JP2006057033A - Material with low water absorbency - Google Patents
Material with low water absorbency Download PDFInfo
- Publication number
- JP2006057033A JP2006057033A JP2004241862A JP2004241862A JP2006057033A JP 2006057033 A JP2006057033 A JP 2006057033A JP 2004241862 A JP2004241862 A JP 2004241862A JP 2004241862 A JP2004241862 A JP 2004241862A JP 2006057033 A JP2006057033 A JP 2006057033A
- Authority
- JP
- Japan
- Prior art keywords
- low water
- poly
- oxamide
- dodecamethylene
- water absorption
- 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
Landscapes
- Polyamides (AREA)
Abstract
Description
本発明は、低吸水性部材（フィルム、シート、成形品、繊維）、特に、自動車用、電気・電子用品用又は精密機械用の低吸水性部材（フィルム、シート、成形品、繊維）に関する。更に詳しくは、吸水率が低くかつ引張破断伸びが大きく耐熱性に優れた該低吸水性部材に関する。 The present invention relates to a low water-absorbing member (film, sheet, molded product, fiber), and more particularly to a low water-absorbing member (film, sheet, molded product, fiber) for automobiles, electrical / electronic products or precision machinery. More specifically, the present invention relates to the low water absorption member having a low water absorption rate, a large tensile elongation at break and excellent heat resistance.
自動車、電気・電子用品、精密機械などの部材（フィルム、シート、成形品、繊維）として使用されているポリアミド（ポリオキサミドを除く；以下同様）は、吸水性を有するため、吸水に伴って機械的物性や各種部材の寸法が変化してくるなどの問題があった。 Polyamides (excluding polyoxamide; the same applies hereinafter) used as components (films, sheets, molded products, fibers) for automobiles, electrical / electronic products, precision machinery, etc. have water absorption properties, so that mechanical properties accompany water absorption. There were problems such as changes in physical properties and dimensions of various members.
ポリアミドの吸水率（重量基準；以下同様）は、一般にポリアミド中のアミド基濃度と関係づけられ、アミド基濃度が低いほど吸水率は小さくなる。例えば、アミド基濃度の指標として、Ｎ／Ｃ値（モノマーユニット当たりの窒素原子と炭素原子の原子比）で整理すると、吸水率は、ポリアミド４，６（Ｎ／Ｃ＝０．２）で１３．５％、ポリアミド６（Ｎ／Ｃ＝０．１７）で９．５％、ポリアミド６，１０（Ｎ／Ｃ＝０．１２５）で３．５％、ポリアミド６，１２（Ｎ／Ｃ＝０．１１）で３．０％、ポリアミド１１（Ｎ／Ｃ＝０．０９）で２．０％、ポリアミド１２（Ｎ／Ｃ＝０．０８）で１．７％である（非特許文献１）。このようにアミド基濃度（Ｎ／Ｃ値）が低くなると吸水率は小さくなるが、その場合、分子間水素結合が弱くなってポリアミドの強度や耐熱性が劣ってくるという傾向があった。 The water absorption rate (weight basis; the same applies hereinafter) of polyamide is generally related to the amide group concentration in the polyamide. The lower the amide group concentration, the smaller the water absorption rate. For example, when the N / C value (atomic ratio of nitrogen atom to carbon atom per monomer unit) is arranged as an index of the amide group concentration, the water absorption is 13 for polyamide 4,6 (N / C = 0.2). 0.5%, polyamide 6 (N / C = 0.17), 9.5%, polyamide 6,10 (N / C = 0.125), 3.5%, polyamide 6,12 (N / C = 0) .11) is 3.0%, polyamide 11 (N / C = 0.09) is 2.0%, and polyamide 12 (N / C = 0.08) is 1.7% (Non-Patent Document 1). . Thus, when the amide group concentration (N / C value) decreases, the water absorption decreases, but in that case, there is a tendency that the intermolecular hydrogen bond is weakened and the strength and heat resistance of the polyamide are deteriorated.
一方、ポリオキサミド（シュウ酸成分とジアミン成分の重縮合により得られるポリアミド）は耐熱性の優れた樹脂として知られていて、その強い分子間凝集力に起因して高い結晶性を有するため、低い吸水率を示すことが期待される。しかし、従来知られているポリオキサミドの吸水率は殆どが１％以上であり、充分に満足できるほどに低いレベルではなかった。 On the other hand, polyoxamide (polyamide obtained by polycondensation of an oxalic acid component and a diamine component) is known as a resin with excellent heat resistance, and has high crystallinity due to its strong intermolecular cohesive force, so it has low water absorption. Expected to show rates. However, the water absorption rate of the conventionally known polyoxamide is almost 1% or more, which is not a sufficiently low level.
例えば、ポリオキサミドの吸水率は、ジアミン成分が、３−エトキシヘキサメチレンジアミン系（Ｎ／Ｃ＝０．２０）では３．４％、ヘキサメチレンジアミン／３−エトキシヘキサメチレンジアミン（５０／５０）系（Ｎ／Ｃ＝０．２２）では２．７７％、ヘキサメチレンジアミン／３−メトキシヘキサメチレンジアミン（５０／５０）系（Ｎ／Ｃ＝０．２４）では３．０％、３−イソブトキシヘキサメチレンジアミン系（Ｎ／Ｃ＝０．１６）では２．０％、ヘキサメチレンジアミン／３−イソブトキシヘキサメチレンジアミン（５８．５／４１．５）系（Ｎ／Ｃ＝０．２１）では１．７４％であることが報告されている（特許文献２）。また、テトラメチレンジアミン系（Ｎ／Ｃ＝０．３３）では、キャストフィルムを更にホットプレスしたサンプルを使用して１００％ＲＨ下で測定すると９．３重量％であることが報告されている（非特許文献２）。 For example, the water absorption of polyoxamide is 3.4% when the diamine component is 3-ethoxyhexamethylenediamine (N / C = 0.20), hexamethylenediamine / 3-ethoxyhexamethylenediamine (50/50) (N / C = 0.22) 2.77%, hexamethylenediamine / 3-methoxyhexamethylenediamine (50/50) system (N / C = 0.24) 3.0%, 3-isobutoxy In the hexamethylenediamine system (N / C = 0.16), 2.0%, in the hexamethylenediamine / 3-isobutoxyhexamethylenediamine (58.5 / 41.5) system (N / C = 0.21) It is reported that it is 1.74% (Patent Document 2). In addition, in the case of tetramethylenediamine (N / C = 0.33), it is reported that it is 9.3% by weight when measured under 100% RH using a sample obtained by further pressing a cast film ( Non-patent document 2).
一方、２，１１−ジアミノドデカンをジアミン成分とするポリオキサミドは、吸水率が０．９６％（１００％ＲＨ下では１．０％）程度と低いレベルではあるが、引張破断伸びが１２％と低いため（特許文献２）、プラスチック成形品としては脆く実用性に欠けるものであった。 On the other hand, polyoxamide containing 2,11-diaminododecane as a diamine component has a low water absorption of about 0.96% (1.0% under 100% RH), but the tensile elongation at break is as low as 12%. Therefore (Patent Document 2), the plastic molded product is brittle and lacks practicality.
本発明は、従来技術が達成できなかった、吸水率が充分に低いレベルであって強度（特に引張破断伸び）も優れている耐熱性の低吸水性部材（特に、自動車用、電気・電子用品用、或いは、精密機械用の低吸水性部材）を提供することを課題とする。なお、本発明で、低吸水性とは吸水率（２３℃のイオン交換水に浸漬した場合の飽和吸水率）が１重量％未満をいう。 The present invention is a heat-resistant, low water-absorbing member (especially for automobiles, electric and electronic products) that has a sufficiently low water absorption rate and excellent strength (particularly tensile elongation at break), which could not be achieved by the prior art. Or a low water-absorbing member for precision machinery). In the present invention, low water absorption means that the water absorption rate (saturated water absorption rate when immersed in ion exchange water at 23 ° C.) is less than 1% by weight.
本発明の課題は、以下の発明により解決される。
１．ポリ（ドデカメチレンオキサミド）を含有してなることを特徴とする低吸水性部材。
２．ポリ（ドデカメチレンオキサミド）の末端基が同一又は異なっていて、アミノ基、アルコキシ基、ホルムアミド基のうちのいずれかである、前記１記載の低吸水性部材。
３．低吸水性部材が、フィルム、シート、成形品、繊維のいずれかである、前記１又は２記載の低吸水性部材。
４．低吸水性部材が、自動車用、電気・電子用品用又は精密機械用の低吸水性部材である、前記３記載の低吸水性部材。
５．ポリ（ドデカメチレンオキサミド）の低吸水性部材としての使用。
６．末端基が同一又は異なっていて、アミノ基、アルコキシ基、ホルムアミド基のうちのいずれかであるポリ（ドデカメチレンオキサミド）。
The problems of the present invention are solved by the following invention.
1. A low water-absorbing member comprising poly (dodecamethylene oxamide).
2. 2. The low water-absorbing member according to 1, wherein the end groups of poly (dodecamethylene oxamide) are the same or different and are any one of an amino group, an alkoxy group, and a formamide group.
3. 3. The low water absorption member according to 1 or 2 above, wherein the low water absorption member is any one of a film, a sheet, a molded product, and a fiber.
4). 4. The low water-absorbing member according to 3 above, wherein the low water-absorbing member is a low water-absorbing member for automobiles, electrical / electronic products or precision machinery.
5. Use of poly (dodecamethylene oxamide) as a low water absorption member.
6). Poly (dodecamethylene oxamide) whose end groups are the same or different and are any one of an amino group, an alkoxy group, and a formamide group.
本発明により、従来技術が達成できなかった、吸水率が充分に低いレベルであって強度（特に引張破断伸び）も優れている耐熱性の低吸水性部材（特に、自動車用、電気・電子用品用又は精密機械用の低吸水性部材）を提供することができる。即ち、後述の実施例に示すように、本発明のポリ（ドデカメチレンオキサミド）を含有してなる低吸水性部材は、吸水率が低いためにポリアミドの欠点とされていた吸水に伴う機械的物性や寸法等の変化が少なく、かつ、耐熱性に優れ、強度（特に引張破断伸び）も優れていることより、自動車、電気・電子用品又は精密機械用の低吸水性部材（フィルム、シート、成形品、繊維）として使用できる。 According to the present invention, a heat-resistant low water-absorbing member (especially for automobiles, electrical and electronic products) that has a sufficiently low water absorption rate and excellent strength (particularly tensile elongation at break), which could not be achieved by the prior art. Or a low water-absorbing member for precision machinery). That is, as shown in the examples described later, the low water absorption member containing the poly (dodecamethylene oxamide) of the present invention is mechanically associated with water absorption, which has been regarded as a drawback of polyamide because of its low water absorption rate. Low change in physical properties, dimensions, etc., excellent heat resistance, and excellent strength (particularly tensile elongation at break). Low water-absorbing members (films, sheets, It can be used as a molded article or fiber).
本発明の低吸水性部材に使用されるポリ（ドデカメチレンオキサミド）は、ドデカメチレンオキサミドユニット（−ＣＯ−ＣＯ−ＮＨ−（ＣＨ２）１２−ＮＨ−）を繰り返しユニットとする、高融点、高結晶性のポリオキサミドであり、その分子量に特に制限はない。強いて言えば、数平均分子量（Ｍｎ）で１０００〜１０００００、更には５０００〜５００００程度であることが好ましい。その末端基は特に制限されないが、シュウ酸源としてシュウ酸ジアルキルを使用した場合は、アミノ基、アルコキシ基、ホルムアミド基のうちのいずれかであり、同一であっても異なっていてもよい。ホルムアミド基の生成については後述する。 The poly (dodecamethylene oxamide) used in the low water-absorbing member of the present invention has a high melting point having a repeating unit of dodecamethylene oxamide units (—CO—CO—NH— (CH 2 ) 12 —NH—). It is a highly crystalline polyoxamide, and there is no particular limitation on its molecular weight. In other words, the number average molecular weight ( Mn ) is preferably about 1,000 to 100,000, more preferably about 5,000 to 50,000. The end group is not particularly limited, but when dialkyl oxalate is used as the oxalic acid source, it is any one of an amino group, an alkoxy group, and a formamide group, which may be the same or different. The formation of the formamide group will be described later.
ポリ（ドデカメチレンオキサミド）は、シュウ酸クロリドとドデカメチレンジアミンとの界面重縮合法のような方法でも製造可能であるが、一般的には、シュウ酸又はそれらのエステルとドデカメチレンジアミンとのエステルアミド交換を伴う重縮合反応によって製造される。シュウ酸源としては、とりわけシュウ酸ジエステルが好ましく、中でもシュウ酸ジアルキルが好ましい。シュウ酸ジアルキルとしては、シュウ酸ジメチル、シュウ酸ジエチル、シュウ酸ジブチルなどが挙げられるが、特にシュウ酸ジブチルが適している。なお、シュウ酸ジエステルには、本発明の効果を損なわない範囲で他の脂肪族ジカルボン酸ジエステルや芳香族ジカルボン酸ジエステルが一部（シュウ酸ジエステルの５０モル％以下）含有されていてもよい。 Poly (dodecamethylene oxamide) can also be produced by a method such as an interfacial polycondensation method of oxalic acid chloride and dodecamethylenediamine, but in general, oxalic acid or an ester thereof and dodecamethylenediamine are used. Produced by a polycondensation reaction involving transesterification. As the oxalic acid source, oxalic acid diester is particularly preferable, and dialkyl oxalate is particularly preferable. Examples of the dialkyl oxalate include dimethyl oxalate, diethyl oxalate, dibutyl oxalate and the like, and dibutyl oxalate is particularly suitable. In addition, the oxalic acid diester may contain a part of other aliphatic dicarboxylic acid diesters or aromatic dicarboxylic acid diesters (50 mol% or less of the oxalic acid diester) as long as the effects of the present invention are not impaired.
ドデカメチレンジアミンはそれ単独であってもよいが、本発明の効果を損なわない範囲でその一部（ドデカメチレンジアミンの５０モル％以下）を他のジアミンで置換することもできる。このようジアミンとしては、例えば、エチレンジアミン、プロパンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、γ−メチルヘキサメチレンジアミン、オクタメチレンジアミン、ノナンジアミン、デカメチレンジアミン、３−メトキシヘキサメチレンジアミン、３−エトキシヘキサメチレンジアミン、３−イソブトキシヘキサメチレンジアミン等の脂肪族ジアミンが挙げられる。 Dodecamethylenediamine may be used alone, but a part thereof (50 mol% or less of dodecamethylenediamine) may be substituted with another diamine within a range not impairing the effects of the present invention. Examples of such diamines include ethylenediamine, propanediamine, tetramethylenediamine, hexamethylenediamine, γ-methylhexamethylenediamine, octamethylenediamine, nonanediamine, decamethylenediamine, 3-methoxyhexamethylenediamine, and 3-ethoxyhexamethylene. Aliphatic diamines such as diamine and 3-isobutoxyhexamethylene diamine are exemplified.
前記の重縮合反応によるポリ（ドデカメチレンオキサミド）の製造は公知の方法によって行うことができる。例えば、溶媒存在下に１工程で反応させる方法で行ってもよく、前工程（溶媒存在下）で一旦プレポリマーを作り、後工程（溶媒不存在下）で高分子量化する２工程で反応させる方法で行ってもよい。この中では、高分子量のものが得られやすいことから、後者の２工程で反応させる方法が適している。また、重縮合反応においては、原料中（シュウ酸源及びドデカメチレンジアミン）の水分や反応系内の水分の影響によりホルムアミド基が生成するため、原料中及び反応系内の水分を所望の分子量が得られる範囲に制御することが好ましい。末端基にホルムアミド基が増加し過ぎると、ポリ（ドデカメチレンオキサミド）の高分子量化を妨げることになる。 Production of poly (dodecamethylene oxamide) by the above polycondensation reaction can be performed by a known method. For example, it may be carried out by a method of reacting in one step in the presence of a solvent, and a prepolymer is formed once in the previous step (in the presence of a solvent) and reacted in two steps of increasing the molecular weight in the subsequent step (in the absence of a solvent) You may carry out by the method. Among these, since a high molecular weight product is easily obtained, the latter two-step reaction method is suitable. In the polycondensation reaction, formamide groups are generated due to the influence of moisture in the raw material (oxalic acid source and dodecamethylenediamine) and moisture in the reaction system, so that the moisture in the raw material and in the reaction system has a desired molecular weight. It is preferable to control within the range obtained. If the formamide group increases too much at the end group, it will hinder the high molecular weight of poly (dodecamethyleneoxamide).
２工程で反応させる場合、前工程と後工程は、例えば、次のように行われる。
（i）前工程：溶媒存在下、シュウ酸ジアルキルとドデカメチレンジアミンを常圧下（好ましくは窒素雰囲気下）に１２０〜１３０℃で３〜５時間反応させた後、溶媒を除去し、プレポリマーを得る。
（ii）後工程：このプレポリマーを溶融下（２４０〜２５０℃）で１００〜０．０１ｍｍＨｇ（１３．３ｋＰａ〜１．３３Ｐａ）程度まで減圧しながら２〜５時間程度反応させて高分子量化する。
When making it react by 2 processes, a pre-process and a post process are performed as follows, for example.
(I) Pre-process: After reacting dialkyl oxalate and dodecamethylenediamine under atmospheric pressure (preferably under nitrogen atmosphere) at 120 to 130 ° C. for 3 to 5 hours in the presence of a solvent, the solvent is removed, and the prepolymer is removed. obtain.
(Ii) Post-process: This prepolymer is reacted for about 2 to 5 hours under reduced pressure to about 100 to 0.01 mmHg (13.3 kPa to 1.33 Pa) under melting (240 to 250 ° C.) to increase the molecular weight. .
なお、溶媒としては、メタノール、エタノール、ブタノール等の低級アルコール、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、クロロベンゼン等のハロゲン化芳香族炭化水素、シクロヘキサン等の脂環式炭化水素などが使用できる。 As the solvent, lower alcohols such as methanol, ethanol and butanol, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, halogenated aromatic hydrocarbons such as chlorobenzene, and alicyclic hydrocarbons such as cyclohexane can be used. .
このようにして得られるポリ（ドデカメチレンオキサミド）を含有してなる本発明の低吸水性部材は、吸水率（２３℃のイオン交換水に浸漬した場合の飽和吸水率）が０．１重量％≦吸水率＜１重量％であり、引張破断伸びが２０〜１００％の範囲のものである。吸水率が１重量％を超えると低吸水性のレベルが充分ではなく、０．１重量％未満になると結晶性が高くなりすぎて成形加工性が低下するので好ましくない。また、引張破断伸びが２０％より小さいと低吸水性部材が脆くなって実用性に欠け、１００％より大きいと剛性や耐熱性が低下して好ましくない。 The low water-absorbing member of the present invention containing poly (dodecamethylene oxamide) thus obtained has a water absorption rate (saturated water absorption rate when immersed in ion exchange water at 23 ° C.) of 0.1 weight. % ≦ water absorption <1% by weight, and the tensile elongation at break is in the range of 20 to 100%. If the water absorption exceeds 1% by weight, the level of low water absorption is not sufficient, and if it is less than 0.1% by weight, the crystallinity becomes too high and the molding processability deteriorates, which is not preferable. On the other hand, if the tensile elongation at break is less than 20%, the low water-absorbing member becomes brittle and lacks practicality. If it exceeds 100%, the rigidity and heat resistance are undesirably lowered.
本発明の低吸水性部材には、本発明の効果を損なわない範囲で、ポリ（ドデカメチレンオキサミド）以外の他のポリオキサミドを初め、芳香族ポリアミド、脂肪族ポリアミド、脂環式ポリアミドなどポリアミド類を混合することが可能である。更に、ポリアミド以外の熱可塑性ポリマー、エラストマー、フィラーや、補強繊維、各種添加剤を同様に配合することができる。 The low water-absorbing member of the present invention includes other polyoxamides other than poly (dodecamethylene oxamide), polyamides such as aromatic polyamides, aliphatic polyamides, and alicyclic polyamides, as long as the effects of the present invention are not impaired. Can be mixed. Furthermore, thermoplastic polymers other than polyamide, elastomers, fillers, reinforcing fibers, and various additives can be similarly blended.
本発明の低吸水性部材は、前記ポリオキサミドを公知の成形法（即ち、押出、射出、中空、プレス、ロール、発泡、真空・圧空等の溶融法）によって、フィルム、シート、成形品、繊維などにすることができる。また、このような溶融法以外に溶媒を使用する溶液法を用いて成形することも可能である。ここで、成形品とは、射出、中空、プレス、発泡、真空・圧空等の型を使用する成形法によって製造される部材をいう。 The low water-absorbing member of the present invention is a film, sheet, molded product, fiber, etc. produced by known methods of forming the polyoxamide (that is, extrusion, injection, hollow, press, roll, foaming, vacuum, pressure, etc.). Can be. Moreover, it is also possible to shape | mold using the solution method which uses a solvent other than such a melting method. Here, the molded article refers to a member manufactured by a molding method using a mold such as injection, hollow, press, foaming, vacuum / pressure air and the like.
次に、実施例及び比較例を挙げて本発明を具体的に説明する。なお、ポリ（ドデカメチレンオキサミド）の分析は次の１）〜３）のように行い、ポリ（ドデカメチレンオキサミド）を含んでなる低吸水部材の物性評価は次の４）〜６）のように行った。 Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, the analysis of poly (dodecamethylene oxamide) is performed as in the following 1) to 3), and the physical property evaluation of the low water absorption member containing poly (dodecamethylene oxamide) is in the following 4) to 6). Went so.
１）還元粘度（ηSP／ｃ）
ポリ（ドデカメチレンオキサミド）のトリフルオロ酢酸溶液（濃度：０．５ｇ／ｄｌ）を調製して２５℃で測定した。
1) Reduced viscosity (η SP / c)
A solution of poly (dodecamethylene oxamide) in trifluoroacetic acid (concentration: 0.5 g / dl) was prepared and measured at 25 ° C.
２）数平均分子量（Ｍｎ）
数平均分子量（Ｍｎ）は、１Ｈ−ＮＭＲスペクトルから求めたシグナル強度をもとに、例えば、シュウ酸源としてシュウ酸ジブチルを用いた場合は下式により算出した。
Ｍｎ＝ｎｐ×２５４．３７＋ｎ（ＮＨ2）×１９９．３６＋ｎ（ＮＨＣＨＯ）×４５．０２＋ｎ（ＯＢｕ）×９４．５７
2) Number average molecular weight (M n )
The number average molecular weight (M n ) was calculated based on the signal intensity obtained from the 1 H-NMR spectrum, for example, when dibutyl oxalate was used as the oxalic acid source by the following formula.
Mn = np * 254.37 + n (NH2) * 199.36 + n (NHCHO) * 45.2 + n (OBu) * 94.57
なお、１Ｈ−ＮＭＲの測定条件は以下の通りである。
・使用機種：日本電子製ＪＮＭ−ＥＸ４００ＷＢ
・溶媒：トルフルオロ酢酸
・積算回数：３２回
・試料濃度：５重量％
In addition, the measurement conditions of 1 H-NMR are as follows.
・ Model used: JEOL JNM-EX400WB
・ Solvent: trifluoroacetic acid ・ Number of integration: 32 times ・ Sample concentration: 5% by weight
また、前記式中の各項は以下のように規定される。
・ｎｐ＝Ｎｐ／［（Ｎ（ＮＨ2）＋Ｎ（ＮＨＣＨＯ）＋Ｎ（ＯＢｕ））／２］
・ｎ（ＮＨ2）＝Ｎ（ＮＨ2）／［（Ｎ（ＮＨ2）＋Ｎ（ＮＨＣＨＯ）＋Ｎ（ＯＢｕ））／２］
・ｎ（ＮＨＣＨＯ）＝Ｎ（ＮＨＣＨＯ）／［（Ｎ（ＮＨ2）＋Ｎ（ＮＨＣＨＯ）＋Ｎ（ＯＢｕ））／２］
・ｎ（ＯＢｕ）＝Ｎ（ＯＢｕ）／［（Ｎ（ＮＨ2）＋Ｎ（ＮＨＣＨＯ）＋Ｎ（ＯＢｕ））／２］
・Ｎｐ＝［（Ｓｐ／ｓｐ）−１］／ｓｐ
・Ｎ（ＮＨ2）＝Ｓ（ＮＨ2）／ｓ（ＮＨ2）
・Ｎ（ＮＨＣＨＯ）＝Ｓ（ＮＨＣＨＯ）／ｓ（ＮＨＣＨＯ）
・Ｎ（ＯＢｕ）＝Ｓ（ＯＢｕ）／ｓ（ＯＢｕ）
Moreover, each term in the said formula is prescribed | regulated as follows.
· N p = Np / [( N (NH2) + N (NHCHO) + N (OBu)) / 2]
N (NH2) = N (NH2) / [(N (NH2) + N (NHCHO) + N (OBu) ) / 2]
N (NHCHO) = N (NHCHO) / [(N (NH2) + N (NHCHO) + N (OBu) ) / 2]
N (OBu) = N (OBu) / [(N (NH2) + N (NHCHO) + N (OBu) ) / 2]
· N p = [(S p / s p) -1] / s p
・ N (NH2) = S (NH2) / s (NH2)
N (NHCHO) = S (NHCHO) / s (NHCHO)
N (OBu) = S (OBu) / s (OBu)
但し、各項は以下の意味を有する。
・Ｎｐ：ポリ（ドデカメチレンオキサミド）の末端ユニットを除いた、分子鎖中の繰り返しユニット総数。
・ｎｐ：分子１本当たりの分子鎖中の繰り返しユニット数。
・Ｓｐ：ポリ（ドデカメチレンオキサミド）の末端を除いた、分子鎖中の繰り返しユニット中のオキサミド基に隣接するメチレン基のプロトンに基づくシグナル（３．４５ｐｐｍ付近）の積分値。
・ｓｐ：積分値Ｓｐにカウントされる水素数（２個）。
・Ｎ（ＮＨ2）：ポリ（ドデカメチレンオキサミド）の末端アミノ基の総数。
・ｎ（ＮＨ2）：分子１本当たりの末端アミノ基の数。
・Ｓ（ＮＨ2）：ポリ（ドデカメチレンオキサミド）の末端アミノ基に隣接するメチレン基のプロトンに基づくシグナル（３．２５ｐｐｍ付近）の積分値。
・ｓ（ＮＨ2）：積分値Ｓ（ＮＨ2）にカウントされる水素数（２個）。
・Ｎ（ＮＨＣＨＯ）：ポリ（ドデカメチレンオキサミド）の末端ホルムアミド基の総数。
・ｎ（ＮＨＣＨＯ）：分子１本当たりの末端ホルムアミド基の数。
・Ｓ（ＮＨＣＨＯ）：ポリ（ドデカメチレンオキサミド）のホルムアミド基のプロトンに基づくシグナル（８．４５ｐｐｍ）の積分値。
・ｓ（ＮＨＣＨＯ）：積分値Ｓ（ＮＨＣＨＯ）にカウントされる水素数（１個）。
・Ｎ（ＯＢｕ）：ポリ（ドデカメチレンオキサミド）の末端ブトキシ基の総数。
・ｎ（ＯＢｕ）：分子１本当たりの末端ブトキシ基の数。
・Ｓ（ＯＢｕ）：ポリ（ドデカメチレンオキサミド）の末端ブトキシ基の酸素原子に隣接するメチレン基のプロトンに基づくシグナル（４．５０ｐｐｍ付近）の積分値。
・ｓ（ＯＢｕ）：積分値Ｓ（ＯＢｕ）にカウントされる水素数（２個）。
However, each term has the following meaning.
· N p: excluding terminal units of the poly (dodecamethylene oxamide), repeating units the total number in the molecular chain.
N p : number of repeating units in the molecular chain per molecule.
· S p: excluding the ends of poly (dodecamethylene oxamide), the integral value of the signal (around 3.45 ppm) based on protons of the methylene group adjacent to the oxamide group in the repeating unit in the molecular chain.
· S p: The number of hydrogens counted in the integration value S p (2 pieces).
N (NH2) : Total number of terminal amino groups of poly (dodecamethyleneoxamide).
N (NH2) : Number of terminal amino groups per molecule.
S (NH2) : integrated value of a signal (around 3.25 ppm) based on the proton of the methylene group adjacent to the terminal amino group of poly (dodecamethyleneoxamide).
S (NH2) : Number of hydrogens (2) counted in the integral value S (NH2 ).
N (NHCHO) : the total number of terminal formamide groups of poly (dodecamethyleneoxamide).
N (NHCHO) : number of terminal formamide groups per molecule.
S (NHCHO) : integrated value of a signal (8.45 ppm) based on the proton of the formamide group of poly (dodecamethyleneoxamide).
S (NHCHO) : The number of hydrogens (one) counted in the integral value S (NHCHO ).
N (OBu) : the total number of terminal butoxy groups of poly (dodecamethyleneoxamide).
N (OBu) : number of terminal butoxy groups per molecule.
S (OBu) : integrated value of a signal (around 4.50 ppm) based on the proton of the methylene group adjacent to the oxygen atom of the terminal butoxy group of poly (dodecamethyleneoxamide).
S (OBu) : The number of hydrogens (2) counted in the integral value S (OBu ).
３）末端基濃度：シュウ酸ジブチルを用いた場合、末端アミノ基濃度［ＮＨ２］、末端ブトキシ基濃度［ＯＢｕ］、末端ホルムアミド基濃度［ＮＨＣＨＯ］は次の式に従ってそれぞれ求めた。
・末端アミノ基濃度［ＮＨ２］＝ｎ（ＮＨ２）／Ｍｎ
・末端ブトキシ基濃度［ＯＢｕ］＝ｎ（ＯＢｕ）／Ｍｎ
・末端ホルムアミド基濃度［ＮＨＣＨＯ］＝ｎ（ＮＨＣＨＯ）／Ｍｎ
3) Terminal group concentration: When dibutyl oxalate was used, terminal amino group concentration [NH 2 ], terminal butoxy group concentration [OBu], and terminal formamide group concentration [NHCHO] were determined according to the following formulae.
Terminal amino group concentration [NH 2 ] = n ( NH 2 ) / M n
Terminal butoxy group concentration [OBu] = n (OBu) / M n
Terminal formamide group concentration [NHCHO] = n (NHCHO) / M n
４）ガラス転移温度（Ｔｇ）、融点（Ｔｍ）、結晶化温度（Ｔｃ）
ＤＳＣにより、窒素気流下で１０℃／分で室温から昇温してＴｇとＴｍを測定した。次いで、完全溶融後に１０℃／分で降温してＴｃを測定した。
4) Glass transition temperature (T g ), melting point (T m ), crystallization temperature (T c )
By DSC, the temperature was raised from room temperature at 10 ° C./min under a nitrogen stream, and T g and T m were measured. Subsequently, the temperature was lowered at 10 ° C./min after complete melting, and Tc was measured.
５）プレス成形
ポリ（ドデカメチレンオキサミド）を２７０℃で３分間予熱して５ＭＰａで３０秒間プレスした後、約１３℃で３分間冷却して厚み２３０μｍのシートを作製した。
5) Press molding Poly (dodecamethylene oxamide) was preheated at 270 ° C. for 3 minutes and pressed at 5 MPa for 30 seconds, and then cooled at about 13 ° C. for 3 minutes to produce a sheet having a thickness of 230 μm.
６）引張試験
前記プレスシートからＪＩＳ２号引張ダンベル試験片を打ち抜いた。この試験片について、２３℃、５０％ＲＨの条件下、引張速度１００ｍｍ／分で試験を行って、引張弾性率、引張降伏点強度、引張破断伸びを求めた。
6) Tensile test A JIS No. 2 tensile dumbbell specimen was punched from the press sheet. The test piece was tested under the conditions of 23 ° C. and 50% RH at a tensile speed of 100 mm / min, and the tensile elastic modulus, tensile yield strength, and tensile breaking elongation were determined.
７）吸水率（飽和吸水率；重量％）
前記プレスシートから５ｃｍ×１０ｃｍの大きさの試験片を切り出して２３℃のイオン交換水に浸漬し、次式により吸水率を経時的に求めて飽和吸水率（重量％）を得た。
吸水率（重量％）＝［（浸漬後の重量−浸漬前の重量）／浸漬前の重量］×１００
7) Water absorption (saturated water absorption; wt%)
A test piece having a size of 5 cm × 10 cm was cut out from the press sheet and immersed in ion-exchanged water at 23 ° C., and the water absorption rate was obtained over time by the following formula to obtain a saturated water absorption rate (% by weight).
Water absorption rate (% by weight) = [(weight after immersion−weight before immersion) / weight before immersion] × 100
〔実施例１〕
（i）前工程（プレポリマーの製造）
５００ｍＬの丸底フラスコ（滴下漏斗と還流冷却器を備える）をオイルバス中に設置し、脱水トルエン２００ｍＬ及びドデカメチレンジアミン２０．０３７ｇを入れ、窒素気流下、オイルバス設定温度を５０℃にして、内容物が均一溶液になるまでマグネチックスターラーで撹拌した。次いで、シュウ酸ジブチル２０．２２５ｇを滴下漏斗からフラスコ内に注加した後、オイルバス設定温度を１２０℃にして窒素気流下で５時間還流を行った。反応終了後、トルエンと生成ブタノールを留去し、フラスコを８０℃で一昼夜加熱真空乾燥してプレポリマー２５．４ｇを得た。
[Example 1]
(I) Pre-process (Prepolymer production)
A 500 mL round bottom flask (equipped with a dropping funnel and a reflux condenser) is placed in an oil bath, 200 mL of dehydrated toluene and 20.037 g of dodecamethylenediamine are added, the oil bath set temperature is set to 50 ° C. under a nitrogen stream, The contents were stirred with a magnetic stirrer until a homogeneous solution was obtained. Next, 20.225 g of dibutyl oxalate was poured into the flask from the dropping funnel, and then the oil bath was set at 120 ° C. and refluxed for 5 hours under a nitrogen stream. After completion of the reaction, toluene and produced butanol were distilled off, and the flask was heated and vacuum dried at 80 ° C. for 24 hours to obtain 25.4 g of a prepolymer.
（ii）後工程（高分子量化）
直径約３０ｍｍφのガラス製反応管（空冷管、窒素導入管、メカニカルスターラーを備える）に、上記プレポリマー１３．９２ｇを仕込んで内部を窒素で置換した。次いで、反応管を１７０℃の塩浴中に設置して、そのまま１７０℃から２５０℃まで１時間かけて昇温した後、２５０℃で減圧を開始し、真空度を徐々に上げながら２時間反応させてポリ（ドデカメチレンオキサミド）を得た。最終到達圧力は０．０７ｍｍＨｇ（９．３Ｐａ）であった。反応中、撹拌は３０ｒｐｍで行った（以下同様）。得られたポリ（ドデカメチレンオキサミド）の分析結果を表１に、ポリ（ドデカメチレンオキサミド）をプレス成形して得られたプレスシートの物性評価結果を表２に示す。
(Ii) Post process (high molecular weight)
13.92 g of the prepolymer was charged into a glass reaction tube (equipped with an air-cooled tube, a nitrogen introduction tube, and a mechanical stirrer) having a diameter of about 30 mmφ, and the inside was replaced with nitrogen. Next, the reaction tube was placed in a 170 ° C. salt bath, and the temperature was raised from 170 ° C. to 250 ° C. over 1 hour. Then, pressure reduction was started at 250 ° C., and the reaction was continued for 2 hours while gradually increasing the degree of vacuum. To obtain poly (dodecamethyleneoxamide). The final ultimate pressure was 0.07 mmHg (9.3 Pa). During the reaction, stirring was performed at 30 rpm (the same applies hereinafter). The analysis results of the obtained poly (dodecamethylene oxamide) are shown in Table 1, and the physical property evaluation results of press sheets obtained by press molding the poly (dodecamethylene oxamide) are shown in Table 2.
〔実施例２〕
（i）前工程（プレポリマーの製造）
２０Ｌのセパラブルフラスコ（滴下漏斗、ジーンスターク付き還流冷却器、メカニカルスターラーを備える）をオイルバス中に設置し、窒素気流下でドデカメチレンジアミン１００２ｇを加え、更に脱水トルエン１０Ｌを投入し、オイルバス設定温度を５０℃にして、内容物が均一溶液になるまで撹拌した。次いで、シュウ酸ジブチル１０１１ｇを滴下漏斗からフラスコ内に注加した後、オイルバス設定温度を１２０℃にして窒素気流下で３時間還流を行った。反応終了後、トルエンと生成ブタノールを留去し、残渣を６０℃で一昼夜加熱真空乾燥してプレポリマー１３１６ｇを得た。
[Example 2]
(I) Pre-process (Prepolymer production)
A 20 L separable flask (with a dropping funnel, a reflux condenser with Gene Stark, and a mechanical stirrer) was placed in the oil bath, 1002 g of dodecamemethylenediamine was added under a nitrogen stream, and 10 L of dehydrated toluene was added. The temperature was set to 50 ° C. and stirred until the contents became a homogeneous solution. Subsequently, 1011 g of dibutyl oxalate was poured into the flask from the dropping funnel, and then the oil bath was set at 120 ° C. and refluxed for 3 hours under a nitrogen stream. After completion of the reaction, toluene and produced butanol were distilled off, and the residue was heated and vacuum dried at 60 ° C. overnight to obtain 1316 g of a prepolymer.
（ii）後工程（高分子量化）
実施例１と同様のガラス製反応管に、上記プレポリマー２５．０ｇを仕込んで内部を窒素で置換した。次いで、反応管を１７０℃の塩浴中に設置して、そのまま１７０℃から２５０℃まで１時間かけて昇温した後、２５０℃で減圧を開始し、真空度を徐々に上げながら２時間反応させてポリ（ドデカメチレンオキサミド）を得た。最終到達圧力は０．０７ｍｍＨｇ（９．３Ｐａ）であった。ポリ（ドデカメチレンオキサミド）の分析結果及びそのプレスシートの物性評価結果を表１及び２にそれぞれ示す。
(Ii) Post process (high molecular weight)
In the same glass reaction tube as in Example 1, 25.0 g of the above prepolymer was charged and the inside was replaced with nitrogen. Next, the reaction tube was placed in a 170 ° C. salt bath, and the temperature was raised from 170 ° C. to 250 ° C. over 1 hour. Then, pressure reduction was started at 250 ° C., and the reaction was continued for 2 hours while gradually increasing the degree of vacuum. To obtain poly (dodecamethyleneoxamide). The final ultimate pressure was 0.07 mmHg (9.3 Pa). The analysis results of poly (dodecamethylene oxamide) and the physical property evaluation results of the press sheet are shown in Tables 1 and 2, respectively.
〔実施例３〕
（i）前工程（プレポリマーの製造）
実施例２と同様に行って得られたプレポリマーを更に１００℃で一昼夜加熱真空乾燥して後工程に使用した。
Example 3
(I) Pre-process (Prepolymer production)
The prepolymer obtained in the same manner as in Example 2 was further dried in a vacuum at 100 ° C. for a whole day and used in the subsequent step.
（ii）後工程（高分子量化）
実施例１と同様のガラス製反応管に、上記プレポリマー２５．０ｇを仕込んで内部を窒素で置換した。次いで、反応管を１７０℃の塩浴中に設置して、そのまま１７０℃から２５０℃まで１時間かけて昇温した後、２５０℃にて減圧を開始し、真空度を徐々に上げながら２．５時間反応させてポリ（ドデカメチレンオキサミド）を得た。ポリ（ドデカメチレンオキサミド）の分析結果及びそのプレスシートの物性評価結果を表１及び２にそれぞれ示す。
(Ii) Post process (high molecular weight)
In the same glass reaction tube as in Example 1, 25.0 g of the above prepolymer was charged and the inside was replaced with nitrogen. Next, the reaction tube was placed in a 170 ° C. salt bath, and the temperature was raised from 170 ° C. to 250 ° C. over 1 hour. Then, pressure reduction was started at 250 ° C., and the degree of vacuum was gradually increased. Reaction was performed for 5 hours to obtain poly (dodecamethylene oxamide). The analysis results of poly (dodecamethylene oxamide) and the physical property evaluation results of the press sheet are shown in Tables 1 and 2, respectively.
〔比較例１〕
ポリ（ドデカメチレンオキサミド）に代えてナイロン６（宇部興産製、ＵＢＥナイロン１０１５Ｂ）を使用した。ナイロン６の分析結果及びそのプレスシートの物性評価結果を表１及び２にそれぞれ示す。
[Comparative Example 1]
Nylon 6 (Ube Industries, UBE nylon 1015B) was used instead of poly (dodecamethylene oxamide). The analysis results of nylon 6 and the physical property evaluation results of the press sheet are shown in Tables 1 and 2, respectively.
本発明の低吸水性部材は、吸水率が低くかつ耐熱性に優れ、強度も優れていることより、自動車、電気・電子用品又は精密機械用の低吸水性部材（フィルム、シート、成形品、繊維）として使用できる。 The low water-absorbing member of the present invention has a low water absorption rate, excellent heat resistance, and excellent strength. Therefore, the low water-absorbing member (film, sheet, molded product, Fiber).
Claims (6)
Poly (dodecamethylene oxamide) whose end groups are the same or different and are any one of an amino group, an alkoxy group, and a formamide group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004241862A JP4487687B2 (en) | 2004-08-23 | 2004-08-23 | Low water absorption member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004241862A JP4487687B2 (en) | 2004-08-23 | 2004-08-23 | Low water absorption member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006057033A true JP2006057033A (en) | 2006-03-02 |
| JP4487687B2 JP4487687B2 (en) | 2010-06-23 |
Family
ID=36104772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004241862A Expired - Lifetime JP4487687B2 (en) | 2004-08-23 | 2004-08-23 | Low water absorption member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4487687B2 (en) |
Cited By (50)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008072754A1 (en) | 2006-12-11 | 2008-06-19 | Ube Industries, Ltd. | Polyamide resin |
| WO2008123534A1 (en) * | 2007-03-27 | 2008-10-16 | Ube Industries, Ltd. | Molding material for fuel component and fuel component using the same |
| WO2008123531A1 (en) | 2007-03-27 | 2008-10-16 | Ube Industries, Ltd. | Method for production of polyamide resin |
| JP2009235224A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Method for producing polyamide resin |
| JP2009235225A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Polyamide resin |
| JP2009235223A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Polyamide resin for automobile member |
| WO2009151145A1 (en) * | 2008-06-10 | 2009-12-17 | 宇部興産株式会社 | Novel polyamide resin composition and polyamide resin-containing product |
| JP2009298859A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition for engine cooling water-system component, and engine cooling water-system component molded from the composition |
| JP2009299206A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Filament |
| JP2009298870A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Internal component of automobile engine room |
| JP2009298855A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition |
| JP2009299722A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Joint for fuel pipe, quick connector for fuel pipe and fuel piping component |
| JP2009298856A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Heat-resistant agent-containing resin composition and molded article formed from the heat-resistant agent-containing resin composition |
| JP2009298854A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate |
| JP2009298852A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Plasticizer-containing polyamide resin composition and molded article |
| JP2009298868A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition and molded article |
| JP2009298858A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Molded member making direct contact with biodiesel fuel |
| JP2009298860A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin-molded component having liquid or vapor barrier property |
| JP2009298861A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Hollow molded part manufactured using polyamide resin and layered silicate |
| JP2009298857A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition and molded article formed from the polyamide resin composition |
| JP2009298867A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide film |
| JP2009298853A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition |
| JP2009298864A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Injection-molding material containing new polyamide resin |
| JP2009298865A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Fuel tank component |
| JP2009298863A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Vehicle interior component produced by using new polyamide resin |
| JP2009298862A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Vehicle exterior component produced by using new polyamide resin |
| JP2010018794A (en) * | 2008-06-10 | 2010-01-28 | Ube Ind Ltd | Conductive polyamide resin composition |
| JP2010077208A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Resin composition containing heat-resistant agent, and molded product formed from the resin composition containing heat-resistant agent |
| JP2010077211A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Extrusion molding material, filament, and polyamide film |
| JP2010077206A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate, and blow molded part |
| JP2010077221A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Plasticizer-containing polyamide resin composition, and molded product |
| JP2010077210A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Injection-molding material containing novel polyamide resin and injection-molded product produced from those |
| JP2010077215A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Molded member directly contacted with bio-diesel fuel |
| JP2010077214A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Vehicle part produced using novel polyamide resin, vehicle interior part, vehicle exterior part, and internal part of vehicle engine room |
| JP2010077213A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin molded part having liquid or vapor-barrier property, fuel tank part, fuel tube, fuel piping coupling, quick connector, and fuel piping part |
| JP2010077209A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition, and molded product formed from the polyamide resin composition |
| JP2010077205A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition |
| JP2010077212A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Metal covering material |
| JP2010077207A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition |
| JP2010100822A (en) * | 2008-09-24 | 2010-05-06 | Ube Ind Ltd | Electroconductive polyamide resin composition and cable housing |
| WO2011016535A1 (en) | 2009-08-07 | 2011-02-10 | 宇部興産株式会社 | Conductive polyamide resin composition |
| WO2011016536A1 (en) | 2009-08-07 | 2011-02-10 | 宇部興産株式会社 | Conductive resin composition |
| JP2011063693A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin |
| JP2011063694A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin |
| WO2011136263A1 (en) | 2010-04-30 | 2011-11-03 | 宇部興産株式会社 | Polyamide resin |
| WO2012036303A1 (en) * | 2010-09-17 | 2012-03-22 | 宇部興産株式会社 | Polyoxamide resin having excellent impact resistance and impact-resistant part |
| JPWO2013062089A1 (en) * | 2011-10-28 | 2015-04-02 | 宇部興産株式会社 | Polyamide resin and molded product comprising the same |
| JP2016204490A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Composition and molded article consisting of the same |
| JP2016204499A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Polyamide elastomer and molded article manufactured by using the same |
| JP2016204488A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Polyamide elastomer and laminate |
-
2004
- 2004-08-23 JP JP2004241862A patent/JP4487687B2/en not_active Expired - Lifetime
Cited By (65)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5056763B2 (en) * | 2006-12-11 | 2012-10-24 | 宇部興産株式会社 | Polyamide resin |
| JPWO2008072754A1 (en) * | 2006-12-11 | 2010-04-02 | 宇部興産株式会社 | Polyamide resin |
| WO2008072754A1 (en) | 2006-12-11 | 2008-06-19 | Ube Industries, Ltd. | Polyamide resin |
| EP2130851A1 (en) * | 2007-03-27 | 2009-12-09 | Ube Industries, Ltd. | Molding material for fuel component and fuel component using the same |
| US20100113738A1 (en) * | 2007-03-27 | 2010-05-06 | Ube Industries, Ltd. | Molding material for fuel parts and fuel part using the same |
| CN101636430B (en) * | 2007-03-27 | 2012-07-04 | 宇部兴产株式会社 | Molding material for fuel component and fuel component using the same |
| EP2130851A4 (en) * | 2007-03-27 | 2012-07-04 | Ube Industries | Molding material for fuel component and fuel component using the same |
| WO2008123531A1 (en) | 2007-03-27 | 2008-10-16 | Ube Industries, Ltd. | Method for production of polyamide resin |
| JP5170085B2 (en) * | 2007-03-27 | 2013-03-27 | 宇部興産株式会社 | Manufacturing method of polyamide resin |
| JP5218399B2 (en) * | 2007-03-27 | 2013-06-26 | 宇部興産株式会社 | Molding material for fuel parts and fuel parts using the same |
| US9090738B2 (en) | 2007-03-27 | 2015-07-28 | Ube Industries, Ltd. | Production method of polyamide resin |
| WO2008123534A1 (en) * | 2007-03-27 | 2008-10-16 | Ube Industries, Ltd. | Molding material for fuel component and fuel component using the same |
| JP2009235225A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Polyamide resin |
| JP2009235223A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Polyamide resin for automobile member |
| JP2009235224A (en) * | 2008-03-27 | 2009-10-15 | Ube Ind Ltd | Method for producing polyamide resin |
| JP2009298860A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin-molded component having liquid or vapor barrier property |
| JP2009298862A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Vehicle exterior component produced by using new polyamide resin |
| JP2009298858A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Molded member making direct contact with biodiesel fuel |
| JP2009298852A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Plasticizer-containing polyamide resin composition and molded article |
| JP2009298861A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Hollow molded part manufactured using polyamide resin and layered silicate |
| JP2009298857A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition and molded article formed from the polyamide resin composition |
| JP2009298867A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide film |
| JP2009298853A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition |
| JP2009298864A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Injection-molding material containing new polyamide resin |
| JP2009298865A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Fuel tank component |
| JP2009298863A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Vehicle interior component produced by using new polyamide resin |
| JP2009298868A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition and molded article |
| JP2010018794A (en) * | 2008-06-10 | 2010-01-28 | Ube Ind Ltd | Conductive polyamide resin composition |
| JP2009298854A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate |
| JP2009298856A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Heat-resistant agent-containing resin composition and molded article formed from the heat-resistant agent-containing resin composition |
| JP2009299722A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Joint for fuel pipe, quick connector for fuel pipe and fuel piping component |
| JP2009298855A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition |
| JP2009298870A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Internal component of automobile engine room |
| JP2009299206A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Filament |
| JP2009298859A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Polyamide resin composition for engine cooling water-system component, and engine cooling water-system component molded from the composition |
| WO2009151145A1 (en) * | 2008-06-10 | 2009-12-17 | 宇部興産株式会社 | Novel polyamide resin composition and polyamide resin-containing product |
| JP2010077221A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Plasticizer-containing polyamide resin composition, and molded product |
| JP2010077214A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Vehicle part produced using novel polyamide resin, vehicle interior part, vehicle exterior part, and internal part of vehicle engine room |
| JP2010077205A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition |
| JP2010077212A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Metal covering material |
| JP2010077207A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition |
| JP2010100822A (en) * | 2008-09-24 | 2010-05-06 | Ube Ind Ltd | Electroconductive polyamide resin composition and cable housing |
| JP2010077213A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin molded part having liquid or vapor-barrier property, fuel tank part, fuel tube, fuel piping coupling, quick connector, and fuel piping part |
| JP2010077208A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Resin composition containing heat-resistant agent, and molded product formed from the resin composition containing heat-resistant agent |
| JP2010077209A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Polyamide resin composition, and molded product formed from the polyamide resin composition |
| JP2010077211A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Extrusion molding material, filament, and polyamide film |
| JP2010077206A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate, and blow molded part |
| JP2010077210A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Injection-molding material containing novel polyamide resin and injection-molded product produced from those |
| JP2010077215A (en) * | 2008-09-24 | 2010-04-08 | Ube Ind Ltd | Molded member directly contacted with bio-diesel fuel |
| WO2011016536A1 (en) | 2009-08-07 | 2011-02-10 | 宇部興産株式会社 | Conductive resin composition |
| US9236163B2 (en) | 2009-08-07 | 2016-01-12 | Ube Industries, Ltd. | Electroconductive resin composition |
| US9206048B2 (en) | 2009-08-07 | 2015-12-08 | Ube Industries, Ltd. | Electroconductive polyamide resin composition |
| WO2011016535A1 (en) | 2009-08-07 | 2011-02-10 | 宇部興産株式会社 | Conductive polyamide resin composition |
| JP2011063694A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin |
| JP2011063693A (en) * | 2009-09-16 | 2011-03-31 | Ube Industries Ltd | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin |
| US8975364B2 (en) | 2010-04-30 | 2015-03-10 | Ube Industries, Ltd. | Polyamide resin |
| WO2011136263A1 (en) | 2010-04-30 | 2011-11-03 | 宇部興産株式会社 | Polyamide resin |
| CN103108900A (en) * | 2010-09-17 | 2013-05-15 | 宇部兴产株式会社 | Polyoxamide resin having excellent impact resistance and impact-resistant part |
| JPWO2012036303A1 (en) * | 2010-09-17 | 2014-02-03 | 宇部興産株式会社 | Polyoxamide resin with excellent impact resistance and impact resistant parts |
| US20130172520A1 (en) * | 2010-09-17 | 2013-07-04 | Ube Industries, Ltd. | Polyoxamide resin having excellent impact resistance and impact-resistant part |
| WO2012036303A1 (en) * | 2010-09-17 | 2012-03-22 | 宇部興産株式会社 | Polyoxamide resin having excellent impact resistance and impact-resistant part |
| JPWO2013062089A1 (en) * | 2011-10-28 | 2015-04-02 | 宇部興産株式会社 | Polyamide resin and molded product comprising the same |
| JP2016204490A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Composition and molded article consisting of the same |
| JP2016204499A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Polyamide elastomer and molded article manufactured by using the same |
| JP2016204488A (en) * | 2015-04-21 | 2016-12-08 | 宇部興産株式会社 | Polyamide elastomer and laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4487687B2 (en) | 2010-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4487687B2 (en) | Low water absorption member | |
| RU2415156C2 (en) | Polycrystalline polyaromatic polyamide | |
| JP5056763B2 (en) | Polyamide resin | |
| WO2008123534A1 (en) | Molding material for fuel component and fuel component using the same | |
| TW201120095A (en) | Polyamide and polyamide composition | |
| JP5796573B2 (en) | Polyamide resin | |
| WO2008123531A1 (en) | Method for production of polyamide resin | |
| JP2009235225A (en) | Polyamide resin | |
| CN101503512A (en) | Semi-aromatic polyamide and preparation thereof | |
| JPWO2016182001A1 (en) | Polyamide elastomer, medical device, and method for producing polyamide elastomer | |
| US20130172520A1 (en) | Polyoxamide resin having excellent impact resistance and impact-resistant part | |
| JP5141331B2 (en) | Manufacturing method of polyamide resin | |
| JP5321434B2 (en) | Polyamide resin composition for SMT connectors | |
| JP2011063694A (en) | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin | |
| JP2013095777A (en) | Polyamide resin composition for printed board surface mounting component and printed board surface mounting component obtained by molding the same | |
| JP6778678B2 (en) | Polyamide elastomers, medical devices and methods for manufacturing polyamide elastomers | |
| JPH05170897A (en) | Crystalline polyamide resin of high molecular weight | |
| JP6451082B2 (en) | Polyamide resin | |
| JPWO2018105649A1 (en) | polyamide | |
| WO2018088496A1 (en) | Polyamide resin, molded body, laminate, medical device, and polyamide resin production method | |
| JP2012072200A (en) | Method for producing polyoxamide resin | |
| CN110527289B (en) | Polyamide resin pellet, process for producing the same, and process for producing polyamide composition | |
| JP5972088B2 (en) | Polyamide resin composition and molded body | |
| JP2011063693A (en) | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin | |
| JP2013095792A (en) | Filler-containing polyamide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060808 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081226 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090609 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090803 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091020 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091217 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100309 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100322 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4487687 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130409 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140409 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |