JPS63101406A - Heat-resistance resin - Google Patents
Heat-resistance resinInfo
- Publication number
- JPS63101406A JPS63101406A JP24889886A JP24889886A JPS63101406A JP S63101406 A JPS63101406 A JP S63101406A JP 24889886 A JP24889886 A JP 24889886A JP 24889886 A JP24889886 A JP 24889886A JP S63101406 A JPS63101406 A JP S63101406A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- heat
- heat resistance
- mol
- resin
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 13
- 239000011347 resin Substances 0.000 title claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005604 random copolymer Polymers 0.000 claims abstract description 3
- 229920006015 heat resistant resin Polymers 0.000 claims description 6
- 238000010558 suspension polymerization method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 229920006026 co-polymeric resin Polymers 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 abstract description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐熱性、流動性、着色性に優れた耐熱性樹脂
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant resin that has excellent heat resistance, fluidity, and colorability.
（従来の技術と問題点）
汎用樹脂として知られているポリスチレン１ｆｆｉ／ｌ
＆やアクリロニトリル−スチレン共重合樹脂等は成形性
に優れているが、耐熱性が劣っている。従来、耐熱性を
改良する方法として、スチレン等に共重合単量体として
無水マレイン酸を用いて重合した後、イミド化する２段
階法（米国特許第８４９２１９６号）や、メタクリル酸
又はα−メチルスチレン等を共重合単量体として用いる
方法があるが、これらは耐熱性を改良できる反面、その
プロセスが複雑であったり、分子内に有するカル゛ボキ
シル基の影響で加工性が著しく低下したり、α−メチル
スチレンを用いる場合は共重合性を向上させるために使
用するアクリロニトリルによって生じる着色問題等、多
くの問題があり、かつ、これらのものの耐熱性も充分と
は言えない。(Conventional technology and problems) Polystyrene 1ffi/l, which is known as a general-purpose resin
& and acrylonitrile-styrene copolymer resins have excellent moldability but poor heat resistance. Conventionally, methods for improving heat resistance include a two-step method in which styrene is polymerized using maleic anhydride as a comonomer and then imidized (US Pat. No. 8,492,196), and methacrylic acid or α-methyl There is a method of using styrene etc. as a comonomer, but while these can improve heat resistance, the process is complicated and processability is significantly reduced due to the influence of carboxyl groups in the molecule. When using .alpha.-methylstyrene, there are many problems such as coloring caused by acrylonitrile used to improve copolymerizability, and the heat resistance of these materials is also not sufficient.
これら問題を解決するために鋭意研究した結果、比粘度
（ηｓｒ）がｏ、ｉ〜０．５で、Ｎ−イソプロピルメタ
クリルアミドとスチレン、メチルメタクレートの１種又
は２種の単量体、および必要に応じ他の共重合可能な単
量体から成る共重合体樹脂はビカット軟化温度約１１０
°Ｃ以上の高い耐熱性をもち、かつ優れた流動性、着色
性を有することを見出し、本発明に至った。As a result of intensive research to solve these problems, we found that the specific viscosity (ηsr) is o, i ~ 0.5, N-isopropyl methacrylamide, one or two monomers of styrene, methyl methacrylate, and The copolymer resin, optionally comprising other copolymerizable monomers, has a Vicat softening temperature of about 110
It was discovered that it has high heat resistance of .degree. C. or higher, as well as excellent fluidity and coloring properties, leading to the present invention.
（問題点を解決するための手段）
すなわち本発明は、
晶
■
０−ＣＨ３
Ｈ８
で表わされる構造単位（５） ２５〜９０モル％と、ｏ
ｏａｎａ
で表わされる１種または２種の構造単位（Ｂ）７５〜１
０モル％
とからなり、比粘度（η８Ｐ） （３ｏｏＣ，Ｎ、Ｎ−
ジメチルホルムアミド０．３％溶液）が０．１〜０，５
である線状ランダム共重合体耐熱性樹脂を内容とする。(Means for Solving the Problems) That is, the present invention provides the following: 25 to 90 mol% of the structural unit (5) represented by crystalline 0-CH3H8;
One or two types of structural units (B) 75-1 represented by oana
0 mol%, specific viscosity (η8P) (3ooC,N,N-
dimethylformamide 0.3% solution) is 0.1 to 0.5
The content is a linear random copolymer heat-resistant resin.
本発明の共重合体樹脂の比粘度（ηｓｒ）は０．１〜０
．５である。比粘度（η８Ｆ）はオストヮルド粘度計を
用い、Ｎ、Ｎ−ジメチルホルムアミド０．３％溶液、３
０°Ｃで測定した値をいう。The specific viscosity (ηsr) of the copolymer resin of the present invention is 0.1 to 0.
．． It is 5. The specific viscosity (η8F) was determined using an Ostold viscometer, using a 0.3% solution of N,N-dimethylformamide, 3
This refers to the value measured at 0°C.
比粘度（ηｓｐ）が０．１より小さい場合、流動性は向
上するが成形品がもろくなり、また０、５より大きい場
合、流動性が著しく低下するために好ましくない。If the specific viscosity (ηsp) is less than 0.1, the fluidity will improve, but the molded product will become brittle, and if it is more than 0.5, the fluidity will drop significantly, which is not preferred.
本発明の共重合体樹脂における構造単位（５）で示され
るＮ−イソプロピルメタクリルアミドの組成比は２５〜
９０モル％である。２５モル％より少ない場合は耐熱性
を向上させる効果がさほど発現されず、また９０モル％
より多い場合は耐熱性は向上するが成形品がもろく、ま
た流動性が低下する。The composition ratio of N-isopropylmethacrylamide represented by the structural unit (5) in the copolymer resin of the present invention is 25 to
It is 90 mol%. If it is less than 25 mol%, the effect of improving heat resistance will not be expressed so much, and if it is less than 90 mol%.
When the amount is larger, heat resistance improves, but the molded product becomes brittle and fluidity decreases.
本発明では、Ｎ−イソプロピルメタクリルアミドに共重
合させる単量体として、共重合性、耐熱性が有り、着色
性にも問題のないスチレンとメチルメタクレートが選ば
れ、任意の割合で使用できるが、スチレンの割合を０〜
２５モル％にすれば、得られる共重合体樹脂の透明性が
よく、またスチレンの割合を２５〜１００モル％、さら
に好ましくは５０〜ｌＯＯモル％にすると流動性が良い
。In the present invention, styrene and methyl methacrylate are selected as monomers to be copolymerized with N-isopropylmethacrylamide, as they have copolymerizability, heat resistance, and do not cause problems in coloring properties, and can be used in any ratio. , the proportion of styrene is 0~
When the proportion of styrene is 25 mol %, the resulting copolymer resin has good transparency, and when the proportion of styrene is 25 to 100 mol %, more preferably 50 to 100 mol %, the fluidity is good.
本発明でいうスチレンとは、スチレン及びパラクロロス
チレン、オルトクロロスチレン、パラメチルスチレン等
の核置換スチレンをいう。Styrene as used in the present invention refers to styrene and nuclear-substituted styrenes such as parachlorostyrene, orthochlorostyrene, and paramethylstyrene.
本発明においては、必要に応じ、添加できる他の共重合
可能な単量体として、メタクリル酸、無水マレイン酸、
Ｎ−フェニルマレイミド、α−メチルスチレン、アクリ
ロニトリル、メタクレートリル等の単量体を単独又は併
用して使用できる。In the present invention, other copolymerizable monomers that can be added as necessary include methacrylic acid, maleic anhydride,
Monomers such as N-phenylmaleimide, α-methylstyrene, acrylonitrile, and methacrylate can be used alone or in combination.
その使用量は０〜１５モル％である。The amount used is 0 to 15 mol%.
本発明における共重合の方法は待に限定されるものでは
なく、通常の懸濁重合法、乳化重合法、塊状重合法、溶
液重合法等が用いられる。特に排水処理、乾燥工程の簡
便な懸濁重合法が好ましい。The method of copolymerization in the present invention is not limited to polymerization, and conventional suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization, etc. can be used. In particular, a suspension polymerization method is preferred because of its simple wastewater treatment and drying steps.
反応に際し、過酸化物、アゾ系化合物などの公知の開始
剤が好適に用いられ、また公知のレドックス系開始剤も
使用できる。また懸濁重合法、乳化重合法等では公知の
分散剤、乳化剤が使用できる。In the reaction, known initiators such as peroxides and azo compounds are suitably used, and known redox initiators can also be used. Further, in the suspension polymerization method, emulsion polymerization method, etc., known dispersants and emulsifiers can be used.
反応は通常３０〜１５０°Ｃの温度で１〜１５時間行な
われる。また分子量の調節のために、ｔ−ドデシルメル
カプタン、２−メルカプトエタノール等の公知の連鎖移
動剤や、ジアリルフタレート。The reaction is usually carried out at a temperature of 30 to 150°C for 1 to 15 hours. In addition, for controlling the molecular weight, known chain transfer agents such as t-dodecylmercaptan and 2-mercaptoethanol, and diallyl phthalate are used.
ジエチレングリコールジアクリレート、エチレングリコ
ールジメタアクリレート等の公知の多官能性化合物を共
重合体樹脂製造時に使用してもよい。Known polyfunctional compounds such as diethylene glycol diacrylate and ethylene glycol dimethacrylate may be used during the production of the copolymer resin.
また、ベヘニン酸、ステアリン酸、流動パラフィン等の
公知の滑剤を共重合体樹脂製造時に添加してもよい。Furthermore, known lubricants such as behenic acid, stearic acid, and liquid paraffin may be added during the production of the copolymer resin.
本発明で得られる共重合体樹脂は、単独は勿論、前記の
滑剤や公知の安定剤、着色剤、難燃剤、顔料その他各種
のポリマーとブレンドして利用してもよい。ブレンドす
る各種ポリマーとしては、ポリ塩化ビニル系樹脂、塩素
化塩化ビニル系樹脂。The copolymer resin obtained in the present invention may be used alone or in a blend with the above-mentioned lubricants, known stabilizers, colorants, flame retardants, pigments, and various other polymers. Various polymers to be blended include polyvinyl chloride resin and chlorinated vinyl chloride resin.
ＭＥＳ系樹脂、塩素化ポリエチレン系樹脂、アクリルゴ
ム系樹脂、ＮＢＲ系圏脂およびポリカーボネート樹脂、
ボリアリレート系樹脂やポリアミド系樹脂等のエンジニ
アリングプラスチック等公知の樹脂がある。MES resin, chlorinated polyethylene resin, acrylic rubber resin, NBR resin and polycarbonate resin,
There are known resins such as engineering plastics such as polyarylate resins and polyamide resins.
本発明の共重合体樹脂は、インジェクション。The copolymer resin of the present invention is an injection method.
ロール、押出成形機で加工成形できる。また、製品形態
としてはプラスチック成形体分野、発泡成形体分野に利
用できる。Can be processed and molded using a roll or extrusion molding machine. Further, as a product form, it can be used in the fields of plastic molded products and foam molded products.
（実施例）
以下に本発明の実施例を示すが、これらは本発明を限定
するものではない。(Example) Examples of the present invention are shown below, but these do not limit the present invention.
本発明の共重合体樹脂の組成は元素分析及び１Ｈ−ＮＭ
Ｒで決定した。The composition of the copolymer resin of the present invention was determined by elemental analysis and 1H-NM
I decided on R.
なお、耐熱性、流動性９着色性、透明性の測定は、樹脂
をロール、プレス後、次に示す方法で行なった。The heat resistance, fluidity, colorability, and transparency were measured by the following methods after the resin was rolled and pressed.
耐熱性：ビカット軟化温度（ＪＩＳ−に−７２０６）５
ｋＱ ／ ｄ加重
流動性二Ｂ法フロー（ＪＩＳ−に−７２１０）、測定温
度２４０°Ｃ，１ＯＯｋｑ／ＣΔ加重透明性： ＪＩＳ
−に−６７１４に従って透過率を測定し、次のように判
定し１こ。Heat resistance: Vicat softening temperature (JIS-ni-7206) 5
kQ/d weighted fluidity 2B method flow (JIS-7210), measurement temperature 240°C, 1OOkq/CΔ weighted transparency: JIS
- Measure the transmittance according to -6714 and judge as follows.
着色性二目視によって次のように判定した。Coloring property was determined by two-eye observation as follows.
実施例１〜３、比較例１〜２
撹拌機つきＢオートクレーブにポリビニルアルコール０
．３ダを溶解した脱イオン水６００ダを入れ、撹拌状態
でＮ−イソプロピルメタクリルアミド６０ｙ１メチルメ
タクレート４０ｆ１およびモノマー合計１００重量部に
対して表１に示す割合の開始剤の混合物を加えた後、窒
素置換した。Examples 1-3, Comparative Examples 1-2 0 polyvinyl alcohol in B autoclave with stirrer
．． After adding 600 da of deionized water in which 3 Da was dissolved, and adding under stirring a mixture of N-isopropyl methacrylamide 60y1 methyl methacrylate 40f1 and an initiator in the proportion shown in Table 1 based on 100 parts by weight of the total monomers, The atmosphere was replaced with nitrogen.
９０°Ｃに昇温し、７時間の重合を行なった後、更に１
２０°Ｃに昇温し４時間重合を行なった。After raising the temperature to 90°C and polymerizing for 7 hours,
The temperature was raised to 20°C and polymerization was carried out for 4 hours.
得られた共重合体樹脂をロール、プレスした後、耐熱性
、流動性、透明性９着色性について測定した。比較例の
結果も併せて表１に示す。また各々の共重合体樹脂の比
粘度（ηｓｐ）を表１に示す。After rolling and pressing the obtained copolymer resin, heat resistance, fluidity, transparency, and colorability were measured. The results of comparative examples are also shown in Table 1. Table 1 also shows the specific viscosity (ηsp) of each copolymer resin.
以下余白
実施例１〜３と比較例１〜２を比較することにより、比
粘度（ηＳＦ）が０．１より小さい場合、流動性は向上
するが、もろくて成形ができなくなり、また０、５より
大きい場合、流動性が著しく低下することが分かる。By comparing Margin Examples 1 to 3 and Comparative Examples 1 to 2 below, it was found that when the specific viscosity (ηSF) is smaller than 0.1, the fluidity improves, but it becomes brittle and cannot be molded; It can be seen that when it is larger, the fluidity is significantly reduced.
実施例４〜８
表２に示した種々の組成の単量体１００重量部に対し、
ベンゾイルパーオキシド０．１０重量部、ｔ−ブチルパ
ーオキシ−８，５，５−トリメチルヘキサノエート０．
１０重量部を用いて実施例１〜３と同様な方法で重合さ
せた後、各物性を測定した。Examples 4 to 8 For 100 parts by weight of monomers having various compositions shown in Table 2,
0.10 parts by weight of benzoyl peroxide, 0.0 parts by weight of t-butylperoxy-8,5,5-trimethylhexanoate.
After polymerizing in the same manner as in Examples 1 to 3 using 10 parts by weight, each physical property was measured.
結果を表２に示す。比較例３〜５として表２に示した種
々の組成の単量体１００重量部に対し、実施例４〜８と
同様の開始剤を用いて実施例１〜３と同様な方法で重合
させた場合の結果を表２に併記した。The results are shown in Table 2. 100 parts by weight of monomers having various compositions shown in Table 2 as Comparative Examples 3 to 5 were polymerized in the same manner as Examples 1 to 3 using the same initiators as in Examples 4 to 8. The results are also listed in Table 2.
比較例６
スチレン７０ｙ１メタクリル酸８０ｙ、ベンゾイルパー
オキシド０．８重量部、ｔ−ブチルパーオキシ−３，５
，５−トリメチルヘキサノエート０．１０重量部の混合
溶液をオートクレーブに入れ、窒素置換後、９０°Ｃに
昇温し、７時間重合を行なった後、更に１２０°Ｃに昇
温し４時間重合を行なった。Comparative Example 6 Styrene 70y1 methacrylic acid 80y, benzoyl peroxide 0.8 parts by weight, t-butylperoxy-3,5
, 0.10 parts by weight of 5-trimethylhexanoate was placed in an autoclave, and after purging with nitrogen, the temperature was raised to 90°C, polymerization was carried out for 7 hours, and then the temperature was further raised to 120°C for 4 hours. Polymerization was carried out.
得られた共重合体樹脂を粉砕し、ロールプレスした後、
各物性を測定した結果を表２に併記した。After crushing and roll pressing the obtained copolymer resin,
The results of measuring each physical property are also listed in Table 2.
以下余白
実施例２．４．５からＮ−イソプロピルメタクリルアミ
ドの組成比を増加させる程、耐熱性を大巾に向上させる
ことができ、比較例３のポリスチレンに対し、約１０°
Ｃ以上の耐熱性を向上できることが分かる。また比較例
４のＮ−イソプロピルメタクリルアミドが２５モル％よ
り少ない場合では耐熱性改良の効果が小さく、比較例５
では流動性の低下が著しく、また脆いことが分かる。ま
た実施例６．７から、表２の単量体（イ）中のスチレン
組成比を２５〜１００モル％にすることにより耐熱性を
維持して、かつ流動性を向上できることが分かる。また
実施例８から、表２の単量体（ロ）を１５モル％用いた
場合、流動性をさほど低下させずに、耐熱性をさらに向
上できることが分かる。From the margin Example 2.4.5 below, as the composition ratio of N-isopropylmethacrylamide is increased, the heat resistance can be greatly improved, and compared to the polystyrene of Comparative Example 3, it is approximately 10°
It can be seen that heat resistance of C or higher can be improved. Furthermore, when the amount of N-isopropylmethacrylamide in Comparative Example 4 is less than 25 mol%, the effect of improving heat resistance is small;
It can be seen that the fluidity has significantly decreased and it is brittle. Moreover, from Example 6.7, it can be seen that by setting the styrene composition ratio in monomer (a) in Table 2 to 25 to 100 mol %, heat resistance can be maintained and fluidity can be improved. Further, from Example 8, it can be seen that when 15 mol% of monomer (b) in Table 2 is used, the heat resistance can be further improved without significantly reducing the fluidity.
本発明の共重合体樹脂は、比較例６のように従来のメタ
クリル酸等を用いる耐熱性向上の方法と比較し、流動性
を著しく向上できる（実施例２．６．７）。The copolymer resin of the present invention can significantly improve fluidity compared to the conventional method of improving heat resistance using methacrylic acid or the like as in Comparative Example 6 (Example 2.6.7).
Claims (5)
０モル％ とからなり、比粘度（ηｓｐ）（３０℃、Ｎ，Ｎ−ジメ
チルホルムアミド０．３％溶液）が０．１〜０．５であ
る線状ランダム共重合体耐熱性樹脂。(1) Formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 25 to 90 mol% of the structural unit (A) represented by and Formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. There is one or two types of structural units (B) 75-1 represented by ▼
A heat-resistant linear random copolymer resin having a specific viscosity (ηsp) (30° C., 0.3% N,N-dimethylformamide solution) of 0.1 to 0.5.
割合が０〜２５モル％である特許請求の範囲第１項記載
の耐熱性樹脂。(2) The heat-resistant resin according to claim 1, wherein the proportion of styrene in the monomer represented by structural unit (B) is 0 to 25 mol%.
割合が２５〜１００モル％である特許請求の範囲第１項
記載の耐熱性樹脂。(3) The heat-resistant resin according to claim 1, wherein the proportion of styrene in the monomer represented by structural unit (B) is 25 to 100 mol%.
割合が５０〜１００モル％である特許請求の範囲第３項
記載の耐熱性樹脂。(4) The heat-resistant resin according to claim 3, wherein the proportion of styrene in the monomer represented by structural unit (B) is 50 to 100 mol%.
〜４項の何れかの項記載の耐熱性樹脂。(5) Claim 1 obtained by suspension polymerization method
The heat-resistant resin according to any one of items 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24889886A JPS63101406A (en) | 1986-10-20 | 1986-10-20 | Heat-resistance resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24889886A JPS63101406A (en) | 1986-10-20 | 1986-10-20 | Heat-resistance resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63101406A true JPS63101406A (en) | 1988-05-06 |
Family
ID=17185075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24889886A Pending JPS63101406A (en) | 1986-10-20 | 1986-10-20 | Heat-resistance resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63101406A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031523A1 (en) * | 2007-09-03 | 2009-03-12 | University Of Yamanashi | Temperature-sensitive polymer, temperature-sensitive fiber and non-woven fabric each using the same, and method for production of temperature-sensitive fiber and non-woven fabric |
-
1986
- 1986-10-20 JP JP24889886A patent/JPS63101406A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009031523A1 (en) * | 2007-09-03 | 2009-03-12 | University Of Yamanashi | Temperature-sensitive polymer, temperature-sensitive fiber and non-woven fabric each using the same, and method for production of temperature-sensitive fiber and non-woven fabric |
| JP2009057522A (en) * | 2007-09-03 | 2009-03-19 | Univ Of Yamanashi | Temperature-responsive polymer, temperature-responsive fiber or nonwoven fabric using the same, and mtehod for producing the same |
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