JPH06207088A - Flame-retardant polycarbonate resin composition - Google Patents
Flame-retardant polycarbonate resin compositionInfo
- Publication number
- JPH06207088A JPH06207088A JP5003273A JP327393A JPH06207088A JP H06207088 A JPH06207088 A JP H06207088A JP 5003273 A JP5003273 A JP 5003273A JP 327393 A JP327393 A JP 327393A JP H06207088 A JPH06207088 A JP H06207088A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- weight
- resin composition
- flame
- alkali metal
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 28
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 28
- 239000003063 flame retardant Substances 0.000 title claims abstract description 16
- 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 15
- -1 alkali metal salt Chemical class 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 239000011342 resin composition Substances 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 8
- 150000005690 diesters Chemical class 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NPPQSCRMBWNHMW-UHFFFAOYSA-N Meprobamate Chemical compound NC(=O)OCC(C)(CCC)COC(N)=O NPPQSCRMBWNHMW-UHFFFAOYSA-N 0.000 description 1
- 101100288971 Mus musculus Lgals3bp gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光拡散性を有する難燃
性ポリカーボネート樹脂組成物に関する。更に詳しく
は、優れた難燃性と光拡散性を有し、光学分野特に液晶
表示のバックライト用として有用な難燃性ポリカーボネ
ート樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a flame-retardant polycarbonate resin composition having a light diffusing property. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition having excellent flame retardancy and light diffusivity, which is useful in the field of optics, especially for backlights of liquid crystal displays.
【０００２】[0002]
【従来の技術】従来より、液晶表示のバックライト用光
拡散板としては、光拡散剤を配合したアクリル樹脂が使
用されている。しかしながら、最近かかる用途に使用す
る光拡散板に難燃性と耐熱性が要求されており、アクリ
ル樹脂では対応し得ず、ポリカーボネート樹脂に特定量
の微粉状炭酸カルシウムとガラス短繊維を分散させたも
のが光拡散板に適していることを知り、先に提案した
（特開平1-209402）。2. Description of the Related Art Conventionally, an acrylic resin containing a light diffusing agent has been used as a light diffusing plate for a backlight of a liquid crystal display. However, recently, the light diffusing plate used for such applications is required to have flame retardancy and heat resistance, which cannot be dealt with by an acrylic resin, and a specific amount of finely powdered calcium carbonate and glass short fibers are dispersed in a polycarbonate resin. We found that the product is suitable for a light diffusion plate, and proposed it earlier (Japanese Patent Laid-Open No. 1-209402).
【０００３】しかしながら、製品の軽薄化や軽量化に伴
い、ポリカーボネート樹脂光拡散板についても、より薄
く且つより高度な難燃性が要求されるようになってい
る。更に光拡散板用樹脂組成物には優れた難燃性のみな
らず、約３５％以上の全光線透過率と約１５°以上の透
過光線の半減角、及び腐食性の強いガスを発生すると内
部のIC基板を損なうことから、腐食性の強いガスを発生
しないことが望まれている。ポリカーボネート樹脂を難
燃化する方法は数多く提案されており、その多くは有機
ハロゲン化合物を添加するものである。しかしながら、
芳香族ポリカーボネート樹脂に自消性や難燃性を付与す
るには、かなりの量の有機ハロゲン化合物を添加する必
要があるため成形時の熱安定性が低下し、更に成形時に
黄変したり腐食性ガスを発生するという欠点がある。However, as the products become thinner and lighter, the polycarbonate resin light diffusing plate is also required to be thinner and have higher flame retardancy. Further, the resin composition for the light diffusion plate is not only excellent in flame retardancy, but also has a total light transmittance of about 35% or more, a half-angle of transmitted light of about 15 ° or more, and a highly corrosive gas when internally generated. It is desired not to generate highly corrosive gas because it damages the IC substrate. Many methods for making a polycarbonate resin flame-retardant have been proposed, and most of them add an organic halogen compound. However,
In order to impart self-extinguishing property and flame retardancy to the aromatic polycarbonate resin, it is necessary to add a considerable amount of organic halogen compound, so the thermal stability at the time of molding decreases, and further yellowing or corrosion occurs at the time of molding. It has the drawback of generating a volatile gas.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、優れ
た難燃性を有し且つ黄変による光学特性の低下がなく、
更に腐食性の強いガスを発生しない、特に液晶表示のバ
ックライト用に適する難燃性ポリカーボネート樹脂組成
物を提供することにある。本発明者は、上記目的を達成
せんとして鋭意検討を重ねた結果、特定量の微粉状炭酸
カルシウムとガラス短繊維を分散させたポリカーボネー
ト樹脂組成物に、難燃剤として特定の有機リン酸ジエス
テルと特定の有機リン酸ジエステルのアルカリ金属塩の
混合物を少量配合することにより上記目的が達成される
ことを見出し、本発明を完成した。DISCLOSURE OF THE INVENTION An object of the present invention is to have excellent flame retardancy and to prevent deterioration of optical properties due to yellowing,
Another object of the present invention is to provide a flame-retardant polycarbonate resin composition which does not generate highly corrosive gas and is particularly suitable for a liquid crystal display backlight. The present inventor, as a result of repeated intensive studies as an attempt to achieve the above objects, a polycarbonate resin composition in which a specific amount of finely powdered calcium carbonate and glass short fibers are dispersed, and a specific organic phosphoric acid diester as a flame retardant is specified. It was found that the above object can be achieved by adding a small amount of the mixture of the alkali metal salt of the organic phosphoric acid diester described in (4) above, and the present invention has been completed.
【０００５】[0005]
【課題を解決するための手段】本発明は、 (A)粘度平均
分子量が１３，０００〜４０，０００のハロゲン非含有
ポリカーボネート樹脂８０〜９８重量％、 (B)微粉状炭
酸カルシウム１〜１９重量％及び (c)ガラス短繊維１〜
１９重量％からなり、 (B)成分と (c)成分の合計量が２
０重量％を越えない樹脂組成物１００重量部に、 (D)下
記一般式［１］及び［２］The present invention comprises: (A) 80 to 98% by weight of a halogen-free polycarbonate resin having a viscosity average molecular weight of 13,000 to 40,000, and (B) 1 to 19% by weight of finely divided calcium carbonate. % And (c) short glass fiber 1
It consists of 19% by weight, and the total amount of component (B) and component (c) is 2
In 100 parts by weight of the resin composition not exceeding 0% by weight, (D) the following general formulas [1] and [2]
【０００６】[0006]
【化３】 [Chemical 3]
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】［式中、Ｘは水素原子又はハロゲン原子で
あり、Ｍはアルカリ金属である。］で表される有機リン
酸ジエステル及び有機リン酸ジエステルのアルカリ金属
塩の混合物を０．００１〜１重量部配合してなる難燃性
ポリカーボネート樹脂組成物に係るものである。[In the formula, X is a hydrogen atom or a halogen atom, and M is an alkali metal. ] It is related with the flame-retardant polycarbonate resin composition which mix | blends 0.001 to 1 weight part of the mixture of the organic phosphoric acid diester and the alkali metal salt of an organic phosphoric acid diester represented by these.
【０００９】本発明で使用するポリカーボネート樹脂
は、二価フェノールより誘導される粘度平均分子量１
３，０００〜４０，０００、好ましくは１５，０００〜
３０，０００のポリカーボネート樹脂であり、通常二価
フェノールとカーボネート前駆体を溶液法又は溶融法で
反応させて製造される。二価フェノールとしては例えば
２，２−ビス（４−ヒドロキシフェニル）プロパン［以
下ビスフェノールＡという］、ビス（４−ヒドロキシフ
ェニル）エタン、２，２−ビス（４−ヒドロキシ−３，
５−ジメチルフェニル）プロパン、２，２−ビス（４−
ヒドロキシ−３，５−ジブロムフェニル）プロパン、
２，２−（４−ヒドロキシ−３−メチルフェニル）プロ
パン、ビス（４−ヒドロキシフェニル）スルフォン等が
あげられる。好ましい二価フェノールはビス（４−ヒド
ロキシフェニル）アルカン、特にビスフェノールＡであ
る。The polycarbonate resin used in the present invention has a viscosity average molecular weight of 1 derived from a dihydric phenol.
3,000-40,000, preferably 15,000-
It is a 30,000 polycarbonate resin and is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [hereinafter referred to as bisphenol A], bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,
5-dimethylphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dibromophenyl) propane,
2,2- (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfone and the like can be mentioned. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, especially bisphenol A.
【００１０】また、カーボネート前駆体としてはカルボ
ニルハライド、ジアリールカーボネートまたはハロホル
メート等があげられ、具体的にはホスゲン、ジフェニル
カーボネート、二価フェノールのジハロホルメート及び
それらの混合物である。芳香族ポリカーボネート樹脂を
製造するに当たり、前記二価フェノールを単独で又は二
種以上を使用することができる。また、適当な分子量調
節剤、分岐剤、反応を促進するための触媒等も使用でき
る。かくして得られたポリカーボネート樹脂の二種以上
を混合しても差支えない。Examples of the carbonate precursor include carbonyl halide, diaryl carbonate, haloformate and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and a mixture thereof. In producing the aromatic polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more kinds. Further, an appropriate molecular weight regulator, branching agent, catalyst for accelerating the reaction and the like can also be used. It is no problem to mix two or more of the polycarbonate resins thus obtained.
【００１１】上記ポリカーボネート樹脂に配合する (B)
成分の微粉状炭酸カルシウムは、市販品をそのまま使用
してもよいが、平均粒径が約４〜６μm で角張ったもの
が好ましい。(c)成分のガラス短繊維は、直径約４〜１
５μm のガラス繊維を長さ１００μm 以下に切断又は粉
砕したものであって、ガラスとしては無アルカリガラス
例えばＥガラスが好ましく、屈折率は使用するポリカー
ボネート樹脂の屈折率と０．０１〜０．０４異なること
が望ましい。かかるガラス短繊維はミルドファイバー又
はガラス粉末として市場から容易に入手できる。Addition to the above polycarbonate resin (B)
As the finely powdered calcium carbonate as a component, a commercially available product may be used as it is, but it is preferable that it has an average particle diameter of about 4 to 6 μm and is angular. The short glass fiber as the component (c) has a diameter of about 4 to 1
5 μm glass fiber cut or crushed to a length of 100 μm or less, non-alkali glass such as E glass is preferable as the glass, and the refractive index differs from that of the polycarbonate resin used by 0.01 to 0.04. Is desirable. Such short glass fibers are easily available on the market as milled fibers or glass powder.
【００１２】これら微粉状炭酸カルシウム及びガラス短
繊維の配合量は、 (A)ポリカーボネート樹脂８０〜９８
重量％、 (B)微粉状炭酸カルシウム１〜１９重量％及び
(c)ガラス短繊維１〜１９重量％で、且つ (B)成分と
(c)成分の合計量が２０重量％を越えない量である。微
粉状炭酸カルシウム及びガラス短繊維の各々の配合量が
１重量％未満では光拡散性を付与するには不充分であ
り、微粉状炭酸カルシウムとガラス短繊維合計量が２０
重量％より多くなると燃焼し難く、本発明を必要としな
い。The compounding amounts of these finely powdered calcium carbonate and short glass fibers are (A) polycarbonate resin 80 to 98
% By weight, (B) 1 to 19% by weight of finely divided calcium carbonate, and
(c) 1 to 19% by weight of glass short fibers, and (B) component
The total amount of the component (c) does not exceed 20% by weight. If the blending amount of each of the finely powdered calcium carbonate and the short glass fiber is less than 1% by weight, it is insufficient to impart the light diffusivity, and the total amount of the finely powdered calcium carbonate and the short glass fiber is 20%.
If it is more than wt%, it is difficult to burn and the present invention is not necessary.
【００１３】本発明で使用する有機リン酸ジエステル
は、前記一般式［１］で表され、式中Ｘは水素原子又は
ハロゲン原子であり、難燃性能の点から全てのＸが臭素
原子であるものが好ましい。また、有機リン酸ジエステ
ルのアルカリ金属塩は前記一般式［２］で表され、式中
Ｍで示されるアルカリ金属としてはナトリウムやカリウ
ムが好ましく、上記有機リン酸ジエステルのアルカリ金
属塩が好ましい。The organic phosphoric acid diester used in the present invention is represented by the above general formula [1], wherein X is a hydrogen atom or a halogen atom, and all X are bromine atoms from the viewpoint of flame retardancy. Those are preferable. The alkali metal salt of an organic phosphoric acid diester is represented by the above general formula [2], and as the alkali metal represented by M in the formula, sodium or potassium is preferable, and the alkali metal salt of the organic phosphoric acid diester is preferable.
【００１４】上記有機リン酸ジエステルと有機リン酸ジ
エステルのアルカリ金属塩を混合して使用することによ
り、得られる組成物の熱安定性が向上する。この際、有
機リン酸ジエステルの使用割合があまりにも小さいと熱
安定性の向上効果が得られ難く、あまりに大きくなると
かえって熱安定性が悪化するようになるので、（有機リ
ン酸ジエステル）／（有機リン酸ジエステルのアルカリ
金属塩）が４／６〜１／９になる範囲が好ましい。By mixing and using the organic phosphoric acid diester and the alkali metal salt of the organic phosphoric acid diester, the thermal stability of the resulting composition is improved. At this time, if the use ratio of the organic phosphoric acid diester is too small, it is difficult to obtain the effect of improving the thermal stability, and if it is too large, the thermal stability is rather deteriorated. Therefore, (organic phosphoric acid diester) / (organic phosphoric acid diester) The range in which the alkali metal salt of phosphoric acid diester) is 4/6 to 1/9 is preferable.
【００１５】有機リン酸ジエステルと有機リン酸ジエス
テルのアルカリ金属塩の混合物の使用量は、芳香族ポリ
カーボネート樹脂、微粉状炭酸カルシウム及びガラス短
繊維からなる樹脂組成物１００重量部に対して、０．０
０１〜１重量部であり、好ましくは０．００５〜０．５
重量部である。０．００１重量部より少いと難燃効果が
得られ難く、１重量部より多くなると得られる組成物の
熱安定性が低下するようになる。また、従来の有機ハロ
ゲン系難燃剤と併用することによって、その難燃効果を
大幅に向上させることができ、両者の使用量を著しく減
少させることもできる。The amount of the mixture of the organic phosphoric acid diester and the alkali metal salt of the organic phosphoric acid diester used is 0. 0 with respect to 100 parts by weight of the resin composition composed of the aromatic polycarbonate resin, the finely powdered calcium carbonate and the glass short fibers. 0
01 to 1 part by weight, preferably 0.005 to 0.5
Parts by weight. If it is less than 0.001 part by weight, the flame-retardant effect is difficult to be obtained, and if it is more than 1 part by weight, the thermal stability of the obtained composition is lowered. In addition, when used in combination with a conventional organic halogen-based flame retardant, the flame retardant effect can be significantly improved, and the amount of both used can be significantly reduced.
【００１６】本発明の組成物は、上記各成分を混合する
ことにより製造される。例えば各成分をＶ型ブレンダ
ー、リボンミキサー又はタンブラー等に投入して均一に
混合した後、一軸又は二軸の通常の押出機で溶融混練
し、冷却した後ペレット状に切断する。このとき、ガラ
ス短繊維や他の成分の一部を押出機の途中から添加して
もよい。また、成分の一部を予め混合・混練した後、更
に残りの成分を添加し押出してもよい。The composition of the present invention is produced by mixing the above components. For example, the respective components are put into a V-type blender, a ribbon mixer, a tumbler or the like and uniformly mixed, and then melt-kneaded by a normal uniaxial or biaxial extruder, cooled, and then cut into pellets. At this time, a part of the glass short fibers and other components may be added in the middle of the extruder. Alternatively, a part of the components may be mixed and kneaded in advance, and then the remaining components may be added and extruded.
【００１７】本発明の組成物には、本発明の目的を損な
わない範囲で、他の難燃剤例えば臭素化ビスフェノール
類、臭素化エポキシ樹脂、臭素化ポリスチレン、臭素化
ポリカーボネート、トリフェニルホスフェート、ホスホ
ン酸アミド、赤リン等を配合してもよく、また安定剤例
えばリン酸エステル、亜リン酸エステル等、酸化防止剤
例えばヒンダードフェノール系化合物等、光安定剤、滑
剤、離型剤、帯電防止剤等を配合してもよい。かくして
得られる組成物は射出成形、押出成形、圧縮成形等の方
法で容易に成形することができる。In the composition of the present invention, other flame retardants such as brominated bisphenols, brominated epoxy resins, brominated polystyrenes, brominated polycarbonates, triphenyl phosphates and phosphonic acids are used as long as the object of the present invention is not impaired. Amides, red phosphorus and the like may be added, and stabilizers such as phosphoric acid esters and phosphorous acid esters, antioxidants such as hindered phenol compounds, light stabilizers, lubricants, release agents and antistatic agents. Etc. may be blended. The composition thus obtained can be easily molded by methods such as injection molding, extrusion molding and compression molding.
【００１８】[0018]
【実施例】以下に実施例をあげて更に説明する。なお、
実施例中の部は重量部であり、燃焼性は UL-９４プラス
チック燃焼試験法により測定し、色調は射出成形して得
た１２７×１５３×３mmの成形板を使用して日本電色工
業（株）製色差計 SZ-Σ８０によりｂ値を測定した。EXAMPLES The present invention will be further described below with reference to examples. In addition,
The parts in the examples are parts by weight, the flammability was measured by the UL-94 plastic combustion test method, and the color tone was measured by using a molded plate of 127 × 153 × 3 mm obtained by injection molding. The b value was measured with a color difference meter SZ-Σ80 manufactured by Co., Ltd.
【００１９】[0019]
【実施例１、２及び比較例１〜４】ビスフェノールＡ、
ホスゲン及び分子量調節剤として p-tert-ブチルフェノ
ールから常法により得た粘度平均分子量２３，０００の
ポリカーボネート樹脂、微粉状炭酸カルシウム［シプロ
化成（株）製シプロン A、平均粒径５μｍ］、ガラス短
繊維［日東紡（株）製 PFB−１０１、平均繊維長２６μ
ｍ，平均直径１０μｍ］、テトラブロモビスフェノール
Ａ、ホスゲン及び分子量調節剤としてフェノールから常
法により得た平均重合度７の粉末状のポリカーボネート
オリゴマー、パーフロロ−n-ブタンスルホン酸カリウム
及び下記式Examples 1 and 2 and Comparative Examples 1 to 4 Bisphenol A,
Polycarbonate resin having a viscosity average molecular weight of 23,000 obtained by a conventional method from phosgene and p-tert-butylphenol as a molecular weight regulator, finely powdered calcium carbonate [Cypron A manufactured by Cypro Kasei Co., average particle size 5 μm], glass short fiber [Nittobo PFB-101, average fiber length 26μ
m, average diameter 10 μm], tetrabromobisphenol A, phosgene, and powdery polycarbonate oligomer having an average degree of polymerization of 7 obtained from phenol as a molecular weight regulator by a conventional method, potassium perfluoro-n-butanesulfonate and the following formula:
【００２０】[0020]
【化５】 [Chemical 5]
【００２１】の有機リン酸ジエステルと下記式Organophosphoric acid diester of
【００２２】[0022]
【化６】 [Chemical 6]
【００２３】の有機リン酸ジエステルのカリウム塩を
２：８の重量割合であらかじめ混合した混合物を、表１
記載の量タンブラーにより３０分間混合し、１２０℃で
４時間乾燥した後、３０mmφの一軸ルーダー［ナカタニ
機械（株）製 VSK−３０］によりシリンダー温度２９０
℃で押出してペレット化した。A mixture prepared by preliminarily mixing the potassium salt of the organic phosphoric acid diester of 2 in a weight ratio of 2: 8 is shown in Table 1.
After mixing for 30 minutes with a tumbler in the indicated amount and drying for 4 hours at 120 ° C, a cylinder temperature of 290 was obtained with a uniaxial ruder of 30 mmφ [VSK-30 manufactured by Nakatani Machinery Co., Ltd.].
It was extruded at 0 ° C and pelletized.
【００２４】得られたペレットを１２０℃の熱風循環式
乾燥機により５時間乾燥した後、射出成形機［住友重機
械工業（株）製ネスタール（サイキャップ４８０／１５
０)]により樹脂温度２９０〜３１０℃、金型温度１００
℃、保持圧力１, ０００ kgf／cm2 、射出速度６５mm／
秒、成形サイクル５５秒（冷却３０秒、射出２秒、保持
圧時間１０秒）で試験片を成形し、得られた試験片を用
いて燃焼性及び色調を測定しその結果を表１に示した。
なお表１では芳香族ポリカーボネート樹脂を「PC」、ガ
ラス短繊維を「GF」、ポリカーボネートオリゴマーを
「PC型難燃剤」、パーフロロ−n-ブタンスルホン酸カリ
ウムを「SK難燃剤」、有機リン酸ジエステルと有機リン
酸ジエステルのカリウム塩の混合物を「 p混合物」と表
示した。The pellets thus obtained were dried by a hot air circulation dryer at 120 ° C. for 5 hours, and then an injection molding machine [NESTAL manufactured by Sumitomo Heavy Industries, Ltd. (CYCAP 480/15
0)], the resin temperature is 290 to 310 ° C., and the mold temperature is 100.
℃, holding pressure 1,000 kgf / cm 2 , injection speed 65 mm /
Seconds, a molding cycle of 55 seconds (cooling 30 seconds, injection 2 seconds, holding pressure time 10 seconds), the test piece was molded, and the flammability and color tone were measured. The results are shown in Table 1. It was
In Table 1, aromatic polycarbonate resin is "PC", glass short fiber is "GF", polycarbonate oligomer is "PC type flame retardant", potassium perfluoro-n-butanesulfonate is "SK flame retardant", organic phosphoric acid diester. The mixture of and the potassium salt of the organic phosphoric acid diester was designated as "p mixture".
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明によれば、優れた難燃性を有し且
つ黄変による光学特性の低下がなく、更に腐食性の強い
ガスを発生しない、特に液晶表示のバックライト用に適
する難燃性ポリカーボネート樹脂組成物を提供すること
が可能になり、その奏する工業的効果は格別なものであ
る。EFFECTS OF THE INVENTION According to the present invention, it has excellent flame retardancy, does not deteriorate optical characteristics due to yellowing, and does not generate highly corrosive gas, and is particularly suitable for a backlight of liquid crystal display. It becomes possible to provide a flammable polycarbonate resin composition, and the industrial effect exerted by the composition is exceptional.
Claims (1)
０，０００のハロゲン非含有ポリカーボネート樹脂８０
〜９８重量％、 (B)微粉状炭酸カルシウム１〜１９重量
％及び (c)ガラス短繊維１〜１９重量％からなり、 (B)
成分と (c)成分の合計量が２０重量％を越えない樹脂組
成物１００重量部に、 (D)下記一般式［１］及び［２］ 【化１】 【化２】 ［式中、Ｘは水素原子又はハロゲン原子であり、Ｍはア
ルカリ金属である。］で表される有機リン酸ジエステル
及び有機リン酸ジエステルのアルカリ金属塩の混合物を
０．００１〜１重量部配合してなる難燃性ポリカーボネ
ート樹脂組成物。1. The (A) viscosity average molecular weight is 13,000 to 4
10,000 Halogen-Free Polycarbonate Resin 80
.About.98% by weight, (B) 1 to 19% by weight of finely divided calcium carbonate, and (c) 1 to 19% by weight of glass short fibers, (B)
100 parts by weight of the resin composition in which the total amount of the component and the component (c) does not exceed 20% by weight, (D) the following general formulas [1] and [2] [Chemical 2] [In the formula, X is a hydrogen atom or a halogen atom, and M is an alkali metal. ] The flame-retardant polycarbonate resin composition which mix | blends 0.001 to 1 weight part of the mixture of the organic phosphoric acid diester and the alkali metal salt of an organic phosphoric acid diester represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5003273A JPH06207088A (en) | 1993-01-12 | 1993-01-12 | Flame-retardant polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5003273A JPH06207088A (en) | 1993-01-12 | 1993-01-12 | Flame-retardant polycarbonate resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06207088A true JPH06207088A (en) | 1994-07-26 |
Family
ID=11552844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5003273A Pending JPH06207088A (en) | 1993-01-12 | 1993-01-12 | Flame-retardant polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06207088A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7067074B2 (en) * | 2000-04-10 | 2006-06-27 | Kureha Corporation | Near-infrared-absorbing composition and optical material |
| JP2012246369A (en) * | 2011-05-26 | 2012-12-13 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded form thereof |
-
1993
- 1993-01-12 JP JP5003273A patent/JPH06207088A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7067074B2 (en) * | 2000-04-10 | 2006-06-27 | Kureha Corporation | Near-infrared-absorbing composition and optical material |
| JP2012246369A (en) * | 2011-05-26 | 2012-12-13 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and molded form thereof |
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