JPS63101407A - Heat-resistant resin - Google Patents
Heat-resistant resinInfo
- Publication number
- JPS63101407A JPS63101407A JP24889986A JP24889986A JPS63101407A JP S63101407 A JPS63101407 A JP S63101407A JP 24889986 A JP24889986 A JP 24889986A JP 24889986 A JP24889986 A JP 24889986A JP S63101407 A JPS63101407 A JP S63101407A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- heat
- styrene
- resistant resin
- structural unit
- 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
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920005604 random copolymer Polymers 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 19
- 238000010558 suspension polymerization method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 5
- 238000000034 method Methods 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 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 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 1
- 229920006026 co-polymeric resin Polymers 0.000 description 17
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004040 coloring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 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
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 239000004793 Polystyrene Substances 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
- 239000013078 crystal Substances 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
- 229920006351 engineering plastic Polymers 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene 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
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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２着色性、透明性に優れた耐
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 is excellent in heat resistance, fluidity, colorability, and transparency.
（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樹脂やアクリ
ロニトリル−スチレン共重合樹脂等は成形性に優ｎ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３４９２１９６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かっ
た。(Prior Art and Problems) Polystyrene resins, acrylonitrile-styrene copolymer resins, and the like, which are known as general-purpose resins, have excellent moldability but are inferior in 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. 3,492,196), 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 the processability is significantly reduced due to the influence of the carboxyl group in the molecule. - When using methylstyrene, there are many problems such as coloring caused by acrylonitrile used to improve copolymerizability, and the heat resistance of these products 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
（ηｓｐ）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より選ば
れる１種又は２種の単量体とメタクリル酸、無水マレイ
ン酸より選ばｎる１種又は２種の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、透明性を有する
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 one or two monomers selected from N-isopropyl methacrylamide, styrene, and methyl methacrylate with a specific viscosity (ηsp) of o, i ~ 0.5. The copolymer resin is composed of one or two monomers selected from methacrylic acid, maleic anhydride, and has high heat resistance with a Vicat softening temperature of approximately 110°C or higher, as well as excellent fluidity and colorability. It was discovered that the material has transparency, 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
雲
０Ｍ８
で表わされる構造単位（５） ２５〜９０モル％、Ｇ！
０００Ｈ３
で表わされる１種または２種の構造単位（Ｂ）７３〜８
モル％
で表わされる１種または２種の構造単位（Ｃ）２〜１５
モル％
（（３）、ω）、（Ｃ））合わせて１００モル％）から
なり、比粘度（ηｓｒ） （８ｏ℃、Ｎ、Ｎ−ジメチル
ホルムアミド０．３％溶液ンが０．１〜０．５である線
状ランダム共重合体耐熱性ｆＭ脂を内容とする。(Means for Solving the Problems) That is, the present invention provides the following: Structural unit (5) represented by crystal cloud 0M8 25 to 90 mol%, G!
One or two types of structural units (B) 73-8 represented by 000H3
One or two types of structural units (C) 2 to 15 expressed in mol%
mol% ((3), ω), (C)) total 100 mol%), specific viscosity (ηsr) (8o C, N,N-dimethylformamide 0.3% solution is 0.1 to 0 The content is a linear random copolymer heat resistant fM resin having a temperature of .5.
本発明の共重合体樹脂の比粘度（ηｓｒ）はＯ，１〜０
．５である。比粘度（ηｓｐ）はオストワルド粘度計を
用い、Ｎ、Ｎ−ジメチルホルムアミド０，１３％溶液、
３０°Ｃで測定した値をいう。The specific viscosity (ηsr) of the copolymer resin of the present invention is O, 1 to 0.
．． It is 5. The specific viscosity (ηsp) was measured using an Ostwald viscometer, using a 0.13% solution of N,N-dimethylformamide,
This refers to the value measured at 30°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（３）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 (3) 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.
本発明の共重合体樹脂における構造単位（Ｂ）で示され
る単量体の組成比は７３〜８モル％である。The composition ratio of the monomer represented by the structural unit (B) in the copolymer resin of the present invention is 73 to 8 mol%.
この単量体としては、共重合性、耐熱性があり、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０〜２
５モル％にすれば、得られる共重合体樹脂の透明性が良
く、またスチレンの割合を２５〜１００モル％、さらに
好ましくは５０〜１００モル％にすると流動性が良い。As this monomer, styrene and methyl methacrylate, which are copolymerizable, heat resistant, and have no coloring problems, are selected, and can be used in any ratio, but the ratio of styrene is 0 to 2.
When the proportion of styrene is 5 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、更に共重合可能な構造単位（Ｃ）で示
される単量体としては、メタクリル酸、無水マレイン酸
があり、耐熱性、透明性向上の効果がある。これらは単
独又は併用して使用できる。In the present invention, the monomer represented by the structural unit (C) which can be further copolymerized includes methacrylic acid and maleic anhydride, which have the effect of improving heat resistance and transparency. These can be used alone or in combination.
構造単位（Ｃ）で示される単量体の組成比は２〜１５モ
ル％である。２モル％未満では耐熱性の向上の効果がな
く、１５モル％をこえると耐熱性を向上できる反面、著
しく流動性が低下する。特に、前記した単量体であるス
チレンの割合が２５モル％以上の場合でも、メタクリル
酸、無水マレイン酸をスチレンに対し１２モル％以上の
割合で用いれば、得られる共重合体樹脂は優れた透明性
、耐熱性を有し、かつ流動性、着色性も良い。The composition ratio of the monomer represented by structural unit (C) is 2 to 15 mol%. If it is less than 2 mol %, there is no effect of improving heat resistance, and if it exceeds 15 mol %, heat resistance can be improved, but fluidity is significantly reduced. In particular, even if the proportion of styrene, which is the monomer mentioned above, is 25 mol% or more, if methacrylic acid or maleic anhydride is used in a proportion of 12 mol% or more relative to styrene, the resulting copolymer resin will be excellent. It has transparency and heat resistance, and also has good fluidity and colorability.
本発明における共重合の方法は特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 particularly limited, and common suspension polymerization methods, emulsion polymerization methods, bulk polymerization methods, solution polymerization methods, 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、乳化剤が吏用できる。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ｐ 流動’ ５ 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。Further, known lubricants such as behenic acid and stearic acid p-fluid' 5 fins may be added at the time of producing 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９着色剤、難燃剤、顔料その他各揮
のポリマーとブレンドして利用してもよい。ブレンドす
る各皿ポリマーとしては、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 other various polymers. The polymers to be blended are polyvinyl chloride resin and chlorinated vinyl chloride resin.
ＭＢＳ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系樹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。MBS 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’Ｈ−ＮＭ
几で決定した。The composition of the copolymer resin of the present invention was determined by elemental analysis and 'H-NM
It was decided by Rin.
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 −Ｋ −７２０６
）５ｋｑ／ｃｄ加重
流動性：Ｂ法７Ｏ−（ＪＩＳ−に−７２１０）、測定温
度２４０°Ｃ，１００ｋＱ／ｄ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
した。Heat resistance: Vicat softening temperature (JIS-K-7206
) 5kq/cd weighted fluidity: B method 7O- (JIS-7210), measurement temperature 240°C, 100kQ/d weighted transparency: JIS-
Transmittance was measured according to -6714 and determined as follows.
透過率 ８５％以上 ８５〜７０７０％以下記号 ◎
○ ×
着色性二目視によって次のように判定した。Transmittance 85% or more 85-7070% or less Symbol ◎
○ × Coloring property: Judgment was made as follows by two-eye observation.
内 容 記号
はとんど着色していない ◎
ごく薄く黄色着色あり ○
黄色に着色 △
実施例１〜３、比較例１〜２
撹拌機つき１１オートクレーブ中、ポリビニルアルコー
ル０．３ダを醍解した脱イオン水６００Ｆに撹拌状態で
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３８ｇ、メタクリル酸２ｆ、およびモノマー１
００重量部に対し、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。９０°Ｃに昇温し、７時間の
重合を行なった後、１２０°Ｃに昇温し、４時間重合を
行なった。Contents Symbols are hardly colored ◎ Very light yellow coloring ○ Yellow coloring △ Examples 1 to 3, Comparative Examples 1 to 2 0.3 Da of polyvinyl alcohol was dissolved in a 11 autoclave equipped with a stirrer. N-isopropylmethacrylamide 60y1 38g methyl methacrylate, 2f methacrylic acid, and 1 monomer in 600F deionized water with stirring
After adding a mixture of initiators in the proportions shown in Table 1 to 00 parts by weight, the atmosphere was purged with nitrogen. After the temperature was raised to 90°C and polymerization was performed for 7 hours, the temperature was raised to 120°C and polymerization was performed for 4 hours.
得られｔこ共重合体樹脂をロール加熱、プレスした後、
耐熱性、流動性、透明性２着色性（こついて測定した。After heating and pressing the obtained copolymer resin with a roll,
Heat resistance, fluidity, transparency, 2 colorability (measured with difficulty).
まｔコ各々の共重合体樹脂の比粘度（ηｓｐ＞を測定し
た。結果を表１に示す。比較例１〜２についても同様に
重合後、各物性を表１に併せ示した。The specific viscosity (ηsp>) of each copolymer resin was measured. The results are shown in Table 1. Table 1 also shows the physical properties of Comparative Examples 1 and 2 after polymerization.
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（η８Ｐ）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ｆ： ０．５
より大きい場合、流動性が著しく低下することが分る。By comparing Margin Examples 1 to 3 and Comparative Examples 1 to 2 below, it is found that when the specific viscosity (η8P) is smaller than 0.1, the fluidity improves, but it becomes brittle and cannot be molded, and f: 0 .5
It can be seen that when it is larger, the fluidity is significantly reduced.
実施例４〜１０
表２＃こ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−３，５，５−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 10 Table 2: 0.10 parts by weight of benzoyl peroxide and 0 parts by weight of t-butylperoxy-3,5,5-trimethylhexanoate for 100 parts by weight of monomers having various compositions shown.
．． 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。The results are shown in Table 2.
比較例３〜６
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０．１重量部、ｔ−ブチルパー
オキシ−３，５，５−）ウメチルヘキサノエート０．１
０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。結果を表２に示す。Comparative Examples 3 to 6 For 100 parts by weight of monomers of various compositions shown in Table 2,
Benzoyl peroxide 0.1 part by weight, t-butylperoxy-3,5,5-)umethylhexanoate 0.1
After polymerizing in the same manner as in Examples 1 to 3 using 0 parts by weight, each physical property was measured. The results are shown in Table 2.
比較例７
スチレン８０ｙ１メタクリル酸２０ｆ１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−８，５
，５−トリメチルヘキサノエート０．１０重合部の混合
溶液をオートクレーブに入れ、窒素置換後９０℃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。得らｎた共重合樹脂を粉砕し、
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。Comparative Example 7 Styrene 80y1 Methacrylic acid 20f1 Benzoyl peroxide 0.8 parts by weight, t-butyl peroxy-8,5
A mixed solution of 0.10 polymerization parts of 5-trimethylhexanoate was placed in an autoclave, and after purging with nitrogen, the temperature was raised to 90°C and polymerized for 7 hours, and then the temperature was further raised to 120°C and polymerized for 4 hours. I did it. The obtained copolymer resin was pulverized,
After roll pressing, 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１５°
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
り少ないと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、また成形品は脆いものであった。From the following blank example 2.4.5, 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, the heat resistance is approximately 15°
It can be seen that heat resistance of C or higher can be improved. Furthermore, when the N-isopropylmethacrylamide content in Comparative Example 4 was less than 25 mol %, the effect of improving heat resistance was small, and in Comparative Example 5, the fluidity decreased significantly and the molded product was brittle.
また実施例４．６．７から、構造単位０３）の表２の単
量体（イ）中のスチレン組成比を増加させる程、流動性
を大巾に向上でき、また単量体（イ）中のメチルメタク
レートの組成比を７５モル％以上にすれば透明性が向上
することが分かる（実施例７）。Furthermore, from Example 4.6.7, the fluidity can be greatly improved as the styrene composition ratio in monomer (a) in Table 2 of structural unit 03) is increased; It can be seen that transparency is improved when the composition ratio of methyl methacrylate is 75 mol % or more (Example 7).
実施例６〜１０から、構造単位（Ｂ）の表２の単量体（
イ）中のスチレンの割合が２５モル％以上の場合でも、
構造単位（Ｃ）の表２の単量体（ロ）のメタクリル酸、
無水マレイン酸をスチレンに対し、１２モル％以上の割
合で用いれば、得られる共重合体樹脂は優れた透明性、
耐熱性を有し、かつ流動性、着色性も良いことが分かる
。また比較例６から、構造単位（Ｃ）で示される表２の
単量体（ロ）の更用量を１５モル％より多くする場合、
流動性が著しく低下することが分かる。From Examples 6 to 10, the monomers in Table 2 of the structural unit (B) (
b) Even if the proportion of styrene in it is 25 mol% or more,
methacrylic acid as monomer (b) in Table 2 of structural unit (C);
If maleic anhydride is used in a proportion of 12 mol% or more based on styrene, the resulting copolymer resin has excellent transparency,
It can be seen that it has heat resistance, and also has good fluidity and colorability. Furthermore, from Comparative Example 6, when the additional amount of the monomer (b) in Table 2 represented by the structural unit (C) is increased to more than 15 mol%,
It can be seen that the fluidity is significantly reduced.
本発明の共重合体樹脂は、比較例７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４）。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 7 (Example 4).
Claims (6)
数式、化学式、表等があります▼及び ▲数式、化学式、表等があります▼ で表わされる１種または２種の構造単位（２）７３〜８
モル％ 式：▲数式、化学式、表等があります▼及び ▲数式、化学式、表等があります▼ で表わされる１種または２種の構造単位（Ｃ）２〜１５
モル％ （（Ａ）、（Ｂ）、（Ｃ）合わせて１００モル％）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. ▼ Structural unit (A) represented by 25 to 90 mol%, Formula: ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ One or two types of structural units (2) 73-8
Mol% Formula: One or two types of structural units (C) 2 to 15 represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
It consists of mol% ((A), (B), (C) total 100 mol%), and has a specific viscosity (ηsp) (30°C, 0.3% N,N-dimethylformamide solution) of 0.1 to 0. A linear random copolymer heat-resistant resin having a temperature of .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%.
して、構造単位（Ｃ）で示される単量体のメタクリル酸
および／又は無水マレイン酸の割合が１２モル％以上で
ある特許請求の範囲第１〜４項の何れかの項記載の耐熱
性樹脂。(5) A patent in which the ratio of methacrylic acid and/or maleic anhydride as a monomer represented by structural unit (C) to styrene as a monomer represented by structural unit (B) is 12 mol% or more A heat-resistant resin according to any one of claims 1 to 4.
〜５項の何れかの項記載の耐熱性樹脂。(6) Claim 1 obtained by suspension polymerization method
The heat-resistant resin according to any one of items 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24889986A JPS63101407A (en) | 1986-10-20 | 1986-10-20 | Heat-resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24889986A JPS63101407A (en) | 1986-10-20 | 1986-10-20 | Heat-resistant resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63101407A true JPS63101407A (en) | 1988-05-06 |
Family
ID=17185089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24889986A Pending JPS63101407A (en) | 1986-10-20 | 1986-10-20 | Heat-resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63101407A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6135644A (en) * | 1998-02-24 | 2000-10-24 | Fujitsu Limited | Structures for optical semiconductor module, optical connector, and shape adapting optical connector |
| 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 JP24889986A patent/JPS63101407A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6135644A (en) * | 1998-02-24 | 2000-10-24 | Fujitsu Limited | Structures for optical semiconductor module, optical connector, and shape adapting optical connector |
| 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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