KR0150764B1 - Inflammable thermoplastic resin composition - Google Patents

Abstract

The thermoplastic resin composition of the present invention (A) (a ₁₎ a thermoplastic polycarbonate resin, 70-96% by weight, containing no halogen, and (a ₂₎ styrene based resin 100 of the copolymers 30-4% by weight of parts by weight, (B) It is a resin composition which mixed 5-20 weight part of phosphorus compounds as a flame retardant, and 0.1-2.0 weight part of (C) fluoro resins.

The phosphorus compound used in the present invention is a phosphorus compound having the following structural formula or a mixture of a phosphorus compound having the following structural formula and a triaryl phosphate.

N is an integer of 1 or more.

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

Description

[Name of invention]

Thermoplastic 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 relates to a thermoplastic resin composition having a flame retardance composed of a base resin composed of a halogen-free thermoplastic polycarbonate resin and a styrene copolymer resin, a phosphorus compound as a flame retardant, and a fluoro resin.

The styrenic copolymer resin is a styrene-containing graft copolymer resin or a styrene-containing graft copolymer resin comprising a styrene-containing copolymer resin. The phosphorus compound may be a single phosphorus compound having a specific structural formula or a mixture of the single phosphorus compound with triaryl phosphate may be used.

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]

Polycarbonate resins are excellent in transparency, impact resistance, and heat resistance, and are used in many applications such as electric and electronic products and automobile parts. However, polycarbonate resins are used in combination with other resins because of poor processability. For example, a mixture of a polycarbonate resin and a styrene resin is a resin mixture having high notch impact strength and improving workability.

Another essential requirement for the resin composition is that the resin must be flame retardant. Many studies have been conducted to impart flame retardancy to the resin composition, and among them, a method of melt-mixing a halogen compound and an antimony compound to a polycarbonate resin has been used to impart flame retardance to the resin composition. In addition, U.S. Patent Nos. 4,983,658 and 4,883,835 used halogenated compounds and phosphate ester-based compounds as flame retardants in polycarbonate resins. The provided resin composition is disclosed. However, these halogen compounds exhibit sufficient flame retardant functions in the event of a fire. However, hydrogen halide gas is generated during resin processing to cause corrosion in the mold, and dioxane or difuran when bromine compound brominated diphenyl ether is used. Toxic gases, which can cause fatal harm, are likely to occur. U.S. Patent No. 4,692,488 also discloses resin compositions comprising halogen-free polycarbonates, styrene and acrylonitrile and halogen-free copolymers, halogen-free phosphorus compounds, tetrafluoroethylene polymers, and additives. Patent 5,204, 394 discloses resin compositions consisting of aromatic polycarbonates, styrene-containing copolymers and / or styrene-containing graft copolymers, and mixtures of phosphate oligomers or phosphate oligomers as flame retardants. Phosphorus compounds used in the US patents include triaryl phosphate and condensed phosphate esters. When triaryl phosphite is used in a polycarbonate resin, vaporized flame retardants are likely to form a layer at the sites of high stress during processing to cause juicing. In addition, the use of triaryl phosphate lowers the heat resistance of the polycarbonate resin, and in the case of a large amount of use, it causes mixing problems in the hopper, causing process problems. When aryl phosphate oligomers, which are condensed phosphate esters, are used in polycarbonate resins, the juice phenomenon is improved but still has the disadvantage that the heat resistance is lowered.

Therefore, the present inventors have developed a flame-retardant resin composition having good processability without preventing the reduction of heat resistance and preventing the occurrence of heat resistance by using a phosphorus compound and a fluoro resin having a specific structure to solve the above problems. will be.

[Purpose of invention]

An object of the present invention is to use a single phosphorus compound or a mixture of a single phosphorus compound and a triaryl phosphate and a fluoro resin in the base resin consisting of polycarbonate and styrene resins, without the occurrence of juice phenomenon and good processability The present invention provides a thermoplastic resin composition having impact resistance and flame retardancy without deterioration of heat resistance.

[Summary of invention]

The thermoplastic resin composition of the present invention comprises (A) (a ₁ ) 70 to 96% by weight of a thermoplastic polycarbonate resin containing no halogen and (a ₂ ) 100 parts by weight of a base resin of 30 to 4% by weight of a styrene-based copolymer, (B) It is a resin composition which mixed 5-20 weight part of phosphorus compounds as a flame retardant, and 0.1-2.0 weight part of (C) fluoro resins. The styrene-based copolymer (a ₂₁ ) 30 to 70% by weight of the rubber having a glass transition temperature of 10 ° C or less; 20 to 55% by weight of one or more compounds selected from styrene, α-substituted styrene, and nuclear substituted styrene; Acrylonitrile 5-25 wt%; And a styrene-containing graft copolymer resin having a graft ratio of 40 to 90% by weight of methyl methacrylate and having a gel content of at least 50% by weight, which is not dissolved in acetone. Weight percent and 10 to 35 weight percent of (a ₂₂ ) acrylonitrile; 60 to 80% by weight of one or more compounds selected from styrene, α-substituted styrene, and nuclear substituted styrene; And 50 to 0 wt% of a styrene-containing copolymer copolymerized with 0 to 20 wt% of methyl methacrylate.

The phosphorus compound used in the present invention is a phosphorus compound having the following structural formula or a mixture of a phosphorus compound having the following structural formula and a triaryl phosphate.

N is an integer of 1 or more.

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

Detailed Description of the Invention

The resin composition which has flame retardance of this invention consists of a base resin which consists of (A) polycarbonate and styrene-type copolymer resin, the compound which is (B), and (C) fluororesin. Description of each of these roofs is as follows.

(A) Basic resin

The base resin is a resin blend of polycarbonate and styrene copolymer resin. Polycarbonate resin is used at 70 to 96% by weight and styrene-based copolymer resin is used at 30 to 4% by weight.

Polycarbonate resins are aromatic polycarbonates, aliphatic polycarbonates, and aromatic polycarbonates depending on the type of substituents, and these may be used alone or in mixture. An aromatic polycarbonate is preferable, and the polycarbonate whose bisphenol A is a structural unit is especially preferable.

The styrenic copolymer resin used in admixture with the polycarbonate resin is a styrene-containing graft copolymer resin or a styrene-containing graft copolymer resin including a styrene-containing graft copolymer resin. Styrene-containing graft copolymer resin is typically represented by ABS resin, 30 to 70% by weight of a rubber having a glass transition temperature of 10 ° C. or less; 20 to 55% by weight of one or more compounds selected from styrene, α-substituted styrene, and nuclear substituted styrene; Acrylonitrile 5-25 wt%; And it is preferable that the copolymer which graft-polymerized 0-20 weight% of methyl methacrylates has the graft ratio of 40 to 90%, and the content of the gel which does not dissolve in acetone is 50 weight% or more. Styrene-containing copolymer resin used in the styrene-containing graft copolymer resin is typically represented by SAN resin 10 to 35% by weight of acrylonitrile; 60 to 80% by weight of one or more compounds selected from styrene, α-substituted styrene, and nuclear substituted styrene; And the copolymer which superposed | polymerized 0-20 weight% of methyl methacrylates. The styrenic copolymer resin is a mixture of 50 to 100 wt% styrene-containing graft copolymer resin and 50 to 2 wt% styrene-containing copolymer resin.

Rubbers used to prepare the styrene-containing graft copolymer resin include acrylic rubber, butadiene rubber, ethylene / propylene rubber, styrene / butadiene rubber, and acrylonitrile / butadiene rubber, among which acrylic rubber and butadiene Rubber is preferred.

(B) phosphorus compounds

The phosphorus compound as a flame retardant used in the present invention is a phosphorus compound having the following structural formula (I) or a mixture of the phosphoric compound of the following structural formula (I) and triaryl phosphate.

N is an integer of 1 or more.

Representative phosphorus compounds among the phosphorus compounds of the above formula (I) are phosphorus compounds having the following formula (II), which is a phosphorus compound when n is 1 in the above formula (I).

Phosphorus compound as a flame retardant is used in 5-20 weight part with respect to 100 weight part of base resins. If this phosphorus compound is a mixture of the phosphorus compound of formula (I) and triaryl phosphate, the content of triaryl phosphate should not exceed 40% by weight relative to the mixture. When the content of triaryl phosphate in the mixture exceeds 40% by weight, the triaryl phosphate has a good volatilization property at a temperature of 200 ° C. or higher, so that the flame retardant volatilized during processing such as injection is hit and the progressive crack ( crack) occurs. Therefore, when using a mixture of the phosphorus compound of formula (I) and triarylfospace as a flame retardant, the content of triaryl phosphate should not exceed 40% by weight relative to the mixture.

Examples of triarylphosphates that can be used in the present invention are triphenylphosphate, tricresylphosphate, tragylenylphosphate, and xylenyldiphenylphosphate.

(C) fluoro resin

Fluoro-based resins are conventionally available resins such as polytetrafluoroethylene, polyvinylidene fluoride, copolymers of tetrafluoroethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and fluoroalkyl vinyl ether, And copolymers of tetrafluoroethylene and hexafluoropropylene. These may be used independently of each other or two or more different mixtures may be used. In order to prevent dripping in the combustor, the fluoro resin forms a fibrillar network in the resin when it is mixed with the resin and extrudes, thereby decreasing the flow rate of the resin during combustion and increasing the shrinkage rate. Prevent dripping. When the fluororesin in an emulsion state is used, the dispersibility of the fluororesin is good with respect to the entire resin, but the process is complicated. Therefore, even if it is a powder state, it can use preferably if it can form a fibrous net by disperse | distributing suitably to all resin. Fluoro-based resins that can be preferably used in the present invention include polytetrafluoroethylene. Polytetrafluoroethylene having a particle size of 20 to 500 microns is suitable for mixing. The amount of the fluoroge resin is 0.1 to 2.0 parts by weight based on 100 parts by weight of the base resin.

The thermoplastic resin composition of the present invention may be added with an inorganic filler, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye according to each use. Additional inorganic fillers include asbestos, glass fibers, talc, and ceramics, which may be used in the range of 0 to 30 parts by weight based on 100 parts by weight of the base resin.

In the thermoplastic resin composition of the present invention, a fluorocarbon compound is used as a flame retardant by using a phosphorus compound of formula (I) or a mixture of the phosphorus compound of formula (I) and triaryl phosphate as a flame retardant in a base resin composed of polycarbonate and a styrene copolymer. By containing the resin, it is possible to prevent the generation of toxic gas, which is a problem when the conventional halogen compound is used as a flame retardant, and the problem of surface condition such as the phenomenon of juice, which is a problem when only the conventional triaryl phosphate is used as the flame retardant, Has the effect of the invention being significantly reduced.

In the thermoplastic resin composition of the present invention, a phosphorus compound of the above formula (I) or a mixture of the phosphorus compound of the above formula (I) and triaryl phosphate is used as a flame retardant in a base resin composed of a polycarbonate resin and a styrene copolymer. The fluororesin is mixed and the necessary inorganic fillers, thermal stabilizers, 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 to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

EXAMPLE

Compounds of (a ₁ ) polycarbonate resins, (a ₂ ) styrene copolymer resins, and (B), which are components of the base resin (A) used in Examples 1 to 4 and Comparative Examples 1 to 2 below And (C) the production and specifications of the fluororesin is as follows.

(A) Basic resin

(a ₁ ) Polycarbonate resin: L-1250W Grade of TEIJIN, Japan was used.

(a ₂ ) Styrene Copolymer Resin

(a ₂₁ ) Styrene-containing graft copolymer resin

50 parts by weight of solid butadiene rubber latex, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 1.0 parts by weight of potassium oleate, an additive necessary for a mixture of 150 parts by weight of deionized water, 0.4 part by weight of cumene hydrophosphate, mercaptan-based chain The reaction was completed by adding 0.3 parts by weight of the transfer agent at 75 ° C. for 5 hours to prepare a styrene-containing graft copolymer resin emulsion. 0.4 weight part of sulfuric acid was added to this resultant resin composition, and it solidified, and the styrene-containing graft copolymer was prepared in powder form.

(a ₂₂ ) Styrene-containing copolymer resin

Styrene-containing copolymer resin was added by suspending polymerization by adding 0.2 parts by weight of azobisisobutyronitrile and 0.5 parts by weight of tricalcium phosphate, which are necessary for a mixture of 70 parts by weight of styrene, 30 parts by weight of acrylonitrile, and 120 parts by weight of deionized water. Was prepared. The copolymer resin was washed with water, dehydrated and dried to prepare a styrene-containing copolymer resin in powder form.

(B) phosphorus compounds

(b ₁ ) Phosphorus compound of formula (I)

110 ml of resorcinol was added to 400 ml of toluene, heated to 70 ° C., and 33 ml of triclophosphine oxide (POC13) was added dropwise for 2 hours. After maintaining the reaction for 30 minutes, 207 ml of chlorodiphenylphosphonate was added for 3 hours, and triethylamine was added dropwise to terminate the reaction. The reaction solution was purified several times to remove the water-soluble by-products, and the required amount of calcium carbonate was added thereto to remove the remaining water and filtered to prepare a phosphorus compound of formula (I) having a purity of 98% or more.

(b ₂ ) Triphenyl phosphate: Triphenyl phosphate (TPP) manufactured by Daihachi, Japan was used.

(b ₃ ) Arylphosphate oligomer: CR-733S from Daihachi, Japan was used.

(C) fluoro resin

Teflon 7AJ from Dupont, USA was used.

EXAMPLES 1-4 AND COMPARATIVE EXAMPLES 1-2

The composition of each component used in Examples 1-4 and Comparative Examples 1-2 is shown in Table 1. Examples 1-4 are Examples concerning the resin composition of this invention. In Comparative Example 1, only triphenylphosphate was used as the phosphorus compound, and in Comparative Example 2, only arylphosphate oligomer, manufactured by Daihachi, Japan, was used.

In Examples 1 to 4 and Comparative Examples 1 and 2, each component was mixed and extruded under extrusion conditions at 250 ° C. to prepare a resin composition in a pellet state.

Flame retardance, heat resistance and impact strength of the test pieces of the resin compositions prepared according to Examples 1 to 4 and Comparative Examples 1 to 2 were measured, and the occurrence of progressive cracking was observed by an optical microscope.

The results are shown in Table 2.

(1) Flame retardant: Measured according to UL 94 VB.

(2) Impact strength: measured based on ASTM D256 (Kgfcm / cm)

(3) Heat resistance: Measured according to ASTM D306. (5Kgf · unit: ° C.)

(4) Progressive crack: After injection, the resultant was maintained in an oven at 80 ° C. for 24 hours and observed with an optical microscope (×: no progressive crack occurred, ○: progressive crack occurred. △: progressive crack occurred depending on injection conditions). .

Claims (5)

(A) (a ₁ ) 100 parts by weight of a base resin composed of 70 to 96% by weight of a thermoplastic polycarbonate resin containing no halogen and (a ₂ ) 30 to 4% by weight of a styrenic copolymer; (B) 5 to 20 parts by weight of the phosphorus compound of the following structural formula with respect to 100 parts by weight of the base resin; And N is an integer of 1 or more. (C) 0.1 to 2.0 parts by weight of fluororesin based on 100 parts by weight of the base resin; A thermoplastic resin composition having flame retardance, characterized in that consisting of. The thermoplastic resin composition according to claim 1, wherein the phosphorus compound (B) is a phosphorus compound of the following structural formula. (A) (a ₁ ) 100 parts by weight of a base resin composed of 70 to 96% by weight of a thermoplastic polycarbonate resin containing no halogen and (a ₂ ) 30 to 4% by weight of a styrenic copolymer; (B) 5 to 20 parts by weight of a mixture of a phosphorus compound of the following structural formula and a triaryl phosphate based on 100 parts by weight of the base resin; And N is an integer of 1 or more. (C) 0.1 to 2.0 parts by weight of fluororesin based on 100 parts by weight of the base resin; A thermoplastic resin composition having flame retardance, characterized in that consisting of. 7. The thermoplastic resin composition of claim 6, wherein the content of the triaryl phosphate is less than 40 wt% based on the phosphorus mixture. 4. The thermoplastic resin composition of claim 3, wherein the phosphorus compound is a phosphorus compound of the following structural formula.