JPS587430A - Method for improving water resistance of polyamide molded article - Google Patents
Method for improving water resistance of polyamide molded articleInfo
- Publication number
- JPS587430A JPS587430A JP10465681A JP10465681A JPS587430A JP S587430 A JPS587430 A JP S587430A JP 10465681 A JP10465681 A JP 10465681A JP 10465681 A JP10465681 A JP 10465681A JP S587430 A JPS587430 A JP S587430A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- water
- weight
- molded article
- water resistance
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000004952 Polyamide Substances 0.000 title claims abstract description 20
- 229920002647 polyamide Polymers 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 5
- -1 alicyclic amine Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229920006122 polyamide resin Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 16
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004677 Nylon Substances 0.000 abstract description 8
- 229920001778 nylon Polymers 0.000 abstract description 8
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 8
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 239000003365 glass fiber Substances 0.000 abstract 1
- 239000002609 medium Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- IDNHOWMYUQKKTI-UHFFFAOYSA-M lithium nitrite Chemical compound [Li+].[O-]N=O IDNHOWMYUQKKTI-UHFFFAOYSA-M 0.000 description 1
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
るものであり、詳しくは水または水系液体と直接接触し
て高温条件下でまたは長年月使用されるボリアミド成形
品の耐久性を向上させるための方法である。DETAILED DESCRIPTION OF THE INVENTION More specifically, it is a method for improving the durability of polyamide molded products that are used under high temperature conditions or for many years in direct contact with water or an aqueous liquid.
本来、ポリアミド樹脂成形品は機械的諸物性。Originally, polyamide resin molded products have various mechanical properties.
耐熱性，耐薬品性に優れているため各種機能部品として
広く使用されているが、高温の水と直接接触して長年月
使用される場合耐久性において必ずしも満足しうるもの
ではない。特にある種のメタルハライド、例えば塩化亜
鉛などを含有する水溶液や各種無機化合物を含む地下水
などでは表面が侵蝕され、あるいは亀裂が発生して破損
を誘起することがある。Due to its excellent heat resistance and chemical resistance, it is widely used in various functional parts, but its durability is not necessarily satisfactory when used for many years in direct contact with high-temperature water. In particular, aqueous solutions containing certain metal halides, such as zinc chloride, and groundwater containing various inorganic compounds may corrode the surface or cause cracks to occur, leading to damage.
これらの現象は高温条件下で特に顕著であることから、
従来銅化合物など各種耐熱安定剤をボリアミド樹脂に添
加するなどの対策が採られてきたがポリアミドの耐水性
を本質的に向上させるものではなくその効果は不充分で
あった。These phenomena are particularly noticeable under high temperature conditions, so
Conventionally, countermeasures have been taken such as adding various heat-resistant stabilizers such as copper compounds to polyamide resins, but they do not essentially improve the water resistance of polyamides and their effects are insufficient.
本発明者らは上記実情に鑑み、ボリアミド樹脂の耐水性
について鋭意検討した結果、ポリアミド樹脂成形品と直
接接触する水または水系液体中に亜硝酸金属塩を含有せ
しめるか、脂環系アミンを含有せしめるか、または該ボ
リアミド樹脂に対し実質的に被吸収能を有する多価アル
コールを含有せしめることにより、長期耐熱水性が向上
することを見出し既にそれぞれ特許出願した。しかし、
その後の数多くの実験の結果、これらを特定の比率で併
用することによって単独使用では見られなかったきわめ
て高度な長期耐熱水性が得られることが判明し本発明に
到達した。すなわち、本発明は、ポリアミド成形品と直
接゛接触する水または水系液体中に該ポリアミドに対し
実質的に被吸収能を有する多価アルコールの少なくとも
１種類を１〜５０重量％、亜硝酸金属塩の少なくとも１
種類を０．１〜３重量％および脂環系アミンの少なくと
も１種類を０．０５〜２重量％含有せしめることを特徴
とするポリアミド成形品の耐水性改良方法である。本発
明は、金属製ボイラーと共通系でポリアミド製パイプが
使用されるヒーティングシステムでは特に有用であり、
パイプの寿命は著しく延長される。In view of the above-mentioned circumstances, the inventors of the present invention have conducted extensive studies on the water resistance of polyamide resins, and have found that water or aqueous liquids that come into direct contact with polyamide resin molded products either contain nitrite metal salts or contain alicyclic amines. It has been discovered that long-term hot water resistance can be improved by allowing the polyamide resin to contain a polyhydric alcohol having a substantial ability to absorb the polyhydric alcohol, and has already applied for a patent for each of the polyhydric alcohols. but,
As a result of many subsequent experiments, it was found that by using these in combination in a specific ratio, an extremely high degree of long-term hot water resistance that could not be obtained by using them alone was achieved, and the present invention was achieved. That is, the present invention provides 1 to 50% by weight of at least one type of polyhydric alcohol having a substantial ability to be absorbed by the polyamide in water or an aqueous liquid that comes into direct contact with the polyamide molded article, and a metal nitrite salt. at least one of
This is a method for improving the water resistance of a polyamide molded article, which is characterized by containing 0.1 to 3% by weight of a type of amine and 0.05 to 2% by weight of at least one type of alicyclic amine. The invention is particularly useful in heating systems where polyamide pipes are used in common with metal boilers,
The life of the pipe is significantly extended.
本発明で使用される多価アルコールきしては、エチレン
グリフール、プロピレングリコール、１．３−プロパン
ジオール、１．：ｊ−ブタンジオール、１．５−ベンタ
ンジオール、ヘキシレングリコール、ジエチレングリコ
ール、トリエチレングリコール、ジプロピレングリフー
ル、ポリエチレングリフール、ポリプロピレングリフー
ル、グリセリン等があげられ、いずれも効果が認められ
るが中でもぎリアミド樹脂に対し、高い被吸収能を有す
るエチレングリコールおよびプロピレングリコールが特
に有効である。The polyhydric alcohols used in the present invention include ethylene glyfur, propylene glycol, 1,3-propanediol, 1. :j-butanediol, 1,5-bentanediol, hexylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glyfur, polypropylene glyfur, glycerin, etc., all of which are recognized to be effective, but among them: Ethylene glycol and propylene glycol, which have a high absorption capacity, are particularly effective for giriamide resins.
本発明で使用される亜硝酸金属塩としては、亜硝酸ナト
リウム、亜硝酸カリウム、亜硝酸リチウム。Examples of nitrite metal salts used in the present invention include sodium nitrite, potassium nitrite, and lithium nitrite.
亜硝酸カルシウム、亜硝酸マグネシウム等があげられ、
いずれも効果が認められるが亜硝酸ナトリウムおよび亜
硝酸カリウムが特に有効である。Examples include calcium nitrite, magnesium nitrite, etc.
All of them are effective, but sodium nitrite and potassium nitrite are particularly effective.
本発明で使用される脂環系アミンとしては、シクロヘキ
シルアミンおよびジシクロヘキシルアミンがあげられ、
ともに効果が認められるがジシクロヘキシルアミンが特
に有効である。Alicyclic amines used in the present invention include cyclohexylamine and dicyclohexylamine,
Although both are effective, dicyclohexylamine is particularly effective.
本発明でいうポリアミド成形品とは、ナイロン６゜ナイ
ロン６６、ナイロン６１Ｏ，ナイロン１１．ナイロン１
２．これらの共重合物またはこれら２種以上の混合物な
ど主鎖にアミド結合を有するポリアミド樹脂を原料とし
、各種改質添加剤および／または捕強材を混合し、また
はせずして押出成形、射出成形、ブロー成形またはモノ
マーキャスティング法などにより成形されたものであり
、特にナイロン６、ナイロン６６、ナイロン６１０から
なる成形品において、また、ガラス繊維強化ポリアミド
成形品において特に顕著な効果が見られる。The polyamide molded products referred to in the present invention include nylon 6°, nylon 66, nylon 61O, nylon 11. Nylon 1
2. Polyamide resins having amide bonds in the main chain, such as these copolymers or mixtures of two or more of these, are used as raw materials, and extrusion molding and injection molding can be performed with or without mixing various modifying additives and/or reinforcing agents. It is molded by molding, blow molding, monomer casting, etc., and particularly remarkable effects are seen in molded products made of nylon 6, nylon 66, and nylon 610, and in glass fiber-reinforced polyamide molded products.
本発明でいうポリアミド成形品と直接接触する水または
水系液体とは、たとえば、ナイロン製攪拌翼、７ｃＩ−
）など液中使用部品ではその各種水溶液、水分散液、成
形品の吸水処理においてはその処理水、ナイロン製殺菌
袋またはボトルの熱水または過熱水処理においてはその
処理液、ナイロンパイプの送液系においてはその送液、
ラジェーターにおいてはその循環水、ナイロンパイプ製
ヒーティングシステムにおいてはその熱媒を意味し、常
時接触による耐久性または比較的短時間でも高温条件下
での耐水性が要求される分野における当該水系液体をい
い、水分散系の場合でも良い。The water or aqueous liquid that comes into direct contact with the polyamide molded article in the present invention includes, for example, nylon stirring blades, 7cI-
), various aqueous solutions and aqueous dispersions for parts used in liquids, treated water for water absorption treatment of molded products, treated liquid for hot water or superheated water treatment of nylon sterilization bags or bottles, and liquid conveyance through nylon pipes. In the system, the liquid delivery,
This refers to the circulating water in a radiator and the heating medium in a nylon pipe heating system, and refers to water-based liquids in fields that require durability due to constant contact or water resistance under high temperature conditions even for relatively short periods of time. Yes, even if it is an aqueous dispersion system.
該水系液体に含有せしめる前記各成分の量は、温度条件
、接触期間２期待する効果によって異なるが、少なくと
も多価アルコール１〜５０重量％。The amount of each component contained in the aqueous liquid varies depending on temperature conditions, contact period 2, and expected effects, but is at least 1 to 50% by weight of polyhydric alcohol.
亜硝酸金属塩０．１〜３重量％、脂環系アミン０．０５
〜２重量％の範囲で著しい効果が得られる。多価アルコ
ールが１重量％より少ないと多価アルコールのポリアミ
ドに対する膨潤効果に乏しく、長期耐久性が得られない
。また、５０重量％より多くしてもそれ以上の効果が得
られないとともに脂環系アミンの均一な分散が得ら′れ
ず、また亜硝酸金属塩の溶解性も低下するため併用効果
が十分発揮できない。Nitrite metal salt 0.1-3% by weight, alicyclic amine 0.05
Significant effects are obtained in the range of ~2% by weight. If the polyhydric alcohol is less than 1% by weight, the swelling effect of the polyhydric alcohol on the polyamide will be poor, and long-term durability will not be obtained. In addition, even if the amount exceeds 50% by weight, no further effect can be obtained, and the alicyclic amine cannot be uniformly dispersed, and the solubility of the nitrite metal salt also decreases, so the combined effect is not fully demonstrated. Can not.
亜硝酸金属塩の含有量が０．１重量％より少ないと長期
耐久性に乏しく、また、脂環系アミンとの併用に、よっ
て３重量％までの添加で十分の効果が得られるとともに
それ以上多くすると成形品の着色が著しく、用途によっ
ては好ましくない。If the content of nitrite metal salt is less than 0.1% by weight, long-term durability will be poor, and when used in combination with alicyclic amine, sufficient effects can be obtained by adding up to 3% by weight, and even more. If the amount is increased, the molded product will be markedly colored, which may be undesirable depending on the application.
脂環系アミンの含有量が０．０５重量％より少ないと併
用効果に乏しく、２重量％より多くしても均一な分散が
得難く、増量効果は認められない。If the content of the alicyclic amine is less than 0.05% by weight, the combined effect will be poor, and if it is more than 2% by weight, it will be difficult to obtain uniform dispersion, and no effect of increasing the amount will be observed.
該水系液体には、上記成分の他目的により防錆剤、防菌
防かび剤２着色剤など各種成分を含有せしめることは可
能であるが、上記各成分を化学的に変化させるもの、ま
たは均質性をそこなう成分を含有せしめた場合は本発明
の十分な効果が得られない。The aqueous liquid may contain various components such as rust preventive agents, antibacterial and fungicide agents, colorants, etc. for purposes other than those mentioned above, but it is also possible to contain various components such as rust preventive agents, antibacterial and fungicidal agents, and coloring agents. If a component that impairs properties is contained, sufficient effects of the present invention cannot be obtained.
つぎに、実施例に基づいて本発明をさらに詳細に説明す
るが、本発明はこれらに限定するものではない。Next, the present invention will be explained in more detail based on Examples, but the present invention is not limited thereto.
実施例１゜
厚み５０ミクロンのナイロン６製、未延伸フィルムを、
そのまま８０℃に加温された１重量％のジシクロヘキシ
ルアミン、１重量％の亜硝酸ナトリウムおよび５０重量
％のエチレングリコールを含有する水溶液中に浸漬させ
、経日的に引張破断伸度を測定し、伸度保持率の経口変
化を調べた。Example 1 An unstretched film made of nylon 6 with a thickness of 50 microns was
It was immersed in an aqueous solution containing 1% by weight of dicyclohexylamine, 1% by weight of sodium nitrite and 50% by weight of ethylene glycol heated to 80°C, and the tensile elongation at break was measured over time. Oral changes in elongation retention were investigated.
実施例２
実施例１と同じフィルムを、そのまま８０℃に加温され
た０、 ５重量％のジシクロヘキシルアミン、１重量％
の亜硝酸ナトリウムおよび４０重量％のエチレングリコ
ールを含有する水溶液中に浸漬させ、経日的に引張破断
伸度を測定し、伸度保持率の経日変化を調べた・
実施例３゜
実施例１と同じフィルムを、そのまま８０℃に加温され
た０、 ２重量−のジシクロヘキシルアミン、０．５重
量％の亜硝酸す） ＩＪウムおよび４０重量％のエチレ
ングリコールを含有する水溶液中に浸漬させ１経日的に
引張破断伸度を測定し、伸度保持率の経日変化を調べた
。Example 2 The same film as in Example 1 was heated to 80°C and treated with 0.5% by weight of dicyclohexylamine and 1% by weight.
Example 3゜Example The same film as in 1 was immersed in an aqueous solution containing 0.2% by weight of dicyclohexylamine, 0.5% by weight of nitrous acid, and 40% by weight of ethylene glycol, which was heated to 80°C. The tensile elongation at break was measured over a period of one day, and the change in elongation retention over time was investigated.
比較例１゜
実施例１と同じフィルムを、そのまま８０℃に加温され
た１および０．５重量％のジシクロヘキシルアミンを含
訃各水溶液中に浸漬させ、経日的に引張破断伸度を測定
し、伸度保持率の経日変化を調べた。Comparative Example 1 The same film as in Example 1 was immersed in an aqueous solution containing 1 and 0.5% by weight of dicyclohexylamine heated to 80°C, and the tensile elongation at break was measured over time. We then investigated the change in elongation retention rate over time.
比較例２゜
実施例１と同じフィルムを、そのまま８０℃に加温され
た１重量％の亜硝醗ナトリウ、ムを含む水溶液中に浸漬
させ、経日的に引張破断伸度を測定し、伸度保持率の経
日変化を調べた◇
比較例３゜
実施例１と同じフィルムを、そのまま８０℃に加温され
た５０および４０重量％のエチレングリコールを含む各
水溶液中に浸漬させ、経日的に引張破断伸度を測定し、
伸度保持率の経日変化を調べた。Comparative Example 2 The same film as in Example 1 was immersed in an aqueous solution containing 1% by weight of sodium nitrite, heated to 80°C, and the tensile elongation at break was measured over time. ◇ Comparative Example 3 The same film as in Example 1 was immersed in each aqueous solution containing 50 and 40% by weight of ethylene glycol heated to 80°C. Measure the tensile elongation at break daily,
The change in elongation retention rate over time was investigated.
比較例４゜
実施例１と同じフィルムを、そのまま８０℃に加温され
た飲料水中に浸漬させ、経日的に引張破断伸度を測定し
、伸度保持率の経日変化を調べた。Comparative Example 4 The same film as in Example 1 was immersed in drinking water heated to 80° C., and the tensile elongation at break was measured over time to examine the change in elongation retention over time.
比較例５
実施例１と同じフィルムを、そのまま８０℃に加温され
た純水中に浸漬させ、経日的に引張破断伸度を測定し、
伸度保持率の経日変化を調べた。Comparative Example 5 The same film as in Example 1 was immersed in pure water heated to 80°C, and the tensile elongation at break was measured over time.
The change in elongation retention rate over time was investigated.
実施例１，２．３および比較例１． ２． ３． ４゜
５の結果をまとめて表Ｉに不す。Examples 1, 2.3 and Comparative Example 1. 2. 3. The results of 4.5 are summarized in Table I.
表Ｉ
表Ｉより明らかなように、ナイロン６製フィルムの耐水
劣化を示す引張破断伸度保持率はジシクロヘキシルアミ
ン水溶液中、亜硝酸ナトリウム水溶液中およびエチレン
グリコール水溶液中、単独でも著しく向上していること
がわかるが、これらを特定の比率で併用した場合、相乗
効果がでてさらに向上しており、きわめて高度な長期、
耐熱水性が得られていることがわかる。Table I As is clear from Table I, the retention of tensile elongation at break, which indicates water resistance deterioration, of the nylon 6 film was significantly improved in dicyclohexylamine aqueous solution, sodium nitrite aqueous solution, and ethylene glycol aqueous solution alone. However, when these are used together in a specific ratio, a synergistic effect appears and further improves the effect, resulting in an extremely advanced long-term,
It can be seen that hot water resistance is obtained.
実施例４および比較例６゜
内径１） ｔｍ 、外径１鴎のナイロン６製パイプヲ用
いて、ボイラーおよび鋼管との組合せでモデルヒーティ
ングシステムを組み、熱媒として０．５重量％のジシク
ロヘキシルアミン、１重量％の亜硝酸ナトリウムおよび
４０重量％のエチレングリフールを含有する飲料水を使
用し、８０℃にて循環し続けた。１８ケ月後にナイロン
パイプを切り出し観察したところ、内壁に異常は認めら
れなかった。Example 4 and Comparative Example 6 Using a nylon 6 pipe with an inner diameter of 1) tm and an outer diameter of 1 mm, a model heating system was constructed in combination with a boiler and a steel pipe, and 0.5% by weight of dicyclohexylamine was used as a heating medium. , 1% by weight of sodium nitrite and 40% by weight of ethylene glyfur was used and kept circulating at 80°C. When the nylon pipe was cut out and observed 18 months later, no abnormalities were found on the inner wall.
また、パイプの切片を９８％硫酸に１ｇ／１００１１１
１溶解し相対粘度を測定した結果、粘度の低下はは七ん
ど詔められなかった。Also, add 1g/100111 of the pipe section to 98% sulfuric acid.
1 and measured the relative viscosity, no decrease in viscosity was found.
比較のため、ジシクロヘキシルアミン、亜硝酸ナトリウ
ムおよびエチレングリコプルを含まない飲料水を用いる
他、実施例４と同じ試験を行なったところ、パイプ内壁
は耐水劣化し肉薄になっていることが確認できた。また
相対粘度を測定したところ大幅に低下していた。For comparison, we conducted the same test as in Example 4, except that we used drinking water that did not contain dicyclohexylamine, sodium nitrite, and ethylene glycopuric acid, and it was confirmed that the inner wall of the pipe had deteriorated in water resistance and had become thinner. . Furthermore, when the relative viscosity was measured, it was found to have significantly decreased.
特許出願人 ユニチカ株に会社Patent applicant: Unitika Co., Ltd.
Claims (1)
中に該ポリアミドに対し実質的に被吸収能を有する多価
アルコールの少なくとも１種類を１〜５０＋１Ｕｉ１％
、亜硝酸金属塩の少なくとも１種類を０．１〜３重量％
および脂環系アミンの少なくとも１種類を０．０５〜２
重量％含有せしめることを特徴とするポリアミド成形品
の耐水性改良方法。 ２ポリアミド成形品が融雪または暖房用ヒーティングシ
ステムの熱媒循環パイプとして使用されるポリアミド樹
脂製パイプである特許請求範囲第１項記載の耐水性改良
方法。[Claims] 1. 1 to 50+1 Ui 1% of at least one type of polyhydric alcohol having a substantial ability to be absorbed by the polyamide in water or an aqueous liquid that comes into direct contact with the polyamide molded article.
, 0.1 to 3% by weight of at least one kind of nitrite metal salt
and at least one type of alicyclic amine from 0.05 to 2
A method for improving the water resistance of a polyamide molded product, characterized by adding % by weight. 2. The method for improving water resistance according to claim 1, wherein the polyamide molded product is a polyamide resin pipe used for snow melting or as a heating medium circulation pipe for a heating system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10465681A JPS587430A (en) | 1981-07-03 | 1981-07-03 | Method for improving water resistance of polyamide molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10465681A JPS587430A (en) | 1981-07-03 | 1981-07-03 | Method for improving water resistance of polyamide molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS587430A true JPS587430A (en) | 1983-01-17 |
| JPH0142296B2 JPH0142296B2 (en) | 1989-09-12 |
Family
ID=14386500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10465681A Granted JPS587430A (en) | 1981-07-03 | 1981-07-03 | Method for improving water resistance of polyamide molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS587430A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6464783A (en) * | 1987-09-02 | 1989-03-10 | Mazda Motor | Method of clamping screw |
| US11990109B2 (en) | 2022-04-21 | 2024-05-21 | Pearl Musical Instrument Co. | Holder system for a drum |
-
1981
- 1981-07-03 JP JP10465681A patent/JPS587430A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6464783A (en) * | 1987-09-02 | 1989-03-10 | Mazda Motor | Method of clamping screw |
| US11990109B2 (en) | 2022-04-21 | 2024-05-21 | Pearl Musical Instrument Co. | Holder system for a drum |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0142296B2 (en) | 1989-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5118434A (en) | Deicing fluids | |
| CN100441657C (en) | engine coolant | |
| JPH0322404B2 (en) | ||
| EP2860220B1 (en) | Moulding material on the basis of a partially aromatic copolyamide | |
| KR101106126B1 (en) | Anti-blackening and anticorrosive / coolant composition with excellent long-term (10 years / 200,000 km) corrosion resistance | |
| FR2627511A1 (en) | STEEL CORROSION INHIBITORS AND AQUEOUS ALKALI METAL HALIDE COMPOSITIONS CONTAINING THEM | |
| JPH0125827B2 (en) | ||
| DE69903915T2 (en) | FROST-RESISTANT HEATING / COOLANT | |
| EP0940444A3 (en) | Polyamide resin composition | |
| DE2054506A1 (en) | Corrosion inhibition in aqueous systems | |
| US20230087114A1 (en) | Solid, non-phosphorous, scale and corrosion inhibitor composition for cooling water treatment | |
| PL172875B1 (en) | Method for producing a shaped cellulose product PL PL PL PL PL | |
| DE4439193A1 (en) | Mixture for corrosion inhibition of metals | |
| JP3399475B2 (en) | Polyamide resin composition | |
| JPH0142296B2 (en) | ||
| JPH0143836B2 (en) | ||
| KR101300238B1 (en) | Compositions of Antifreezing Liquid or Cooling Liquid with Improvements in Anticorrosion and pH Buffering | |
| US5391370A (en) | Gelled peg biocidal treatments | |
| CN109592800A (en) | A kind of eliminating sludge in pipe antirust agent and preparation method thereof | |
| JPS6335667B2 (en) | ||
| CN110527501A (en) | Salt-tolerant oil sludge profile control agent and preparation method thereof | |
| JPS5853073B2 (en) | steel anticorrosion agent | |
| JP5801893B2 (en) | Salt-resistant polyamide composition | |
| JPS6329696B2 (en) | ||
| JPS5993886A (en) | Anticorrosive for metal |