TW201229132A - Polycarbonate resin composition having good transparency and flame retardancy - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molding body used thereof. Specificity, the polycarbonate resin having the repeating structural unit represented by chemical formula 1, including defined content of sulfonate-based flame retardant, and using lactone-modified to have flame retardancy. As a polycarbonate-based resin, it not only contains straight-chain polycarbonate resin, but also branched-chain polycarbonate resin. Such that obtaining the polycarbonate resin which maintain the transparency and good flame retardancy (UL94-V0) of the molding body.

Description

[Technical Field] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition which is obtained by using the following Chemical Formula 1 a sulfonate-based flame retardant having a flame retarding effect of a polycarbonate resin having a structural unit, wherein the polycarbonate resin contains a predetermined amount of a sulfonate-based flame retardant modified with a lactone, and As a polycarbonate-based resin, in addition to the linear polycarbonate resin, it also includes a branched polycarbonate resin which can simultaneously satisfy excellent transparency and flame retardancy. [Prior Art] Polycarbonate (hereinafter referred to as ρ〇 is an amorphous polymer with excellent mechanical properties] belongs to five general engineering plastics, namely, polystyrene (PA), polycarbonate (PC), and polyoxymethylene. One of (poM), modified polyphenylene (MPP0), poly(p-butylene dicarboxylate)/polyethylene terephthalate (PBT/PET), applied to a glazing sheet, Automotive products, electrical appliances, optical products, etc., have a growing market demand. PC also has excellent thermal stability at a maximum temperature of 310 ° C, and has an excellent transparency of about 89%. The so-called thermal stability refers to : The PC in a dry state is exposed to a hot environment at a temperature of 320 ° C for several hours or at a high temperature of 33 〇 _ 35 〇 c > c, and excellent thermal properties of decomposition are hardly occurred. Under such hot conditions, yellowing caused by thermal oxidative decomposition reaction occurs, so that an additional heat-resistant stabilizer such as a phosphite, a phosphinate, an epoxide compound or an organic hydrazine compound may be added. This 201229132 outside 'temperature at 400 ° C On the top, 'severe decomposition and cracking phenomenon will occur. Depending on the molecular weight or degree of crosslinking, PC has an oxygen index of 21-24 (ASTMD 2863-7...) because PC has a different height from other general-purpose resins. Because of its heat resistance and its own flame retardant properties, PC has a V2 grade in the international standard UL (Undenvdtei > s Laboratory) 94 for dividing the flame retardant properties of plastic resins. To further improve the flame retardant properties, PC has been added. Brominated oligomers, tetra-BPA Getrabromo-BPA), or alkali metal salts (alkaH metals) or gas-containing additives, or, in order to improve dripping characteristics, sometimes add polytetrafluoroethylene (PTFEp) However, in the case of ptfe as an anti-drip agent, even if it is used in a small amount, the transparency of the pc itself is lowered, so it is restricted to use in a transparent product, and in addition, for the Br/a type flame retardant, in order to have a vo grade, it is necessary. Use of 1% by weight or more, which may lower the transparency or other mechanical properties and thermal properties of the PC resin itself. In addition, when using bromine or gas-based flame retardants, due to environmental problems, Internationally, it has been restricted. After the mid-1980s, after the possibility of carcinogens was proposed in Europe, the possibility of toxicity of flammable substances has become a matter of debate. In particular, $ has been used for the flame retardancy of organic polymer materials, and bromine-containing flame retardants are widely used. After the discovery of the incineration of flame retardants, the possibility of diluting will be generated. Harmful debate. At present, the definition of non-primary products depends on the IEC61349-2.21 international standard and IPC4101B, which are defined by the total amount of poisonous/odor and wind. 201229132 1) Wind · Maximum amount 900ρρπι 2) Bromine: Maximum amount 900ppm 3) Total _ prime · Maximum amount 15〇〇ppm With the gradual strengthening of the stability of plastic materials for fire, concern for flame retardants and flame retardant PC resins It is also gradually increasing. However, in reality, the thermal properties, transparency, mechanical properties and environmental problems of the flame retardant PC resin have to be sacrificed to some extent. In particular, brominated flame retardants are flame retardants that are still in use in disregard of environmental hazards and will continue to be used as long as there are no alternatives. In addition, since environmentally-friendly compounds do not exist, it is necessary to develop a flame-retardant PC product in which an effective flame retardant effect can be achieved by using a small amount of additives without deteriorating heat resistance and mechanical properties inherent as PC products. At the same time, it is also able to maintain the transparency of the flame retardant Pc product. In order to improve the flame retardant properties of PC products, new flame retardants having other flame retardant properties are being used, which are different from conventional Br flame retardants. A representative flame retardant that has recently received attention is a sulphonate flame retardant. In the case of a sulfonate flame retardant, unlike conventional radical scavenging, intumescence, and endothermic, which are typical flame retardant technologies, cross-linking is utilized. Coke (char) is formed to exert a flame retardant effect. It is understood that if a sulfonate flame retardant of less than 1% is used, it will have UL94_v〇 characteristics. A sulph〇ne-suiphonate flame retardant containing a potassium salt functions as a crosslinking accelerator. It decomposes at the initial decomposition temperature to form s〇3, which acts as a promoter for the strong crosslinking reaction. In the case of 201229132 of pc using such a sulfonate flame retardant, coke produced by cross-linking eliminates the flame and also has the effect of suppressing dripping, so it has a UL94-V0 rating. The sulfonate flame retardants mainly used in PC products are roughly classified into three types. The first, potassium diphenylsulfone sulfonate represented by the following Chemical Formula 2, is generally referred to as KSS. When 0.1 to 5% by weight is used in the PC, the original transparency of the PC is maintained, and the UL94-V0 grade is exhibited when the melt flow index is 2 and the thickness is 3.2 mm. In order to improve the dripping characteristics, polymethylphenyl oxime (PMPS) or ptfE is added, and when the content of 1 is 0.2 to 0.6%, UL94-V0 can be secured at 1.6 mm. Further, the above flame retardant is a non-sulfan flame retardant which does not use a substance such as bromine or chlorine.

Second, the flame retardant used is potassium butyl perfluorosulfonate (KBPFS) shown in the following Chemical Formula 3, which has the same basic flame retarding principle as KSS, and the sulfonate group promotes the crosslinking during PC decomposition. Union. Generally, 〇6~0.1% is added to obtain 3.2mm V0, and sometimes KSS and KBPFS are mixed to improve the transparency and flame retardancy of the PC. This flame retardant contains fluorine ' F ions as a halogen substance to act as a radical scavenger in a vapor phase of a flame, and extinguishes the fire. F is not a bromine or a gas which restricts the object substance as a substance, so in the case of a pc using such a flame retardant, it can be regarded as a non-halogen product. 201229132 Chemical Formula 3 : Ο

II

C4F9—S—O'K^ G The last-species will use the three-gas stupid acid shown in the following chemical formula 4 Chemical Formula 4: C1

Although KBB and KBPFS are mainly used for the flame retardant for PC, in the case of using a flame retardant for a clock, there is a disadvantage that the haze of the product is deteriorated depending on the use content or the processing temperature. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in the prior art, and an object thereof is to provide a polycarbonate flame retardant resin composition which does not use a bromine or gas flame retardant but uses sulfonate. Acid-based flame retardant, therefore, does not occur in the mechanical properties and thermal properties of the PC resin, and the use of a certain proportion of branched PC, both improved flame retardant properties, but also retains polycarbonate The transparency of ester resins in the past. 201229132 The above object of the present invention can be fully achieved by the following description of the present invention. The polycarbonate resin composition of the present invention will be described in detail below. In the present invention, the polycarbonate-based resin comprises a sulfonate-based flame retardant modified with a lactone in an amount of from 1 to 3 % by weight. Carbonate The above polycarbonate-based resin has a repeating structural unit represented by the following Chemical Formula 1, and may have a weight average molecular weight of 20,000 to 40,000. Chemical formula 1:

Bisphenol (A) Carbonate (Part A) (Part B) In addition, the above polycarbonate-based resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a linear polycarbonate resin and a branched product. Mixture of polycarbonate resin 'However, with the adjustment of the molecular weight of polycarbonate or the content of flame retardant, one 〇〇wt% linear polycarbonate can be used to have the specified flame retardant properties, but 'when using 1 〇 weight When the branched polycarbonate of ❶/❶ is used, the flame retardant property is improved as compared with the case where the linear polycarbonate is used alone, and at the same time, the effect of minimizing the content of the flame retardant is also obtained. The polycarbonate resin used in the present invention has a repeating structure represented by the following chemical formula, which can be produced by a usual production method, i.e., interfacial polymerization or Melt transesterification. Chemical formula 1 201229132

Double Expectation (A) (Part A) Carbonate (Part B) The following reaction formulas represent the reaction of the interfacial polymerization method and the smelting transesterification method for polymerizing and manufacturing PC. Reaction formula 1: PC interface polymerization method

OH ♦ 2N00H SRQ Sodium hydroxide Νβ'σ-^Ι^-0-Νβ* ♦ 2H20 Di-sodium bisphenate N〇 ^ 2 CI^C, 0

O bisphenol disodium

CDC

2NaCI ♦ Gasified sodium QCF 〇〇 ro o Bisphenol disodium PC oligomer

ΝίΤ ♦ WoCi η· and W -Cl * Na' σ-^f — 4 NaC,

Final PC

PC (CDC: carbonium dichloride, BCF: bis-carbamate, PC: polycarbonate) Reaction Scheme 2: PC melt transesterification method 201229132

CH2-CH2 + C02 V CH2-CH2 CH2-CH26 6 6 6 ,

CH30H

CH30C0CH3 + H0CH2CH20H EO EC CHSOCOCH3* 2 ^-OH - Phenol

DUX 2CH30C0 b MFC

Sc r weaving Qix ICmOCO-^j +2CH30H (11PC UsOH CH30C0CH3 * otf,c <g)-oco^〇) *〇η-^〇)όη — Η·

EG ο-^\^οι~'ο~© * ^0H -η·10-20 PC prepolymer phenol (EO: ethylene oxide, EG: ethylene glycol, EC: ethylene carbonate, DMC: Didecyl carbonate, MPC: methyl phenyl carbonate, DPC: diphenyl carbonate, BPA: bisphenol A, PC: polycarbonate) Specifically, 2,2-dual represented by the following Chemical Formula 5 4-Hydroxyphenyl)propane (hereinafter referred to as bisphenol A) is dissolved in an aqueous sodium hydroxide solution, and then introduced into dichlorohydrazine (MDC) as a solvent, and phosgene gas is blown thereinto in an aqueous solution - The interface of the organic solvent is subjected to polycondensation to form PC. Chemical Formula 5: After washing the resin in the emulsion state after the hydrochloric acid neutralization reaction with water, the water and the organic solvent are centrifuged, or precipitated using an anti-solvent or warm water, and then evaporated by using a vented extruder or the like. The method is carried out to thereby purify the polymer. The polymerization catalyst uses triethylamine or 201229132 quaternary ammonium salt, and the reaction terminator is phenol or p-tert-butyl. In the melt transesterification reaction, phenol is phosgenated to form diphenyl carbonate (DPC), and then polycondensed by transesterification with bisphenol a to form PC. The polymerization catalyst includes lithium dendrite, lithium hydroxide, lithium hydroxide, borane and the like. In order to remove phenol by distillation, the reaction temperature was gradually increased to 220-320. (: The polycarbonate resin used in the present invention has a viscosity average molecular weight of usually preferably 10,000 to 1 Å, 〇〇〇, particularly, more preferably a resin in the range of 15 Å to 40,000. The carbonyl source used in the production of polycarbonate can utilize phosgene used in ordinary interfacial polycondensation, such as triphosgene or bromine phosgene, etc. In addition, the transesterification method can be oxidized using diallyl carbonate or the like. As the carbonation method, carbon monoxide or the like can be used. In the reaction terminator used in the production of the polycarbonate of the present invention, i-type is used, and p-tert-butylphenol, p-cumylphenol, p-tert-octylbenzene are mainly used. Further, the branching agent used in the production of the polycarbonate of the present invention is 1,1,1-3(4-hydroxyphenyl)ethane, 4,4-[1-[4-[ 1-(hydroxyphenyl)·1·decylethyl] benzyl]ethylidene], phloroglycine, trimellitic acid, o-cresol, 3,3-bis (3- 3,3-bis (3-methyl-4-hydroxyphenyl oxyindole), etc., which have three or more functional groups, In order to branch the polycarbonate chain. Sulphonated flame retardant 201229132

Preferably 0.05 to 0.3% by weight, Chengshe ____

In the case of 疋υ υ 垔 垔 , , , , , , , , , , , , , , , 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃 阻燃The following flame retardant is used in the polycarbonate manufacturing process having flame retardant properties used in the present invention to improve its flame retardant properties. In other words, the diphenyl sulfonate sulfonate (KSS) of the following chemical formula 2, the potassium butyl perfluorosulfonate (KBpFS) of the following chemical formula 3, and the polystyrene sulfonate of the following chemical formula 6 can be used for the above-mentioned acid salt-based flame retardant. Potassium acid salt, or phenyl-substituted eucalyptus oil (ie, phenyl tridecyl oxime). In particular, if potassium butyl perfluorosulfonate (KBPFS) modified with a lactone compound is used alone or not modified The combined use of KBPFS will result in further enhanced flame retardant and optical properties. [Chemical Formula 2] Diphenyl sulfonate (KSS)

[Chemical Formula 3] Potassium butyl perfluorosulfonate (KBPFS) Ο

II

— O.IC G

[Chemical Formula 4] Polyphenylene sulfonate potassium salt 201229132 [Chemical Formula 6]

As a substance which modifies the above-mentioned sulfonate flame retardant, an intrinsic compound is used, which is a general term for a few acid vinegars having a heterocyclic form of a _c〇〇-bond in a molecule. However, [the acid-potassium salt has a good flame retarding effect of 4, but there is a disadvantage that the knife-scattering property of the PC tree is reduced] and a high temperature is required for processing. However, when the potassium sulfonate salt is modified by a lactone compound, the compatibility with the pc resin is improved, and the color characteristics are improved under the processing conditions. c=o 〇Γ In the lactone compound of the above Chemical Formula 7, R1 may be a divalent aliphatic hydrocarbon, a substituted hydrocarbon having 2 to 20 carbon atoms or an alkylene chain having 4 to 12 carbon atoms. (alkylene chain ). As examples of lactones, it may be selected from the group consisting of pivalolactone, Δ-valerolactone, ε·caprolactone and α-caprolactone, α-mercaptopropiolactone, β-methyl-β-propene The group consisting of lactones 'but is not limited thereto. In order to improve the compatibility of the butyl perfluoro acid clock (Kbpf S, Chemical Formula 3) as an acid salt compound with an organic resin, it is permeable to a lactone compound when modified by the lactone compound of the above Chemical Formula 7 The ring opening addition reaction is carried out. When the butyl perfluoropropionate (KBPFS) and the lactone compound are mixed in a certain molar ratio, the lactone compound is used in an amount of 0.05 to 3.0 mol ratio, preferably o.h. When the compound of 201229132 is used at less than 0.05 molar ratio, the modification effect is insufficient, thereby causing a decrease in compatibility with the organic resin phase; conversely, when used at a ratio of more than 3.0 moles, the presence is lowered. The shortcomings of the thermal and chemical properties of potassium perfluorosulfonate (KbpfS) require the use of an appropriate amount of lactone compound. For the ring-opening addition reaction of the internal vinegar compound, a catalyst is used. Preferred catalysts include, for example, n-butyhin trioctate, dibutylyhin, dimethyltin dichloride, dimethyltin dichloride, and the like. Or an organic compound, an organic titanium compound, a tetrabutylammonium fluoride, a potassium fluoride, a fluoride salt such as a fluorinated planer, etc., and the catalyst as described above may be used singly or in combination. The content of the catalyst is butyl perfluoro. Based on the mixture of acid desorption (KBpFs) and internal vinegar compound, using 〇〇11〇% by weight, preferably 0.02-4 ̄m under the open-loop addition reaction and in the presence of solvent, at 80- It is preferably carried out at a temperature of 200 ° C, preferably at a temperature of i (8) · (10) ° c for 1 to 20 hours to carry out hydrocarbons such as anti-heptane. The type of solvent used is hexane, 'or as Ethyl acetate such as ethyl or butyl acetate, such as acetone or methyl ethyl ketone, used alone or in combination. Potassium butyl perfluorosulfonate (KBPFS) and internal vinegar are added at the same time. After the compound, the reaction is carried out while stirring, or the butyl all-acid acid unloading (KBPFS) is first introduced, and the internal ruthenium compound is added and reacted in a dropwise manner, and the catalyst used at this time can be used. Simultaneously, it is added in the process: it is added dropwise in the process, and the modified state after the reaction can be confirmed by IR spectroscopy. 201229132 Adding hydrazine: The effect is to make the carbonic acid (4), and various additives can be used without impairing the present invention. The polycarbonate group may further comprise a resin selected from the group consisting of an antioxidant m-line agent, a light stabilizer, an internal lubricant, a fluidity modifier, a flame retardant auxiliary, and a release agent' compatibilizing agent. Among the groups consisting of antistatic agents and colorants, one or more kinds of additives are selected. In particular, 'anti-oxidants such as hindered phenols, esters, phosphates, amines, benzotriazoles, and the like can be used. UV absorbers such as benzophenones and malonic esters, light stabilizers such as hindered amines, aliphatic antiseptic Sbs, chain-burning hydrocarbons, internal lubricants such as Shiki oil and hydrazine, fluidity modifiers, Compatibilizer, mold release agent, antistatic A coloring agent may be used for coloring, etc. Polycarbonate flame retardant wax: The polycarbonate flame retardant resin composition of the present invention has a weight average molecular weight of 10,000 to 50,000 and a melt viscosity index of 2 to 100. Further, the polycarbonate flame retardant resin composition according to the present invention has a transparency of 85% or more and a haze of less than 2% and a flame retardant property of UL94-V0. [Embodiment] Hereinafter, in order to facilitate understanding of the present invention While the preferred embodiment has been described, it will be understood by those skilled in the art Modifications are of course also within the scope of the claims. 201229132 A sample was fabricated using the following method and the physical properties of the sample were measured.劁i tells you: the production of samples and test pieces is based on the product produced by the interfacial polymerization method. The product has a weight average molecular weight of 40,000 (MFR3) and a weight average molecular weight of 30,000. (MFR14), a product having a weight average molecular weight of 20,000 (MFR3〇), for a branched product, a product having a weight average molecular weight of 36,000 to 37,000 (1^«?112-3) is used, and the above products are mixed in a certain ratio. It constitutes a resin composition. For the raw material blending and pellet production, a twin-screw co-rotating extruder (L/D: 32) with a screw diameter of 47 mm was used, and the produced rope was cut into pellets using a rotary cutter already provided. . Test pieces for measuring flame retardancy and overall physical properties were produced by extrusion molding. Examples: (1) Flame Retardant Performance (UL94V) UL94V 'is a test piece of a predetermined thickness by extrusion molding. After the test piece is erected vertically, the test piece is ignited by a burner, and the fire on the test piece is required here. It will be extinguished by itself within a certain period of time. At this time, according to the degree of extinguishment of the fire on the test piece, it is divided into V-2, V-1, and V-0. 1) V-0 level ··Ignition for 1 〇 second after installing the test piece, after taking the burner, the test piece should not burn for more than 1 second, and 5 test pieces should be used as a group. The same experiment, the total burning time can not exceed 50 shifts. Here, the spark that falls during combustion cannot be burnt to the absorbent cotton placed under 30 cm. 201229132 2) V-1 level: basic experimental method and v_G level After the burner, the test piece cannot be burned for more than 3. Second, through the experiment, the total burning time should be within 25 〇 seconds. In the second, you can burn the cotton wool underneath. The next cremation is not 3) V-2 level: After taking the burner, the test piece burns for more than 30 seconds, and the 乂^ level is not within the second. In this case, it is not n M U., the burning time should be 250 ', no smashing, the spark that falls can be burned to take off P. (2) Color measurement (ΥΙ, haze, transmittance) 曰# A three-sided molded product was produced by extrusion molding, and the transmittance, haze, and yellowness index of the test piece were measured by a mrnterlab colorimeter. (YI D1925). ^ ^ (3) Flowability of Resin According to ASTM D 1238, the amount of resin flowing out through the nozzle was measured under a condition of 30 〇m 2 kg, and the amount of resin was determined by (10). (4) Mechanical physical properties A test piece produced by an extrusion molding method was used to measure the tensile properties according to ASTM D638 through a universal testing machine, and a notched IZOD impact test was carried out in accordance with ASTM D256. (5) Analysis of additive components The molecular weight of the produced resin was measured using a gel chromatograph, and the release agent was measured by a liquid chromatograph (HPLC), and the light stabilizer was qualitatively and quantitatively analyzed using a uv viscometer. Example 1 E 6 and the ratio of the example 1 s ^ . 201229132 The needle is mixed with the composition ratio of the composition shown in Table 1, and the twin-screw extrusion is used: = resin temperature ride, screw rotation number ~, under the condition of "dissolving" ; and extruded and obtained a variety of pellets. Using the obtained pellets, a sample σ for measuring flame retardant properties and various physical properties was produced by extrusion molding, and for the analysis of the produced samples, the flame retardant properties were carried out using the methods described in the examples. And measurement of mechanical physical properties and analysis of additive components, etc., and the evaluation results are shown in Table 1. [Table 1] - Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Resin ------ PC 99.37 99.27 99.17 99.27 99.22 99.27 99.37 ~.*·- -- 98.95 Heat-resistant three (2,4-two 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 stabilizer t-butyl stupid ^~--- i) phosphate UV and three sigma sitting 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Agent - internal quaternary tetraol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Lubricant four hard ------ oxime ester - benzene hard performance 0.2 0.2 resistance acid salt (KSS) butyl butyl perfluorate 0.05 0.2 0.02 acid Potassium IKBPFS) 19 201229132 Modified-KBPFS 0.1 0.2 0.35 Poly (stupyl vinyl sulfonate potassium salt) 0.1 Stupid substituted nickel oil 0.5 Total (%) 100 100 100 100 100 100 100 100 Various physical properties and flame retardancy haze % (280°C) 0.42 1.33 29.55 0.53 1.3 84 0.55 0.5 Haze% (300°〇0.38 0.52 8.32 0.48 1.3 79 0.44 0.51 Permeability % (300°C) 90.03 89.88 80.5 90.04 89.05 70 90.88 91.3 Tensile strength (Mpa) 64.9 63.3 62 65.8 66.8 65 68.6 67.2 Tensile elongation (%) 120 117 110 117 120 119 127 125 Izod impact (J/m) 910 897 890 890 905 899 903 893 Hot Deformation temperature (°c) 140.1 140 139 140.7 141 139 141 139.8 UL94@ 1.5mm V2 Y0 VO V2 V2 VO V2 V2 20 201229132

UL94@2.0mm VO VO VO V2 V2 VO V2 V2 UL94@ 3.2mm VO VO VO VO VO VO V2 VO FIGS. 1A and 1B show transmission of butyl perfluorosulfonate modified with a lactone according to an embodiment of the present invention. Potassium acid (KBPFS) flame retardants and unmodified butyl perfluoro acid recovery (KBPFS) flame retardants were subjected to IR analysis to compare the compositions. 1A is a spectrum diagram showing the IR analysis peak of a lactone-modified potassium butyl perfluorosulfonate (KBPFS) flame retardant according to an embodiment of the present invention. FIG. 1B shows an unmodified D. A spectrum of the peak of the IR analysis of a flame retardant based on a perfluoro acid clock (KBPF S ). In order to impart flame retardant properties to the polycarbonate resin, a flame retardant containing no bromine or gas, in particular, a resin composition produced by using potassium butyl perfluorocarbonate (KBPFS) modified with a lactone is used. The IR spectrum of FIG. 1 a and FIG. 1B was compared by using potassium butyl perfluorosulfonate (KBPFS) as a flame retardant of the present invention and potassium butyl perfluorosulfonate (KBPFS) modified with a lactone compound. The figure shows the peak characteristics. According to the IR spectrum of the modified-butyl perfluoroacid potassium (KBPFS) of Fig. 1A, it is found that a peak appears at a nearby wavelength. Due to the above ridge value, it was confirmed that the sulfonate flame retardant had been modified. According to the physical property evaluation of Table 1, it was confirmed that a resin composition having UL94_V0 characteristics can be produced depending on the type of the flame retardant to be used. For the sulfonate flame retardant, it is confirmed that it is different from other flame retardants and exhibits good flame retardant properties at a low content. The reason is as described above, the 201229132 sulphonate group is Promote and link in the PC decomposition process. This increase in the degree of crosslinking is as shown in Fig. 2, and it can be confirmed by the increase in the relative strength of the pc/continuation 交Z fuel mixture resin composition 'corresponding to the temperature. ° Μ Especially in the case of potassium butyl perfluorosulfonate (KBPFS), test pieces of different thicknesses do not show uniform flame retardancy because the contained fluoride ions exert free radical trapping in the flame vapor phase. The role of the agent, the real = the effect of the spark. / In the case of using potassium lactone butyl perfluorosulfonate (KBPFS) as in Examples 1 and 2, it was confirmed that the haze was maintained at a molding temperature of 3 〇〇〇c, which was excellent in haze of less than 1%. The transparency was also confirmed, and it was confirmed that the flame retardancy of the flame-retardant sample showed uniform flame retardancy. As the content of the flame retardant increases, the flame retardancy also increases, but as seen from the comparative example i, when the amount exceeds 〇3 wt%, the increase in haze increases, and the transparency decreases, so it is preferably 0.3. It is used in weight% or less. In Comparative Example 2 and Comparative Example 3, the transparency of the diphenylsulfone sulfonate (KSS) was good. However, it was confirmed that the flame retardancy was lowered when the thickness was low, as shown in Comparative Example 4, potassium butyl perfluorosulfonate. In the case of (KBpFs), the flame retardancy corresponding to the thickness of the test piece is excellent. However, as the temperature of the lift increases, the degree of increase in haze also increases, so that the transparency is lowered. In particular, in the case of a potassium sulfonate-containing flame retardant, the haze varies depending on the molding temperature, and particularly, at a processing temperature of 3 〇〇〇C or higher, exhibits low haze and transparency. In order to improve the transparency of the molded article, 300 is required. (: The above high temperature. 22 201229132 The potassium butyl perfluorosulfonate (KBPFS) and the lactone compound related to Examples 1 and 2 were compared and modified, and a conventional butyl group was added. Comparative Example 4 of perfluoro-potassium hydride (KBPFS) and Comparative Examples 2, 3, 4 and 6 to which other carbonate-based flame retardants were added, it is understood that the resin compositions according to Examples 1 and 2 are provided without reducing the test piece. At the same time of transparency, it has uniform flame retardant properties with respect to different test piece thicknesses. In addition, as shown in Table 2 below, in the case of using a branched PC resin mixed with a linear ratio and chain branching in a certain ratio The result of the flame retardant test is that under the same flame retardant content, the flame extinguishing time is short, and the dripping property is improved, and it is understood that when a branched resin is used at a certain content or more, the resistance can be improved. In addition, in the case of a branched PC resin, since the strong shearing force in the resin molding process exists, the branched branches are oriented in the shear direction as compared with the resin composition having the same flow index. Improved mobility Properties, and therefore have the advantage of being able to improve processability. [Table 2] Example 3 Example 4 Example 5 Example 6 Linear polycarbonate 99.3 99.2 9.3 Q 9 Branched polycarbonate 90 ΟΛ Three (2, 4 -di-tert-butylphenyl)phosphite 0.03 0.03 0.03 yyj 0.03 UV absorber (stupid triazole) 0.2 0.2 0.2 〇9 Pentaerythritol tetrastearate 0.3 0.3 0.3 Π ο Modified-KBPFS 0.2 0.25 0.2 -- --- 0.25 23 201229132

Industrial Applicability: According to the present invention, the use of a flame retardant containing no bromine or gas or the like ensures the flame retardancy of the pc resin, particularly the use of a carbonated flame retardant, even with a low content of UL94-V0. The flame retardant properties enable the manufacture of a resin group of dots that does not degrade the transparency, haze, and mechanical and thermal properties of the original PC resin. In addition, additives such as light stabilizers, lubricants, and heat resistance stability can be added in accordance with the use of the final product, and the properties are lowered (4). Moreover, is it used to enhance the flame retardant properties? (: When the drip characteristics are further improved, the flame retardant performance can be improved. This flame retardant PC composition can be used for optical components, photomasks, electrical/electronic materials, automobiles, building materials, etc., which require flame retardancy. The above-mentioned embodiments are merely exemplified for convenience of description, and the scope of the claims of the present invention is based on the above-mentioned embodiments as described in the scope of the patent application. [Fig. 1A shows the present invention. The embodiment of the invention relates to the use of a lactone-modified potassium butyl perfluorosulfonate (KBPFS) flame retardant for the analysis of the peak of the luminescence peak 201229132. FIG. 1B shows the unmodified potassium butyl perfluorosulfonate ( KBPFS) Spectrogram of IR analysis peak of flame retardant. Fig. 2 is a graph showing the relative intensity with respect to temperature according to an embodiment of the present invention (〇: PC, ·: PC/sulfonate flame retardant) Apparatus for measuring flame retardant energy Fig. 3 is a schematic view of an embodiment of the present invention. [Explanation of main component symbols] None.

Claims (1)

201229132 VII. Patent application scope: 1 _ A polycarbonate flame retardant resin composition characterized in that, in the polycarbonate-based resin, one of 001 to 03% by weight of an acid ester modified with a lactone is used. Flame retardant. 2. The polycarbonate flame retardant resin composition according to claim 1, wherein the polycarbonate-based resin has a weight average molecular weight of 20,000 to 40,000 ' and the polycarbonate-based resin has the following chemical formula Repeated structural unit shown in 丄: Bisphenol (A) (Part A) Carbonate (Part B) 3. The polycarbonate flame retardant resin composition as described in claim 1, wherein the polycarbonate resin is linear polycarbonate An ester resin, a branched polycarbonate resin, or a mixture of a linear polycarbonate resin and a branched polycarbonate resin. 4. The polycarbonate flame retardant resin composition according to claim 1, wherein the sulfonate flame retardant is selected from the group consisting of diphenyl sulfonate (KSS) and butyl perfluorosulfonic acid. A group consisting of potassium (KBPFS), poly(sodium styrene sulfonate), and phenyltrimethyloxane. 5. The polycarbonate flame retardant resin composition according to claim 4, wherein the sulfonate flame retardant is potassium butyl perfluorosulfonate (KBPFS). 26 201229132 6- The polycarbonate flame retardant resin composition according to claim 1, wherein the lactone is selected from the group consisting of pivalolactone, Δ-valerolactone, ε-caprolactone and a group consisting of α-caprolactone, methyl _ _ _ propyl lactone, and 曱 曱 _ _ _ _ propyl lactone. 7. The polycarbonate flame retardant resin composition as described in claim 2, wherein the polycarbonate flame retardant resin composition has a weight average molecular weight of 10,000 to 50,000 and a melt viscosity coefficient of 2 to 100. . 8. The polycarbonate flame retardant resin composition as described in claim 1, wherein the polycarbonate flame retardant resin composition has a transparency of 85% or more, a haze of less than 2%, and UL94-V0. Flame retardant properties. 9. The polycarbonate flame retardant resin composition according to claim 1, wherein the polycarbonate flame retardant resin composition further comprises at least one additive selected from the group consisting of antioxidants, ultraviolet absorbers, light stabilizers, and interiors. A group consisting of a lubricant, a fluidity modifier, a flame retardant aid, a mold release agent, a compatibilizer, an antistatic agent, and a colorant. 10. The polycarbonate flame retardant resin composition according to claim 3, wherein the polycarbonate-based resin is a mixture of a linear polycarbonate resin and a branched polycarbonate resin, and is relative to The polycarbonate-based resin contains at least 10% by weight of the branched polycarbonate resin, based on the total weight of the polycarbonate-based resin. Eight, schema (see next page): 27