JP3546978B2 - Method for producing modified polyester resin - Google Patents
Method for producing modified polyester resin Download PDFInfo
- Publication number
- JP3546978B2 JP3546978B2 JP29862595A JP29862595A JP3546978B2 JP 3546978 B2 JP3546978 B2 JP 3546978B2 JP 29862595 A JP29862595 A JP 29862595A JP 29862595 A JP29862595 A JP 29862595A JP 3546978 B2 JP3546978 B2 JP 3546978B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyester resin
- molecular weight
- acid
- resin
- 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.)
- Expired - Fee Related
Links
Description
【０００１】
【産業上の利用分野】
本発明は塗料、接着剤、コーティング剤等の用途に適したポリマーの末端以外に官能基を有する変性ポリエステル樹脂の製造方法に関するものである。
【０００２】
【従来の技術】
ポリエステル樹脂は機械的特性や耐熱性が優れ、原料の選択により多様な物性が得られること等から塗料、接着剤、コーティング剤あるいは成型品等に用いられている。しかしポリエステル樹脂は化学反応に寄与する官能基は一般的にポリマーの末端の水酸基やカルボン酸基だけである。末端基の数を増やすために三官能以上の分岐剤を原料の一部とする分岐状ポリエステル樹脂が知られている。硬化剤との反応性の向上、極性の高い材料への接着性の改良等のためにポリマーの末端以外に水酸基やカルボン酸基等の官能基を導入することが有効であることが知られている。そのための方法としては、ポリエステル樹脂ではトリメチロールプロパン、グリセリン、トリメリット酸、ペンタエリスリトール、ジペンタエリスリトール等の三官能以上の成分を共重合する方法やポリエステル樹脂に無水フタル酸、無水トリメリット酸のような酸無水物を付加して酸価を高めることが一般的に用いられている。
【０００３】
【発明が解決しようとする課題】
ポリエステル樹脂の末端以外に水酸基やカルボン酸基等の官能基を導入するためにトリメチロールプロパン、グリセリン、トリメリット酸、ペンタエリスリトール、ジペンタエリスリトール等の三官能以上の成分を共重合する方法や、無水トリメリット酸や無水ピロメリット酸をポリエステル樹脂に後付加する方法では、分岐点濃度が高くなればなる程ゲル化の危険性があり、得られるポリマーの分子量は高くできない。またアミノ基を有するエステル形成性原料を使用してポリエステル樹脂中にアミノ基を導入することは、３級のアミノ基の場合でも高分子量の樹脂は得にくい。
本発明の目的はポリマーの末端以外に高濃度の水酸基、カルボン酸基あるいはアミノ基を有するポリエステル樹脂を容易に製造する方法を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者はポリエステル樹脂の製造方法を鋭意検討した結果、ポリエステル樹脂を形成するエステル結合を利用することにより、水酸基、カルボン酸基、アミノ基等の官能基を高濃度で導入できることを見いだし、本発明に到達した。すなわち本発明は、数平均分子量５，０００〜１００，０００のポリエステル樹脂（Ａ）を、１分子中に下記のＸから選ばれる官能基１種以上と下記のＹから選ばれる官能基１種以上とを有する数平均分子量が３００〜１５，０００である化合物（Ｂ）で解重合することを特徴とする変性ポリエステル樹脂の製造方法である。Ｘ：１級ＯＨ基、２級ＯＨ基、１級ＣＯＯＨ基、２級ＣＯＯＨ基、１級アミノ基、２級アミノ基
Ｙ：２級ＯＨ基、３級ＯＨ基、２級ＣＯＯＨ基、３級ＣＯＯＨ基、３級アミノ基（ただし、ＸとＹとは異なる。）
【０００５】
ポリエステル樹脂（Ａ）の解重合で使用する化合物（Ｂ）はＸの群から選ばれる官能基を１種以上とＹの群から選ばれる官能基を１種以上有する。Ｘの群から選ばれる官能基はポリエステル樹脂（Ａ）中のエステル結合と反応してエステル交換あるいはアミド化反応を起こさせる。Ｙの群から選ばれる官能基がエステル交換反応しうる官能基である場合には、ＸはＹの群から選ばれる官能基よりもエステル交換反応性が高いものが良い。Ｘとしては１級ＯＨ基、１級ＣＯＯＨ基、１級アミノ基が好ましく、特に１級ＯＨ基が好ましい。Ｘの群から選ばれる官能基は化合物（Ｂ）１分子中に１〜１０個の範囲が好ましく、特に１〜５個が好ましい。Ｙの群から選ばれる官能基は高濃度の水酸基、カルボン酸基あるいはアミノ基をポリエステル樹脂（Ａ）中に導入するために利用される。Ｙの群から選ばれる官能基は、化合物（Ｂ）１分子中に１個以上、特に５個以上が好ましく、
Ｘの群から選ばれる官能基よりも多く含まれるほうがよい。
【０００６】
化合物（Ｂ）の分子量は３００〜１５，０００の範囲のものを用い、特に５００〜５，０００が好ましい。分子量が３００以下では解重合によるポリエステル樹脂（Ａ）の分子量の低下が大きく、分子量が１５，０００を超えるとポリエステル樹脂（Ａ）との相溶性が悪くなりすぎ、解重合が円滑に進行しない。化合物（Ｂ）はＸ、Ｙの群から選ばれる官能基を分子中に高濃度で含み、比較的分子量の高い化合物である。そのため、ポリエステル樹脂（Ａ）との相溶性は良くなく、ＯＨ基、ＣＯＯＨ基やアミノ基等のエステル結合を分解できる官能基を多量に含んでも、解重合による分子量低下やゲル化は実用上問題とならない程度までに制御できる。
【０００７】
解重合で使用する化合物（Ｂ）の具体的な例としてはＨＯ−（ＣＨ２ −ＣＨＯＨ−ＣＨ２ Ｏ）ｎ Ｈの一般式で表されるポリグリセリン、Ｘから選ばれる官能基とＹから選ばれる官能基を有するモノマーを共重合したアクリル系あるいはオレフィン系共重合体、セルロース、キトサン等の天然高分子あるいはその部分変性物等が挙げられ、ポリグリセリン化合物、共重合アクリル系化合物が好ましい。
【０００８】
本発明において解重合のために使用する化合物（Ｂ）は得られた変性ポリエステル樹脂（Ａ）中で１〜５０重量％の範囲になるように使用することが望ましく、５〜３０重量（ｗｔ）％が特に望ましい。１重量％未満では変性による効果が見られず、５０重量％を超えるとポリエステル樹脂（Ａ）の分子量の低下が非常に大きくなる。
【０００９】
本発明で使用する数平均分子量５，０００〜１００，０００のポリエステル樹脂（Ａ）のカルボン酸成分としては、テレフタル酸、イソフタル酸、オルソフタル酸、１，５−ナフタル酸、２，６−ナフタル酸、４，４’−ジフェニルジカルボン酸、２，２’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸等の芳香族ジカルボン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、ダイマー酸等の脂肪族二塩基酸、１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸等の脂環族二塩基酸が挙げられ、特にテレフタル酸、イソフタル酸、アジピン酸、セバシン酸が望ましい。
【００１０】
グリコール成分はエチレングリコ−ル、プロピレングリコ−ル、１，３−プロパンジオ−ル、１，４−ブタンジオ−ル、１，３−ブタンジオール、１，２−ブタンジオール、２−メチル−１，３−プロパンジオール、１，５−ペンタンジオ−ル、１，６−ヘキサンジオ−ル、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコ−ル、ジエチレングリコ−ル、ジプロピレングリコ−ル、２，２，４−トリメチル−１，３−ペンタンジオ−ル、シクロヘキサンジメタノ−ル、ネオペンチルヒドロキシピバリン酸エステル、ビスフェノ−ルＡのエチレンオキサイド付加物およびプロピレンオキサイド付加物、水素化ビスフェノ−ルＡのエチレンオキサイド付加物およびプロピレンオキサスド付加物、１，９−ノナンジオール、２−メチルオクタンジオール、１，１０−ドデカンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、トリシクロデカンジメタノール等が挙げられ、これらのうちエチレングリコ−ル、ネオペンチルグリコ−ル、シクロヘキサンジメタノ−ル、ネオペンチルヒドロキシピバリン酸エステル、２−ブチル−２−エチル−１，３プロパンジオール、トリシクロデカンジメタノールが好ましい。また、ポリテトラメチレングリコール、ポリプロピレングリコール、ポリエチレングリコール等のポリエーテルも挙げられる。
【００１１】
本発明で使用するポリエステル樹脂（Ａ）の数平均分子量は５，０００〜１００，０００の範囲のもの、好ましくは数平均分子量１０，０００〜４０，０００を使用する。本発明での解重合により得られる変性ポリエステル樹脂の分子量はもとの分子量より低下するため、ポリエステル樹脂（Ａ）の数平均分子量が５，０００未満では機械的特性が悪い。また、ポリエステル樹脂（Ａ）の数平均分子量が１００，０００を超えると、溶融粘度が高くなりすぎ、解重合が均一に進行しない。
【００１２】
本発明におけるポリエステル樹脂（Ａ）の化合物（Ｂ）による変性は溶融状態でも溶媒中でもかまわないが、エステル交換反応やアミド化反応が起こる温度で、溶融状態で行うのが、反応効率から望ましい。変性に用いる装置はニーダー、押し出し機、反応釜等が挙げられる。ポリエステル重合反応と連続して変性を実施しても別個に行ってもよい。
解重合反応において通常用いられているエステル交換反応やアミド化反応の触媒を用いてもよい。
【００１３】
【作用】
本発明のポリエステル樹脂の変性は、ポリエステル樹脂中に高濃度で存在するエステル結合に着目し、特定の官能基を有する比較的分子量の高い化合物でポリエステル樹脂を解重合するものである。ポリエステル樹脂と解重合に使用する化合物との相溶性が良くないことを利用しているため、ポリエステル樹脂の分子量の低下が小さく、また、解重合中にゲル化することがない。
【００１４】
【実施例】
以下実施例により本発明を具体的に例示する。実施例中に単に部とあるのは重量部を示す。
実施例１
ジメチルテレフタレート１９４部、ジメチルイソフタレート１９４部、エチレングリコール１４９部、ネオペンチルグリコール１６６部、テトラブチルチタネート０．０７部をオートクレーブに仕込み、１８０〜２１０℃で４時間エステル交換反応を実施し、次いで反応系を２０分かけて５ｍｍＨｇまで減圧し、この間２７０℃まで昇温した。更に、２７０℃で重縮合反応を１００分間行い、最終的に圧力は０．５ｍｍＨｇまでの減圧度に至った。窒素ガスにより常圧にもどし、２２０℃まで冷却した後、分子量７６０のポリグリセリン（ＰＧＬ−１０）１００部を投入し、３０分間反応させ若干不透明な変性ポリエステル樹脂（１）を得た。得られたポリエステル樹脂（１）と変性前のポリエステル樹脂の分子量をテトラヒドロフラン（ＴＨＦ）溶液でのゲル浸透クロマトグラフィーによる分析により、また、樹脂の酸価（当量／トン）を１／１０規定ＫＯＨエタノール溶液での滴定による分析により求めた。また、変性前後のポリエステル樹脂の組成分析をＮＭＲにより行った。さらに、ポリエステル樹脂（１）をメチルエチルケトン／トルエン＝１／１溶液に固形分濃度が２０％になるように８０℃で溶解し、溶液の保存性を１週間４℃に放置して観察した。溶液は溶解初期から濁ってるが、層分離や沈澱の発生は見られなかった。結果を表１に示す。
【００１５】
さらに、ポリエステル樹脂（１）のメチルエチルケトン／トルエン＝１／１の固形分濃度２０％溶液にメラミン樹脂（住友化学社製「スミマールＭ−４０Ｓ」）を固形分重量比率で１００対２０になるように加え、硬化触媒としてＰ−トルエンスルホン酸をポリエステル樹脂に対し０．１重量％添加した。この溶液を脱脂した冷延鋼板に乾燥後の厚みで１０μｍになるように塗布し１５０℃で２分間乾燥させた。得られた塗膜の硬化性をキシレン擦りにより評価した。結果を表３に示す。
【００１６】
実施例２〜４
実施例１と同様に、ただし実施例１で用いたポリグリセリン （ＰＧＬ−１０） の代わりに分子量１，５００のポリグリセリン（ＰＧＬ−２０）を表１に記載した割合で使用して変性ポリエステル樹脂（２）を得た。変性前後の分析値を表１に示す。同様にして表１に記載したポリグリセリンにより変性ポリエステル樹脂（３）及び（４）を得た。
【００１７】
比較例１
実施例１で用いたポリグリセリンを、実施例１のエステル交換反応が終了した後に添加し、ついで重縮合反応を実施例１と同じ条件で行った。反応系を２０分かけて５ｍｍＨｇまで減圧し２７０℃まで昇温した時点でゲル化した。
【００１８】
比較例２
実施例１と同様にエステル交換反応を行い、ついで重縮合反応を開始して分子量が３，８００の時点で重縮合反応を終了し、実施例１と同様にポリグリセリンにより変性した。得られた変性ポリエステル樹脂の分析結果を表１に示す。
【００１９】
比較例３〜４
実施例１と同様に、ただし実施例１で用いたポリグリセリン（ＰＧＬ−１０）の代わりに分子量１６６のジグリセリン、分子量２４０のトリグリセリンを用いて解重合した。得られたポリエステル樹脂の分析結果を表１に示す。
【００２０】
比較例５
実施例１でのポリグリセリン添加前のポリエステル樹脂（分子量２３，０００、酸価１２当量／トン ）のメチルエチルケトン／トルエン＝１／１の固形分濃度２０％の溶液に実施例２で用いたポリグリセリンをポリエステル樹脂とポリグリセリンの重量比率が７５：２５となるように室温で添加した。得られた溶液は１日後２層に分離した。
【００２１】
実施例５〜７
樹脂１トン当り酸価が８当量、分子量２５，０００のポリエステル樹脂（組成：テレフタル酸／イソフタル酸／２−メチル−１，３−プロピレングリコール＝５０／５０／１００モル比）と表２に示した共重合樹脂−１を用いて、２軸押し出し機により混合温度２２５℃、混合時間５分で変性した。得られた変性ポリエステル樹脂（５）の分析結果を表２に示す。同様に、共重合樹脂−２及び共重合樹脂−３を用いて変性ポリエステル樹脂（６）及び（７）の分析結果を表２に示す。また、実施例１と同様にメチルエチルケトン／トルエン＝１／１の固形分濃度２０％溶液の保存性を１週間４℃に放置して観察した。さらに実施例１と同様にメラミン樹脂での硬化性を調べた。結果を表２と３に示す。
【００２２】
比較例６〜７
実施例５で用いたポリエステル樹脂を表２に示した化合物により、実施例５と同じ条件で変性した。ただし、比較例６では変性に用いた化合物が分子量６，０００のポリエチレングリコールで分子中には末端に１級のＯＨ基だけがあり、比較例７では用いた化合物中には３級のカルボン酸のみが存在する。比較例７で得た樹脂のメチルエチルケトン／トルエン溶液は一日後、層分離を起こした。
【００２３】
【表１】
変性剤（Ｂ）の比率（ｗｔ％）は、変性ポリエステル中の変性剤の重量％を表す。
表中の略号は以下の通り。
Ｔ ：テレフタル酸
Ｉ ：イソフタル酸
ＥＧ ：エチレングリコール
ＮＰＧ ：ネオペンチルグリコール
【００２５】
【表２】
表中の略号は以下の通り。
共重合樹脂−１：スチレン／メタクリル２−ヒドロキシエチルメタクリレート（５０／４０／１０モル比）
共重合樹脂−２：スチレン／メタクリル酸／アクリル酸（５０／４０／１０モル比）
共重合樹脂−３：メチルメタアクリレート／ジメチルアミノエチルメタアクリレート／２−ヒドロキシエチルメタクリレート （７５／１５／１０モル比）
共重合樹脂−４：スチレン／メタクリル酸（６０／４０モル比）
【００２７】
【表３】
硬化性：塗膜をキシレンを含浸させたウェスで擦り、鋼板が見えるまでの擦り回数を測定した。
○：５０回以上；△：５０〜１０回；×：１０回以下
【００２９】
【発明の効果】
本発明におけるポリエステル樹脂の変性により、ポリエステル樹脂に水酸基、カルボキシル基あるいはアミノ基を高濃度で導入することができ、かつ、ポリエステル樹脂と変性剤との相溶性の悪さ加減を利用しているため、分子量の低下が小さく、かつゲル化が起こることもない。[0001]
[Industrial applications]
The present invention relates to a method for producing a modified polyester resin having a functional group other than the terminal of a polymer suitable for applications such as paints, adhesives, and coating agents.
[0002]
[Prior art]
Polyester resins are used in paints, adhesives, coating agents, molded products, and the like because they have excellent mechanical properties and heat resistance, and various properties can be obtained by selecting raw materials. However, in the polyester resin, the functional groups that contribute to the chemical reaction are generally only a hydroxyl group or a carboxylic acid group at the terminal of the polymer. In order to increase the number of terminal groups, a branched polyester resin using a trifunctional or higher functional branching agent as a part of a raw material is known. It is known that it is effective to introduce a functional group such as a hydroxyl group or a carboxylic acid group other than the terminal of the polymer for the purpose of improving reactivity with a curing agent, improving adhesiveness to a highly polar material, and the like. I have. As a method for that, in the polyester resin trimethylolpropane, glycerin, trimellitic acid, pentaerythritol, dipentaerythritol or other trifunctional or more functional components copolymerized polyester resin phthalic anhydride, trimellitic anhydride It is generally used to increase the acid value by adding such an acid anhydride.
[0003]
[Problems to be solved by the invention]
A method of copolymerizing trifunctional or more components such as trimethylolpropane, glycerin, trimellitic acid, pentaerythritol, and dipentaerythritol to introduce a functional group such as a hydroxyl group or a carboxylic acid group other than the terminal of the polyester resin, In the method of post-adding trimellitic anhydride or pyromellitic anhydride to the polyester resin, the higher the branch point concentration, the higher the risk of gelation, and the resulting polymer cannot have a high molecular weight. In addition, when an amino group is introduced into a polyester resin using an ester-forming raw material having an amino group, it is difficult to obtain a high molecular weight resin even with a tertiary amino group.
An object of the present invention is to provide a method for easily producing a polyester resin having a high concentration of a hydroxyl group, a carboxylic acid group or an amino group in addition to the terminal of the polymer.
[0004]
[Means for Solving the Problems]
As a result of intensive studies of the method for producing a polyester resin, the present inventors have found that functional groups such as a hydroxyl group, a carboxylic acid group, and an amino group can be introduced at a high concentration by using an ester bond that forms the polyester resin. The invention has been reached. That is, the present invention provides a polyester resin (A) having a number-average molecular weight of 5,000 to 100,000, in which one or more functional groups selected from the following X and one or more functional groups selected from the following Y in one molecule. And depolymerizing with a compound (B) having a number average molecular weight of 300 to 15,000 having the following formula: X: Primary OH group, secondary OH group, primary COOH group, secondary COOH group, primary amino group, secondary amino group Y: secondary OH group, tertiary OH group, secondary COOH group, tertiary COOH group, tertiary amino group (X and Y are different.)
[0005]
The compound (B) used in the depolymerization of the polyester resin (A) has one or more functional groups selected from the group X and one or more functional groups selected from the group Y. The functional group selected from the group of X reacts with an ester bond in the polyester resin (A) to cause transesterification or amidation reaction. When the functional group selected from the group Y is a functional group capable of transesterification, X preferably has a higher transesterification reactivity than the functional group selected from the group Y. X is preferably a primary OH group, a primary COOH group, or a primary amino group, and particularly preferably a primary OH group. The number of functional groups selected from the group of X is preferably in the range of 1 to 10, more preferably 1 to 5, in one molecule of the compound (B). The functional group selected from the group of Y is used to introduce a high concentration of a hydroxyl group, a carboxylic acid group or an amino group into the polyester resin (A). The functional group selected from the group of Y is preferably one or more, particularly preferably five or more in one molecule of the compound (B),
It is better to include more than the functional groups selected from the group of X.
[0006]
The molecular weight of the compound (B) is in the range of 300 to 15,000, particularly preferably 500 to 5,000. If the molecular weight is 300 or less, the decrease in the molecular weight of the polyester resin (A) due to depolymerization is large, and if the molecular weight exceeds 15,000, the compatibility with the polyester resin (A) becomes too poor, and the depolymerization does not proceed smoothly. The compound (B) is a compound having a high concentration of a functional group selected from the group of X and Y in the molecule and having a relatively high molecular weight. Therefore, the compatibility with the polyester resin (A) is not good, and even if a large amount of a functional group capable of decomposing an ester bond such as an OH group, a COOH group or an amino group is contained, a decrease in molecular weight or gelation due to depolymerization is a practical problem. It can be controlled to the extent that it does not become.
[0007]
Specific examples of the compound (B) used in the depolymerization include polyglycerin represented by a general formula of HO— (CH 2 —CHOH—CH 2 O) n H, a functional group selected from X and a group selected from Y. Acrylic or olefin copolymers obtained by copolymerizing a monomer having a functional group to be used, natural polymers such as cellulose and chitosan, or partially modified products thereof, and the like, and polyglycerin compounds and copolymerized acrylic compounds are preferable.
[0008]
In the present invention, the compound (B) used for depolymerization is desirably used in an amount of 1 to 50% by weight in the obtained modified polyester resin (A), and 5 to 30% by weight (wt). % Is particularly desirable. If the amount is less than 1% by weight, the effect of the modification is not observed, and if it exceeds 50% by weight, the decrease in the molecular weight of the polyester resin (A) becomes extremely large.
[0009]
The carboxylic acid component of the polyester resin (A) having a number average molecular weight of 5,000 to 100,000 used in the present invention includes terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-diphenyletherdicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, Aliphatic dibasic acids such as dimer acid and the like, alicyclic dibasic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, and particularly terephthalic acid, isophthalic acid, adipic acid, and sebacic acid desirable.
[0010]
The glycol components are ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1, 3-propanediol, 1,5-pentaneddiol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2, 2,4-trimethyl-1,3-pentaneddiol, cyclohexanedimethanol, neopentyl hydroxypivalate, ethylene oxide adduct and propylene oxide adduct of bisphenol A, ethylene of hydrogenated bisphenol A Oxide adduct and propylene oxas adduct, 1,9-nonanediol, 2-methyl Butanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecanedimethanol, and the like. Of these, ethylene glycol, neopentyl glycol, and cyclohexanediol Methanol, neopentyl hydroxypivalate, 2-butyl-2-ethyl-1,3 propanediol, and tricyclodecane dimethanol are preferred. Further, polyethers such as polytetramethylene glycol, polypropylene glycol, and polyethylene glycol are also included.
[0011]
The number average molecular weight of the polyester resin (A) used in the present invention is in the range of 5,000 to 100,000, preferably 10,000 to 40,000. Since the molecular weight of the modified polyester resin obtained by the depolymerization in the present invention is lower than the original molecular weight, if the number average molecular weight of the polyester resin (A) is less than 5,000, the mechanical properties are poor. On the other hand, when the number average molecular weight of the polyester resin (A) exceeds 100,000, the melt viscosity becomes too high, and the depolymerization does not proceed uniformly.
[0012]
The modification of the polyester resin (A) with the compound (B) in the present invention may be carried out in a molten state or in a solvent, but it is desirable to carry out the modification in a molten state at a temperature at which a transesterification reaction or an amidation reaction occurs. Examples of an apparatus used for denaturation include a kneader, an extruder, and a reaction vessel. The modification may be performed continuously or separately from the polyester polymerization reaction.
A catalyst for a transesterification reaction or an amidation reaction generally used in a depolymerization reaction may be used.
[0013]
[Action]
The modification of the polyester resin of the present invention focuses on an ester bond present at a high concentration in the polyester resin, and depolymerizes the polyester resin with a compound having a specific functional group and a relatively high molecular weight. Since the fact that the compatibility between the polyester resin and the compound used in the depolymerization is not good is used, the decrease in the molecular weight of the polyester resin is small, and no gelation occurs during the depolymerization.
[0014]
【Example】
Hereinafter, the present invention will be specifically illustrated by way of examples. In the examples, “parts” means “parts by weight”.
Example 1
194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 149 parts of ethylene glycol, 166 parts of neopentyl glycol and 0.07 part of tetrabutyl titanate were charged into an autoclave, and transesterification was carried out at 180 to 210 ° C. for 4 hours, followed by reaction. The system was evacuated to 5 mmHg over 20 minutes, during which time the temperature was raised to 270 ° C. Further, a polycondensation reaction was performed at 270 ° C. for 100 minutes, and finally the pressure reached a degree of pressure reduction to 0.5 mmHg. After returning to normal pressure with nitrogen gas and cooling to 220 ° C., 100 parts of polyglycerin (PGL-10) having a molecular weight of 760 was charged and reacted for 30 minutes to obtain a slightly opaque modified polyester resin (1). The molecular weights of the obtained polyester resin (1) and the unmodified polyester resin were analyzed by gel permeation chromatography in a tetrahydrofuran (THF) solution, and the acid value (equivalent / ton) of the resin was determined to be 1/10 N KOH ethanol. It was determined by analysis by titration with a solution. The composition of the polyester resin before and after the modification was analyzed by NMR. Further, the polyester resin (1) was dissolved in a methyl ethyl ketone / toluene = 1/1 solution at 80 ° C. so that the solid content concentration became 20%, and the storage stability of the solution was observed by leaving it at 4 ° C. for one week. The solution was cloudy from the initial stage of dissolution, but no layer separation or precipitation was observed. Table 1 shows the results.
[0015]
Further, a melamine resin (“Sumimar M-40S” manufactured by Sumitomo Chemical Co., Ltd.) is added to a 20% solid content concentration solution of the polyester resin (1) in methyl ethyl ketone / toluene = 1/1 so that the weight ratio of the solid content becomes 100: 20. In addition, 0.1% by weight of P-toluenesulfonic acid was added as a curing catalyst to the polyester resin. This solution was applied to a degreased cold-rolled steel sheet so as to have a thickness after drying of 10 μm, and dried at 150 ° C. for 2 minutes. The curability of the obtained coating film was evaluated by xylene rubbing. Table 3 shows the results.
[0016]
Examples 2 to 4
Modified polyester resin in the same manner as in Example 1 except that polyglycerin (PGL-20) having a molecular weight of 1,500 was used in place of the polyglycerin (PGL-10) used in Example 1 at a ratio shown in Table 1. (2) was obtained. The analytical values before and after denaturation are shown in Table 1. Similarly, modified polyester resins (3) and (4) were obtained with polyglycerin shown in Table 1.
[0017]
Comparative Example 1
The polyglycerin used in Example 1 was added after the transesterification reaction of Example 1 was completed, and the polycondensation reaction was performed under the same conditions as in Example 1. The reaction system was reduced in pressure to 5 mmHg over 20 minutes and gelled when heated to 270 ° C.
[0018]
Comparative Example 2
The transesterification reaction was carried out in the same manner as in Example 1, and then the polycondensation reaction was started. When the molecular weight reached 3,800, the polycondensation reaction was terminated, and the product was modified with polyglycerin as in Example 1. Table 1 shows the analysis results of the modified polyester resin obtained.
[0019]
Comparative Examples 3 and 4
Depolymerization was performed in the same manner as in Example 1 except that diglycerin having a molecular weight of 166 and triglycerin having a molecular weight of 240 were used instead of the polyglycerin (PGL-10) used in Example 1. Table 1 shows the analysis results of the obtained polyester resin.
[0020]
Comparative Example 5
Polyglycerol used in Example 2 in a solution of the polyester resin (molecular weight 23,000, acid value 12 equivalents / ton) of methyl ethyl ketone / toluene = 1/1 with a solid concentration of 20% before addition of polyglycerin in Example 1 Was added at room temperature such that the weight ratio of the polyester resin to the polyglycerin was 75:25. The resulting solution separated into two layers after one day.
[0021]
Examples 5 to 7
Table 2 shows a polyester resin having an acid value of 8 equivalents and a molecular weight of 25,000 per ton of resin (composition: terephthalic acid / isophthalic acid / 2-methyl-1,3-propylene glycol = 50/50/100 molar ratio). The copolymer resin-1 was denatured by a twin screw extruder at a mixing temperature of 225 ° C. for a mixing time of 5 minutes. Table 2 shows the analysis results of the modified polyester resin (5) obtained. Similarly, Table 2 shows the analysis results of modified polyester resins (6) and (7) using copolymer resin-2 and copolymer resin-3. Also, as in Example 1, the storage stability of a 20% solution of methyl ethyl ketone / toluene = 1/1 solid content was observed at 4 ° C. for one week. Further, the curability with a melamine resin was examined in the same manner as in Example 1. The results are shown in Tables 2 and 3.
[0022]
Comparative Examples 6 and 7
The polyester resin used in Example 5 was modified with the compounds shown in Table 2 under the same conditions as in Example 5. However, in Comparative Example 6, the compound used for modification was polyethylene glycol having a molecular weight of 6,000, and the molecule had only a primary OH group at the terminal. In Comparative Example 7, the compound used was tertiary carboxylic acid. Only exists. After one day, the resin obtained in Comparative Example 7 in a methyl ethyl ketone / toluene solution was subjected to layer separation.
[0023]
[Table 1]
The ratio (wt%) of the modifier (B) represents the weight% of the modifier in the modified polyester.
Abbreviations in the table are as follows.
T: terephthalic acid I: isophthalic acid EG: ethylene glycol NPG: neopentyl glycol
[Table 2]
Abbreviations in the table are as follows.
Copolymer resin-1: styrene / methacryl 2-hydroxyethyl methacrylate (50/40/10 molar ratio)
Copolymer resin-2: styrene / methacrylic acid / acrylic acid (50/40/10 molar ratio)
Copolymer resin-3: methyl methacrylate / dimethylaminoethyl methacrylate / 2-hydroxyethyl methacrylate (75/15/10 molar ratio)
Copolymer resin-4: styrene / methacrylic acid (60/40 molar ratio)
[0027]
[Table 3]
Curability: The coating film was rubbed with a cloth impregnated with xylene, and the number of times of rubbing until the steel sheet was visible was measured.
：: 50 times or more; Δ: 50 to 10 times; ×: 10 times or less
【The invention's effect】
By the modification of the polyester resin in the present invention, a hydroxyl group, a carboxyl group or an amino group can be introduced at a high concentration into the polyester resin, and the poor compatibility between the polyester resin and the modifying agent is used, and The decrease in molecular weight is small, and gelation does not occur.
Claims (1)
Ｘ：１級ＯＨ基、２級ＯＨ基、１級ＣＯＯＨ基、２級ＣＯＯＨ基、１級アミノ基、２級アミノ基
Ｙ：２級ＯＨ基、３級ＯＨ基、２級ＣＯＯＨ基、３級ＣＯＯＨ基、３級アミノ基（ただし、ＸとＹとは異なる。）A polyester resin (A) having a number average molecular weight of 5,000 to 100,000 has a number average having at least one functional group selected from the following X and at least one functional group selected from the following Y in one molecule. A method for producing a modified polyester resin, comprising depolymerizing with a compound (B) having a molecular weight of 300 to 15,000.
X: Primary OH group, secondary OH group, primary COOH group, secondary COOH group, primary amino group, secondary amino group Y: secondary OH group, tertiary OH group, secondary COOH group, tertiary COOH group, tertiary amino group (however, X and Y are different)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29862595A JP3546978B2 (en) | 1995-11-16 | 1995-11-16 | Method for producing modified polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29862595A JP3546978B2 (en) | 1995-11-16 | 1995-11-16 | Method for producing modified polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09136948A JPH09136948A (en) | 1997-05-27 |
| JP3546978B2 true JP3546978B2 (en) | 2004-07-28 |
Family
ID=17862162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29862595A Expired - Fee Related JP3546978B2 (en) | 1995-11-16 | 1995-11-16 | Method for producing modified polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3546978B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348366A (en) * | 2001-03-19 | 2002-12-04 | Toyobo Co Ltd | Manufacturing method of biodegradable polyester |
| JP4934911B2 (en) * | 2001-03-19 | 2012-05-23 | 東洋紡績株式会社 | Biodegradable polyester and coating |
| WO2020230692A1 (en) | 2019-05-15 | 2020-11-19 | 東洋紡株式会社 | Modified copolymer polyester resin and aqueous dispersion thereof |
-
1995
- 1995-11-16 JP JP29862595A patent/JP3546978B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09136948A (en) | 1997-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107922597B (en) | Polyester composition | |
| JP3546978B2 (en) | Method for producing modified polyester resin | |
| JP4975296B2 (en) | Polylactic acid copolymer resin and method for producing the same | |
| JPWO2018180335A1 (en) | Polyester resin with excellent storage stability | |
| JPH0569151B2 (en) | ||
| AU708869B2 (en) | Amourphous and/or semicrystalline copolyesters containing beta-hydroxyalkylamide groups, method for their manufacture, and utilisation of the esters | |
| JP2000504362A (en) | Low release binder for coatings | |
| JP7423917B2 (en) | Polyester resin with excellent pigment dispersibility and thermal stability | |
| JP7201978B2 (en) | Polyester resin and method for producing polyester resin | |
| JP3424857B2 (en) | Polyester resin, its production method, paint and adhesive | |
| JP7415282B2 (en) | Copolymerized polyester and water dispersion | |
| JP3374616B2 (en) | Method for producing aliphatic polyester copolymer | |
| JPH06128363A (en) | Thermoplastic polyester elastomer | |
| TW202225254A (en) | Crosslinked aromatic polyester resin composition and production method therefor | |
| EP4085082A1 (en) | Hybrid alkyd-acrylic based pressure sensitive adhesives and methods of making and using thereof | |
| JP3770350B2 (en) | High molecular weight unsaturated polyester resin and method for producing the same | |
| JP2001354842A (en) | Polyester composition for calender forming | |
| JPH08120061A (en) | Branched polyester and its production | |
| JP2895441B2 (en) | Polyester resin composition and use thereof | |
| JP2002121363A (en) | Polyester composition, use of its aqueous solution or aqueous dispersion and its use | |
| JPH05271615A (en) | Coating composition containing polyfunctional polycarbonatepolyol | |
| JP2001040278A (en) | Composition for coating inner surface of can | |
| JP3847849B2 (en) | Polyester resin composition for powder coating and powder coating | |
| JP2004083759A (en) | Thermosetting coating composition | |
| JP3753061B2 (en) | Production method of copolyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040319 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040325 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040407 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080423 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090423 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090423 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100423 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100423 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110423 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110423 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120423 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120423 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130423 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130423 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140423 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |