JPH0552339B2 - - Google Patents
Info
- Publication number
- JPH0552339B2 JPH0552339B2 JP59194884A JP19488484A JPH0552339B2 JP H0552339 B2 JPH0552339 B2 JP H0552339B2 JP 59194884 A JP59194884 A JP 59194884A JP 19488484 A JP19488484 A JP 19488484A JP H0552339 B2 JPH0552339 B2 JP H0552339B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- weight
- curing agent
- polyglycidyl ether
- parts
- 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
- 239000004952 Polyamide Substances 0.000 claims description 24
- 229920002647 polyamide Polymers 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000004193 piperazinyl group Chemical group 0.000 claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 bis-aminopropyl Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、硬化性のポリアミド樹脂組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable polyamide resin composition.
［従来の技術］
従来、主鎖にピペラジン環を有するポリアミド
は公知である（特公昭52−30196号公報）。このポ
リアミドは吸湿性または制電性を有する優れたポ
リアミドである。[Prior Art] Polyamides having a piperazine ring in the main chain are conventionally known (Japanese Patent Publication No. 30196/1983). This polyamide has excellent hygroscopic and antistatic properties.
また特公昭54−22229号公報にはピペラジン環
を有するポリアミドが印写材料用途に用いられる
との記載がある。 Further, Japanese Patent Publication No. 54-22229 states that polyamides having a piperazine ring are used for printing materials.
［発明が解決しようとする問題点］
本発明者らは、主鎖にピペラジン環を有するポ
リアミドを広い用途に展開する検討を続けた。例
えば、インクビヒクル、インク改質剤、水溶性接
着剤、団結剤、水性ペイント基材、表面改質剤、
防曇処理剤、易染化剤、繊維所理剤、無機繊維サ
イジング剤、感光剤の添加剤、香粧品基材、セラ
ミツクのバインダー、樹脂の改質剤等について検
討した。元来主鎖によるピペラジン環を有するポ
リアミドはその組成によるが水溶性あるいはアル
コール可溶性を示し、溶液状で取扱える利点を有
している。しかし、その反面そのまま使用すると
耐水性や耐溶剤性が悪く、耐久性に欠けると言う
問題がある。[Problems to be Solved by the Invention] The present inventors have continued to study the development of a polyamide having a piperazine ring in its main chain in a wide range of applications. For example, ink vehicles, ink modifiers, water-soluble adhesives, binding agents, water-based paint bases, surface modifiers,
We investigated antifogging agents, dye-enabling agents, textile treatment agents, inorganic fiber sizing agents, photosensitive additives, cosmetic base materials, ceramic binders, resin modifiers, etc. Polyamide, which originally has a piperazine ring in its main chain, exhibits water solubility or alcohol solubility, depending on its composition, and has the advantage that it can be handled in the form of a solution. However, on the other hand, if used as is, there is a problem that water resistance and solvent resistance are poor, and durability is lacking.
そこで本発明者らは上記公知のポリアミドを使
用する場合、耐久性を与える処方を鋭意検討し本
発明に到達した。 Therefore, the present inventors conducted extensive studies on formulations that would provide durability when using the above-mentioned known polyamides, and arrived at the present invention.
［問題点を解決するための手段］
本発明の上記目的は主鎖にピペラジン環を有す
るポリアミド100重量部に、ジグリセローポリグ
リシジルエーテルおよびソルビトールポリグリシ
ジルエーテルから選ばれた少なくとも１種の硬化
剤を50〜500重量部の割合混合してなる硬化性の
ポリアミド樹脂組成物とすることによつて達成で
きる。[Means for Solving the Problems] The above object of the present invention is to add at least one curing agent selected from diglycerose polyglycidyl ether and sorbitol polyglycidyl ether to 100 parts by weight of a polyamide having a piperazine ring in the main chain. This can be achieved by mixing 50 to 500 parts by weight of a curable polyamide resin composition.
以下本発明に係る組成物の製法およびその製法
によつて得られた組成物の性質を述べる。 The method for producing the composition according to the present invention and the properties of the composition obtained by the method will be described below.
まず主鎖のピペラジン環を有するポリアミド
（以下本明細書においは単にポリアミドと称する）
を用意する。このポリアミドはビスアミノプロピ
ルビペラジン、アミノエチルピペラジンおよびピ
ペラジン等のピペラジン環を有するジアミンとア
ジピン酸やセバシン酸等の脂肪族ジカルボン酸と
から誘導される均質重合体や、さらにその均質重
合体成分とラクタムやω−アミノ酸から得られる
ポリアミド成分および／または前記ジアミン以外
のジアミンと脂肪族ジカルボン酸とかる誘導され
るポリアミド成分との共重合体または前記均質重
合体や共重合体の単独物の２種類以上もしくは前
記均質重合体と共重合体との混合重合体であつて
もよい。 First, a polyamide having a piperazine ring in the main chain (hereinafter simply referred to as polyamide)
Prepare. This polyamide is a homopolymer derived from a diamine having a piperazine ring such as bis-aminopropyl biperazine, aminoethylpiperazine, and piperazine and an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or a homogeneous polymer component thereof. and a polyamide component obtained from a lactam or an ω-amino acid, and/or a copolymer of a polyamide component derived from a diamine other than the above-mentioned diamine and an aliphatic dicarboxylic acid, or a single product of the above-mentioned homopolymer or copolymer. It may be a mixed polymer of more than one kind or a copolymer and the above-mentioned homogeneous polymer.
これらのポリアミドは好ましくは水またはアル
コール、特にメタノールまたはエタノール溶液で
用いられる。次に硬化剤としてのポリエポキシ化
合物を準備する。 These polyamides are preferably used in water or alcohol, especially methanol or ethanol solution. Next, a polyepoxy compound as a curing agent is prepared.
本発明で使用する硬化剤は、ジグリセロールポ
リグリシジルエーテルおよびソルビトールポリグ
リシジルエーテルから選ばれた少なくとも１種で
ある。 The curing agent used in the present invention is at least one selected from diglycerol polyglycidyl ether and sorbitol polyglycidyl ether.
この硬化剤はそのままでも配合され得るが、市
販されている水エマルジヨンその他の有機溶液等
でも使用される。 This curing agent can be blended as it is, but it can also be used in commercially available water emulsions and other organic solutions.
前記の、少なくと２種の原料が用意されたら、
前記原料を混合する。混合は前記ポリアミド100
重量部に硬化剤を50〜500重量部の割合、混合す
る。 Once at least the two types of raw materials mentioned above are prepared,
Mix the raw materials. Mixed with the above polyamide 100
A curing agent is mixed in a ratio of 50 to 500 parts by weight.
混合方法はポリアミドまたはポリアミド水溶液
あるいはアルコール溶液等と、硬化剤またはその
水エマルジヨン、アルコール溶液等を撹拌、ある
いは混練して均一溶液、エマルジヨン、ペースト
状等にする。 The mixing method involves stirring or kneading the polyamide or polyamide aqueous solution or alcohol solution, etc., and the curing agent or its water emulsion, alcohol solution, etc. to form a homogeneous solution, emulsion, paste, etc.
かくして熱による反応硬化性の優れたポリアミ
ド樹脂組成物が得られるが、この組成物を硬化処
理して得られた硬化物は、ポリエステルやポリア
ミドに対して密着性および耐水性がよく、酸性染
料で染まり易い。この組成物はインク、接着剤、
塗料ないしはコーチング材、繊維や粉末のバイン
ダ、繊維、布帛、フイルム等の表面改質剤等に使
用される。また前記組成物はそれ自体でフイルム
状等に成型できる。 In this way, a polyamide resin composition with excellent thermal reaction curability is obtained, and the cured product obtained by curing this composition has good adhesion and water resistance to polyester and polyamide, and is resistant to acid dyes. Easy to stain. This composition can be used for inks, adhesives,
It is used in paints or coating materials, binders for fibers and powders, and surface modifiers for fibers, fabrics, films, etc. Further, the composition itself can be molded into a film or the like.
これらの組成物の硬化は加熱されることによつ
て達成される。加熱温度は100〜300℃である。 Curing of these compositions is accomplished by heating. Heating temperature is 100-300°C.
［実施例］
比較例１〜２、実施例１〜４
２−アミノエチルピペラジンとアジピン酸との
塩90重量部とε−カプロラクタム10重量部とを常
法に従つて、重合せしめて得られたポリアミドを
50重量部と第１表に示した硬化剤を50重量％含有
する水溶液100重量部とを混合して硬化性ポリア
ミド樹脂組成物（ポリアミド100重量部に硬化剤、
100重量部の割合で、含有する組成物）を得た。
その組成物をフイルム状にポリエステルフイルム
の上に塗布し、100℃に加熱された乾燥機中で水
分を除去した後、150℃に昇温し、30分間保持し
前記ポリアミドを硬化せしめた。得られたフイル
ムの上に形成された塗膜の硬化性を測定した。測
定方法は70℃の温水に30分間前記塗膜を浸漬し、
その塗膜の形態を観察した。[Examples] Comparative Examples 1 to 2, Examples 1 to 4 Polymerization of 90 parts by weight of a salt of 2-aminoethylpiperazine and adipic acid and 10 parts by weight of ε-caprolactam according to a conventional method polyamide
A curable polyamide resin composition (100 parts by weight of polyamide, curing agent,
A composition containing 100 parts by weight was obtained.
The composition was applied in the form of a film onto a polyester film, and after removing moisture in a dryer heated to 100°C, the temperature was raised to 150°C and held for 30 minutes to cure the polyamide. The curability of the coating film formed on the obtained film was measured. The measurement method is to immerse the coating film in warm water at 70℃ for 30 minutes,
The morphology of the coating film was observed.
その結果を第１表に示す。第１表中○印は形態
の変化はが全く認められないものを、△印は部分
的に形態が崩れているものを、そして×印は水に
完全に溶けて形態を残していないものを夫々意味
する。 The results are shown in Table 1. In Table 1, the ○ mark indicates that no change in form has been observed, the △ mark indicates that the form has partially collapsed, and the × mark indicates that the form has completely dissolved in water and no form remains. each meaning.
第１表
硬化剤の種類 硬化性
比較例１ なし ×
２ クロロプレンゴム △
実施例１ ジグリセロールポリ
グリシジルエーテル ○
２ ソリビトールポリ
グリシジエーテル ○
［発明の効果］
本発明は特定のポリアミドに特定の硬化剤が配
合されているので、ポリアミドの耐水性、耐有機
溶剤性が大幅に向上する。さらに硬化剤そのもの
が本来単独で有する硬化性をこの発明に使用され
るポリアミド自身が改善すると言う意外な効果を
発揮する。 Table 1 Type of curing agent Curing Comparative Example 1 None × 2 Chloroprene rubber △ Example 1 Diglycerol polyglycidyl ether ○ 2 Sorbitol polyglycidyl ether ○ [Effects of the invention] The present invention provides specific curing to specific polyamides. Since the agent is blended, the water resistance and organic solvent resistance of polyamide are greatly improved. Furthermore, the polyamide used in this invention exhibits the unexpected effect of improving the curability that the curing agent itself originally has alone.
Claims (1)
重量部に、ジグリセドロールポリグリシジルエー
テルおよびソルビトールポリグリシジルエーテル
から選ばれた少なくとも１種の硬化剤を50〜500
重量部の割合混合してなる硬化性のポリアミド樹
脂組成物。1 Polyamide 100 with piperazine ring in the main chain
50 to 500 parts by weight of at least one curing agent selected from diglycedrol polyglycidyl ether and sorbitol polyglycidyl ether.
A curable polyamide resin composition formed by mixing parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19488484A JPS6173734A (en) | 1984-09-19 | 1984-09-19 | Curable polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19488484A JPS6173734A (en) | 1984-09-19 | 1984-09-19 | Curable polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6173734A JPS6173734A (en) | 1986-04-15 |
| JPH0552339B2 true JPH0552339B2 (en) | 1993-08-05 |
Family
ID=16331921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19488484A Granted JPS6173734A (en) | 1984-09-19 | 1984-09-19 | Curable polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6173734A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0739395B1 (en) * | 1993-11-03 | 1998-12-02 | H.B. Fuller Automotive Products, Inc. | Heat curable toughened epoxy resin compositions |
| US5962629A (en) * | 1995-11-16 | 1999-10-05 | Shell Oil Company | Amine-terminated polyamide in oil-in-water emulsion |
| US6500912B1 (en) | 2000-09-12 | 2002-12-31 | Resolution Performance Products Llc | Epoxy resin system |
| AU2003222325A1 (en) * | 2002-01-14 | 2003-09-02 | Atofina | Thermoset materials with improved impact strength |
-
1984
- 1984-09-19 JP JP19488484A patent/JPS6173734A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6173734A (en) | 1986-04-15 |
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