JP2005194330A - Polyamide resin composition - Google Patents
Polyamide resin composition Download PDFInfo
- Publication number
- JP2005194330A JP2005194330A JP2003435792A JP2003435792A JP2005194330A JP 2005194330 A JP2005194330 A JP 2005194330A JP 2003435792 A JP2003435792 A JP 2003435792A JP 2003435792 A JP2003435792 A JP 2003435792A JP 2005194330 A JP2005194330 A JP 2005194330A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- resin composition
- ppm
- filter
- acid
- 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.)
- Withdrawn
Links
Abstract
Description
本発明は、ガソリンタンク材、飲料用ボトルをはじめとする中空成形容器、フィルム、シ−トなどの成形体の素材として好適に用いられるポリアミド樹脂組成物に関するものである。また、それらを重合および成形する際の熱安定性に良好で、かつ、色調に優れ、かつ、フィルター背圧上昇の少なく、生産性に優れたポリアミド樹脂組成物に関する。 The present invention relates to a polyamide resin composition that can be suitably used as a material for molded articles such as gasoline tank materials, beverage bottles, hollow molded containers, films, sheets, and the like. Further, the present invention relates to a polyamide resin composition having excellent thermal stability when polymerizing and molding them, excellent color tone, little increase in filter back pressure, and excellent productivity.
ポリアミドは物理的、機械的特性に優れていることから中空成形容器、フィルム、シート包装材料、エンジニアプラスチック、繊維などの用途に幅広く使用されている。ナイロン６６などの脂肪族ポリアミドが代表例であるが、これら他の、パラキシリレンジアミン（ＰＸＤＡ）やメタキシリレンジアミン（ＭＸＤＡ）などの芳香族ジアミンを原料として用い、吸水性の低減や弾性率の向上などを実現したポリアミドも多数知られている。 Polyamides are widely used in applications such as hollow molded containers, films, sheet packaging materials, engineer plastics, and fibers because of their excellent physical and mechanical properties. Typical examples are aliphatic polyamides such as nylon 66, but these other aromatic diamines such as paraxylylenediamine (PXDA) and metaxylylenediamine (MXDA) are used as raw materials to reduce water absorption and elastic modulus. A number of polyamides that realize such improvements are also known.
ポリアミドは、熱に対してポリエステル等より比較的不安定であり、熱劣化や熱酸化劣化によりゲル化や黄変等を起こすことがある。 Polyamide is relatively unstable with respect to heat than polyester and the like, and may cause gelation or yellowing due to thermal deterioration or thermal oxidative deterioration.
ポリアミドの熱劣化を抑える方法として、ポリアミド中にホスホン酸化合物もしくは亜リン酸化合物およびアルカリ金属を添加する方法が提案されている（例えば、特許文献１参照）。これらは、ポリアミド中の三次元化した網状構造のゲル化の防止の方策であって、添加剤等のフィルター詰りに及ぼす影響については記載が無い。 As a method for suppressing the thermal degradation of the polyamide, a method of adding a phosphonic acid compound or a phosphorous acid compound and an alkali metal to the polyamide has been proposed (for example, see Patent Document 1). These are measures for preventing gelation of a three-dimensional network structure in polyamide, and there is no description about the influence of additives and the like on filter clogging.
ポリアミドの熱劣化を抑える方法として、ポリアミド中にホスフィン酸化合物、亜ホスホン酸化合物、ホスホン酸化合物もしくは亜リン酸化合物およびアルカリ金属とフェニレンジアミンおよび／またはその誘導体をポリアミドに対して０．０１〜２重量％と配合する方法が提案されている（例えば、特許文献２参照）。これらについても、ポリアミド中の三次元化した網状構造のゲル化防止の方策であって、添加剤等のフィルター詰り等異物に関する記載が無い。 As a method for suppressing thermal degradation of polyamide, 0.01 to 2 of phosphinic acid compound, phosphonous acid compound, phosphonic acid compound or phosphorous acid compound and alkali metal and phenylenediamine and / or a derivative thereof are contained in the polyamide. A method of blending with wt% has been proposed (see, for example, Patent Document 2). These are also measures for preventing gelation of the three-dimensional network structure in polyamide, and there is no description regarding foreign matters such as filter clogging of additives and the like.
ポリアミドの融点以下でかつ酸素の存在しない系での熱劣化について防止する方法として、ピロ亜燐酸塩、有機ホスフィン酸のアミド化合物、亜リン酸のモノもしくはジエステルのマグネシウム塩もしくはバリウム塩、オルトリン酸のモノもしくはジエステルのバリウム塩などを添加する方法が提案されている（例えば、特許文献３〜６参照）。しかし、これらの文献にも、添加剤等のフィルター詰りについての記載等は無く、後工程における生産性について、考慮していない。 Methods for preventing thermal degradation in systems below the melting point of polyamide and in the absence of oxygen include pyrophosphites, organic phosphinic acid amide compounds, phosphorous acid mono- or diester magnesium or barium salts, orthophosphoric acid A method of adding a barium salt of a mono- or diester has been proposed (see, for example, Patent Documents 3 to 6). However, these documents also do not describe the filter clogging of additives and the like, and do not consider the productivity in the subsequent process.
また、メタキシリレンジアミンとアジピン酸からなるポリアミドのゲル化物の防止対策として滑剤、有機リン系安定剤、ヒンダードフェノール類化合物、ヒンダードアミン類化合物から選ばれた少なくとも１種類以上を０．０００５〜０．５重量部添加して検討している（例えば、特許文献７参照）。これについても、フィルターに異物詰りの対策等の記載は確認できない。
本発明者らは前記の従来技術の問題点を解決するために鋭意検討の結果、ジアミン成分として、主にメタキシリレンジアミン（ＭＸＤＡ）を、ジカルボン酸成分として、主にアジピン酸（ＡＡ）を含むポリアミド樹脂を含有するポリアミド樹脂組成物であって、この組成物中のリン原子（Ｐ）とナトリウム金属（Ｎａ）の含有量について特定の範囲に規定することにより、フィルターを通過する際に、詰り物が少なく、色調も良好で生産性が高く、かつ重合時および成形時の熱劣化や熱酸化劣化が少ないポリアミド樹脂組成物を提供することを目的とする。 As a result of intensive studies to solve the problems of the prior art, the present inventors have mainly used metaxylylenediamine (MXDA) as a diamine component, and mainly adipic acid (AA) as a dicarboxylic acid component. A polyamide resin composition containing a polyamide resin, wherein the content of phosphorus atoms (P) and sodium metal (Na) in the composition is specified within a specific range, when passing through a filter, An object of the present invention is to provide a polyamide resin composition with less clogging, good color tone, high productivity, and little thermal degradation or thermal oxidation degradation during polymerization and molding.
上記目的を達成するため、本発明においては、ジアミン成分として、主にメタキシリレンジアミン（ＭＸＤＡ）を、ジカルボン酸成分として、主にアジピン酸（ＡＡ）を含むポリアミド樹脂を含有するポリアミド樹脂組成物であって、前記ポリアミド樹脂組成物のリン原子（Ｐ）とナトリウム原子（Ｎａ）の含有量について下記式（１）および（２）：
３０≦Ｐ＜２００ｐｐｍ…（１）
３．０＜Ｎａ／Ｐモル比＜７．０…（２）
を満たすポリアミド樹脂組成物が提供される。
In order to achieve the above object, in the present invention, a polyamide resin composition containing a polyamide resin mainly containing metaxylylenediamine (MXDA) as a diamine component and mainly containing adipic acid (AA) as a dicarboxylic acid component. And about the content of the phosphorus atom (P) and sodium atom (Na) of the said polyamide resin composition, following formula (1) and (2):
30 ≦ P <200 ppm (1)
3.0 <Na / P molar ratio <7.0 ... (2)
A polyamide resin composition satisfying the above requirements is provided.
好ましい実施形態において、本発明のポリアミド樹脂組成物は、カラーｂ値（Ｃｏ−ｂ）が下記式（３）：
−３＜Ｃｏ−ｂ＜５…（３）
を満たし得る。
In a preferred embodiment, the polyamide resin composition of the present invention has a color b value (Co-b) of the following formula (3):
-3 <Co-b <5 (3)
Can meet.
好ましい実施形態において、本発明のポリアミド樹脂組成物は、背圧上昇係数Ｋ＊について、下記式（４）：
０＜Ｋ＊＜１５… （４）
を満たし得、
ここで、Ｋ＊は背圧上昇係数
Ｋ＊＝［ΔＰ（ＭＰａ）／Ｔ（ｈｒ）］／［Ｑ（ｋｇ／ｈｒ）／Ｓ（ｃｍ２）］
であり、式中、ΔＰ（ＭＰａ）は、ギヤポンプ二次圧のＴ時間後の圧力−初期圧であり、Ｔ（ｈｒ）は、ポリアミド樹脂組成物をフィルターで濾過した時間であり、Ｑ（ｋｇ／ｈｒ）は、ポリアミド樹脂組成物の吐出量であり、そしてＳ（ｃｍ２）は、フィルターの濾過面積であり、
フィルター濾過径は２０μｍである。
In a preferred embodiment, the polyamide resin composition of the present invention has the following formula (4) for the back pressure increase coefficient K *:
0 <K * <15 ... (4)
Can meet
Here, K * is a back pressure increase coefficient K * = [ΔP (MPa) / T (hr)] / [Q (kg / hr) / S (cm 2 )]
In the formula, ΔP (MPa) is a pressure-initial pressure after T hours of the secondary pressure of the gear pump, T (hr) is a time when the polyamide resin composition is filtered with a filter, and Q (kg / Hr) is the discharge amount of the polyamide resin composition, and S (cm 2 ) is the filtration area of the filter,
The filter filtration diameter is 20 μm.
本発明は、ガソリンタンク材、飲料用ボトルをはじめとする中空成形容器、フィルム、シ−トなどの成形体の素材として好適に用いられるポリアミド樹脂組成物に関するものである。また、重合する際やそれらを成形する際の熱安定性に良好で、かつ、黄変の程度が少なく色調に優れ、かつ、フィルター背圧上昇が少なく、生産性に優れたポリアミド樹脂組成物に関する。本発明によれば、特定の量および比でリン化合物とナトリウム化合物とを含有することにより、フィルター詰まりを低く抑える一方で、重合および成形時の熱劣化に起因する黄変を生じにくいポリアミド樹脂組成物が提供される。 The present invention relates to a polyamide resin composition that can be suitably used as a material for molded articles such as gasoline tank materials, beverage bottles, hollow molded containers, films, sheets, and the like. The present invention also relates to a polyamide resin composition having good thermal stability when polymerizing or molding them, excellent in color tone with little yellowing, and little increase in filter back pressure, and excellent productivity. . According to the present invention, a polyamide resin composition that contains a phosphorus compound and a sodium compound in a specific amount and ratio to keep filter clogging low, and is less likely to cause yellowing due to thermal degradation during polymerization and molding. Things are provided.
以下、本発明のポリアミド樹脂組成物の実施の形態を具体的に説明する。 Hereinafter, embodiments of the polyamide resin composition of the present invention will be specifically described.
本発明に用いられるポリアミド樹脂のジカルボン酸成分として、主にアジピン酸を使用し、その他にセバシン酸、スベリン酸、アゼライン酸、ウンデカンカルボン酸、ウンデカン二酸、ダイマー酸等の脂肪族ジカルボン酸、１，４−シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、オルソフタル酸、キシリレンジカルボン酸、ナフタレンジカルボン酸などの芳香族ジカルボン酸等を１種もしくは２種以上を任意の割合で使用できる。 As the dicarboxylic acid component of the polyamide resin used in the present invention, adipic acid is mainly used. In addition, aliphatic dicarboxylic acids such as sebacic acid, suberic acid, azelaic acid, undecane carboxylic acid, undecanedioic acid, dimer acid, etc. , 4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, xylylene dicarboxylic acid, naphthalenedicarboxylic acid and other aromatic dicarboxylic acids, etc. Can be used.
本発明のポリアミド樹脂組成物に含まれるポリアミド樹脂は、ジカルボン酸成分として、主にアジピン酸を含み、好ましくは８０モル％以上、より好ましくは９０モル％以上、さらに好ましくは９５モル％以上含む。 The polyamide resin contained in the polyamide resin composition of the present invention mainly contains adipic acid as the dicarboxylic acid component, preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.
前記のポリアミド樹脂組成物中のポリアミド樹脂のジアミン成分として、主にメタキシリレンジアミンを使用し、その他にエチレンジアミン、１−メチルエチレンジアミン、１，３−プロピレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン等の脂肪族ジアミン類、シクロヘキサンジアミン、ビス−（４−アミノシクロへキシル）メタン等の脂環式ジアミン類、パラキシリレンジアミン、パラ−ビス−（２−アミノエチル）ベンゼンのような芳香族ジアミン類が使用できる。 As the diamine component of the polyamide resin in the polyamide resin composition, metaxylylenediamine is mainly used. Besides, ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexa Aliphatic diamines such as methylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, cyclohexane diamine, bis- (4-aminocyclohexyl) methane, etc. Aromatic diamines such as alicyclic diamines, paraxylylenediamine, para-bis- (2-aminoethyl) benzene can be used.
これらジアミンは、１種もしくは２種以上を任意の割合で組み合わせても使用できる。 These diamines can be used by combining one kind or two or more kinds in any ratio.
本発明のポリアミド樹脂組成物に含まれるポリアミド樹脂は、ジアミン成分として、主にメタキシリレンジアミンを含み、好ましくは８０モル％以上、より好ましくは９０モル％以上、さらに好ましくは９５モル％以上含む。 The polyamide resin contained in the polyamide resin composition of the present invention mainly contains metaxylylenediamine as a diamine component, preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. .
前記のジアミン及び、ジカルボン酸以外にも、ε−カプロラクタムやラウロラクタム等のラクタム類、アミノカプロン酸、アミノウンデカン酸等の脂肪族アミノカルボン酸類、パラ−アミノメチル安息香酸のような芳香族アミノカルボン酸等も共重合成分として使用できる。とりわけ、ε−カプロラクタムの使用が望ましい。 In addition to the diamine and dicarboxylic acid, lactams such as ε-caprolactam and laurolactam, aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid Etc. can also be used as a copolymerization component. In particular, the use of ε-caprolactam is desirable.
本発明のポリアミド樹脂組成物に含まれ得る重合体の例としてはポリメタキシリレンアジパミドのような単独重合体、及びメタキシリレンジアミン／アジピン酸／イソフタル酸共重合体、メタキシリレン／パラキシリレンアジパミド共重合体等が挙げられる。 Examples of polymers that can be included in the polyamide resin composition of the present invention include homopolymers such as polymetaxylylene adipamide, and metaxylylenediamine / adipic acid / isophthalic acid copolymers, metaxylylene / paraxylylene. Examples include adipamide copolymers.
本発明のポリアミド樹脂組成物中のリン原子およびナトリウム原子の含有量としては、リン原子（Ｐ）とナトリウム原子（Ｎａ）が下記式（１）、（２）の範囲を満たすことが好ましい。 As content of the phosphorus atom and sodium atom in the polyamide resin composition of this invention, it is preferable that a phosphorus atom (P) and a sodium atom (Na) satisfy | fill the range of following formula (1), (2).
３０≦Ｐ＜２００ｐｐｍ…（１） ｐｐｍはポリマー１ｋｇ当りの量（ｍｇ）
３．０＜Ｎａ／Ｐモル比＜７．０…（２）
リン原子の含有量Ｐに関して、下限はより好ましくは４０ｐｐｍ、さらに好ましくは５０ｐｐｍ、特に好ましくは９０ｐｐｍである。上限としては好ましくは１７０ｐｐｍ、より好ましくは１６０ｐｐｍ、さらに好ましくは１５０ｐｐｍ、特に好ましくは１３０ｐｐｍである。リン原子含有量が少なすぎる場合には、熱安定性が低下しやすく、ポリマーの色調を悪化させやすい。また、逆にリン原子の含有量多すぎる場合には、添加剤にかかる原料費が多くなり、コストアップの一因となったり、フィルターの異物詰りが多くくなり、後工程での生産性の低下が懸念される。
30 ≦ P <200 ppm (1) ppm is the amount per kg of polymer (mg)
3.0 <Na / P molar ratio <7.0 ... (2)
Regarding the phosphorus atom content P, the lower limit is more preferably 40 ppm, still more preferably 50 ppm, and particularly preferably 90 ppm. The upper limit is preferably 170 ppm, more preferably 160 ppm, still more preferably 150 ppm, and particularly preferably 130 ppm. When the phosphorus atom content is too small, the thermal stability tends to be lowered, and the color tone of the polymer tends to be deteriorated. On the other hand, if the phosphorus atom content is too high, the raw material costs for the additive will increase, leading to an increase in cost, and increasing the number of foreign substances clogged in the filter. There is concern about the decline.
また、Ｎａ／Ｐモル比に関して、下限はより好ましくは３．５、さらに好ましくは４．０、さらに好ましくは４．５である。上限はより好ましくは６．５、さらに好ましくは６．０、いっそう好ましくは５．５である。Ｎａ／Ｐモル比が小さすぎる場合、粘度上昇が激しく、成形時のゲル化物の混入が多くなる危険性があり、溶融濾過時の背圧上昇を生じやすい。また、逆にＮａ／Ｐモル比が大きすぎる場合、重合反応速度が非常に遅くなりやすく、生産性が低下しやすい。 In addition, regarding the Na / P molar ratio, the lower limit is more preferably 3.5, still more preferably 4.0, and still more preferably 4.5. The upper limit is more preferably 6.5, still more preferably 6.0, and still more preferably 5.5. When the Na / P molar ratio is too small, the viscosity rises drastically, and there is a risk that the gelled product will be mixed during molding, and the back pressure during melt filtration tends to increase. Conversely, when the Na / P molar ratio is too large, the polymerization reaction rate tends to be very slow, and the productivity tends to decrease.
ナトリウム原子含有量の下限は、好ましくは８０ｐｐｍ、より好ましくは１２０ｐｐｍ、さらに好ましくは１５０ｐｐｍ、特に好ましくは２００ｐｐｍである。上限としては好ましくは９００ｐｐｍ、より好ましくは６００ｐｐｍである。 The lower limit of the sodium atom content is preferably 80 ppm, more preferably 120 ppm, still more preferably 150 ppm, and particularly preferably 200 ppm. The upper limit is preferably 900 ppm, more preferably 600 ppm.
本発明に用いられるポリアミド樹脂組成物中のリン原子を含有する化合物としては、下記化学式（Ｃ−１）〜（Ｃ−４）で表される化合物が挙げられる。 Examples of the compound containing a phosphorus atom in the polyamide resin composition used in the present invention include compounds represented by the following chemical formulas (C-1) to (C-4).
化学式（Ｃ−１）で表されるホスフィン酸化合物としては、ジメチルホスフィン酸、フェニルメチルホスフィン酸、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸エチル、
As the phosphinic acid compound represented by the chemical formula (C-1), dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, ethyl hypophosphite,
化学式（Ｃ−２）で表される亜ホスホン酸化合物としては、フェニル亜ホスホン酸、フェニル亜ホスホン酸ナトリウム、フェニル亜ホスホン酸エチルなどがある。 Examples of the phosphonous acid compound represented by the chemical formula (C-2) include phenylphosphonous acid, sodium phenylphosphonite, and ethyl phenylphosphonite.
化学式（Ｃ−３）で表されるホスホン酸化合物としてはフェニルホスホン酸、エチルホスホン酸、フェニルホスホン酸ナトリウム、フェニルホスホン酸ジエチル、エチルホスホン酸ナトリウムなどがある。
化学式（Ｃ−４）で表される亜リン酸化合物としては、亜リン酸、亜リン酸水素ナトリウム、亜リン酸ナトリウム、亜リン酸トリエチル、亜リン酸トリフェニル、ピロ亜リン酸などがある。 また、本発明のポリアミド樹脂組成物において使用され得るナトリウム金属化合物としては、水酸化ナトリウム、酢酸ナトリウム、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、ナトリウムブトキシド、炭酸ナトリウムなどが挙げられるが、とりわけ、水酸化ナトリウム、酢酸ナトリウムを使用するのが好ましい。但し、いずれもこれらの化合物に限定されるものではない。
Examples of the phosphonic acid compound represented by the chemical formula (C-3) include phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, diethyl phenylphosphonate, and sodium ethylphosphonate.
Examples of the phosphorous acid compound represented by the chemical formula (C-4) include phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid and the like. . Examples of the sodium metal compound that can be used in the polyamide resin composition of the present invention include sodium hydroxide, sodium acetate, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium carbonate, etc. Sodium hydroxide and sodium acetate are preferably used. However, any of them is not limited to these compounds.
本発明で用いられるポリアミド樹脂組成物に前記リン原子含有化合物を配合するには、ポリアミドの重合前の原料、重合中に添加するかあるいは該重合体に溶融混合してもよい。固相重合の際のポリアミドの熱劣化を防止する目的のためには、重合開始前にリン原子含有化合物を添加しておくことが好ましい。 In order to add the phosphorus atom-containing compound to the polyamide resin composition used in the present invention, it may be added during the polymerization of the raw material before the polymerization of the polyamide, or may be melt mixed with the polymer. For the purpose of preventing thermal degradation of the polyamide during solid phase polymerization, it is preferable to add a phosphorus atom-containing compound before the start of polymerization.
また、本発明のポリアミド樹脂組成物は、チップに成形した際のＣｏ−ｂ値が下記式（３）を満たすことが望ましい。 Moreover, as for the polyamide resin composition of this invention, it is desirable for the Co-b value at the time of shape | molding to a chip | tip to satisfy | fill following formula (3).
−３＜Ｃｏ−ｂ＜５…（３）
Ｃｏ−ｂ値の上限は、好ましくは４であり、より好ましくは３であり、さらに好ましくは２である。Ｃｏ−ｂ値が高すぎる場合、ボトル、フィルム、繊維等の後工程の加工時に黄色の着色が目立ち製品としての品位が落ちやすい。また、Ｃｏ−ｂ値を過度に低くしようとすると、リン原子含有化合物等の安定剤の添加量が多くなり過ぎやすく、コスト面で不利に働き、かつ添加剤に起因するフィルター詰まりが起こりやすい。
-3 <Co-b <5 (3)
The upper limit of the Co-b value is preferably 4, more preferably 3, and even more preferably 2. When the Co-b value is too high, yellow coloration is conspicuous during post-processing of bottles, films, fibers, and the like, and the quality of the product tends to deteriorate. On the other hand, if the Co-b value is attempted to be excessively low, the amount of stabilizer such as a phosphorus atom-containing compound added tends to be excessive, which is disadvantageous in terms of cost, and filter clogging due to the additive tends to occur.
本発明ポリアミド樹脂組成物は、ジアミンとジカルボン酸から生成するアミノカルボン酸塩の水溶液を加圧下および常圧下に加熱して反応させる方法あるいは常圧下でジアミンとジカルボン酸を加熱して直接反応させる方法により製造することができる。また、これらの溶融重縮合反応により得られた前記ポリアミドのチップを固相重合することによって、さらに高粘度のポリアミド樹脂組成物を得ることができる。 The polyamide resin composition of the present invention is a method in which an aqueous solution of an aminocarboxylate salt formed from a diamine and a dicarboxylic acid is heated and reacted under pressure and normal pressure, or a method in which a diamine and dicarboxylic acid are heated and reacted directly under normal pressure Can be manufactured. Furthermore, a polyamide resin composition having a higher viscosity can be obtained by solid-phase polymerization of the polyamide chips obtained by the melt polycondensation reaction.
前記のポリアミド樹脂組成物の製造における重縮合反応は、回分式反応装置で行っても良いしまた連続式反応装置で行っても良い。 The polycondensation reaction in the production of the polyamide resin composition may be performed in a batch reactor or a continuous reactor.
本発明のポリアミド樹脂組成物は、背圧上昇係数Ｋ＊について、下記式（４）を満たすことが好ましい。 The polyamide resin composition of the present invention preferably satisfies the following formula (4) for the back pressure increase coefficient K *.
０＜Ｋ＊＜１５ … （４）
Ｋ＊は背圧上昇係数
Ｋ＊＝［ΔＰ（ＭＰａ）／Ｔ（ｈｒ）］／［Ｑ（ｋｇ／ｈｒ）／Ｓ（ｃｍ２）］
であり、フィルター濾過径は２０μｍである。
ポリアミド樹脂組成物を一軸押出機（ヒーター設定温度２８５℃、平均滞留時間１０分）を使用し、溶解させ、ギヤポンプを使用し、３〜６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録し、４ｈｒ流した後のその圧力差を下記式にあてはめ、背圧上昇係数（Ｋ＊）を求めた。
0 <K * <15 (4)
K * is a back pressure increase coefficient K * = [ΔP (MPa) / T (hr)] / [Q (kg / hr) / S (cm 2 )]
The filter filtration diameter is 20 μm.
The polyamide resin composition was dissolved using a single screw extruder (heater set temperature 285 ° C., average residence time 10 minutes) and extruded at a constant rate of 3 to 6 g / min using a gear pump. Foreign matter in the polymer is filtered through a filter with a filtration diameter of 20 μm, the pressure on the secondary side of the gear pump is recorded over time, the pressure difference after flowing for 4 hours is applied to the following formula, and the back pressure increase coefficient (K *) Asked.
Ｋ＊＝［ΔＰ（ＭＰａ）／Ｔ（ｈｒ）］／［Ｑ（ｋｇ／ｈｒ）／Ｓ（ｃｍ２）］
ΔＰ（ＭＰａ）：ギヤポンプ二次圧の４ｈｒ後の圧力−初期圧
Ｔ（ｈｒ）：ポリアミド樹脂組成物をフィルターで濾過した時間 （４ｈｒ）
Ｑ（ｋｇ／ｈｒ）：ポリアミド樹脂組成物の吐出量 （３〜６ｇ／ｍｉｎ）
Ｓ（ｃｍ２）：フィルターの濾過面積 （１．５３８ｃｍ２）
背圧上昇係数Ｋ＊はより好ましくは１０以下、さらに好ましくは８以下、ひときわ好ましくは７以下、いっそう好ましくは６以下、特に好ましくは５未満である。
K * = [ΔP (MPa) / T (hr)] / [Q (kg / hr) / S (cm 2 )]
ΔP (MPa): Pressure after 4 hours of gear pump secondary pressure-initial pressure T (hr): Time when the polyamide resin composition is filtered through a filter (4 hours)
Q (kg / hr): discharge amount of polyamide resin composition (3 to 6 g / min)
S (cm 2 ): Filtration area of the filter (1.538 cm 2 )
The back pressure increase coefficient K * is more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less, still more preferably 6 or less, and particularly preferably less than 5.
背圧上昇係数Ｋ＊の下限については、添加剤の配合なしのときのＫ＊と同じ値にまで下げることが好ましく、添加剤なしの場合のＫ＊の値が現実的には下限の一つの目安となる。Ｋ＊の下限は、特に限定されないが、１つの実施態様では１であり、別の実施態様では１．５であり、さらに別の実施態様では２であり、さらなる実施態様では２．５である。 The lower limit of the back pressure increase coefficient K * is preferably lowered to the same value as K * when no additive is added, and the value of K * without additive is practically one of the lower limits. It becomes a standard. The lower limit of K * is not particularly limited, but is 1 in one embodiment, 1.5 in another embodiment, 2 in yet another embodiment, and 2.5 in a further embodiment. .
また、背圧上昇係数Ｋ＊が高すぎる場合には、ボトル成形時、フィルムの製膜時などフィルター濾過を必要とする後工程において、詰りの発生頻度が高くなりやすく、生産性の低下によるコストアップとなる可能性が高い。Ｋ＊が５以上１５未満の場合には、わずかにフィルターの目詰まりが観察されるが、実用上問題となるレベルではなく、十分に本発明の目的を達成することができる。ただし、極めて長時間の連続生産を行う場合には、目詰まりが増大する可能性があり得るので、極めて長時間の連続生産を行う場合には、Ｋ＊が５未満であることが好ましい。 In addition, if the back pressure increase coefficient K * is too high, clogging is likely to occur more frequently in subsequent processes that require filter filtration, such as when forming a bottle or when forming a film. There is a high possibility of being up. When K * is 5 or more and less than 15, clogging of the filter is slightly observed, but it is not at a practically problematic level, and the object of the present invention can be sufficiently achieved. However, there is a possibility that clogging may increase when continuous production is performed for an extremely long time. Therefore, it is preferable that K * is less than 5 when continuous production is performed for an extremely long time.
以下本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定させるものではない。なお、本明細書中における主な特性値の測定法を以下に説明する。
（１）ポリアミド樹脂組成物の相対粘度（ＲＶ）
試料０．２５ｇを９６％硫酸２５ｍｌに溶解し、この溶液１０ｍｌをオストワルド粘度管にて２０℃で測定、下式より求めた。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The main characteristic value measuring methods in this specification will be described below.
(1) Relative viscosity (RV) of polyamide resin composition
0.25 g of a sample was dissolved in 25 ml of 96% sulfuric acid, and 10 ml of this solution was measured at 20 ° C. with an Ostwald viscosity tube and obtained from the following formula.
ＲＶ＝ｔ／ｔ０
ｔ０：溶媒の落下秒数
ｔ：試料溶液の落下秒数
（２）ポリアミド樹脂組成物のカラーｂ値
カラーメーター（日本電色社製、Ｍｏｄｅｌ １００１ＤＰ）を使用し、重合後に得られたチップ状の樹脂を測定セルに詰めて得られた測定サンプルのカラーｂ値を測定した。
（３）Ｐの分析
試料を炭酸ソーダ共存下において乾式灰化分解するか、硫酸・硝酸・過塩素酸系または硫酸・過酸化水素水系において湿式分解し、リンを正リン酸とした。次いで、１ｍｏｌ／Ｌ硫酸溶液中においてモリブデン酸塩を反応させて、リンモリブデン酸とし、これを硫酸ヒドラジンで還元して生ずるヘテロポリ青の８３０ｎｍの吸光度を吸光光度計（島津製作所製、ＵＶ−１５０−０２）で測定して比色定量した。
（４）Ｎａ、Ｌｉの分析
試料を白金ルツボにて、灰化分解し、６ｍｏｌ／Ｌ塩酸を加えて蒸発乾固した。１．２ｍｏｌ／Ｌ塩酸で溶解し、その溶液を原子吸光（島津製作所製、ＡＡ−６４０−１２）で定量した。
（５）背圧上昇試験
ポリアミド樹脂組成物を一軸押出機（ヒーター設定温度２８５℃、平均滞留時間１０分）を使用し、溶解させ、ギヤポンプを使用し、３〜６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後のその圧力差を下記式にあてはめ、背圧上昇係数（Ｋ＊）を求めた。
RV = t / t 0
t 0 : number of seconds the solvent falls
t: Number of seconds for dropping the sample solution (2) Color b value of the polyamide resin composition Using a color meter (Model 1001DP, manufactured by Nippon Denshoku), the chip-shaped resin obtained after polymerization was packed in a measurement cell. The color b value of the obtained measurement sample was measured.
(3) Analysis of P The sample was subjected to dry ashing decomposition in the presence of sodium carbonate, or wet decomposition in sulfuric acid / nitric acid / perchloric acid system or sulfuric acid / hydrogen peroxide system, and phosphorus was converted to normal phosphoric acid. Subsequently, the molybdate is reacted in a 1 mol / L sulfuric acid solution to form phosphomolybdic acid, and this is reduced with hydrazine sulfate. The absorbance at 830 nm of the heteropoly blue produced is a spectrophotometer (Shimadzu Corporation, UV-150- 02) and colorimetrically determined.
(4) Analysis of Na and Li The sample was incinerated and decomposed with a platinum crucible, and 6 mol / L hydrochloric acid was added to evaporate to dryness. The resultant was dissolved in 1.2 mol / L hydrochloric acid, and the solution was quantified by atomic absorption (manufactured by Shimadzu Corporation, AA-640-12).
(5) Back pressure increase test The polyamide resin composition was dissolved using a single screw extruder (heater set temperature 285 ° C., average residence time 10 minutes), and a certain amount was extruded at 3 to 6 g / min using a gear pump. . Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The pressure difference after flowing for 4 hours was applied to the following formula to determine the back pressure increase coefficient (K *).
Ｋ＊＝［ΔＰ（ＭＰａ）／Ｔ（ｈｒ）］／［Ｑ（ｋｇ／ｈｒ）／Ｓ（ｃｍ２）］
ΔＰ（ＭＰａ）：ギヤポンプ二次圧の４ｈｒ後の圧力−初期圧
Ｔ（ｈｒ）：ポリアミド樹脂組成物をフィルターで濾過した時間 （４ｈｒ）
Ｑ（ｋｇ／ｈｒ）：ポリアミド樹脂組成物の吐出量 （３〜６ｇ／ｍｉｎ）
Ｓ（ｃｍ２）：フィルターの濾過面積 （１．５３８ｃｍ２）
実施例１
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７．６６ｋｇ、アジピン酸２９．６５ｋｇを内温８５℃にて調合し、透明な溶液とした。添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ １．３７ｇ、ＣＨ３ＣＯＯＮａ ３．７１ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度１９０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の相対粘度（ＲＶ）は２．１０、Ｃｏ−ｂ値は３．３であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、冷却後チップを得た。水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝４０ｐｐｍ、Ｎａ＝１３４ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は２．５であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
K * = [ΔP (MPa) / T (hr)] / [Q (kg / hr) / S (cm 2 )]
ΔP (MPa): Pressure after 4 hours of gear pump secondary pressure-initial pressure T (hr): Time when the polyamide resin composition is filtered through a filter (4 hours)
Q (kg / hr): discharge amount of polyamide resin composition (3 to 6 g / min)
S (cm 2 ): Filtration area of the filter (1.538 cm 2 )
Example 1
In a 250-liter preparation can equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 27.66 kg of metaxylylenediamine and 29.65 kg of adipic acid were precisely weighed to an internal temperature of 85 ° C. To make a clear solution. As additives, 1.37 g of NaH 2 PO 2 .H 2 O and 3.71 g of CH 3 COONa were added and stirred for 15 minutes. The solution was transferred to a reaction can having an internal volume of 270 liters, and reacted by stirring under conditions of a can internal temperature of 190 ° C. and a can internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The obtained resin had a relative viscosity (RV) of 2.10 and a Co-b value of 3.3. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and a chip was obtained after cooling. The moisture content was 200 ppm. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 40 ppm, Na = 134 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 2.5. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例２
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ １．７１ｇ、ＣＨ３ＣＯＯＮａ ３．９７ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．２３、Ｃｏ−ｂ値は３．１であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、冷却後チップを得た。その時の水分率は２５０ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝５０ｐｐｍ、Ｎａ＝１４８ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は３．５であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 2
The polyamide polymerization method was carried out in the same manner as in Example 1 except that 1.71 g of NaH 2 PO 2 .H 2 O and 3.97 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.23 and a Co-b value of 3.1. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and a chip was obtained after cooling. The moisture content at that time was 250 ppm. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 50 ppm, Na = 148 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 3.5. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例３
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ３．４２ｇ、ＣＨ３ＣＯＯＮａ ６．６２ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は−０．８であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は−１．１、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１００ｐｐｍ、Ｎａ＝２６０ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は１４であった。フィルターを確認したところ、目詰まりがわずかに観察されたが、実用上問題とならないレベルであった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 3
The polyamide polymerization method was carried out in the same manner as in Example 1 except that 3.42 g of NaH 2 PO 2 .H 2 O and 6.62 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of -0.8. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was -1.1, and the moisture content was 200 ppm. Further, the residual amounts of phosphorus atom, sodium atom and lithium atom were P = 100 ppm, Na = 260 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 14. When the filter was checked, clogging was slightly observed, but it was at a level that does not cause any practical problems. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例４
ポリアミドの溶融重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ３．４２ｇ、ＣＨ３ＣＯＯＮａ ７．９５ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１０、Ｃｏ−ｂ値は−０．９であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃、１２ｈｒで乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は−１．３、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１００ｐｐｍ、Ｎａ＝２９７ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は７．８であった。フィルターを確認したところ、目詰まりがわずかに観察されたが、実用上問題とならないレベルであった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 4
The polyamide melt polymerization method was carried out in the same manner as in Example 1 except that 3.42 g of NaH 2 PO 2 .H 2 O and 7.95 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.10 and a Co-b value of -0.9. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and further solid phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was -1.3, and the moisture content was 200 ppm. Further, the residual amounts of phosphorus atom, sodium atom and lithium atom were P = 100 ppm, Na = 297 ppm, and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 7.8. When the filter was checked, clogging was slightly observed, but it was at a level that does not cause any practical problems. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例５
ポリアミドの溶融重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ３．４２ｇ、ＣＨ３ＣＯＯＮａ １０．５９ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１２、Ｃｏ−ｂ値は１．０であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させた。その時のリン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１００ｐｐｍ、Ｎａ＝３７１ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は３．７であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 5
Polyamide melt polymerization was carried out in the same manner as in Example 1 except that 3.42 g of NaH 2 PO 2 .H 2 O and 10.59 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.12 and a Co-b value of 1.0. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours. The residual amounts of phosphorus atoms, sodium atoms, and lithium atoms at that time were P = 100 ppm, Na = 371 ppm, and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The coefficient of increase in back pressure (K *) after flowing for 4 hours was 3.7. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例６
ポリアミドの溶融重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ３．４２ｇ、ＣＨ３ＣＯＯＮａ １０．５９ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１２、Ｃｏ−ｂ値は１．０であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は２．０、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１００ｐｐｍ、Ｎａ＝３７１ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は４．５であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 6
Polyamide melt polymerization was carried out in the same manner as in Example 1 except that 3.42 g of NaH 2 PO 2 .H 2 O and 10.59 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.12 and a Co-b value of 1.0. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was 2.0, and the moisture content was 200 ppm. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 100 ppm, Na = 371 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 4.5. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例７
ポリアミドの溶融重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ５．１３ｇ、ＣＨ３ＣＯＯＮａを１５．８９ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は−０．８であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．５０、Ｃｏ−ｂ値は１．５、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１５０ｐｐｍ、Ｎａ＝５５７ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は５．２であった。フィルターを確認したところ、目詰まりがわずかに観察されたが、実用上問題とならないレベルであった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 7
Polyamide melt polymerization was carried out in the same manner as in Example 1 except that 5.13 g of NaH 2 PO 2 .H 2 O and 15.89 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of -0.8. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.50, the Co-b value was 1.5, and the moisture content was 200 ppm. Further, the residual amounts of phosphorus atom, sodium atom and lithium atom were P = 150 ppm, Na = 557 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 5.2. When the filter was checked, clogging was slightly observed, but it was at a level that does not cause any practical problems. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例８
ポリアミドの溶融重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ６．５０ｇ、ＣＨ３ＣＯＯＮａを２５．１６ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は３．５であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．１０、Ｃｏ−ｂ値は２．５、水分率は２５０ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１９０ｐｐｍ、Ｎａ＝８４６ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は４．０であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 8
The polyamide melt polymerization method was carried out in the same manner as in Example 1 except that 6.50 g of NaH 2 PO 2 .H 2 O and 25.16 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of 3.5. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.10, the Co-b value was 2.5, and the moisture content was 250 ppm. Moreover, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 190 ppm, Na = 846 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 4.0. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例９
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７．６６ｋｇ、アジピン酸２６．４１ｋｇ、テレフタル酸３．３４ｋｇを内温１００℃にて調合し、透明な溶液とした。添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ５．１３ｇ、ＣＨ３ＣＯＯＮａを１３．９１ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度１９０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の相対粘度（ＲＶ）は２．３５、Ｃｏ−ｂ値は４．９であった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１５０ｐｐｍ、Ｎａ＝５０１ｐｐｍ、Ｌｉ＝０ｐｐｍであった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、冷却後チップを得た。その時のＲＶは２．３５、Ｃｏ−ｂ値は４．９、水分率は２５０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は１４であった。フィルターを確認したところ、目詰まりがわずかに観察されたが、実用上問題とならないレベルであった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 9
In a 250 liter preparation can equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 27.66 kg of metaxylylenediamine precisely weighed, 26.41 kg of adipic acid, 3.34 kg of terephthalic acid Was prepared at an internal temperature of 100 ° C. to obtain a transparent solution. As additives, 5.13 g of NaH 2 PO 2 .H 2 O and 13.91 g of CH 3 COONa were added and stirred for 15 minutes. The solution was transferred to a reaction can having an internal volume of 270 liters, and reacted by stirring under conditions of a can internal temperature of 190 ° C. and a can internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The obtained resin had a relative viscosity (RV) of 2.35 and a Co-b value of 4.9. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 150 ppm, Na = 501 ppm and Li = 0 ppm. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and a chip was obtained after cooling. At that time, the RV was 2.35, the Co-b value was 4.9, and the moisture content was 250 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 14. When the filter was checked, clogging was slightly observed, but it was at a level that does not cause any practical problems. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
実施例１０
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７．６６ｋｇ、アジピン酸２６．４１ｋｇ、シクロヘキサンジカルボン酸３．４５ｋｇを内温１００℃にて調合し、透明な溶液とした。添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ５．１３ｇ、ＣＨ３ＣＯＯＮａを１３．９１ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度１９０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の相対粘度（ＲＶ）は２．３、Ｃｏ−ｂ値は６．６であった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１５０ｐｐｍ、Ｎａ＝５０１ｐｐｍ、Ｌｉ＝０ｐｐｍであった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、冷却後チップを得た。その時のＲＶは２．３０、Ｃｏ−ｂ値は−２．３、水分率は２５０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は１２であった。フィルターを確認したところ、目詰まりがわずかに観察されたが、実用上問題とならないレベルであった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Example 10
In a 250-liter preparation can equipped with a stirrer, a condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction pipe, 27.66 kg of metaxylylenediamine, 26.41 kg of adipic acid, cyclohexanedicarboxylic acid 3. 45 kg was prepared at an internal temperature of 100 ° C. to obtain a transparent solution. As additives, 5.13 g of NaH 2 PO 2 .H 2 O and 13.91 g of CH 3 COONa were added and stirred for 15 minutes. The solution was transferred to a reaction can having an internal volume of 270 liters, and reacted by stirring under conditions of a can internal temperature of 190 ° C. and a can internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The obtained resin had a relative viscosity (RV) of 2.3 and a Co-b value of 6.6. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 150 ppm, Na = 501 ppm and Li = 0 ppm. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and a chip was obtained after cooling. At that time, the RV was 2.30, the Co-b value was -2.3, and the moisture content was 250 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 12. When the filter was checked, clogging was slightly observed, but it was at a level that does not cause any practical problems. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
比較例１
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ６．８４ｇ、ＣＨ３ＣＯＯＮａを１０．５９ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は−２．２であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は−２．９、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝２００ｐｐｍ、Ｎａ＝４４０ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は２０であった。フィルターを確認したところ、目詰まりが観察された。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Comparative Example 1
Polyamide polymerization was performed in the same manner as in Example 1 except that 6.84 g of NaH 2 PO 2 .H 2 O and 10.59 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of -2.2. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was -2.9, and the moisture content was 200 ppm. The residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 200 ppm, Na = 440 ppm, and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 20. When the filter was checked, clogging was observed. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
比較例２
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ４．５５ｇ、ＣＨ３ＣＯＯＮａ ３．５２ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は−１．０であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は−１．７、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１３３ｐｐｍ、Ｎａ＝１９０ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は２９であった。フィルターを確認したところ、目詰まりが観察された。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物が観察された。
Comparative Example 2
Polyamide polymerization was carried out in the same manner as in Example 1 except that 4.55 g of NaH 2 PO 2 .H 2 O and 3.52 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of -1.0. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was -1.7, and the moisture content was 200 ppm. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 133 ppm, Na = 190 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 29. When the filter was checked, clogging was observed. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was observed.
比較例３
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ０．８６ｇ、ＣＨ３ＣＯＯＮａ ２．６５ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１１、Ｃｏ−ｂ値は５．０であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、冷却後チップを得た。その時の水分率は２５０ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝２５ｐｐｍ、Ｎａ＝９３ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させ、ギヤポンプを使用して６ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は４．５であった。フィルターを確認したところ、目詰まりは無かった。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物は観察されなかった。
Comparative Example 3
The polyamide polymerization method was carried out in the same manner as in Example 1 except that 0.86 g of NaH 2 PO 2 .H 2 O and 2.65 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.11 and a Co-b value of 5.0. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours, and a chip was obtained after cooling. The moisture content at that time was 250 ppm. Further, the residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 25 ppm, Na = 93 ppm and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 6 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 4.5. When the filter was checked, there was no clogging. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was not observed.
比較例４
ポリアミドの重合方法は添加剤としてＮａＨ２ＰＯ２・Ｈ２Ｏ ５．１３ｇ、ＣＨ３ＣＯＯＮａ ３．４２ｇを投入した以外は実施例１と同様に行った。得られた樹脂の相対粘度（ＲＶ）は２．１５、Ｃｏ−ｂ値は−１．０であった。その得られた樹脂を１００Ｌのブレンダーで内温１２０℃にて１２ｈｒ乾燥させ、さらに内温１８０℃で固相重合させ、冷却後チップを得た。その時のＲＶは２．６５、Ｃｏ−ｂ値は−１．５、水分率は２００ｐｐｍであった。また、リン原子、ナトリウム原子およびリチウム原子の残存量はＰ＝１００ｐｐｍ、Ｎａ＝２２０ｐｐｍ、Ｌｉ＝０ｐｐｍであった。そのポリアミド樹脂組成物を、一軸押出機を使用し、溶融させて、ギヤポンプを使用して３ｇ／ｍｉｎで一定量押出した。ポリマー中の異物を濾過径２０μｍのフィルターで濾過し、ギヤポンプの二次側の圧力を経時的に記録した。４ｈｒ流した後の背圧上昇係数（Ｋ＊）は１７であった。フィルターを確認したところ、目詰まりが観察された。得られた押出し成形品の熱劣化状態を観察したところ、熱劣化によるゲル化物が観察された。
Comparative Example 4
The polyamide polymerization method was carried out in the same manner as in Example 1 except that 5.13 g of NaH 2 PO 2 .H 2 O and 3.42 g of CH 3 COONa were added as additives. The obtained resin had a relative viscosity (RV) of 2.15 and a Co-b value of -1.0. The obtained resin was dried with a 100 L blender at an internal temperature of 120 ° C. for 12 hours and further solid-phase polymerized at an internal temperature of 180 ° C. to obtain a chip after cooling. At that time, the RV was 2.65, the Co-b value was -1.5, and the moisture content was 200 ppm. The residual amounts of phosphorus atoms, sodium atoms and lithium atoms were P = 100 ppm, Na = 220 ppm, and Li = 0 ppm. The polyamide resin composition was melted using a single screw extruder and extruded at a constant rate of 3 g / min using a gear pump. Foreign matter in the polymer was filtered through a filter having a filtration diameter of 20 μm, and the pressure on the secondary side of the gear pump was recorded over time. The back pressure increase coefficient (K *) after flowing for 4 hours was 17. When the filter was checked, clogging was observed. When the heat deterioration state of the obtained extrusion-molded product was observed, a gelled product due to heat deterioration was observed.
Claims (3)
３０≦Ｐ＜２００ｐｐｍ…（１）
３．０＜Ｎａ／Ｐモル比＜７．０…（２） A polyamide resin composition comprising a polyamide resin mainly containing metaxylylenediamine (MXDA) as a diamine component and mainly containing adipic acid (AA) as a dicarboxylic acid component, wherein a phosphorus atom (P ) And sodium atom (Na) content satisfy the following formulas (1) and (2):
30 ≦ P <200 ppm (1)
3.0 <Na / P molar ratio <7.0 ... (2)
−３＜Ｃｏ−ｂ＜５…（３） The polyamide resin composition according to claim 1, wherein the color b value (Co-b) satisfies the following formula (3):
-3 <Co-b <5 (3)
０＜Ｋ＊＜１５… （４）
ここで、Ｋ＊は背圧上昇係数
Ｋ＊＝［ΔＰ（ＭＰａ）／Ｔ（ｈｒ）］／［Ｑ（ｋｇ／ｈｒ）／Ｓ（ｃｍ２）］
であり、式中、ΔＰ（ＭＰａ）は、ギヤポンプ二次圧のＴ時間後の圧力と初期圧との差であり、Ｔ（ｈｒ）は、ポリアミド樹脂組成物をフィルターで濾過した時間であり、Ｑ（ｋｇ／ｈｒ）は、ポリアミド樹脂組成物の吐出量であり、そしてＳ（ｃｍ２）は、フィルターの濾過面積であり、
フィルター濾過径は２０μｍである。 The polyamide resin composition according to claim 1 or 2, wherein the back pressure increase coefficient K * satisfies the following formula (4):
0 <K * <15 ... (4)
Here, K * is a back pressure increase coefficient K * = [ΔP (MPa) / T (hr)] / [Q (kg / hr) / S (cm 2 )]
Where ΔP (MPa) is the difference between the initial pressure and the pressure after T hours of the gear pump secondary pressure, and T (hr) is the time when the polyamide resin composition is filtered through a filter, Q (kg / hr) is the discharge amount of the polyamide resin composition, and S (cm 2 ) is the filtration area of the filter,
The filter filtration diameter is 20 μm.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003435792A JP2005194330A (en) | 2003-12-26 | 2003-12-26 | Polyamide resin composition |
| US10/584,268 US7687562B2 (en) | 2003-12-26 | 2004-12-21 | Polyamide resin composition |
| EP04807411A EP1698667A4 (en) | 2003-12-26 | 2004-12-21 | Polyamide resin composition |
| PCT/JP2004/019054 WO2005063888A1 (en) | 2003-12-26 | 2004-12-21 | Polyamide resin composition |
| KR1020067014230A KR20070012634A (en) | 2003-12-26 | 2004-12-21 | Polyamide resin composition |
| TW093140176A TWI381020B (en) | 2003-12-26 | 2004-12-23 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003435792A JP2005194330A (en) | 2003-12-26 | 2003-12-26 | Polyamide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005194330A true JP2005194330A (en) | 2005-07-21 |
Family
ID=34815752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003435792A Withdrawn JP2005194330A (en) | 2003-12-26 | 2003-12-26 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005194330A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031475A (en) * | 2005-07-22 | 2007-02-08 | Mitsubishi Gas Chem Co Inc | Polyamide resin |
| WO2007139200A1 (en) * | 2006-05-31 | 2007-12-06 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| JP2010007055A (en) * | 2008-05-29 | 2010-01-14 | Mitsubishi Gas Chemical Co Inc | Method for producing polyamide |
| WO2011145498A1 (en) | 2010-05-17 | 2011-11-24 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| WO2012115171A1 (en) | 2011-02-24 | 2012-08-30 | 三菱瓦斯化学株式会社 | Masterbatch, and method of preparing polyamide resin composition using masterbatch |
| JPWO2011145497A1 (en) * | 2010-05-17 | 2013-07-22 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| WO2014126110A1 (en) | 2013-02-13 | 2014-08-21 | 三菱瓦斯化学株式会社 | Multi-layer bottle and method for producing same |
| JP2017516913A (en) * | 2014-05-30 | 2017-06-22 | アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニーＡｓｃｅｎｄ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｏｐｅｒａｔｉｏｎｓ Ｌｌｃ | Low phosphorus low color polyamide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945960A (en) * | 1972-09-07 | 1974-05-02 | ||
| JPS4953945A (en) * | 1972-09-27 | 1974-05-25 | ||
| JP2003012907A (en) * | 2001-04-24 | 2003-01-15 | Toyobo Co Ltd | Polyester composition and mold made of the same |
| JP2003105095A (en) * | 2001-09-27 | 2003-04-09 | Mitsubishi Engineering Plastics Corp | Method for manufacturing polyamide resin composition |
| JP2003252986A (en) * | 2001-12-27 | 2003-09-10 | Toyobo Co Ltd | Method for continuously manufacturing polyamide resin composition |
| JP2003342455A (en) * | 2002-03-19 | 2003-12-03 | Toyobo Co Ltd | Polyester composition and molding made from the same |
-
2003
- 2003-12-26 JP JP2003435792A patent/JP2005194330A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945960A (en) * | 1972-09-07 | 1974-05-02 | ||
| JPS4953945A (en) * | 1972-09-27 | 1974-05-25 | ||
| JP2003012907A (en) * | 2001-04-24 | 2003-01-15 | Toyobo Co Ltd | Polyester composition and mold made of the same |
| JP2003105095A (en) * | 2001-09-27 | 2003-04-09 | Mitsubishi Engineering Plastics Corp | Method for manufacturing polyamide resin composition |
| JP2003252986A (en) * | 2001-12-27 | 2003-09-10 | Toyobo Co Ltd | Method for continuously manufacturing polyamide resin composition |
| JP2003342455A (en) * | 2002-03-19 | 2003-12-03 | Toyobo Co Ltd | Polyester composition and molding made from the same |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031475A (en) * | 2005-07-22 | 2007-02-08 | Mitsubishi Gas Chem Co Inc | Polyamide resin |
| WO2007139200A1 (en) * | 2006-05-31 | 2007-12-06 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| JP2010007055A (en) * | 2008-05-29 | 2010-01-14 | Mitsubishi Gas Chemical Co Inc | Method for producing polyamide |
| US9650474B2 (en) | 2010-05-17 | 2017-05-16 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| WO2011145498A1 (en) | 2010-05-17 | 2011-11-24 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| JPWO2011145497A1 (en) * | 2010-05-17 | 2013-07-22 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| US9657159B2 (en) | 2010-05-17 | 2017-05-23 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
| JP5949546B2 (en) * | 2010-05-17 | 2016-07-06 | 三菱瓦斯化学株式会社 | Polyamide resin composition |
| WO2012115171A1 (en) | 2011-02-24 | 2012-08-30 | 三菱瓦斯化学株式会社 | Masterbatch, and method of preparing polyamide resin composition using masterbatch |
| US8993655B2 (en) | 2011-02-24 | 2015-03-31 | Mitsubishi Gas Chemical Company, Inc. | Masterbatch, and method of preparing polyamide resin composition using masterbatch |
| KR20150117642A (en) | 2013-02-13 | 2015-10-20 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Multi-layer bottle and method for producing same |
| WO2014126110A1 (en) | 2013-02-13 | 2014-08-21 | 三菱瓦斯化学株式会社 | Multi-layer bottle and method for producing same |
| US10144548B2 (en) | 2013-02-13 | 2018-12-04 | Mitsubishi Gas Chemical Company, Inc. | Multi-layer bottle and method for producing same |
| JP2017516913A (en) * | 2014-05-30 | 2017-06-22 | アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニーＡｓｃｅｎｄ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｏｐｅｒａｔｉｏｎｓ Ｌｌｃ | Low phosphorus low color polyamide |
| JP2020002362A (en) * | 2014-05-30 | 2020-01-09 | アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニーＡｓｃｅｎｄ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｏｐｅｒａｔｉｏｎｓ Ｌｌｃ | Low-phosphorus, low-color polyamides |
| US10865288B2 (en) | 2014-05-30 | 2020-12-15 | Ascend Performance Materials Operations Llc | Low phosphorus low color polyamides |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4857634B2 (en) | Polyamide resin | |
| JP5200335B2 (en) | Polyamide resin composition | |
| CN108291023B (en) | Polyamide resin, molded article, and method for producing polyamide resin | |
| JP5637144B2 (en) | Copolymerized polyamide resin, process for producing the same, resin composition, and molded article comprising the same | |
| JP5531409B2 (en) | Polyamide resin composition | |
| US5663284A (en) | Copolymerized polyamide and a production process/thereof | |
| JP2005194328A (en) | Polyamide resin composition | |
| JP5481776B2 (en) | Method for producing polyamide | |
| US9260563B2 (en) | Process for production of polyamide | |
| JP2009114429A (en) | Continuous production method of polyamide | |
| JP5194573B2 (en) | Polyamide resin composition | |
| JP2007092053A (en) | Polyamide and composition containing the polyamide | |
| JP2005194330A (en) | Polyamide resin composition | |
| US7687562B2 (en) | Polyamide resin composition | |
| JP2007092054A (en) | Polyamide and polyamide composition comprising the same | |
| JP2008208248A (en) | Polyamide composition and polyamide molded article comprising the same | |
| JP2013057003A (en) | Polyamide resin composition and molding by molding the same | |
| JP2005194329A (en) | Polyamide resin composition | |
| JP2008056842A (en) | Polyamide composition and polyamide molded product composed of the same | |
| JP2009203422A (en) | Continuously production method for polyamide | |
| JP2012149238A (en) | Method for producing semi-aromatic polyamide raw material, and method for producing semi-aromatic polyamide | |
| EP3896113A1 (en) | Semi-aromatic polyamide resin and method for manufacturing same | |
| JP5347227B2 (en) | Polyamide composition and polyamide molded body comprising the same | |
| US20210032406A1 (en) | Semi-aromatic polyamide resin and method for producing same | |
| CN112236463B (en) | Polyamide resin, molded article, and method for producing polyamide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061121 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20100226 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Effective date: 20100426 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110208 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110405 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111227 |
|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20120209 |