JPH01129011A - Molding material - Google Patents
Molding materialInfo
- Publication number
- JPH01129011A JPH01129011A JP28540987A JP28540987A JPH01129011A JP H01129011 A JPH01129011 A JP H01129011A JP 28540987 A JP28540987 A JP 28540987A JP 28540987 A JP28540987 A JP 28540987A JP H01129011 A JPH01129011 A JP H01129011A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- wholly aromatic
- thermoplastic
- molding material
- weight
- 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
- 239000012778 molding material Substances 0.000 title claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 66
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 35
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 35
- 229920001225 polyester resin Polymers 0.000 claims abstract description 27
- 239000004645 polyester resin Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920001400 block copolymer Polymers 0.000 claims abstract description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 abstract description 30
- 230000003287 optical effect Effects 0.000 abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001412 amines Chemical class 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 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 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- UDKBLXVYLPCIAZ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-3,6-di(propan-2-yl)phenyl]phenol Chemical compound C=1C=C(O)C=CC=1C=1C(C(C)C)=CC=C(C(C)C)C=1C1=CC=C(O)C=C1 UDKBLXVYLPCIAZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- -1 and among these Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、その成形物が優れた透明性を有し、吸湿性が
低く、かつ、光学的歪みが非常に小さい、主として光学
機器用の製造材料として有用な成形材料に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a molded product having excellent transparency, low hygroscopicity, and very small optical distortion. The present invention relates to a molding material useful primarily as a manufacturing material for optical equipment.
（従来技術及びその問題点）
光学的機器用の成形物の製造原料として用いられる成形
材料としては、透明性に優れ、吸湿性が低く、かつ、光
学的歪みの特に小°さいことが要求される場合が多い、
しかしながら、かかる条件を、充分に満たし得る成形材
料は見出だされていない。(Prior art and its problems) Molding materials used as raw materials for manufacturing molded products for optical devices are required to have excellent transparency, low hygroscopicity, and particularly low optical distortion. In many cases,
However, no molding material has been found that satisfactorily satisfies these conditions.
（発明が解決しようとする問題点）
本発明は、光学的機器用の成形材料における上記の問題
点を解決し、透明性に優れ、吸湿性が低く、かつ、光学
的歪みの特に小さい成形物を得ることができる光学的機
器用の成形材料を提供することを目的とするものである
。(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems in molding materials for optical devices, and provides a molded product with excellent transparency, low hygroscopicity, and particularly small optical distortion. The object of the present invention is to provide a molding material for optical equipment that can obtain the following properties.
［発明の構成］
（問題点を解決するための手段及び作用）本発明の成形
材料は、熱可塑性全芳香族ポリエステル及びスチレン系
重合体のブロック共重合体である熱可塑性変性全芳香族
ポリエステル樹脂から構成される成形材料であって、
前記熱可塑性変性全芳香族ポリエステル樹脂中における
スチレン系重合体の含有量が１０〜５５重量％であるこ
とを特徴とする特
本発明の成形材料を構成する熱可塑性変性全芳香族ポリ
エステル樹脂は、熱可塑性全芳香族ポリエステルに、ス
チレン系モノマー又はスチレン系重合体を反応せしめ、
化学的に結合せしめることにより製造することができる
。[Structure of the invention] (Means and effects for solving the problems) The molding material of the present invention is a thermoplastic modified wholly aromatic polyester resin which is a block copolymer of a thermoplastic wholly aromatic polyester and a styrene polymer. The molding material of the present invention is characterized in that the content of the styrene polymer in the thermoplastic modified wholly aromatic polyester resin is 10 to 55% by weight. Thermoplastic modified wholly aromatic polyester resin is produced by reacting a thermoplastic wholly aromatic polyester with a styrenic monomer or a styrenic polymer,
It can be manufactured by chemically bonding.
熱可塑性変性全芳香族ポリエステル樹脂の製造に用いる
熱可塑性全芳香族ポリエステル（以下、単に「全芳香族
ポリエステル」と略記する）は、芳香族ジカルボン酸と
芳香族ジヒドロキシ化合物とを反応させることにより得
られる重合体である。The thermoplastic wholly aromatic polyester (hereinafter simply referred to as "wholly aromatic polyester") used in the production of the thermoplastic modified wholly aromatic polyester resin is obtained by reacting an aromatic dicarboxylic acid with an aromatic dihydroxy compound. It is a polymer that can be used.
ここで用いる芳香族ジカルボン酸としては、テレフタル
酸、イソフタル酸、核ハロゲン置換テレフタル酸、イソ
フタル酸などを例示することができ、これらの中でもテ
レフタル酸又はイソフタル酸が好ましい。Examples of the aromatic dicarboxylic acid used here include terephthalic acid, isophthalic acid, nuclear halogen-substituted terephthalic acid, and isophthalic acid, and among these, terephthalic acid and isophthalic acid are preferred.
芳香族ジヒドロキシ化合物としては、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」と略記する）、テトラメチルビスフェノールＡ
、テトラブロモビスフェノールＡ、ビス（４−ヒドロキ
シフェニル）−ｐ−ジイソプロピルベンゼン、ハイ下ロ
キノン、レゾルシノール、４．４′−ジヒドロキシジフ
ェニルなどを例示することができ、これらの中でも特に
ビスフェノールＡが好ましい。As the aromatic dihydroxy compound, 2,2-bis(4
-Hydroxyphenyl)propane (hereinafter abbreviated as "bisphenol A"), tetramethylbisphenol A
, tetrabromobisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, and 4,4'-dihydroxydiphenyl, among which bisphenol A is particularly preferred.
かかる全芳香族ポリエステルとしては、夛ルバーミエー
ションクロマトグラフィー（ＧＰＣ）により測定した重
量平均分子量が、１５．０００〜ｔｏｏ、ｏｏｏのもの
が好ましい。Such wholly aromatic polyesters preferably have a weight average molecular weight of 15.000 to too, ooo as measured by concentration chromatography (GPC).
全芳香族ポリエステルとしては、市販されている゛°Ｕ
ポリマーｒＵ−１００Ｊ” （商品名：ユニチカ■製
）を例示することができる。As wholly aromatic polyester, commercially available ゛°U
Polymer rU-100J" (trade name: manufactured by Unitika ■) can be exemplified.
熱可塑性変性全芳香族ポリエステル樹脂の製造に際して
全芳香族ポリエステルに反応せしめるスチレン系モノマ
ーとしては、スチレン、α−メチルスチレン、ｐ−メチ
ルスチレン及び核ハロゲン置換スチレンなどを例示する
ことができる。これらのスチレン系七ノ マーは、単独
でもしくは２種以上を組合わせて用いることができる。Styrene, α-methylstyrene, p-methylstyrene, nuclear halogen-substituted styrene, and the like can be exemplified as the styrene monomer reacted with the wholly aromatic polyester in producing the thermoplastic modified wholly aromatic polyester resin. These styrene heptanomers can be used alone or in combination of two or more.
また、熱可塑性変性全芳香族ポリエステル樹脂の製造に
際しては、必要に応じて金子ツマー使用量の１０重量％
を超えない量の、スチレン系モノマーと共重合可能な他
の不飽和上ツマ−を単独で又は組合わせて用いることが
できる。かかる不飽和モノマーとしては、メチルメタク
リレート、アクリロニトリル、ブチルメタクリレート、
メチルアクリレートなどを例示することができる。In addition, in the production of thermoplastic modified wholly aromatic polyester resin, if necessary, 10% by weight of the amount of Kaneko Zuma used may be added.
Other unsaturated monomers copolymerizable with the styrenic monomer may be used alone or in combination in amounts not exceeding . Such unsaturated monomers include methyl methacrylate, acrylonitrile, butyl methacrylate,
Examples include methyl acrylate.
また、熱可塑性変性全芳香族ポリエステル樹脂の製造に
際して全芳香族ポリエステルに反応せしめるスチレン系
重合体は、上記のスチレン系モノマー及び必要に応じて
他のモノマーを重合せしめることにより得ることができ
る。In addition, the styrenic polymer to be reacted with the wholly aromatic polyester during the production of the thermoplastic modified wholly aromatic polyester resin can be obtained by polymerizing the above-mentioned styrenic monomer and, if necessary, other monomers.
かかるスチレン系重合体は、ＧＰＣによる重量平均分子
量が５０，０００〜３００．０００の範囲内であること
が好ましい、この分子量が、あまり小さすぎる場合は、
得られる成形材料が光学的歪みが小さいことなどの優れ
た光学的性質を保持することができず、また、あまり分
子量が大きすぎる場合は、得られる成形材料の成形性が
低下することから好ましくない。It is preferable that such a styrenic polymer has a weight average molecular weight determined by GPC within the range of 50,000 to 300,000. If this molecular weight is too small,
If the obtained molding material cannot maintain excellent optical properties such as small optical distortion, and if the molecular weight is too large, the moldability of the obtained molding material will decrease, which is undesirable. .
次に、本発明の成形材料を構成する熱可塑性変性全芳香
族ポリエステル樹脂の製造方法について２つの製造例を
掲げて説明する。Next, a method for producing the thermoplastic modified wholly aromatic polyester resin constituting the molding material of the present invention will be described with reference to two production examples.
（１）まず、全芳香族ポリエステルをテトラヒドロフラ
ンに溶解させたものに、アリルアミンを添加し、反応さ
せることにより、全芳香族ポリエステルの末端に反応性
のビニル基を導入し、次いで、スチレン系モノマーを添
加し、重合させる方法を掲げることができる。(1) First, allylamine is added to a fully aromatic polyester dissolved in tetrahydrofuran and reacted to introduce a reactive vinyl group to the end of the fully aromatic polyester, and then a styrene monomer is added to the solution. Methods of adding and polymerizing can be listed.
全芳香族ポリエステルは、塩基性化合物の存在下では不
安定であり、特に、アルカリや有機アミンなどの存在に
より容易に主鎖が切断されてしまう、しかしながら、有
機アミンとしてアリルアミンに代表される不飽和炭素二
重結合を有するアミンを反応系に存在させることにより
、主鎖の切断末端に反応性のビニル基を導入することが
できる。この方法で用いるアリルアミンの量は、全芳香
族ポリエステルｔｇ当たりアリルアミンが０．１−１０
１Ｌｕの範囲にあることが好ましい。Fully aromatic polyesters are unstable in the presence of basic compounds, and the main chain is easily cleaved especially in the presence of alkalis or organic amines. However, unsaturated organic amines such as allylamine By allowing an amine having a carbon double bond to be present in the reaction system, a reactive vinyl group can be introduced to the cut end of the main chain. The amount of allylamine used in this method is 0.1-10 allylamine per tg of fully aromatic polyester.
It is preferably in the range of 1 Lu.
この値があまり小さすぎる場合には、熱可塑性変性全芳
香族ポリエステル樹脂の収量が少なくなり、また、あま
り大きすぎる場合には全熱可塑性変性全芳香族ポリエス
テル樹脂中の芳香族ポリエステル連鎖が短くなりすぎる
ために成形材料の耐衝撃性が低下する。If this value is too small, the yield of thermoplastically modified wholly aromatic polyester resin will be low, and if this value is too large, the aromatic polyester chains in the thermoplastically modified wholly aromatic polyester resin will be shortened. Because of this, the impact resistance of the molding material decreases.
全芳香族ポリエステルとアリルアミンは、全芳香族ポリ
エステルをテトラヒドロフランに０．０５〜０．２ｇ／
ｍｊＬの割合で溶解させた溶液に、所定量のアリルアミ
ンを添加し、攪拌したのち、オートクレーブ中で、９０
℃で２時間反応させる０次いで、この反応液に、重合後
のメタクリル酸エステル系重合体の含有量が１０〜５５
重量％になる量のスチレン系モノマーを添加し、反応系
内を窒素ガスで置換したのち、９０℃で７時間重合反応
を行う、この重合反応に際しては、重合触媒を使用する
ことが好ましい、この重合触媒は、スチレン系モノマー
に溶解するものであれば如何なるものであってもよいが
１例えば、過酸化ベンゾイル、アゾビスイソブチロニト
リルなどが好ましい。For the fully aromatic polyester and allylamine, add the fully aromatic polyester to tetrahydrofuran at 0.05 to 0.2 g/
A predetermined amount of allylamine was added to the solution dissolved in mjL ratio, stirred, and then dissolved in an autoclave at 90%
℃ for 2 hours. Then, the content of the methacrylic acid ester polymer after polymerization is 10 to 55%.
After adding a styrene monomer in an amount of % by weight and purging the reaction system with nitrogen gas, a polymerization reaction is carried out at 90°C for 7 hours. It is preferable to use a polymerization catalyst during this polymerization reaction. The polymerization catalyst may be any catalyst as long as it is soluble in the styrene monomer, but preferred examples include benzoyl peroxide and azobisisobutyronitrile.
次いで、反応終了後、生成した熱可塑性変性全芳香族ポ
リエステル樹脂を１分離し、洗浄したのち、乾燥する。Then, after the reaction is completed, the produced thermoplastic modified wholly aromatic polyester resin is separated, washed, and then dried.
（２）もう一方の方法としては、スチレン系モノマーに
所定量のアリルアミンを添加、混合したのち重合反応を
行い、得られたスチレン系重合体と全芳香族ポリエステ
ルとの所定割合を溶融混合する方法を掲げることができ
る。(2) The other method is to add and mix a predetermined amount of allylamine to a styrene monomer, perform a polymerization reaction, and melt-mix a predetermined ratio of the obtained styrenic polymer and wholly aromatic polyester. can be raised.
スチレン系モノマーとアリルアミンの混合割合は、スチ
レン系モノマー１００重量部に対してアリルアミンが０
．０１〜０．１重量部が好ましい、ここでアリルアミン
の量があまり少なすぎる場合には、熱可塑性変性全芳香
族ポリエステルの収量が低く、また、あまり多すぎる場
合には、スチレン系重合体の分子量を充分に高めること
ができず、熱可塑性変性全芳香族ポリエステルが架橋し
てしまうために好ましくない。The mixing ratio of styrene monomer and allylamine is 0 parts by weight of allylamine per 100 parts by weight of styrene monomer.
．． If the amount of allylamine is too small, the yield of the thermoplastically modified wholly aromatic polyester will be low, and if it is too large, the molecular weight of the styrenic polymer will be reduced. It is not preferable because the thermoplastically modified wholly aromatic polyester cannot be sufficiently increased and the thermoplastically modified wholly aromatic polyester is crosslinked.
重合反応時には上記の重合触媒を用いることが好ましく
、また、反応系は窒素ガスで置換する。It is preferable to use the above polymerization catalyst during the polymerization reaction, and the reaction system is purged with nitrogen gas.
重合は、６０〜１１０℃で２〜１０時間行う。Polymerization is carried out at 60-110°C for 2-10 hours.
得られたスチレン系重合体と全芳香族ポリエステルとの
溶融混合は、２６０〜３４０℃で行なう、このように溶
融混合を行うことにより、スチレン系重合体中のアリル
アミン由来の７ミノ基によってポリエステル連鎖を一部
切断しながら、スチレン系重合体をポリエステル連鎖に
化学的に結合させ、最終的に熱可塑性変性全芳香族ポリ
エステルを生成せしめることができる。なお、熱可塑性
変性全芳香族ポリエステルの製造方法は上記方法のみに
限定されるものではなく、またアリルアミンの使用のみ
に限定されるものではい。The obtained styrenic polymer and wholly aromatic polyester are melt-mixed at 260 to 340°C. By melt-mixing in this way, the polyester chain is formed by the 7-mino group derived from allylamine in the styrenic polymer. The styrenic polymer can be chemically bonded to the polyester chain while partially cutting the polyester, and finally a thermoplastic modified wholly aromatic polyester can be produced. The method for producing the thermoplastically modified wholly aromatic polyester is not limited to the above method, nor is it limited to the use of allylamine.
このようにして得られる熱可塑性変性全芳香族ポリエス
テル中のスチレン系重合体の含有量は、１０〜５５重量
％であり、好ましくは２５〜５０重量％である。この含
有量が１０重量％未満の場合には、光学的歪みの小さい
成形材料を得ることができず、また、５５重量％を超え
る場合には機械的特性の低下、特に耐衝撃性の低下が顕
著になるために好ましくない。The content of the styrenic polymer in the thermoplastic modified wholly aromatic polyester thus obtained is 10 to 55% by weight, preferably 25 to 50% by weight. If this content is less than 10% by weight, it is impossible to obtain a molding material with small optical distortion, and if it exceeds 55% by weight, mechanical properties may deteriorate, especially impact resistance. Undesirable because it becomes noticeable.
熱可塑性変性全芳香族ポリエステル樹脂は、ＧＰＣ法に
よる重量平均分子量が２０．０００〜１５０．０００、
好ましくは°２０．０００〜１００．０００ものがよい
、ここで分子量があまり小さすぎる場合には、成形材料
の成形後の機械的特性が低下し、また、あまり大きすぎ
る場合には光学的歪みの小さい成形材料を得ることがで
きない。The thermoplastic modified wholly aromatic polyester resin has a weight average molecular weight of 20.000 to 150.000 by GPC method,
Preferably, the molecular weight is between 20,000° and 100,000°. If the molecular weight is too small, the mechanical properties of the molding material after molding will deteriorate, and if it is too large, optical distortion may occur. It is not possible to obtain small molding materials.
このようにして得られた熱可塑性変性全芳香族ポリエス
テル樹脂は、全芳香族ポリエステルとスチレン系重合体
とのブロック共重合体であり、すなわち再構成成分は、
化学的に結合しているものである０本来、全芳香族ポリ
エステルとスチレン系重合体は、相溶性が悪いことから
、青成分を単に混合した場合には均質な成形材料を得る
ことができないが、上記のとおり、本発明で用いる熱可
塑性変性全芳香族ポリエステル樹脂においては、全芳香
族ポリエステルとスチレン系重合体が化学的に結合した
状態で存在していることから、かかる問題は生じない。The thermoplastic modified wholly aromatic polyester resin thus obtained is a block copolymer of a wholly aromatic polyester and a styrene polymer, that is, the reconstituting components are:
Since fully aromatic polyester and styrene polymer are chemically bonded, they are not compatible with each other, so it is not possible to obtain a homogeneous molding material by simply mixing the blue component. As mentioned above, in the thermoplastic modified wholly aromatic polyester resin used in the present invention, such a problem does not occur because the wholly aromatic polyester and the styrene polymer exist in a chemically bonded state.
本発明の成形材料は、かかる熱可塑性変性全芳香族ポリ
エステル樹脂から構成されるが、必要に応じて、化学的
に結合していない全芳香族ポリエステル及び／又はスチ
レン系重合体を、製造時の未反応物として又は製造後の
添加物として、２５重量％以下の範囲内で存在させるこ
ともできる。The molding material of the present invention is composed of such a thermoplastic modified wholly aromatic polyester resin, but if necessary, a wholly aromatic polyester and/or styrene polymer that is not chemically bonded may be added to the resin during production. It can also be present in an amount up to 25% by weight, either as an unreacted product or as an additive after production.
また、熱可塑性変性全芳香族ポリエステル樹脂の熱分解
による着色、透明性の低下を防止する目的から亜リン酸
エステル類、ヒンダントフェノール類を、熱可塑性変性
全芳香族ポリエステルに対して０．０１−１重量％配合
することができる。In addition, for the purpose of preventing coloration and reduction in transparency due to thermal decomposition of the thermoplastic modified wholly aromatic polyester resin, phosphite esters and hintant phenols are added at 0.01% of the thermoplastic modified wholly aromatic polyester resin. -1% by weight can be blended.
ここで用いる亜リン酸エステル類としては、トリフェニ
ルホスファイト、トリデシルホスファイト、トリブチル
ホスファイト、トリース（２−エチルヘキシル）ホスフ
ァイト、トリクレジルホスファイトなどを例示すること
ができる。ヒンダントフェノール類としては、２，６−
シーｔｅｒｔ−ブチル、４−メチルフェノール、アイオ
ノックスー１００．３３０（商品名；シェル化学■製）
、イルガノックス−２４５，１０７６（商品名；チバガ
イギー■製）、ドパノール−ＣＡ（商品名；アイ・シー
・アイ■製）、ヨシノックス−ＢＢ（商品名；吉富製薬
■製）などを例示することができる。Examples of the phosphites used here include triphenyl phosphite, tridecyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, and tricresyl phosphite. Hindant phenols include 2,6-
Tert-butyl, 4-methylphenol, ionox-100.330 (product name; manufactured by Shell Chemical ■)
, Irganox-245,1076 (trade name; manufactured by Ciba Geigy ■), Dopanol-CA (trade name; manufactured by ICI ■), Yoshinox-BB (trade name; manufactured by Yoshitomi Pharmaceutical ■), etc. can.
かかる亜リン酸エステル類等の熱可塑性変性全芳香族ポ
リエステル樹脂への配合方法としては、例えば、トライ
ブレンド法、押出し機によりペレット化する際に溶融混
合する方法、前記溶融混合法により亜リン酸エステル類
等の含有量の高いマスターペレット及び亜リン酸エステ
ル類等を含有しない熱可塑性変性全芳香族ポリエステル
樹脂のみのペレットを製造し、両者をトライブレンドす
る方法を適用することができる。Methods for blending such phosphorous acid esters into thermoplastic modified wholly aromatic polyester resins include, for example, the triblend method, the method of melt-mixing when pelletizing with an extruder, and the method of blending phosphorous esters with the thermoplastic modified wholly aromatic polyester resin. A method can be applied in which master pellets with a high content of esters and the like and pellets of thermoplastic modified wholly aromatic polyester resin containing no phosphite esters are produced and the two are triblended.
（実施例） 以下、実施例を掲げ、本発明をさらに詳しく説明する。(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.
なお、以下において「部」及び１％」は、いずれも重量
基準である。In addition, in the following, both "part" and "1%" are based on weight.
実施例１
まず、全芳香族ポリエステル（パＵポリマーｒＵ−１０
０Ｊ”；ユニチカ■製）２０ｇを５００ｍＪ１ビーカー
中で３００ｍＭのテトラヒドロフランに溶解させた。次
いで、４０ｔＬｌのアリルアミンを添加し、攪拌したの
ち、内容積５００ｍ１のオートクレーブ中に入れ、９０
℃で、２時間反応させた。反応終了後、室温まで放冷し
たのち、攪拌機付反応器に内容物を入れ、さらにスチレ
ン１５ｇ及びアゾビスイソブチロニトリルｏ 、０５ｇ
を仕込んだ、その後、反応器内部を窒素ガスで置換し、
９０℃の湯浴中で７時間重合反応を行った。反応路、了
後、反応液中にメタノールを添加して熱可塑性変性全芳
香族ポリエステル樹脂を沈澱させた。その後、沈澱物を
採取し、９０℃で一夜真空乾燥して、最終的に３３ｇの
本発明の成形材料である熱可塑性変性全芳香族ポリエス
テル樹脂（ポリエステルＡ）を得た。Example 1 First, fully aromatic polyester (P-U polymer rU-10
0J" (manufactured by Unitika) was dissolved in 300mM tetrahydrofuran in a 500mJ1 beaker. Next, 40tLl of allylamine was added and stirred, then placed in an autoclave with an internal volume of 500m1, and
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, the contents were allowed to cool to room temperature, and then the contents were placed in a reactor equipped with a stirrer, and 15 g of styrene and 0.5 g of azobisisobutyronitrile were added.
After that, the inside of the reactor was replaced with nitrogen gas,
The polymerization reaction was carried out in a 90°C water bath for 7 hours. After completing the reaction, methanol was added to the reaction solution to precipitate a thermoplastic modified wholly aromatic polyester resin. Thereafter, the precipitate was collected and vacuum dried at 90° C. overnight to finally obtain 33 g of a thermoplastic modified wholly aromatic polyester resin (polyester A) which is the molding material of the present invention.
得られた熱可塑性変性全芳香族ポリエステル樹脂の重量
平均分子量（ＧＰＣ法による。以下、同様である。）は
、８４，０００であり、そのポリスチレンの含有ｉ （
ＮＭＲ分析による。以下、同様である。）は３９％であ
った。The weight average molecular weight (based on GPC method; the same applies hereinafter) of the obtained thermoplastic modified wholly aromatic polyester resin was 84,000, and the polystyrene content i (
By NMR analysis. The same applies hereafter. ) was 39%.
実施例２
アリルアミンの使用量を６５１ＬＪｌにした以外は、実
施例１と同様にして３０ｇの本発明の成形材料である熱
可塑性変性全芳香族ポリエステル（ポリエステルＢ）を
得た。得られた樹脂の重量平均分子量は９５，０００で
あり、ポリスチレンの含有量は３４％であった。Example 2 30 g of a thermoplastically modified wholly aromatic polyester (polyester B), which is a molding material of the present invention, was obtained in the same manner as in Example 1, except that the amount of allylamine used was 651 LJl. The weight average molecular weight of the resulting resin was 95,000, and the polystyrene content was 34%.
比較例１
スチレンモノマーの使用量を３ｇにした以外は実施例１
と同様にして２１．５ｇの熱可塑性変性全芳香族ポリエ
ステル（ポリエステルＣ）を得た。得られた樹脂の重量
平均分子量は７５．０００であり、ポリスチレンの含有
量は６％であった。Comparative Example 1 Example 1 except that the amount of styrene monomer used was 3 g
In the same manner as above, 21.5 g of thermoplastic modified wholly aromatic polyester (Polyester C) was obtained. The weight average molecular weight of the obtained resin was 75.000, and the polystyrene content was 6%.
実施例３〜６及び比較例２〜５
下記表に示す各全熱可塑性変性全芳香族ポリエステル樹
脂に対して亜リン酸トリフェニルを１００ ｐ ｐｍ添
加して種々の成形材料を得た。Examples 3 to 6 and Comparative Examples 2 to 5 Various molding materials were obtained by adding 100 ppm of triphenyl phosphite to each fully thermoplastic modified fully aromatic polyester resin shown in the table below.
次いで、得られた成形材料を用い、射出成形機（日本製
鋼所■製、ＮＴ−３５Ａ）により、表に示す成形条件で
厚さ１．３ｍｍ、幅１ｃｍ及び長さ５ｃｍの試験片を成
形した。同時に高化式フローテスターによって、２９０
℃、せん断速度１０３ｓｅｃ’におけるみかけの溶融粘
度η を溶融流動性の目安とした。複屈折については。Next, using the obtained molding material, a test piece with a thickness of 1.3 mm, a width of 1 cm, and a length of 5 cm was molded using an injection molding machine (manufactured by Japan Steel Works, Ltd., NT-35A) under the molding conditions shown in the table. . At the same time, 290
The apparent melt viscosity η at a shear rate of 103 sec' at a temperature of 103 sec' was used as a measure of melt fluidity. Regarding birefringence.
試験片の根元（溶融樹脂の入口方向）から２．５ｃｍの
位置での複屈折（Δｎｚ）をカールツアイス偏光ＪＩｉ
微鏡により測定した数値で評価した。これらの結果を表
に示す。Birefringence (Δnz) at a position 2.5 cm from the base of the test piece (inlet direction of molten resin) is calculated using Carl Zeiss polarization JIi.
Evaluation was made using numerical values measured using a microscope. These results are shown in the table.
［発明の効果］
本発明の成形材料から得られる成形物は、透明性に優れ
ており、また吸湿性が低く、光学的歪みも非常に小さい
ものである。[Effects of the Invention] Molded products obtained from the molding material of the present invention have excellent transparency, low hygroscopicity, and very small optical distortion.
Claims (1)
ブロック共重合体である熱可塑性変性全芳香族ポリエス
テル樹脂からなる成形材料であって、 前記熱可塑性変性全芳香族ポリエステル樹脂中における
スチレン系重合体の含有量が１０〜５５重量％であるこ
とを特徴とする成形材料。[Scope of Claims] A molding material comprising a thermoplastic modified wholly aromatic polyester resin which is a block copolymer of a thermoplastic wholly aromatic polyester and a styrene polymer, wherein the thermoplastic modified wholly aromatic polyester resin comprises: A molding material characterized in that the content of the styrenic polymer is 10 to 55% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28540987A JPH01129011A (en) | 1987-11-13 | 1987-11-13 | Molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28540987A JPH01129011A (en) | 1987-11-13 | 1987-11-13 | Molding material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01129011A true JPH01129011A (en) | 1989-05-22 |
Family
ID=17691142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28540987A Pending JPH01129011A (en) | 1987-11-13 | 1987-11-13 | Molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01129011A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0481817A2 (en) * | 1990-10-18 | 1992-04-22 | Nippon Steel Corporation | Process for preparing aromatic polyester-polystyrene block copolymers |
| EP0482935A2 (en) * | 1990-10-24 | 1992-04-29 | Unitika Ltd. | Process for preparing aromatic polyester-polystyrene block copolymers |
| US5314954A (en) * | 1990-10-24 | 1994-05-24 | Unitika Ltd. | Process for preparing aromatic polyester-polystyrene block copolymers |
| US6642322B2 (en) * | 1998-01-21 | 2003-11-04 | The University Of North Carolina At Chapel Hill | Methods of making telechelic oligomers, methods of making block copolymers, and novel block copolymers |
-
1987
- 1987-11-13 JP JP28540987A patent/JPH01129011A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0481817A2 (en) * | 1990-10-18 | 1992-04-22 | Nippon Steel Corporation | Process for preparing aromatic polyester-polystyrene block copolymers |
| US5256735A (en) * | 1990-10-18 | 1993-10-26 | Nippon Steel Corporation | Process for preparing aromatic polyester-polystyrene block copolymers |
| EP0482935A2 (en) * | 1990-10-24 | 1992-04-29 | Unitika Ltd. | Process for preparing aromatic polyester-polystyrene block copolymers |
| US5314954A (en) * | 1990-10-24 | 1994-05-24 | Unitika Ltd. | Process for preparing aromatic polyester-polystyrene block copolymers |
| US6642322B2 (en) * | 1998-01-21 | 2003-11-04 | The University Of North Carolina At Chapel Hill | Methods of making telechelic oligomers, methods of making block copolymers, and novel block copolymers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2958673A (en) | Graft polymer and method of making | |
| JPH0139688B2 (en) | ||
| JPH01129011A (en) | Molding material | |
| JPS6149325B2 (en) | ||
| JPS60141753A (en) | Low-profile unsaturated polyester resin composition | |
| US3297794A (en) | Polymer product comprising methacrylic ester and alpha-methylstyrene, and processes of producing same | |
| TWI732307B (en) | Vinylidene substituted aromatic monomer and cyclic (meth)acrylate ester polymers | |
| KR910008326B1 (en) | Process for the preparation of methacrylimide group containing polymer | |
| KR100841927B1 (en) | Triphenyl phosphate-grafted polymer resin having butadiene moiety and preparing process thereof | |
| EP0913408B1 (en) | Process for making poly(alkyl (meth)acrylate) rubber latex | |
| CN113015767A (en) | Chain-extended or branched copolymers of vinylidene aromatic monomers with unsaturated compounds having nucleophilic groups | |
| EP0426436A2 (en) | Preparation of ketone containing photodegradable polymers | |
| KR930010235B1 (en) | Polyester/polycarbonate alloy resin composition | |
| JPS63215705A (en) | New methyl methacrylate copolymer and heat-resistant resin composition containing the same | |
| JP2794802B2 (en) | Low shrinkage unsaturated polyester resin composition | |
| US4187259A (en) | Polymer blends with improved hydrolytic stability comprising a linear aromatic polyester and a methacrylate cross-linked acrylate copolymer | |
| JPH0425303B2 (en) | ||
| JPH04266965A (en) | Thermoplastic resin composition | |
| JPS6060111A (en) | Thermoplastic polymer | |
| JP3662055B2 (en) | Styrenic resin composition with excellent thermal stability and processability | |
| JPH01129010A (en) | Molding material | |
| JPH01129012A (en) | Molding material | |
| JPH09255703A (en) | Production of styrene polymer | |
| JP2824265B2 (en) | Styrene resin composition | |
| JPS5891748A (en) | Styrenic resin composition |