JPH01217055A - Flame retardant resin composition - Google Patents
Flame retardant resin compositionInfo
- Publication number
- JPH01217055A JPH01217055A JP4399288A JP4399288A JPH01217055A JP H01217055 A JPH01217055 A JP H01217055A JP 4399288 A JP4399288 A JP 4399288A JP 4399288 A JP4399288 A JP 4399288A JP H01217055 A JPH01217055 A JP H01217055A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- flame retardant
- flame
- chlorine
- intrinsic viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 2
- 238000002485 combustion reaction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- -1 phosphorus halide compound Chemical class 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LABRPRANVKSMGP-UHFFFAOYSA-N 1,3,2-dioxaphosphinane Chemical compound C1COPOC1 LABRPRANVKSMGP-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MOABYHZDQQELLG-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC MOABYHZDQQELLG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- XHTMGDWCCPGGET-UHFFFAOYSA-N tris(3,3-dichloropropyl) phosphate Chemical compound ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl XHTMGDWCCPGGET-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は優れた耐熱性と機械的強度を有した透明な難燃
性熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a transparent flame-retardant thermoplastic resin composition having excellent heat resistance and mechanical strength.
（従、来の技術→
メタクリル樹脂は優れた光学的性質及び耐候性を有し、
良好な耐熱性と機械的性質を持っているため、照明材料
、電子機器部品、０Ａｌｌ器、自動車部品、エフステリ
ア等の建築部品などに広く用いられている。一方メタク
リル樹脂は易燃性であるため、種々の制限を受ける事が
多く、例えば家電製品、ＯＡ機器等に対する米国ＵＬ（
アンダーライターズ・ラボラトリ−）規格等があり、そ
れ等に適合した燃焼性を保持するために、一般のアクリ
ル樹脂を難燃化する場合は通常ある種のハロゲン化リン
化合物の様な難燃剤をあらかじめ添加する方法（特開昭
４９−１０７３５２号公報、特開閉５１−５８４５２号
公報）が既に知られている。(Previous technology → Methacrylic resin has excellent optical properties and weather resistance,
Because it has good heat resistance and mechanical properties, it is widely used in lighting materials, electronic equipment parts, 0All appliances, automobile parts, and architectural parts such as Fsteria. On the other hand, since methacrylic resin is easily flammable, it is often subject to various restrictions, such as the US UL (
Underwriters Laboratory) standards, etc., and in order to maintain flammability that meets these standards, when making general acrylic resin flame retardant, a flame retardant such as a certain type of phosphorus halide compound is usually used. A method of adding in advance (JP-A-49-107352, JP-A-51-58452) is already known.
（発明が解決しようとする問題点）
しかしこれ等の合ハロゲン化リン化合物は可塑化作用が
強い上、難燃性をＵＬ規格Ｖ−２クラスに適合するため
には、２０％以上の難燃剤が必要であり（特開昭４９−
１０７３５２号公報、特許公報５５−４１４２号、特許
公報５６−２６２６４号）、得られる成形品の耐熱性及
び機械的強度を著しく低下させ、実用性を損うと言う問
題点を有している。また成形時に受ける熱により樹脂成
形品を着色させたり、分解等による外観の損傷によって
光学的性能を低下させる問題がある。さらに多量のハロ
ゲン化リン化合物含有樹脂成形品を屋外で使用した場合
、吸水によるクレーズやブリード等による白化現象が発
生したり、耐候性の低下による着色等の欠点があった。(Problem to be solved by the invention) However, these halogenated phosphorus compounds have a strong plasticizing effect, and in order to meet the UL standard V-2 class for flame retardancy, it is necessary to add 20% or more of flame retardant. is necessary (Unexamined Japanese Patent Publication No. 1983-
107352, Japanese Patent Publication No. 55-4142, Japanese Patent Publication No. 56-26264), the heat resistance and mechanical strength of the resulting molded product are significantly reduced, impairing its practicality. Further, there is a problem in that the resin molded product is colored by the heat received during molding, and its optical performance is deteriorated due to damage to its appearance due to decomposition or the like. Furthermore, when a resin molded product containing a large amount of a halogenated phosphorus compound is used outdoors, there are drawbacks such as whitening phenomena due to craze and bleed due to water absorption, and discoloration due to a decrease in weather resistance.
従って、本発明の目的は従来の難燃化アクリル成形材料
の上述の欠点を改普し、優れた透明性、良好な耐熱性及
び機械的性質を有する組成物を得る事にある。Therefore, the object of the present invention is to overcome the above-mentioned drawbacks of conventional flame-retardant acrylic molding materials and to obtain a composition having excellent transparency, good heat resistance and mechanical properties.
本発明者等はかかる状況に鑑み、優れた透明性と耐熱性
を保持した難燃性樹脂組成物について鋭意検討した結果
本発明に到達したものであって、特定の固有粘度または
特定の固有粘度と熱天秤による分解開始温度を有するメ
タクリル酸メチル重合体およびアクリル酸の低級アルキ
ルエステルメタクリル酸メチル共重合体と含塩素リン酸
エステル類及びその誘導体とからなる樹脂組成物によっ
て、すぐれた透明性と耐熱性を有する難燃性組成物が得
られることを見い出した。In view of this situation, the present inventors have arrived at the present invention as a result of intensive studies on flame-retardant resin compositions that maintain excellent transparency and heat resistance. A resin composition consisting of a methyl methacrylate polymer and a lower alkyl ester of acrylic acid methyl methacrylate copolymer and a chlorine-containing phosphate ester and its derivatives has excellent transparency and It has been found that a flame retardant composition having heat resistance can be obtained.
（問題点を解決するための手段）
すなわち上記の目的は本発明によれば、メタクリル酸メ
チル９２重量％以上とアクリル酸の低級アルキルエステ
ル８重量％以下とよりなり、クロロホルム中２０℃にお
ける固有粘度が０．３５〜０．５５ （ｄｉ／ｇｒ）で
あるアクリル樹脂（Ｉ）８２〜９２重量％と含塩素リン
酸エステル類及びその誘導体（ＩＩ）８〜１８重量％か
らなる難燃性樹脂組成物によって達成される。(Means for solving the problem) That is, according to the present invention, the above object consists of 92% by weight or more of methyl methacrylate and 8% by weight or less of a lower alkyl ester of acrylic acid, and the intrinsic viscosity at 20°C in chloroform is A flame-retardant resin composition consisting of 82 to 92% by weight of an acrylic resin (I) having a di/gr of 0.35 to 0.55 (di/gr) and 8 to 18% by weight of a chlorine-containing phosphate ester and its derivative (II) achieved by things.
さらに上記目的は本発明によれば、メタクリル酸メチル
９２Ｎ！量％とアクリル酸の低級アルキルエステル８重
量％以下とよりなり、クロロホルム中２０℃における固
有粘度が０．３５〜０．５５（ｄｌｌ／ｇｒ）で、かつ
熱天秤による分解開始温度がＮ２雰囲気下、昇温速度１
０℃／ ｍ ｉ ｎの条件で５３３〜５６３’にである
アクリル樹脂（Ｉ＞８２〜９２ｆ！量％と含塩素リン酸
エステル類及びその誘導体（ＩＩ）８〜１８重量％から
なる難燃性樹脂組成物によって達成される。Furthermore, the above object is achieved according to the present invention with methyl methacrylate 92N! % and 8% by weight or less of lower alkyl ester of acrylic acid, has an intrinsic viscosity of 0.35 to 0.55 (dll/gr) at 20°C in chloroform, and has a decomposition start temperature on a thermobalance under an N2 atmosphere. , heating rate 1
Flame-retardant acrylic resin (I > 82-92f!% by weight and 8-18% by weight of chlorine-containing phosphate esters and their derivatives (II)) with a temperature of 533 to 563' at 0°C/min. This is achieved by a resin composition.
（作用）
本発明で用いるアクリル樹脂（Ｉ）は一般に公知の技術
である塊状重合、懸濁重合、溶液重合、乳化重合方法等
で得ることができる。このアクリル樹脂（Ｉ）の２０℃
クロロホルム中における固有粘度は０．３５〜０．５５
（ｄ、１２／ｇｒ）であり、より好ましくは０．４０
〜０．５０ ＜ｄｌ／ｇｒ）である、固有粘度が０．３
５ （ｄＪ／ｇｒ）未満では機械的強度が著しく低下し
、また燃焼時に糸状に樹脂が垂れるため燃焼が継続し、
ＵＬ規格Ｖ−２クラスの規準に適合せず好ましくない。(Function) The acrylic resin (I) used in the present invention can be obtained by generally known techniques such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization. 20℃ of this acrylic resin (I)
Intrinsic viscosity in chloroform is 0.35-0.55
(d, 12/gr), more preferably 0.40
~0.50<dl/gr), the intrinsic viscosity is 0.3
If it is less than 5 (dJ/gr), the mechanical strength will be significantly reduced, and the resin will drip in the form of threads during combustion, resulting in continued combustion.
It does not meet the criteria of UL standard V-2 class and is not desirable.
一方固有粘度が０．５５ （ｄＪ／ｇｒ）を超える場合
は難燃効果の発現性が低く、ＵＬ規格Ｖ−２クラスに適
合するためには難燃剤の添加量を２０％以上にする必要
があり、耐熱性、Ｉｌ械的強度等が低下し、好ましくな
い。On the other hand, if the intrinsic viscosity exceeds 0.55 (dJ/gr), the flame retardant effect will be low, and the amount of flame retardant added must be 20% or more in order to comply with the UL standard V-2 class. However, heat resistance, Il mechanical strength, etc. decrease, which is not preferable.
本発明にいうメタクリル酸メチル９０重量％以上とアク
リル酸の低級アルキルエステル８２Ｉ！量％以下とより
なるアクリル樹脂とは、メタクリル酸メチル重合体又は
８重量％以下の（メタ）アクリル酸エステルと共重合し
ているメタクリル酸メチル重合体をいい、またアクリル
酸の低級アルキルエステルとしては、アクリル酸メチル
、アクリル酸エチル、アクリル酸グロピル、アクリル酸
ブチルがあげられる。これらの共重合成分は単独で用い
てもよく、二種以上を組み合わせても良い。共重合成分
が８重量％を超える場合には、得られる成形品の耐熱性
が不足したり、燃焼時の樹脂型れにより燃焼が継続し易
く十分な難燃効果が得られなくなる。90% by weight or more of methyl methacrylate and lower alkyl ester of acrylic acid 82I as used in the present invention! The acrylic resin consisting of 8% by weight or less refers to a methyl methacrylate polymer or a methyl methacrylate polymer copolymerized with 8% by weight or less of (meth)acrylic acid ester, and also as a lower alkyl ester of acrylic acid. Examples include methyl acrylate, ethyl acrylate, glopyl acrylate, and butyl acrylate. These copolymerization components may be used alone or in combination of two or more. If the copolymerization component exceeds 8% by weight, the heat resistance of the obtained molded product may be insufficient, or the resin mold may deform during combustion, causing combustion to continue easily and sufficient flame retardant effects may not be obtained.
また、本発明を構成する上記アクリル樹脂（Ｉ）は熱天
秤による分解開始温度がＮ２雰囲気下、昇温速度１０℃
／ ｍ ｉ ｎにおいて５３３〜５６３（Ｋ）の範囲に
あるものが好ましい。アクリル樹脂（Ｉ）の分解温度が
５６３（Ｋ）を超える場合は難燃効果の発現性能が低く
なる傾向を示し、−方分解温度が５３３（”Ｋ＞未満の
場合は、燃焼時における樹脂の軟化が激しく、炎が高く
なり燃焼の継続が容易になる傾向を示すため、難燃効果
を高めるためにはアクリル樹脂（Ｉ）は前記特定の固有
粘度と熱天秤による分解開始温度とを有することが更に
好ましい。Furthermore, the above-mentioned acrylic resin (I) constituting the present invention has a decomposition start temperature determined by a thermobalance at a heating rate of 10° C. under an N2 atmosphere.
/ min is preferably in the range of 533 to 563 (K). When the decomposition temperature of acrylic resin (I) exceeds 563 (K), the performance of flame retardant effect tends to decrease. Since the acrylic resin (I) exhibits a tendency to soften violently, raise the flame height, and facilitate continuation of combustion, in order to enhance the flame retardant effect, the acrylic resin (I) must have the above-mentioned specific intrinsic viscosity and decomposition start temperature determined by thermobalance. is even more preferable.
本発明に用いる含塩素リン酸エステル類及びその誘導体
は例えばトリス（クロロエチル）ホスフェート、トリス
（ジ−クロロプロピル）ホスフェート、エチレン（ビス
クロロエチルホスフェート）、ビス（２０ログロビル）
モノオクチルホスフェート、ポリオキシエチレンビス（
ビスクロロエチルホスフェート）、ジ（１，３，２−ジ
オキサフォスホリナネ、５．５−ジメチル−２−オキサ
イド−２メチル）−ジクロロメチルメタン、含塩素縮合
リン酸エステル類等の一般に難燃剤として知られている
含塩素リン酸エステル類及びその誘導体であり、その添
加量は８〜１８重量％、好ましくは９〜１６重呈％重量
る。含塩素リン酸エステル類及びその誘導体の添加量が
８重量％未満の場合はＨ燃効果が低く、ＵＬ規格Ｖ−２
クラスに適合せず、１８重量部を超える場合は、得られ
た成形品の耐熱性や機械的物性の低下が著しい他、難燃
剤の可塑効果が強く、燃焼時に燃焼を継続する原因とな
る樹脂型れが発生し易く、ＵＬ規規格−２に適合しなく
なる。また一般に市販されている難燃剤として含臭素リ
ン酸エステル類及びその誘導体があるが、射出成形時に
強く着色したり、臭気が強く作業環境を悪化させたり、
耐候性の低下が大きく好ましくない。Examples of the chlorine-containing phosphate esters and derivatives thereof used in the present invention include tris(chloroethyl)phosphate, tris(di-chloropropyl)phosphate, ethylene(bischloroethylphosphate), and bis(20logrovir).
Monooctyl phosphate, polyoxyethylene bis(
Generally flame retardants such as di(1,3,2-dioxaphosphorinane, 5,5-dimethyl-2-oxide-2-methyl)-dichloromethylmethane, chlorine-containing condensed phosphoric acid esters, etc. These are chlorine-containing phosphate esters and derivatives thereof known as chlorine-containing phosphate esters and derivatives thereof, and the amount added is 8 to 18% by weight, preferably 9 to 16% by weight. If the amount of chlorine-containing phosphate esters and their derivatives added is less than 8% by weight, the H combustion effect will be low and the UL standard V-2
If it does not meet the class and exceeds 18 parts by weight, the heat resistance and mechanical properties of the resulting molded product will be significantly reduced, and the plasticizing effect of the flame retardant will be strong, causing the resin to continue burning during combustion. Deformation is likely to occur, and it no longer complies with UL Standard-2. Bromine-containing phosphate esters and their derivatives are commonly commercially available flame retardants, but they tend to be strongly colored during injection molding, have a strong odor, and worsen the working environment.
This is not preferable because it greatly reduces weather resistance.
本発明に用いる含塩素リン酸エステル類及びその誘導体
は単独又は二種類以上を組合せても良い。The chlorine-containing phosphate esters and derivatives thereof used in the present invention may be used alone or in combination of two or more.
本発明のアクリル難燃樹脂組成物は用いる難燃剤の種類
により若干着色する事があり、それ等を防止するなめ小
量の亜リン酸エステル類を用いる事ができ、特に効果の
大きい亜リン酸エステルとしては、ジステアリルペンタ
エリスリトールジホスファイト、ビス（ノニルフェニル
）ペンタエリスリトールジホスファイト、トリス（ノニ
ルフェニル）ホスファイト、ビス（トリデシル）ペンタ
エリスリトールジホスファイト等であり、難燃樹脂組成
物１００重量部に対し０．０５〜０．５重量部用いる事
ができる。The acrylic flame retardant resin composition of the present invention may be slightly colored depending on the type of flame retardant used, and a small amount of phosphites can be used to prevent this, and phosphorous esters are particularly effective. Examples of the ester include distearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tris(nonylphenyl) phosphite, bis(tridecyl)pentaerythritol diphosphite, and flame retardant resin composition 100. It can be used in an amount of 0.05 to 0.5 parts by weight.
本発明に用いる難燃性樹脂組成物は必要に応じて滑剤類
、紫外線吸収剤、熱安定剤、酸化防止剤、染顔料等を一
般に用いられている量を添加する事ができ、その配合す
る手段は重合前の調合時にあらかしめ溶解する方法又は
重合後のペレットに添加する方法等といずれでも良い。The flame-retardant resin composition used in the present invention may contain lubricants, ultraviolet absorbers, heat stabilizers, antioxidants, dyes and pigments, etc. in commonly used amounts, as necessary. The method may be either a pre-dissolving method at the time of preparation before polymerization or a method of adding it to pellets after polymerization.
本発明で用いるアクリル樹脂、含塩素リン酸エステル及
びその誘導体、および本発明に必要な添加剤等を混合す
る方法は通常行われている方法で可能であり、例えばタ
ンブラ−、ヘンシェルミキサー等で混合し、押出工程を
経てベレットを得る方法が効率良く生産性に優れている
が、アクリル樹脂を製造するための単量体に溶解させて
重合し目的とする難燃樹脂組成物を得ることができる。The acrylic resin, chlorine-containing phosphate ester and its derivatives used in the present invention, and the additives necessary for the present invention can be mixed by a commonly used method, such as a tumbler, a Henschel mixer, etc. However, the method of obtaining pellets through an extrusion process is efficient and has excellent productivity, but it is also possible to obtain the desired flame-retardant resin composition by dissolving it in a monomer for producing acrylic resin and polymerizing it. .
従来含塩素リン酸エステル類の難燃作用は燃焼 “によ
り分解したリンがメタリン酸を経てポリリン酸と順次変
化し、生成したポリリン酸膜が樹脂表面に形成し酸素を
遮断するため、あるいは燃焼熱により同様に発生した塩
素ガスが樹脂周囲を覆い、酸素を遮断するなめであると
言われている。Conventionally, the flame retardant effect of chlorine-containing phosphate esters is due to the fact that phosphorus decomposed by combustion changes sequentially to polyphosphoric acid via metaphosphoric acid, and a polyphosphoric acid film is formed on the resin surface to block oxygen, or due to combustion heat. It is said that the chlorine gas generated in the same way covers the resin and blocks out oxygen.
しかしながら本発明で用いる難燃性樹脂組成物は、燃焼
状態における樹脂の粘度が適度な粘性を持っているため
、樹脂表面への難燃剤の移行が順調に進むこと、そして
燃焼の境界部では、燃焼熱により樹脂の熱分解反応が起
り、部分的な粘度の低下により燃焼部が落下して、鎮火
するため燃焼が停止することを特徴とし゛ている。However, since the flame retardant resin composition used in the present invention has an appropriate viscosity in the combustion state, the flame retardant transfers smoothly to the resin surface, and at the boundary of combustion, The heat of combustion causes a thermal decomposition reaction of the resin, and a partial drop in viscosity causes the combustion part to fall, causing the combustion to stop in order to extinguish the fire.
（発明の効果）
以上述べてきたように、本発明の難燃性樹脂組成物は特
定量の含塩素リン酸エステル類及びその誘導体を用い、
特定の固有粘度または特定の固有粘度と特定の熱天秤に
よる分解温度を有するアクリル樹脂（Ｉ＞からなるもの
であるから、添加する難燃剤量が少ない量で高い難燃効
果が得られるので、アクリル樹脂本来の特性である光学
的性質を損わず、耐熱性を保持したａ時的強度の低下の
少ない難燃性樹脂組成物を得ることができ、弱電分野、
ＯＡｌ’ｌ器等に特に有用であり、デイスプレー、建材
部品等としても有用である。(Effects of the invention) As described above, the flame-retardant resin composition of the present invention uses a specific amount of chlorine-containing phosphate esters and derivatives thereof,
Since it consists of an acrylic resin (I>) that has a specific intrinsic viscosity or a specific intrinsic viscosity and a specific decomposition temperature determined by thermobalance, a high flame retardant effect can be obtained with a small amount of added flame retardant. It is possible to obtain a flame-retardant resin composition that does not impair the optical properties that are the original characteristics of the resin, maintains heat resistance, and shows little decrease in strength over time, and is useful in the light electrical field,
It is particularly useful for OAl'l appliances, etc., and also useful as displays, building material parts, etc.
（実施例）
以下実施例により本発明をより具体的に説明するが、本
発明はこれ等によって限定されるものではない、実施例
における「％」及び［部ｊはすべて［重量％」及び［重
、ｉ部］を表わす。実施例における物性評価及び難燃性
の評価は次の（１）〜（５）の方法に基づいて実施した
。(Example) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. weight, i part]. Evaluations of physical properties and flame retardancy in Examples were conducted based on the following methods (1) to (5).
（１）固有粘度： （ｄｌ／ｇｒ）
クロロホルム中に一定濃度（ｄｇ／ｄｌのアクリル樹脂
（Ｉ＞を溶解して、２０℃にして自動粘度計（仏ｆｉｃ
ａ社製）で測定した。(1) Intrinsic viscosity: (dl/gr) Dissolve acrylic resin (I) at a constant concentration (dg/dl) in chloroform and heat to 20°C using an automatic viscometer (French fic
(manufactured by company a).
（２）分解開始温度（′Ｋ）
熱天秤（’１’Ｇ−２０型 島津製作所製）を用いて、
あらかじめ８０℃２４時間乾燥した試料１０ｍ２を昇温
速度１０℃／ｍｉｎ、Ｎｚガス３０ｍ、９７ｍ１ｎの条
件で熱分解曲線を測定し、［高分子の熱分析手順とデー
タ解析（高分子素材センター刊）」の解析法に従った。(2) Decomposition start temperature ('K) Using a thermobalance (model '1'G-20, manufactured by Shimadzu Corporation),
Thermal decomposition curves of 10 m2 of samples previously dried at 80°C for 24 hours were measured under the conditions of a heating rate of 10°C/min, Nz gas of 30 m, and 97 m of 1 nm, and the results were determined using the following method: [Polymer Thermal Analysis Procedures and Data Analysis (Published by Polymer Materials Center)] ” analysis method was followed.
（３） ｖ ｉ ｃ ａ ｒ を軟化点（’Ｃ）２０
Ｘ２０Ｘ３．２（關）のテストピースを射出成形法で作
製し、ＡＳＴＭＤＩ ５２５の方法で測定した。(3) v i c a r is the softening point ('C) 20
A test piece of X20X3.2 (size) was produced by injection molding and measured according to the ASTMDI 525 method.
（４）引張強度
ＡＳＴＭＤ６３８に準じたダンベル■型を成形し、引張
強度を測定した。(4) Tensile strength A dumbbell shape according to ASTM D638 was molded, and the tensile strength was measured.
（５）難燃性の評価
１２７Ｘ２７Ｘ３．２ （ｏｎ）のテストピースを射出
成形法で成形し、ＵＬ規格９４号に準じ、テストピース
を垂直に吊し、下部より規定の発熱量を持ったガスを用
いて規定の大きさの炎をもやし、１０秒経過後、直ちに
炎を離し、テストピースの炎が消火したら、再度直ちに
炎を当て消火するまでの秒数を測定し、ＵＬ規格Ｖ−２
クラス（ＳＥ−Ｉｆ ） ヲＭ準トし、Ｖ−２クラス適
合物は離燃性能を適合品とし、効果有と判定した。(5) Evaluation of flame retardancy A test piece of 127 x 27 x 3.2 (on) was molded by injection molding, and according to UL Standard No. 94, the test piece was hung vertically and a gas with a specified calorific value was poured from the bottom. After 10 seconds have elapsed, the flame of the specified size is started, and the flame is immediately removed. When the flame on the test piece is extinguished, the flame is immediately applied again and the number of seconds until the flame is extinguished is measured. UL standard V-2
The class (SE-If) was determined to be equivalent to M, and the V-2 class compliant product had combustibility performance and was judged to be effective.
実施例１
７５ｉ！耐圧反応槽中に懸濁安定剤としてポリメタクリ
ル酸カリウム水溶液１５０ｇｒ、リン酸水素２ナトリウ
ム１００ｇｒ、リン酸２水素ナトリウム３ｇｒを溶解し
た脱イオン水３２．４ｋｇ、メタクリル酸メチル２０．
５ｋｉｒ、アクリル酸メチル１．０８ｋｇ、ｎオクチル
メルカプタフ５４ｇｒ、アゾビスインブチロニトリル２
１．６ｇｒ、ステアリルアルコール２１ｇｒ、紫外線吸
収剤（チバガイギー製：チヌビンＰ）４．３ｇｒを入れ
、８０℃２時間重合し、発熱ピーク後１２０℃１時間加
熱重合せしめた。得られたビーズ状共重合体を水洗、乾
燥した後固有粘度を測定した結果０．４０ （ｄｊ！／
ｇｒ）であった。またこのビーズを熱天秤で分解開始温
度を測定した結果は５４８（Ｋ）であった、このビーズ
８７％とトリス（ジクロロプロピル）ホスフェート１３
％をヘンシェルミキサーで混合した後、混合物１００部
に対してビス（ノニルフェニル）ペンタエリスリトール
ジホスファイト（城北化学製：ＪＰＰ−３１）０．１部
を加え、シリンダー径４０ＩｌＩＩの押出機でペレット
化した。このベレットを射出成型機（日本製鋼所要：Ｎ
−７０Ａ型）で、シリンダー温度２１０℃、金型温度５
０℃の条件で燃焼試験用、ｖｉｃａｒｔ軟化点測定用、
引張試験用の各試験片を成形し、評価した。結果を第１
表に示すが、引張強度 ４６０ｋｇ／ｃｄ、ｖｉ ｃ
ａｒｔ軟化点９７℃と高く、外観も着色のない成形品が
得られた。ＵＬ規格に従って燃焼試験を実施した結果、
Ｖ−２クラスに適合している。Example 1 75i! In a pressure-resistant reaction tank, 32.4 kg of deionized water in which 150 gr of an aqueous solution of potassium polymethacrylate, 100 gr of disodium hydrogen phosphate, and 3 gr of sodium dihydrogen phosphate were dissolved as suspension stabilizers, and 20 gr of methyl methacrylate.
5kir, methyl acrylate 1.08kg, n-octyl mercaptaf 54gr, azobisin butyronitrile 2
1.6gr of stearyl alcohol, 21gr of stearyl alcohol, and 4.3gr of ultraviolet absorber (Tinuvin P manufactured by Ciba Geigy Co., Ltd.) were added, polymerized at 80°C for 2 hours, and after the exothermic peak was heated, polymerization was carried out at 120°C for 1 hour. After washing and drying the obtained bead-like copolymer, the intrinsic viscosity was measured and the result was 0.40 (dj!/
gr). In addition, the decomposition initiation temperature of these beads was measured using a thermobalance, and the result was 548 (K).
% in a Henschel mixer, 0.1 part of bis(nonylphenyl)pentaerythritol diphosphite (manufactured by Johoku Kagaku: JPP-31) was added to 100 parts of the mixture, and the mixture was pelletized using an extruder with a cylinder diameter of 40IlII. did. This pellet is molded into an injection molding machine (Nippon Steel Required: N
-70A type), cylinder temperature 210℃, mold temperature 5
For combustion test under 0℃ condition, for Vicart softening point measurement,
Each specimen for tensile testing was molded and evaluated. Results first
As shown in the table, the tensile strength is 460 kg/cd, VIC
A molded product with a high art softening point of 97° C. and a non-colored appearance was obtained. As a result of conducting a combustion test according to UL standards,
Conforms to V-2 class.
（比較例１）
実施例１と同様の反応槽を用いて、ｎオクチルメルカプ
タン３２ｇｒに変更した以外はずべて実施例１と同様の
仕込量、及び条件で重合を行い、ビーズを得た。このビ
ーズの固有粘度は０．６２（ｄｌ／ｇｒ）であり熱分解
開始温度は５５０（”Ｋ）であった。得られたアクリル
樹脂（Ｉ）と難燃剤、他の添加剤を実施例１と同様の割
合で混合し、得られたベレットで実施例１と同様の条件
で得られた試験片を評価した結果、第１表に示した様に
引張強度、Ｖｉｃａｒｔ軟化点は良好であるが、難燃性
能が低くＶ−２に適合せず、ＨＢクラスであった。(Comparative Example 1) Using the same reaction tank as in Example 1, polymerization was carried out under the same charge amount and conditions as in Example 1 except that n-octyl mercaptan was changed to 32 gr, and beads were obtained. The intrinsic viscosity of these beads was 0.62 (dl/gr), and the thermal decomposition onset temperature was 550 (K).The obtained acrylic resin (I), flame retardant, and other additives were mixed in Example 1. As a result of evaluating test pieces obtained under the same conditions as in Example 1 using the obtained pellets, the tensile strength and Vicart softening point were good as shown in Table 1. , the flame retardant performance was low and did not meet V-2, and was in the HB class.
（実施例２〜７）
第１表で示した割合で各成分を調合し、実施例１と同様
の条件で重合して得られたアクリル樹脂（Ｉ）と含塩素
リン酸エステル類及びその誘導体（ｎ）である難燃剤の
合計が１００％の混合物を実施例１と同様の方法でペレ
ット化後、各試験片を得た。(Examples 2 to 7) Acrylic resin (I), chlorine-containing phosphate esters, and derivatives thereof obtained by blending each component in the proportions shown in Table 1 and polymerizing it under the same conditions as Example 1. A mixture containing 100% of the flame retardant (n) in total was pelletized in the same manner as in Example 1 to obtain each test piece.
実施例２〜４は異った共重合成分の種類と量のアクリル
樹脂（Ｉ）と含塩素リン酸エステル類及びその誘導体の
種類と添加量を変化せしめたものであるが、アクリル樹
脂（Ｉ）の固有粘度と分解開始温度、共重合成分が特許
請求の範囲にあれば難燃性能はＵｔ、規格ｖ−２クラス
に適合した上、ＶｉｃａｒＬ軟化点は９０℃以上保持し
、引張強度の低下も小さく良好である。実施例５〜６は
共重合成分の上限及びメタクリル酸メチルのホモポリマ
ーであるアクリル樹脂（Ｉ）を用いての難燃化樹脂組成
物を作製したものであるが、ＵＬ規格Ｖ−２クラスに適
合しているものが得られた。実施例７は実施例２と対比
しており、難燃剤の添加量の範囲について実施したもの
で、難燃剤の添加量が上限、下限共に難燃性及び１ｌｌ
ｌ熱性、Ｒ時的強度共遜色ないものであった。In Examples 2 to 4, the type and amount of acrylic resin (I) with different copolymer components and the type and amount of chlorine-containing phosphate esters and their derivatives were changed. ), if the intrinsic viscosity, decomposition start temperature, and copolymerization components are within the claimed range, the flame retardant performance will be Ut, and it will meet the standard V-2 class, and the Vicar L softening point will be maintained at 90°C or higher, and the tensile strength will decrease. It is also small and good. In Examples 5 and 6, flame-retardant resin compositions were prepared using the upper limit of copolymerization components and acrylic resin (I), which is a homopolymer of methyl methacrylate, but did not meet the UL standard V-2 class. I found something suitable. Example 7 is compared with Example 2, and was carried out for a range of flame retardant addition amounts, and both the upper and lower limits of the flame retardant addition amount were flame retardant and 1 liter.
The heat resistance and R-temperature strength were comparable.
（比較例２〜５）
比較例２．３は固有粘度が特許請求の範囲の下限に満た
ない場合であり、この場合には粘度が低ずざるため燃焼
が継続し、ＵＬ規格ｖ−２クラスに適合しない上強度の
低下も大きい結果を示した。(Comparative Examples 2 to 5) Comparative Examples 2 and 3 are cases where the intrinsic viscosity is less than the lower limit of the claimed range. In addition to not meeting the requirements, the results showed a large decrease in strength.
比較例４はアクリル樹脂の共重合成分が多い例であり、
固有粘度が範囲内であっても、燃焼部の落下が起りにく
く、ＨＢクラスであった。比較例５．６は用いる難燃剤
の量を変化させたものであり、添加する難燃剤が少ない
場合は難燃効果が不足するため、ＨＢクラスであり、一
方多い場合は難燃剤の可塑効果により、燃焼時に樹脂垂
れが発生し、燃焼が継続するためやはりＨＢクラスを示
しな。Comparative Example 4 is an example with a large amount of copolymerized components of acrylic resin,
Even if the intrinsic viscosity was within the range, the combustion part was less likely to fall and was in the HB class. In Comparative Examples 5 and 6, the amount of flame retardant used was changed, and if the amount of flame retardant added is small, the flame retardant effect is insufficient, so it is in the HB class. However, since resin drips during combustion and combustion continues, it is still classified as HB class.
（実施例８）
メタクリル酸メチル４．７５１ｑｒ、アクリル酸メチル
０．２５ｋｇ、ｎドデシルメルカプタン１２゜５ｇｒ、
ステアリン酸モノグリセライド５ｇｒ、紫外線吸収剤（
チバガイギー製：チヌビンＰ）１、Ｏｇｒ、ラウロイル
パーオキサイド１０ｇｒを加え溶解、混合を十分行った
後、二枚のガラス板の間に塩化ビニール製チューブを介
してなるセルに注入し、７０℃で重合した。発熱ピーク
後１１０℃で９０分間熱重合を行い、冷却後取り出した
。得られたキャスト板のクロロホルム中の固有粘度は０
．４８ （ｄＪ２／ｇｒ）、熱分解開始温度は５４３（
Ｋ）であった。この注型板を粉砕機で粉砕後、粉砕した
樹脂４．３７５ｋｇとジ（１，３゜２−ジオキサスホス
ホリナネ、５．５−ジメチル−２オキシド−２メチル）
ジクロロメチルメタン０．６２５１ｑｒをヘンシェルミ
キサーで混合し、４０ａｍ押出機でペレット化した。こ
のベレットを用いて実施例１と同様の条件で射出成形し
各試験片で評価した結果、難・燃性はＵ Ｌ規格Ｖ−２
に適合しており、Ｖｉｃａｒｔ軟化点、引張強度は各々
９８℃、４７０ｋｇ／−で十分実用に耐えるものであっ
た。(Example 8) Methyl methacrylate 4.751qr, methyl acrylate 0.25kg, n-dodecylmercaptan 12°5gr,
Stearic acid monoglyceride 5gr, ultraviolet absorber (
Tinuvin P) 1 (manufactured by Ciba Geigy), Ogr, and 10 gr of lauroyl peroxide were added, dissolved and mixed thoroughly, and then poured into a cell formed by a vinyl chloride tube between two glass plates, and polymerized at 70°C. After the exothermic peak, thermal polymerization was carried out at 110° C. for 90 minutes, and the product was taken out after cooling. The intrinsic viscosity of the obtained cast plate in chloroform is 0.
．． 48 (dJ2/gr), thermal decomposition start temperature is 543 (
K). After pulverizing this casting plate with a pulverizer, 4.375 kg of the pulverized resin and di(1,3゜2-dioxasphosphorine, 5,5-dimethyl-2 oxide-2 methyl) were added.
0.6251 qr of dichloromethylmethane was mixed in a Henschel mixer and pelletized in a 40am extruder. Using this pellet, injection molding was performed under the same conditions as in Example 1, and each test piece was evaluated. As a result, the flame retardance and flame resistance were UL standard V-2.
The Vicart softening point and tensile strength were 98° C. and 470 kg/−, respectively, which were sufficient for practical use.
Claims (2)
の低級アルキルエステル８重量％以下とよりなり、クロ
ロホルム中２０℃における固有粘度が０．３５〜０．５
５（ｄｌ／ｇｒ）であるアクリル樹脂（ I ）８２〜９
２重量％と含塩素リン酸エステル類及びその誘導体 （II）８〜１８重量％とからなる難燃性樹脂組成物。(1) Consists of 92% by weight or more of methyl methacrylate and 8% by weight or less of lower alkyl ester of acrylic acid, and has an intrinsic viscosity of 0.35 to 0.5 at 20°C in chloroform.
5 (dl/gr) acrylic resin (I) 82-9
A flame-retardant resin composition comprising 2% by weight of chlorine-containing phosphoric acid esters and their derivatives (II) and 8-18% by weight.
の低級アルキルエステル８重量％以下とよりなり、クロ
ロホルム中２０℃における固有粘度が０．３５〜０．５
５（ｄｌ／ｇｒ）で、かつ熱天秤による分解開始温度が
Ｎ＿２雰囲気下、昇温速度１０℃／ｍｉｎの条件で ５３３〜５６３°Ｋであるアクリル樹脂（ I ）８２〜
９２重量％と含塩素リン酸エステル類及びその誘導体（
II）８〜１８重量％とからなる難燃性樹脂組成物。(2) Consists of 92% by weight or more of methyl methacrylate and 8% by weight or less of lower alkyl ester of acrylic acid, and has an intrinsic viscosity of 0.35 to 0.5 at 20°C in chloroform.
5 (dl/gr) and whose decomposition start temperature by thermobalance is 533 to 563 °K under N_2 atmosphere and temperature increase rate of 10 °C/min (I) 82~
92% by weight and chlorine-containing phosphate esters and their derivatives (
II) A flame retardant resin composition comprising 8 to 18% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63043992A JPH0747674B2 (en) | 1988-02-26 | 1988-02-26 | Flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63043992A JPH0747674B2 (en) | 1988-02-26 | 1988-02-26 | Flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01217055A true JPH01217055A (en) | 1989-08-30 |
| JPH0747674B2 JPH0747674B2 (en) | 1995-05-24 |
Family
ID=12679214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63043992A Expired - Fee Related JPH0747674B2 (en) | 1988-02-26 | 1988-02-26 | Flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0747674B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132802A (en) * | 2007-11-30 | 2009-06-18 | Sumitomo Chemical Co Ltd | Methacrylic resin composition and process for producing methacrylic resin composition |
| DE102008001231A1 (en) * | 2008-04-17 | 2009-10-22 | Evonik Röhm Gmbh | Flameproof PMMA molding compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4885639A (en) * | 1972-02-19 | 1973-11-13 | ||
| JPS5525225A (en) * | 1978-08-10 | 1980-02-22 | Hitachi Cable Ltd | Laying method for inductive radio cable |
| JPS59184242A (en) * | 1983-03-31 | 1984-10-19 | レ−ム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Flame retardant forming material based on methyl polymethacrylate |
| JPS62115056A (en) * | 1985-11-14 | 1987-05-26 | Mitsubishi Rayon Co Ltd | Resin composition |
-
1988
- 1988-02-26 JP JP63043992A patent/JPH0747674B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4885639A (en) * | 1972-02-19 | 1973-11-13 | ||
| JPS5525225A (en) * | 1978-08-10 | 1980-02-22 | Hitachi Cable Ltd | Laying method for inductive radio cable |
| JPS59184242A (en) * | 1983-03-31 | 1984-10-19 | レ−ム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Flame retardant forming material based on methyl polymethacrylate |
| JPS62115056A (en) * | 1985-11-14 | 1987-05-26 | Mitsubishi Rayon Co Ltd | Resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132802A (en) * | 2007-11-30 | 2009-06-18 | Sumitomo Chemical Co Ltd | Methacrylic resin composition and process for producing methacrylic resin composition |
| DE102008001231A1 (en) * | 2008-04-17 | 2009-10-22 | Evonik Röhm Gmbh | Flameproof PMMA molding compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0747674B2 (en) | 1995-05-24 |
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