KR101209103B1 - Non-halogen Flame-retarding Polycarbonate Resin Composition - Google Patents

Abstract

The present invention (A) 50 to 100 parts by weight of polycarbonate resin; (B) 0-50 parts by weight of a rubber modified styrene resin; Basic resin (A) + (B) consisting of 100 parts by weight; (C) 0.5 to 30 parts by weight of the cyclic phosphonate compound represented by the following formula (1); And (D) optionally, 0 to 20 parts by weight of an aromatic phosphate ester compound.

≪ Formula 1 >

In the above formula, R ₁ , R ₁ ′, R ₂ and R ₂ ′ each independently represent hydrogen, C _1-8 alkyl, C _6-20 aryl, or C _1-8 alkyl substituted C _6-20 aryl groups.

The polycarbonate-based composition according to the present invention provides an environmentally friendly flame-retardant polycarbonate-based resin composition that is stable against fire and does not use a halogen-based flame retardant and does not cause environmental pollution during combustion.

Polycarbonate resin, rubber modified styrene resin, cyclic benzyl methyl phosphonate, phosphorus compound

Description

Non-halogen flame-retardant polycarbonate resin composition {Non-halogen Flame-retarding Polycarbonate Resin Composition}

Field of invention

The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention relates to a non-halogen flame retardant polycarbonate resin composition having excellent flame retardancy by applying a phosphonate compound and an aromatic phosphate ester compound as a flame retardant to a blend using a polycarbonate resin and a rubber modified styrene resin. .

BACKGROUND OF THE INVENTION

Blends of polycarbonate / styrene-containing copolymers are resin mixtures that improve processability while maintaining high notch impact strength and are therefore inherently flame retardant and heat resistant, as they are applied to large heat dissipating materials such as computer housings or other office equipment. And high mechanical strength.

In order to impart flame retardance to such a resin composition, a halogen-based flame retardant and an antimony compound have been conventionally used. However, when halogen-based flame retardants are used, the demand for resins that do not contain halogen-based flame retardants has been rapidly expanded recently due to the problem of human health of gases generated during combustion.

As a technique for imparting flame retardancy without using a halogen flame retardant, the most common at present is to use a phosphate ester flame retardant. U.S. Patent 4,692,488 discloses thermoplastic resin compositions consisting of non-halogen aromatic polycarbonate resins, non-halogen styrene-acrylonitrile copolymers, non-halogen phosphorus compounds, tetrafluoroethylene polymers and small amounts of ABS copolymers. U. S. Patent No. 5,061, 745 discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, an ABS graft copolymer, a copolymer and a monomeric phosphate ester. However, there is a problem in that a certain amount or more must be added in order to exhibit an effect of flame retardancy by adding phosphate ester.

An object of the present invention is to provide a flame retardant polycarbonate-based resin composition that is stable against fire.

Another object of the present invention is to use an environmentally friendly compound as a flame retardant without the use of halogen-based flame retardants that cause environmental pollution during processing or combustion of the resin, and an environmentally friendly flame retardant polycarbonate having excellent flame retardancy even when a small amount of flame retardant is added. It is for providing a system resin composition.

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

Summary of the Invention

The present invention (A) 50 to 100 parts by weight of polycarbonate resin; (B) 0-50 parts by weight of a rubber modified styrene resin; Basic resin (A) + (B) consisting of 100 parts by weight; (C) 0.5 to 30 parts by weight of the cyclic phosphonate compound represented by the following formula (1); And optionally, (D) 0 to 20 parts by weight of the aromatic phosphate ester compound, providing a flame retardant polycarbonate resin composition.

≪ Formula 1 >

In the above formula, R ₁ , R ₁ ′, R ₂ and R ₂ ′ each independently represent hydrogen, C _1-8 alkyl, C _6-20 aryl or C _1-8 alkyl substituted C _6-20 aryl groups.

The (B) rubber-modified styrene resin is more specifically (B-1) 4 to 65% by weight of the rubber-like polymer 30 to 95% by weight of the aromatic vinyl monomer, monomers 1 to copolymerizable with the aromatic vinyl monomer 20 to 100% by weight of graft copolymer resin graft polymerized by adding 20% by weight and 0 to 15% by weight of additional monomers for workability or heat resistance addition; And (B-2) 60 to 90% by weight of an aromatic vinyl monomer and copolymerizes by adding 10 to 40% by weight of a monomer copolymerizable with the aromatic vinyl monomer and 0 to 30% by weight of an additional monomer for processability or heat resistance addition. Copolymer resin 0 to 80% by weight; may be made.

The (D) aromatic phosphate ester compound may have a structure of Formula 2 more specifically.

<Formula 2>

Wherein R ₃ , R ₄ , R ₅ , R ₃ ', R ₄ ', R ₅ ', R ₃ ", R ₄ ", R ₅ ", R ₃ "', R ₄ "'and R ₅ "' Are each independently hydrogen or an alkyl group of C ₁ -C ₄ , X is an aryl group of C ₆ -C ₂₀ or a C ₆ -C ₂₀ aryl group substituted with an alkyl group of C ₁ -C ₄ , and n is It is an integer of 0-4.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

The present invention comprises (A) 50 to 100 parts by weight of polycarbonate resin, (B) 100 to parts by weight of base resin (A) + (B), and (C) cyclic phosphonate, which is composed of 0 to 50 parts by weight of rubber-modified styrene resin. It provides 0.5-30 weight part of system compounds, and (D) optionally 0-20 weight part of aromatic phosphate ester compounds, The flame-retardant polycarbonate-type resin composition characterized by the above-mentioned.

In particular, the present inventors apply the cyclic benzyl phosphonate compound represented by Formula 1 to a polycarbonate-based resin and styrene-based resin blend as a flame retardant to solve the problems of conventional flame-retardant thermoplastic resin, flame retardant polycarbonate with fire stability It is early to develop a system resin composition.

Hereinafter, each component of the polycarbonate resin composition of this invention is demonstrated in detail.

(A) polycarbonate resin

The polycarbonate-based resin, which is the component (A) used in the preparation of the resin composition of the present invention, may be prepared by specifically reacting diphenols represented by the following formula (2) with phosgene, halogen formate or diester carbonate. have.

<Formula 2>

In the above formula, A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ to C ₆ cycloalkylidene, -S- or -SO _2- .

Specific examples of the diphenol of the formula (2) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl)- 2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3 , 5-dichloro-4-hydroxyphenyl) -propane and the like. As the diphenol compound, compounds such as hydroquinone and resorcinol can be used. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Hydroxyphenyl) -cyclohexane and the like, and the most preferred and most industrially used aromatic polycarbonate is prepared from 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A.

Suitable polycarbonates used in the production of the resin composition of the present invention include those having a weight average molecular weight of 10,000 to 200,000, preferably 15,000 to 80,000.

As the polycarbonate used in the preparation of the resin composition of the present invention, a branched chain may be used, preferably 0.05 to 2 mol% of a tri- or more polyfunctional compound based on the total amount of diphenols used for polymerization, For example, it may be prepared by adding a compound having a trivalent or more phenol group.

Examples of the polycarbonate used in the production of the resin composition of the present invention include homo polycarbonates and copolycarbonates, and may also be used in the form of a blend of copolycarbonates and homo polycarbonates.

In addition, the polycarbonate used in the production of the resin composition of the present invention may be partially or entirely replaced by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, such as a bifunctional carboxylic acid.

(B) rubber modified styrene resin

Rubber modified styrene resin refers to a polymer in which a rubber polymer is dispersed in a particulate form in a matrix (continuous phase) made of a vinyl aromatic polymer, and an aromatic vinyl monomer and a monomer copolymerizable with these in the presence of a rubber polymer. It is prepared by adding and polymerizing. Such rubber-modified styrenic resins can be produced by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and are usually mixed with graft copolymer resin (B-1) and copolymer resin (B-2). Produced by extrusion. In the case of the bulk polymerization, the rubber modified styrene resin is produced by only one step reaction without producing graft copolymer resin and the copolymer resin, but in any case, the rubber content of the final rubber modified styrene resin component is (B) rubber. It is suitable that it is 5-30 weight% in the whole modified styrene resin. Examples of such resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins, and the like. .

Examples of the rubber-modified styrene resin (B) may be applied in combination of a graft resin alone or a graft copolymer resin and a copolymer resin, and are preferably blended in consideration of their compatibility.

More specifically, in one embodiment of the present invention, (B) the rubber-modified styrene resin is (B-1) 4 to 65% by weight of the rubber polymer 30 to 95% by weight of the aromatic vinyl monomer, the aromatic vinyl monomer 20 to 100% by weight of a graft copolymer resin copolymerized with 1 to 20% by weight of a monomer copolymerizable with 0 to 15% by weight of an additional monomer for processability or heat resistance addition and (B-2) aromatic vinyl Copolymer resin 0 to 80 weight% by adding 10 to 40% by weight of monomer capable of copolymerizing with the aromatic vinyl monomer and 0 to 30% by weight of additional monomer for processability or heat resistance addition to 60 to 90% by weight of the monomer. It may consist of%.

If the content of the (B-1) graft copolymer resin to include a lot out of the above range compared to the content of the (B-2) copolymer resin, there may be a problem of fluidity deterioration, while (B-2) If the copolymer resin content is to include a lot out of the above range compared to the content of the (B-1) graft copolymer resin may have a problem of lowering the impact strength.

Hereinafter, each of the graft copolymer resin (B-1) and the copolymer resin (B-2) will be described.

(B-1) Graft Copolymer Resin

Examples of the rubber used for the graft copolymer resin include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubbers and isoprene rubbers in which hydrogen is added to the diene rubber. , Acrylic rubbers such as chloroprene rubber, butyl polyacrylate, and ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be cited, but in particular, diene rubber is preferable, and butadiene rubber is more preferable. . The content of rubber is appropriately 4 to 65% by weight in the weight of the graft copolymer resin.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methyl styrene, p-methyl styrene, and the like may be used, and among these, styrene is most preferable, and copolymerizable with the aromatic vinyl monomer One or more monomers are introduced and applied. As such a monomer to be introduced, vinyl cyanide-based compounds such as acrylonitrile and unsaturated nitrile-based compounds such as methacrylonitrile are preferable.

Preferably, in the total components of the (B-1) graft copolymer resin, the rubbery polymer is 5 to 65% by weight, the aromatic vinyl monomer is 30 to 95% by weight, and can be copolymerized to the aromatic vinyl monomer. Monomer is added in an amount of 1 to 20% by weight and graft copolymerized.

In addition, in order to impart properties such as workability and heat resistance during the preparation of the (B-1) graft copolymer resin, a monomer such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade may be selectively added to the graph Can be polymerized. The amount added is in the range of 0 to 15% by weight of the graft copolymer resin (B-1) as a whole.

The graft copolymer resin may preferably be butadiene-styrene-acrylonitrile-based.

In consideration of the impact strength and appearance when preparing the graft copolymer, the average size of the rubber particles is suitably in the range of 0.1 to 4 m.

(B-2) copolymer resin

The copolymer resin is prepared according to the monomer ratio and compatibility of the graft copolymer resin (B-1) prepared by the above composition except for rubber, and the components thereof are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methyl styrene, p-methyl styrene, and the like may be added, of which styrene is most preferred, and the amount of the aromatic vinyl monomer added in the entire component of the copolymer resin (B-2). Silver is preferably 60 to 90% by weight.

One or more types of monomers copolymerizable with the aromatic vinyl monomers are introduced into such copolymer resins. The copolymerizable monomer is preferably a vinyl cyanide compound or an unsaturated nitrile compound such as acrylonitrile or methacrylonitrile. These monomers are introduced at 10 to 40% by weight of the total components of the copolymer resin (B-2).

In addition, the copolymer resin may be optionally copolymerized with 0 to 30% by weight of monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade in order to impart properties such as workability and heat resistance. .

The copolymer resin (B-2) may preferably be a styrene-acrylonitrile-based.

The weight average molecular weight of the suitable copolymer resin (B-2) used for manufacture of the resin composition of this invention is 80000-300000.

(C) cyclic benzyl phosphonate compounds

The (C) cyclic phosphonate compound is used in the range of 0.5 to 30 parts by weight with a phosphonate compound represented by the following formula (1) or a mixture thereof, preferably 10 to 25 parts by weight. In the composition according to the present invention, when the (C) cyclic benzyl phosphonate compound is used in an amount of less than 0.5 parts by weight, there may be a problem that a desired degree of flame retardancy may not be achieved. There may be a problem of deterioration of the same physical properties.

&Lt; Formula 1 >

In the above formula, R ₁ , R ₁ ′, R ₂ and R ₂ ′ each independently represent hydrogen, C _1-8 alkyl, C _6-20 aryl, or C _1-8 alkyl substituted C _6-20 aryl groups.

Preferably, Ar is a phenyl group or C ₁ to C ₄ alkyl substituted phenyl group.

(D) Aromatic Phosphate Ester Compounds

The aromatic phosphate ester compound used in the present invention has a structure represented by the following general formula (2).

<Formula 2>

Wherein R ₃ , R ₄ , R ₅ , R ₃ ', R ₄ ', R ₅ ', R ₃ ", R ₄ ", R ₅ ", R ₃ "', R ₄ "'and R ₅ "' Are each independently hydrogen or an alkyl group of C ₁ -C ₄ , X is an aryl group of C ₆ -C ₂₀ or a C ₆ -C ₂₀ aryl group substituted with an alkyl group of C ₁ -C ₄ , and n is It is an integer of 0-4.

Preferably, X may be derived from a dialcohol of resorcinol, hydroquinol, bisphenol-A.

Examples of the compound corresponding to Chemical Formula 2 include triphenyl phosphate and tri (2,6-dimethyl) phosphate when n is 0, and when n is 1, resorcinol bis (diphenyl) phosphate or resorcinol bis (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dit-butylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-dit -Butylphenyl) phosphate, etc. are mentioned. These aromatic phosphate ester compounds may be applied alone or in each mixture.

In the flame retardant polycarbonate-based resin composition of the present invention, the (D) aromatic phosphate ester compound may be preferably contained in an amount of 0 to 10 parts by weight. When the content of the (D) aromatic phosphate ester compound exceeds 10 parts by weight, there may be a problem of deterioration in fluidity and impact strength.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. In the method for producing a thermoplastic resin composition according to the present invention, a plasticizer, a heat stabilizer, an antioxidant, an antidrip agent, a compatibilizer, a light stabilizer, a pigment, a dye, and / or an inorganic additive may be added according to each use. Examples of the added inorganic additives include asbestos, glass fibers, talc, ceramics, sulfates, and the like, which may be used in an amount of 30 parts by weight or less based on the total resin composition.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example

The components used in the Examples and Comparative Examples of the present invention are as follows.

(A) Polycarbonate-based resin: Bisphenol- having a weight average molecular weight (Mw) of 25,000

                     A type polycarbonate was used.

(B) rubber modified styrene resin

 (B-1) Styrene-acrylonitrile-containing graft copolymer resin

 50 parts by weight of butadiene rubber latex, 36 parts by weight of styrene polymerized monomer, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water in a mixture of 1.0 parts by weight of potassium oleate and cumene hydride based on the total solids of the mixture. 0.4 parts by weight of loper oxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of pyrophosphate sodium salt were added, and the reaction was completed by maintaining the temperature at 75 ° C. for 5 hours. ™ copolymer (G-ABS) latex was prepared. 0.4 parts by weight of sulfuric acid was added to the resulting resin composition solid and solidified to prepare a graft copolymer resin (G-ABS) in powder form.

 (B-2) Styrene-acrylonitrile-containing copolymer resin

 Styrene was added by adding 75 parts by weight, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of mercaptan-based chain transfer agent. Styrene / acrylonitrile copolymer resin (SAN) was prepared by raising the temperature from room temperature to 80 ° C. for 90 minutes and then holding at this temperature for 180 minutes. This was washed with water, dehydrated and dried to prepare a powdered styrene / acrylonitrile copolymer resin (SAN). The weight average molecular weight of the produced styrene / acrylonitrile copolymer resin was about 80,000 to 100,000.

(C) cyclic benzyl phosphonate

(1) toluene solution of neopentylglycol methoxy phosphite

2,2-dimethylpropanediol (104.15g, 1.0mol) and dichloromethane (200 mL) were placed in a vessel with phosphorus trichloride (151 g, 1.1 mol) was added dropwise at 0 ° C, and the temperature was gradually raised to room temperature. At this time, the generated hydrochloric acid gas was neutralized and exhausted into a sodium hydroxide solution of 1N concentration through a corrosion prevention hose mounted on a side branch. Neopentylglycol chloro phosphite intermediate solution was obtained by continuing additional stirring for 4 hours after generation of hydrochloric acid gas was stopped, and then dichloromethane and the remaining excess phosphorus trichloride as a solvent were removed by vacuum distillation. Toluene (200 mL) was added dropwise thereto, and the mixture was cooled to 0 ° C., stirred under a nitrogen atmosphere, and triethylamine (111.31 g, 1.1 mol) and anhydrous methanol (45 mL, 1.1 mol) were gradually added in this order. After the addition, the mixture was slowly heated to room temperature and stirred for 4 hours. The neopentylglycol methoxy phosphite solution was obtained by removing the triethyl ammonium chloride salt which generate | occur | produced in reaction through the pressure reduction filter.

(2) Cyclic Benzyl Phosphonate Synthesis

Benzyl bromide (257 g, 1.5 mol) is added to the methoxy neopentylglycol phosphite intermediate dissolved in toluene, and then heated to 130 ° C to reflux for 16 hours. After completion of the reaction, toluene was removed by distillation under reduced pressure, and the remaining residual solution was poured into an excess of cold nucleic acid to solidify, and a cyclic benzyl phosphonate having a purity of 98% or more and a yield of 78% was obtained through a reduced pressure filter.

(D) Bisphenol A diphosphate (trade name: CR-741) manufactured by Daihachi, Japan, was used.

Examples 1-3

The pellets were prepared by extruding the above components in a temperature range of 200 to 280 ° C. in a conventional twin screw extruder according to the contents shown in Table 1 below. The prepared pellets were dried at 80 ° C. for 2 hours, and then injected into the injection mold under conditions of a molding temperature of 180˜280 ° C. and a mold temperature of 40˜80 ° C. to prepare a flame retardant specimen. The prepared specimens were measured for flame retardancy at a thickness of 1/8 ″ according to UL 94 VB flame retardant regulations.

Comparative Examples 4-6

As shown in Table 1, except that the content of each component was adjusted, the specimens were prepared in the same manner as in Examples 1 to 5, and physical properties thereof were measured. All the measurement results are shown in Table 1.

From the results of Table 1, it can be seen that when using the cyclic benzyl phosphonate excellent flame retardancy at a thickness of 1/8 "than when the aromatic phosphate ester compound is applied alone.

The flame retardant polycarbonate-based resin composition of the present invention is stable against fire and does not cause environmental pollution during processing or combustion, and thus has an environmentally friendly and excellent flame retardancy.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

100 parts by weight of a basic resin (A) + (B) consisting of 50 to 100% by weight of (A) polycarbonate resin and 0 to 50% by weight of (B) rubber-modified styrene resin; And (C) 0.5 to 20 parts by weight of the cyclic benzyl phosphonate compound represented by the following formula (1); Flame retardant polycarbonate-based resin composition comprising: &Lt; Formula 1 >

In the above formula, R ₁ , R ₁ ', R ₂ and R ₂ ' are each independently hydrogen, C _1-8 alkyl, C _6-20 aryl or C _1-8 alkyl substituted C _6-20 aryl group, Ar group is a phenyl group, a C _1-4 alkyl substituted phenyl group. The flame-retardant polycarbonate-based resin composition according to claim 1, further comprising (D) more than 0 and 20 parts by weight or less of the aromatic phosphate ester compound. delete The method of claim 1, wherein the (B) rubber modified styrene resin (B-1) 4 to 65 wt% of the rubbery polymer, 30 to 95 wt% of the aromatic vinyl monomer, 1 to 20 wt% of the monomer copolymerizable with the aromatic vinyl monomer, and acrylic acid, methacrylic acid and maleic anhydride. 20 to 100% by weight of a graft copolymer resin graft-polymerized by adding 0-15% by weight of a monomer selected from the group consisting of N, and N-substituted maleimide; And (B-2) 10 to 40% by weight of the monomer capable of copolymerizing with the aromatic vinyl monomer in 60 to 90% by weight of the aromatic vinyl monomer, and acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide. 0 to 80% by weight of copolymer resin copolymerized by adding 0 to 30% by weight of monomer selected from the group; Flame retardant polycarbonate-based resin composition, characterized in that consisting of. The (B-1) graft copolymer resin of the (B) rubber-modified styrene resin is a butadiene-styrene-acrylonitrile-based resin, and the (B-2) copolymer resin is a styrene-acryl. It is a nitrile-based flame retardant polycarbonate resin composition. The flame retardant polycarbonate-based resin composition of claim 2, wherein the (D) aromatic phosphate ester compound has a structure represented by the following Chemical Formula 2: <Formula 2>

Wherein R ₃ , R ₄ , R ₅ , R ₃ ', R ₄ ', R ₅ ', R ₃ ", R ₄ ", R ₅ ", R ₃ "', R ₄ "'and R ₅ "' Are each independently hydrogen or an alkyl group of C ₁ -C ₄ , X is an aryl group of C ₆ -C ₂₀ or a C ₆ -C ₂₀ aryl group substituted with an alkyl group of C ₁ -C ₄ , and n is It is an integer of 0-4. According to claim 1, At least one additive selected from the group consisting of plasticizers, heat stabilizers, antioxidants, anti-dripping agents, compatibilizers, light stabilizers, pigments, dyes and inorganic additives to 100 parts by weight of the polycarbonate resin composition excluding the additives Flame retardant polycarbonate-based resin composition, characterized in that it further comprises 30 parts by weight or less. A molded article prepared from the flame-retardant polycarbonate-based resin composition according to any one of claims 1, 2 and 4 to 7.