JPH0347656B2 - - Google Patents
Info
- Publication number
- JPH0347656B2 JPH0347656B2 JP24316786A JP24316786A JPH0347656B2 JP H0347656 B2 JPH0347656 B2 JP H0347656B2 JP 24316786 A JP24316786 A JP 24316786A JP 24316786 A JP24316786 A JP 24316786A JP H0347656 B2 JPH0347656 B2 JP H0347656B2
- Authority
- JP
- Japan
- Prior art keywords
- poly
- film
- terephthalamide
- moisture absorption
- mechanical properties
- 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.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 17
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- -1 aromatic cyclic diamine Chemical class 0.000 description 20
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000005606 hygroscopic expansion Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000004760 aramid Substances 0.000 description 8
- 229920003235 aromatic polyamide Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ASNGJIKJXXHDRE-UHFFFAOYSA-N [3-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)phenyl]-(7-azabicyclo[4.1.0]hepta-1,3,5-trien-7-yl)methanone Chemical compound C(C1=CC(C(=O)N2C3=C2C=CC=C3)=CC=C1)(=O)N1C3=C1C=CC=C3 ASNGJIKJXXHDRE-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Description
〔産業上の利用分野〕
本発明は、表面変性ポリ−パラフエニレンテレ
フタルアミド（以下PPTAという）系ポリマー成
型物の製造法に関するものである。更に詳しく
は、PPTA系ポリマー成型物を損傷させることな
く表面のみを変性させ、吸湿寸法変化率の改善さ
れたPPTA系ポリマー成型物を得る方法に関する
ものである。
〔従来の技術〕
耐熱性高分子として、アミド結合にて結合され
た二価の炭化水素基のすべてが芳香族環性基であ
る、いわゆる全芳香族ポリアミドからなる繊維、
フイルム等の成型物は、高強力、高弾性率、優れ
た耐熱性の故に、種々の用途に有用である。特
に、かかる繊維は、その高強力、高弾性率の性質
のため、強化用繊維として種々の熱可塑性樹脂、
ゴムおよび熱硬化性樹脂に添加され、該組成物の
力学的性質、耐熱性等が検討されている〔例え
ば、ポリマーエンジニアリングアンドサイエン
ス、第14巻、633頁（1974）、ジヤーナルアプライ
ドポリマーサイエンス、第20巻、435頁（1976）、
ラバーケミストリーアンドテクノロジー、第50
巻、945頁（1977）参照〕。
〔発明が解決しようとする問題点〕
しかしながら、全芳香族ポリアミドは、該ポリ
アミドのアミド基間の水素結合のため、一般に、
吸湿およびそれによる寸法変化が大きく、例え
ば、全芳香族ポリアミドフイルムは、ポリイミド
フイルムと比較して10倍以上も吸湿膨張率が大き
い。ジヤーナルオブポリマーサイエンス、ポリマ
ーケミストリーエデイシヨン第19巻、1133頁
（1981）には、ジメチルスルホキシド中で全芳香
族ポリアミドをＮ−アルキル置換する技術が開示
されていて、これによつて吸湿率の低下、あるい
は吸湿安定性の向上が期待できるが、実際には、
この方法の中間体であるＮ−金属化全芳香族ポリ
アミドおよびＮ−アルキル化全芳香族ポリアミド
表面が損傷を受けたり、表面に緻密層が存在する
場合には、それが破壊されたりするため、吸湿率
の低下、吸湿安定性の向上は、実現しないことが
判明した。また、Ｎ−アルキル置換されたアミド
基が、表面アミド基の一部であつたとしても、機
械的特性を支持するアミド基間の水素結合を少な
からず破壊している結果となり、該成型物の特性
上好ましくない。また、全芳香族ポリアミドの熱
処理が特開昭47−43419号公報等に開示されてお
り、これにより結晶性が上り、それに伴つて吸湿
特性が向上することも考えられるが、その程度
は、非常に小さく、また、該全芳香族ポリアミド
が脆くなつてしまうなどの欠点もある。
〔問題点を解決するための手段〕
本発明者は、前記問題を解決するため鋭意研究
の結果、PPTA系ポリマー成型物の機械的特性を
維持しているアミド結合間の水素結合を損なうこ
とのないPPTA系ポリマー成型物の表面のフエニ
ル基をハロゲンアルキル化することで、前記問題
を解決できることを見い出し、本発明に到達し
た。
すなわち、本発明はPPTA系ポリマー成型物
（一般式−NH−Ar1−NH−CO−Ar2−CO−及
び／又は−NH−Ar3−CO−なる繰り返し単位
（式中、Ar1、Ar2、Ar3はそれぞれ独立に二価の
芳香族環性基を表わす））を、一般式Ｒ−CO−
R′（式中、Ｒ及びR′は、Ｈ、CH3、C2H5、の中か
ら選ばれる１種又は２種の置換基を示す）で表わ
される化合物、一般式Ｈ−Ｘ（式中、Ｘは、Cl又
はBrを示す）で表わされるハロゲン化水素、及
び塩化亜鉛よりなる混合物で処理することを特徴
とする表面変性PPTA系ポリマー成型物の製造方
法である。
本発明に用いられるPPTA系ポリマーは、アミ
ド結合の少なくとも85モル％以上が芳香族環性ジ
アミン、芳香族環性ジカルボン酸成分より得られ
るものである。その構造例としては、ポリパラベ
ンズアミド、ポリパラフエニレンテレフタルアミ
ド、ポリー４，4′−ジアミノベンズアニリドテレ
フタルアミド、ポリオルソフエニレンフタルアミ
ド、ポリメタフエニレンフタルアミド、ポリパラ
フエニレンフタルアミド、ポリオルソフエニレン
イソフタルアミド、ポリメタフエニレンイソフタ
ルアミド、ポリパラフエニレンイソフタルアミ
ド、ポリオルソフエニレンテレフタルアミド、ポ
リメタフエニレンテレフタルアミド、ポリー４，
4′−ジフエニレン−オルソ−フタルアミド、ポリ
ー４，４−ジフエニレンイソフタルアミド、また
は芳香族ジアミンが３，3′−オキシジフエニレン
ジアミン、３，4′−オキシジフエニレンジアミン
等のエーテル基、アルキル基、−Ｓ−、−SO2−、
[Industrial Application Field] The present invention relates to a method for producing a surface-modified poly-paraphenylene terephthalamide (hereinafter referred to as PPTA) polymer molded product. More specifically, the present invention relates to a method of modifying only the surface of the PPTA polymer molded article without damaging it, thereby obtaining a PPTA polymer molded article with an improved moisture absorption dimensional change rate. [Prior Art] Fibers made of so-called fully aromatic polyamides, in which all of the divalent hydrocarbon groups bonded through amide bonds are aromatic cyclic groups, are used as heat-resistant polymers.
Molded products such as films are useful for a variety of uses because of their high strength, high elastic modulus, and excellent heat resistance. In particular, due to its high strength and high modulus properties, such fibers can be used as reinforcing fibers such as various thermoplastic resins,
It is added to rubber and thermosetting resins, and the mechanical properties, heat resistance, etc. of the compositions have been studied [for example, Polymer Engineering and Science, Vol. 14, p. 633 (1974), Journal Applied Polymer Science, Vol. Volume 20, page 435 (1976),
Rubber Chemistry and Technology, No. 50
vol., p. 945 (1977)]. [Problems to be Solved by the Invention] However, fully aromatic polyamides generally have hydrogen bonds between the amide groups of the polyamides.
Moisture absorption and resulting dimensional changes are large; for example, fully aromatic polyamide film has a hygroscopic expansion rate that is more than 10 times greater than that of polyimide film. Journal of Polymer Science, Polymer Chemistry Edition, Vol. 19, p. 1133 (1981) discloses a technique for substituting fully aromatic polyamides with N-alkyl in dimethyl sulfoxide, thereby reducing moisture absorption. , or can be expected to improve moisture absorption stability, but in reality,
The surface of N-metalized wholly aromatic polyamide and N-alkylated wholly aromatic polyamide, which are intermediates of this method, may be damaged or if a dense layer exists on the surface, it may be destroyed. It was found that a decrease in moisture absorption rate and an improvement in moisture absorption stability were not achieved. Furthermore, even if the N-alkyl-substituted amide group is a part of the surface amide group, it will destroy a considerable amount of the hydrogen bonds between the amide groups that support mechanical properties, resulting in the formation of the molded product. Unfavorable characteristics. In addition, heat treatment of wholly aromatic polyamide is disclosed in Japanese Patent Application Laid-Open No. 47-43419, etc., and it is thought that this increases crystallinity and improves moisture absorption properties, but the extent of this is extremely uncertain. Moreover, the wholly aromatic polyamide becomes brittle. [Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted intensive research and found a solution to the problem that impairs the hydrogen bonds between amide bonds that maintain the mechanical properties of PPTA polymer molded products. The inventors have discovered that the above problem can be solved by halogen alkylating the phenyl groups on the surface of a PPTA-based polymer molded product, and have arrived at the present invention. That is, the present invention provides a PPTA-based polymer molded product (repeating units having the general formula -NH-Ar 1 -NH-CO-Ar 2 -CO- and/or -NH-Ar 3 -CO- (in the formula, Ar 1 , Ar 2 , Ar 3 each independently represents a divalent aromatic cyclic group)) with the general formula R-CO-
A compound represented by R' (wherein R and R' represent one or two substituents selected from H, CH 3 , C 2 H 5 ), a compound represented by the general formula H-X (formula This is a method for producing a surface-modified PPTA-based polymer molded article, which is characterized in that it is treated with a mixture of hydrogen halide (wherein X represents Cl or Br) and zinc chloride. In the PPTA-based polymer used in the present invention, at least 85 mol% or more of the amide bonds are obtained from aromatic cyclic diamine and aromatic cyclic dicarboxylic acid components. Examples of its structure include polyparabenzamide, polyparaphenylene terephthalamide, poly4,4'-diaminobenzanilide terephthalamide, polyorthophenylene phthalamide, polymetaphenylene phthalamide, polyparaphenylene phthalamide, Polyorthophenylene isophthalamide, polymetaphenylene isophthalamide, polyparaphenylene isophthalamide, polyorthophenylene terephthalamide, polymetaphenylene terephthalamide, poly 4,
4'-diphenylene-ortho-phthalamide, poly 4,4-diphenylene isophthalamide, or aromatic diamine with ether group such as 3,3'-oxydiphenylene diamine, 3,4'-oxydiphenylene diamine, etc. , alkyl group, -S-, -SO2- ,
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ないことはいうまでもない。
なお、実施例において、吸湿膨張率は、試料を窒
素気流下、100℃で絶乾し、室温まで冷却後、相
対湿度90％の雰囲気下でTMA（熱応力歪測定装
置）にて、その伸びを測定することにより、以下
の式を用いて算出した。
吸湿膨張率（mm／mm・％RH）＝試料の伸
び（mm）／試料の元の長さ（mm）×90（％RH）
また、引張強度及び引張モジユラスは、フイル
ムの厚さを、直径２mmの測定面を持つたダイヤル
ゲージで測定し、定速伸長型強伸度測定機によ
り、フイルム試料をマシンデイレクシヨンを長辺
方向にした100mm×10mmの長方形に切り取り、最
初のつかみ長さ30mm、引張り速度30mm／分で荷重
−伸長曲線を５回描き、これより算出したもので
ある。
実施例 １
37％ホルマリン50ｇに、30％塩酸85.2ｇを添加
し、25℃にて約１時間撹拌し、次いで塩化亜鉛
9.54ｇを添加し、更に、60℃で0.5時間撹拌して
処理溶液とした。長さ３cm、巾３cmのポリ（ｐ−
フエニレンテレフタルアミド）フイルム（特公昭
57−17886号公報の方法による）を該処理溶液に、
60℃にて約２時間浸漬し、その後水次いでアセト
ンにて洗浄し、風乾した。このようにして、表面
を変性したポリ（−パラフエニレンテレフタルアミ
ド）フイルムの吸湿膨張率は、4.0×10-5mm／
mm・％RHであり、未処理のポリ−（パラフエニレ
ンテレフタルアミド）フイルムのそれ（10.5×
10-5mm／mm・％RH）に比べ、約６割も吸湿によ
る寸法変化を抑えることができた。機械的特性に
ついては後述する。
実施例 ２
3.7％ホルマリン50ｇに、50％臭素酸水79ｇを
添加し、25℃にて約１時間撹拌し、次いで塩化亜
鉛16.8ｇを添加し、更に60℃で２時間撹拌して処
理溶液とした。長さ３cm、巾３cmのポリ（ｐ−フ
エニレンテレフタルアミド）フイルム（特公昭57
−17886号公報の方法による）を、該処理溶液に、
60℃にて約１時間浸漬し、その後水次いでアセト
ンにて洗浄し、風乾した。このようにして、表面
を変性したポリ（−パラフエニレンテレフタルアミ
ド）フイルムの吸湿膨張率は、4.3×10-5mm／
mm・％RHであり、未処理のポリ（パラフエニレ
ンテレフタルアミド）フイルムのそれ（10.5×
10-5mm／mm・％RH）に比べ、約６割も吸湿によ
る寸法変化を抑えることができた。機械的特性に
ついては後述する。
実施例 ３
アセトアルデヒド27.3ｇに30％塩酸113.2ｇを
添加し、20℃にて１時間撹拌した。次いで、塩化
亜鉛25.4ｇを添加し、65℃にて30分間撹拌し、処
理溶液とした。長さ５cm、巾５cmのポリ（ｐ−フ
エニレンテレフタルアミド）フイルム（特公昭57
−17886号公報の方法による）を、該処理溶液に、
60℃にて約２時間浸漬し、その後水次いでアセト
ンにて洗浄し、風乾した。このようにして、表面
を疎水化したポリ（−パラフエニレンテレフタルア
ミド）フイルムの吸湿膨張率は、5.2×10-5mm／
mm・％RHであり、未処理のポリ（−パラフエニレ
ンテレフタルアミド）フイルムのそれ（10.5×
10-5mm／mm・％RH）に比べ、約５割も吸湿にす
る寸法変化を抑えることができた。機械的特性に
ついては後述する。
実施例 ４
50％臭化水素酸80ｇ及びアセトン29ｇを混合
し、20℃にて１時間撹拌した。次いで、塩化亜鉛
13.6ｇを添加し、65℃にて30分間撹拌し、処理溶
液とした。長さ３cm、巾３cmのポリ（ｐ−フエニ
レンテレフタルアミド）フイルム（特公昭57−
17886号公報の方法による）を、該処理溶液に、
60℃にて約１時間浸漬し、その後水次いでアセト
ンにて洗浄し、風乾した。このようにして、表面
を疎水化したポリ（−パラフエニレンテレフタルア
ミド）フイルムの吸湿膨張率は、61×10-5mm／
mm・％RHであり、未処理のポリ（−パラフエニレ
ンテレフタルアミド）フイルムのそれ（10.5×
10-5mm／mm・％RH）に比べ、約４割も吸湿によ
る寸法変化を抑えることができた。機械的特性に
ついては後述する。
実施例 ５
ジオキサン50ｇにジエチルケトン34.4ｇを溶解
し、常法により発生させた塩化水素ガスを−10℃
にて重量増加15.3ｇまで吹込んだ。その後20℃に
て１時間撹拌後、塩化亜鉛8.2ｇを添加し、70℃
にて30分間撹拌した。長さ３cm、巾３cmのポリ
（ｐ−フエニレンテレフタルアミド）フイルム
（特公昭57−17886号の方法による）を、該処理溶
液に、70℃にて約２時間浸漬し、その後水次いで
アセトンにて洗浄し、風乾した。このようにし
て、表面を疎水化したポリ（−パラフエニレンテレ
フタルアミド）フイルムの吸湿膨張率は、6.3×
10-5mm／mm・％RHであり、未処理のポリ（−パラ
フエニレンテレフタルアミド）フイルムのそれ
（10.5×10-5mm／mm・％RH）に比べ、約４割も吸
湿による寸法変化を抑えることができた。機械的
特性については後述する。
実施例 ６
ジオキサン60ｇにエチルメチルケトン36.1ｇを
混合した溶液に、塩化水素ガスを重量増加20.1ｇ
まで、−10℃にて吹込み、その後20℃にて１時間
撹拌した。この溶液に塩化亜鉛9.5ｇを添加し、
70℃にて30分間撹拌し、処理溶液とした。長さ３
cm、巾３cmのポリ（ｐ−フエニレンテレフタルア
ミド）フイルム（特公昭57−17886の方法による）
を、該処理溶液に、70℃にて約２時間浸漬し、そ
の後水次いでアセトンにて洗浄し、風乾した。こ
のようにして、表面を疎水化したポリ（−パラフエ
ニレンテレフタルアミド）フイルムの吸湿膨張率
は、6.0×10-5mm／mm・％RHであり、未処理のポ
リ（−パラフエニレンテレフタルアミド）フイルム
のそれ（10.5×10-5mm／mm・％RH）に比べ、約
４割も吸湿による寸法変化を抑えることができ
た。
前記、実施例１〜６にて得られたポリ（−パラフ
エニレンテレフタルアミド）フイルムの機械的特
性を、未処理の該フイルムと共に第１表に記す。
EXAMPLES Hereinafter, the present invention will be described with reference to Examples in order to further clarify the present invention, but it goes without saying that the scope of the present invention is not limited to these Examples.
In addition, in the examples, the hygroscopic expansion coefficient is determined by drying the sample at 100°C under a nitrogen stream, cooling it to room temperature, and measuring the elongation using a TMA (thermal stress strain measuring device) in an atmosphere with a relative humidity of 90%. was calculated using the following formula. Hygroscopic expansion coefficient (mm/mm・%RH) = Elongation of sample (mm)/Original length of sample (mm) x 90 (%RH) Tensile strength and tensile modulus are calculated using the film thickness and diameter Measurement was performed using a dial gauge with a 2 mm measurement surface, and the film sample was cut into a 100 mm x 10 mm rectangle with the machine direction in the long side direction using a constant speed extension type strength and elongation measuring machine, and the initial grip length was measured. The load-elongation curve was drawn five times at 30 mm and a tensile speed of 30 mm/min, and the calculation was made from this. Example 1 85.2 g of 30% hydrochloric acid was added to 50 g of 37% formalin, stirred at 25°C for about 1 hour, and then added with zinc chloride.
9.54 g was added and further stirred at 60° C. for 0.5 hour to obtain a treatment solution. Polyester (p-
Phenylene terephthalamide) film (Tokukosho
57-17886) into the treatment solution,
It was immersed at 60°C for about 2 hours, then washed with water and then acetone, and air-dried. The hygroscopic expansion coefficient of the poly(-paraphenylene terephthalamide) film whose surface has been modified in this way is 4.0×10 -5 mm/
mm・%RH and that of untreated poly(paraphenylene terephthalamide) film (10.5×
10 -5 mm/mm・%RH), we were able to suppress dimensional changes due to moisture absorption by approximately 60%. The mechanical properties will be described later. Example 2 79 g of 50% bromic acid water was added to 50 g of 3.7% formalin, stirred at 25°C for about 1 hour, then 16.8 g of zinc chloride was added, and further stirred at 60°C for 2 hours to form a treatment solution. did. Poly(p-phenylene terephthalamide) film with a length of 3 cm and a width of 3 cm (Special Publication Showa 57)
- according to the method of Publication No. 17886) into the treatment solution,
It was immersed at 60°C for about 1 hour, then washed with water and then acetone, and air-dried. The hygroscopic expansion coefficient of the surface-modified poly(-paraphenylene terephthalamide) film is 4.3×10 -5 mm/
mm・%RH and that of untreated poly(paraphenylene terephthalamide) film (10.5×
10 -5 mm/mm・%RH), we were able to suppress dimensional changes due to moisture absorption by approximately 60%. The mechanical properties will be described later. Example 3 113.2 g of 30% hydrochloric acid was added to 27.3 g of acetaldehyde, and the mixture was stirred at 20°C for 1 hour. Next, 25.4 g of zinc chloride was added and stirred at 65° C. for 30 minutes to obtain a treatment solution. Poly(p-phenylene terephthalamide) film 5cm long and 5cm wide (Special Publication Showa 57)
- according to the method of Publication No. 17886) into the treatment solution,
It was immersed at 60°C for about 2 hours, then washed with water and then acetone, and air-dried. The hygroscopic expansion coefficient of the poly(-paraphenylene terephthalamide) film whose surface has been made hydrophobic in this way is 5.2×10 -5 mm/
mm・%RH and that of untreated poly(-paraphenylene terephthalamide) film (10.5×
10 -5 mm/mm・%RH), we were able to suppress dimensional changes that lead to moisture absorption by approximately 50%. The mechanical properties will be described later. Example 4 80 g of 50% hydrobromic acid and 29 g of acetone were mixed and stirred at 20° C. for 1 hour. Then zinc chloride
13.6g was added and stirred at 65°C for 30 minutes to obtain a treatment solution. Poly(p-phenylene terephthalamide) film 3cm long and 3cm wide.
17886) into the treatment solution,
It was immersed at 60°C for about 1 hour, then washed with water and then acetone, and air-dried. The hygroscopic expansion coefficient of the poly(-paraphenylene terephthalamide) film whose surface has been made hydrophobic in this way is 61×10 -5 mm/
mm・%RH and that of untreated poly(-paraphenylene terephthalamide) film (10.5×
10 -5 mm/mm・%RH), we were able to suppress dimensional changes due to moisture absorption by approximately 40%. Mechanical properties will be described later. Example 5 34.4 g of diethyl ketone was dissolved in 50 g of dioxane, and hydrogen chloride gas was generated by a conventional method at -10°C.
It was injected to a weight increase of 15.3g. Then, after stirring for 1 hour at 20℃, 8.2g of zinc chloride was added and the mixture was heated to 70℃.
The mixture was stirred for 30 minutes. A poly(p-phenylene terephthalamide) film (according to the method disclosed in Japanese Patent Publication No. 57-17886) with a length of 3 cm and a width of 3 cm was immersed in the treatment solution at 70°C for about 2 hours, and then soaked in water and then acetone. Washed and air dried. The hygroscopic expansion coefficient of the poly(-paraphenylene terephthalamide) film whose surface has been made hydrophobic in this way is 6.3×
10 -5 mm/mm・%RH, which is approximately 40% smaller than that of untreated poly(-paraphenylene terephthalamide) film (10.5×10 −5 mm/mm・%RH) due to moisture absorption. I was able to control the changes. Mechanical properties will be described later. Example 6 Hydrogen chloride gas was added to a solution of 60 g of dioxane and 36.1 g of ethyl methyl ketone to increase the weight by 20.1 g.
The mixture was stirred at -10°C for 1 hour at 20°C. Add 9.5g of zinc chloride to this solution,
The mixture was stirred at 70°C for 30 minutes to obtain a treatment solution. length 3
cm, width 3 cm poly(p-phenylene terephthalamide) film (according to the method of Japanese Patent Publication No. 17886, 1986)
was immersed in the treatment solution at 70° C. for about 2 hours, then washed with water, then acetone, and air-dried. The hygroscopic expansion coefficient of the poly(-paraphenylene terephthalamide) film whose surface has been made hydrophobic in this way is 6.0×10 -5 mm/mm・%RH, and the untreated poly(-paraphenylene terephthalamide) film Compared to the amide (amide) film (10.5 x 10 -5 mm/mm・%RH), it was possible to suppress dimensional changes due to moisture absorption by about 40%. The mechanical properties of the poly(-paraphenylene terephthalamide) films obtained in Examples 1 to 6 are listed in Table 1 together with the untreated films.
本発明の方法による表面変性PPTA系ポリマー
成型物の特徴は、PPTA系ポリマー成型物の機械
的特性を損なうことなくフエニル基へ疎水性基を
導入したことによる吸湿率及び吸湿膨張率の減少
である。これは、該成型物の機械的特性を維持し
ているアミド結合間の水素結合を損なうことな
く、表面アミド基の極く近傍のフエニル基へ導入
した疎水性のかさ高いハロゲンアルキル基が、表
面を覆うためであろうと推察できる。尚、アミド
結合を損なわない効果としての機械的特性とは、
PPTA系ポリマー成型物がもつている該特徴、例
えば、高強度、高モジユラス、耐熱性、高い引裂
抵抗、高温での寸法安定性などであり、本発明の
方法によれば、これらの該特徴を殆んど犠牲にす
ることなく、表面疎水化できるのである。
A feature of the surface-modified PPTA-based polymer molded product produced by the method of the present invention is a reduction in the moisture absorption rate and hygroscopic expansion coefficient due to the introduction of hydrophobic groups into the phenyl group without impairing the mechanical properties of the PPTA-based polymer molded product. . This is because the bulky hydrophobic halogen alkyl group introduced into the phenyl group in the very vicinity of the surface amide group can be used on the surface without damaging the hydrogen bond between the amide bonds that maintains the mechanical properties of the molded product. It can be inferred that this was to cover the In addition, the mechanical properties as an effect of not damaging the amide bond are:
The characteristics of PPTA-based polymer molded products, such as high strength, high modulus, heat resistance, high tear resistance, and dimensional stability at high temperatures, can be achieved by the method of the present invention. The surface can be made hydrophobic with almost no sacrifice.
Claims (1)
リマー成型物を、一般式Ｒ−CO−R′（式中、Ｒ及
びR′は、Ｈ、CH3、C2H5の中から選ばれる１種
又は２種の置換基を示す）で表わされる化合物、
一般式Ｈ−Ｘ（式中、Ｘは、Cl又はBrを示す）で
表わされるハロゲン化水素、及び塩化亜鉛よりな
る混合溶液で処理することを特徴とする表面変性
成型物の製造方法。1 A poly-paraphenylene terephthalamide polymer molded product having the general formula R-CO-R' (wherein R and R' are one or two selected from H, CH 3 , C 2 H 5 (representing a substituent of species),
1. A method for producing a surface-modified molded article, which comprises treating with a mixed solution of hydrogen halide represented by the general formula H-X (wherein X represents Cl or Br) and zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24316786A JPS6397638A (en) | 1986-10-15 | 1986-10-15 | Production of molded product having modified surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24316786A JPS6397638A (en) | 1986-10-15 | 1986-10-15 | Production of molded product having modified surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6397638A JPS6397638A (en) | 1988-04-28 |
| JPH0347656B2 true JPH0347656B2 (en) | 1991-07-22 |
Family
ID=17099806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24316786A Granted JPS6397638A (en) | 1986-10-15 | 1986-10-15 | Production of molded product having modified surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6397638A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02277132A (en) * | 1989-04-18 | 1990-11-13 | Omron Corp | Inheritance processing system for frame type knowledge expression |
-
1986
- 1986-10-15 JP JP24316786A patent/JPS6397638A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6397638A (en) | 1988-04-28 |
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