JPH01254719A - Polysiloxane group-containing polymer - Google Patents
Polysiloxane group-containing polymerInfo
- Publication number
- JPH01254719A JPH01254719A JP8214088A JP8214088A JPH01254719A JP H01254719 A JPH01254719 A JP H01254719A JP 8214088 A JP8214088 A JP 8214088A JP 8214088 A JP8214088 A JP 8214088A JP H01254719 A JPH01254719 A JP H01254719A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymer
- polysiloxane
- integer
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Polysiloxane group Polymers 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims abstract description 83
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005227 gel permeation chromatography Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 6
- 229920001296 polysiloxane Polymers 0.000 abstract description 40
- 238000006116 polymerization reaction Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 14
- 229920000058 polyacrylate Polymers 0.000 abstract description 11
- 239000003607 modifier Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 7
- 150000002978 peroxides Chemical class 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 229920001400 block copolymer Polymers 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 20
- 239000004926 polymethyl methacrylate Substances 0.000 description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000007664 blowing Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリシロキサン基含有重合体に関するもので、
塗料用樹脂や粘着剤樹脂等の改質剤、あるいはコーティ
ング材料として幅広い分野で使用れるものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polysiloxane group-containing polymer,
It is used in a wide range of fields as a modifier for paint resins and adhesive resins, and as a coating material.
（従来の技術）
ポリシロキサンは低表面張力であり、耐熱性、耐寒性、
離型性等の他のポリマーにはみられない独自の特性を有
している。粘接着剤に対する離型紙や、離型性を有する
塗料などにポリシロキサンを含有する重合体が使用され
ていることが、例えば特開昭６１−１３６５７２号公報
、特開昭６２−２２８８１号公報等で公知である。また
、ポリシロキサン鎖を有するブロックまたはグラフト共
重合体が表面活性であることが報告され、高分子材料の
表面改質剤として有用であることが見い出されている。(Conventional technology) Polysiloxane has low surface tension, heat resistance, cold resistance,
It has unique properties not found in other polymers, such as mold releasability. For example, JP-A-61-136572 and JP-A-62-22881 disclose that polymers containing polysiloxane are used in release papers for adhesives and paints with release properties. etc. are publicly known. It has also been reported that block or graft copolymers having polysiloxane chains are surface active and have been found to be useful as surface modifiers for polymeric materials.
例えばマクロモレフェルス（Ｍａｃｒｏｍｏｌｅｃｕｌ
ｅｓ ５巻、８２頁（１９７２）において、ポリスチレ
ンとポリシロキサンとからなるブロック共重合体が表面
活性であり、このブロック共重合体をポリスチレンに添
加するとブロック共重合体が表面に配向してポリスチレ
ンの表面張力を下げることを報告している。また、高分
子加工３４巻、５４７頁（１９８５）でポリシロキサン
とポリスチレンとからなるグラフト共重合体が表面活性
であることを、高分子学会予稿集３４巻、２９３頁（１
９８５）でポリメタクリル酸メチルとポリシロキサンと
からなるブロック共重合体が表面活性であることを報告
している。更に特公昭６０−３０７１５号公報では、ポ
リシロキサンがグラフトしたシリコーン系やグラフト共
重合体は表面活性であり、塗料用樹脂に添加することに
よって塗膜表面にポリシロキサンの機能が付与されると
報告している。For example, Macromolecules
ES Vol. 5, p. 82 (1972), a block copolymer consisting of polystyrene and polysiloxane is surface-active, and when this block copolymer is added to polystyrene, the block copolymer is oriented on the surface and the polystyrene It has been reported that it lowers surface tension. In addition, in Proceedings of the Society of Polymer Engineers Vol. 34, p. 547 (1985), it was reported that a graft copolymer consisting of polysiloxane and polystyrene has surface activity.
(985) reported that a block copolymer consisting of polymethyl methacrylate and polysiloxane has surface activity. Furthermore, Japanese Patent Publication No. 60-30715 reports that silicone systems and graft copolymers grafted with polysiloxane are surface active, and when added to paint resins, the functionality of polysiloxane is imparted to the surface of the coating film. are doing.
（発明が解決しようとする課題）
ところで、離型材料への塗布剤や塗料などのコーティン
グ材料として用いる場合には、基材との密着性とコーテ
イング膜表面の離型性などの諸物性との両立が求められ
るが、実用的にはこれらの物性の両立が達成されている
とはいえずさらに改良が求められている。また、表面改
質剤として用いる場合には、高分子材料表面に効果的に
ポリシロキサンの機能が付与されることと、改質効果の
持続性が長期に持続できることの両立が求められている
。しかし、未だこの両特性を兼ねそなえる表面改質剤は
なく、さらに検討を加える必要があった。(Problems to be Solved by the Invention) By the way, when used as a coating agent for a mold release material or a coating material such as a paint, various physical properties such as adhesion with the base material and mold release properties of the coating film surface are important. However, it cannot be said that both of these physical properties have been achieved practically, and further improvements are required. Furthermore, when used as a surface modifier, it is required to effectively impart polysiloxane functions to the surface of a polymeric material and to maintain the modification effect for a long period of time. However, there is still no surface modifier that has both of these properties, and further investigation was required.
本発明者らは、前記問題点を解決するために鋭意研究し
た結果、特定の構造のポリシロキサン基含有重合体が求
められている要求特性を満足することを確認して本発明
に至ったものである。As a result of intensive research to solve the above-mentioned problems, the present inventors confirmed that a polysiloxane group-containing polymer with a specific structure satisfies the required properties, leading to the present invention. It is.
（課題を解決するための手段）
本発明はアクリル系重合体にポリシロキサン基が結合し
たポリシロキサン基含有重合体部分（以下型合体Ａ部分
とする）及びアクリル系重合体部分（以下重合体Ｂ部分
とする）からなるＡ−Ｂ型ブロック共重合体であるこ七
を特徴としたポリシロキサン基含有重合体である。(Means for Solving the Problems) The present invention provides a polysiloxane group-containing polymer portion (hereinafter referred to as a type polymer A portion) in which a polysiloxane group is bonded to an acrylic polymer and an acrylic polymer portion (hereinafter referred to as a polymer B portion). This is a polysiloxane group-containing polymer characterized by an AB type block copolymer consisting of
本発明のポリシロキサン基含有重合体における重合体Ａ
部分は、下記一般式（Ｉ）〜（ｎ）で示される化合物の
１種または２種以上の混合物に基づく構成単位５〜８５
重量％及びメタクリル酸、メタクリル酸エステル、アク
リル酸、アクリル酸エステル、脂肪酸ビニルエステルか
らなる群から選ばれる１種または２種以上に基づく構成
単位１５〜９５重量％からなることが不可欠である。Polymer A in the polysiloxane group-containing polymer of the present invention
The moiety is a structural unit 5 to 85 based on one type or a mixture of two or more types of compounds represented by the following general formulas (I) to (n).
It is essential that it consists of 15 to 95% by weight of structural units based on one or more types selected from the group consisting of methacrylic acid, methacrylic ester, acrylic acid, acrylic ester, and fatty acid vinyl ester.
一般式
〔式中、Ｒ１は水素原子又はメチル基を、Ｒ２はメチル
基、エチル基、フェニル基又は
Ｒ３Ｒ。General formula [wherein R1 is a hydrogen atom or a methyl group, R2 is a methyl group, an ethyl group, a phenyl group, or R3R.
（式中、Ｒ６は水素原子、フェニル基又はＣｐ Ｈ２Ｆ
＋１を、Ｒ６はメチル基、エチル基又はフェニル基をそ
れぞれ示し、ｍは１以上の整数、ｐは１〜１ｏの整数で
ある。）を、Ｒ４は水素原子、フェニル基又はＣ，Ｈ，
□１を、Ｒ４はメチル基、エチル基又はフェニル基をそ
れぞれ示し、ｎは１以上の整数、Ｐは１〜１０の整数で
ある。〕
一般式
〔式中、Ｒ１は水素原子又はメチル基を、Ｒ２はメチル
基、エチル基、フェニル基又ハ
ｈｓ ｈ。(In the formula, R6 is a hydrogen atom, a phenyl group, or a Cp H2F
+1, R6 represents a methyl group, an ethyl group, or a phenyl group, m is an integer of 1 or more, and p is an integer of 1 to 1o. ), R4 is a hydrogen atom, a phenyl group, or C, H,
□1, R4 each represents a methyl group, an ethyl group, or a phenyl group, n is an integer of 1 or more, and P is an integer of 1 to 10. ] General formula [In the formula, R1 is a hydrogen atom or a methyl group, and R2 is a methyl group, an ethyl group, a phenyl group, or a hsh.
式中、Ｒ３は水素原子、フェニル基又はＣｐＨ２Ｐ＋１
を、Ｒ１はメチル基、エチル基又はフェニル基をそれぞ
れ示し、ｍは１以上の整数、ｐは１〜１０の整数である
。）を、Ｒ１は水素原子、フェニル基又はＣｐ Ｈ２ｐ
＊１をそれぞれ示し、ｎは１以上の整数、ｐは１〜１０
の整数である。］
一般式（１）、（Ｉｉ）におけるＲｔ、Ｒｓ、Ｒａは、
上記で規定した置換基の中で同一であっても異なっても
良い。In the formula, R3 is a hydrogen atom, a phenyl group, or CpH2P+1
, R1 represents a methyl group, an ethyl group, or a phenyl group, m is an integer of 1 or more, and p is an integer of 1 to 10. ), R1 is a hydrogen atom, a phenyl group, or Cp H2p
*1 is shown respectively, n is an integer of 1 or more, p is 1 to 10
is an integer. ] Rt, Rs, and Ra in general formulas (1) and (Ii) are,
The substituents defined above may be the same or different.
ポリシロキサンの分子量が数平均分子量で３００以下で
は得られるポリシロキサン基含有重合体の表面活性が生
ぜず、数平均分子量が５ｏｏｏｏを越すとポリシロキサ
ンの導入が困難となり、また表面活性能が低下する傾向
にある。好ましい数平均分子量は５００以上、４０００
０以下であり、更に好ましくは１０００以上、３０００
以下である。If the molecular weight of polysiloxane is less than 300 in number average molecular weight, the surface activity of the obtained polysiloxane group-containing polymer will not occur, and if the number average molecular weight exceeds 5oooo, it will be difficult to introduce polysiloxane and the surface active ability will decrease. There is a tendency. The preferred number average molecular weight is 500 or more, 4000
0 or less, more preferably 1000 or more, 3000
It is as follows.
一般式（Ｉ）のポリシロキサンは市販品として入手でき
る。例えば商品名ＦＭ０７１１．ＦＭ０７１５．ＦＭＯ
７２１゜ＦＭＯ７２５（チッソ■〕等がこの化合物に相
当する。Polysiloxanes of general formula (I) are available commercially. For example, product name FM0711. FM0715. FMO
721°FMO725 (Chisso ■) and the like correspond to this compound.
一般式（［）のポリシロキサンは一般に知られている反
応で得ることができる。例えば、市販品〔チッソ■製、
ＰＳシリーズなど〕として入手することができる両末端
シラノールポリシロキサン１モルに対して、トリエチル
アミン、ピリジン等塩（式中、Ｒ１は水素原子又はメチ
ル基を、Ｒ２＋ Ｒ３はメチル基、エチル基、又はフェ
ニル基をそれぞれ示す。）２モルを室温から６０°Ｃ程
度の温度範囲で反応させて得られる化合物が、一般式（
ｎ）の化は公知の化合物であり、 （メタ）アクリル酸
アリルエステルとケイ素化合物との反応によって得るこ
とができる。一般式（Ｉ）、（ＩＩ）で示されるポリシ
ロキサンの使用重量比に制限はなく、ポリシロキシサン
基導入量として、表面活性能が発現できるために、重合
体Ａ部分中５重量％以上あればよい。また、ポリシロキ
サン基導入量が８５重量％を越えると、ポリシロキサン
基含有重合体をコーティング材料などに使用した場合に
基材との密着性が低下するという弊害が生じる。このた
め、好ましい範囲は５重量％から８５重量％である。Polysiloxanes of general formula ([) can be obtained by generally known reactions. For example, commercially available products [manufactured by Chisso ■,
Triethylamine, pyridine, etc. salt (in the formula, R1 is a hydrogen atom or a methyl group, R2+ R3 is a methyl group, an ethyl group, or a phenyl group) per mole of a double-terminated silanol polysiloxane available as A compound obtained by reacting 2 moles of each group at a temperature range from room temperature to about 60°C has the general formula (
The compound (n) is a known compound and can be obtained by reacting allyl (meth)acrylic acid ester with a silicon compound. There is no limit to the weight ratio of the polysiloxanes represented by general formulas (I) and (II), and the amount of polysiloxane groups introduced must be 5% by weight or more in the polymer A portion in order to exhibit surface activity. Bye. Moreover, if the amount of polysiloxane group introduced exceeds 85% by weight, when the polysiloxane group-containing polymer is used as a coating material, there will be a problem that the adhesion to the substrate will be reduced. Therefore, the preferred range is 5% to 85% by weight.
重合体Ａ部分の幹成分と重合体Ｂ部分はメタクリル酸、
メタクリル酸エステル、アクリル酸、アクリル酸エステ
ル、脂肪酸ビニルエステルからなる群から選ばれる１種
または２種以上に基づく構成単位であることが不可欠で
ある。重合体Ａ部分、の幹成分と重合体Ｂ部分の構成単
位は同一であっても異なってもよい。この重合体Ａ部分
の幹成分と重合体Ｂ部分を構成する単量体としては、例
えば（メタ）アクリル酸メチル〔（メタ）アクリル酸メ
チルとはメタアクリル酸メチルまたはアクリル酸メチル
のことをいう。以下同様。〕 （メタ）アクリル酸エチ
ル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリ
ル酸グリシジルなどの低級アルキル（メタ）アクリレー
ト； （メタ）アクリル酸ｎ−ブチル、（メタ）アクリ
ル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル
、（メタ）アクリル酸ステアリルなどの高級（メタ）ア
クリレート；酢酸ビニル、プロピオン酸ビニル、酪酸ビ
ニル、２−エチルヘキサン酸ビニル、ラウリン酸ビニル
などの脂肪酸ビニル、（メタ）アクリル酸ヒドロキシエ
チル、（メタ）アクリル酸ヒドロキシプロピルなどの水
酸基含有（メタ）アクリル酸エステル、（メタ）アクリ
ル酸などを用いることが適切である。The backbone component of the polymer A part and the polymer B part are methacrylic acid,
It is essential that the structural unit is based on one or more selected from the group consisting of methacrylic acid ester, acrylic acid, acrylic ester, and fatty acid vinyl ester. The structural units of the polymer A portion and the polymer B portion may be the same or different. The monomers constituting the backbone component of the polymer A part and the polymer B part are, for example, methyl (meth)acrylate [(meth)acrylate refers to methyl methacrylate or methyl acrylate. . Same below. ] Lower alkyl (meth)acrylates such as ethyl (meth)acrylate, n-propyl (meth)acrylate, and glycidyl (meth)acrylate; n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Higher (meth)acrylates such as lauryl (meth)acrylate and stearyl (meth)acrylate; fatty acid vinyls such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and (meth)acrylates. It is appropriate to use hydroxyl group-containing (meth)acrylic esters such as hydroxyethyl acid and hydroxypropyl (meth)acrylate, (meth)acrylic acid, and the like.
本発明のポリシロキサン基含有重合体における重合体Ａ
部分と重合体Ｂ部分との比率は、重量比率で２５／７５
〜９０／１０である。重合体Ａ部分が２５重量２以下で
あると表面活性が低下する。また９０％を越えると、コ
ーティング材料として用いた場合に基材との密着性が低
下し、また高分子材料の表面改質剤として用いた場合に
、表面改質効果の持続性が低下する傾向にある。Polymer A in the polysiloxane group-containing polymer of the present invention
The ratio of the part to the polymer B part is 25/75 by weight.
~90/10. When the polymer A portion is less than 25% by weight, the surface activity decreases. If it exceeds 90%, the adhesion with the substrate tends to decrease when used as a coating material, and the sustainability of the surface modification effect tends to decrease when used as a surface modifier for polymeric materials. It is in.
本発明のポリシロキサン基含有重合体の分子量は、テト
ラヒドロフランを溶離液を用いてゲルパーミェーション
クロマトグラフィーで測定したポリスチレン換算の数平
均分子量が４０００〜１ｏｏｏｏｏである。分子量が４
０００に満たない場合は、本発明のポリシロキサン基含
有重合体をコーティング材料に使用した際のコーテイン
グ膜強度が弱くなる。The polysiloxane group-containing polymer of the present invention has a number average molecular weight of 4000 to 1 ooooo in terms of polystyrene, as measured by gel permeation chromatography using tetrahydrofuran as an eluent. molecular weight is 4
If it is less than 000, the strength of the coating film will be weak when the polysiloxane group-containing polymer of the present invention is used as a coating material.
また分子量が１０００００を越えると、表面改質剤とし
て使用した場合に表面配向性が低下する傾向にある。If the molecular weight exceeds 100,000, surface orientation tends to decrease when used as a surface modifier.
本発明におけるポリシロキサン基含有重合体の合成は公
知の方法により行うことができる。例えばポリメリック
ペルオキシドを開始剤として２段階の重合によって得ら
れる。例えば次に示すようにポリメリックペルオキシド
を用いて、重合体Ｂ部分となり得る単量体の１種又は２
種以上を重合する。この際、ポリメリックペルオキシド
の活性酸素量を約５０％残存させたところで重合を停止
させることにより、ペルオキシ結合を含有する重合体を
得ることができる。更に、このものを開始剤として、重
合体Ａ部分になり得る、前記一般式（Ｉ）、（ＩＩ）で
示したポリシロキサンの１種または２種以上、及びその
他の単量体を共重合することによって本発明のポリシロ
キサン基含有重合体を得ることができる。なお、ポリメ
リックペルオキシドを用い、第１段重合でペルオキシ結
合を含有する重合体Ａ部分を得、次いで重合体Ｂ部分を
ブロック化反応することもできる。The polysiloxane group-containing polymer in the present invention can be synthesized by a known method. For example, it can be obtained by two-stage polymerization using polymeric peroxide as an initiator. For example, as shown below, using a polymeric peroxide, one or two of the monomers that can become the polymer B portion are
Polymerize more than one species. At this time, a polymer containing peroxy bonds can be obtained by stopping the polymerization when about 50% of the active oxygen amount remains in the polymeric peroxide. Furthermore, using this product as an initiator, one or more polysiloxanes represented by the general formulas (I) and (II) and other monomers, which can become the polymer A portion, are copolymerized. By this process, the polysiloxane group-containing polymer of the present invention can be obtained. In addition, it is also possible to obtain a polymer A portion containing a peroxy bond in the first stage polymerization using a polymeric peroxide, and then to perform a blocking reaction on the polymer B portion.
（発明の効果）
本発明の最も重要な特徴とするところは、アクリル系重
合体に枝状にポリシロキサン基が結合した重合体部分に
さらにアクリル系重合体が結合していることにある。(Effects of the Invention) The most important feature of the present invention is that an acrylic polymer is further bonded to the polymer portion in which polysiloxane groups are bonded in a branched manner to the acrylic polymer.
このため、種々の基材へのコーティング材料とし用いた
場合や高分子材料の表面改質剤として用いた場合に、基
材との密着性や高分子材料との混和性に優れ、また表面
にポリシロキサンの機能を極めて効果的に付与できる、
従来のものより優れたポリシロキサン基含有重合体であ
る。For this reason, when used as a coating material for various base materials or as a surface modifier for polymeric materials, it has excellent adhesion with the substrate and miscibility with the polymeric material, and also has excellent surface properties. The functions of polysiloxane can be imparted extremely effectively.
This is a polysiloxane group-containing polymer that is superior to conventional polymers.
（実施例）
次に、本発明を実施例及び比較例により説明する。なお
、各実施例、比較例における部数及びχは全て重量基準
である。(Example) Next, the present invention will be explained with reference to Examples and Comparative Examples. Note that the number of parts and χ in each Example and Comparative Example are all based on weight.
実施例１
（Ａ）ペルオキシ結合含有重量体の合成温度計、撹拌器
及び還流冷却器を備えた反応器に、メチルエチルケトン
を５７ｇ仕込み、窒素ガスを吹き込みながら７０°Ｃに
加熱し、それにメチルエチルケトン ５７ｇ
メタクリル酸メチル ４８ｇ
２ｇ
ＯＣ２ＩＳ Ｏ
ＩＩ Ｉ １１
ｆｃ（Ｃ１ｈ） ６ＣＨ（ＣＨ２） ｖｃＯＯ−１−＋
。 ６ｇ＊ ａ） Ｍｎ” ５０００
からなる混合液を２時間かけて仕込み、更に４時間重合
反応を行なった。メタクリル酸メチルの重合転化率は、
ガスクロマトグラフィ（ＧＳ）で残存モノマーを測定し
たところ、９６χであることがわかった。次いでポリマ
ー溶液から、エバポレーターを用いて、メチルエチルケ
トンを常温で減圧除去し、得られたポリマーの固体を粉
砕機で微粉末となるまで粉砕した。更に、得られた粉砕
のうち２０ｇを前記反応装置に仕込み、ｎ−ヘキサン３
００ｇを加えて室温で２０時間撹拌し、未反応のポリシ
ロキサンを抽出する操作を行なった。Example 1 (A) Synthesis of a heavy body containing peroxy bonds 57 g of methyl ethyl ketone was charged into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 70°C while blowing nitrogen gas. Methyl acid 48g 2g OC2IS O II I 11 fc(C1h) 6CH(CH2) vcOO-1-+
. 6g* a) A mixed solution consisting of Mn" 5000 was charged over 2 hours, and the polymerization reaction was further carried out for 4 hours. The polymerization conversion rate of methyl methacrylate was as follows:
When the residual monomer was measured by gas chromatography (GS), it was found to be 96χ. Next, methyl ethyl ketone was removed from the polymer solution under reduced pressure using an evaporator at room temperature, and the resulting polymer solid was ground using a grinder until it became a fine powder. Furthermore, 20 g of the obtained pulverization was charged into the reaction apparatus, and 3 g of n-hexane was added.
00g was added and stirred at room temperature for 20 hours to extract unreacted polysiloxane.
微粉末を濾別後、回収したｎ−ヘキサン溶液からｎ−ヘ
キサンを留去したところ、５．３ｇの粘稠な化合物が得
られた。ＮＭＲ分析、ＧＰＣ分析の結果、粘稠な化合物
は低分子量のポリメタクリル酸メチルを１５重量％、未
反応ポリシロキサンを８５重量２を含有することが明ら
かであった。濾別して取り出した微粉末はＮＭＲ分析の
結果、ポリメタクリル酸メチルとポリシロキサンの重量
比率が約７５／２５からなる重合体であることが明らか
となった。また、この微粉末は活性酸素量が０．１４％
であり、ペルオキシ結合を有することが示された。ＧＰ
Ｃで測定したポリスチレン換算の数平均分子量は２１０
００であった。After filtering off the fine powder, n-hexane was distilled off from the recovered n-hexane solution, yielding 5.3 g of a viscous compound. As a result of NMR analysis and GPC analysis, it was clear that the viscous compound contained 15% by weight of low molecular weight polymethyl methacrylate and 85% by weight of unreacted polysiloxane. NMR analysis of the fine powder taken out by filtration revealed that it was a polymer consisting of polymethyl methacrylate and polysiloxane in a weight ratio of approximately 75/25. In addition, this fine powder has an active oxygen content of 0.14%.
and was shown to have a peroxy bond. G.P.
The number average molecular weight in terms of polystyrene measured by C is 210
It was 00.
（Ｂ）ブロック共重合体の合成
前記（Ａ）で得た、未反応ポリシロキサンを除去した微
粉末１４ｇ、メタクリル酸メチル７ｇ、トルエン２９ｇ
を混合溶解後、窒素置換したアンプル中に仕込み、振騰
しながら７０°Ｃで４時間、更に８０″Ｃで４時間反応
させて、ブロック共重合体を合成した。(B) Synthesis of block copolymer 14 g of the fine powder obtained in (A) above from which unreacted polysiloxane was removed, 7 g of methyl methacrylate, and 29 g of toluene.
After mixing and dissolving the mixture, the mixture was charged into an ampoule purged with nitrogen, and reacted with shaking at 70°C for 4 hours and then at 80''C for 4 hours to synthesize a block copolymer.
得られたポリマー溶液は無色透明であった。ＧＣによる
残存メタクリル酸メチルの測定から、重合転化率が９８
χであることが、ＧＰＣ測定から数平均分子量が３２０
００であることが明らかとなった。得られたポリマー溶
液をメタノールで再沈して充分に乾燥後ＮＭＩ？分析を
行なった結果、ポリメタクリル酸メチルとポリシロキサ
ンの重量比率が約８２／１８であることが示された。こ
れらの結果から、得られた重合体は、ポリメタクリル酸
メチルにポリシロキサンが枝状にグラフトした重合体（
重量比７０／３０）とポリメタクリル酸メチルからなる
ブロック共重合体であり、ブロック共重合体における両
型合体部分の重量比は約７０／３０であることが明らか
となった。The obtained polymer solution was colorless and transparent. From the measurement of residual methyl methacrylate by GC, the polymerization conversion rate was 98.
The number average molecular weight is 320 from GPC measurement.
It became clear that it was 00. The resulting polymer solution was reprecipitated with methanol and thoroughly dried, followed by NMI? Analysis showed that the weight ratio of polymethyl methacrylate to polysiloxane was approximately 82/18. From these results, the obtained polymer is a polymer in which polysiloxane is grafted in a branched manner to polymethyl methacrylate (
It was revealed that it is a block copolymer consisting of polymethyl methacrylate (weight ratio 70/30) and polymethyl methacrylate, and the weight ratio of both types of combined parts in the block copolymer is approximately 70/30.
実施例２
実施例１の（Ａ）において仕込んだ
３２ｇの代わりに
６ｇ
本ａ）いずれもＭｒ＋”５０００
を仕込む他は全て実施例１と同じ方法でブロック共重合
体を合成した。実施例１と同様に未反応ポリシロキサン
を除去後に分析したペルオキシ結合含有重合体における
ポリメタクリル酸メチルとポリシロキサンの重量比率は
約６７／３３であった。また活性酸素量は０．１４χ、
数平均分子量は３４０００であった。更に、ブロック共
重合体合成後に分析した結果から、ポリメタクリル酸メ
チルにポリシロキサンが枝状に結合した重合体部分とポ
リメタクリル酸メチルとからなるブロック共重合体であ
り、ブロック共重合体における再重合体部分の重量比が
約ＴＯ／３０であることが明らかとなった。また数平均
分子量は４２０００であった。Example 2 A block copolymer was synthesized in the same manner as in Example 1 except that 6 g was used instead of 32 g charged in (A) of Example 1.A) In both cases, a block copolymer was synthesized in the same manner as in Example 1 except that Mr+"5000 was charged. Similarly, the weight ratio of polymethyl methacrylate to polysiloxane in the peroxy bond-containing polymer analyzed after removing unreacted polysiloxane was about 67/33.The amount of active oxygen was 0.14χ,
The number average molecular weight was 34,000. Furthermore, the results of analysis after the block copolymer synthesis revealed that it is a block copolymer consisting of polymethyl methacrylate and a polymer portion in which polysiloxane is branched to polymethyl methacrylate, and that regeneration in the block copolymer is The weight ratio of the polymer portion was found to be approximately TO/30. Moreover, the number average molecular weight was 42,000.
実施例３〜５、比較例１〜２
（八）ペルオキシ結合金有基重合体の合成実施例１と同
じ反応装置にトルエン４００部を仕込み、窒素ガスを吹
き込みなから７０°Ｃに加熱し、それに
トルエン １７０部メタクリ
ル酸メチル ２８０部アクリル酸２−エ
チルヘキシル ８０部アクリル酸２−ヒドロキシエ
チル ４０部からなる混合液を２時間かけて仕込み、
更に４時間重合反応を行なった。重合転化率は９６％で
あり、得られた重合体の数平均分子量は１３０００であ
った。Examples 3 to 5, Comparative Examples 1 to 2 (8) Synthesis of peroxy-bonded gold-based polymer 400 parts of toluene was charged into the same reactor as in Example 1, heated to 70°C without blowing nitrogen gas, A mixture of 170 parts of toluene, 280 parts of methyl methacrylate, 80 parts of 2-ethylhexyl acrylate, and 40 parts of 2-hydroxyethyl acrylate was added over 2 hours.
The polymerization reaction was further carried out for 4 hours. The polymerization conversion rate was 96%, and the number average molecular weight of the obtained polymer was 13,000.
（Ｂ）ブロック共重合体の合成
上記（Ａ）で合成したホリマー溶液５０部を上記と同じ
反応装置に仕込み、窒素ガスを吹きこみながら７０°Ｃ
で第４表に示す組成の混合物を３０分かけて仕込み、更
に７０°Ｃで３時間、８０゛Ｃで３時間重合反応を行な
った。重合終了後の固形分濃度を第１表ニ示す。尚、ポ
リシロキサンは数平均分子量が１００００の下記の構造
のものを用いた。(B) Synthesis of block copolymer 50 parts of the polymer solution synthesized in (A) above was charged into the same reactor as above, and heated to 70°C while blowing nitrogen gas.
A mixture having the composition shown in Table 4 was charged over 30 minutes, and a polymerization reaction was further carried out at 70°C for 3 hours and at 80°C for 3 hours. The solid content concentration after the completion of polymerization is shown in Table 1. The polysiloxane used had the following structure and had a number average molecular weight of 10,000.
ポリシロキサン−１
ポリシロキサン−２
次いで実施例１と同様の操作により、未反応のポリシロ
キサンを抽出した。第１段重合の重合転化率、ＧＣで分
析したメタクリル酸メチル、メタクリル酸ブチルの残存
量及び抽出ポリシロキサン量からポリシロキサン基含有
重合体部分のポリシロキサン含有量およびポリシロキサ
ン基含有重合体部分とポリシロキサン基を含有しない重
合体部分との重量比率を求めた。結果を第１表に示す。Polysiloxane-1 Polysiloxane-2 Next, by the same operation as in Example 1, unreacted polysiloxane was extracted. The polysiloxane content of the polysiloxane group-containing polymer portion and the polysiloxane group-containing polymer portion are determined from the polymerization conversion rate of the first stage polymerization, the residual amount of methyl methacrylate and butyl methacrylate analyzed by GC, and the amount of extracted polysiloxane. The weight ratio with the polymer portion not containing polysiloxane groups was determined. The results are shown in Table 1.
実施例６〜１０
（Ａ）ペルオキシ結合含有重合体の合成実施例１と同じ
反応装置にトルエン４００部を仕込み、窒素ガスを吹き
込みながら７０°Ｃに加熱し、それに
トルエン １７０部メタク
リル酸メチル １６０部メククリル酸
ｎ−ブチル １８０部メタクリル酸２−ヒ
ドロキシエチル ６０部ＯＣ２１１５０
ＴＣ（ＣＨｚ）６ＣＨ（ＣＨｚ）９ＣＯＯ廿、。
３０部からなる混合液を２時間かけて仕込み、更に４時
間重合反応を行なった。重合転化率は９６χであり、得
られた重合体の数平均分子量は１４０００であった。Examples 6 to 10 (A) Synthesis of peroxy bond-containing polymer 400 parts of toluene was charged into the same reactor as in Example 1, heated to 70°C while blowing nitrogen gas, and 170 parts of toluene and 160 parts of methyl methacrylate were added. n-Butyl meccrylate 180 parts 2-hydroxyethyl methacrylate 60 parts OC21150 TC(CHz)6CH(CHz)9COO.
A mixed solution consisting of 30 parts was charged over 2 hours, and the polymerization reaction was further carried out for 4 hours. The polymerization conversion rate was 96χ, and the number average molecular weight of the obtained polymer was 14,000.
（Ｂ）ブロック共重合体の合成
上記で合成したポリマー溶液５０部を上記と同じ反応装
置に仕込み、窒素ガスを吹き込みなから７０゛Ｃで第２
表に示す組成の混合物を３０分かけて仕込み、更に７０
゛Ｃで３時間、８０°Ｃで３時間重合反応を行なった。(B) Synthesis of block copolymer 50 parts of the polymer solution synthesized above was charged into the same reactor as above, and heated to 70°C without blowing nitrogen gas.
A mixture of the composition shown in the table was prepared over 30 minutes, and then 70 minutes
The polymerization reaction was carried out at 80°C for 3 hours and at 80°C for 3 hours.
重合終了後の固形分濃度を第１表に示す。次いで実施例
１と同様の操作により、未反応のポリシロキサンを抽出
した。第１段重合の重合転化率、ＧＣで分析したメタク
リル酸メチル、メタクリル酸ブチルの残存量及び抽出ポ
リシロキサン量からポリシロキサン基含有重合体部分の
ポリシロキサン基含有量およびポリシロキサン基含有重
合体部分とポリシロキサン基を含有しない重合体部分の
重量比率を求めた。結果を第２表に示す。Table 1 shows the solid content concentration after completion of polymerization. Next, unreacted polysiloxane was extracted by the same operation as in Example 1. The polysiloxane group content of the polysiloxane group-containing polymer portion and the polysiloxane group-containing polymer portion based on the polymerization conversion rate of the first stage polymerization, the residual amount of methyl methacrylate and butyl methacrylate analyzed by GC, and the amount of extracted polysiloxane. and the weight ratio of the polymer portion not containing polysiloxane groups was determined. The results are shown in Table 2.
比較例３
実施例１で使用した反応装置にトルエンを５７ｇ仕込み
、窒素ガスを吹き込みなから７５°Ｃに加熱し、それに
トルエン ６０ｇ
メタクリル酸メチル ４８ｇ
Ｃ１１３（ＣＨｚ）ｚｃＨ（Ｃｚｔｌｓ）ＣＯＯｔＢｕ
３ｇ本ａ） Ｍｎ ＝５０００
からなる混合液を２時間かけて仕込み、更に５時間同温
度で反応を続け、次いで８５°Ｃに昇温して４時間反応
を行ない、グラフト共重合体を合成した。Comparative Example 3 57g of toluene was charged into the reactor used in Example 1, heated to 75°C without blowing nitrogen gas, and 60g of toluene, 48g of methyl methacrylate, C113(CHz)zcH(Cztls)COOtBu
3g bottle a) A mixed solution consisting of Mn = 5000 was charged over 2 hours, the reaction was continued at the same temperature for an additional 5 hours, and then the temperature was raised to 85°C and the reaction was carried out for 4 hours to synthesize a graft copolymer. .
実施例１と同じ方法により、種々の分析を行ない次の結
果を得た。Various analyzes were performed using the same method as in Example 1, and the following results were obtained.
メタクリル酸メチルの重合体転化率：９５％数平均分子
量：２２０００
未反応ポリシロキサン除去後のグラフト共重合体におけ
るポリメタクリル酸メチルとポリシロキサンとの重量比
率： ７２／２８
比較例４
ポリマージャーナル（Ｐｌｏｙｍｅｒ Ｊａｒｎａｌ）
１７巻、１３３頁（１９８５）及び高分子学会予稿集３
５巻、３０６頁（１９８６）記載の方法を参考にして、
ポリシロキサンとポリメタクリル酸メチルからなるブロ
ック共重合体を下記のように合成した。Polymer conversion rate of methyl methacrylate: 95% Number average molecular weight: 22000 Weight ratio of polymethyl methacrylate to polysiloxane in the graft copolymer after removal of unreacted polysiloxane: 72/28 Comparative example 4 Polymer Journal (Ploymer Journal)
Volume 17, page 133 (1985) and Proceedings of the Society of Polymer Science 3
With reference to the method described in Volume 5, page 306 (1986),
A block copolymer consisting of polysiloxane and polymethyl methacrylate was synthesized as follows.
（Ａ）片末端に二重結合を有するポリメタクリル酸メチ
ルの合成
製造例１で使用した反応装置にテトラヒドロフラン１０
０ｇ、メタクリル酸メチル１００ｇ、チオグリコール酸
２．０ｇ、及び２，２′−アゾビスイソブチロニトリル
２．０ｇを仕込み、窒素ガスを吹き込みながら６０°Ｃ
に加熱し３時間反応を行ない、末端にカルボン酸基を持
つポリメタクリル酸メチルを合成した。実施例１と同じ
方法により分析を行なった結果、メタクリル酸メチルの
重合転化率は４３χであり、数平均分子量は７２００で
あった。次に、メタノールで再沈後に充分に乾燥して取
り出したポリメタクリル酸メチルの粉末３５ｇとメタク
リル酸グリシジル４．０ｇをキシレン１００ｇに溶解後
、上記と同じ反応装置に仕込んで、キシレンの沸点下で
１０時間反応を続けた。ＧＣで経時的に測定したメタク
リル酸グリシジルの変化量から、反応６時間の時点でポ
リメタクリル酸メチル末端のカルボン酸基が定量的にメ
タクリル酸グリシジルと反応していることが確認できた
。反応終了後、メタノールで再沈させ、濾別後充分に乾
燥して片末端に二重結合を持つポリメタクリル酸メチル
の粉体を得た。この粉体の数平均分子量は７０００であ
った。(A) Synthesis of polymethyl methacrylate having a double bond at one end. Tetrahydrofuran 10 was added to the reaction apparatus used in Production Example 1.
0 g, 100 g of methyl methacrylate, 2.0 g of thioglycolic acid, and 2.0 g of 2,2'-azobisisobutyronitrile were heated at 60°C while blowing nitrogen gas.
The reaction mixture was heated for 3 hours to synthesize polymethyl methacrylate having a carboxylic acid group at the end. As a result of analysis performed by the same method as in Example 1, the polymerization conversion rate of methyl methacrylate was 43χ, and the number average molecular weight was 7,200. Next, 35 g of polymethyl methacrylate powder and 4.0 g of glycidyl methacrylate, which had been sufficiently dried and taken out after reprecipitation with methanol, were dissolved in 100 g of xylene, and then charged into the same reactor as above and heated under the boiling point of xylene. The reaction continued for 10 hours. From the amount of change in glycidyl methacrylate measured over time by GC, it was confirmed that the carboxylic acid group at the terminal of polymethyl methacrylate had quantitatively reacted with glycidyl methacrylate at the time of 6 hours of reaction. After the reaction was completed, the mixture was reprecipitated with methanol, filtered, and thoroughly dried to obtain a powder of polymethyl methacrylate having a double bond at one end. The number average molecular weight of this powder was 7,000.
（Ｂ）ブロック共重合体の合成 実施例１で使用した反応装置に、トルエン１００ｇ。(B) Synthesis of block copolymer 100 g of toluene was added to the reactor used in Example 1.
上記（Ａ）で得た片末端二重結合を有するポリメタクリ
ル酸メチルの粉体２０ｇ 、 ＩＩ□ＰｔＣ］６０．５
ｇ−、及びｂ）
Ｈ５ｉ（ＣＨ：＋）ｚ （Ｓｉ（ＣＨ：＋）ｚＯ〕ｎ５
ｉ（Ｃ１ｂ）ｚＨ１０ｇ本ｂ）数平均分子量５０００、
チッソ■製ＦＭ１１２１を仕込み、７０°Ｃに加熱して
６時間ヒドロシリル化反応を行なって、ポリシロキサン
の両末端にポリメタクリル酸メチルが連結した構造のプ
ロ・ンク共重合体を合成した。実施例１と同じ方法で遊
離のポリシロキサンを除去して得たブロック共重合体は
次のような物性値を有するものであった。20 g of powder of polymethyl methacrylate having one terminal double bond obtained in (A) above, II□PtC] 60.5
g-, and b) H5i(CH:+)z (Si(CH:+)zO]n5
i(C1b)zH10g b) Number average molecular weight 5000,
FM1121 manufactured by Chisso ■ was charged and heated to 70°C to carry out a hydrosilylation reaction for 6 hours to synthesize a Pro-Nc copolymer having a structure in which polymethyl methacrylate was connected to both ends of polysiloxane. A block copolymer obtained by removing free polysiloxane in the same manner as in Example 1 had the following physical properties.
（ＧＰＣ測定から）数平均分子量： ２１０００（ＮＭ
Ｒ測定から）ポリメタクリル酸メチル部分とポリシロキ
サン部分との重量比： ７３／２７参考例１〜６
実施例１で使用した反応装置にトルエンを２５０部仕込
み、窒素ガスを吹き込みなから７５°Ｃに加熱し、それ
に
トルエン ２５０部メタクリ
ル酸メチル １９２部メタクリル酸ｎ
−ブチル ２１６部メタクリル酸２−ヒド
ロキシエチル ７２部ＧＨｚ（ＣＪ）ｚｃＨ（（：ｚ
Ｈｓ）ＣＯＯｔＢｕ ２０部からなる混合液を
２時間かけて仕込み、更に５時間同温度で反応を続け、
次いで８５°Ｃに昇温して４時間反応を行ないアクリル
ポリマーを合成した。(From GPC measurement) Number average molecular weight: 21000 (NM
From R measurement) Weight ratio of polymethyl methacrylate part to polysiloxane part: 73/27 Reference Examples 1 to 6 250 parts of toluene was charged into the reaction apparatus used in Example 1, and nitrogen gas was blown into the reactor, and then heated to 75°C. 250 parts of toluene 192 parts of methyl methacrylate
-Butyl 216 parts 2-hydroxyethyl methacrylate 72 parts GHz(CJ)zcH((:z
Hs) A mixed solution consisting of 20 parts of COOtBu was charged over 2 hours, and the reaction was continued at the same temperature for an additional 5 hours.
Next, the temperature was raised to 85°C and reaction was carried out for 4 hours to synthesize an acrylic polymer.
重合転化率は９８χてあり、数平均分子量は１９０００
であった。得られたポリマー溶液をトルエンで希釈して
２０重量％溶液を調整した。The polymerization conversion rate is 98χ, and the number average molecular weight is 19000.
Met. The obtained polymer solution was diluted with toluene to prepare a 20% by weight solution.
次いで、実施例１．２、比較例１．２で合成した重合体
及び数平均分子量が５０００のポリジメチルシロキサン
の表面改質剤としての特性を比較した。Next, the properties of the polymers synthesized in Example 1.2 and Comparative Example 1.2 and polydimethylsiloxane having a number average molecular weight of 5000 as surface modifiers were compared.
上記で得たアクリルポリマー溶液１０００部に日本ポリ
ウレタン■製コロネートＥＨを４７部、ジブチルチンジ
ラウレートを２．０８Ｘ１０−’部、トルエンを１８８
部加えて２０χ溶液を調整した。このポリマー溶液に、
実施例１〜２、比較例１〜２で合成した重合体もしくは
ポリジメチルシロキサンを所定量添加後、ウォッシュプ
ライマー処理した鉄板上に乾燥後の膜厚が５０μｍにな
るように成膜し、８０°Ｃで４時間放置後に硬化塗膜を
得た。次いで硬化塗膜の表面物性を測定した。各測定法
を第３表の下に示し、また得られた結果を第３表に示す
。To 1000 parts of the acrylic polymer solution obtained above, 47 parts of Coronate EH manufactured by Nippon Polyurethane, 2.08 x 10-' parts of dibutyltin dilaurate, and 188 parts of toluene.
% to prepare a 20x solution. In this polymer solution,
After adding a predetermined amount of the polymer or polydimethylsiloxane synthesized in Examples 1 to 2 and Comparative Examples 1 to 2, a film was formed on an iron plate treated with a wash primer so that the film thickness after drying was 50 μm, and the film was heated at 80° A cured coating film was obtained after being left at C for 4 hours. Next, the surface properties of the cured coating were measured. Each measurement method is shown below in Table 3, and the results obtained are shown in Table 3.
第３表の結果から、本発明のポリシロキサン基含有重合
体が、従来のポリシロキサン或いはポリシロキサンを含
有するグラフト共重合体、ブロック共重合体よりも、初
期の改質効果（初期物性）の付与及び改質効果の持続性
の両特性を満足できる点で優れていることが明らかであ
る。From the results in Table 3, it is clear that the polysiloxane group-containing polymer of the present invention has a better initial modification effect (initial physical properties) than conventional polysiloxanes or graft copolymers and block copolymers containing polysiloxanes. It is clear that it is excellent in that it can satisfy both the characteristics of imparting and the sustainability of the modification effect.
参考例７〜１１
参考例１と同じ方法により、実施例３〜５、比較例１〜
２で合成したポリシロキサン基含有重合体の表面改質剤
としての性能を評価した。得られた結果を第４表に示す
。Reference Examples 7-11 By the same method as Reference Example 1, Examples 3-5 and Comparative Examples 1-
The performance of the polysiloxane group-containing polymer synthesized in 2 as a surface modifier was evaluated. The results obtained are shown in Table 4.
この結果から、本発明のポリシロキサン基含有重合体に
よってアクリルポリマー表面にポリシロキサンの機能が
付与され、なおかつ改質効果の持続性が良好なことが示
される。これに対し、比較例１から示されるようにポリ
シロキサン基含有量があまりに低すぎると初期物性が低
下する傾向にあった。また、比較例２から示されるよう
にポリシロキサン基含有量が高すぎると改質効果の持続
性が低下する傾向にあった。This result shows that the polysiloxane group-containing polymer of the present invention imparts polysiloxane functionality to the surface of the acrylic polymer, and that the modification effect is sustained well. On the other hand, as shown in Comparative Example 1, if the polysiloxane group content was too low, the initial physical properties tended to deteriorate. Furthermore, as shown in Comparative Example 2, when the polysiloxane group content was too high, the sustainability of the modification effect tended to decrease.
参考例１２〜１８
実施例６〜１０で合成したポリシロキサン基含有重合体
をトルエンで溶解して２０χ溶液を調整した。Reference Examples 12 to 18 The polysiloxane group-containing polymers synthesized in Examples 6 to 10 were dissolved in toluene to prepare 20χ solutions.
次いで、このポリマー溶液をアプリケーターを用いて乾
燥後の膜厚め（２０μｍになるように、ＰＥＴフィルム
、アルミニウム板、鋼板上に成膜した。また、比較とし
て参考例１で合成したアクリルポリマー、およびこのア
クリルポリマーに数平均分子ｆｆ１５０００のポリジメ
チルシロキサンを、アクリルポリマーの有効成分に対し
て１０χ添加したものを前記の同様の方法で塗布した。Next, this polymer solution was formed into a film using an applicator on a PET film, an aluminum plate, and a steel plate so that the film thickness after drying was 20 μm.For comparison, the acrylic polymer synthesized in Reference Example 1 and this An acrylic polymer to which polydimethylsiloxane having a number average molecular weight of 15,000 was added in an amount of 10x based on the active ingredient of the acrylic polymer was applied in the same manner as described above.
充分に乾燥後の 塗膜表面の接触角、離型性、基材との
密着性を測定した。測定方法、測定結果を第５表に示す
。After sufficiently drying, the contact angle, releasability, and adhesion to the substrate of the coating film surface were measured. The measurement method and measurement results are shown in Table 5.
この結果から、本発明のポリシロキサン基含有重合体を
各種基材に塗布した場合、基材との密着性がよく、しか
も塗膜表面にはポリシロキサンに由来する特性が良好に
付与されることがわかった。These results show that when the polysiloxane group-containing polymer of the present invention is applied to various substrates, it has good adhesion to the substrate, and the coating surface is well endowed with properties derived from polysiloxane. I understand.
特許出願人 日本油脂株式会社Patent applicant: NOF Corporation
Claims (1)
種または２種以上の混合物に基づく構成単位５〜８５重
量％と下記一般式（III）〜（IV）で示される化合物の
１種または２種以上の混合物に基づく構成単位１５〜９
５重量％とからなるポリシロキサン基含有重合体部分Ａ
と、一般式（III）〜（IV）で示される化合物の１種ま
たは２種以上の混合物に基づく構成単位からなる重合体
部分ＢとからなるＡ−Ｂ型ブロック共重合体であって、
前記重合体部分Ａと、前記重合体部分Ｂとの重量比率が
２５／７５〜９０／１０であり、テトラヒドロフランを
溶離液に用いてゲルパーミエーションクロマトグラフィ
ーで測定したポリスチレン換算の数平均分子量が４００
０〜１０００００であることを特徴とするポリシロキサ
ン基含有重合体。 一般式 ▲数式、化学式、表等があります▼…（ I ） 〔式中、Ｒ＿１は水素原子又はメチル基を、Ｒ＿２はメ
チル基、エチル基、フェニル基又は ▲数式、化学式、表等があります▼ （式中、Ｒ＿５は水素原子、フェニル基又はＣ＿ｐＨ＿
２＿ｐ＿＋＿１を、Ｒ＿６はメチル基、エチル基又はフ
ェニル基をそれぞれ示し、ｍは１以上の整数、ｐは１〜
１０の整数である。）を、Ｒ＿３は水素原子、フェニル
基又はＣ＿ｐＨ＿２＿ｐ＿＋＿１を、Ｒ＿４はメチル基
、エチル基又はフェニル基をそれぞれ示し、ｎは１以上
の整数、ｐは１〜１０の整数である。〕 一般式 ▲数式、化学式、表等があります▼…（II） 〔式中、Ｒ＿１は水素原子又はメチル基を、Ｒ＿２はメ
チル基、エチル基、フェニル基又は ▲数式、化学式、表等があります▼ （式中、Ｒ＿５は水素原子、フェニル基又はＣ＿ｐＨ＿
２＿ｐ＿＋＿１を、Ｒ＿６はメチル基、エチル基又はフ
ェニル基をそれぞれ示し、ｍは１以上の整数、ｐは１〜
１０の整数である。）を、Ｒ＿３は水素原子、フェニル
基又はＣ＿ｐＨ＿２＿ｐ＿＋＿１をそれぞれ示し、ｎは
１以上の整数、ｐは１〜１０の整数である。〕 一般式 ▲数式、化学式、表等があります▼…（III） 〔式中、Ｒ＿１は水素原子又はメチル基を、Ｒ＿６は水
素原子、グリシジル基、Ｃ＿ｐＨ＿２＿ｐ＿＋＿１（ｐ
は１〜２０の整数であり、Ｃ＿ｐＨ＿２＿ｐ＿＋＿１基
は直鎖状でも分枝状でもよい。）又はＣ＿ｑＨ＿２＿ｑ
ＯＨ（ｑは１〜１０の整数であり、ＯＨ基は１級でも２
級でもよい。） 一般式 ▲数式、化学式、表等があります▼…（IV） 〔式中、Ｒ＿７はＣ＿ｐＨ＿２＿ｐ＿＋＿１を示し、ｐ
は１〜２０の整数でありＣ＿ｐＨ＿２＿ｐ＿＋＿１は直
鎖状でも分枝状でもよい。〕[Claims] 1. 1 of the compounds represented by the following general formulas (I) to (II)
5 to 85% by weight of structural units based on a species or a mixture of two or more types and 15 to 9 structural units based on a mixture of one or two or more types of compounds represented by the following general formulas (III) to (IV)
Polysiloxane group-containing polymer portion A consisting of 5% by weight
and a polymer portion B consisting of a structural unit based on one type or a mixture of two or more compounds represented by general formulas (III) to (IV),
The weight ratio of the polymer portion A and the polymer portion B is 25/75 to 90/10, and the number average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as an eluent is 400.
A polysiloxane group-containing polymer having a molecular weight of 0 to 100,000. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) [In the formula, R_1 is a hydrogen atom or methyl group, R_2 is a methyl group, ethyl group, phenyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5 is a hydrogen atom, a phenyl group, or a C_pH_
2_p_+_1, R_6 represents a methyl group, ethyl group, or phenyl group, m is an integer of 1 or more, and p is 1 to
It is an integer of 10. ), R_3 represents a hydrogen atom, a phenyl group or C_pH_2_p_+_1, R_4 represents a methyl group, an ethyl group or a phenyl group, n is an integer of 1 or more, and p is an integer of 1 to 10. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼…(II) [In the formula, R_1 is a hydrogen atom or methyl group, R_2 is a methyl group, ethyl group, phenyl group, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_5 is a hydrogen atom, a phenyl group, or C_pH_
2_p_+_1, R_6 represents a methyl group, ethyl group, or phenyl group, m is an integer of 1 or more, and p is 1 to
It is an integer of 10. ), R_3 represents a hydrogen atom, a phenyl group, or C_pH_2_p_+_1, n is an integer of 1 or more, and p is an integer of 1 to 10. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼… (III) [In the formula, R_1 is a hydrogen atom or a methyl group, R_6 is a hydrogen atom, a glycidyl group, C_pH_2_p_+_1 (p
is an integer from 1 to 20, and the C_pH_2_p_+_1 group may be linear or branched. ) or C_qH_2_q
OH (q is an integer from 1 to 10, and the OH group can be primary or secondary
It can also be a grade. ) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) [In the formula, R_7 represents C_pH_2_p_+_1, p
is an integer from 1 to 20, and C_pH_2_p_+_1 may be linear or branched. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8214088A JP2658152B2 (en) | 1988-04-05 | 1988-04-05 | Polysiloxane group-containing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8214088A JP2658152B2 (en) | 1988-04-05 | 1988-04-05 | Polysiloxane group-containing polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01254719A true JPH01254719A (en) | 1989-10-11 |
| JP2658152B2 JP2658152B2 (en) | 1997-09-30 |
Family
ID=13766122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8214088A Expired - Lifetime JP2658152B2 (en) | 1988-04-05 | 1988-04-05 | Polysiloxane group-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2658152B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000103931A (en) * | 1998-09-30 | 2000-04-11 | Dow Corning Toray Silicone Co Ltd | Thermoplastic resin composition |
| US6420504B1 (en) | 1997-06-12 | 2002-07-16 | Dow Corning Toray Silicone Co., Ltd. | Branched siloxane/silalkylene copolymer, silicone-containing organic polymer, and process for producing the same |
| JP2016204456A (en) * | 2015-04-17 | 2016-12-08 | 日油株式会社 | Polysiloxane group-containing graft copolymer and adhesive composition |
| JP2018532824A (en) * | 2015-08-31 | 2018-11-08 | ビイク−ヒエミー ゲゼルシャフト ミツト ベシユレンクテル ハフツングＢＹＫ−Ｃｈｅｍｉｅ ＧｍｂＨ | Copolymers having polysiloxane macromonomer units, methods for making the copolymers, and use of the copolymers in coating compositions and polymer molding compounds |
| JP2020063328A (en) * | 2018-10-15 | 2020-04-23 | 大日本印刷株式会社 | Block copolymer, surface control agent, adhesive composition, adhesive sheet, adhesive protective sheet, laminate, optical member, and electronic member |
-
1988
- 1988-04-05 JP JP8214088A patent/JP2658152B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420504B1 (en) | 1997-06-12 | 2002-07-16 | Dow Corning Toray Silicone Co., Ltd. | Branched siloxane/silalkylene copolymer, silicone-containing organic polymer, and process for producing the same |
| JP2000103931A (en) * | 1998-09-30 | 2000-04-11 | Dow Corning Toray Silicone Co Ltd | Thermoplastic resin composition |
| JP2016204456A (en) * | 2015-04-17 | 2016-12-08 | 日油株式会社 | Polysiloxane group-containing graft copolymer and adhesive composition |
| JP2018532824A (en) * | 2015-08-31 | 2018-11-08 | ビイク−ヒエミー ゲゼルシャフト ミツト ベシユレンクテル ハフツングＢＹＫ−Ｃｈｅｍｉｅ ＧｍｂＨ | Copolymers having polysiloxane macromonomer units, methods for making the copolymers, and use of the copolymers in coating compositions and polymer molding compounds |
| JP2020063328A (en) * | 2018-10-15 | 2020-04-23 | 大日本印刷株式会社 | Block copolymer, surface control agent, adhesive composition, adhesive sheet, adhesive protective sheet, laminate, optical member, and electronic member |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2658152B2 (en) | 1997-09-30 |
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