KR0165587B1 - The composition of anti-flammable thermoplastic polycarbonate resin - Google Patents

Abstract

The thermoplastic polycarbonate-based resin composition of the present invention comprises (A) ₁₀₀ to 60% by weight of a thermoplastic polycarbonate containing (A ₁ ) halogen and 0 to 70% by weight of (A ₂ ) (A ₂₁ ) styrene copolymer. (A ₂₂ ) 100 parts by weight of a base resin composed of 0 to 40% by weight of a styrene polymer composed of 100 to 30% by weight of a styrene graft polymer: (B) the structure of formula (I) Phosphoric acid ester compound having 2 to 20 parts by weight: and

(C) 0.1 to 2.0 parts by weight of a fluororesin based on 100 parts by weight of the base resin.

Description

[Name of invention]

Thermoplastic polycarbonate resin composition having flame retardancy

Detailed description of the invention

[Field of Invention]

The present invention relates to a thermoplastic resin composition having flame retardancy.

More specifically, the present invention provides an excellent base material comprising halogen-free polycarbonate resin, styrene copolymer, and styrene graft polymer, containing a specific phosphate ester compound as a phosphorus flame retardant and a fluoro resin for dropping prevention effect. A polycarbonate thermoplastic resin composition having flame retardancy.

The thermoplastic resin composition of the present invention may be added in the required amount of inorganic additives, heat stabilizers, antioxidants, dyes and / or pigments depending on the respective use of the resin composition.

[Background of invention]

In general, polycarbonate resins are widely used in applications such as electric and electronic products and automobile parts requiring high strength due to excellent transparency, impact resistance, and heat resistance. However, the polycarbonate resin itself has a disadvantage that processing is difficult because the notch impact strength is low and the flowability is particularly poor. Therefore, in order to improve processability and notch impact strength, it is blended with other kinds of resins, especially graft copolymer resins. For example, a mixture of polycarbonate resin and styrene resin is a resin mixture which maintains high notch impact strength and improves workability. Since the resin finished with this composition is usually applied to large heat dissipating materials such as computer housing or other office equipment, the other essential requirements for such resin composition are that the resin must be flame retardant and high mechanical Strength must be maintained. Many studies have been conducted to impart flame retardancy to the resin composition, and among them, the most commonly used flame retardant technique is to impart flame retardancy to the resin composition by melt-mixing a halogen compound and an antimony compound to a polycarbonate resin. The method of making is known and used by a well-known technique. However, the halogen compound used in the above composition exhibits sufficient flame retardant functions in the event of a fire, but hydrogen halide gas is generated during resin processing, causing mold corrosion and environmental pollution problems, and using brominated diphenyl ether bromide. In this case, it is likely that toxic gases such as dioxins or difuran are generated that can cause fatal harm to the human body. In addition, the use of antimony lowers the thermal stability and weather resistance, and thus has the weakness of deteriorating the physical properties during long-term stay in the injection molding machine. In order to improve the problem, in order to exclude the use of antimony compounds, a technique of using a halogen compound and a phosphate ester compound in a polycarbonate resin as a flame retardant simultaneously imparting flame retardancy to the resin is disclosed in European Patent Publication Nos. 174,493, 286,965 and 287,895. It is disclosed in the call. The patented technology improves processability and flame retardancy by phosphorus-based compounds, but it does not improve the problem of causing mold corrosion due to volatilization of halogen compounds used as main flame retardants during processing, and also does not cope with environmental problems. to be. Therefore, in order to supplement the above problems, US Patent Nos. 4,692,488, 4,914,144, and 5,204,394 and Japanese Patent Laid-Open No. Hei 3-182542 disclose a resin composition in which flame retardance is imparted using a phosphate ester compound and a fluorine compound. Doing. Examples of the phosphate ester-based flame retardant used most often include condensed phosphate esters and triaryl phosphates. Examples of the triaryl phosphate include triphenyl phosphate, tricresyl phosphate, trigylenyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, and the remaining triaryl phosphates except for trephenyl phosphate are liquid in their phase, Triphenylphosphate having a solid phase was mainly used. When triaryl phosphate is used as a flame retardant in polycarbonate blends, it is highly likely to cause cracking phenomenon that causes cracks as vaporized flame retardant forms a layer where stress is high during processing, and characteristics of polycarbonate resin It greatly reduces phosphorus heat resistance. In addition, when resorcinol diphosphate, a condensed phosphate ester, is used as a flame retardant, although the degree is smaller than that of the conventional triaryl phosphate, it also has a juice phenomenon and the liquid property is required to install a liquid mixing device during processing. There is a problem.

In order to solve the above problems, the present inventors have come to develop a thermoplastic polycarbonate-based resin composition using a phosphate ester compound having a specific structure.

[Purpose of invention]

It is an object of the present invention to provide a thermoplastic polycarbonate-based resin composition that does not contain a halogen element does not cause environmental pollution problems caused by halogen elements, does not cause juice phenomenon, excellent flame retardancy, processability and fusion line strength will be.

[Summary of invention]

The thermoplastic polycarbonate resin composition of the present invention comprises (A) (A ₁ ) 100 to 60% by weight of a thermoplastic polycarbonate resin containing no halogen, (A ₂ ) and (A ₂₁ ) 0 to 70% by weight of a styrene copolymer ( A ₂₂ ) 100 parts by weight of a base resin composed of 0 to 40% by weight of a styrene polymer composed of 100 to 30% by weight of a styrene graft polymer: (B) the following formula (I) or (II) 2 to 20 parts by weight of a phosphate ester compound having a structure of:

Wherein R ¹ and R ⁶ are each independently a hydrocarbon group having 1 to 20 carbon atoms that do not contain halogen, and they may have 0 to 3 oxygen or nitrogen atoms in addition to carbon and hydrogen, and n or n ' 0 or 1 and m or m 'is an integer between 1 and 3, and R ² , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently hydrogen or halogen-free carbon number 1 to An alkyl or aryl group of 10, which may have from 0 to 3 oxygen or nitrogen atoms in addition to carbon and hydrogen, respectively; and (C) 0.1 to 2.0 parts by weight of a fluororesin based on 100 parts by weight of the base resin: It is related with the resin composition characterized by the above-mentioned.

In the resin composition of the present invention, an inorganic additive, a heat stabilizer, a light stabilizer, a pigment, and / or a dye may be added according to the use of the resin.

Detailed Description of the Invention

The thermoplastic resin composition having flame retardancy of the present invention comprises (A) a base resin containing a polycarbonate resin, (B) a phosphorus compound and a (C) fluoro resin. Description of each of these components is as follows.

[A] Basic Resin

Base resin in the present invention (A) comprises a thermoplastic polyurethane containing no halogen polycarbonate resin (A ₁₎ and a styrene-based polymer (A _2).

The converged polycarbonate resin (A ₁ ) is a compound represented by [-OROOC-], and an aliphatic, aliphatic-aromatic, or aromatic polycarbonate can be used, and preferably, an aromatic polycarbonate is used.

The styrene polymer (A ₂ ) consists of a styrene copolymer (A ₂₁ ) and a styrene graft polymer (A ₂₂ ). Styrene copolymer (A ₂₁ ) refers to a copolymer obtained by copolymerizing styrene or 1r-methylstyrene with one or more substances selected from N-phenylmaleimide, maleic anhydride, methyl methacrylate and (meth) acrylonitrile. In addition, styrene graft polymer (A ₂₂ ) is one of styrene or 1r-methylstyrene and N-phenylmaleimide, maleic anhydride, methyl methacrylate and (meth) acrylonitrile in rubber having a glass transition temperature of 10 ° C. or less. It means a graft polymer grafted. In the styrene graft polymer (A ₂₂ ), the rubber having a glass transition temperature of 10 ° C. or less includes acrylic, butadiene, EPR, EPDM, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like. The styrene graft polymer (A ₂₂ ) has a rubber content of 30 to 70% by weight, the amount of monomer to be grafted is 70 to 30% by weight, and the graft ratio is in the range of 40 to 90%.

The styrene polymer (A ₂ ) consists of 0 to 70% by weight of styrene copolymer (A ₂₁ ) and 100 to 30% by weight of styrene graft polymer (A ₂₂ ). In the styrene graft polymer (A ₂₂ ), butadiene is preferably used as the rubber, and examples of the styrene graft polymer (A ₂₂ ) using butadiene include ABS, MBS, ASA, AES, and the like. The method for producing the styrene graft polymer (A ₂₂ ) is not particularly limited, and conventional polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization may be applied.

[B] Phosphate Ester Compounds

The phosphate ester compound used in the present invention has a structure of formula (I) or (II):

In the above formula, R ¹ and R ⁶ are each independently a hydrocarbon group having 1 to 20 carbon atoms that do not contain halogen, and they may have 0 to 3 oxygen or nitrogen atoms in addition to carbon and hydrogen. Wherein n or n 'is 0 or 1 and m or m' is an integer between 1 and 3. And R ² , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are each independently hydrogen or an alkyl or aryl group containing 1 to 10 carbon atoms that do not contain halogen, and they are oxygen or nitrogen in addition to carbon and hydrogen. It can have from 0 to 3 atoms each.

Representative examples of the structural formula (I) include N-hydroxyphthalimidyl diphenyl phosphate, which is represented by the following structural formula (III).

N-hydroxyphthalimidyl diphenyl phosphate of the formula (III) can be prepared by the following method. Diphenylchlorophosphate (268.64 g) was added dropwise to the chloroform solution (500 ml) containing N-hydroxyphthalimide (163.13 g) and triethylamine (160 g) for 5 hours, followed by stirring at room temperature for 12 hours. The reaction solution was washed three times with distilled water and then water was removed with MgSO ₄ and filtered to evaporate the solvent of the resulting solution under reduced pressure. Recrystallization twice from ethyl acetate / normal hexane to give N-hydroxyphthalimidyldiphenylphosphate (316.10 g: 80% yield).

Representative examples of the structural formula (II) include N-hydroxyphthalimidyl diphenyl phosphate, which is represented by the following structural formula (IV).

N-hydroxyphthalimidyl diphenyl phosphate of the above formula (IV) may be prepared by the following method. Diphenylchlorophosphate (268.64 g) was added dropwise to the chloroform solution (500 ml) containing N-hydroxyphthalimide (115.09 g) and triethylamine (160 g) for 5 hours, followed by stirring at room temperature for 12 hours. The reaction solution was washed three times with distilled water and then water was removed with MgSO ₄ and filtered to evaporate the solvent of the resulting solution under reduced pressure. Recrystallization twice from ethyl acetate / normal hexane to give N-hydroxyphthalimidyldiphenylphosphate (291.50 g: 84% yield).

The phosphate ester compound (B) is used in an amount of 2 to 20 parts by weight based on 100 parts by weight of the base resin (A).

[C] fluoro resins

Fluoro resins are conventionally available resins such as polytetrafluoroethylene, polyvinylidene fluoride, copolymers of tetrafluoroethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and fluoroalkyl vinyl ether, and tetra Fluoroethylene and hexafluoropropylene copolymers. These may be used independently from each other, or a mixture of two or more different from each other may be used. In order to prevent dripping during combustion, fluorine-based resins form a fibrillar network in the resin when mixed and extruded together with the resin to lower the flow viscosity and increase the shrinkage rate of the resin during combustion. Prevent dripping. When the fluorine-based resin in an emulsion state is used, the dispersibility of the fluorine-based resin is good with respect to the entire resin, but the disadvantage is that the process is complicated. Therefore, even if it is a powder state, if it can disperse | distribute suitably to all resin and can form a fibrous net, it can apply preferably. Fluorine-based resins that can be preferably used are polytetrafluoroethylene. The particle size of the polytetrafluoroethylene which can be preferably used in the present invention is 20 to 5001 is suitable for the mixing in the form of powder, the amount of use is 0.1 to 2.0% by weight relative to 100% by weight of the base resin.

The thermoplastic resin composition of the present invention may be added with an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye according to each use. The inorganic additives to be added include asbestos, glass fibers, talc and ceramics, which may be used in the range of 0 to 30% by weight based on 100% by weight of the base resin including polycarbonate. The thermoplastic resin composition of the present invention may add 2 to 20% by weight of a phosphate ester compound such as Structural Formula (I) or (II) to the base resin. When the phosphate ester compound having such a composition is used as a flame retardant, an excellent flame retardant effect can be obtained, and generation of toxic gas, which is a problem when using a conventional halogen flame retardant, can be prevented. It has the effect of the invention having the characteristics that it is possible to improve the problem of the poor surface condition and the deterioration of mechanical properties.

In the thermoplastic resin composition of the present invention, a phosphate ester compound represented by Structural Formula (I) or (II) is applied to a base resin containing polycarbonate as a flame retardant, a fluororesin is mixed, and an inorganic additive and a heat stabilizer required for the mixture are used. , Antioxidants, light stabilizers, pigments and / or dyes are added and mixed in a conventional mixer. This mixture is prepared into pellet resin composition through an extruder.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

EXAMPLE

Preparation and specifications of (A) base resin, (B) phosphate ester compound and (C) fluororesin resin used in Examples 1-6 and Comparative Examples 1-6 below are as follows.

(A) Basic resin

(A ₁ ) Polycarbonate resin: A 1250W grade manufactured by TEIJIN, Japan was used.

(A ₂ ) Styrene-based polymer

(A ₂₁ ) Styrene-based copolymer: 70% by weight of styrene and 30% by weight of acrylonitrile, 120% by weight of deionized water and 0.2% by weight of azobisisobutyronitrile are added, and 0.5% by weight of tricalcium phosphate is added. The suspension was polymerized to prepare a copolymer (SAN).

(A ₂₂ ) Styrene-based graft polymer: A _total weight of butadiene-golate latex is 50% by weight and the monomer is grafted, and 36% by weight of styrene, 14% by weight of acrylonitrile and 150% by weight of deionized water are added. 1.0% by weight of potassium oleate, 0.4% by weight of cumene hydroperoxide, and 0.3% by weight of mercaptane chain transfer agent were added thereto, maintained at 75 ° C. for 5 hours, and the reaction was completed to prepare graft ABS latex. The graft ABS (G-ABS) powder was prepared by adding 0.3% by weight to solids and solidifying.

(B) phosphate ester compound

(B ₁ ) N-hydroxyphthalimidyldiphenyl phosphate.

The material of formula III was prepared as follows.

Diphenylchlorophosphate (268.64 g) was added dropwise to the chloroform solution (500 ml) containing N-hydroxyphthalimide (163.13 g) and triethylamine (160 g) for 5 hours, followed by stirring at room temperature for 12 hours. After washing three times with distilled water, and then remove the moisture with MgSO ₄ and filtered the solvent of the resulting solution is evaporated under reduced pressure. Recrystallization twice from ethyl acetate / normal hexane to give N-hydroxyphthalimidyldiphenylphosphate (316.10 g; 80% yield). N-hydroxyphthalimide and diphenylchlorophosphate as used herein are manufactured and sold by Aldrich Co. The triethylamine was used after removing water and purification before use.

(B ₂ ) N-hydroxyphthalimidyldiphenyl phosphate.

The material of formula IV was prepared as follows.

Diphenylchlorophosphate (268.64 g) was added dropwise to the chloroform solution (500 ml) containing N-hydroxysuccinimide (115.09 g) and triethylamine (160 g) for 5 hours, followed by stirring at room temperature for 12 hours. The reaction solution was washed three times with distilled water and then water was removed with MgSO ₄ and filtered to evaporate the solvent of the resulting solution under reduced pressure. Recrystallization twice from ethyl acetate / normal nucleic acid gives N-hydroxyphthalimidyldiphenylphosphate (291.50 g; 84% yield). As used herein, N-hydroxysuccinamide is Aldrich Co. It is a product manufactured and sold by. Chloroform, ethyl acetate and normal nucleic acid were used after removing water and purifying water before use.

(C) fluoro resin

Teflon 7AJ from Dupont, USA was used.

Examples 1-6 below are examples according to the present invention, and Comparative Examples 1-6 are examples for comparing with the present invention. Examples 1 to 3 and Comparative Examples 1 to 3 used N-hydroxyphthalimidyl diphenyl phosphate (B ₁ ) as the phosphate ester compound (B), and its composition and test results are shown in Table 1 below. It was.

Example 4-6 and Comparative Example 4-6 were used as the N-hydroxysuccinimidyl diphenyl phosphate (B) as an ester compound which is phosphoric acid phosphoric acid, and its composition and test results are shown in Table 2 below. It was.

Physical properties shown in Table 1 and Table 2 were measured by the following method.

Flame retardancy: measured according to UL 94 VB.

Heat resistance: measured according to ASTM D 306.

Flexural strength: measured according to ASTM D 730.

Surface appearance: 3 × 100 × 100 mm specimens were injected and observed with the naked eye. (◎: Very good,: Excellent, ×: Bad).

As can be seen from the results of the physical properties of Table 1 and Table 2, the resin composition according to the present invention was found to be good flame retardancy, heat resistance, flexural strength and surface appearance.

Simple modifications or variations of the present invention can be readily made by those skilled in the art, and all such variations or modifications are considered to be included within the scope of the present invention.

Claims (4)

(A) ₁₀₀ to 60% by weight of (A ₁ ) halogen-free thermoplastic polycarbonate resin, 0 to 70% by weight of (A ₂ ) (A ₂₁ ) styrene copolymer and (A ₂₂ ) styrene graft polymer 100 to 30 100 parts by weight of a base resin composed of 0 to 40% by weight of a styrenic polymer made of% by weight; (B) 2-20 weight part of the phosphate ester compound which has a structure of following formula (I) with respect to 100 weight part of said base resins: Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms which is independently halogen-free, and they have 0 to 3 oxygen or nitrogen atoms in addition to carbon and hydrogen, and n is 0 or 1 and m is 1 and An integer between 3 and R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen or an alkyl or aryl group containing 1 to 10 carbon atoms that are free of halogen, and are oxygen or nitrogen atoms other than carbon and hydrogen, respectively; It may have from 0 to 3: and (C) 0.1 to 2.0 parts by weight of a fluororesin based on 100 parts by weight of the base resin; Thermoplastic polycarbonate-based resin composition, characterized in that consisting of. The styrene graft polymer (A ₂₂ ) is styrene or 1r-methylstyrene and N-phenylmaleimide, maleic anhydride, methyl methacrylate in 30 to 70% by weight of rubber having a glass transition temperature of 10 ° C or less. And (meth) acrylonitrile, a thermoplastic polycarbonate-based resin comprising a graft polymer obtained by grafting one material from 70% to 30% by weight of one material selected from the group consisting of 40% to 90%. Composition. (A) ₁₀₀ to 60% by weight of (A ₁ ) halogen-free thermoplastic polycarbonate resin, 0 to 70% by weight of (A ₂ ) (A ₂₁ ) styrene copolymer and (A ₂₂ ) styrene graft polymer 100 to 30 100 parts by weight of a base resin composed of 0 to 40% by weight of a styrenic polymer made of% by weight; (B) 2-20 weight part of the phosphate ester compound which has a structure of following formula (II) with respect to 100 weight part of said base resins; In the above formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, each independently containing halogen, and having 0 to 3 oxygen or nitrogen atoms in addition to carbon and hydrogen, and n 'is 0 or 1 and m' is An integer between 1 and 3, and R ⁷ and R ⁸ are each independently hydrogen or an alkyl or aryl group containing 1 to 10 carbon atoms that do not contain halogen; these are 0 to 3 oxygen or nitrogen atoms other than carbon and hydrogen, respectively. It may have up to: and (C) 0.1 to 2.0 parts by weight of a fluororesin based on 100 parts by weight of the base resin; Thermoplastic polycarbonate-based resin composition, characterized in that consisting of. The styrene graft polymer (A22) according to claim 5, wherein the styrene graft polymer (A22) comprises styrene or 1r-methylstyrene and N-phenylmaleimide, maleic anhydride, methyl methacrylate and 30 to 70% by weight of rubber having a glass transition temperature of 10 ° C or less. A thermoplastic polycarbonate-based resin composition, characterized in that it is a graft polymer obtained by grafting 70-30% by weight of one substance selected from the group consisting of (meth) acrylonitrile to a graft rate of 40-90%.