JPH0337585B2 - - Google Patents
Info
- Publication number
- JPH0337585B2 JPH0337585B2 JP60126713A JP12671385A JPH0337585B2 JP H0337585 B2 JPH0337585 B2 JP H0337585B2 JP 60126713 A JP60126713 A JP 60126713A JP 12671385 A JP12671385 A JP 12671385A JP H0337585 B2 JPH0337585 B2 JP H0337585B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- nylon
- maleic anhydride
- ethylene
- 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
- 229920001038 ethylene copolymer Polymers 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 230000003252 repetitive effect Effects 0.000 claims 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
Description
本発明はヘキサメチレンジアミン（HMDA）、
テレフタル酸（TA）およびε−カプラクタム
（CL）、又はHMDA、およびアジピン酸（AA）
又はイソフタル酸（IA）のいずれかの混合物か
ら作られる結晶性コーポリアミドの樹脂組成物に
関するものである。
従来、CLからのポリアミド（ナイロン６）、
HMDAとAAからのポリアミド（ナイロン６，
６）は成型品として高汎な用途があるが融点
（Tm）はそれぞれ215℃、259℃でありガラスフ
アイバーを入れても熱変形温度の限界はそれぞれ
融点どまりである。
最近、耐熱性の用途が増加するにつれて、全芳
香族系のポリアミド、ポリアミドイミド、ポリイ
ミド、ポリエーテル、ポリエステルなどが市場に
出はじめているが、加工性が悪いこと、又原料モ
ノマーが高価なこと、重合法も複雑なことから、
ナイロン６、ナイロン66などに比べて数倍の価格
になつている。
最近、ナイロン６、ナイロン66より耐熱性が向
上し、安価な原料で且つ溶融成形が可能な
HMDA／TA／CL、HMDA／TA／IA又は
HMDA／TA／AAから成る高結晶性コーポリア
ミドが提案されているが、ナイロン６、ナイロン
66などに比べるともろくなつている。
本発明者らはこのもろさ、すなわち耐衝撃性を
改良するため鋭意検討したところ特定量の無水マ
レイン酸又はエポキシ基を含有するエチレン共重
合体を加えることにより耐衝撃性を改良すること
に成功し、本発明に到達した。
即ち、本発明は次の反復成分
（式中Ｒは炭素数６ないし18の脂肪族基、
The present invention relates to hexamethylene diamine (HMDA),
Terephthalic acid (TA) and ε-calactam (CL), or HMDA, and adipic acid (AA)
or isophthalic acid (IA). Conventionally, polyamide (nylon 6) from CL,
Polyamide (nylon 6,
6) has a wide range of uses as a molded product, but its melting point (Tm) is 215°C and 259°C, respectively, and even if glass fiber is inserted, the limit of heat distortion temperature remains at the melting point. Recently, as heat-resistant applications have increased, fully aromatic polyamides, polyamideimides, polyimides, polyethers, polyesters, etc. have begun to appear on the market, but they have poor processability, and the raw material monomers are expensive. Since the polymerization method is complicated,
It is several times more expensive than nylon 6, nylon 66, etc. Recently, it has improved heat resistance than nylon 6 and nylon 66, is a cheaper raw material, and can be melt-molded.
HMDA/TA/CL, HMDA/TA/IA or
Highly crystalline copolyamides consisting of HMDA/TA/AA have been proposed, but nylon 6, nylon
It is more fragile than 66 etc. The present inventors conducted intensive studies to improve this brittleness, that is, impact resistance, and succeeded in improving impact resistance by adding a specific amount of maleic anhydride or an ethylene copolymer containing epoxy groups. , arrived at the present invention. That is, the present invention uses the following iterative component (In the formula, R is an aliphatic group having 6 to 18 carbon atoms,
【式】R1は炭素数４ないし 18の脂肪族基、又は[Formula] R 1 is an aliphatic group having 4 to 18 carbon atoms, or
【式】である。）
からなり、(A)60−99重量％及び(B)又は／及び(C)が
40−１重量％からなる結晶性コーポリアミド99.9
重量部から60重量部、無水マレイン酸又はエポキ
シ基を含有するエチレン共重合体0.1重量部から
40重量部と溶融混練したことを特徴とする樹脂組
成物に関するものである。
本発明を実施するにあたり、結晶性コーポリア
ミドは上述したような構造のものであるが、還元
粘度は0.5〜3.0dl／ｇ（ｃ＝0.5ｇ／100c.c.濃硫酸
溶媒中で30℃で測定）が好ましい。
本発明における無水マレイン酸単位を含有する
エチレン共重合体としてはエチレン・アクリル酸
メチル・無水マレイン酸共重合体、エチレン・ア
クリル酸エチル・無水マレイン酸共重合体等のエ
チレン・アクリル酸エステル・無水マレイン酸共
重合体があげられる。本発明におけるエポキシ基
を含有するエチレン共重合体としてはエチレン・
グリシジルメタクリレート共重合体、エチレン・
グリシジルメタクリレート・メチルアクリレート
共重合体、エチレン・グリシジルメタクリレー
ト・エチルアクリレート共重合体、エチレン・グ
リシジルメタクリレート・酢酸ビニル共重合体等
のグリシジルメタクリレート単位を含有するエチ
レン共重合体が代表的にあげられる。
本発明の結晶性コーポリアミドは融点が高いの
で300℃以上の高温で成形する必要がある。無水
マレイン酸変性ポリオレフインのごとく、ポリマ
ー主鎖を形成していない無水マレイン酸単位は高
温では熱分解を起こし安い。そこで本発明は無水
マレイン酸単位が主鎖結合を形成しているエチレ
ン共重合体を使用している。
結晶性コーポリアミドとエチレン共重合体の組
成割合は前者が99.9重量部から60重量部好ましく
は99.0重量部から70重量部である。後者は0.1重
量部から40重量部好ましくは１重量部から80重量
部である。溶融混練する方法としては、例えばニ
ーダー、ブラベンダー、一軸押出し機、二軸押出
し機などである。好ましくは押出し機タイプがよ
い。
本発明の用途は射出成形、押出し成形などによ
り、機械部品用途、自動車用途、電機、電子部品
用途など特に耐熱性の要求される分野である。
本発明の樹脂組成物は安定剤、難燃剤、ガラス
繊維、タルクなどの無機充てん剤、有機系のポリ
マー、例えばナイロン６，ナイロン66、ポリエチ
レンテレフタレート、ポリブチレンテレフタレー
トなどのポリマーをブレンドしてもよい。特に好
ましいのはガラス繊維であり、５〜60重量部加え
ることにより、耐熱性と高衝撃性を兼ねそなえた
樹脂組成物を得ることが出来る。
実施例１〜４，比較例１，２
HMDA／TAナイロン塩の50％水溶液160部と
CL20部を重合反応器に仕込んだ。反応器を窒素
ガスで完全に置換したのち加熱し、水蒸気圧を
10.0Kg／cm2に保ち240℃〜260℃で重合した。さら
に加圧後水蒸気を除いて常圧で２−４時間重合し
た。
得られたポリマーは十分冷却して取り出し、粉
砕器を用いて粉状化し、次いで水分率が0.1％以
下になるよう90℃以下で十分乾燥した。還元粘度
は0.15dl／ｇであつた。乾燥したポリマーをベン
ト口が１つ以上ある２軸押出機で反応させ、カツ
テイングしてペレツト化した。押出機の温度は
320〜330℃、スクリユー回転数10〜20r.p.m、ポ
リマーの平均滞留時間５〜10分、ホツパー口を窒
素雰囲気下で行つた。ベント口は減圧、常圧開放
どちらでもよく、また押出機ノズルから出てくる
ポリマーはすぐに水中に入れるなどして冷却し、
高温で空気に触れない様にした。このポリマーの
還元粘度は1.0dl／ｇであつた。得られたポリマ
ーペレツトは水分率が0.1％以下になる様90℃以
下で十分乾燥した後、変性ポリオレフインと表１
のような組成でブレンドし、２軸押出機で造粒し
た。造粒温度は約300℃〜340℃である。
次いで約100から200℃に保つた金型へ射出圧力
1000Kg／cm2で射出した。バレル温度は300〜350℃
であつた。[Formula]. ), with (A) 60-99% by weight and (B) or/and (C)
Crystalline copolyamide 99.9 consisting of 40-1% by weight
From 60 parts by weight, from 0.1 parts by weight of maleic anhydride or ethylene copolymer containing epoxy groups
The present invention relates to a resin composition characterized in that it is melt-kneaded with 40 parts by weight. In carrying out the present invention, the crystalline copolyamide has the structure described above, but has a reduced viscosity of 0.5 to 3.0 dl/g (c=0.5 g/100 c.c. at 30°C in concentrated sulfuric acid solvent). measurement) is preferred. Examples of ethylene copolymers containing maleic anhydride units in the present invention include ethylene/methyl acrylate/maleic anhydride copolymers, ethylene/ethyl acrylate/maleic anhydride copolymers, etc. Examples include maleic acid copolymers. In the present invention, the ethylene copolymer containing an epoxy group is ethylene.
Glycidyl methacrylate copolymer, ethylene/
Representative examples include ethylene copolymers containing glycidyl methacrylate units, such as glycidyl methacrylate/methyl acrylate copolymers, ethylene/glycidyl methacrylate/ethyl acrylate copolymers, and ethylene/glycidyl methacrylate/vinyl acetate copolymers. Since the crystalline copolyamide of the present invention has a high melting point, it is necessary to mold it at a high temperature of 300°C or higher. Maleic anhydride units that do not form a polymer main chain, such as maleic anhydride-modified polyolefins, easily undergo thermal decomposition at high temperatures. Therefore, the present invention uses an ethylene copolymer in which maleic anhydride units form main chain bonds. The composition ratio of the crystalline copolyamide and the ethylene copolymer is 99.9 parts by weight to 60 parts by weight, preferably 99.0 parts by weight to 70 parts by weight. The latter is present in an amount of 0.1 to 40 parts by weight, preferably 1 part to 80 parts by weight. Examples of the melt-kneading method include a kneader, Brabender, single-screw extruder, and twin-screw extruder. Preferably, an extruder type is used. Applications of the present invention include injection molding, extrusion molding, etc. in fields where heat resistance is particularly required, such as mechanical parts, automobiles, electrical equipment, and electronic parts. The resin composition of the present invention may be blended with stabilizers, flame retardants, glass fibers, inorganic fillers such as talc, and organic polymers such as nylon 6, nylon 66, polyethylene terephthalate, and polybutylene terephthalate. . Particularly preferred is glass fiber, and by adding 5 to 60 parts by weight, a resin composition having both heat resistance and high impact strength can be obtained. Examples 1 to 4, Comparative Examples 1 and 2 160 parts of a 50% aqueous solution of HMDA/TA nylon salt
20 parts of CL was charged into a polymerization reactor. After completely purging the reactor with nitrogen gas, heat it and raise the water vapor pressure.
Polymerization was carried out at 240°C to 260°C while maintaining the temperature at 10.0 Kg/cm 2 . After further pressurization, water vapor was removed and polymerization was carried out at normal pressure for 2 to 4 hours. The obtained polymer was sufficiently cooled and taken out, pulverized using a pulverizer, and then thoroughly dried at 90° C. or lower so that the moisture content was 0.1% or less. The reduced viscosity was 0.15 dl/g. The dried polymer was reacted in a twin-screw extruder with one or more vents and cut into pellets. The temperature of the extruder is
The temperature was 320-330°C, the screw rotation speed was 10-20 rpm, the average residence time of the polymer was 5-10 minutes, and the hopper opening was under a nitrogen atmosphere. The vent port can be opened to either reduced pressure or normal pressure, and the polymer coming out of the extruder nozzle is immediately cooled by putting it in water, etc.
Avoid contact with high temperature air. The reduced viscosity of this polymer was 1.0 dl/g. The obtained polymer pellets were sufficiently dried at 90°C or lower so that the moisture content was 0.1% or less, and then mixed with modified polyolefin as shown in Table 1.
The composition was blended and granulated using a twin-screw extruder. The granulation temperature is approximately 300°C to 340°C. Then, injection pressure is applied to the mold kept at about 100 to 200℃.
Injected at 1000Kg/ cm2 . Barrel temperature is 300-350℃
It was hot.
【表】
実施例 ５
HMDA／TAナイロン塩の50％水溶液150部、
HMDA／アジピン酸のナイロン塩の50％水溶液
50部から実施例１に従つて結晶性コーポリアミド
を合成した。還元粘度は1.1dl／ｇであつた。こ
れに10重量部のエチレン（70部）−アクリル酸エ
ステル（28部）−無水マレイン酸（２部）を溶融
混練した。アイゾツト衝撃値は変性ポリオレフイ
ンを加えた時に３倍も向上した。
実施例 ６
HMDA／TAナイロン塩の50％水溶液150部、
HMDA／イソフタル酸のナイロン塩の50％水溶
液50部から実施例１に従つて結晶性コーポリアミ
ドを合成した。これに５重量部の無水マレイン酸
変性EPRおよび30部のガラス繊維を溶融混練し
たところ、アイゾツト衝撃値は変性EPRを加え
ない時の２倍にも向上した。[Table] Example 5 150 parts of a 50% aqueous solution of HMDA/TA nylon salt,
HMDA/50% aqueous solution of nylon salt of adipic acid
A crystalline copolyamide was synthesized according to Example 1 from 50 parts. The reduced viscosity was 1.1 dl/g. This was melt-kneaded with 10 parts by weight of ethylene (70 parts)-acrylic ester (28 parts)-maleic anhydride (2 parts). Izod impact value was improved three times when modified polyolefin was added. Example 6 150 parts of a 50% aqueous solution of HMDA/TA nylon salt,
A crystalline copolyamide was synthesized according to Example 1 from 50 parts of a 50% aqueous solution of HMDA/nylon salt of isophthalic acid. When 5 parts by weight of maleic anhydride-modified EPR and 30 parts of glass fiber were melt-kneaded to this, the Izod impact value was twice as high as that without the addition of modified EPR.
Claims (1)
【式】R′は炭素数４ないし 18の脂肪族基又は【式】である。） からなり、(A)60−99重量％及び(B)又は／及び(C)が
40−１重量％である結晶性コーポリアミド99.9重
量部から60重量部、無水マレイン酸又はエポキシ
基を含有するエチレン共重合体0.1重量部から40
重量部を溶融混練したことを特徴とする樹脂組成
物。[Claims] First-order repetitive component (In the formula, R is an aliphatic group having 6 to 18 carbon atoms or [Formula] R' is an aliphatic group having 4 to 18 carbon atoms or [Formula].), consisting of 60-99% by weight of (A) and (B) or/and (C)
99.9 to 60 parts by weight of a crystalline copolyamide that is 40-1% by weight, 0.1 to 40 parts by weight of an ethylene copolymer containing maleic anhydride or epoxy groups.
A resin composition characterized in that parts by weight are melt-kneaded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12671385A JPS61283653A (en) | 1985-06-11 | 1985-06-11 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12671385A JPS61283653A (en) | 1985-06-11 | 1985-06-11 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61283653A JPS61283653A (en) | 1986-12-13 |
| JPH0337585B2 true JPH0337585B2 (en) | 1991-06-06 |
Family
ID=14942016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12671385A Granted JPS61283653A (en) | 1985-06-11 | 1985-06-11 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61283653A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63170459A (en) * | 1987-01-07 | 1988-07-14 | Mitsubishi Kasei Corp | Polyamide resin composition |
| JPS63235365A (en) * | 1987-03-24 | 1988-09-30 | Sumitomo Chem Co Ltd | Production of impact-resistant polyamide resin composition |
| DE3716681A1 (en) * | 1987-05-19 | 1988-12-01 | Bayer Ag | IMPACT TOOL POLYAMIDE MOLDS |
| JPS63308057A (en) * | 1987-06-09 | 1988-12-15 | Sumitomo Naugatuck Co Ltd | Thermoplastic polymer composition |
| JP2634528B2 (en) * | 1991-12-27 | 1997-07-30 | 矢崎総業株式会社 | connector |
| JP2677236B2 (en) * | 1995-03-31 | 1997-11-17 | 東レ株式会社 | Flame retardant polyamide resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59136369A (en) * | 1983-01-25 | 1984-08-04 | Mitsubishi Chem Ind Ltd | Adhesive composition for metal |
| JPS59155427A (en) * | 1983-02-16 | 1984-09-04 | アモコ・コ−ポレ−ション | Crystalline copolyamide from terephthalic acid, hexamethylenediamine and trimethylhexamethylene diamine |
| JPS59155426A (en) * | 1983-02-16 | 1984-09-04 | アモコ・コ−ポレ−ション | Polyamide composition |
| JPS6071661A (en) * | 1983-09-29 | 1985-04-23 | Asahi Chem Ind Co Ltd | Thermoplastic polyamide composition |
| JPS6094407A (en) * | 1983-10-01 | 1985-05-27 | ヘミツシエ・ウエルケ・ヒユールス・アクチエンゲゼルシヤフト | Manufacture of functionalized poly-alpha- olefin rubber and use for manufacturing impact-resistant thermoplastic composition |
-
1985
- 1985-06-11 JP JP12671385A patent/JPS61283653A/en active Granted
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59136369A (en) * | 1983-01-25 | 1984-08-04 | Mitsubishi Chem Ind Ltd | Adhesive composition for metal |
| JPS59155427A (en) * | 1983-02-16 | 1984-09-04 | アモコ・コ−ポレ−ション | Crystalline copolyamide from terephthalic acid, hexamethylenediamine and trimethylhexamethylene diamine |
| JPS59155426A (en) * | 1983-02-16 | 1984-09-04 | アモコ・コ−ポレ−ション | Polyamide composition |
| JPS6071661A (en) * | 1983-09-29 | 1985-04-23 | Asahi Chem Ind Co Ltd | Thermoplastic polyamide composition |
| JPS6094407A (en) * | 1983-10-01 | 1985-05-27 | ヘミツシエ・ウエルケ・ヒユールス・アクチエンゲゼルシヤフト | Manufacture of functionalized poly-alpha- olefin rubber and use for manufacturing impact-resistant thermoplastic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61283653A (en) | 1986-12-13 |
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