.4 59 58.5 HMSAN1 10 20 30 HMSAN2 3 7 10 HMSAN3 0.6 One 1.5 TBBA 20 20 20 20 20 20 20 20 20 Sb ₂ O ₃ 20 20 20 20 20 20 20 20 20 CPE 4 4 4 4 4 4 4 4 4 Other additives 3 3 3 3 3 3 3 3 3 Properties Impact Strength (㎏ · cm / ㎝) 26.6 27.0 32.6 24.0 25.1 25.5 26.5 26.4 26.4 Fluidity (g / 10min) 8.7 2.9 0.7 9.6 4.5 0.9 9.8 7.4 5.3 Flameproof Afterflaming time (sec) One One 2 One One One One One One Remaining time (sec) One One One One 2 One One One 3 Carbonization Length (cm) 8.0 8.1 8.5 8.0 7.8 7.9 8.9 7.9 7.8 Bullet area (㎠) 36.0 35.8 32.1 32.7 33.6 32.5 33.7 30.2 30.0

As shown in Table 2, Examples 5 to 7 prepared by adding 10, 20, 30 parts by weight of a high molecular weight styrene-containing copolymer (HMSAN1) having a weight average molecular weight of 900,000 is a high molecular weight of 2,300,000 Compared to Examples 2 to 4 to which the styrene-containing copolymer is added, the impact reduction effect is slightly decreased, but the improvement is clearly shown as the content is increased. 3, 7, 10 parts by weight of high molecular weight styrene-containing copolymers (HMSAN2) each having a weight average molecular weight of 4,000,000, and 0.6, 1.0 and 1.5 parts by weight of high molecular weight styrene-containing copolymers (HMSAN3) having a weight average molecular weight of 5,000,000 respectively. It can be seen that Examples 8 to 13 show the same impact modality as the Examples 2 to 7 even with the addition of a small amount due to the very high molecular weight.

As described above, the flame retardant resin composition according to the present invention is added to the flame retardant, flame retardant and polyethylene chloride in a certain ratio and a high molecular weight styrene-containing copolymer is added to the styrene-containing copolymer to increase the melt strength at high temperature It is a useful invention that exhibits excellent flame retardancy with a markedly reduced carbonization area.

While the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and variations are included in the appended claims. It is natural to belong.

Claims (12)

10 to 70 parts by weight of rubber-modified styrene-containing graft copolymer, 10 to 60 parts by weight of styrene-containing copolymer having a weight average molecular weight of 50,000 to 150,000, and high molecular weight styrene-containing copolymer having a weight average molecular weight of 500,000 to 6,000,000 0.6 to 30 100 parts by weight of the base mixed resin consisting of parts by weight; Flame retardant 1 to 30 parts by weight; 1 to 25 parts by weight of flame retardant; And 1 to 10 parts by weight of polyethylene chloride; Flame retardant resin composition, characterized in that comprises a. The method of claim 1, The rubber-modified styrene-containing graft copolymer is a copolymer obtained by grafting 30 to 65% by weight of a styrene compound and 10 to 30% by weight of an acrylic or vinyl cyanide compound to 10 to 60% by weight of a diene rubber. Flame retardant resin composition. The method of claim 1, The styrene-containing copolymer and the high molecular weight styrene-containing copolymer is an acrylonitrile-styrene copolymer comprising 50 to 80 parts by weight of styrene monomer and 20 to 50 parts by weight of acrylonitrile monomer. The method of claim 1, The flame retardant is a flame retardant resin composition, characterized in that at least one member selected from the group consisting of halogen compounds, phosphorus compounds and epoxy compounds. The method of claim 4, wherein The halogen compound is tetra bromo bisphenol A (TBBA), TBBA-based phenoxy resin, TBBA-based carbonate oligomer, brominated epoxy oligomer (BEO), octabromodiphenyloxide , Decabromodiphenyloxide, tribromophenoxyethane, tribromophenoxyethane, hexabromodiphenoxyethane, decabromodiphenylethane, ethylenebis (tetrabromophthalimide) {ethylenebis (tetrabromophthalimide)}, and 2,4,6, -tris (2,4,6, -tribromophenoxy) 1,3,5-triazine {2,4,6, -tris (2, 4,6, -tribromophenoxy) 1,3,5-triazine} flame-retardant resin composition, characterized in that it is selected from the group consisting of. The method of claim 4, wherein Flame-retardant resin composition characterized in that the phosphorus compound is selected from the group consisting of triphenyl phosphate (tirphenylphosphate), tri (hydroxy phenyl) phosphate {tri (hydroxypheny) phosphate} and tricresyl phosphate. The method of claim 4, wherein Flame-retardant resin composition, characterized in that the epoxy compound is a brominated epoxy oligomer substituted by the epoxy terminal with tribromophenol. The method of claim 7, wherein Flame-retardant resin composition characterized in that the epoxy compound has a molecular weight of 500 to 4000, an epoxy oligomer of the general formula (1): [Formula 1] Wherein X is Br or Cl, a, b, c and d are natural numbers of 1 to 4, and n is one or more natural numbers. The method of claim 1, The flame retardant auxiliary agent is a flame retardant resin composition, characterized in that at least one selected from the group consisting of antimony oxide, zinc compound, barium borate, zirconium oxide, talc and mica. The method of claim 9, Flame retardant resin composition, characterized in that the antimony oxide is selected from the group consisting of antimony trioxide, antimony tetraoxide and antimony pentoxide. The method of claim 9, Flame retardant resin composition, characterized in that the zinc compound is selected from the group consisting of zinc borate, molybdenum zinc and zinc sulfide. The method of claim 1, The flame retardant styrene-based thermoplastic resin composition further comprises at least one additive selected from the group consisting of lubricants, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers.