JPH0379659A - Molding material for optical application - Google Patents
Molding material for optical applicationInfo
- Publication number
- JPH0379659A JPH0379659A JP1214060A JP21406089A JPH0379659A JP H0379659 A JPH0379659 A JP H0379659A JP 1214060 A JP1214060 A JP 1214060A JP 21406089 A JP21406089 A JP 21406089A JP H0379659 A JPH0379659 A JP H0379659A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- molding material
- gel
- parts
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 19
- 239000012778 molding material Substances 0.000 title claims abstract description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 17
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 17
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 5
- -1 if necessary Chemical compound 0.000 abstract description 3
- 239000006082 mold release agent Substances 0.000 abstract description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 abstract description 2
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 abstract description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical compound CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 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
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 241000519995 Stachys sylvatica Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- URFNSYWAGGETFK-UHFFFAOYSA-N 4,4'-Dihydroxybibenzyl Chemical compound C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- 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、光ディスク、レンズ、プリズムなどの光学用
成形品を製造するに好適な耐熱性、成形性などに優れた
ポリカーボネート樹脂の光学用成形材料に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to optical molding of polycarbonate resin having excellent heat resistance and moldability, which is suitable for manufacturing optical molded products such as optical discs, lenses, and prisms. Regarding materials.
最近、ポリカーボネート樹脂は、その透明性、耐熱性、
耐加水分解性、寸法安定性などの特徴を活かして、レン
ズ、光情報ディスク用基板材料等として広く用いられる
ようになって来た。Recently, polycarbonate resin has been improved due to its transparency, heat resistance,
Taking advantage of its characteristics such as hydrolysis resistance and dimensional stability, it has come to be widely used as a substrate material for lenses, optical information disks, etc.
特に、コンパクトディスク（ＣＤ）をはじめ、信号の書
込み、書換えの出来る光情報ディスクは新しいメモリー
材料として大きな期待が寄せられている。光デイスク基
板としての性能の中でレーザー光線を乱反射させる異物
の混入は最も避けるべき問題であり、同様に成形仮定で
生じるポリカーボネートの分解生成物であるゲル状物も
出来るだけ低減させなければならない。このゲル状物の
化学構造についての詳細は不明であるが、ポリカーボネ
ートを塩化メチレンに溶解した場合、不溶物として検出
され光散乱法によって定量することができ、その大きさ
はおよそ０．５〜１０ｕｙＡ程度のものである。In particular, optical information discs, such as compact discs (CDs), on which signals can be written and rewritten, are highly anticipated as new memory materials. In terms of performance as an optical disk substrate, the most important problem to avoid is the inclusion of foreign matter that causes diffuse reflection of laser beams, and similarly, gel-like matter, which is a decomposition product of polycarbonate that occurs during molding, must be reduced as much as possible. The details of the chemical structure of this gel-like substance are unknown, but when polycarbonate is dissolved in methylene chloride, it is detected as an insoluble substance and can be quantified by light scattering, and its size is approximately 0.5 to 10 uyA. It is of a certain degree.
従来のポリカーボネート樹脂では上記のようなゲル状物
が温度３００〜３８０℃のような高温で成形する場合、
樹脂１ｇあたり１０４〜１０５個程度の数発生し、光デ
ィスクとしてのノイズレベル悪化の大きな原因の一つで
あった。With conventional polycarbonate resin, when the above gel-like material is molded at a high temperature of 300 to 380 degrees Celsius,
Approximately 104 to 105 particles were generated per gram of resin, and this was one of the major causes of deterioration in the noise level of optical discs.
このゲル状物の発生を低減させるために種々の熱安定剤
が提案されているが、従来知られている有機ホスファイ
ト、有機ホスホナイトは加水分解性を有し、高温多湿環
境下に長期開明されるとかえって樹脂の加水分解を促進
して、白点の生成を促進するという別の欠点が生じる。Various heat stabilizers have been proposed to reduce the generation of gel-like substances, but conventionally known organic phosphites and organic phosphonites are hydrolyzable and have not been developed for a long time in high-temperature and humid environments. On the contrary, another disadvantage arises in that it accelerates the hydrolysis of the resin and promotes the formation of white spots.
また、有機ホスフィンや有機ホスフィンオキシトはゲル
状物発生の抑制効果は不十分であった。Furthermore, organic phosphine and organic phosphine oxyto had insufficient effect of suppressing the generation of gel-like substances.
本発明は、ポリカーボネート樹脂の加熱溶融時の分解劣
化によるゲル状物の発生を低減させると共に、高温多湿
環境下においてもポリカーボネートの加水分解を促進し
ない安定剤について鋭意検討した結果、完成したもので
ある。The present invention was completed as a result of extensive research into a stabilizer that reduces the generation of gel-like substances due to decomposition and deterioration during heating and melting of polycarbonate resin, and does not promote hydrolysis of polycarbonate even in high-temperature and humid environments. .
即ち、本発明は、粘度平均分子量１２．０００〜３０．
０００のポリカーボネート樹脂１００重量部あたり、下
記一般式（１）で表されるペンタエリスリトールのモノ
−乃至テトラ−チオプロピオネートｏ、ｏｏｉ〜Ｏ０３
重量部を配合してなる光学用成形材料である。That is, the present invention has a viscosity average molecular weight of 12.000 to 30.00.
Per 100 parts by weight of polycarbonate resin of 000, mono- to tetra-thiopropionate of pentaerythritol represented by the following general formula (1) o, ooi to O03
It is an optical molding material made by blending parts by weight.
一般式（１） ： （Ｒ−３−ＣＨ，ＣＨ，Ｃ００Ｃ
Ｈ，）、 Ｃ（ＣＨ，ＯＨ）、。General formula (1): (R-3-CH,CH,C00C
H,), C(CH,OH),.
（式中のＲは互いに同一でも異なっていても良く水素又
は炭素数１〜２２のアルキル基を示し、ｍは１〜４の整
数を示す。）
以下、本発明の構成について説明する。(R in the formula may be the same or different and represent hydrogen or an alkyl group having 1 to 22 carbon atoms, and m represents an integer of 1 to 4.) Hereinafter, the structure of the present invention will be explained.
本発明のポリカーボネート樹脂とは、二価フェノールと
ホスゲンやジフェニルカーボネート等のカーボネート前
駆体との反応により得られるホモ、コーポリカーボネー
ト樹脂、更に分岐化されたもの、末端に長鎖アルキル基
やエステル基を導入したもの：コーモノマーや末端停止
剤として炭素−炭素不飽和二重結合を有するビスフェノ
ールやビニルフェノールなどを用いて得た変性ポリカー
ボネート樹脂にスチレンなどをグラフトしたもの、更に
ホスゲンの一部としてテレフタル酸クロライド、イソフ
タル酸クロライドを用いた一部にエステル結合を有する
もの、又はフェノール性水酸基等をコーモノマーとして
使用してなる変性ポリスチレンにポリカーボネート樹脂
をグラフト重合したものなど何れでも使用可能なものと
して例示され、粘度平均分子量が１２．０００〜３０．
０００程度のものであり、１２．０００〜２３．０００
の領域は射出底形用として、２３．０００〜３０．００
０の領域は押出成形してシート状とし、光ディスクや光
カード基板として使用するに適する。The polycarbonate resin of the present invention is a homo- or co-polycarbonate resin obtained by the reaction of dihydric phenol with a carbonate precursor such as phosgene or diphenyl carbonate, a further branched resin, or a resin with a long-chain alkyl group or ester group at the end. Introduced: Modified polycarbonate resin obtained by using bisphenol, vinylphenol, etc., which have carbon-carbon unsaturated double bonds as a comonomer or terminal capping agent, and grafted with styrene, etc., and terephthalic acid chloride as a part of phosgene. , isophthalic acid chloride with some ester bonds, or modified polystyrene using phenolic hydroxyl groups as a comonomer and graft polymerized with polycarbonate resin. Average molecular weight is 12.000-30.
000, and 12,000 to 23,000
The area is 23.000 to 30.00 for injection bottom type.
The 0 region is extruded into a sheet shape, which is suitable for use as an optical disk or optical card substrate.
ここに、二価フェノールとしては、２．２−ビス（４−
ヒドロキシフェニル）プロパン（＝ビスフェノールＡ）
、ビス（４−ヒドロキシフェニル）メタン、１．２−ビ
ス（４−ヒドロキシフェニル）エタン、２．２−ビス（
４−ヒドロキシフェニル）ブタン、１．１−ビス（４−
ヒドロキシフェニル）−１−フェニルメタン、１゜１−
ビス（４−ヒドロキシフェニル−１，１−ジフェニル）
メタン、１．１−ビス（４−ヒドロキシフェニル）シク
ロヘキサン、ビス（４−ヒドロキシフェニル）エーテル
、ビス（４−ヒドロキシフェニル）スルフィド、ビス（
４−ヒドロキシフェニル）スルホン、さらにこれらのフ
ェニル基に低級アルキル基やハロゲン原子を置換したも
のなどが例示され、特にビスフェノールＡが最も代表的
である。Here, as the dihydric phenol, 2.2-bis(4-
hydroxyphenyl)propane (=bisphenol A)
, bis(4-hydroxyphenyl)methane, 1,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(
4-hydroxyphenyl)butane, 1,1-bis(4-
Hydroxyphenyl)-1-phenylmethane, 1゜1-
Bis(4-hydroxyphenyl-1,1-diphenyl)
Methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(
Examples include 4-hydroxyphenyl) sulfone, and those in which a lower alkyl group or a halogen atom is substituted for these phenyl groups, and bisphenol A is particularly representative.
上記のポリカーボネート樹脂に配合する本発明の上記一
般式（１）で表されるペンタエリスリトールのモノ−乃
至テトラ−チオプロピオネートは、ポリカーボネート樹
脂の加熱溶融時の分解劣化によるゲル状物の発生を低減
させると共に、高温多湿環境下においてもポリカーボネ
ートの加水分解を抑制し白点の発生を抑制する効果を有
するものである。代表的にはペンタエリスリトールテト
ラキス−（β−ラウリル−チオプロピオネート）（＝ス
ミライザーＴＰ−Ｄ 、住友化学■製）が挙げられる。The mono- or tetra-thiopropionate of pentaerythritol represented by the above general formula (1) of the present invention, which is blended into the above polycarbonate resin, prevents the generation of gel-like substances due to decomposition and deterioration during heating and melting of the polycarbonate resin. It also has the effect of suppressing the hydrolysis of polycarbonate and suppressing the generation of white spots even in high temperature and high humidity environments. A typical example is pentaerythritol tetrakis-(β-lauryl-thiopropionate) (=Sumilizer TP-D, manufactured by Sumitomo Chemical ■).
特に、白点防止効果は、光学用材料としての信頼性の向
上にとって重要であり、従来の安定剤においては不十分
なものであった。In particular, the white spot prevention effect is important for improving reliability as an optical material, and conventional stabilizers have been insufficient.
この一般式（１）の化合物の添加量は、ポリカーボネー
ト樹脂１００重量部に対して０．００１〜０．３重量部
であり、０．００１重量部未満ではゲル状物発生を抑制
する効果が不十分であり、０．３重量部を超えて用いる
と高温多湿環境下の劣化を逆に促進するので好ましくな
い。なお、本発明のペンタエリスリトールのモノ−乃至
テトラーチオプロピオネートは、当然に他の亜リン酸、
有機ホスファイト、有機ホスホナイト、立体障害性フェ
ノール系酸化防止剤などと併用してもよいものである。The amount of the compound of general formula (1) added is 0.001 to 0.3 parts by weight per 100 parts by weight of the polycarbonate resin, and if it is less than 0.001 parts by weight, the effect of suppressing the generation of gel-like substances is insufficient. However, if it is used in an amount exceeding 0.3 parts by weight, it is not preferable because it accelerates deterioration in a high temperature and humid environment. Incidentally, the pentaerythritol mono- or tetrathiopropionate of the present invention can naturally be used with other phosphorous acids,
It may be used in combination with organic phosphites, organic phosphonites, sterically hindered phenolic antioxidants, and the like.
本発明の光学用成形材料は上記の成分を必須とするもの
であるが、添加剤として転写性を改良するための離型剤
、その他を添加できる。離型剤としては脂肪酸エステル
、特に多価アルコールの部分エステルや長鎖脂肪酸、パ
ラフィン、シリコーンオイルなどが例示され、特に炭素
数１０〜２２の飽和脂肪酸と多価アルコールとの部分エ
ステル０．０００１〜０．０１重量部と炭素数１０〜３
０の飽和脂肪酸と炭素数３０以下の一価アルコールとの
エステル０．００５〜０．２重量部とを併用して用いる
方法が好ましい。Although the optical molding material of the present invention essentially contains the above-mentioned components, a release agent for improving transferability and others may be added as additives. Examples of mold release agents include fatty acid esters, particularly partial esters of polyhydric alcohols, long-chain fatty acids, paraffin, silicone oil, etc. Particularly partial esters of saturated fatty acids having 10 to 22 carbon atoms and polyhydric alcohols from 0.0001 to 0.01 part by weight and carbon number 10-3
A preferred method is to use a combination of 0.005 to 0.2 parts by weight of an ester of 0 saturated fatty acids and a monohydric alcohol having 30 or less carbon atoms.
以下、実施例等により本発明を説明する。 The present invention will be explained below with reference to Examples.
なお、実施例等中の％、部などは特に断らない限り重量
基準であり、ゲル状物の定量並びに外観及び長期耐湿試
験は下記方法によって測定した。Note that %, parts, etc. in Examples and the like are based on weight unless otherwise specified, and the quantitative determination, appearance, and long-term moisture resistance test of the gel-like material were measured by the following method.
ベレットおよび成形品をそれぞれＩｇ／１０（７の濃度
で塩化メチレンに溶解し、光散乱法で不溶異物として定
量し、その差（Δ）を成形時のゲル状物発生数とした。The pellet and the molded article were each dissolved in methylene chloride at a concentration of Ig/10 (7), and the insoluble foreign matter was quantified by a light scattering method, and the difference (Δ) was taken as the number of gel-like materials generated during molding.
測定機器はバイアロック／ロイコ社製の微粒子カウンタ
ー４１００型を使用した。The measuring device used was a particulate counter model 4100 manufactured by Vialock/Leuco.
〔なお、上記方法の場合、ゲル状物として、ゲル状物以
外の異物も計測される。しかし、異物をＰＴＦＢ製メン
ブランフィルタ−で補足し、８ＰＭＡにて定量分析する
ことにより、ゲル状物とその他の異物とは明白に区別さ
れる。この方法により、増加分は実質的にゲル状物であ
ることが確認されている。〕
外観及び長期耐湿試験（白点数）
ベレットを３．０オンス射出成形機（住友重機■製、デ
ィスク５１Ｊ３型）を用い、樹脂温度３２０℃、金型温
度１０５℃で厚み１．２ｍｍ、直径１３０ｍｍの円板を
底形し、この円板の色相、焼け、フローマーク、鎖状の
発生の有無を目視観察する（外観）。[Note that in the case of the above method, foreign substances other than gel-like substances are also measured as gel-like substances. However, by capturing the foreign matter with a PTFB membrane filter and quantitatively analyzing it with 8PMA, gel-like matter and other foreign matter can be clearly distinguished. By this method, it has been confirmed that the increased amount is essentially a gel-like material. ] Appearance and long-term moisture resistance test (white point score) Using a 3.0 oz injection molding machine (manufactured by Sumitomo Heavy Industries ■, disc 51J3 model), the pellet was molded into a resin temperature of 320°C and a mold temperature of 105°C, with a thickness of 1.2 mm and a diameter of 130 mm. The disc is bottom-shaped, and the disc is visually observed for hue, burns, flow marks, and the presence or absence of chain-like formations (exterior appearance).
又、この円板を８０℃、９０％ＲＨの環境試験機に入れ
５００時間エージング後、ディスク中に発生した５０−
以上の白点の個数を光学顕微鏡で読み取る。In addition, after putting this disk in an environmental tester at 80°C and 90% RH for 500 hours, the 50-
The number of white spots above is read using an optical microscope.
実施例１〜Ｇ及び比較例１〜３
ビスフェノールＡの苛性ソーダ水溶液と塩化メチレフ
（＝ＭＣ）を２０℃で攪拌しつつ、ホスゲンを導入した
。次にｐ−ｔｅｒｔ−ブチルフェノールとトリエチルア
ミンを加え、強撹拌下に１時間反応させた後、反応生成
混合物の塩化メチレン溶液を分離し水で繰り返し洗浄し
た。Examples 1 to G and Comparative Examples 1 to 3 Caustic soda aqueous solution of bisphenol A and methylene chloride
While stirring (=MC) at 20°C, phosgene was introduced. Next, p-tert-butylphenol and triethylamine were added, and the mixture was reacted for 1 hour with strong stirring, after which a methylene chloride solution of the reaction product mixture was separated and washed repeatedly with water.
この溶液１００容量部に ｎ−へブタン（＝ｎＨ）を２
５容量部添加混合し、混合溶液を温水中に滴下し、つい
で１００℃まで温度を上げて溶媒を留去してスラリー状
のポリカーボネート粉末を得た。Add 2 parts of n-hebutane (=nH) to 100 parts by volume of this solution.
5 parts by volume were added and mixed, the mixed solution was dropped into warm water, and then the temperature was raised to 100°C and the solvent was distilled off to obtain a slurry of polycarbonate powder.
この粉末を濾過して取り出し、１２０℃で８時間乾燥し
て、粘度平均分子量１５．０００のポリカーボネートを
得た。This powder was filtered out and dried at 120°C for 8 hours to obtain polycarbonate with a viscosity average molecular weight of 15.000.
このポリカーボネート粉末に第１表記載の添加剤および
離型剤としてポリカーボネート樹脂１００部に対してス
テアリン酸モノグリセリド０．０１部とブチルステアレ
ート０．０３部とを混合して２５０〜２７０℃の樹脂温
度で押出しベレット化し成形材料を得た。To this polycarbonate powder, 0.01 part of stearic acid monoglyceride and 0.03 part of butyl stearate were mixed with 100 parts of polycarbonate resin as additives and mold release agents listed in Table 1, and the resin temperature was adjusted to 250 to 270°C. The material was extruded into pellets to obtain a molding material.
上記のベレットを使用し、厚さＬ２ｍｍ、直径１２０閣
の円板を底形し、ゲル状物の定量並びに外観及び長期耐
湿試験をした結果を第１表に示した。Using the above pellet, a disk with a thickness of 2 mm and a diameter of 120 mm was shaped into a bottom shape, and the gel-like material was quantitatively determined, and the appearance and long-term moisture resistance tests were conducted. Table 1 shows the results.
第１表 注） 料 ： 安定剤は下記によった。Table 1 note) Fee: The stabilizer was as follows.
以上、本発明の芳香族ポリカーボネート樹脂の光学用成
形材料は押出や射出成形等の成形工程に於ける分子量低
下や焼けの発生が少なく、ゲル状物の発生も少ない。ま
た、高温多湿環境下において使用することを余儀無くさ
れる場合にも、加水分解による白点の生成が少ない。こ
の結果、信号の読み取り或いは書込み用として用いられ
る光ディスクなどの初期のノイズレベル低減に効果があ
るばかりでなく、長期使用や長期保存後の使用において
も優れた信頼性を確保できるものである。As described above, the optical molding material of the aromatic polycarbonate resin of the present invention has less molecular weight reduction and less occurrence of burning during molding processes such as extrusion and injection molding, and less generation of gel-like substances. Further, even when the product is forced to be used in a high temperature and high humidity environment, there is little generation of white spots due to hydrolysis. As a result, it is not only effective in reducing the initial noise level of optical discs used for reading or writing signals, but also ensures excellent reliability during long-term use or use after long-term storage.
Claims (1)
ボネート樹脂１００重量部あたり、下記一般式（１）で
表されるペンタエリスリトールのモノ−乃至テトラ−チ
オプロピオネート０．００１〜０．３重量部を配合して
なる光学用成形材料。 一般式（１）：（Ｒ−Ｓ−ＣＨ＿２ＣＨ＿２ＣＯＯＣＨ
＿２）＿ｍＣ（ＣＨ＿２ＯＨ）＿４＿−＿ｍ（式中のＲ
は互いに同一でも異なっていても良く水素又は炭素数１
〜２２のアルキル基を示し、ｍは１〜４の整数を示す。 ）[Scope of Claims] 0.001 to 0.001 to tetra-thiopropionate of pentaerythritol represented by the following general formula (1) per 100 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 12,000 to 30,000. An optical molding material containing 0.3 parts by weight. General formula (1): (R-S-CH_2CH_2COOCH
_2)_mC(CH_2OH)_4_-_m (R in the formula
may be the same or different from each other, and hydrogen or carbon number 1
-22 alkyl group is shown, and m is an integer of 1-4. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1214060A JPH0379659A (en) | 1989-08-22 | 1989-08-22 | Molding material for optical application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1214060A JPH0379659A (en) | 1989-08-22 | 1989-08-22 | Molding material for optical application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0379659A true JPH0379659A (en) | 1991-04-04 |
Family
ID=16649597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1214060A Pending JPH0379659A (en) | 1989-08-22 | 1989-08-22 | Molding material for optical application |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0379659A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005529969A (en) * | 2002-06-20 | 2005-10-06 | アイシー・ベック・リミテッド | Sulfur-containing phospholipid derivatives |
| US7902399B2 (en) | 2000-03-03 | 2011-03-08 | Thia Medica As | Fatty acids analogous |
| JP2016084402A (en) * | 2014-10-24 | 2016-05-19 | 三菱化学株式会社 | Polycarbonate resin composition and molded article thereof |
-
1989
- 1989-08-22 JP JP1214060A patent/JPH0379659A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7902399B2 (en) | 2000-03-03 | 2011-03-08 | Thia Medica As | Fatty acids analogous |
| JP2005529969A (en) * | 2002-06-20 | 2005-10-06 | アイシー・ベック・リミテッド | Sulfur-containing phospholipid derivatives |
| US8178713B2 (en) | 2002-06-20 | 2012-05-15 | Pronovo Biopharma Norge AS | Sulfur-containing phospholipid derivatives |
| JP2016084402A (en) * | 2014-10-24 | 2016-05-19 | 三菱化学株式会社 | Polycarbonate resin composition and molded article thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6921784B2 (en) | Polycarbonate-based molding material and optical disk substrates | |
| JP3964557B2 (en) | Aromatic polycarbonate resin composition and optical molded article | |
| JPH0379659A (en) | Molding material for optical application | |
| JPH0379660A (en) | Molding material for optical application | |
| JPS62207358A (en) | Polycarbonate resin composition for optical disc | |
| JPH1060247A (en) | Molding material for optical use | |
| JPH01284549A (en) | Optical molding material | |
| JP3992508B2 (en) | Method for producing aromatic polycarbonate resin composition for optical disk substrate | |
| US5254614A (en) | Polycarbonate resin composition for optical use | |
| JP3442556B2 (en) | Aromatic polycarbonate resin and method for producing the same | |
| JP3031401B2 (en) | Molding material for optical recording media | |
| JPH01315459A (en) | Optical molding material | |
| JPH01242660A (en) | Optical molding material | |
| JP4091693B2 (en) | Optical polycarbonate resin molding material and optical disk substrate | |
| JPH11166113A (en) | Polycarbonate material for optical disk substrate | |
| JPH09176477A (en) | Aromatic polycarbonate resin composition | |
| JPH01146950A (en) | Optical molding material | |
| JP3574720B2 (en) | Use of carbonate as a release agent for thermoplastic polycarbonate. | |
| JPH11165342A (en) | Manufacture of polycarbonate molding | |
| JP2000001608A (en) | Polycarbonate resin composition, substrate for optical recording medium formed therefrom and optical recording medium | |
| JPH09183894A (en) | Aromatic polycarbonate resin composition | |
| JP4318346B2 (en) | Polycarbonate composition for optical information substrate and optical information substrate | |
| JPH02219855A (en) | Optical molding material | |
| JP4798839B2 (en) | Polycarbonate resin composition and substrate for information recording medium | |
| JP3380101B2 (en) | Aromatic polycarbonate resin composition |