JP2002097267A - New semi-aromatic polyamide and its production method - Google Patents
New semi-aromatic polyamide and its production methodInfo
- Publication number
- JP2002097267A JP2002097267A JP2000291341A JP2000291341A JP2002097267A JP 2002097267 A JP2002097267 A JP 2002097267A JP 2000291341 A JP2000291341 A JP 2000291341A JP 2000291341 A JP2000291341 A JP 2000291341A JP 2002097267 A JP2002097267 A JP 2002097267A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyamide
- group
- semi
- formula
- aromatic
- 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.)
- Pending
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- Polyamides (AREA)
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は着色が少なく、溶剤
等への溶解性が優れた耐熱性新規半芳香族ポリアミド
と、その製造法に関する。更に詳しくは、特定の芳香族
ジカルボン酸と、特定の脂肪族ジアミンとを重合させて
得られる、半芳香族ポリアミドおよび、重合時に縮合剤
を用いることで、比較的温和な条件で該半芳香族ポリア
ミドを得る製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-resistant semi-aromatic polyamide having little coloring and excellent solubility in solvents and the like, and a method for producing the same. More specifically, a semi-aromatic polyamide obtained by polymerizing a specific aromatic dicarboxylic acid and a specific aliphatic diamine, and a semi-aromatic polyamide under relatively mild conditions by using a condensing agent during polymerization. The present invention relates to a method for producing a polyamide.
【０００２】[0002]
【従来の技術】芳香族環を主鎖中に有するポリアミド
は、従来より、ジアミンとジカルボン酸ジクロリド、ジ
イソシアネートとジカルボン酸あるいは、これら誘導体
の反応で得られ、一般に軟化温度が極めて高く高耐熱性
で、難燃性や、強度・弾性率等に優れた特性を有し注目
されている。しかしながら、従来開発されてきた芳香族
含有ポリアミドは、ガラス転移温度が高く、溶解し得る
溶剤が非常に少ないため、加工性に乏しい。また、吸湿
性が高く、多くの場合着色が大きいという欠点を有す
る。2. Description of the Related Art Polyamides having an aromatic ring in the main chain have been conventionally obtained by reacting a diamine with dicarboxylic acid dichloride or a diisocyanate with dicarboxylic acid or a derivative thereof, and generally have a very high softening temperature and high heat resistance. It has attracted attention because of its excellent properties such as flame retardancy, strength and elastic modulus. However, conventionally-developed aromatic-containing polyamides have a high glass transition temperature and very few soluble solvents, and therefore have poor processability. In addition, they have a disadvantage that they have high hygroscopicity and are often colored.
【０００３】[0003]
【発明が解決しようとする課題】本発明の課題は、芳香
族ポリアミドが本来有する優れた耐熱性等を損なうこと
なく、着色が抑えられ、多くの溶剤、アクリル類やエポ
キシ類モノマー、オリゴマーや、他のポリマー類への溶
解性や相溶性に優れ、加工性が良く、種々の分野に有用
な、新規半芳香族ポリアミドを提供することである。SUMMARY OF THE INVENTION An object of the present invention is to suppress the coloring without impairing the excellent heat resistance and the like inherent to the aromatic polyamide, and to use a large number of solvents, acrylic and epoxy monomers, oligomers, An object of the present invention is to provide a novel semi-aromatic polyamide which has excellent solubility and compatibility with other polymers, has good processability, and is useful in various fields.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため、鋭意研究の結果、多くの溶剤、アクリ
ル類やエポキシ類モノマー、オリゴマーや、他のポリマ
ー類への溶解性や相溶性に優れ、かつ着色が抑えた半芳
香族ポリアミドを見出し、さらに比較的温和な条件で該
半芳香族ポリアミドを製造し得る方法も見出し、本発明
を完成した。すなわち本発明は、 （１）一般式（Ａ）Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that their solubility in many solvents, acrylic and epoxy monomers and oligomers, and other polymers can be improved. The inventors have found a semi-aromatic polyamide having excellent compatibility and suppressed coloring, and have also found a method capable of producing the semi-aromatic polyamide under relatively mild conditions, thereby completing the present invention. That is, the present invention provides: (1) General formula (A)
【０００５】[0005]
【化４】 （式（Ａ）中Ｒ１は１つ以上のフェノール性水酸基を含
有する２価の芳香族基を表し、Ｒ２は炭素数２〜２０の
２価の脂肪族基または脂環族基を表す。）で表される繰
り返し単位を有する半芳香族ポリアミド （２）一般式（１）Embedded image (In the formula (A), R1 represents a divalent aromatic group containing one or more phenolic hydroxyl groups, and R2 represents a divalent aliphatic or alicyclic group having 2 to 20 carbon atoms.) (2) General formula (1) having a repeating unit represented by the following formula:
【０００６】[0006]
【化５】 （式（１）中Ｒ１は前記と同じである。）で表される芳
香族ジカルボン酸またはそれと他のジカルボン酸との混
合物と、一般式（２）Embedded image (Wherein R1 in the formula (1) is the same as described above) or a mixture of the aromatic dicarboxylic acid and another dicarboxylic acid with a general formula (2)
【０００７】[0007]
【化６】 （式（２）中Ｒ２は前記と同じである。）で表されるジ
アミンまたはそれと他のジアミンとの混合物とを、無機
塩存在下で縮合剤を用い、重合させることを特徴とする
請求項１記載の半芳香族ポリアミドの製造方法 （３）上記（１）記載の半芳香族ポリアミドに硬化性官
能基を修飾した、硬化性官能基含有半芳香族ポリアミド
に関する。Embedded image (Wherein R2 in the formula (2) is the same as described above) or a mixture of the diamine and another diamine, and the mixture is polymerized in the presence of an inorganic salt using a condensing agent. (3) The present invention relates to a curable functional group-containing semi-aromatic polyamide obtained by modifying the semi-aromatic polyamide according to (1) with a curable functional group.
【０００８】[0008]
【発明の実施の形態】本発明の半芳香族ポリアミドを得
るため用いる一般式（１）で表される芳香族ジカルボン
酸は、構造中に１つ以上のフェノール性水酸基を含有す
るジカルボン酸化合物であれば、特に制限はないが、一
般式（３）BEST MODE FOR CARRYING OUT THE INVENTION The aromatic dicarboxylic acid represented by the general formula (1) used for obtaining the semi-aromatic polyamide of the present invention is a dicarboxylic acid compound having at least one phenolic hydroxyl group in the structure. If there is no particular limitation, the general formula (3)
【０００９】[0009]
【化７】 Embedded image
【００１０】（式（３）中Ｒ３はハロゲン原子、炭素数
１〜４のアルキル基又はハロゲン化アルキル基、炭素数
１〜４のアルコキシ基又はハロゲン化アルコキシ基、炭
素数１〜４のアルキルチオ基又はハロゲン化アルキルチ
オ基、アセチル基、ニトロ基、シアノ基、メチルスルホ
ニル基からなる群から選ばれる１種以上を、Ｒ４は直接
結合、酸素原子、硫黄原子、炭素数１〜４のアルキレン
基およびハロゲン化アルキレン基、カルボニル基、スル
ホニル基、スルホキシル基、アゾ基、ジチオ基からなる
群から選ばれる１種以上を、ａは０〜３の整数を、ｂは
０〜５の整数をそれぞれ表す。）で表される化合物から
選ばれる１種以上が好ましく、具体例としては、５−ヒ
ドロキシイソフタル酸、４−ヒドロキシイソフタル酸、
２−ヒドロキシイソフタル酸、４，６−ジヒドロキシイ
ソフタル酸、２−ヒドロキシテレフタル酸、２，５−ジ
ヒドロキシテレフタル酸や、４−ヒドロキシフタル酸な
どが挙げられる。本発明の半芳香族ポリアミドを調製す
るにあたって 式（１）の芳香族ジカルボン酸以外の、
別のジカルボン酸を混合して使用しても支障はない。他
のジカルボン酸としては、ジカルボン酸であれば特に制
限はないが、コハク酸、マレイン酸、フマル酸、イソフ
タル酸や、テレフタル酸等が挙げられ、その混合比は全
ジカルボン酸成分の５０モル％以下が好ましい。(In the formula (3), R3 is a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group, an alkoxy group having 1 to 4 carbon atoms or a halogenated alkoxy group, an alkylthio group having 1 to 4 carbon atoms. Or one or more selected from the group consisting of a halogenated alkylthio group, an acetyl group, a nitro group, a cyano group, and a methylsulfonyl group, wherein R4 is a direct bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 4 carbon atoms, and halogen. (A represents an integer of 0 to 3 and b represents an integer of 0 to 5, respectively, at least one selected from the group consisting of an alkylene group, a carbonyl group, a sulfonyl group, a sulfoxyl group, an azo group, and a dithio group.) One or more selected from compounds represented by the following are preferable, and specific examples thereof include 5-hydroxyisophthalic acid,
Examples thereof include 2-hydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2-hydroxyterephthalic acid, 2,5-dihydroxyterephthalic acid, and 4-hydroxyphthalic acid. In preparing the semi-aromatic polyamide of the present invention, other than the aromatic dicarboxylic acid of the formula (1),
There is no problem even if another dicarboxylic acid is mixed and used. The other dicarboxylic acid is not particularly limited as long as it is a dicarboxylic acid, and examples thereof include succinic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid. The mixing ratio is 50 mol% of the total dicarboxylic acid component. The following is preferred.
【００１１】一般式（２）で表されるジアミンは、炭素
数２〜２０の脂肪族または脂環族ジアミン化合物であれ
ば、特に制限はないが、一般式（４）The diamine represented by the general formula (2) is not particularly limited as long as it is an aliphatic or alicyclic diamine compound having 2 to 20 carbon atoms.
【００１２】[0012]
【化８】 Embedded image
【００１３】（式（４）中Ｒ５は炭素数２〜２０の酸
素、硫黄、窒素、ハロゲンを含んでも良い炭化水素基
を、Ｒ６は直接結合または、炭素数１〜５のアルキレン
基およびハロゲン化アルキレン基をそれぞれ表す。）で
表される構造が好ましく、具体例としては、エチレンジ
アミン、１，３−プロピレンジアミン、１，４−ブタン
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、シクロペンタンジアミ
ン、シクロヘキサンジアミン、ビスアミノメチルシクロ
ペンタン、ビスアミノメチルシクロヘキサン、ビスアミ
ノメチルノルボルナンや、ビスアミノメチルトリシクロ
デカンなどが挙げられる。 本発明の半芳香族ポリアミ
ドを調製するにあたって 式（１）のジアミン以外の、
別のジアミンを混合して使用しても支障はない。他のジ
アミンとしては、ジアミンであれば特に制限はないが、
フェニレンジアミン、ジアミノジフェニルエーテル、ジ
アミノジフェニルスルホン、ジアミノビフェニル、ジア
ミノベンゾフェノン、ジアミノジフェニルメタン、ビス
（アミノジエチルフェニル）メタンや、ジアミノナフタ
レン等が挙げられ、その混合比は全ジアミン成分の５０
モル％以下が好ましい。(In the formula (4), R5 represents a hydrocarbon group having 2 to 20 carbon atoms which may contain oxygen, sulfur, nitrogen and halogen, and R6 represents a direct bond or an alkylene group having 1 to 5 carbon atoms and a halogenated group. And a structure represented by the following formulas: ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylene Diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, cyclopentanediamine, cyclohexanediamine, bisaminomethylcyclopentane, bisaminomethylcyclohexane, bisaminomethylnorbornane, Such as aminomethyl tricyclo decane. In preparing the semi-aromatic polyamide of the present invention, other than the diamine of the formula (1),
There is no problem even if another diamine is mixed and used. Other diamines are not particularly limited as long as they are diamines,
Examples include phenylenediamine, diaminodiphenyl ether, diaminodiphenylsulfone, diaminobiphenyl, diaminobenzophenone, diaminodiphenylmethane, bis (aminodiethylphenyl) methane, diaminonaphthalene, and the like.
It is preferably at most mol%.
【００１４】式（Ａ）で表される半芳香族ポリアミド
は、式（１）の芳香族ジカルボン酸化合物またはそれと
他のジカルボン酸との混合物と、式（２）のジアミン化
合物またはそれと他のジアミンとの混合物とを、無機塩
存在下で縮合剤を用い、反応させることによって、温和
な条件下で得られる。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、式
（１）の芳香族ジカルボン酸化合物１．０モルに対し
て、通常０．５〜５．０モル、好ましくは１．０〜３．
０モルである。The semi-aromatic polyamide represented by the formula (A) comprises an aromatic dicarboxylic acid compound of the formula (1) or a mixture thereof with another dicarboxylic acid, and a diamine compound of the formula (2) or another diamine. And a mixture thereof with a condensing agent in the presence of an inorganic salt to obtain a mixture under mild conditions. Specific examples of the inorganic salt include lithium chloride, calcium chloride, sodium sulfate, and a mixture thereof. The amount of the inorganic salt to be used is generally 0.5 to 5.0 mol, preferably 1.0 to 3.0 mol, per 1.0 mol of the aromatic dicarboxylic acid compound of the formula (1).
0 mol.
【００１５】縮合剤としては、亜リン酸エステル系縮合
剤が好ましく、通常三級アミンと共に用いられる。反応
は、必要により不活性溶媒、例えばＮ−メチル−２−ピ
ロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジ
メチルホルムアミド、Ｎ−メチルカプロラクタム、Ｎ，
Ｎ−ジメチルイミダゾリドン、ジメチルスルホキシド、
テトラメチル尿素、ピリジンのような非プロトン性極性
溶媒、トルエン、ヘキサン、ヘプタン等の無極性溶媒、
テトラヒドロフラン、ジグライム、ジオキサンや、トリ
オキサンなど、またはこれらの混合溶媒中で行ってもよ
い。これら溶媒の使用量は、芳香族ジカルボン酸化合物
０．１モルに対して、通常０〜５００ｍｌ、好ましくは
５０〜３００ｍｌである。また、反応温度は通常２０〜
１５０℃、好ましくは５０〜１２０℃である。反応時間
は通常３０分〜２４時間、好ましくは１〜１０時間であ
る。As the condensing agent, a phosphite condensing agent is preferable, and is usually used together with a tertiary amine. The reaction is optionally carried out with an inert solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylcaprolactam,
N-dimethylimidazolidone, dimethylsulfoxide,
Aprotic polar solvents such as tetramethylurea and pyridine, nonpolar solvents such as toluene, hexane and heptane;
The reaction may be performed in tetrahydrofuran, diglyme, dioxane, trioxane, or the like, or a mixed solvent thereof. The amount of the solvent to be used is generally 0 to 500 ml, preferably 50 to 300 ml, relative to 0.1 mol of the aromatic dicarboxylic acid compound. The reaction temperature is usually 20 to
The temperature is 150 ° C, preferably 50 to 120 ° C. The reaction time is usually 30 minutes to 24 hours, preferably 1 to 10 hours.
【００１６】用い得る亜リン酸エステル系縮合剤の具体
例としては、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
ルや、亜リン酸トリ−ｐ−クロロフェニルなどが挙げら
れ、その使用量は、用い得るジアミン化合物１．０モル
に対して、通常１．０〜３．０モル、好ましくは１．５
〜２．５モルである。Specific examples of phosphite-based condensing agents that can be used include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, and phosphorous acid. Tri-m-tolyl, di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, tri-p-chlorophenyl phosphite, etc. Is usually 1.0 to 3.0 mol, preferably 1.5 mol, per 1.0 mol of the diamine compound that can be used.
~ 2.5 mol.
【００１７】上記亜リン酸エステル系縮合剤と共に用い
得る三級アミンの具体例としては、ピリジン、ピコリ
ン、ルチジンや、トリエチルアミンなどが挙げられ、そ
の使用量は、用い得るジアミン化合物１．０モルに対し
て、通常１．０〜３．０モル、好ましくは１．５〜２．
５モルである。反応は、芳香族ジカルボン酸化合物、無
機塩、亜リン酸エステル系縮合剤、三級アミンと、必要
により不活性溶媒とを所定量仕込み、均一に溶解または
分散させた後、必要により窒素置換を行い、所定温度に
昇温後、ジアミン化合物を所定量滴下あるいは、芳香族
ジカルボン酸化合物、ジアミン化合物、無機塩、三級ア
ミンと、必要により不活性溶媒とを所定量仕込み、均一
に溶解または分散させた後、必要により窒素置換を行
い、所定温度に昇温後、亜リン酸エステル系縮合剤を所
定量滴下し行う。Specific examples of the tertiary amine which can be used together with the phosphite-based condensing agent include pyridine, picoline, lutidine, triethylamine and the like. On the other hand, it is usually 1.0 to 3.0 mol, preferably 1.5 to 2.
5 moles. The reaction is performed by charging a predetermined amount of an aromatic dicarboxylic acid compound, an inorganic salt, a phosphite-based condensing agent, a tertiary amine, and an inert solvent, if necessary, and uniformly dissolving or dispersing the mixture. After the temperature is raised to a predetermined temperature, a predetermined amount of a diamine compound is dropped, or a predetermined amount of an aromatic dicarboxylic acid compound, a diamine compound, an inorganic salt, a tertiary amine and, if necessary, an inert solvent are charged and uniformly dissolved or dispersed. After that, if necessary, the atmosphere is replaced with nitrogen. After the temperature is raised to a predetermined temperature, a predetermined amount of a phosphite-based condensing agent is dropped.
【００１８】上記半芳香族ポリアミドは、反応混合液を
室温まで冷却した後、貧溶媒の使用や溶媒除去等で析出
させ、再溶解再沈殿および／または洗浄後、濾過し、乾
燥させ単離することができる。用い得る貧溶媒は半芳香
族ポリアミドが溶解しにくい溶媒であれば良く、具体例
としては、水、メタノール、エタノール、プロパノー
ル、ブタノール、アセトン、メチルエチルケトン、シク
ロヘキサノンや、これらを含有する混合溶媒等が挙げら
れる。また、半芳香族ポリアミドを単離した後、構造中
に有するフェノール性水酸基を、硬化性官能基で修飾す
ることもできる。例えば、不活性溶媒等に単離した半芳
香族ポリアミドを溶解させ、塩基性化合物存在下で、
（メタ）アクリロイルクロリドやエピクロロヒドリン等
を、フェノール性水酸基と反応させ、硬化性官能基含有
半芳香族ポリアミドが得られる。After cooling the reaction mixture to room temperature, the semi-aromatic polyamide is precipitated by using a poor solvent, removing the solvent, etc., re-dissolved and re-precipitated and / or washed, filtered, dried and isolated. be able to. The poor solvent that can be used may be any solvent in which the semi-aromatic polyamide is difficult to dissolve, and specific examples include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, cyclohexanone, and a mixed solvent containing these. Can be Further, after isolating the semi-aromatic polyamide, the phenolic hydroxyl group contained in the structure can be modified with a curable functional group. For example, the isolated semi-aromatic polyamide is dissolved in an inert solvent or the like, and in the presence of a basic compound,
By reacting (meth) acryloyl chloride, epichlorohydrin and the like with a phenolic hydroxyl group, a curable functional group-containing semi-aromatic polyamide is obtained.
【００１９】ここで、硬化性官能基とは、（メタ）アク
リル基、ビニル基や、エポキシ基等、加熱操作または紫
外線や電子線などのエネルギー線照射により硬化する官
能基を表し、必要により、上記反応中または反応後に硬
化性官能基を修飾できる。例えば、用いる芳香族ジカル
ボン酸化合物に対し、等モル以上のジアミン化合物を反
応させ、末端アミンの半芳香族ポリアミドとし、更に
（メタ）アクリル酸、（メタ）アクリル基含有カルボン
酸化合物や、エポキシ基含有カルボン酸化合物を反応さ
せ、または、用いるジアミン化合物に対し、等モル以上
の芳香族ジカルボン酸化合物を反応させ、末端カルボン
酸の半芳香族ポリアミドとし、更に（メタ）アクリル基
含有ジアミン化合物やエポキシ基含有ジアミン化合物を
反応させ末端硬化性官能基含有半芳香族ポリアミドが得
られる。Here, the curable functional group refers to a functional group that is cured by a heating operation or irradiation of energy rays such as ultraviolet rays or electron beams, such as a (meth) acrylic group, a vinyl group, and an epoxy group. The curable functional group can be modified during or after the reaction. For example, an aromatic dicarboxylic acid compound to be used is reacted with a diamine compound in an equimolar amount or more to form a semi-aromatic polyamide having a terminal amine, and a (meth) acrylic acid, a (meth) acrylic group-containing carboxylic acid compound, or an epoxy group. A carboxylic acid-containing compound is reacted or a diamine compound to be used is reacted with an equimolar or more aromatic dicarboxylic acid compound to form a semi-aromatic polyamide having a terminal carboxylic acid, and a (meth) acrylic group-containing diamine compound or epoxy. The terminal-curable functional group-containing semi-aromatic polyamide is obtained by reacting the group-containing diamine compound.
【００２０】本発明の半芳香族ポリアミドは、着色が少
なく、フェノール性水酸基を有するため、多くの溶剤等
への溶解性、他ポリマーとの相溶性や、種々基盤への密
着性が優れ、耐熱性にも優れるため、種々の用途に有用
である。また、機能性添加剤として、本樹脂含有組成物
を容易に形成でき、例えば、不活性な有機又は無機顔
料、染料、カブリ防止剤、退色防止剤、ハレーション防
止剤、蛍光増白剤、界面活性剤、可塑剤、難燃剤、酸化
防止剤、充填剤、静電防止剤、消泡剤、流動調整剤、促
進剤、遅延剤、光安定剤、防かび剤、抗菌剤、磁性体
や、ゴム弾性を持たせるためポリマールその他の可とう
性プレポリマー等と、必要により溶剤を混合することが
できる。Since the semi-aromatic polyamide of the present invention has little coloring and has a phenolic hydroxyl group, it is excellent in solubility in many solvents and the like, compatibility with other polymers, adhesion to various substrates, and heat resistance. Because of its excellent properties, it is useful for various applications. Further, as a functional additive, the present resin-containing composition can be easily formed, for example, an inert organic or inorganic pigment, a dye, an antifoggant, an anti-fading agent, an antihalation agent, an optical brightener, a surfactant. Agents, plasticizers, flame retardants, antioxidants, fillers, antistatic agents, defoamers, flow regulators, accelerators, retarders, light stabilizers, fungicides, antibacterial agents, magnetic substances, and rubber For imparting elasticity, a solvent can be mixed with a polymer or other flexible prepolymer or the like, if necessary.
【００２１】さらに硬化性官能基含有半芳香族ポリアミ
ドは、他硬化性モノマーやオリゴマー類と反応し得るた
め、重合開始剤と、本硬化性官能基含有半芳香族ポリア
ミドとを含有する重合性組成物として有用である。重合
開始剤としては、熱重合開始剤、光重合開始剤などのラ
ジカル重合を起こしうるものであれば特に制限はく、熱
重合開始剤の具体例としては、過酸化ベンゾイル、過酸
化アセチル、過酸化ラウロイル、ｔ−ブチルハイドロパ
ーオキサイド、クメンハイドロパーオキサイド、アゾビ
スイソブチロニトリル、アゾビス−２，４−ジメチルバ
レロニトリル、アゾビスシクロヘキサンカルボニトリル
等が挙げられ、光重合開始剤の具体例としては、２，４
−ジエチルチオキサントン、ベンゾフェノン、４−ジメ
チルアミノイソアミルベンゾエート、４−ジメチルアミ
ノエチルベンゾエート等が挙げられる。Further, since the curable functional group-containing semi-aromatic polyamide can react with other curable monomers and oligomers, a polymerizable composition containing a polymerization initiator and the present curable functional group-containing semi-aromatic polyamide is used. Useful as a thing. The polymerization initiator is not particularly limited as long as it can cause radical polymerization, such as a thermal polymerization initiator or a photopolymerization initiator. Specific examples of the thermal polymerization initiator include benzoyl peroxide, acetyl peroxide, and acetyl peroxide. Examples include lauroyl oxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and specific examples of the photopolymerization initiator. Is 2,4
-Diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoethylbenzoate and the like.
【００２２】上記重合性組成物は通常、硬化性官能基含
有半芳香族ポリアミド１００重量部に対して、通常重合
開始剤０．０１〜２０重量部を必須の成分とするが、好
適な比率は、重合開始剤の種類や硬化方法、混在物の種
類や量、温度、湿度（水分量）、塗膜厚等さまざまな要
因を考慮することにより決められる。硬化性官能基含有
半芳香族ポリアミドと重合開始剤の溶解を容易にするた
め、予め両者を適当な溶媒（例えば、プロピレンカーボ
ネート、カルビトール、カルビトールアセテート、ブチ
ロラクトン等）に溶解して使用することができ、混合、
溶解あるいは混練等の方法により調製することもでき
る。The above-mentioned polymerizable composition usually contains 0.01 to 20 parts by weight of a polymerization initiator as an essential component with respect to 100 parts by weight of a curable functional group-containing semi-aromatic polyamide. It is determined by taking into account various factors such as the type and polymerization method of the polymerization initiator, the type and amount of the mixture, the temperature, the humidity (moisture content), and the thickness of the coating film. In order to facilitate the dissolution of the curable functional group-containing semi-aromatic polyamide and the polymerization initiator, both are dissolved in a suitable solvent (for example, propylene carbonate, carbitol, carbitol acetate, butyrolactone, etc.) before use. Can be mixed,
It can also be prepared by a method such as dissolution or kneading.
【００２３】本発明の半芳香族ポリアミド含有組成物
は、電気材料、金属、木材、ゴム、プラスチック、ガラ
ス、セラミックス製品等に使用することができる。さら
に、本発明の具体的用途としては、フォトレジスト、液
状レジスト、電子写真、ダイレクト刷版材料、ホログラ
ム材料、接着剤、粘着剤、粘接着剤、封止剤、塗料、コ
ーティング剤、インキ、成形材料、注型材料、パテ、ガ
ラス繊維含浸剤、目止め剤等が挙げられる。The semi-aromatic polyamide-containing composition of the present invention can be used for electrical materials, metals, woods, rubbers, plastics, glasses, ceramic products and the like. Further, specific applications of the present invention include photoresists, liquid resists, electrophotography, direct plate materials, hologram materials, adhesives, adhesives, adhesives, sealants, paints, coatings, inks, Examples include molding materials, casting materials, putties, glass fiber impregnating agents, fillers, and the like.
【００２４】[0024]
【実施例】以下に実施例によって本発明を更に詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００２５】実施例１ 温度計、環流冷却器、滴下ロート、窒素導入装置、攪拌
装置のついた５００ｍｌの反応器に、５−ヒドロキシイ
ソフタル酸２９．１３６ｇ（０．１６０モル）、塩化リ
チウム７．００ｇ（０．１６５モル）と、亜リン酸トリ
フェニル９９．２９ｇ（０．３２０モル）を仕込み、乾
燥窒素を流しながら、Ｎ−メチル−２−ピロリドン２３
５ｇと、ピリジン３２．００ｇ（０．４０５モル）を加
え、攪拌しながら反応器内が９５℃になるまで徐々に加
熱し、固形分を溶解させた。その後、反応器内を攪拌し
９５℃に保ち、２，５−ビス（アミノメチル）ノルボル
ナン２４．６７７ｇ（０．１６０モル）を２時間で滴下
し、さらに１時間反応させた。次に、反応器内が１２０
℃になるまで徐々に加熱し、さらに１２０℃で２時間反
応させた。Example 1 In a 500 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device, 29.136 g (0.160 mol) of 5-hydroxyisophthalic acid and lithium chloride 7. 00 g (0.165 mol) and 99.29 g (0.320 mol) of triphenyl phosphite were charged, and N-methyl-2-pyrrolidone 23 was added thereto while flowing dry nitrogen.
5 g and 32.00 g (0.405 mol) of pyridine were added, and the mixture was gradually heated with stirring to 95 ° C. in the reactor to dissolve solids. Thereafter, the reactor was stirred and maintained at 95 ° C., and 24.677 g (0.160 mol) of 2,5-bis (aminomethyl) norbornane was added dropwise over 2 hours, and the reaction was further performed for 1 hour. Next, 120
The mixture was gradually heated until the temperature reached 120 ° C., and further reacted at 120 ° C. for 2 hours.
【００２６】反応終了後、反応溶液を室温まで冷却した
後、１，０００ｍｌ容器に移し、室温で攪拌しながら、
蒸留水２００ｇを加えた後、３，０００ｍｌ容器に蒸留
水２，０００ｇを仕込み、激しく攪拌しながら、前記溶
液を加え、生成物を析出させた。析出物を濾過した後、
２，０００ｍｌ容器にメタノール６００ｇを仕込、攪拌
しながら、前記析出物を徐々に加え、１時間攪拌洗浄し
た。その後、蒸留水６００ｇを加え、さらに１時間攪拌
洗浄した後、濾過した。次に、この析出物を１，０００
ｍｌ容器に仕込み、蒸留水７００ｇを加え、室温で１時
間攪拌洗浄し、乾燥させて式（５）After the completion of the reaction, the reaction solution was cooled to room temperature, transferred to a 1,000 ml container, and stirred at room temperature.
After adding 200 g of distilled water, 2,000 g of distilled water was charged into a 3,000 ml container, and the solution was added with vigorous stirring to precipitate a product. After filtering the precipitate,
600 g of methanol was charged into a 2,000 ml container, and the precipitate was gradually added thereto with stirring, followed by washing for 1 hour with stirring. Thereafter, 600 g of distilled water was added, and the mixture was further stirred and washed for 1 hour, and then filtered. Next, this precipitate was removed for 1,000 times.
Then, 700 g of distilled water was added, and the mixture was stirred and washed at room temperature for 1 hour, dried, and dried according to the formula (5).
【００２７】[0027]
【化９】 （式中ｎは繰り返し数を表す。）で表される半芳香族ポ
リアミドを得た（収率９１．３％）。この半芳香族ポリ
アミド樹脂粉末０．１００ｇをＮ，Ｎ−ジメチルアセト
アミド２０．０ｍｌに溶解させ、３０℃で測定した対数
粘度は、０．２３ｄｌ／ｇであった。Embedded image (In the formula, n represents the number of repetitions.) A semi-aromatic polyamide represented by the following formula was obtained (yield: 91.3%). 0.100 g of this semi-aromatic polyamide resin powder was dissolved in 20.0 ml of N, N-dimethylacetamide, and the logarithmic viscosity measured at 30 ° C. was 0.23 dl / g.
【００２８】[0028]
【発明の効果】本発明の半芳香族ポリアミドは、芳香族
ポリアミドが本来有する優れた耐熱性等を損なうことな
く、着色が抑えられ、多くの溶剤、アクリル類やエポキ
シ類モノマー、オリゴマーや、他のポリマー類への溶解
性や相溶性に優れ、種々基盤への密着性にも優れ、加工
性が良く、作業性の良好な機能性添加剤として、コーテ
ィング剤、インキ、塗料、接着剤、レジスト、封止剤、
製版材、絶縁材などの種々の分野で極めて有用である。The semi-aromatic polyamide of the present invention can suppress coloring, without impairing the excellent heat resistance and the like inherent to the aromatic polyamide, and can be used in many solvents, acrylic and epoxy monomers, oligomers, etc. As a functional additive with excellent solubility and compatibility with polymers, excellent adhesion to various substrates, good workability, and good workability, coating agents, inks, paints, adhesives, resists , Sealant,
It is extremely useful in various fields such as plate making materials and insulating materials.
Claims (3)
有する２価の芳香族基を表し、Ｒ２は炭素数２〜２０の
２価の脂肪族基または脂環族基を表す。）で表される繰
り返し単位を有する半芳香族ポリアミド。1. A compound of the general formula (A) (In the formula (A), R1 represents a divalent aromatic group containing one or more phenolic hydroxyl groups, and R2 represents a divalent aliphatic or alicyclic group having 2 to 20 carbon atoms.) The semi-aromatic polyamide which has a repeating unit represented by these.
香族ジカルボン酸またはそれと他のジカルボン酸との混
合物と、一般式（２） 【化３】 （式（２）中Ｒ２は前記と同じである。）で表されるジ
アミンまたはそれと他のジアミンとの混合物とを、無機
塩存在下で縮合剤を用い、重合させることを特徴とする
請求項１記載の半芳香族ポリアミドの製造方法。2. A compound of the general formula (1) (In the formula (1), R1 is the same as described above.) And a mixture of the aromatic dicarboxylic acid and another dicarboxylic acid with the aromatic dicarboxylic acid represented by the general formula (2): (Wherein R2 in the formula (2) is the same as described above) or a mixture of the diamine and another diamine, and the mixture is polymerized in the presence of an inorganic salt using a condensing agent. 2. The method for producing a semi-aromatic polyamide according to 1.
性官能基を修飾した、硬化性官能基含有半芳香族ポリア
ミド。3. A semi-aromatic polyamide containing a curable functional group, wherein the semi-aromatic polyamide according to claim 1 is modified with a curable functional group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000291341A JP2002097267A (en) | 2000-09-26 | 2000-09-26 | New semi-aromatic polyamide and its production method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000291341A JP2002097267A (en) | 2000-09-26 | 2000-09-26 | New semi-aromatic polyamide and its production method |
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| Publication Number | Publication Date |
|---|---|
| JP2002097267A true JP2002097267A (en) | 2002-04-02 |
Family
ID=18774425
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| JP2000291341A Pending JP2002097267A (en) | 2000-09-26 | 2000-09-26 | New semi-aromatic polyamide and its production method |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002241494A (en) * | 2001-02-16 | 2002-08-28 | Nippon Kayaku Co Ltd | New semi-aromatic polyamide and its production method |
| JP2012062404A (en) * | 2010-09-16 | 2012-03-29 | Tosoh Corp | New polyamide and method for production thereof |
| JP2012062403A (en) * | 2010-09-16 | 2012-03-29 | Tosoh Corp | New polyamide and method for production thereof |
| WO2016001949A1 (en) * | 2014-07-02 | 2016-01-07 | 東洋インキＳｃホールディングス株式会社 | Heat-curable resin composition, polyamide, adhesive sheet, cured article, and printed wiring board |
| CN105418915A (en) * | 2014-09-11 | 2016-03-23 | 艾克伦聚合物***公司 | Solution Of Aromatic Polyamide For Producing Display Element, Optical Element, Illumination Element Or Sensor Element |
-
2000
- 2000-09-26 JP JP2000291341A patent/JP2002097267A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002241494A (en) * | 2001-02-16 | 2002-08-28 | Nippon Kayaku Co Ltd | New semi-aromatic polyamide and its production method |
| JP2012062404A (en) * | 2010-09-16 | 2012-03-29 | Tosoh Corp | New polyamide and method for production thereof |
| JP2012062403A (en) * | 2010-09-16 | 2012-03-29 | Tosoh Corp | New polyamide and method for production thereof |
| WO2016001949A1 (en) * | 2014-07-02 | 2016-01-07 | 東洋インキＳｃホールディングス株式会社 | Heat-curable resin composition, polyamide, adhesive sheet, cured article, and printed wiring board |
| CN105418915A (en) * | 2014-09-11 | 2016-03-23 | 艾克伦聚合物***公司 | Solution Of Aromatic Polyamide For Producing Display Element, Optical Element, Illumination Element Or Sensor Element |
| JP2016056357A (en) * | 2014-09-11 | 2016-04-21 | 住友ベークライト株式会社 | Aromatic polyamide solution for manufacturing display element, optical element, lighting element or sensor element |
| CN105418915B (en) * | 2014-09-11 | 2018-04-10 | 艾克伦聚合物***公司 | Aromatic polyamide solution for the manufacture of display element, optical elements, illumination element or sensor element |
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