JPH04268343A - Production of flame-resistant film and flame-resistant film produced thereby - Google Patents
Production of flame-resistant film and flame-resistant film produced therebyInfo
- Publication number
- JPH04268343A JPH04268343A JP5042291A JP5042291A JPH04268343A JP H04268343 A JPH04268343 A JP H04268343A JP 5042291 A JP5042291 A JP 5042291A JP 5042291 A JP5042291 A JP 5042291A JP H04268343 A JPH04268343 A JP H04268343A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- film
- resistant film
- resistant
- heat treatment
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 229920006254 polymer film Polymers 0.000 abstract description 4
- 150000001718 carbodiimides Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- DHKVCYCWBUNNQH-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,5,7-tetrahydropyrazolo[3,4-c]pyridin-6-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)C=NN2 DHKVCYCWBUNNQH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- -1 tetrachloroethylene, trichloroethylene, tetrahydrofuran Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は耐炎化フィルムの製造方
法及びその方法により製造した耐炎化フィルムに関し、
更に詳しくは、構造材や産業資材などに利用される、フ
レキシビリティを有し且つ高強度高弾性の高分子耐炎化
フィルムの製造方法及びその方法により製造した高分子
耐炎化フィルムに関するものである。[Industrial Application Field] The present invention relates to a method for producing a flame-resistant film and a flame-resistant film produced by the method.
More specifically, the present invention relates to a method for producing a flame-resistant polymer film having flexibility and high strength and high elasticity, which is used for structural materials, industrial materials, etc., and a flame-resistant polymer film produced by the method.
【０００２】0002
【従来の技術】一般に、耐炎化フィルムと称される材料
は、炎に接しても、赤熱するだけで、炎をあげて燃焼し
ないので、耐炎材料の一つとして有用であり、このよう
な耐炎化フィルムを得るには、例えば、酸素の存在下に
高分子フィルムを加熱処理すればよいことも知られてい
る。[Prior Art] In general, a material called a flame-resistant film is useful as a flame-resistant material because it only becomes red hot when it comes in contact with flame, but does not catch fire and burn. It is also known that in order to obtain a chemical film, for example, a polymer film may be heat-treated in the presence of oxygen.
【０００３】このような耐炎化フィルムを得ことを目的
として、従来より熱処理が試みられた高分子としては、
フェノ−ル−ホルムアルデヒド樹脂，ポリアクリロニト
リル，セルロ−ス，ポリブタジエン，ポリ塩化ビニルな
どがあるが、これらの高分子より得られた耐炎化フィル
ムは、いずれもが、強度が低いばかりか、もろく、フレ
キシビリティが不足したものであった。[0003] Polymers for which heat treatment has been attempted for the purpose of obtaining such flame-resistant films include:
There are phenol-formaldehyde resins, polyacrylonitrile, cellulose, polybutadiene, polyvinyl chloride, etc., but the flame-resistant films obtained from these polymers not only have low strength, but are also brittle and flexible. It lacked functionality.
【０００４】0004
【発明が解決しようとする課題】即ち、耐炎化フィルム
を製造するについての問題点は、加熱処理して得られる
耐炎化フィルムに、強度、弾性率及びフレキシビリティ
という種々の好ましい特性を付与することのできる高分
子材料を、いかに見つけ出すかという点にある。[Problems to be Solved by the Invention] That is, the problem in producing a flame-resistant film is to impart various desirable properties such as strength, elastic modulus, and flexibility to the flame-resistant film obtained by heat treatment. The key issue is how to find polymeric materials that can do this.
【０００５】本発明は、以上説明したような耐炎化フィ
ルムの製造における問題点を解決することを目的として
なされたものであり、特殊な構造を有する高分子フィル
ムを加熱処理するという方法により、フレキシビリティ
に豊み、高強度且つ高弾性な耐炎化フィルムを提供する
ものである。The present invention was made with the aim of solving the problems in the production of flame-retardant films as explained above. The present invention provides a flame-resistant film that is rich in properties, has high strength, and has high elasticity.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に本発明が採用した耐炎化フィルムの製造方法は、ポリ
カルボジイミド樹脂フィルムを、１５０℃乃至３５０℃
の温度範囲内で加熱処理することを特徴とするものであ
り、又、本発明の耐炎化フィルムは、かかる本発明の方
法により製造されることを特徴とするものである。[Means for Solving the Problems] In order to achieve the above object, the method for producing a flame-resistant film adopted by the present invention is to produce a polycarbodiimide resin film at a temperature of 150°C to 350°C.
The flame-resistant film of the present invention is characterized by being produced by the method of the present invention.
【０００７】即ち、本発明の発明者らは、フィルム成形
性がよく、炭素含量が高く、しかも比較的低温で付加、
環化等をおこすポリカルボジイミド樹脂に着目し、鋭意
検討した結果、このポリカルボジイミド樹脂フィルムを
、１５０℃乃至３５０℃の温度範囲内で加熱処理すると
、耐炎化フィルムが得られること、及び得られたフィル
ムが、フレキシビリティに豊み、強度及び弾性率共に優
れた性質を持つことを見い出し、本発明の完成に至った
。That is, the inventors of the present invention have found that the film has good formability, a high carbon content, and can be added at a relatively low temperature.
Focusing on polycarbodiimide resin that causes cyclization, as a result of intensive study, it was found that a flame-resistant film can be obtained by heat-treating this polycarbodiimide resin film within a temperature range of 150°C to 350°C. It was discovered that the film has rich flexibility and excellent properties in both strength and elastic modulus, leading to the completion of the present invention.
【０００８】以下に本発明を詳細に説明する。The present invention will be explained in detail below.
【０００９】本発明に用いられる、ポリカルボジイミド
としては、一般式
−Ｒ−Ｎ＝Ｃ＝Ｎ （１）
（式中Ｒは、有機ジイソシアネ−ト残基を表わす）で示
される、少なくも１種の繰返し単位からなる単独重合体
又は共重合体を挙げることができる。The polycarbodiimide used in the present invention is at least one type represented by the general formula -R-N=C=N (1) (wherein R represents an organic diisocyanate residue). A homopolymer or a copolymer consisting of repeating units can be mentioned.
【００１０】上記式（１）における有機ジイソシアネ−
ト残基Ｒとしては、中でも芳香族ジイソシアネ−ト残基
が好適である（ここで、有機ジイソシアネ−ト残基とは
、有機ジイソシアネ−ト基（ＮＣＯ）を除いた残りの部
分である。）このような、ポリカルボジイミド重合体の
具体例としては、次のようなものを例示することができ
る。Organic diisocyanate in the above formula (1)
Among these, aromatic diisocyanate residues are preferable as the residue R (here, the organic diisocyanate residue is the remainder after removing the organic diisocyanate group (NCO)). Specific examples of such polycarbodiimide polymers include the following.
【化１】[Chemical formula 1]
【００１１】上記各式中において、ｎは、１０〜１０，
０００の範囲をとることができる。尚、好ましくは、ｎ
は５０〜５，０００の範囲が良い。In each of the above formulas, n is 10 to 10,
It can range from 000 to 000. Note that preferably n
is preferably in the range of 50 to 5,000.
【００１２】次に、上記ポリカルボジイミド樹脂をフィ
ルム状に賦形する。そのためには、適宜の溶媒を用いて
フィルム賦形用原液をつくり、そして、この原液をＴダ
イスリットノズル又はコ−タ−を用いて、乾式法或いは
湿式法によりフィルム状とした後、乾燥させ、ポリカル
ボジイミド樹脂フィルムを得るのである。尚、前記ポリ
カルボジイミド樹脂を溶解する溶媒としては、テトラク
ロロエチレン，トリクロロエチレン，テトラヒドロフラ
ン，ジオキサン，モノクロロベンゼン，ジクロロベンゼ
ン，ジメチルホルムアミド，ｎ−メチル−２−ピロリド
ン，ジメチルアセトアミド，ジメチルスルフォキシド等
を挙げることができる。Next, the above polycarbodiimide resin is shaped into a film. To do this, a film-forming stock solution is prepared using an appropriate solvent, and this stock solution is formed into a film using a dry or wet method using a T-die slit nozzle or coater, and then dried. , a polycarbodiimide resin film is obtained. Incidentally, examples of the solvent for dissolving the polycarbodiimide resin include tetrachloroethylene, trichloroethylene, tetrahydrofuran, dioxane, monochlorobenzene, dichlorobenzene, dimethylformamide, n-methyl-2-pyrrolidone, dimethylacetamide, dimethylsulfoxide, and the like. can.
【００１３】又、ポリカルボジイミド樹脂フィルムは、
通常の熱可塑性樹脂について使用される成形方法、例え
ば、インフレ−ション法、Ｔダイ法、カレンダ−法など
によっても容易に成形することができる。更に、粉末の
場合は、圧縮成形、ロ−ル成形、射出成形やトランスフ
ァ−成形等によってもよい。これらによりフィルムの厚
みとしては数μｍ乃至３ｍｍ程度のものを容易に得るこ
とができる。[0013] Furthermore, the polycarbodiimide resin film is
It can also be easily molded by molding methods commonly used for thermoplastic resins, such as the inflation method, T-die method, and calender method. Furthermore, in the case of powder, compression molding, roll molding, injection molding, transfer molding, etc. may be used. By using these methods, it is possible to easily obtain a film having a thickness of approximately several μm to 3 mm.
【００１４】即ち、このポリカルボジイミド樹脂フィル
ムは、耐炎化処理されて、溶融することなく耐炎化フィ
ルムを与えるプレカ−サ−となるものである。尚、プレ
カ−サ−を製造するとき、フィルムが収縮しないように
緊張して処理すると、強度の大きなプレカ−サ−を得る
ことができる。That is, this polycarbodiimide resin film is flame-resistant treated and becomes a precursor that provides a flame-resistant film without melting. Incidentally, when manufacturing the precursor, if the film is treated under tension so as not to shrink, a precursor with great strength can be obtained.
【００１５】次にこのプレカ−サ−を１５０℃乃至３５
０℃の温度で加熱処理することにより、本発明の耐炎化
フィルムを得ることができる。この熱処理において、１
５０℃以下の熱処理温度では、耐炎化フィルムの耐炎性
が不良であり、又、３５０℃以上の熱処理温度では、耐
炎化フィルムの可撓性が落ち、好ましくない。Next, this precursor was heated to 150°C to 35°C.
The flame resistant film of the present invention can be obtained by heat treatment at a temperature of 0°C. In this heat treatment, 1
If the heat treatment temperature is 50° C. or lower, the flame resistance of the flame resistant film will be poor, and if the heat treatment temperature is 350° C. or higher, the flexibility of the flame resistant film will deteriorate, which is not preferable.
【００１６】尚、加熱処理は、上記１５０℃乃至３５０
℃の温度範囲内での加熱時間が、少なくとも３０分とな
るようにして行ない、加熱温度が低いほど、加熱時間を
長くするものとする。[0016] The heat treatment is carried out at a temperature between 150°C and 350°C.
The heating time within the temperature range of °C is at least 30 minutes, and the lower the heating temperature, the longer the heating time.
【００１７】このようにして得られた耐炎化フィルムは
、炎に入れても赤熱するだけで炎をあげて燃焼すること
はない。従って、本発明の耐炎化フィルムは、炭素フィ
ルムや黒鉛フィルムの原料として重要である。[0017] Even when the flame-resistant film thus obtained is put into a flame, it only becomes red hot and does not catch fire and burn. Therefore, the flame-resistant film of the present invention is important as a raw material for carbon films and graphite films.
【００１８】次に本発明を実施例により更に詳細に説明
する。Next, the present invention will be explained in more detail with reference to Examples.
【００１９】[0019]
【実施例１】フィルムの作成Ａ
２，４−トリレンジイソシアネ−ト／２，６−トリレン
ジイソシアネ−トの混合割合８０：２０の混合物（ＴＤ
Ｉ）５４ｇを、テトラクロロエチレン５００ｍｌ中で、
カルボジイミド化触媒（１−フェニル−３−メチルホス
フォレンオキサイド）０．１２ｇと共に１２０℃で４時
間反応させ、ポリカルボジイミド溶液を得た。この溶液
を使用して、乾式法により厚さ５０μｍのポリカルボジ
イミドフィルム（プレカ−サ−フィルム）を作成した。[Example 1] Production of film A A mixture of 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate in a mixing ratio of 80:20 (TD
I) 54 g in 500 ml of tetrachloroethylene,
The mixture was reacted with 0.12 g of a carbodiimidation catalyst (1-phenyl-3-methylphosphorene oxide) at 120° C. for 4 hours to obtain a polycarbodiimide solution. Using this solution, a polycarbodiimide film (precursor film) having a thickness of 50 μm was prepared by a dry method.
【００２０】上記方法により作成したプレカ−サ−フイ
ルムを、空気中で、１５０℃から、昇温速度２℃／分で
３５０℃まで昇温して熱処理し、耐炎化フィルムを得た
。The precursor film produced by the above method was heat-treated in air by raising the temperature from 150° C. to 350° C. at a heating rate of 2° C./min to obtain a flame-resistant film.
【００２１】[0021]
【実施例２】前記方法により作成したプレカ−サ−フイ
ルムを、空気中で、１５０℃から、昇温速度１℃／分で
３００℃まで昇温して熱処理し、耐炎化フィルムを得た
。[Example 2] A precursor film prepared by the above method was heat-treated in air by increasing the temperature from 150°C to 300°C at a heating rate of 1°C/min to obtain a flame-resistant film.
【００２２】[0022]
【実施例３乃至８】前記方法により作成したプレカ−サ
−フイルムを、空気中で、１５０℃から、昇温速度１℃
／分で所定の温度まで加熱すると共に所定時間熱処理し
、耐炎化フィルムを得た。処理時間と熱処理時間は以下
のようであった。
実施例 処理時間 熱処理温度実施例
３ ３０分 ３００℃実施例
４ １時間 ３００℃実施例
５ ３時間 ２００℃実施例
６ １２時間 ２００℃実施例７
２４時間 ２００℃実施例８
３６時間 １５０℃[Examples 3 to 8] Precursor films prepared by the above method were heated at a heating rate of 1°C from 150°C in air.
/min to a predetermined temperature and heat-treated for a predetermined time to obtain a flame-resistant film. The treatment time and heat treatment time were as follows. Examples Treatment time Heat treatment temperature Example 3 30 minutes 300°C Example 4 1 hour 300°C Example 5 3 hours 200°C Example 6 12 hours 200°C Example 7
24 hours 200℃ Example 8
36 hours 150℃
【００２３】[0023]
【実施例９】実施例１により作成したプレカーサーフイ
ルムを、真空中で、１５０℃から、昇温速度１℃／分で
３５０℃まで昇温して熱処理し、耐炎化フィルムを得た
。[Example 9] The precursor film prepared in Example 1 was heat-treated in a vacuum by increasing the temperature from 150°C to 350°C at a temperature increase rate of 1°C/min to obtain a flame-resistant film.
【００２４】[0024]
【実施例１０】上記フィルムの作成Ａで得られたプレカ
−サ−フィルムを、２２０℃にて２０秒間一軸延伸を行
ない（延伸倍率５倍）、配向プレカ−サ−フィルムを作
成した。このプレカ−サ−フィルムを緊張させたまま、
実施例３と同様の方法で熱処理を行ない、耐炎化フィル
ムを得た。Example 10 The precursor film obtained in the above film preparation A was uniaxially stretched at 220° C. for 20 seconds (stretching ratio: 5 times) to prepare an oriented precursor film. Keeping this precursor film under tension,
Heat treatment was performed in the same manner as in Example 3 to obtain a flame-resistant film.
【００２５】[0025]
【実施例１１乃至１３】フィルムの作成Ｂメチレンジフ
ェニルジイソシアネ−ト（ＭＤＩ）５０ｇを、テトラヒ
ドロフラン８８０ｍｌ中で、カルボジイミド化触媒（１
−フェニル−３−メチルホスフォレンオキサイド）０．
１３ｇと共に６８℃で１２時間反応させ、ポリカルボジ
イミド溶液を得た。この溶液を使用して、乾式法により
厚さ５０μｍのポリカルボジイミドフィルム（プレカ−
サ−フィルム）を作成した。[Examples 11 to 13] Film Preparation B 50 g of methylene diphenyl diisocyanate (MDI) was added to 880 ml of tetrahydrofuran with a carbodiimidization catalyst (1
-phenyl-3-methylphosphorene oxide) 0.
A polycarbodiimide solution was obtained by reacting with 13 g at 68° C. for 12 hours. Using this solution, a polycarbodiimide film (precursor) with a thickness of 50 μm was produced using a dry method.
A surf film) was created.
【００２６】上記Ｂで得られたプレカ−サ−フィルムを
、先に記載した実施例と同様の方法で熱処理を行ない、
耐炎化フィルムを得た。
実施例 熱処理条件
実施例１１ 実施例３
実施例１２ 実施例６
実施例１３ 実施例９The precursor film obtained in step B above was heat treated in the same manner as in the example described above,
A flame-resistant film was obtained. Examples Heat treatment conditions Example 11 Example 3 Example 12 Example 6 Example 13 Example 9
【００２７】フィルムの作成Ｃ
ジフェニルエ−テルジイソシアネ−ト５０ｇを、テトラ
ヒドロフラン８５０ｍｌ中で、カルボジイミド化触媒（
１−フェニル−３−メチルホスフォレンオキサイド）０
．１３ｇと共に６８℃で１２時間反応させ、ポリカルボ
ジイミド溶液を得た。この溶液を使用して、乾式法によ
り厚さ２０μのポリカルボジイミドフィルム（プレカ−
サ−フィルム）を作成した。Film Preparation C: 50 g of diphenyl ether diisocyanate was added to 850 ml of tetrahydrofuran with carbodiimidization catalyst (
1-phenyl-3-methylphosphorene oxide) 0
．． It was reacted with 13 g at 68° C. for 12 hours to obtain a polycarbodiimide solution. Using this solution, a polycarbodiimide film (precursor) with a thickness of 20 μm was produced using a dry method.
A surf film) was created.
【００２８】[0028]
【実施例１４乃至１６】上記Ｃで得られたプレカ−サ−
フィルムを、先に記載した実施例と同様の方法で熱処理
を行ない、耐炎化フィルムを得た。
実施例 熱処理条件
実施例１４ 実施例３
実施例１５ 実施例６
実施例１６ 実施例９[Examples 14 to 16] Precursor obtained in the above C
The film was heat treated in the same manner as in the example described above to obtain a flame resistant film. Examples Heat treatment conditions Example 14 Example 3 Example 15 Example 6 Example 16 Example 9
【００２９】[0029]
【実施例１７】上記Ｃで得られたプレカーサーフイルム
を、空気中、３５０℃で３０分間熱処理し、耐炎化フィ
ルムを得た。Example 17 The precursor film obtained in step C above was heat treated in air at 350°C for 30 minutes to obtain a flame resistant film.
【００３０】[0030]
【実施例１８】フィルムの作成Ｄ
パラフェニレンジイソシアネ−ト５０ｇを、テトラクロ
ロエチレン５００ｍｌ中で、カルボジイミド化触媒（１
−フェニル−３−メチルホスフォレンオキサイド）０．
１３ｇと共に１２０℃で５時間反応させた。[Example 18] Film Preparation D 50 g of paraphenylene diisocyanate was added in 500 ml of tetrachloroethylene with a carbodiimidization catalyst (1
-phenyl-3-methylphosphorene oxide) 0.
The mixture was reacted with 13 g at 120° C. for 5 hours.
【００３１】この溶液を冷却することにより、ポリカル
ボジイミドが沈殿した。この沈殿物を濾過し、１００℃
で２時間乾燥し、ポリカルボジイミド粉末を得た。この
粉末を、プレス温度１８０℃、プレス圧８０Ｋｇ／ｃｍ
２プレス成形し、厚さ８０μｍのポリカルボジイミドフ
ィルム（プレカ−サ−フィルム）を作成した。By cooling this solution, polycarbodiimide precipitated. This precipitate was filtered and heated to 100°C.
The mixture was dried for 2 hours to obtain polycarbodiimide powder. This powder was pressed at a pressing temperature of 180°C and a pressing pressure of 80 kg/cm.
2 press molding to create a polycarbodiimide film (precursor film) with a thickness of 80 μm.
【００３２】上記Ｄで得られたプレカ−サ−フィルムを
、先に記載した実施例３と同様の方法で熱処理を行ない
、耐炎化フィルムを得た。The precursor film obtained in the above D was heat treated in the same manner as in Example 3 described above to obtain a flame resistant film.
【００３３】[0033]
【比較例１】日本ゴム製ポリブタジエン（ＲＢ８１０）
を用い、１４０℃の温度で、Ｔ−ダイ押し出し成形法に
より、厚さ１１０μｍのフィルムを作成した。このフィ
ルムに対し、実施例５と同様の処理を行なったが、得ら
れたフィルムは形状を保つことができず、非常に脆いた
め、力学的特性の測定は不可能であった。[Comparative Example 1] Nippon Rubber Polybutadiene (RB810)
A film with a thickness of 110 μm was produced using a T-die extrusion method at a temperature of 140° C. This film was subjected to the same treatment as in Example 5, but the resulting film could not maintain its shape and was extremely brittle, making it impossible to measure its mechanical properties.
【００３４】[0034]
【比較例２】ノボラック型フェノ−ル樹脂／メタノ−ル
／ホルマリンを重量比３／３／１の割合で混合した溶液
を、ガラス板上に流し、その後３０分間風乾し、メタノ
−ルを除去した。その後、５Ｎの塩酸内に入れ、７０℃
で１００分間処理し、温水で洗浄することにより、厚さ
５０μｍのフェノ−ル樹脂フィルムを作成した。このフ
ィルムに対し、実施例５と同様の処理を行なったが、得
られたフィルムは硬く、フレキシビリティのないもので
あった。[Comparative Example 2] A solution of novolac type phenolic resin/methanol/formalin mixed at a weight ratio of 3/3/1 was poured onto a glass plate and then air-dried for 30 minutes to remove methanol. did. Then, put it in 5N hydrochloric acid and 70°C.
A phenolic resin film with a thickness of 50 μm was prepared by treating with water for 100 minutes and washing with warm water. This film was subjected to the same treatment as in Example 5, but the obtained film was hard and had no flexibility.
【００３５】[0035]
【比較例３】前記実施例１の方法により作成したプレカ
−サ−フイルムを、空気中で、１３０℃の温度で１００
分間熱処理した。[Comparative Example 3] A precursor film prepared by the method of Example 1 was heated in air at a temperature of 130°C for 100 min.
Heat treated for minutes.
【００３６】[0036]
【比較例４】前記実施例１の方法により作成したプレカ
−サ−フイルムを、空気中で、１５０℃から、昇温速度
２℃／分で所定の温度まで加熱すると共に所定時間熱処
理した。[Comparative Example 4] A precursor film prepared by the method of Example 1 was heated in air from 150°C to a predetermined temperature at a heating rate of 2°C/min, and was heat-treated for a predetermined period of time.
【００３７】上記実施例１乃至１８及び比較例１乃至４
で得られたフィルムの物性を以下の表に示す。[0037] Above Examples 1 to 18 and Comparative Examples 1 to 4
The physical properties of the film obtained are shown in the table below.
【表１】[Table 1]
【００３８】尚、表１において、引張強度及びヤング率
を示す数値の単位は、Ｋｇ／ｍｍ２であり、又、「処理
時間」は、表中の処理温度で加熱した時間を示し、単位
は分である。可橈性の欄における「良好」フレキシビリ
ティがありハンドリングがしやすいことを示し、「不良
」はフレキシビリティがなく脆いことを示し、耐炎性の
欄における「不良」は炎をあげて燃え広がったことを示
す。[0038] In Table 1, the unit of numerical values indicating tensile strength and Young's modulus is Kg/mm2, and "processing time" indicates the time heated at the processing temperature in the table, and the unit is minutes. It is. "Good" in the flexibility column indicates that it has flexibility and is easy to handle, "poor" indicates that it has no flexibility and is brittle, and "poor" in the flame resistance column indicates that it caught fire and spread. shows.
【００３９】又、表１において、比較例４の処理時間の
欄に記載されている「１００、１５」は、１５０℃〜３
５０℃での処理時間が１００分間、３５０℃〜３８０℃
での処理時間が１５分間であることを示している。In addition, in Table 1, "100, 15" written in the column of processing time of Comparative Example 4 means 150°C to 3
Processing time at 50°C: 100 minutes, 350°C to 380°C
This indicates that the processing time is 15 minutes.
Claims (8)
１５０℃乃至３５０℃の温度範囲内で加熱処理すること
を特徴とする耐炎化フィルムの製造方法。[Claim 1] A polycarbodiimide resin film,
A method for producing a flame-resistant film, characterized by heat treatment within a temperature range of 150°C to 350°C.
Ｒ−Ｎ＝Ｃ＝Ｎ− （Ｒは有機ジイソシアネ−ト残基を表わす。）で示され
る、少なくとも１種の繰返し単位からなる単独重合体又
は共重合体である請求項１記載の耐炎化フィルムの製造
方法。[Claim 2] The polycarbodiimide resin has the general formula -
The flame-resistant film according to claim 1, which is a homopolymer or copolymer consisting of at least one type of repeating unit represented by R-N=C=N- (R represents an organic diisocyanate residue). manufacturing method.
シアネ−ト残基である請求項２記載の耐炎化フィルムの
製造方法。3. The method for producing a flame-resistant film according to claim 2, wherein R in the general formula is an aromatic diisocyanate residue.
加熱処理を、少なくとも３０分以上行なう請求項１乃至
３のいずれかに記載の耐炎化フィルムの製造方法。4. The method for producing a flame-resistant film according to claim 1, wherein the heat treatment is carried out at a temperature range of 150° C. to 350° C. for at least 30 minutes.
温度範囲で昇温しつつ行なう請求項１乃至４のいずれか
に記載の耐炎化フィルムの製造方法。5. The method for producing a flame-resistant film according to claim 1, wherein the heat treatment is performed while increasing the temperature in a temperature range of 150° C. to 350° C.
緊張した状態で加熱処理する請求項１乃至５のいずれか
に記載の耐炎化フィルムの製造方法。[Claim 6] A polycarbodiimide resin film,
6. The method for producing a flame-resistant film according to claim 1, wherein the heat treatment is carried out under tension.
１５０乃至３５０℃に加熱処理して得られた耐炎化フィ
ルムを、更に加熱処理する１乃至６のいずれかに記載の
耐炎化フィルムの製造方法。[Claim 7] A polycarbodiimide resin film,
7. The method for producing a flame resistant film according to any one of 1 to 6, wherein the flame resistant film obtained by heat treatment at 150 to 350°C is further heat treated.
法により製造されることを特徴とする耐炎化フィルム。8. A flame-resistant film produced by the method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042291A JP3205875B2 (en) | 1991-02-22 | 1991-02-22 | Manufacturing method of flame resistant film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042291A JP3205875B2 (en) | 1991-02-22 | 1991-02-22 | Manufacturing method of flame resistant film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04268343A true JPH04268343A (en) | 1992-09-24 |
| JP3205875B2 JP3205875B2 (en) | 2001-09-04 |
Family
ID=12858431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5042291A Expired - Fee Related JP3205875B2 (en) | 1991-02-22 | 1991-02-22 | Manufacturing method of flame resistant film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3205875B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0767197A1 (en) * | 1995-10-03 | 1997-04-09 | Nisshinbo Industries, Inc. | Insulating film for use in motor of refrigeration compressor |
| EP0752712A3 (en) * | 1995-06-28 | 1997-08-27 | Nisshin Spinning | Insulating material for enameled wire of motor of refrigeration compressor |
-
1991
- 1991-02-22 JP JP5042291A patent/JP3205875B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0752712A3 (en) * | 1995-06-28 | 1997-08-27 | Nisshin Spinning | Insulating material for enameled wire of motor of refrigeration compressor |
| EP0767197A1 (en) * | 1995-10-03 | 1997-04-09 | Nisshinbo Industries, Inc. | Insulating film for use in motor of refrigeration compressor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3205875B2 (en) | 2001-09-04 |
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