KR20120088090A - Thermoplastic resin having good flame retardancy and transparence - Google Patents

Abstract

PURPOSE: A thermoplastic resin composition having high hardness is provided to maintain improved impact strength, mobility, and transparency and to enhance mechanical strength and flame resistance. CONSTITUTION: A thermoplastic resin composition comprises 100.0 parts by weight of basic resins and 10-35 parts by weight of bromine based organic flame retardant. The basic resin is composed of 20-100 weight% of a methylmethacrylate-acrylonitrile-butadiene-styrene copolymer and 0-80 weight% of a methylmethacrylate-styrene acrylonitrile copolymer. The content of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer is 45-70 weight% and is manufactured by emulsion graft polymerization.

Description

Thermoplastic resin having good flame retardancy and transparence

The present invention relates to a thermoplastic resin composition, and more particularly, to a methylmethacrylate-acrylonitrile-butadiene-styrene copolymer resin containing a bromine-based organic compound as a flame retardant, having excellent flame resistance and scratch resistance. It relates to a high hardness thermoplastic flame-retardant ABS resin composition excellent in properties, impact strength and colorability.

Generally, methylmethacrylate-acrylonitrile-butadiene-styrene (MABS) resin has transparency due to refractive index control of components in the resin, stiffness and chemical resistance of acrylonitrile, butadiene and Due to the processability and mechanical strength of styrene, it is widely used as an exterior material for electrical, electronic products, and office equipment. However, the MABS resin itself is easily burned and has little fire resistance.

Because of these problems, MABS resins used in electrical and electronic products and office equipment must meet the flame retardant specifications to ensure the fire safety of electrical and electronic products.

However, due to the thermal decomposition characteristics of methyl methacrylate, which is the main component of MABS, it is not easy to give high flame retardancy to the MABS resin, and there is a problem in that mechanical properties are greatly deteriorated due to a relatively large amount of flame retardant.

Therefore, it is still required to develop a MABS resin having excellent flame resistance while maintaining excellent impact strength and flowability.

An object of the present invention is to provide a thermoplastic flame-retardant resin composition excellent in flame retardancy while maintaining excellent impact strength, flowability and transparency.

It is another object of the present invention to provide a high hardness thermoplastic flame retardant ABS resin composition excellent in scratch resistance and colorability.

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) 20 to 100% by weight of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) and methyl methacrylate-styrene-acrylonitrile (methylmethacrylate-styrene -acrylonitrile, MSAN) 100 parts by weight of the base resin consisting of 0 to 80% by weight of the copolymer; And (B) 10 to 35 parts by weight of a bromine-based organic flame retardant; and the rubber content of the methyl methacrylate-acrylonitrile-butadiene-styrene is 45 to 70% by weight. To provide.

The present invention relates to a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and a methyl methacrylate-styrene-acrylonitrile copolymer in which tris (tribromophenyl) cyanurate and an antimony compound, which is a bromine organic flame retardant, are used. By adding together, there is an effect of providing a thermoplastic resin composition having excellent flame resistance while maintaining excellent scratch resistance, transparency, impact strength and fluidity.

Hereinafter, the present invention will be described in detail.

The present inventors have described tris (tribromophenyl) cyanurate or bromate which is a brominated organic compound flame retardant in methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-styrene-acrylonitrile copolymer. Thermoplastic transparent resin composition prepared using the indane and antimony-based compound was confirmed that excellent impact strength and transparency, but also excellent flame retardancy, to complete the present invention based on this.

The thermoplastic resin composition having excellent flame retardancy of the present invention is (A) 20 to 100% by weight of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 0 to 80% by weight of methyl methacrylate-styrene-acrylonitrile copolymer It comprises a 60 to 100 parts by weight of a basic resin consisting of 10 to 35 parts by weight of (B) bromine-based organic flame retardant.

The bromine-based organic flame retardant is preferably included in 10 to 35 parts by weight based on 100 parts by weight of the base resin, the thermoplastic resin composition produced within this range does not significantly lower the mechanical strength and fluidity, excellent thermal stability and weatherability It has the effect of having.

The bromine-based organic flame retardant is not particularly limited as long as it can be generally used in a thermoplastic resin, for example, hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromo diphenol oxide, octave Lomodiphenyl oxide, decabromodiphenylethane, brominated indane, ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris ( At least one selected from the group consisting of tribromophenyl) cyanurate and tetrabromobisphenol A bis (allyl ether) is used, but is not limited thereto.

In particular, tris (tribromophenyl) cyanurate or brominated indan is preferably used.

Tris (tribromophenyl) cyanurate is represented by the following formula (1).

In addition, brominated indane is represented by following formula (2).

Wherein m + n is a number from 7 to 8.

The methyl methacrylate-acrylonitrile-butadiene-styrene copolymer of (A) is prepared by emulsion graft polymerization, and the rubber content is preferably 45 to 70% by weight.

When the rubber content is less than 45% by weight, the impact resistance decreases, and when the rubber content exceeds 70% by weight, there is a problem that the productivity is greatly reduced.

 In addition, the methyl methacrylate-acrylonitrile-styrene copolymer of the above (A) has a weight average molecular weight of 50,000 to 150,000, the content of the methyl methacrylate monomer is preferably 50 to 80% by weight, single or 2 It can mix and use species.

The methyl methacrylate-acrylonitrile-styrene copolymer prepared within the molecular weight and the content range of methyl methacrylate is characterized by excellent impact resistance and transparency.

The methyl methacrylate-acrylonitrile-butadiene-styrene copolymer is not particularly limited but is added to a conjugated diene rubber latex mixture having a particle diameter of 1600Å to 3500Å, a gel content of 70% to 95%, and a swelling index of 12 to 30. The monomer to be grafted onto is composed of a methacrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound, and is produced by an emulsion polymerization method. The refractive index of the monomer mixture used at this time absolutely affects the transparency, and this refractive index is controlled by the amount of the monomer used and the mixing ratio. That is, in order to have transparency, the refractive index of the conjugated diene compound used as the seed to be grafted and the refractive index of the entire grafted component should be about the same, so the amount of the monomer used and the mixing ratio are very important. The refractive index of each component used at this time is about 1.518 butadiene, about 1.49 methyl methacrylate, about 1.59 styrene, and about 1.518 acrylonitrile. The graft addition method of each component in the grafting polymerization reaction may be a method of collectively administering each component and a method of continuously (sequentially) administering all or part of the components, in the present invention, by adjusting the batch administration and continuous administration methods Take the complex form you use.

The emulsion graft polymerization is 45 to 50 parts by weight of butadiene rubber, 0.6 to 2 parts by weight of the emulsifier, 0.2 to the molecular weight regulator based on 100 parts by weight of the total monomer content contained in the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer A monomer mixture consisting of 50 to 80 parts by weight of methyl methacrylate, 5 to 40 parts by weight of acrylonitrile and 5 to 20 parts by weight of styrene is added to a mixed solution consisting of 1 part by weight and 0.05 to 0.5 parts by weight of a polymerization initiator. It is desirable to.

Preferably, the thermoplastic resin composition further comprises 0 to 3 parts by weight of an antimony compound based on 100 parts by weight of the base resin.

When the antimony-based compound exceeds 3 parts by weight, transparency is greatly lowered.

The antimony-based compound greatly improves the flame retardancy of the thermoplastic resin composition prepared by synergistic effect when used with the bromine-based organic flame retardant as a flame retardant aid. Antimony-based compounds include antimony trioxide and antimony pentoxide, but antimony trioxide is most preferably used antimony pentoxide because of its characteristic whiteness and opacity.

The thermoplastic resin composition may further include one or more additives selected from the group consisting of impact modifiers, lubricants, thermal stabilizers, antidrip agents, antioxidants, light stabilizers, sunscreen agents, pigments, and inorganic fillers.

Transparent ABS resin production method used in the present invention is prepared by the emulsion polymerization method 100 parts by weight of 1,3 butadiene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, molecular weight regulator 0.1 to 0.5 parts by weight, ion-exchanged water 90 to 130 parts by weight in a batch to react at 50 ℃ to 65 ℃ for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of a molecular weight modifier further 55 to 55 hours for 5 to 15 hours A small diameter polybutadiene rubber latex having a swelling index of about 12% to about 30% is prepared.

3.0 to 4.0 parts by weight of acetic acid aqueous solution was slowly added to 100 parts by weight of the small-diameter rubber latex for 1 hour to enlarge the particles, and then the stirring was stopped. The particle size was 2600Å to 5000Å, the gel content was 70% to 95%, and the swelling index was 12 to 30. A large-diameter rubber latex is prepared.

In order to manufacture large diameter rubber latex with high gel content and short time, a small diameter rubber latex with high gel content is first prepared by the same method as described above, and an acidic substance is added to these particles to make the large diameter rubber latex. This is preferred.

20 to 40 parts by weight of a methacrylic acid alkylester compound or an acrylic acid alkylester compound or a mixture of 15 to 25 parts by weight of an aromatic vinyl compound in a mixture of 5 to 25 parts by weight of a large-diameter polybutadiene rubber latex prepared by the above method, and 3 to 15 parts by weight of a large diameter rubber latex Graft copolymerization is carried out using 1 to 20 parts by weight of the vinyl cyan compound, 0.2 to 0.6 parts by weight of an emulsifier, 0.2 to 0.6 parts by weight of a molecular weight regulator, and 0.05 to 0.3 parts by weight of a polymerization initiator. The polymerization conversion rate of the latex obtained after the completion of the polymerization was 98% or more, and the latex was administered with an antioxidant and a stabilizer to coagulate with an aqueous calcium chloride solution at a temperature of 80 ° C. or higher, followed by dehydration and drying to obtain a total butadiene content of 50% -70%. Get powder.

20 to 100 parts by weight of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) of methyl methacrylate-acrylonitrile-styrene copolymer (MSAN) having an average molecular weight of 50,000 to 150,000 10 to 35 parts by weight of tris (tribromophenyl) cyanurate or brominated indane, 0.5 parts by weight of a black colorant, 0.3 parts by weight of antioxidant, and 1.5 parts by weight of lubricant, added to a brominated organic flame retardant and uniformly using a Henschel mixer After mixing, a thermoplastic resin composition in pellet form is prepared through a twin screw extruder.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example  One

Transparent ABS resin manufacturing method used in the present invention is prepared by the emulsion polymerization method 100 parts by weight of 1,3 butadiene, 3 parts by weight of emulsifier, 0.3 parts by weight of polymerization initiator, 0.5 parts by weight of electrolyte, 0.3 parts by weight of molecular weight regulator, ion exchange 110 parts by weight of a batch of water was reacted at 58 ° C. for 10 hours, and then 0.6 parts by weight of a molecular weight modifier was further added to prepare a small-diameter polybutadiene rubber latex having a swelling index of about 75% for about 8 hours.

3.5 parts by weight of an aqueous acetic acid solution was slowly added to 100 parts by weight of the small-diameter rubber latex for 1 hour to enlarge the particles, and then the stirring was stopped to prepare a large-diameter rubber latex having a particle size of 3800 kPa, a gel content of 83% and a swelling index of 20.

30 parts by weight of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, 20 parts by weight of an aromatic vinyl compound, and 10 parts by weight of a vinyl cyan compound in a mixture of 15 parts by weight of a large diameter rubber latex of 9 parts by weight of a small diameter polybutadiene rubber latex prepared by the above method Graft copolymerization was carried out using 0.4 part by weight of an emulsifier, 0.4 part by weight of a molecular weight regulator and 0.1 part by weight of a polymerization initiator. The polymerization conversion rate of the latex obtained after the completion of the polymerization was 98%, and the latex was administered with an antioxidant and a stabilizer to coagulate with an aqueous calcium chloride solution at a temperature of 80 ° C., followed by dehydration and drying to obtain a total butadiene content of 50% (BD- 50 MABS).

1400 g of methyl methacrylate-acrylonitrile-styrene copolymer (MSAN) having an average molecular weight of about 120,000 to 600 g of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (BD-50 MABS), a bromine-based organic flame retardant 600 g of tris (tribromophenyl) cyanurate (manufacturer: ICL, trade name: SR245), 6 g of antioxidant, 30 g of lubricant, 1 g of coloring agent were added and mixed uniformly using a Henschel mixer, and then pelletized through a twin screw extruder. A thermoplastic resin composition was prepared.

The pellet-type thermoplastic resin composition was injection molded to prepare a physical and flame retardant test specimen.

Example  2

Except for using brominated indane (manufacturer: ICL, trade name: FR-1808) instead of tris (tribromophenyl) cyanurate, which is a bromine-based organic flame retardant, was carried out in the same manner as in Example 1. .

Example  3

Except for using Example 1 except that 540 g of tris (tribromophenyl) cyanurate, which is a brominated organic flame retardant, and 20 g of antimony pentoxide (Sb ₂ O ₅ ) having a particle diameter of 5 to 30 nm as a flame retardant aid. It carried out in the same way.

Comparative example  One

Except that in Example 1, butadiene content of 40% methyl methacrylate-acrylonitrile-butadiene-styrene (BD-40 MABS) copolymer was used in the same manner as in Example 1.

Comparative example  2

In Example 1, 760 g of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer having a butadiene content of 40% was used to equalize the butadiene content in the entire resin, and methyl methacrylate-acrylonitrile-styrene air was used. The same procedure as in Example 1 was conducted except that 1240 g of coalescence (MSAN) was used.

Comparative example  3

In Example 2, 760 g of acrylonitrile-butadiene-styrene copolymer having a butadiene content of 40% was used to equalize the butadiene content in the entire resin, and 1240 g of methyl methacrylate-acrylonitrile-styrene copolymer (MSAN) Except that was used in the same manner as in Example 2.

Comparative example  4

In Example 3, 760 g of acrylonitrile-butadiene-styrene copolymer having a butadiene content of 40% was used to equalize the butadiene content in the entire resin, and 1240 g of methyl methacrylate-acrylonitrile-styrene copolymer (MSAN) Except that was used in the same manner as in Example 3.

Comparative example  5

Except that 30 parts by weight of tetrabromobisphenol A (manufacturer: Albemarl, trade name: Saytex CP-2000) as a flame retardant in Comparative Example 2 was carried out in the same manner as in Comparative Example 2.

Example (parts by weight) Comparative example (parts by weight) One 2 3 One 2 3 4 5 MABS BD-50
MABS ^{1 )} 30 30 30 - - - - - BD-40
MABS ^{2 )} - - - 30 38 38 38 38 MSAN ^{3 )} 70 70 70 70 62 62 62 62 Flame retardant TBPC ^{4 )} 30 - 27 30 30 - 27 - Br-ID ^{5 )} - 30 - - - 30 - - TBBA ^{6 )} - - - - - - - 30 Flame Retardant
Supplements Sb ₂ O ₅ - - One - - - - - -Sb ₂ O ₃ - - - - - - One - coloring agent 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Note 1) BD-50 MABS: Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (butadiene content: 50% by weight)

2) BD-40 MABS: Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (butadiene content: 40% by weight)

3) MSAN: Methyl methacrylate-styrene-acrylonitrile

4) TBPC: tris (tribromophenyl) cyanurate

5) Br-ID: brominated indane

6) TBBA: tetrabromobisphenol A

[Test Example]

The flame retardancy of the thermoplastic flame retardant resin composition specimens prepared in Examples and Comparative Examples was measured by the following method and the results are shown in Table 2 below.

Notched Izod Impact Strength: Measured according to ASTM D-256 using a 1/8 "thick specimen.

* Pencil Hardness: Measured according to ASTM D-3365.

* Colorability: Measures the degree of coloring of 3 parts by weight of the colorant based on black using a color meter (SUGA Color Computer) and displays it as L, a, and b values, where L is a numerical value representing brightness. The lower the value, the stronger the degree of black.

* Flame Flame Ignition test: A 1/8 "thick, 10 × 10 specimen was measured according to IEC TS 62441.

Example Comparative example One 2 3 One 2 3 4 5 Impact strength 14.5 15.6 13.4 7.5 11.2 12.3 9.2 12.7 Pencil hardness B B B B 3B 3B 3B 3B Degree of coloring 12.37 13.42 14.21 12.21 12.91 14.21 14.21 23.86 Flame retardancy
(Spark Remaining Time, sec) 55 42 31 61 67 58 42 35

As can be seen from the above results, Examples 1 and 2 using butadiene content of 50% methylmethacrylate-acrylonitrile-butadiene-styrene copolymer showed excellent impact strength and pencil hardness. Butadiene content 40% Methyl methacrylate-acrylonitrile-butadiene-styrene copolymers in the same amount compared to 1 showed a significant decrease in impact resistance due to the reduction of the overall rubber content. Comparative Examples 2 and 3, which made the total rubber content the same, showed comparatively good impact strengths compared with Examples 1 and 2, but the total amount of methylmethacrylate-acrylonitrile-butadiene-styrene copolymer was added. Pencil hardness is greatly reduced due to the decrease in compatibility of the interface that appears as the increase. Example 3 applying 20 g (1 part by weight) of antimony pentoxide, 5 to 30 nanometers, which is a flame retardant, showed the same level of flame retardancy and relatively good transparency colorability while minimizing the decrease in physical properties. Implementing flame retardancy by applying antimony pentoxide may also be a method of achieving excellent transparency and pencil hardness. In Comparative Example 5, the flame retardant was changed to tetrabisphenol A having a high refractive index, and in this case, the transparency of the resin was largely inhibited due to the intrinsic refractive index of the flame retardant, and the colorability and transparency were greatly reduced.

As can be seen from the above results, the methyl acrylate-acrylonitrile-butadiene-styrene copolymer having an increased butadiene content from 40% to 50% is used, and tris (tribromophenyl) cyanurate or bromine having a low refractive index is used. When the flame retardance is imparted to the resin using the mined indane, a thermoplastic resin composition capable of maintaining excellent mechanical strength and transparency can be obtained.

Claims (9)

(A) 100 parts by weight of a basic resin consisting of 20 to 100% by weight of methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and 0 to 80% by weight of methylmethacrylate-styrene-acrylonitrile copolymer; And
(B) 10 to 35 parts by weight of bromine organic flame retardant;
It comprises, and the rubber content of the methyl methacrylate-acrylonitrile-butadiene-styrene is 45 to 70% by weight of the thermoplastic resin composition. The bromine-based organic flame retardant is hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, decabromo diphenol oxide, octabromodiphenyl oxide, decabromodiphenyl Ethane, brominated indane, ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris (tribromophenyl) cyanurate and tetra A bromobisphenol A bis (allyl ether) is at least one member selected from the group consisting of thermoplastic resin compositions. The thermoplastic resin composition of claim 2, wherein the bromine-based organic flame retardant is tris (tribromophenyl) cyanurate represented by the following Chemical Formula 1.
[Formula 1]

The thermoplastic resin composition according to claim 2, wherein the bromine-based organic flame retardant is brominated indan represented by the following Chemical Formula 2.
(2)

Wherein m + n is a number from 7 to 8. The thermoplastic resin composition of claim 1, wherein the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer of (A) is prepared by emulsion graft polymerization. According to claim 1, wherein the methyl methacrylate-acrylonitrile-styrene copolymer of (A) has a weight average molecular weight of 50,000 to 150,000, the content of the methyl methacrylate monomer is 50 to 80% by weight Thermoplastic resin composition. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises 0 to 3 parts by weight of an antimony flame retardant aid based on 100 parts by weight of the base resin. 8. The thermoplastic resin composition according to claim 7, wherein the antimony flame retardant aid is antimony trioxide or antimony pentoxide. The method of claim 1, wherein the thermoplastic resin composition comprises at least one additive selected from the group consisting of impact modifiers, lubricants, heat stabilizers, anti-drip agents, antioxidants, light stabilizers, sunscreen agents, pigments and inorganic fillers. A thermoplastic resin composition, further comprising.