JPH04239036A - Polyphenylene ether film - Google Patents
Polyphenylene ether filmInfo
- Publication number
- JPH04239036A JPH04239036A JP116291A JP116291A JPH04239036A JP H04239036 A JPH04239036 A JP H04239036A JP 116291 A JP116291 A JP 116291A JP 116291 A JP116291 A JP 116291A JP H04239036 A JPH04239036 A JP H04239036A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyphenylene ether
- examples
- anhydride
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- -1 poly(2,6-dimethyl-1,4- phenylene ether) Polymers 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 5
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- BILVIMICBJCGQC-UHFFFAOYSA-N 2,6-dimethyl-3-phenylphenol Chemical compound CC1=C(O)C(C)=CC=C1C1=CC=CC=C1 BILVIMICBJCGQC-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 108010021119 Trichosanthin Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ポリフェニレンエーテ
ル系フィルムに関する。本発明のフィルムは、優れた誘
電特性、耐熱性を示し、電気産業、電子産業、宇宙・航
空機産業等の分野において誘電材料、絶縁材料、耐熱材
料等に用いることができる。FIELD OF THE INVENTION This invention relates to polyphenylene ether films. The film of the present invention exhibits excellent dielectric properties and heat resistance, and can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in fields such as the electrical industry, electronic industry, and space/aircraft industry.
【０００２】0002
【従来の技術】近年、通信用、民生用、産業用等の電子
機器の分野における実装方法の小型化、高密度化への指
向は著しいものがあり、それに伴って材料の面でもより
優れた耐熱性、寸法安定性、電気特性が要求させつつあ
る。特にポリフェニレンエーテルは、高周波領域での誘
電特性に優れている為、近年、注目されてきている。[Prior Art] In recent years, there has been a remarkable trend toward smaller packaging methods and higher density mounting methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Heat resistance, dimensional stability, and electrical properties are becoming increasingly required. In particular, polyphenylene ether has attracted attention in recent years because of its excellent dielectric properties in the high frequency range.
【０００３】ポリフェニレンエーテルの熱成膜法として
は、溶融押出法、カレンダー法などがある。しかしなが
ら、これらの方法では溶融粘度が高く、表面が平滑なフ
ィルムは得られない。また低温でフィルム化する方法と
しては、溶媒を利用するキャスティング法があるが、ポ
リフェニレンエーテル単独では、成膜性がないので、乾
燥中にヒビ割れ等が発生しフィルムが得られない。[0003] Examples of thermal film forming methods for polyphenylene ether include melt extrusion and calendering. However, these methods do not provide a film with a high melt viscosity and a smooth surface. Further, as a method for forming a film at a low temperature, there is a casting method using a solvent, but polyphenylene ether alone does not have film-forming properties, so cracks occur during drying and a film cannot be obtained.
【０００４】ポリフェニレンエーテル系フィルムに成膜
性を付与するため、成膜性良好な樹脂を配合する方法が
ある。特開昭６１−２１８６５２号公報には、ポリフェ
ニレンエーテルと、スチレン系熱可塑性ポリマ−、なら
びに、トリアリルイソシアヌレートおよび／またはトリ
アリルシアヌレートとの組み合わせが開示されている。
しかしながら、これらの樹脂は高周波領域での誘電特性
が劣っている為、結果としてポリフェニレンエーテル系
フィルム自身の誘電特性を損なうこととなっている。[0004] In order to impart film-forming properties to a polyphenylene ether film, there is a method of blending a resin with good film-forming properties. JP-A-61-218652 discloses a combination of polyphenylene ether, a styrenic thermoplastic polymer, and triallyl isocyanurate and/or triallyl cyanurate. However, these resins have poor dielectric properties in a high frequency range, and as a result, the dielectric properties of the polyphenylene ether film itself are impaired.
【０００５】[0005]
【発明が解決しようとする課題】本発明は以上のような
事情に鑑みてなされたものであり、ポリフェニレンエー
テルに成膜性を付与し、優れた誘電特性を維持したフィ
ルムを提供しようとするものである。[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and aims to provide a film that provides film-forming properties to polyphenylene ether and maintains excellent dielectric properties. It is.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上述のよう
な問題を解決するため鋭意検討を重ねた結果、本発明の
目的に沿ったポリフェニレンエーテル系フィルムを見い
出し発明を完成するに到った。すなわち本発明は、ポリ
フェニレンエーテルと不飽和カルボン酸または酸無水物
との反応生成物からなるフィルムを提供する。[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a polyphenylene ether film that meets the purpose of the present invention and have completed the invention. Ta. That is, the present invention provides a film made of a reaction product of polyphenylene ether and an unsaturated carboxylic acid or acid anhydride.
【０００７】以下にこの発明を詳しく説明する。本発明
において使用されるポリフェニレンエーテルは次の一般
式化１で表わされる。The present invention will be explained in detail below. The polyphenylene ether used in the present invention is represented by the following general formula 1.
【０００８】[0008]
【化１】[Chemical formula 1]
【０００９】一般式ＡにおけるＲ１ 〜Ｒ４ の低級ア
ルキル基の例としては、メチル基、エチル基、ｎ−プロ
ピル基、イソプロピル基、ｎ−ブチル基、イソブチル基
、ｓｅｃ−ブチル基等が挙げられる。アリール基の例と
しては、フェニル基等が挙げられる。ハロアルキル基の
例としては、ブロモメチル基、クロロメチル基等が挙げ
られる。ハロゲン原子の例としては、臭素、塩素等が挙
げられる。Examples of lower alkyl groups for R1 to R4 in general formula A include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl. Examples of aryl groups include phenyl groups. Examples of haloalkyl groups include bromomethyl group, chloromethyl group, and the like. Examples of halogen atoms include bromine, chlorine, and the like.
【００１０】化１のＱの代表的な例としては、次の４種
の一般式化２で表わされる化合物群が挙げられる。Typical examples of Q in Formula 1 include the following four groups of compounds represented by Formula 2.
【００１１】[0011]
【化２】[Case 2]
【００１２】（式中、Ａ１ 、Ａ２ は同一または異な
る炭素数１〜４の直鎖状アルキル基を表わし、Ｘは脂肪
族炭化水素残基およびそれらの置換誘導体、アラルキル
基およびそれらの置換誘導体、酸素、硫黄、スルホニル
基、カルボニル基を表わし、Ｙは脂肪族炭化水素残基お
よびそれらの置換誘導体、芳香族炭化水素残基およびそ
れらの置換誘導体、アラルキル基およびそれらの置換誘
導体を表わし、Ｚは酸素、硫黄、スルホニル基、カルボ
ニル基を表わしＡ２ と直接結合した２つのフェニル基
、Ａ２ とＸ、Ａ２とＹ、Ａ２ とＺの結合位置はすべ
てフェノール性水酸基のオルト位およびパラ位を示し、
ｒは０〜４、Ｓは２〜６の整数を表わす。）具体例とし
て、下記化３〜化４等があげられる。(wherein A1 and A2 represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aralkyl group and substituted derivatives thereof, represents oxygen, sulfur, sulfonyl group, carbonyl group, Y represents aliphatic hydrocarbon residues and substituted derivatives thereof, aromatic hydrocarbon residues and substituted derivatives thereof, aralkyl group and substituted derivatives thereof, Z represents Two phenyl groups representing oxygen, sulfur, a sulfonyl group, and a carbonyl group are directly bonded to A2, and the bonding positions of A2 and X, A2 and Y, and A2 and Z all indicate the ortho and para positions of the phenolic hydroxyl group,
r represents an integer of 0 to 4, and S represents an integer of 2 to 6. ) Specific examples include the following compounds 3 to 4.
【００１３】[0013]
【化３】[Chemical formula 3]
【００１４】[0014]
【化４】
等が挙げられる。一般式化１中のＪで表わされるポリフ
ェニレンエーテル鎖中には、一般式Ａで表わされる単位
の他、次の一般式化５で表わされる単位が含まれていて
もよい。[Chemical formula 4] etc. In addition to the unit represented by the general formula A, the polyphenylene ether chain represented by J in the general formula 1 may contain a unit represented by the following general formula 5.
【００１５】[0015]
【化５】 等が挙げられる。[C5] etc.
【００１６】本発明に用いられる一般式化１のポリフェ
ニレンエーテル樹脂の好ましい例としては、２，６−ジ
メチルフェノールの単独重合で得られるポリ（２，６ジ
メチル−１，４−フェニレンエーテル）、ポリ（２，６
−ジメチル−１，４−フェニレンエーテル）のスチレン
グラフト共重合体、２，６−ジメチルフェノールと２，
３，６−トリメチルフェノールの共重合体、２，６−ジ
メチルフェノールと２，６−ジメチル−３−フェニルフ
ェノールの共重合体、２，６−ジメチルフェノールと多
官能性フェノール化合物 Ｑ（Ｈ）ｍ（ｍは２〜６の
整数）の存在下で重合して得られた多官能性ポリフェニ
レンエーテル樹脂、例えば特開昭６３−３０１２２２号
公報、特開平１−２９７４２８号公報に開示されている
ような一般式ＡおよびＢの単位を含む共重合体等が挙げ
られる。Preferred examples of the polyphenylene ether resin of general formula 1 used in the present invention include poly(2,6 dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol; (2,6
-dimethyl-1,4-phenylene ether), styrene graft copolymer of 2,6-dimethylphenol and 2,
Copolymer of 3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and 2,6-dimethyl-3-phenylphenol, 2,6-dimethylphenol and polyfunctional phenol compound Q(H)m (m is an integer of 2 to 6), such as those disclosed in JP-A-63-301222 and JP-A-1-297428. Examples include copolymers containing units of general formulas A and B.
【００１７】以上述べたポリフェニレンエーテル樹脂の
分子量については、３０℃、０．５ｇ／ｄｌのクロロホ
ルム溶液で測定した粘度数ηｓｐ／ｃが０．１〜１．０
の範囲にあるものが良好に使用できる。特に強度等の点
からは０．３〜１．０が好ましい。本発明に用いられる
反応生成物は、上記のポリフェニレンエーテル樹脂を不
飽和カルボン酸または酸無水物と反応させることによっ
て製造される。適当な酸および酸無水物の例としては、
アクリル酸、メタクリル酸、無水マレイン酸、フマル酸
、イタコン酸、無水イタコン酸、無水グルタコン酸、無
水シトラコン酸等が挙げられる。特に無水マレイン酸が
入手のし易さ、取り扱い易さの面で好まれる。反応はポ
リフェニレンエーテル樹脂と不飽和カルボン酸または酸
無水物を１００℃〜３９０℃の温度範囲で加熱すること
によって行われる。この際ラジカル開始剤を共存させて
もよい。溶液法と溶融混合法の両方が使用できるが、押
出し機等を用いる溶融混合法の方が簡便に行うことがで
き、本発明の目的に適している。不飽和カルボン酸また
は酸無水物の割合は、ポリフェニレンエーテル樹脂１０
０重量部に対し、０．０１〜５．０重量部、好ましくは
０．１〜３．０重量部である。Regarding the molecular weight of the polyphenylene ether resin described above, the viscosity number η sp/c measured in a 0.5 g/dl chloroform solution at 30° C. is 0.1 to 1.0.
Those within this range can be used satisfactorily. In particular, from the viewpoint of strength etc., 0.3 to 1.0 is preferable. The reaction product used in the present invention is produced by reacting the polyphenylene ether resin described above with an unsaturated carboxylic acid or acid anhydride. Examples of suitable acids and anhydrides include:
Examples include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and the like. Maleic anhydride is particularly preferred in terms of availability and ease of handling. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range of 100°C to 390°C. At this time, a radical initiator may be present. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be carried out more easily and is suitable for the purpose of the present invention. The proportion of unsaturated carboxylic acid or acid anhydride is 10% of polyphenylene ether resin.
The amount is 0.01 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight.
【００１８】上記の反応生成物を成膜する方法としては
、特に限定されないが、溶媒を用いる乾式法（キャステ
ィング法）、湿式法、少量の溶媒でポリフェニレンエー
テルを可塑化する溶融成膜法等が挙げられる。溶媒成膜
に用いられる溶媒としては、ジクロロメタン、クロロホ
ルム、トリクロロエチレン等のハロゲン系溶媒、ベンゼ
ン、トルエン、キシレン等の芳香族系溶媒等が単独で、
あるいは二種以上を組み合わせて用いられる。Methods for forming a film from the above reaction product include, but are not particularly limited to, a dry method (casting method) using a solvent, a wet method, a melt film forming method in which polyphenylene ether is plasticized with a small amount of solvent, etc. Can be mentioned. Solvents used for film formation include halogen solvents such as dichloromethane, chloroform, and trichloroethylene, aromatic solvents such as benzene, toluene, and xylene, etc.
Alternatively, two or more types can be used in combination.
【００１９】樹脂の濃度は、最終的に得られるフィルム
の厚みによって適切にコントロールして用いることがで
き、特に限定されない。フィルムの厚みについても特に
限定されず、任意の厚みのフィルムが製造できる。乾燥
方法も特に制限されることなく通常の熱風乾燥、遠赤外
線乾燥等が使用できる。また本発明のポリフェニレンエ
ーテル樹脂の成膜性を損わないかぎりにおいてポリフェ
ニレンエーテル樹脂等の各種熱可塑性樹脂、熱硬化性樹
脂、酸化防止剤等を添加しても良い。The concentration of the resin can be appropriately controlled depending on the thickness of the final film, and is not particularly limited. The thickness of the film is not particularly limited either, and a film of any thickness can be manufactured. The drying method is not particularly limited, and conventional hot air drying, far infrared drying, etc. can be used. Further, various thermoplastic resins such as polyphenylene ether resin, thermosetting resins, antioxidants, etc. may be added as long as they do not impair the film-forming properties of the polyphenylene ether resin of the present invention.
【００２０】[0020]
【実施例】以下、本発明を一層明確にするために実施例
を挙げて説明するが、本発明の範囲をこれらの実施例に
限定するものではない。[Examples] The present invention will be explained below with reference to examples in order to make it more clear, but the scope of the present invention is not limited to these examples.
【００２１】[0021]
【参考例１】３０℃、０．５ｇ／ｄｌのクロロホルム溶
液で測定した粘度数ηｓｐ／ｃが０．５４のポリ（２，
６−ジメチル−１，４−フェニレンエーテル）１００重
量部と、無水マレイン酸１．５重量部、および２，５−
ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサ
ン（日本油脂（株）製 パーヘキサ２５Ｂ）１．０重
量部を室温でドライブレンドした後、シリンダー温度３
００℃、スクリュー回転数２３０ｒｐｍの条件で二軸押
出し機により押出した。この反応生成物をＡとする。[Reference Example 1] Poly(2,
6-dimethyl-1,4-phenylene ether), 1.5 parts by weight of maleic anhydride, and 2,5-
After dry blending 1.0 parts by weight of dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, manufactured by NOF Corporation) at room temperature, the cylinder temperature was 3.
It was extruded using a twin-screw extruder under the conditions of 00°C and screw rotation speed of 230 rpm. This reaction product is designated as A.
【００２２】[0022]
【参考例２】参考例１と同様の方法で測定した粘度数η
ｓｐ／ｃが０．６０のポリ（２，６−ジメチル−１，４
−フェニレンエーテル）１００重量部と、無水マレイン
酸１．５重量部を室温でドライブレンドした後、シリン
ダー温度３００℃、スクリュー回転数２３０ｒｐｍの条
件で二軸押出し機により押出した。この反応生成物をＢ
とする。[Reference Example 2] Viscosity number η measured in the same manner as Reference Example 1
Poly(2,6-dimethyl-1,4
-phenylene ether) and 1.5 parts by weight of maleic anhydride were dry blended at room temperature, and then extruded using a twin-screw extruder at a cylinder temperature of 300°C and a screw rotation speed of 230 rpm. This reaction product is B
shall be.
【００２３】[0023]
【実施例１〜４】上記ポリマ−Ａ又はＢを表１に示した
溶媒に溶解し、塗工機を用いてガラス板上に塗布した。
乾燥後のフィルムの厚さは約５０μｍであった。成膜性
はいずれも良好であった。また実施例１〜４について、
得られたフィルムの誘電率を測定したところ、２．５〜
２．６であった。結果を表１に示す。Examples 1 to 4 Polymer A or B was dissolved in the solvent shown in Table 1 and coated on a glass plate using a coating machine. The thickness of the film after drying was approximately 50 μm. Film formability was good in all cases. Further, regarding Examples 1 to 4,
When the dielectric constant of the obtained film was measured, it was 2.5~
It was 2.6. The results are shown in Table 1.
【００２４】さらに、実施例２について得られたフィル
ムの引張強度を測定したところ、７００ｋｇ／ｃｍ２
であった。Furthermore, when the tensile strength of the film obtained in Example 2 was measured, it was found to be 700 kg/cm2.
Met.
【００２５】[0025]
【比較例１、２】上記ポリマ−Ａ又は、Ｂの代わりに、
３０℃、０．５ｇ／ｄｌのクロロホルム溶液で測定した
粘度数ηｓｐ／ｃが０．５４のポリ（２，６−ジメチル
−１，４−フェニレンエーテル）を用いて表１の組成で
実施例１〜４と同じ操作を繰り返した。成膜性がない為
ヒビ割れが発生し、外観が良好なフィルムはいずれも得
られなかった。[Comparative Examples 1 and 2] Instead of the above polymer A or B,
Example 1 with the composition shown in Table 1 using poly(2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp/c of 0.54 measured in a chloroform solution of 0.5 g/dl at 30°C. The same operations as steps 4 to 4 were repeated. Cracks occurred due to lack of film formability, and no film with good appearance could be obtained.
【００２６】[0026]
【表１】[Table 1]
【００２７】[0027]
【発明の効果】本発明のポリフェニレンエーテル系フィ
ルムは、溶媒成膜性が良好であり、取り扱い性に優れた
フィルムが得られる。従って本発明の材料は、電気産業
、電子産業、宇宙・航空機産業等の分野において誘電材
料、絶縁材料、耐熱材料等として用いることができる。[Effects of the Invention] The polyphenylene ether film of the present invention has good solvent film formability and can be obtained with excellent handling properties. Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in fields such as the electrical industry, the electronic industry, and the space/aircraft industry.
Claims (1)
ボン酸または酸無水物との反応生成物からなるフィルム
。1. A film comprising a reaction product of polyphenylene ether and an unsaturated carboxylic acid or acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3001162A JPH085977B2 (en) | 1991-01-09 | 1991-01-09 | Polyphenylene ether film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3001162A JPH085977B2 (en) | 1991-01-09 | 1991-01-09 | Polyphenylene ether film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04239036A true JPH04239036A (en) | 1992-08-26 |
| JPH085977B2 JPH085977B2 (en) | 1996-01-24 |
Family
ID=11493745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3001162A Expired - Lifetime JPH085977B2 (en) | 1991-01-09 | 1991-01-09 | Polyphenylene ether film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085977B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001081451A1 (en) * | 2000-04-21 | 2001-11-01 | Asahi Kasei Kabushiki Kaisha | Modified polyphenylene ether resin |
| US7645838B2 (en) | 2001-06-29 | 2010-01-12 | Asahi Kasei Kabushiki Kaisha | Conjugated non-aromatic diene or dienophilic compound-modified polyphenylene ethers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03106934A (en) * | 1989-08-18 | 1991-05-07 | General Electric Co <Ge> | Cross-linking polyphenylene ether having capped reactive terminal |
-
1991
- 1991-01-09 JP JP3001162A patent/JPH085977B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03106934A (en) * | 1989-08-18 | 1991-05-07 | General Electric Co <Ge> | Cross-linking polyphenylene ether having capped reactive terminal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001081451A1 (en) * | 2000-04-21 | 2001-11-01 | Asahi Kasei Kabushiki Kaisha | Modified polyphenylene ether resin |
| US6841629B1 (en) | 2000-04-21 | 2005-01-11 | Asahi Kasei Kabushiki Kaisha | Modified polyphenylene ether resin |
| US7645838B2 (en) | 2001-06-29 | 2010-01-12 | Asahi Kasei Kabushiki Kaisha | Conjugated non-aromatic diene or dienophilic compound-modified polyphenylene ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085977B2 (en) | 1996-01-24 |
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