JP2006335941A - Manufacturing process of aromatic polyamide resin varnish - Google Patents
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Abstract
Description
本発明は純度が高く工業的に効率の良い芳香族ポリアミド樹脂ワニスの製造方法に関する。 The present invention relates to a method for producing an aromatic polyamide resin varnish having high purity and industrial efficiency.
ポリアミド樹脂、特に主鎖に芳香族基を含有するポリアミド樹脂は、耐熱性、機械強度等に優れた特性を持ち、さまざまな工業用途に応用が期待されている。これらポリアミド樹脂は一般にジカルボン酸とジアミンを原料とし、重縮合反応により得られるが、反応を進行させるために加えられる縮合剤や触媒、添加剤、副生成物等に由来するイオン性の不純物を含有するため、電気的絶縁性を求められる用途への使用が制限されている。特に、ジアミンとジカルボン酸を芳香族亜リン酸エステルとピリジン誘導体の存在下で縮合される方法は広く行われている重縮合反応であるが、本法で合成されたポリアミド樹脂中には芳香族亜リン酸エステルに由来するリン系のイオン性不純物が残留しやすい。特許文献１には、ポリアミド樹脂を洗浄性の良い微粉末として取り出すことにより不純物の少ないポリアミド樹脂を製造する方法が記載されているが、ますます高度化する電気絶縁性の要求水準を満足させるまでには至っていない。また、特許文献２においてはポリアミド樹脂を反応溶液から微粉末として析出させ、反応溶液から単離されたポリアミド樹脂の微粉末から低分子量成分を水蒸気洗浄した後、更に溶剤に溶解し塩基性化合物を添加して処理し、再度微粉末として析出させる方法が記載されている。この場合は微粉末の水蒸気洗浄が不均一系での洗浄であり突沸やその結果としての収率の低下などの問題が指摘されている。また、トリエチルアミンがポリアミド樹脂の微粉末中に残存し、その後の樹脂組成物の物性に悪影響を与える点も問題視されている。 Polyamide resins, particularly polyamide resins containing aromatic groups in the main chain, have excellent heat resistance and mechanical strength, and are expected to be applied to various industrial applications. These polyamide resins are generally obtained by polycondensation reaction using dicarboxylic acid and diamine as raw materials, but contain ionic impurities derived from condensing agents, catalysts, additives, by-products, etc. added to advance the reaction. For this reason, use in applications requiring electrical insulation is limited. In particular, the method of condensing diamine and dicarboxylic acid in the presence of an aromatic phosphite ester and a pyridine derivative is a widely used polycondensation reaction, but the polyamide resin synthesized by this method has an aromatic property. Phosphorus ionic impurities derived from phosphites tend to remain. Patent Document 1 describes a method of producing a polyamide resin with less impurities by taking out the polyamide resin as fine powder having good cleaning properties, but until an increasingly demanded level of electrical insulation is satisfied. It has not reached. In Patent Document 2, the polyamide resin is precipitated as a fine powder from the reaction solution, and after washing the low molecular weight component with water vapor from the fine powder of the polyamide resin isolated from the reaction solution, the basic compound is further dissolved in a solvent. A method of adding, treating and precipitating again as a fine powder is described. In this case, steam cleaning of the fine powder is cleaning in a heterogeneous system, and problems such as bumping and a resulting decrease in yield have been pointed out. Another problem is that triethylamine remains in the fine powder of the polyamide resin and adversely affects the physical properties of the subsequent resin composition.
本発明は、高度な電気絶縁性を要する分野の材料としても使用できるレベルまで不純物が少なく工程も簡略で安全なポリアミド樹脂ワニスの製造方法を提供することを目的としたものである。 An object of the present invention is to provide a method for producing a polyamide resin varnish that is safe and has a simple process and is low in impurities to a level that can be used as a material in a field requiring high electrical insulation.
本発明者らは上記課題を解決するため鋭意検討の結果、本発明を完成した。 The present inventors have completed the present invention as a result of intensive studies to solve the above problems.
すなわち本発明は
（１）下記式（ａ）
That is, the present invention provides (1) the following formula (a)
（式中Ａｒ３は二価の芳香族基を表す。）
で表される芳香族ジアミン及び下記式（ｂ）
(In the formula, Ar 3 represents a divalent aromatic group.)
And an aromatic diamine represented by the following formula (b)
（式中Ａｒ２はフェノール性水酸基を有する二価の芳香族基を表す。）
で表されるフェノール性水酸基含有芳香族ジカルボン酸
並びに必要により下記式（ｃ）
(In the formula, Ar 2 represents a divalent aromatic group having a phenolic hydroxyl group.)
And a phenolic hydroxyl group-containing aromatic dicarboxylic acid represented by formula (c)
で表される芳香族ジカルボン酸
を縮合剤として、芳香族亜リン酸エステルの存在下に有機溶剤中で縮合重合した後、加熱下で反応溶液中に水を滴下して残存する縮合剤を加水分解した後、更に水の滴下を続け、樹脂層と水層とが層分離を始めた段階で静置し、上層の水層のみを除去する工程を含み、必要により残留物への有機溶剤の添加と前記工程を繰り返す工程後に、加熱減圧下で樹脂溶液中に含まれる水分や低分子量不純物等を除去する工程を含むことを特徴とする下記式（１）
After the condensation polymerization in an organic solvent in the presence of an aromatic phosphite ester using the aromatic dicarboxylic acid represented by the formula (1) as a condensing agent, water is dropped into the reaction solution under heating to hydrolyze the remaining condensing agent. After decomposing, further dripping of water is continued, and it is allowed to stand at the stage where the resin layer and the aqueous layer start to separate layers, and only the upper aqueous layer is removed, and if necessary, the organic solvent can be added to the residue. After the step of adding and repeating the above step, the method includes the step of removing moisture, low molecular weight impurities, and the like contained in the resin solution under heating and decompression, the following formula (1)
（式中、ｍ、ｎは平均値でありｍ＋ｎは２〜２００の正数であり、ｎは０．１以上の正数である。Ａｒ１、Ａｒ３は二価の芳香族基、Ａｒ２はフェノール性水酸基を有する二価の芳香族基である。）
で表される芳香族ポリアミド樹脂と有機溶剤を含有する芳香族ポリアミド樹脂ワニスの製造方法。
（２）縮合重合をピリジン誘導体の存在下でに行う上記（１）記載の芳香族ポリアミド樹脂ワニスの製造方法、
を、提供するものである。
(In the formula, m and n are average values, m + n is a positive number of 2 to 200, and n is a positive number of 0.1 or more. Ar 1 and Ar 3 are divalent aromatic groups, Ar 2. Is a divalent aromatic group having a phenolic hydroxyl group.)
The manufacturing method of the aromatic polyamide resin varnish containing the aromatic polyamide resin represented by these, and an organic solvent.
(2) The method for producing an aromatic polyamide resin varnish according to (1), wherein the condensation polymerization is performed in the presence of a pyridine derivative,
Is provided.
本発明の製法によれば、不純物の少ない芳香族ポリアミド樹脂ワニスを効率的に製造することが出来る。 According to the production method of the present invention, an aromatic polyamide resin varnish with few impurities can be efficiently produced.
本発明におけるポリアミド樹脂が溶媒に溶解した本発明のポリアミド樹脂ワニスは、フェノール性水酸基含有芳香族ジカルボン酸と芳香族ジアミンを原料とし、縮合反応により生成するポリアミド樹脂と、該ポリアミド樹脂が可溶な有機溶剤とを必須成分とし、原料、縮合剤、副生物、触媒、添加剤等を含有し得る溶液である。 The polyamide resin varnish of the present invention in which the polyamide resin of the present invention is dissolved in a solvent uses a phenolic hydroxyl group-containing aromatic dicarboxylic acid and an aromatic diamine as raw materials, and a polyamide resin formed by a condensation reaction, and the polyamide resin is soluble. An organic solvent is an essential component and can contain raw materials, condensing agents, by-products, catalysts, additives and the like.
以下、本発明の製造方法について説明する。本発明において、ポリアミド樹脂の製造は、有機溶媒中で前記式（ａ）の芳香族ジアミンを、式（ｂ）のフェノール性水酸基含有芳香族ジカルボン酸（及び必要により式（ｃ）の芳香族ジカルボン酸）のモル数に対して過剰、好ましくはモル比で１．００１〜２倍、好ましくは１．００５〜１．５倍になるように仕込んで縮合重合して行う。 Hereinafter, the production method of the present invention will be described. In the present invention, the polyamide resin is produced by converting the aromatic diamine of the formula (a) into the phenolic hydroxyl group-containing aromatic dicarboxylic acid of the formula (b) (and optionally the aromatic dicarboxylic acid of the formula (c) in an organic solvent. The acid polymerization is carried out by condensation polymerization in an excess amount, preferably in a molar ratio of 1.001 to 2 times, preferably 1.005 to 1.5 times.
式（ａ）で表される芳香族ジアミンの例としてはジアミノベンゼン、ジアミノトルエン、ジアミノフェノール、ジアミノメチルベンゼン、ジアミノメシチレン、ジアミノクロロベンゼン、ジアミノニトロベンゼン、ジアミノアゾベンゼン、ジアミノナフタレン、ジアミノビフェニル、ジアミノジメトキシビフェニル、ジアミノジフェニルエーテル、ジアミノジメチルジフェニルエーテル、メチレンジアニリン、メチレンビス（メトキシアニリン）、メチレンビス（ジメトキシアニリン）、メチレンビス（エチルアニリン）、メチレンビス（ジエトキシアニリン）、メチレンビス（エトキシアニリン）、メチレンビス（ジエトキシアニリン）、メチレンビス（ジブロモアニリン）、イソプロピリデンジアニリン、ヘキサフルオロイソプロピリデンジアニリン、ジアミノベンゾフェノン、ジアミノジメチルベンゾフェノン、ジアミノアントラキノン、ジアミノジフェニルチオエーテル、ジアミノジフェニルスルホキシドやジアミノフルオレンなどが挙げられ、中でもジアミノジフェニルエーテルまたはメチレンビス（ジエチルアニリン）が好ましい。 Examples of the aromatic diamine represented by the formula (a) include diaminobenzene, diaminotoluene, diaminophenol, diaminomethylbenzene, diaminomesitylene, diaminochlorobenzene, diaminonitrobenzene, diaminoazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, Diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylene dianiline, methylene bis (methoxyaniline), methylene bis (dimethoxyaniline), methylene bis (ethylaniline), methylene bis (diethoxyaniline), methylene bis (ethoxyaniline), methylene bis (diethoxyaniline), methylene bis (Dibromoaniline), isopropylidene dianiline, hexafluoroisopropylide Dianiline, diamino benzophenone, diamino dimethyl benzophenone, diaminoanthraquinone, diaminodiphenyl thioether, etc. diaminodiphenyl sulfoxide and diaminofluorene. Among them diaminodiphenyl ether or methylene bis (diethyl aniline) are preferred.
式（ｂ）で表されるフェノール性水酸基含有芳香族ジカルボン酸としては、ヒドロキシイソフタル酸、ヒドロキシテレフタル酸、ジヒドロキシイソフタル酸、ジヒドロキシテレフタル酸などのヒドロキシフタル酸類が挙げられる。式（ｃ）で表される芳香族ジカルボン酸の例としてはフタル酸、イソフタル酸、テレフタル酸、ベンゼン二酢酸、ベンゼンジプロピオン酸、ビフェニルジカルボン酸、オキシジ安息香酸、チオジ安息香酸、ジチオジ安息香酸、ジチオビス（ニトロ安息香酸）、カルボニルジ安息香酸、スルホニルジ安息香酸、ナフタレンジカルボン酸、メチレンジ安息香酸、イソプロピリデンジ安息香酸、ヘキサフルオロイソプロピリデン安息香酸などのベンゼンジカルボン酸類やピリジンジカルボン酸などが挙げられる。
式（ｃ）の化合物を使用する場合、式（ｂ）の化合物と式（ｃ）の化合物の使用割合はｂ／ｃのモル比で通常０．０１〜０．７、好ましくは０．０２〜０．６である。
Examples of the phenolic hydroxyl group-containing aromatic dicarboxylic acid represented by the formula (b) include hydroxyphthalic acids such as hydroxyisophthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid. Examples of the aromatic dicarboxylic acid represented by the formula (c) include phthalic acid, isophthalic acid, terephthalic acid, benzenediacetic acid, benzenedipropionic acid, biphenyldicarboxylic acid, oxydibenzoic acid, thiodibenzoic acid, dithiodibenzoic acid, Examples include benzenedicarboxylic acids such as dithiobis (nitrobenzoic acid), carbonyldibenzoic acid, sulfonyldibenzoic acid, naphthalenedicarboxylic acid, methylenedibenzoic acid, isopropylidenedibenzoic acid, hexafluoroisopropylidenebenzoic acid, and pyridinedicarboxylic acid. .
When the compound of the formula (c) is used, the use ratio of the compound of the formula (b) and the compound of the formula (c) is usually 0.01 to 0.7, preferably 0.02 to b / c. 0.6.
本製造方法に使用される溶媒は、ポリアミド樹脂と溶媒和を起こす溶媒であれば特に制限は無いが、具体例としてはＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド等やこれらの混合溶媒が挙げられるが、特にＮ−メチル−２−ピロリドンが好ましい。また溶液中のポリアミド樹脂の濃度は２〜５０重量％が好ましく、生産効率と操作性の良い溶液粘度とを考慮すると５〜３０重量％が特に好ましい。 The solvent used in this production method is not particularly limited as long as it is a solvent that solvates with the polyamide resin. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2. -Pyrrolidone, dimethyl sulfoxide, and the like, and mixed solvents thereof are mentioned, and N-methyl-2-pyrrolidone is particularly preferable. Further, the concentration of the polyamide resin in the solution is preferably 2 to 50% by weight, and particularly preferably 5 to 30% by weight in consideration of the production efficiency and the solution viscosity with good operability.
縮合重合反応は、縮合剤としての芳香族亜リン酸エステルの存在下に行う。また、反応の進行を促進するために、これとピリジン誘導体を併用するのが好ましい。 The condensation polymerization reaction is performed in the presence of an aromatic phosphite as a condensing agent. Moreover, in order to accelerate | stimulate progress of reaction, it is preferable to use this and a pyridine derivative together.
ここで用いられる芳香族亜リン酸エステルとしては、亜リン酸トリフェニル、亜リン酸ジフェニル、亜リン酸トリ−ｏ−トリル、亜リン酸ジ−ｏ−トリル、亜リン酸トリ−ｍ−トリル、亜リン酸ジ−ｍ−トリル、亜リン酸トリ−ｐ−トリル、亜リン酸ジ−ｐ−トリル、亜リン酸トリ−ｐ−クロロフェニルなどが挙げられる。芳香族亜リン酸エステルの使用量は、式（ａ）の芳香族ジアミン１モルに対して通常０．５〜３モル、好ましくは１〜２．５モルである。 The aromatic phosphite used here includes triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite. , Di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, tri-p-chlorophenyl phosphite and the like. The usage-amount of aromatic phosphite is 0.5-3 mol normally with respect to 1 mol of aromatic diamines of Formula (a), Preferably it is 1-2.5 mol.
ピリジン誘導体としては、ピリジン、２−ピコリン、３−ピコリン、４−ピコリン、２，４−ルチジン、２，６−ルチジン、３，５−ルチジンなどが挙げられる。ピリジン誘導体の使用量は式（ａ）の芳香族ジアミン１モルに対して通常１〜５モル、好ましくは２〜４モルである。 Examples of pyridine derivatives include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 2,6-lutidine, and 3,5-lutidine. The usage-amount of a pyridine derivative is 1-5 mol normally with respect to 1 mol of aromatic diamines of a formula (a), Preferably it is 2-4 mol.
反応に際して、触媒として無機塩を用いると反応が進行しやすくなり、好ましい。無機塩の具体例としては、塩化リチウム、塩化カルシウム、硫酸ナトリウムや、これらの混合物が挙げられる。これら無機塩の使用量は、用いる式（ａ）の芳香族ジアミン１．０モルに対して、通常０．１〜２．０モル、好ましくは０．２〜１．０モルである。 In the reaction, an inorganic salt is preferably used as a catalyst because the reaction easily proceeds. Specific examples of the inorganic salt include lithium chloride, calcium chloride, sodium sulfate, and mixtures thereof. The amount of these inorganic salts used is usually 0.1 to 2.0 mol, preferably 0.2 to 1.0 mol, per 1.0 mol of the aromatic diamine of the formula (a) used.
本発明の製造方法では、縮合重合反応終了後に反応系内に水が滴下される。水を添加する際は、通常撹拌下６０〜１１０℃、好ましくは７０〜１００℃の範囲で添加される。水の添加量は反応液の総重量に対して通常１０〜２００重量％であり、好ましくは２０〜１５０重量％である。 In the production method of the present invention, water is dropped into the reaction system after completion of the condensation polymerization reaction. When adding water, it is normally added in the range of 60 to 110 ° C., preferably 70 to 100 ° C. with stirring. The amount of water added is usually 10 to 200% by weight, preferably 20 to 150% by weight, based on the total weight of the reaction solution.
水の滴下時間は通常、３０分〜１５時間であり、好ましくは１〜１０時間である。残存する縮合剤は、この水の滴下工程においてリン酸イオン及びフェノール類へ加水分解される。水の滴下は撹拌下において樹脂層と水層とが層分離を起こし始めるまで続ける。 The dropping time of water is usually 30 minutes to 15 hours, preferably 1 to 10 hours. The remaining condensing agent is hydrolyzed to phosphate ions and phenols in this water dropping step. The dripping of water is continued under stirring until the resin layer and the aqueous layer begin to cause layer separation.
層分離が始まった時点で撹拌を止め静置することにより、上層（水層）と下層（樹脂層）とに分け、上層の水層を除去する。この場合、通常樹脂層は粘度が高くスラリー状になっているのでデカンテーションなどによって容易に水層は除去できる。またポンプなどで系外に送液することも可能である。水層中にはリン酸、亜リン酸、触媒、フェノール類、ピリジンなどの不純物及び溶剤の一部が含まれている。 When the layer separation starts, the stirring is stopped and the mixture is allowed to stand to separate the upper layer (aqueous layer) and the lower layer (resin layer), and the upper aqueous layer is removed. In this case, since the resin layer usually has a high viscosity and is in the form of a slurry, the aqueous layer can be easily removed by decantation or the like. It is also possible to send liquid outside the system with a pump or the like. The aqueous layer contains impurities such as phosphoric acid, phosphorous acid, catalyst, phenols, pyridine, and a part of the solvent.
水層を除去して残された樹脂層は溶剤も一部取り除かれており、粘度がかなり上昇して扱いにくいため、再度有機溶剤を加えて希釈することもできる。この場合使用し得る有機溶剤はＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシドなどである。使用する溶剤の量は粘度が十分に下がる範囲であれば特に規定はされないが、通常洗浄前の反応液の重量に対して５〜１００重量％であり、好ましくは１０〜８０重量％である。
本発明により得られるポリアミド樹脂含有ワニスのポリアミド樹脂濃度は、５〜５０重量％が好ましく、１０〜４５重量％が特に好ましい。
Since a part of the solvent is removed from the resin layer left after the removal of the aqueous layer and the viscosity is considerably increased and it is difficult to handle, it can be diluted by adding an organic solvent again. In this case, the organic solvent which can be used is N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. The amount of the solvent to be used is not particularly limited as long as the viscosity is sufficiently lowered, but is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the weight of the reaction solution before washing.
The polyamide resin concentration of the polyamide resin-containing varnish obtained by the present invention is preferably 5 to 50% by weight, particularly preferably 10 to 45% by weight.
上述の洗浄工程（水の添加と除去工程）を通常３〜１０回繰り返し樹脂層からイオン性不純物及び低分子量の有機化合物を除去する。塩素イオンやリン酸イオンなどのイオン性不純物の低減の度合いは廃水をイオンクロマトグラフィーにより分析することが出来る。 The above washing step (water addition and removal step) is usually repeated 3 to 10 times to remove ionic impurities and low molecular weight organic compounds from the resin layer. The degree of reduction of ionic impurities such as chlorine ions and phosphate ions can be analyzed for wastewater by ion chromatography.
十分にイオン性不純物が低減されたことが確認された後、樹脂層を前記有機溶剤で希釈した後、系内を加熱減圧して樹脂相中に含まれる水分及び残存するフェノール等を有機溶剤と同時に留去する。加熱時の温度は通常５０〜１５０℃、減圧度は通常５〜２００ｍｍＨｇである。この工程により芳香族ポリアミド樹脂は、１２０℃×２０時間のプレッシャークッカーテストにおいて測定される塩素イオン、リン酸イオン、亜リン酸イオンの合計濃度が１０００ｐｐｍ以下となる。 After confirming that the ionic impurities have been sufficiently reduced, the resin layer is diluted with the organic solvent, and the system is heated and decompressed to remove moisture contained in the resin phase, residual phenol, and the like with the organic solvent. Distill off at the same time. The temperature during heating is usually 50 to 150 ° C., and the degree of vacuum is usually 5 to 200 mmHg. By this step, the aromatic polyamide resin has a total concentration of chlorine ions, phosphate ions, and phosphite ions measured in a pressure cooker test at 120 ° C. for 20 hours of 1000 ppm or less.
次いで、樹脂相中の固形分濃度を測定し所望の固形分濃度、好ましくは５〜５０重量％特に好ましくは１０〜４５重量％になるよう、有機溶剤を追加して希釈することにより目的とする芳香族ポリアミド樹脂ワニスを得ることが出来る。 Subsequently, the solid content concentration in the resin phase is measured, and the desired solid content concentration is obtained by adding an organic solvent and diluting so that the desired solid content concentration, preferably 5 to 50% by weight, particularly preferably 10 to 45% by weight, is obtained. An aromatic polyamide resin varnish can be obtained.
本発明により得られる芳香族ポリアミド樹脂ワニスに含まれる芳香族ポリアミド樹脂の固有粘度値（３０℃における０．５ｇ／ｄｌのＮ，Ｎ−ジメチルアセトアミド溶液で測定）は０．１〜４．０ｄｌ／ｇの範囲にあるものが好ましい。一般に好ましい平均重合度を有するか否かは、固有粘度を参照することにより判断する。固有粘度が０．１ｄｌ／ｇより小さいと、成膜性や芳香族ポリアミド樹脂としての性質出現が不十分であるため、好ましくない。逆に固有粘度が４．０ｄｌ／ｇより大きいと、重合度が高すぎ溶剤溶解性が悪くなり、かつ成形加工性が悪くなるといった問題が発生する。
なお、式（１）のｍとｎの値は式（ｂ）の化合物と式（ｃ）の化合物の仕込み比によって決定され、通常平均値で２〜２００であり、好ましくは５〜１５０である。
The aromatic polyamide resin contained in the aromatic polyamide resin varnish obtained by the present invention has an intrinsic viscosity value (measured with a 0.5 g / dl N, N-dimethylacetamide solution at 30 ° C.) of 0.1 to 4.0 dl / Those in the range of g are preferred. In general, whether or not the polymer has a preferable average degree of polymerization is determined by referring to the intrinsic viscosity. An intrinsic viscosity of less than 0.1 dl / g is not preferable because the film formability and the appearance of properties as an aromatic polyamide resin are insufficient. On the other hand, if the intrinsic viscosity is larger than 4.0 dl / g, there is a problem that the degree of polymerization is too high, the solvent solubility is deteriorated, and the moldability is deteriorated.
The values of m and n in the formula (1) are determined by the charging ratio of the compound of the formula (b) and the compound of the formula (c), and are usually 2 to 200 as an average value, preferably 5 to 150. .
本発明の製法により得られるワニスに含まれるポリアミド樹脂はフェノール性水酸基、末端アミノ基などの官能基を有するためエポキシ樹脂、硬化剤、硬化触媒、シアネート樹脂などと組み合わせることにより、硬化性樹脂組成物として使用することが出来る。具体的な用途例としては、リジッド基板材料、フレキシブル基板材料、ビルドアップ基板材料、半導体用封止材、ソルダーレジスト、塗料、接着剤などである。 Since the polyamide resin contained in the varnish obtained by the production method of the present invention has a functional group such as a phenolic hydroxyl group and a terminal amino group, the polyamide resin is combined with an epoxy resin, a curing agent, a curing catalyst, a cyanate resin, etc. Can be used as Specific examples of applications include rigid substrate materials, flexible substrate materials, build-up substrate materials, semiconductor encapsulants, solder resists, paints, adhesives, and the like.
次に本発明を更に実施例により具体的に説明するが、以下において部は特に断わりのない限り重量部である。 EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified.
実施例１
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、５−ヒドロキシイソフタル酸１６３．８部、イソフタル酸１６．６部、３，４’−ジアミノジフェニルエーテル２０４部、塩化リチウム１０．５部、Ｎ−メチルピロリドン１１１２．８部、ピリジン２３１．５部を加え撹拌溶解させた後、亜リン酸トリフェニル５０２．２部を加えて９５℃で４時間縮合反応をさせ、ポリアミド樹脂の反応液（Ａ）を得た。この反応液（Ａ）中に１００℃で水５６０部を２時間かけて滴下し、６０℃にまで冷却して３０分静置した。上層が水層、下層が油層（樹脂層）に層分離したため、上層をデカンテーションによって除去した。廃水の量は１１７０部であった。油層（樹脂層）にＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）３９０部を加えて希釈した。次いで１００℃まで昇温し水２８０部を1時間かけて滴下した。上層が水層、下層が油層（樹脂層）に層分離したため、上層をデカンテーションによって除去した。廃水の量は１０３０部であった。このＤＭＦと水による水洗工程を６回繰り返した後にＤＭＦを追加して溶液量を２０１０部にした。６度目の廃水をイオンクロマトグラフィーを用いて分析したところ塩素２７ｐｐｍ、亜リン酸イオン１．８ｐｐｍ、リン酸イオン２９ｐｐｍであった。この溶液を１００℃、５０ｍｍＨｇの減圧度で濃縮を行った後、固形分濃度を測定し、ＤＭＦを加えて下記式（２）
Example 1
While subjecting a flask equipped with a thermometer, condenser, fractionator, and stirrer to nitrogen purge, 163.8 parts of 5-hydroxyisophthalic acid, 16.6 parts of isophthalic acid, 204 parts of 3,4'-diaminodiphenyl ether, After adding 10.5 parts of lithium chloride, 112.8 parts of N-methylpyrrolidone and 231.5 parts of pyridine and dissolving with stirring, 502.2 parts of triphenyl phosphite was added, and a condensation reaction was carried out at 95 ° C. for 4 hours. A reaction solution (A) of polyamide resin was obtained. In this reaction liquid (A), 560 parts of water was dripped at 100 degreeC over 2 hours, it cooled to 60 degreeC, and left still for 30 minutes. Since the upper layer was separated into an aqueous layer and the lower layer was separated into an oil layer (resin layer), the upper layer was removed by decantation. The amount of waste water was 1170 parts. The oil layer (resin layer) was diluted by adding 390 parts of N, N-dimethylformamide (DMF). Next, the temperature was raised to 100 ° C., and 280 parts of water was added dropwise over 1 hour. Since the upper layer was separated into an aqueous layer and the lower layer was separated into an oil layer (resin layer), the upper layer was removed by decantation. The amount of waste water was 1030 parts. This water washing step with DMF and water was repeated 6 times, and then DMF was added to make the amount of solution 2010 parts. The sixth wastewater was analyzed using ion chromatography. The result was 27 ppm chlorine, 1.8 ppm phosphite ion, and 29 ppm phosphate ion. This solution was concentrated at 100 ° C. and a reduced pressure of 50 mmHg, then the solid content concentration was measured, DMF was added, and the following formula (2)
（式中ｍ＝３６、ｎ＝４）
で表される芳香族ポリアミド樹脂を３０重量％の濃度で含むワニス１１１３部を調製した。
(Where m = 36, n = 4)
1113 parts of a varnish containing an aromatic polyamide resin represented by the formula (1) at a concentration of 30% by weight was prepared.
なお、この芳香族ポリアミド樹脂ワニスを多量の水中に滴下し、固形分を濾過・乾燥することにより式（２）で表されるポリアミド樹脂を単離した。得られたポリアミド樹脂５部に純水５０部を加え、１２０℃×２０時間の条件でプレッシャークッカーテスト（ＰＣＴ）を行い、抽出水をイオンクロマトグラフィーで分析したところ固形分換算にて塩素イオン３８ｐｐｍ、リン酸イオン４ｐｐｍ、亜リン酸イオン１４ｐｐｍであった。 The aromatic polyamide resin varnish was dropped into a large amount of water and the solid content was filtered and dried to isolate the polyamide resin represented by the formula (2). 50 parts of pure water was added to 5 parts of the obtained polyamide resin, a pressure cooker test (PCT) was performed at 120 ° C. for 20 hours, and the extracted water was analyzed by ion chromatography. And 4 ppm phosphate ions and 14 ppm phosphite ions.
Claims (2)
で表される芳香族ジアミン及び下記式（ｂ）
で表されるフェノール性水酸基含有芳香族ジカルボン酸
並びに必要により下記式（ｃ）
で表される芳香族ジカルボン酸
を縮合剤として、芳香族亜リン酸エステルの存在下に有機溶剤中で縮合重合した後、加熱下で反応溶液中に水を滴下し樹脂層と水層とが層分離を始めた段階で静置し、上層の水層を除去する工程を含み、必要により残留物への有機溶剤の添加と前記工程を繰り返す工程後に、加熱減圧下で樹脂溶液中に含まれる水分や低分子量不純物等を除去する工程を含むことを特徴とする、下記式（１）
下記式（１）
で表される芳香族ポリアミド樹脂と有機溶剤を含有する芳香族ポリアミド樹脂ワニスの製造方法。 The following formula (a)
And an aromatic diamine represented by the following formula (b)
And a phenolic hydroxyl group-containing aromatic dicarboxylic acid represented by formula (c)
Using the aromatic dicarboxylic acid represented by the following formula as a condensing agent, after condensation polymerization in an organic solvent in the presence of an aromatic phosphite ester, water is dropped into the reaction solution under heating to form a resin layer and an aqueous layer. It is allowed to stand at the stage of starting the layer separation and includes a step of removing the upper aqueous layer. If necessary, after adding the organic solvent to the residue and repeating the step, it is contained in the resin solution under heating and reduced pressure. The following formula (1) characterized by including a step of removing moisture, low molecular weight impurities and the like
Following formula (1)
The manufacturing method of the aromatic polyamide resin varnish containing the aromatic polyamide resin represented by these, and an organic solvent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60206829A (en) * | 1984-03-30 | 1985-10-18 | Toshiba Corp | Production of aromatic polyester-amide |
| JPH08143661A (en) * | 1994-09-21 | 1996-06-04 | Tomoegawa Paper Co Ltd | Aromatic copolyamide, its production, composition containing the same and film comprising the same composition |
| JP2002053664A (en) * | 2000-08-08 | 2002-02-19 | Asahi Kasei Corp | Hydroxy polyamide and composition thereof |
| JP2006124545A (en) * | 2004-10-29 | 2006-05-18 | Nippon Kayaku Co Ltd | Method for producing aromatic polyamide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60206829A (en) * | 1984-03-30 | 1985-10-18 | Toshiba Corp | Production of aromatic polyester-amide |
| JPH08143661A (en) * | 1994-09-21 | 1996-06-04 | Tomoegawa Paper Co Ltd | Aromatic copolyamide, its production, composition containing the same and film comprising the same composition |
| JP2002053664A (en) * | 2000-08-08 | 2002-02-19 | Asahi Kasei Corp | Hydroxy polyamide and composition thereof |
| JP2006124545A (en) * | 2004-10-29 | 2006-05-18 | Nippon Kayaku Co Ltd | Method for producing aromatic polyamide resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014001313A (en) * | 2012-06-18 | 2014-01-09 | Asahi Kasei Chemicals Corp | Polyamide, and molded article thereof |
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