JPS6323949A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPS6323949A JPS6323949A JP16847186A JP16847186A JPS6323949A JP S6323949 A JPS6323949 A JP S6323949A JP 16847186 A JP16847186 A JP 16847186A JP 16847186 A JP16847186 A JP 16847186A JP S6323949 A JPS6323949 A JP S6323949A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- vinylidene fluoride
- polyvinylidene fluoride
- unit
- vdf
- 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
- 239000011342 resin composition Substances 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 229920001577 copolymer Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000002033 PVDF binder Substances 0.000 abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 27
- 229920000058 polyacrylate Polymers 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FQMIAEWUVYWVNB-UHFFFAOYSA-N 3-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OC(C)CCOC(=O)C=C FQMIAEWUVYWVNB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- -1 and in many cases Polymers 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（従来の技術）
本発明は改良された物性的特性を有するポリフッ化ビニ
リデン系重合体とアクリレート系樹脂とから成る樹脂組
成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Prior Art) The present invention relates to a resin composition comprising a polyvinylidene fluoride polymer and an acrylate resin having improved physical properties.
ポリフッ化ビニリデン樹脂は、耐熱性、耐薬品性に優れ
ており、さらに機械的性質、電気的性質にも優れている
ことは広く知られている。It is widely known that polyvinylidene fluoride resin has excellent heat resistance and chemical resistance, as well as excellent mechanical properties and electrical properties.
また、フッ素樹脂の中でも特に加工性に富んでいる為、
金属へのラミネート材料、電線被覆材料、コーテイング
材等、種々の工業的用途に用いられている。In addition, it is particularly easy to process among fluororesins, so
It is used in a variety of industrial applications, such as laminating materials for metals, wire sheathing materials, and coating materials.
しかしながら、ＰＶＤＦは、結晶性樹脂であシ結晶化速
度も大きい。この結晶化度の高いことが、当該成形品の
良好な機械的特性を発揮することに寄与しているが、逆
に、この結晶性の為に当該成形品が柔軟性に欠け、用途
によっては、これが欠点となることがある。However, PVDF is a crystalline resin and has a high crystallization rate. This high degree of crystallinity contributes to the molded product exhibiting good mechanical properties, but on the other hand, due to this crystallinity, the molded product lacks flexibility and may be used depending on the application. , this can be a drawback.
例えばポリフッ化ビニリデン系ポリマーよシ延伸フィル
ムを作成する場合、高度の分子配付が生じ、この引裂強
度が十分でなく、延伸シートの用途によっては、破損が
発生し易い等の不都合が生ずる。For example, when a stretched film is made from a polyvinylidene fluoride polymer, a high degree of molecular distribution occurs, resulting in insufficient tear strength and, depending on the use of the stretched sheet, problems such as easy breakage.
そこで、このポリフッ化ビニリデン系ポリマーの結晶性
を抑制する為に、当該ポリマーに対して相溶性のある他
の樹脂あるいは可塑剤をブレンドする方法がとられてい
る。Therefore, in order to suppress the crystallinity of this polyvinylidene fluoride-based polymer, a method has been adopted in which other resins or plasticizers that are compatible with the polymer are blended.
しかしながら、ブレンドする他の樹脂あるいは可塑剤と
してはポリフッ化ビニリデンポリマーとの相溶性の良い
ものが少なく、多くの場合、これら添加剤をブレンドし
たポリフッ化ビニリデン樹脂組成物は不均質混合物を形
成しておシ、その物理的性質に悪影響を及ぼすことが多
い。However, there are few other blended resins or plasticizers that have good compatibility with polyvinylidene fluoride polymers, and in many cases, polyvinylidene fluoride resin compositions blended with these additives form a heterogeneous mixture. Oshi, often has a negative effect on its physical properties.
ポリフッ化ビニリデンと相溶性の良い樹脂としては、特
公昭５５−４５０４２号公報に示されたメチルメタクリ
レート樹脂が知られておシ、その他にメチルメタクリレ
ート樹脂の類似化合物である他のアクリレート重合体あ
るいは共重合体もポリフッ化ビニリデンと相溶性がある
ことが知られている。As a resin having good compatibility with polyvinylidene fluoride, methyl methacrylate resin disclosed in Japanese Patent Publication No. 55-45042 is known, and other acrylate polymers or copolymer resins which are similar compounds of methyl methacrylate resin are also known. Polymers are also known to be compatible with polyvinylidene fluoride.
（発明が解決しようとする問題点）
しかしながら、ポリフッ化ビニリデンポリマーにこれら
のアクリレート系重合体をブレンドして得−られる樹脂
組成物においてもポリフッ化ビニリデンポリマ含有量の
多い組成物では、加熱ニよシ、ポリフッ化ビニリデンが
結晶化する為に、その耐熱安定性に難がある。また逆に
当該樹脂組成物中のポリフッ化ビニリデン含有割合の少
ない樹脂組成物よシ作られた成型物はそ。(Problems to be Solved by the Invention) However, even in resin compositions obtained by blending these acrylate polymers with polyvinylidene fluoride polymers, compositions containing a large amount of polyvinylidene fluoride polymers are susceptible to heating. However, since polyvinylidene fluoride crystallizes, its heat stability is poor. Conversely, molded products made from resin compositions with a low content of polyvinylidene fluoride in the resin composition.
の機械的特性が著しく低下するという欠点があり、この
ような不都合のないポリフッ化ビニリデン系重合体組成
物の開発が強く望まれている。However, there is a strong desire to develop a polyvinylidene fluoride polymer composition that does not have such disadvantages.
（問題点を解決するための手段）
そこで、本発明者等は、上述した如き不都合のない成型
品を作シ得るポリフッ化ビニリデン系樹脂を得ることを
目的として検討した結果、テトフフルオロエチレン（以
下、ＴＦｇと略記する）とヘキサフルオロプロピレンＣ
Ｌｌ 下ＲＦＰと略記する）をフッ化ビニリデン（以下
ＶＤＦと略記する）と共重合することによシ、有利に、
その目的が達成され得ることを見い出したものでちり、
本発明によれば、ポリフッ化ビニリデン系ポリマーよシ
作られた成型品の有する柔軟性、耐衝撃性等の力学的性
質とアクリレート系重合体の優れた透明性、加工性等の
特性を併ね備えた樹脂組成物を得るととに成功したので
ある。(Means for Solving the Problems) Therefore, the present inventors investigated with the aim of obtaining a polyvinylidene fluoride resin that can produce molded products without the above-mentioned disadvantages. , TFg) and hexafluoropropylene C
Advantageously, by copolymerizing Ll (hereinafter abbreviated as RFP) with vinylidene fluoride (hereinafter abbreviated as VDF),
I have found that the purpose can be achieved,
According to the present invention, the mechanical properties such as flexibility and impact resistance of molded products made from polyvinylidene fluoride polymers are combined with the excellent transparency and processability properties of acrylate polymers. They succeeded in obtaining a resin composition with the following properties.
本発明を実施するに際して用いるポリフッ化ビニリデン
系ポリマーはＶＤＦ単位が４０〜９８モ／１／チ、ＴＦ
’Ｅ単位が１〜４０モ／Ｉ／チ、ＨＦ’Ｐ単位が１〜４
０モ／Ｉ／チからなる共重合体組成を有している点に特
徴がある。The polyvinylidene fluoride polymer used in carrying out the present invention has VDF units of 40 to 98 mo/1/ti, TF
'E unit is 1-40 mo/I/chi, HF'P unit is 1-4
It is characterized by having a copolymer composition consisting of 0 mo/I/ti.
本発明で用いるポリフッ化ビニリデン系ポリマー中のＶ
ＤＦ共重合割合が、前記の範囲を越えて多すぎるポリマ
ーは、その耐熱安定性に難があ）、ポリフッ化ビニリデ
ン系ポリマート併用するアクリレート系重合体との相溶
性が低下する。またＶＤＦＯ共重合量が余シに少な過ぎ
るポリフッ化ビニリデン系重合体は、その成形加工性が
低下すると共に、その成型品の機械的特性が損われる為
に好ましくない。V in the polyvinylidene fluoride polymer used in the present invention
Polymers in which the DF copolymerization ratio exceeds the above-mentioned range have poor heat resistance stability, and the compatibility with the acrylate polymer used in combination with the polyvinylidene fluoride polymer decreases. Furthermore, a polyvinylidene fluoride polymer having an excessively small amount of VDFO copolymerized is not preferable because its moldability decreases and the mechanical properties of the molded product are impaired.
ＴＦＥ単位及びＨＦＰ単位の共重合については、本発明
のポリフッ化ビニリデン系ポリマー組成物の成形加工性
、その成型品の低温特性、耐薬品性、及び両ポリマーの
相溶性の良好さなどから、前記範囲を選定するのが好ま
しい。特にＨＦＰ単位は前記範囲以上使用するとポリフ
ッ化ビニリデン系ポリマーを重合する際の系の重合速度
が低くなり実用的でない。Regarding the copolymerization of TFE units and HFP units, the above-mentioned method is considered based on the moldability of the polyvinylidene fluoride polymer composition of the present invention, the low-temperature properties of the molded product, the chemical resistance, and the good compatibility of both polymers. It is preferable to select a range. In particular, if the HFP unit is used in excess of the above range, the polymerization rate of the system when polymerizing polyvinylidene fluoride polymers becomes low, making it impractical.
マタ、上記ポリフッ化ビニリデン系共重合体と混合する
アクリレート系共重合体は、一般式％式％
（式中Ｘ＝Ｈ及びＣＨ３を、Ｙ＝Ｈ及び炭素数１〜１０
の炭化水素基を示す）で示される単量体を重合すること
によって得られるものでちる。The acrylate copolymer to be mixed with the polyvinylidene fluoride copolymer has the general formula % (in the formula, X=H and CH3, Y=H and carbon number 1 to 10
(representing a hydrocarbon group) is obtained by polymerizing a monomer represented by
上記一般式で示される化ツマ−としては例えばメチルメ
タクリレート、エチルメタクリレート、１−プロピルメ
タクリレート、ｔ−ブチルメタクリレート、アクリル酸
、ベンジルアクリレート、２−エチルへキシルアク＋Ｊ
ｔ、’−ト、等を挙げることかでき、これら化ツマ−は
単独で、又は適宜組合せて重合することによ）、本発明
で用いるアクリレート系重合体とすることができる。Chemical compounds represented by the above general formula include, for example, methyl methacrylate, ethyl methacrylate, 1-propyl methacrylate, t-butyl methacrylate, acrylic acid, benzyl acrylate, 2-ethylhexyl acrylate + J
The acrylate polymer used in the present invention can be prepared by polymerizing these polymers alone or in appropriate combinations.
本発明で用いるフッ化ビニリデン系共重合体を合成する
方法としては、溶液重合法、懸濁重合法、乳化重合法な
ど各種重合方法を用いることができ、溶液重合法を実施
するに際して用いる溶媒としては、例えば、トリクロロ
モノフルオロメタン、トリクロロトリフルオロエタン、
パーフルオロシクロブタンの如きフッ化系溶媒、あるい
は、フッ素化塩素化系溶媒、飽和炭化水素からなるいわ
ゆるフロン系溶媒や第３級プクリーμの如きアルコール
系溶媒などの有機溶媒を挙げることができる。Various polymerization methods can be used to synthesize the vinylidene fluoride copolymer used in the present invention, such as solution polymerization, suspension polymerization, and emulsion polymerization. For example, trichloromonofluoromethane, trichlorotrifluoroethane,
Examples include organic solvents such as fluorinated solvents such as perfluorocyclobutane, fluorinated chlorinated solvents, so-called chlorofluorocarbon solvents made of saturated hydrocarbons, and alcoholic solvents such as tertiary plasticizer μ.
また、重合は一り０℃〜１５０℃程度の温度で、比較的
低い反応圧力、例えば１〜５［］ｋｇ／ｃｒｎ２ 程
度の圧力で行なうことができる。又、水性重合媒体とし
て使用し、懸濁重合法や乳化重合法によってポリフッ化
ビニリデン系ポリマーを作ることもでき、乳化重合にお
いては、フッ素系乳化剤を使用し、例えば５０〜１００
℃程度の温度で５０〜２００に９／α２程度の圧力で行
なうことができる。懸濁重合法では重合触媒としてレド
ックス系開始剤を使用し、−２０℃〜５０℃程度の低温
度において重合することができる。Further, the polymerization can be carried out at a temperature of about 0 DEG C. to 150 DEG C. and a relatively low reaction pressure, for example, a pressure of about 1 to 5 kg/crn2. It is also possible to use it as an aqueous polymerization medium to produce polyvinylidene fluoride polymers by suspension polymerization or emulsion polymerization. In emulsion polymerization, a fluorine-based emulsifier is used, for example
It can be carried out at a temperature of about 50°C to 200°C and a pressure of about 9/α2. In the suspension polymerization method, a redox initiator is used as a polymerization catalyst, and polymerization can be carried out at a low temperature of about -20°C to 50°C.
次に本発明の実施例および比較例を示す。Next, Examples and Comparative Examples of the present invention will be shown.
実施例１
攪拌機を有して、外部に温度調節用ジャケットを有する
容積２ｔのオートクレーブに脱イオン脱酸素をした水５
００ｇ、過硫酸アンモニウム１．２９ 、バーフルオロ
オクタン酸アンモニウム２．０ｇ、酸性亜硫酸ナトリウ
ムＣＬ４ｇを仕込み、更に水酸化ナトリウム１１ｇを加
える。オートクレーブ内を窒素ガスで３回置換した後、
フッ化ビニリデンモノマー８０ｇ、テトラフルオロエチ
レン２０ｇ、ヘキサフルオロプロピレン５０ｇを仕込み
攪拌しながら６０℃の温度で８時間反応を行なった。反
応生成物はラテックス状態で得られた。このヲテツクヌ
を凝固させてポリマーを分離し、水洗の後、ｎ−ヘキサ
ンにて洗浄した后真空乾燥して白色粉末よシなるポリフ
ッ化ビニリデン系重合体８５ダを得た。Example 1 Deionized and deoxidized water 5 was placed in a 2 t capacity autoclave equipped with a stirrer and an external temperature control jacket.
00 g, 1.29 g of ammonium persulfate, 2.0 g of ammonium perfluorooctanoate, and 4 g of acidic sodium sulfite CL, and further added 11 g of sodium hydroxide. After replacing the inside of the autoclave with nitrogen gas three times,
80 g of vinylidene fluoride monomer, 20 g of tetrafluoroethylene, and 50 g of hexafluoropropylene were charged and reacted at a temperature of 60° C. for 8 hours with stirring. The reaction product was obtained in a latex state. The polymer was coagulated to separate the polymer, washed with water and n-hexane, and then vacuum dried to obtain a polyvinylidene fluoride polymer 85 as a white powder.
この共重合体は、Ｖ Ｄ Ｆ／Ｔ Ｆ Ｅ／ＨＦ Ｐ（
６６／２５／９モ）Ｖチ）の組成を有し、示差熱分析に
よる融点は１２５℃を示した。This copolymer has V D F/T F E/HF P (
It had a composition of 66/25/9mo)Vchi), and the melting point according to differential thermal analysis was 125°C.
上記フッ化ビニリデン系共重合体４０ｇにオリメチルメ
タクリレート６０ｇを加えてなる横指組成物を１９０℃
〜２１０℃で溶融混練後、押出しベレット状とした。こ
のベレットを対比成型して試験片を乍成し、その透明性
、および衝撃強度を測定した。衝撃強度はＡＳＴＭ−Ｄ
−２５６に準じたＶノツチアイゾツト衝撃拭けにて行な
い、透明性はＡＳＴＭ−Ｄ−１００３に準じて全光線透
過率を測定した。その物性を第１表に示した。A horizontal composition obtained by adding 60 g of olymethyl methacrylate to 40 g of the above vinylidene fluoride copolymer was heated at 190°C.
After melt-kneading at ~210°C, it was extruded into a pellet shape. This pellet was comparatively molded to form a test piece, and its transparency and impact strength were measured. Impact strength is ASTM-D
-256, and the total light transmittance was measured in accordance with ASTM-D-1003. Its physical properties are shown in Table 1.
実施例２〜４及び比較例１
実施例１において得たフッ化ビニリデン系共重合体とポ
リメチμメタクリレートとの混合は同様にして混合樹脂
組成物を得た。その物性は第１表に示した。Examples 2 to 4 and Comparative Example 1 The vinylidene fluoride copolymer obtained in Example 1 and polymethymu methacrylate were mixed in the same manner to obtain a mixed resin composition. Its physical properties are shown in Table 1.
第 １ 表
」
川
° １
実施例５
実施例１において用いたフッ化ビニリデン系共重合体と
混合するポリマーとしてメチルメタクリレートとメチル
アクリレート（９０／１０重量％）からなる共重合体を
ポリメチμメタクｊＪ Ｖ −）に変えて用いた以外は
実施例１と全くした。その物性は全光線透過率が９１％
であシ、アイゾツト衝撃強度は３１′Ｋｇ・ｃｍ／ｃｍ
であった。Table 1 1 Example 5 A copolymer consisting of methyl methacrylate and methyl acrylate (90/10% by weight) was used as a polymer to be mixed with the vinylidene fluoride copolymer used in Example 1. The procedure of Example 1 was repeated except that V-) was used instead. Its physical properties include a total light transmittance of 91%.
Ashi, Izotsu impact strength is 31'Kg・cm/cm
Met.
実施例６〜７及び比較例２〜３
実施例１においてフッ化ビニリデン系共重合体を得る際
のモノマー組成を第２表のごとく変更した以外は、実施
例１と同様にして、ポリフッ化ビニリデン系重合体を得
、ポリメチルメタクリレートを実施例１と同様にして加
え樹脂組成物を得た。次いで試験片を作成した。Examples 6 to 7 and Comparative Examples 2 to 3 Polyvinylidene fluoride was produced in the same manner as in Example 1, except that the monomer composition when obtaining the vinylidene fluoride copolymer in Example 1 was changed as shown in Table 2. A system polymer was obtained, and polymethyl methacrylate was added in the same manner as in Example 1 to obtain a resin composition. Next, test pieces were prepared.
その透明性の測定は、試験片を８０℃で１００時間加熱
処理を行ない、その前後での全光線通）過率の変化を測
定し、その結果を第２表に示した。The transparency was measured by heating the test piece at 80° C. for 100 hours and measuring the change in total light transmission rate before and after the heat treatment. The results are shown in Table 2.
第 ２ 表
実施例８
ＶＤＦ、ＴＨＥ及びＲＦＰを用い実施例１と同様にして
重合を行ない、ＶＤＦ／ＴＦＥ／ＨＦＰ−７０／１ Ｂ
／１２ （モルチ〕の組成の共重合体を得た。このフッ
化ビニリデン系共重合体３０重量部と、メチルアクリレ
ート８０重量部、１．３−ブチレングリコールジアクリ
レート２０重量部、ハイドロキノン１０１重量部、１−
ヒドロキシンクロへキンμフエニρケトン１１５重量部
を混合し、均一溶解したシラツブ状ポリマー溶液をロー
ルコータ−にてポリエステルフィルム上に５０μｍの厚
さで流延した後、窒素ガス雰囲気下、超高圧水銀灯の光
を照射して光硬化させた。Table 2 Example 8 Polymerization was carried out in the same manner as in Example 1 using VDF, THE and RFP, and VDF/TFE/HFP-70/1 B
A copolymer having the following composition was obtained: 30 parts by weight of this vinylidene fluoride copolymer, 80 parts by weight of methyl acrylate, 20 parts by weight of 1,3-butylene glycol diacrylate, and 101 parts by weight of hydroquinone. , 1-
After mixing 115 parts by weight of hydroxyl chlorohequine μphenyrho ketone and uniformly dissolving the silty polymer solution, it was cast onto a polyester film to a thickness of 50 μm using a roll coater, and then cast under an ultra-high pressure mercury lamp under a nitrogen gas atmosphere. It was photocured by irradiating it with light.
得られたフィルムは、厚さ４５１ｓｍ 、光線透過率９
２％の均一で柔軟で、かつしなやかな透明フィルムであ
った。The obtained film has a thickness of 451 sm and a light transmittance of 9
It was a 2% uniform, flexible, and pliable transparent film.
Claims (1)
オロエチレン単位が１〜４０モル％、ヘキサフルオロプ
ロピレン単位が１〜４０モル％からなるフッ化ビニリデ
ン共重合体１〜９０重量％と下記式（１）で表わされる
単量体を主成分とする重合体９９〜１重量％とを混合し
てなる樹脂組成物。 ▲数式、化学式、表等があります▼…（１） 式中Ｘ＝Ｈ及びＣＨ＿３を Ｙ＝Ｈ及び炭素数１〜１０の炭化水素基 を示す。[Scope of Claims] Vinylidene fluoride copolymer comprising 40 to 98 mol% of vinylidene fluoride units, 1 to 40 mol% of tetrafluoroethylene units, and 1 to 40 mol% of hexafluoropropylene units, 1 to 90% by weight % and 99 to 1% by weight of a polymer whose main component is a monomer represented by the following formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) In the formula, X=H and CH_3 represent Y=H and a hydrocarbon group having 1 to 10 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16847186A JPS6323949A (en) | 1986-07-17 | 1986-07-17 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16847186A JPS6323949A (en) | 1986-07-17 | 1986-07-17 | Resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6323949A true JPS6323949A (en) | 1988-02-01 |
Family
ID=15868719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16847186A Pending JPS6323949A (en) | 1986-07-17 | 1986-07-17 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6323949A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03204215A (en) * | 1989-12-30 | 1991-09-05 | Casio Comput Co Ltd | Digital filter device |
| US5872198A (en) * | 1995-05-26 | 1999-02-16 | Mosbach; Klaus | Molecularly imprinted beaded polymers and stabilized suspension polymerization of the same in perfluorocarbon liquids |
| JP2002338706A (en) * | 2001-05-16 | 2002-11-27 | Denki Kagaku Kogyo Kk | Vinylidene fluoride based resin film |
| JP2009114719A (en) * | 2007-11-06 | 2009-05-28 | Daikure Co Ltd | Channel |
| WO2017043565A1 (en) * | 2015-09-11 | 2017-03-16 | 三菱レイヨン株式会社 | Resin composition comprising vinylidene fluoride-based resin, molded article, and film |
-
1986
- 1986-07-17 JP JP16847186A patent/JPS6323949A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03204215A (en) * | 1989-12-30 | 1991-09-05 | Casio Comput Co Ltd | Digital filter device |
| US5872198A (en) * | 1995-05-26 | 1999-02-16 | Mosbach; Klaus | Molecularly imprinted beaded polymers and stabilized suspension polymerization of the same in perfluorocarbon liquids |
| US5959050A (en) * | 1995-05-26 | 1999-09-28 | Mosbach; Klaus | Supports useful for molecular imprinting technology |
| JP2002338706A (en) * | 2001-05-16 | 2002-11-27 | Denki Kagaku Kogyo Kk | Vinylidene fluoride based resin film |
| JP2009114719A (en) * | 2007-11-06 | 2009-05-28 | Daikure Co Ltd | Channel |
| WO2017043565A1 (en) * | 2015-09-11 | 2017-03-16 | 三菱レイヨン株式会社 | Resin composition comprising vinylidene fluoride-based resin, molded article, and film |
| JPWO2017043565A1 (en) * | 2015-09-11 | 2017-09-07 | 三菱ケミカル株式会社 | Resin composition, molded body, and film containing vinylidene fluoride resin |
| US10435553B2 (en) | 2015-09-11 | 2019-10-08 | Mitsubishi Chemical Corporation | Resin composition, molded article and film including vinylidene fluoride-based resin |
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