JPS63145311A - Modified polyvinylidene fluoride molding and its preparation - Google Patents
Modified polyvinylidene fluoride molding and its preparationInfo
- Publication number
- JPS63145311A JPS63145311A JP29448286A JP29448286A JPS63145311A JP S63145311 A JPS63145311 A JP S63145311A JP 29448286 A JP29448286 A JP 29448286A JP 29448286 A JP29448286 A JP 29448286A JP S63145311 A JPS63145311 A JP S63145311A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinylidene fluoride
- modified
- producing
- molded article
- graft
- 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
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 113
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 113
- 238000000465 moulding Methods 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title 1
- 238000010894 electron beam technology Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 2
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 38
- 239000000853 adhesive Substances 0.000 description 32
- 238000005470 impregnation Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 7
- 238000000638 solvent extraction Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- -1 aromatic vinyl compound Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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、ポリフッ化ビニリデンの特性を保持しつつ接
着性・表面親水性が改善された変性ポリフッ化ビニリデ
ン成形体およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a modified polyvinylidene fluoride molded article that maintains the properties of polyvinylidene fluoride and has improved adhesiveness and surface hydrophilicity, and a method for producing the same.
（従来の技術）
ポリフッ化ビニリデン（Ｐ Ｖ ｄ Ｆ）は機械的諸性
質に優れ、耐薬品性、耐水性も良好であり、特に、優れ
た耐候性を有しているため、フィルムや金属板への被覆
材料１例えば、建築物の外装材や特殊ライニング材とし
て用いられている。しかしポリフッ化ビニリデンは上記
価れた特性を有するものの、金属や他の樹脂への接着性
が悪い。表面親水性にも欠ける。(Prior art) Polyvinylidene fluoride (PVdF) has excellent mechanical properties, good chemical resistance and water resistance, and in particular, excellent weather resistance, so it can be used in films and metal plates. Coating material 1 For example, it is used as an exterior material or special lining material for buildings. However, although polyvinylidene fluoride has the above-mentioned excellent properties, it has poor adhesion to metals and other resins. It also lacks surface hydrophilicity.
ポリフッ化ビニリデンの接着性を改善するために２種々
の試みがなされている。例えば、特公昭５４−２２２５
号公報には、接着性に優れた熱硬化性グリシジル変性ア
クリル樹脂をポリフッ化ビニリデンにブレンドした組成
物が開示されている。しかし、この組成物は、接着性に
は優れるものの、ポリフッ化ビニリデンと他の樹脂との
ブレンド物であり、ブレンドによりポリフッ化ビニリデ
ンの優れた特性が損われる。特開昭５６−１３３３０９
号公報には、ポリフッ化ビニリデン骨格上に（メタ）ア
クリル酸重合体のグラフト結合部を有する組成物が開示
されている。この組成物は接着性に優れかつポリフッ化
ビニリデンの特性を有する。しかし。Two different attempts have been made to improve the adhesion of polyvinylidene fluoride. For example, Tokuko Sho 54-2225
The publication discloses a composition in which a thermosetting glycidyl-modified acrylic resin with excellent adhesiveness is blended with polyvinylidene fluoride. However, although this composition has excellent adhesive properties, it is a blend of polyvinylidene fluoride and other resins, and the blend impairs the excellent properties of polyvinylidene fluoride. Japanese Patent Publication No. 56-133309
The publication discloses a composition having a graft bond of a (meth)acrylic acid polymer on a polyvinylidene fluoride skeleton. This composition has excellent adhesive properties and properties of polyvinylidene fluoride. but.
これはアクリル系のグラフト結合部を有するため。This is because it has an acrylic graft bond.
ポリフッ化ビニリデンの優れた特性を完全に保持してい
るとはいえない。しかも、この組成物は。It cannot be said that the excellent properties of polyvinylidene fluoride are completely maintained. Moreover, this composition...
あらかじめＴ線照射したポリフッ化ビニリデンにアクリ
ル系重合体をグラフト共重合して得られるため、γ線の
照射によりポリフッ化ビニリデンが分解・劣化するおそ
れがある。それにより、ポリフッ化ビニリデンの特性が
損われる。接着性を有するポリフッ化ビニリデンとして
、芳香族ビニル化合物、エチレン性不飽和カルボン酸エ
ステル化合物を主体とする樹脂成分と、ゴム状重合体と
からなる熱可塑性樹脂をポリフッ化ビニリデンに積層し
た積層物も提案されている（特開昭５９−１７８２５０
号公報に開示）。同様の積層体として、エチレン重合体
や酢酸ビニル重合体およびこれらのグラフト共重合体を
フッ素系樹脂に積層した積層体（特開昭５９−２１４６
４５号公報）、アクリル系樹脂含有フン化ビニリデン系
樹脂と熱可塑性樹脂とからなる積層体（特開昭５９−２
１５８６３号公報）などが開示されている。しかし、こ
れらは、ポリフッ化ビニリデン樹脂自体の接着性を改善
する代わりに、ポリフッ化ビニリデンにビニル系樹脂な
どの熱可塑性樹脂を積層したにすぎず、得られた積層物
は熱可塑性樹脂の性質を強く帯びている。そのために。Since it is obtained by graft copolymerizing an acrylic polymer to polyvinylidene fluoride that has been irradiated with T-rays in advance, there is a risk that the polyvinylidene fluoride will be decomposed and deteriorated by irradiation with γ-rays. This impairs the properties of polyvinylidene fluoride. As polyvinylidene fluoride with adhesive properties, there is also a laminate in which a thermoplastic resin consisting of a resin component mainly consisting of an aromatic vinyl compound and an ethylenically unsaturated carboxylic acid ester compound and a rubber-like polymer is laminated on polyvinylidene fluoride. It has been proposed (Japanese Unexamined Patent Publication No. 59-178250)
(disclosed in the publication). A similar laminate is a laminate in which ethylene polymer, vinyl acetate polymer, and their graft copolymers are laminated on a fluororesin (Japanese Patent Laid-Open No. 59-2146).
No. 45), a laminate consisting of an acrylic resin-containing vinylidene fluoride resin and a thermoplastic resin (JP-A No. 59-2
15863) and the like are disclosed. However, instead of improving the adhesive properties of polyvinylidene fluoride resin itself, these methods merely laminate thermoplastic resin such as vinyl resin onto polyvinylidene fluoride, and the resulting laminate does not have the properties of thermoplastic resin. strongly tinged. for that.
ポリフッ化ビニリデンの優れた特性が著しく損われてい
る。The excellent properties of polyvinylidene fluoride are significantly impaired.
（発明が解決しようとする問題点）
本発明は上記従来の問題点を解決するものであり、その
目的とするところは、ポリフッ化ビニリデンの特性を保
持しつつ接着性・表面親水性が改善された変性ポリフッ
化ビニリデン成形体およびその製造方法を提供すること
にある。(Problems to be Solved by the Invention) The present invention solves the above conventional problems, and its purpose is to improve adhesiveness and surface hydrophilicity while maintaining the properties of polyvinylidene fluoride. An object of the present invention is to provide a modified polyvinylidene fluoride molded article and a method for producing the same.
（問題点を解決するための手段）
本発明は、ポリフッ化ビニリデンをグラフト化して接着
性を付与するに際し、接着性を要するのはポリフッ化ビ
ニリデン成形体の表面部分に限られるため１表面部分に
のみグラフト化ポリフッ化ビニリデンを形成すれば、ポ
リフッ化ビニリデンの優れた特性を保持しつつ接着性・
表面親水性が改善された変性ポリフッ化ビニリデン成形
体が得られる。このような変性ポリフッ化ビニリデン成
形体は、グラフト鎖となるモノマーおよび／またはオリ
ゴマーをポリフッ化ビニリデンに含浸させた後、これに
電子線を照射することにより形成される。との発明者の
知見にもとづいて完成された。(Means for Solving the Problems) The present invention provides adhesive properties only to the surface portion of the polyvinylidene fluoride molded product when grafting polyvinylidene fluoride to impart adhesive properties. If only grafted polyvinylidene fluoride is formed, adhesiveness and
A modified polyvinylidene fluoride molded article with improved surface hydrophilicity is obtained. Such a modified polyvinylidene fluoride molded article is formed by impregnating polyvinylidene fluoride with a monomer and/or oligomer that will become a graft chain, and then irradiating the impregnated polyvinylidene fluoride with an electron beam. It was completed based on the inventor's knowledge.
本発明の変性ポリフッ化ビニリデン成形体は。The modified polyvinylidene fluoride molded article of the present invention.
アクリル酸単位、メタクリル酸単位、および炭素原子数
が１〜４のアルキル基でエステル化されたアクリル系ア
ルキルエステル単位のうちの少な（とも一種からなるグ
ラフト鎖を有するポリフッ化ビニリデングラフト共重合
体の層が表面部分に形成され、そのことにより上記目的
が達成される。A polyvinylidene fluoride graft copolymer having a graft chain consisting of acrylic acid units, methacrylic acid units, and acrylic alkyl ester units esterified with an alkyl group having 1 to 4 carbon atoms. A layer is formed on the surface portion, thereby achieving the above objective.
本発明の変性ポリフッ化ビニリデン成形体の製造方法は
、上記変性ポリフッ化ビニリデン成形体を製造する方法
であって、（１）アクリル酸のモノマーおよび／または
オリゴマー、メタクリル酸のモノマーおよび／またはオ
リゴマー、および該アクリル系アルキルエステルのモノ
マーおよび／またはオリゴマーのうちの少なくとも一種
のグラフト成分をポリフッ化ビニリデン成形体に含浸さ
せる工程、および（２）該含浸成形体に電子線を照射す
る工程、を包含し、そのことにより上記目的が達成され
る。The method for producing a modified polyvinylidene fluoride molded article of the present invention is a method for producing the above-mentioned modified polyvinylidene fluoride molded article, comprising (1) an acrylic acid monomer and/or oligomer, a methacrylic acid monomer and/or oligomer, and (2) impregnating the polyvinylidene fluoride molded body with at least one graft component of the acrylic alkyl ester monomer and/or oligomer, and (2) irradiating the impregnated molded body with an electron beam. , thereby achieving the above objective.
上記アクリル酸エステルには２例えば、メチルアクリレ
ート、メチルメタクリレート、エチルアクリレートエチ
ルメタクリレート、ブチルアクリレート、ブチルメタク
リレートがある。Examples of the acrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.
このグラフト共重合体のグラフ）ＩＪｆの重合度は。The degree of polymerization of this graft copolymer (graph) IJf is:
１〜２００．好ましくは１０〜５０の範囲とされる。２
００を上まわると、グラフト鎖の割合が幹ポリマーに対
して相対的に高くなるため、ポリフッ化ビニリデンの優
れた特性が損われる。ポリフッ化ビニリデングラフト共
重合体層の厚さは１〜５００μｍ。1-200. Preferably it is in the range of 10-50. 2
When it exceeds 00, the excellent properties of polyvinylidene fluoride are impaired because the proportion of graft chains becomes relatively high with respect to the backbone polymer. The thickness of the polyvinylidene fluoride graft copolymer layer is 1 to 500 μm.
好ましくは１０〜２００μｍの範囲に調整される。１μ
ｍを下まわると、変性ポリフッ化ビニリデン成形体の所
望の接着性が得られない。５００μｍを上まわると、ポ
リフッ化ビニリデンの優れた特性が損われる。グラフト
鎖となるアクリル酸単位、メタクリル酸単位および上記
アクリル系アルキルエステル単位はポリフッ化ビニリデ
ンとの相溶性が良好である。そのために１表面部分のポ
リフッ化ビニリデングラフト共重合体層と内部のポリフ
ッ化ビニリデン層とが相分離を起こすおそれがない。Preferably, it is adjusted to a range of 10 to 200 μm. 1μ
If it is less than m, the desired adhesiveness of the modified polyvinylidene fluoride molded article cannot be obtained. If it exceeds 500 μm, the excellent properties of polyvinylidene fluoride will be impaired. The acrylic acid unit, methacrylic acid unit, and the above-mentioned acrylic alkyl ester unit that form the graft chain have good compatibility with polyvinylidene fluoride. Therefore, there is no possibility that phase separation will occur between the polyvinylidene fluoride graft copolymer layer on one surface portion and the internal polyvinylidene fluoride layer.
このようなポリフッ化ビニリデン成形体の製造では、ま
ず、アクリル酸のモノマーおよび／またはオリゴマー、
メタクリル酸のモノマーおよび／またはオリゴマー、お
よび上記アクリル系アルキルエステルのモノマーおよび
／またはオリゴマーが、グラフト成分として、単独もし
くは組み合わせてポリフッ化ビニリデン成形体に含浸さ
れる。In the production of such polyvinylidene fluoride molded bodies, first, acrylic acid monomers and/or oligomers,
A monomer and/or oligomer of methacrylic acid and a monomer and/or oligomer of the above-mentioned acrylic alkyl ester are impregnated into the polyvinylidene fluoride molded body as a graft component, singly or in combination.
ポリフッ化ビニリデン成形体は、押出成形、射出成形、
ブロー成形など公知の成形方法により得られる。この成
形体は、フィルム状、シート状、パイプ、異形体など所
望の形状に成形される。Polyvinylidene fluoride molded products can be manufactured by extrusion molding, injection molding,
It can be obtained by a known molding method such as blow molding. This molded body is molded into a desired shape such as a film, a sheet, a pipe, or a deformed body.
グラフト成分のアクリル酸オリゴマー、メタクリル酸オ
リゴマーおよび上記アクリル系アルキルエステルオリゴ
マーの分子量は１０００以下、好ましくは５００以下に
設定される。分子量が１０００を上まわると、該オリゴ
マーが均一にポリフッ化ビニリデン中に分散せず、改質
効果がない。アクリル酸。The molecular weight of the acrylic acid oligomer, methacrylic acid oligomer and the above-mentioned acrylic alkyl ester oligomer as graft components is set to 1000 or less, preferably 500 or less. If the molecular weight exceeds 1000, the oligomer will not be uniformly dispersed in polyvinylidene fluoride, and there will be no modification effect. acrylic acid.
メタクリル酸および上記アクリル系アルキルエステルの
モノマーおよび／またはオリゴマーの含浸は１例えば、
このモノマーおよび／またはオリゴマーの溶液中にポリ
フッ化ビニリデン成形体を浸潰し加熱して行われる。加
熱温度は４０〜１００℃が好ましい。これらのグラフト
成分のうち七ツマ−は液体であるため、１００％のモノ
マー溶液で用いられてもよい。他方、これらのグラフト
成分のオリゴマーは１通常、適当な溶剤に溶解させて用
いられる。溶剤には９例えばアセトンがある。含浸量は
ポリフッ化ビニリデン成形体１００重量部に対し、グラ
フト成分が０．１〜５０重量部、好ましくは。Impregnation with methacrylic acid and the above-mentioned acrylic alkyl ester monomers and/or oligomers can be carried out in one way, for example:
This is carried out by immersing a polyvinylidene fluoride molded article in a solution of this monomer and/or oligomer and heating it. The heating temperature is preferably 40 to 100°C. Among these graft components, the monomer is a liquid and may therefore be used as a 100% monomer solution. On the other hand, the oligomers of these graft components are generally used after being dissolved in a suitable solvent. Solvents include, for example, acetone. The amount of the graft component to be impregnated is preferably 0.1 to 50 parts by weight per 100 parts by weight of the polyvinylidene fluoride molded body.
０．５〜１０重量部の範囲とされる。０．１重量部を下
まわると、ポリフッ化ビニリデン成形体の表面部分にお
けるボリフフ化ビニリデングラフト共重合体層の形成が
不充分となり、ポリフッ化ビニリデン成形体の所望の接
着性が得られない。５０重量部を上まわると、ポリフッ
化ビニリデン成形体が膨潤体となり、厚みなどの形状が
著しく変化する。The range is 0.5 to 10 parts by weight. If it is less than 0.1 part by weight, the polyvinylidene fluoride graft copolymer layer will not be formed sufficiently on the surface of the polyvinylidene fluoride molded product, and the desired adhesiveness of the polyvinylidene fluoride molded product will not be obtained. When the amount exceeds 50 parts by weight, the polyvinylidene fluoride molded product becomes a swollen product, and its shape such as thickness changes significantly.
形状は含浸前の成形体とかなり異なってくる。ポリフッ
化ビニリデン成形体の表面部分だけでなく内部にまでポ
リフッ化ビニリデングラフト共重合体の層が形成される
おそれもあり、そのためにポリフッ化ビニリデンの優れ
た特性が損われる。The shape will be quite different from that of the molded product before impregnation. There is a possibility that a layer of the polyvinylidene fluoride graft copolymer will be formed not only on the surface portion of the polyvinylidene fluoride molded article but also within the interior thereof, thereby impairing the excellent properties of polyvinylidene fluoride.
グラフト成分が含浸されたポリフッ化ビニリデン成形体
には２次いで、電子線が照射される。電子線の照射によ
りラジカルが発生し、このラジカルを開始剤としてポリ
フッ化ビニリデンにアクリル酸単位、メタクリル酸単位
および上記アクリル系アルキルエステル単位のうちの少
なくとも一種からなるグラフト鎖が形成される。この電
子線の透過有効厚さは１〜５００μｍ、好ましくは１０
〜２００μｍの範囲とされる。１μｍを下まわると、ポ
リフッ化ビニリデン成形体の表面部分に形成されるボリ
フフ化ビニリデングラフト共重合体層の厚さが薄り、そ
のために、ポリフッ化ビニリデン成形体の所望の接着性
が得られない。５００μｍを上まわると、ポリフッ化ビ
ニリデン成形体の表面部分だけでな（内部にまで電子線
が透過し、ポリフッ化ビニリデンが分解・劣化するなど
ポリフッ化ビニリデンの優れた特性が損われる。電子線
の照射量は０．５〜５０Ｍｒａｄの範囲が好ましい。The polyvinylidene fluoride molded body impregnated with the graft component is then irradiated with an electron beam. Irradiation with an electron beam generates radicals, and using these radicals as initiators, a graft chain consisting of at least one of acrylic acid units, methacrylic acid units, and the above-mentioned acrylic alkyl ester units is formed on polyvinylidene fluoride. The effective thickness of the electron beam is 1 to 500 μm, preferably 10 μm.
The range is 200 μm. If it is less than 1 μm, the thickness of the polyvinylidene fluoride graft copolymer layer formed on the surface of the polyvinylidene fluoride molded product becomes thin, and therefore the desired adhesiveness of the polyvinylidene fluoride molded product cannot be obtained. . If it exceeds 500 μm, the excellent properties of polyvinylidene fluoride will be impaired, such as the electron beam penetrating not only the surface part of the polyvinylidene fluoride molded product (into the interior), but also decomposing and degrading the polyvinylidene fluoride. The irradiation dose is preferably in the range of 0.5 to 50 Mrad.
電子線が照射されたポリフッ化ビニリデン成形体には、
未反応のグラフト成分および溶剤を除去するべく、溶剤
抽出が施される。The polyvinylidene fluoride molded body that has been irradiated with an electron beam has
Solvent extraction is performed to remove unreacted graft components and solvent.
（実施例） 以下に本発明を実施例について説明する。(Example) The present invention will be described below with reference to Examples.
尖脩炎上
ポリフッ化ビニリデン（ＫＦｌｏｏＯ，呉羽化学社製）
の粉体を２００℃、 ２００ｋｇ／ａｄの条件下で圧
縮（プレス）成形し、厚さ１ｆｌのポリフッ化ビニリデ
ン成形体シートを得た。この成形体シートをメチルメタ
クリレートの１００％溶液に８０℃で２時間浸漬した後
、透過有効厚さが約１００μｍの電子線を３Ｍｒａｄの
照射量でシートの両面に照射した。電子線照射後、未反
応のメチルメタクリレートを溶剤抽出した。含浸前の成
形体と含浸後の成形体との重量変化により、メチルメタ
クリレートの含浸量を測定したところ、含浸量は２．５
重量％であった。Polyvinylidene fluoride (KFlooO, manufactured by Kureha Chemical Co., Ltd.)
The powder was compression molded at 200° C. and 200 kg/ad to obtain a polyvinylidene fluoride molded sheet having a thickness of 1 fl. After this molded sheet was immersed in a 100% solution of methyl methacrylate at 80° C. for 2 hours, both sides of the sheet were irradiated with an electron beam having an effective transmission thickness of about 100 μm at a dose of 3 Mrad. After electron beam irradiation, unreacted methyl methacrylate was extracted with a solvent. When the amount of methyl methacrylate impregnated was measured based on the weight change between the molded product before impregnation and the molded product after impregnation, the amount of impregnation was 2.5.
% by weight.
さらに、含浸後の成形体と溶剤抽出後の成形体との重量
変化によりメチルメタクリレートのグラフト化固定量を
測定したところ、固定量は２．５重量％であり、含浸し
たメチルメタクリレートはすべてグラフト化していた。Furthermore, when the amount of grafted immobilization of methyl methacrylate was measured based on the weight change of the molded object after impregnation and the molded object after solvent extraction, the amount immobilized was 2.5% by weight, indicating that all of the impregnated methyl methacrylate was grafted. was.
得られた変性ポリフッ化ビニリデン成形体について１次
のようにして接着性・表面親水性を評価した。これらの
結果を下表に示す。The adhesiveness and surface hydrophilicity of the obtained modified polyvinylidene fluoride molded article were evaluated in the following manner. These results are shown in the table below.
（１）接着性
上記方法により得られた２枚の変性ポリフッ化ビニリデ
ン成形体シートにエポキシ系接着剤（アラルダイト、昭
和高分子社Ｉ！りを均一に塗布した後、２枚のシートを
重ね合わせて接着剪断試験（Ｊ Ｉ Ｓ Ｋ６８５０）
を行ったところ、接着剪断強度は１５．１ｋｇ／ｃＪで
あり、接着面には界面破壊現象が発生した。上記変性ポ
リフッ化ビニリデン成形体シートを、同様のエポキシ系
接着剤を用いてアルミニウム板に接着した。これを同様
の方法により接着剪断試験にかけたところ、接着剪断強
度は３６．３ｋｇ ／ ｃｄであり、接着面には界面破
壊現象が発生した。(1) Adhesion After uniformly applying an epoxy adhesive (Araldite, Showa Kobunshi I!) to the two modified polyvinylidene fluoride molded sheets obtained by the above method, the two sheets are stacked. Adhesive shear test (JIS K6850)
As a result, the adhesive shear strength was 15.1 kg/cJ, and an interfacial failure phenomenon occurred on the adhesive surface. The modified polyvinylidene fluoride molded sheet was adhered to an aluminum plate using the same epoxy adhesive. When this was subjected to an adhesive shear test using the same method, the adhesive shear strength was 36.3 kg/cd, and an interfacial failure phenomenon occurred on the adhesive surface.
（２）表面親水性
変性ポリフッ化ビニリデン成形体シートの表面に水を滴
下し、水とシート表面との接触角により表面親水性を評
価した。その結果、接触角は８５．７゜であった。(2) Surface Hydrophilicity Water was dropped onto the surface of the modified polyvinylidene fluoride molded sheet, and the surface hydrophilicity was evaluated by the contact angle between the water and the sheet surface. As a result, the contact angle was 85.7°.
尖指尉）
メチルメタクリレートに代えて、アクリル酸（１００％
溶液）を用いたこと以外は、実施例１と同様の方法によ
り変性ポリフッ化ビニリデン成形体シートを得た。ただ
し、含１漫量は３．８重量％であった。得られた変性ポ
リフッ化ビニリデン成形体について、実施例１と同様に
して接着性・表面親水性を評価した。その結果、変性ポ
リフッ化ビニリデン成形体どうしの接着剪断強度は１７
．２ｋｇ／ｃｄ。Acrylic acid (100%) instead of methyl methacrylate
A modified polyvinylidene fluoride molded sheet was obtained in the same manner as in Example 1, except that the solution was used. However, the content per volume was 3.8% by weight. The adhesiveness and surface hydrophilicity of the obtained modified polyvinylidene fluoride molded article were evaluated in the same manner as in Example 1. As a result, the adhesive shear strength between the modified polyvinylidene fluoride molded bodies was 17
．． 2kg/cd.
アルミニウム板との接着剪断強度は４０．９ｋｇ／ｃＪ
であり、接触角は８０．１°であった。接着剪断試験の
際、接着面には界面破壊現象が発生した。これらの結果
を下表に示す。Adhesive shear strength with aluminum plate is 40.9 kg/cJ
The contact angle was 80.1°. During the adhesive shear test, an interfacial failure phenomenon occurred on the adhesive surface. These results are shown in the table below.
、比較」ロー
実施例１と同様の方法により得た未変性のポリフッ化ビ
ニリデン成形体シートについて、実施例１と同様にして
接着性・表面親水性を評価した。, Comparison ``Row'' An unmodified polyvinylidene fluoride molded sheet obtained by the same method as in Example 1 was evaluated for adhesiveness and surface hydrophilicity in the same manner as in Example 1.
その結果、変性ポリフッ化ビニリデン成形体どうしの接
着剪断強度は９ 、１ ｋｇ ／ ｃｔｌ 、アルミニ
ウム板との接着剪断強度は１９．８ｋｇ／ｃＪであり、
接触角は１０３．７ ”であった。接着剪断試験の際、
接着面には界面破壊現象が発生した。これらの結果を下
表に示す。As a result, the adhesive shear strength between the modified polyvinylidene fluoride molded bodies was 9.1 kg/ctl, and the adhesive shear strength with the aluminum plate was 19.8 kg/cJ.
The contact angle was 103.7”. During the adhesive shear test,
An interfacial failure phenomenon occurred on the adhesive surface. These results are shown in the table below.
ｉ較五ｌ
未変性のポリフッ化ビニリデン成形体シートに何も含浸
させずに、実施例１と同様の電子線を照射した。得られ
た変性ポリフッ化ビニリデン成形体について、実施例１
と同様にして接着性・表面親水性を評価した。その結果
、ポリフッ化ビニリデン成形体どうしの接着剪断強度は
１０．２ｋｇ／ｃｎｉ。Comparison 5l An unmodified polyvinylidene fluoride molded sheet was irradiated with the same electron beam as in Example 1 without being impregnated with anything. Example 1 Regarding the obtained modified polyvinylidene fluoride molded product
Adhesion and surface hydrophilicity were evaluated in the same manner as above. As a result, the adhesive shear strength between the polyvinylidene fluoride molded bodies was 10.2 kg/cni.
アルミニウム板との接着剪断強度は２４．１ｋｇ／ｃｏ
！であり、接触角は９７．５ ”であった。接着剪断試
験の際、接着面には界面破壊現象が発生した。これらの
結果を下表に示す。Adhesive shear strength with aluminum plate is 24.1 kg/co
! The contact angle was 97.5''. During the adhesive shear test, an interfacial failure phenomenon occurred on the adhesive surface. These results are shown in the table below.
止較±１
実施例１と同様の方法により、ポリフッ化ビニリデン成
形体シートにメチルメタクリレート溶液を含浸させた。Comparison ±1 In the same manner as in Example 1, a polyvinylidene fluoride molded sheet was impregnated with a methyl methacrylate solution.
この含浸成形体の接触角と、この成形体に電子線を照射
せずに溶剤抽出した成形体の接触角および接着剪断強度
を測定したところ。The contact angle of this impregnated molded body, and the contact angle and adhesive shear strength of the molded body extracted with a solvent without irradiating this molded body with an electron beam were measured.
ポリフッ化ビニリデン成形体どうしの接着剪断強度は１
０．６ｋｇ／ｃｏ！、アルミニウム板との接着剪断強度
は２６．３ｋｇ／ｃａｌであり、接触角は８７．９°で
あった。The adhesive shear strength between polyvinylidene fluoride molded bodies is 1
0.6kg/co! The adhesive shear strength with the aluminum plate was 26.3 kg/cal, and the contact angle was 87.9°.
接着剪断試験の際、接着面には界面破壊現象が発生した
。含浸前の成形体と含浸後の成形体との重量変化により
、メチルメタクリレートの含浸量を測定したところ、含
浸量は２．５重量％であった。During the adhesive shear test, an interfacial failure phenomenon occurred on the adhesive surface. The amount of methyl methacrylate impregnated was measured based on the weight change between the molded product before impregnation and the molded product after impregnation, and the amount of impregnation was 2.5% by weight.
溶剤抽出後の成形体は、溶剤抽出によりポリフッ化ビニ
リデンが一部溶出したため、含浸前の成形体に比べて重
量が減少した。これらの結果を下表に示す。The weight of the molded body after solvent extraction was reduced compared to the molded body before impregnation, because polyvinylidene fluoride was partially eluted by the solvent extraction. These results are shown in the table below.
凡教拠↓
実施例１と同様の方法により、ポリフッ化ビニリデン成
形体シートにアクリル酸溶液を含浸させた。この含浸成
形体の接触角と、この成形体に電子線を照射せずに溶剤
抽出した成形体の接触角および接着剪断強度を測定した
ところ、ポリフッ化ビニリデン成形体どうしの接着剪断
強度は１１．５ｋｇ／−、アルミニウム板との接着剪断
強度は２９．７ｋｇ／−であり、接触角は８６．７°で
あった。接着剪断試験の際、接着面には界面破壊現象が
発生した。含浸前の成形体と含浸後の成形体との重量変
化により、メチルメタクリレートの含浸量を測定したと
ころ、含浸量は３．８重量％であった。溶剤抽出後の成
形体は、溶剤抽出によりポリフッ化ビニリデンが一部溶
出したため、含浸前の成形体に比べて重量が減少した。Common knowledge↓ By the same method as in Example 1, a polyvinylidene fluoride molded sheet was impregnated with an acrylic acid solution. When the contact angle of this impregnated molded product and the contact angle and adhesive shear strength of the molded product obtained by solvent extraction without irradiating this molded product with an electron beam were measured, the adhesive shear strength of the polyvinylidene fluoride molded products was 11. 5 kg/-, the adhesive shear strength with the aluminum plate was 29.7 kg/-, and the contact angle was 86.7°. During the adhesive shear test, an interfacial failure phenomenon occurred on the adhesive surface. The amount of methyl methacrylate impregnated was measured based on the weight change between the molded product before impregnation and the molded product after impregnation, and the amount of impregnation was 3.8% by weight. The weight of the molded body after solvent extraction was reduced compared to the molded body before impregnation, because polyvinylidene fluoride was partially eluted by the solvent extraction.
これらの結果を下表に示す、表
実施例および比較例から明らかなように９本発明の変性
ポリフッ化ビニリデン成形体シートは。These results are shown in the table below, and as is clear from the table Examples and Comparative Examples, the modified polyvinylidene fluoride molded sheet of the present invention has the following properties.
接着剪断強度が高く、接着力に優れている。特に。High adhesive shear strength and excellent adhesive strength. especially.
金属との接着性が良好である。水との接触角も小さく表
面親水性に富んでいる。グラフト化していない未変性の
ポリフッ化ビニリデン成形体シートは、接着力が低く表
面親水性も有しない。未変性のポリフッ化ビニリデン成
形体シートに電子線を照射しただけの成形体や、未変性
のポリフッ化ビニリデン成形体にメチルメタクリレート
やアクリル酸を含浸させて電子線を照射せずに溶剤抽出
した成形体も同様に、接着力や表面親水性に欠ける。Good adhesion to metal. The contact angle with water is small and the surface is highly hydrophilic. A non-grafted, unmodified polyvinylidene fluoride molded sheet has low adhesive strength and no surface hydrophilicity. Moldings made by simply irradiating an unmodified polyvinylidene fluoride molded sheet with an electron beam, or moldings made by impregnating an unmodified polyvinylidene fluoride molding with methyl methacrylate or acrylic acid and extracting it with a solvent without irradiating it with an electron beam. The body similarly lacks adhesive strength and surface hydrophilicity.
（発明の効果） 本発明の変性ポリフッ化ビニリデン成形体は。(Effect of the invention) The modified polyvinylidene fluoride molded article of the present invention.
このように、アクリル酸、メタクリル酸およびアクリル
系アルキルエステルの少なくとも一種のグラフト鎖を有
するポリフッ化ビニリデングラフト共重合体層が表面部
分に形成されているため、接着性および表面親水性に優
れている。このような変性ポリフッ化ビニリデン成形体
は、上記グラフト鎖となるグラフト成分のモノマーおよ
び／またはオリゴマーをポリフッ化ビニリデン成形体に
含浸させればよく、容易に得られる。その結果１本発明
の変性ポリフッ化ビニリデン成形体は、金属などへの被
覆材料２例えば耐候性に優れたラベル。In this way, since a polyvinylidene fluoride graft copolymer layer having at least one kind of graft chain of acrylic acid, methacrylic acid, and acrylic alkyl ester is formed on the surface portion, it has excellent adhesiveness and surface hydrophilicity. . Such a modified polyvinylidene fluoride molded product can be easily obtained by impregnating the polyvinylidene fluoride molded product with the monomer and/or oligomer of the graft component that will become the graft chain. Results 1. The modified polyvinylidene fluoride molded article of the present invention can be used as a coating material for metals, etc. 2. For example, labels with excellent weather resistance.
ルーズライニング管、窓枠のシーリング材などに有効に
利用され得る。It can be effectively used for loose lining pipes, window frame sealants, etc.
以上that's all
Claims (1)
子数が１〜４のアルキル基でエステル化されたアクリル
系アルキルエステル単位のうちの少なくとも一種からな
るグラフト鎖を有するポリフッ化ビニリデングラフト共
重合体の層が表面部分に形成された変性ポリフッ化ビニ
リデン成形体。 ２、前記アクリル系アルキルエステル単位が、メチルア
クリレート、メチルメタクリレート、エチルアクリレー
ト、エチルメタクリレート、ブチルアクリレートおよび
ブチルメタクリレートのうちの少なくとも一種のモノマ
ー単位からなる特許請求の範囲第１項に記載の変性ポリ
フッ化ビニリデン成形体。 ３、前記グラフト鎖の重合度が１〜２００の範囲である
特許請求の範囲第１項に記載の変性ポリフッ化ビニリデ
ン成形体。 ４、前記ポリフッ化ビニリデングラフト共重合体層の厚
さが１〜５００μｍの範囲である特許請求の範囲第１項
に記載の変性ポリフッ化ビニリデン成形体。 ５、アクリル酸単位、メタクリル酸単位、および炭素原
子数が１〜４のアルキル基でエステル化されたアクリル
系アルキルエステル単位のうちの少なくとも一種からな
るグラフト鎖を有するポリフッ化ビニリデングラフト共
重合体の層が表面部分に形成された変性ポリフッ化ビニ
リデン成形体の製造方法であって、 （１）アクリル酸のモノマーおよび／またはオリゴマー
、メタクリル酸のモノマーおよび／またはオリゴマー、
および該アクリル系アルキルエステルのモノマーおよび
／またはオリゴマーのうちの少なくとも一種のグラフト
成分をポリフッ化ビニリデン成形体に含浸させる工程、
および （２）該含浸成形体に電子線を照射する工程、を包含す
る変性ポリフッ化ビニリデン成形体の製造方法。 ６、前記アクリル系アルキルエステルが、メチルアクリ
レート、メチルメタクリレート、エチルアクリレート、
エチルメタクリレート、ブチルアクリレートおよびブチ
ルメタクリレートのうちの少なくとも一種のモノマー単
位からなる特許請求の範囲第５項に記載の変性ポリフッ
化ビニリデン成形体の製造方法。 ７、前記グラフト成分の分子量が１０００以下である特
許請求の範囲第５項に記載の変性ポリフッ化ビニリデン
成形体の製造方法。 ８、前記ポリフッ化ビニリデン成形体１００重量部に対
し、前記グラフト成分が０．１〜５０重量部の範囲で含
浸された特許請求の範囲第５項に記載の変性ポリフッ化
ビニリデン成形体の製造方法。 ９、前記電子線の透過有効厚さが、１〜５００μｍの範
囲である特許請求の範囲第５項に記載の変性ポリフッ化
ビニリデン成形体の製造方法。 １０、前記電子線の照射量が０．１〜５０Ｍｒａｄの範
囲である特許請求の範囲第５項に記載の変性ポリフッ化
ビニリデン成形体の製造方法。 １１、前記グラフト鎖の重合度が１〜２００の範囲であ
る特許請求の範囲第５項に記載の変性ポリフッ化ビニリ
デン成形体の製造方法。 １２、前記ポリフッ化ビニリデングラフト共重合体層の
厚さが１〜５００μｍの範囲である特許請求の範囲第５
項に記載の変性ポリフッ化ビニリデン成形体の製造方法
。[Scope of Claims] 1. Polyfluoride having a graft chain consisting of at least one of acrylic acid units, methacrylic acid units, and acrylic alkyl ester units esterified with an alkyl group having 1 to 4 carbon atoms. A modified polyvinylidene fluoride molded product with a vinylidene graft copolymer layer formed on its surface. 2. The modified polyfluoride according to claim 1, wherein the acrylic alkyl ester unit comprises a monomer unit of at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. Vinylidene molded body. 3. The modified polyvinylidene fluoride molded article according to claim 1, wherein the degree of polymerization of the graft chain is in the range of 1 to 200. 4. The modified polyvinylidene fluoride molded article according to claim 1, wherein the polyvinylidene fluoride graft copolymer layer has a thickness in the range of 1 to 500 μm. 5. A polyvinylidene fluoride graft copolymer having a graft chain consisting of at least one of acrylic acid units, methacrylic acid units, and acrylic alkyl ester units esterified with an alkyl group having 1 to 4 carbon atoms. A method for producing a modified polyvinylidene fluoride molded article having a layer formed on the surface portion, comprising: (1) an acrylic acid monomer and/or oligomer, a methacrylic acid monomer and/or oligomer,
and a step of impregnating the polyvinylidene fluoride molded body with at least one graft component of the acrylic alkyl ester monomer and/or oligomer;
and (2) a method for producing a modified polyvinylidene fluoride molded body, which includes the step of irradiating the impregnated molded body with an electron beam. 6. The acrylic alkyl ester is methyl acrylate, methyl methacrylate, ethyl acrylate,
The method for producing a modified polyvinylidene fluoride molded article according to claim 5, which comprises a monomer unit of at least one of ethyl methacrylate, butyl acrylate, and butyl methacrylate. 7. The method for producing a modified polyvinylidene fluoride molded article according to claim 5, wherein the graft component has a molecular weight of 1000 or less. 8. The method for producing a modified polyvinylidene fluoride molded body according to claim 5, wherein 100 parts by weight of the polyvinylidene fluoride molded body is impregnated with the graft component in a range of 0.1 to 50 parts by weight. . 9. The method for producing a modified polyvinylidene fluoride molded article according to claim 5, wherein the effective thickness through which the electron beam is transmitted is in the range of 1 to 500 μm. 10. The method for producing a modified polyvinylidene fluoride molded article according to claim 5, wherein the irradiation amount of the electron beam is in the range of 0.1 to 50 Mrad. 11. The method for producing a modified polyvinylidene fluoride molded article according to claim 5, wherein the degree of polymerization of the graft chain is in the range of 1 to 200. 12. Claim 5, wherein the polyvinylidene fluoride graft copolymer layer has a thickness in the range of 1 to 500 μm.
A method for producing a modified polyvinylidene fluoride molded article as described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29448286A JPS63145311A (en) | 1986-12-09 | 1986-12-09 | Modified polyvinylidene fluoride molding and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29448286A JPS63145311A (en) | 1986-12-09 | 1986-12-09 | Modified polyvinylidene fluoride molding and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63145311A true JPS63145311A (en) | 1988-06-17 |
Family
ID=17808332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29448286A Pending JPS63145311A (en) | 1986-12-09 | 1986-12-09 | Modified polyvinylidene fluoride molding and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63145311A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03163182A (en) * | 1989-08-31 | 1991-07-15 | Daikin Ind Ltd | Adhesive |
| JP2005015793A (en) * | 2003-06-06 | 2005-01-20 | Arkema | Method for grafting fluoropolymer and multilayered structure containing obtained grafted polymer |
-
1986
- 1986-12-09 JP JP29448286A patent/JPS63145311A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03163182A (en) * | 1989-08-31 | 1991-07-15 | Daikin Ind Ltd | Adhesive |
| JP2005015793A (en) * | 2003-06-06 | 2005-01-20 | Arkema | Method for grafting fluoropolymer and multilayered structure containing obtained grafted polymer |
| JP2008239998A (en) * | 2003-06-06 | 2008-10-09 | Arkema France | Process for grafting fluoropolymer and multilayered structure containing obtained graft polymer |
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