JPH09136948A - Preparation of modified polyester resin - Google Patents
Preparation of modified polyester resinInfo
- Publication number
- JPH09136948A JPH09136948A JP29862595A JP29862595A JPH09136948A JP H09136948 A JPH09136948 A JP H09136948A JP 29862595 A JP29862595 A JP 29862595A JP 29862595 A JP29862595 A JP 29862595A JP H09136948 A JPH09136948 A JP H09136948A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyester resin
- molecular weight
- acid
- sec
- 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.)
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Links
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified polyester resin having a functional group other than the terminal of a polymer, which is suitable for applications such as paints, adhesives and coating agents.
【０００２】[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。2. Description of the Related Art Polyester resins are used in paints, adhesives, coating agents or molded products because they have excellent mechanical properties and heat resistance and various physical 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 hydroxyl groups and carboxylic acid groups at the ends of the polymer. A branched polyester resin in which a trifunctional or higher functional branching agent is used as a part of the raw material in order to increase the number of terminal groups is known. It is known that it is effective to introduce a functional group such as a hydroxyl group or a carboxylic acid group in addition to the terminal of the polymer in order to improve the reactivity with a curing agent and the adhesion to a highly polar material. There is. As a method therefor, in the polyester resin, trimethylolpropane, glycerin, trimellitic acid, pentaerythritol, a method of copolymerizing a trifunctional or more components such as dipentaerythritol and polyester resin phthalic anhydride, trimellitic anhydride It is generally used to increase the acid value by adding such an acid anhydride.
【０００３】[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。In order to introduce functional groups such as hydroxyl groups and carboxylic acid groups in addition to the terminals of the polyester resin, trifunctional or higher functional groups such as trimethylolpropane, glycerin, trimellitic acid, pentaerythritol and dipentaerythritol. In the method of copolymerizing the components of, or 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 molecular weight of the obtained polymer. Can't be high. Further, introduction of an amino group into a polyester resin by using an ester-forming raw material having an amino group makes it difficult to obtain a high-molecular-weight resin even in the case of 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 polymer terminal.
【０００４】[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Ｃ
ＯＯＨ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Ｃ
ＯＯＨ基、３級アミノ基 （ただし、ＸとＹとは異なる。）Means for Solving the Problems As a result of extensive studies on the method for producing a polyester resin, the present inventor has found that functional groups such as a hydroxyl group, a carboxylic acid group and an amino group can be formed by utilizing an ester bond forming a polyester resin. They have found that they can be introduced at a high concentration and arrived at the present invention. That is, in the present invention, a polyester resin (A) having a number average molecular weight of 5,000 to 100,000 has at least one functional group selected from the following X and one or more functional groups selected from the following Y in one molecule. And a compound (B) having a number average molecular weight of 300 to 15,000 and having the following formula. X: primary OH group, secondary OH group, primary COOH group, secondary C
OOH group, primary amino group, secondary amino group Y: secondary OH group, tertiary OH group, secondary COOH group, tertiary C
OOH group, tertiary amino group (however, X and Y are different)
【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。The compound (B) used in the depolymerization of the polyester resin (A) has at least one functional group selected from the group X and at least one functional group selected from the group Y. The functional group selected from the group X reacts with the 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. As X, a primary OH group, a primary COOH group and a primary amino group are preferable, and a primary OH group is particularly preferable. The number of the functional groups selected from the group of X is preferably 1 to 10 in one molecule of the compound (B), and particularly preferably 1 to 5. The functional group selected from the group Y is used to introduce a high concentration of hydroxyl group, carboxylic acid group or amino group into the polyester resin (A). The number of functional groups selected from the group of Y is preferably 1 or more, and particularly preferably 5 or more, in one molecule of the compound (B),
It is better to contain more than the functional group selected from the group of X.
【０００６】化合物（Ｂ）の分子量は３００〜１５，０
００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１
５，０００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、Ｏ
Ｈ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。The molecular weight of the compound (B) is 300 to 15,0.
The range of 00 is used, and the range of 500 to 5,000 is particularly preferable. When the molecular weight is 300 or less, the decrease in the molecular weight of the polyester resin (A) due to depolymerization is large, and the molecular weight is 1
If it exceeds 5,000, the compatibility with the polyester resin (A) becomes too poor, and depolymerization does not proceed smoothly. The compound (B) is a compound containing a functional group selected from the group of X and Y at a high concentration in the molecule and having a relatively high molecular weight. Therefore, the compatibility with the polyester resin (A) is not good, and O
Even if a large amount of functional groups capable of decomposing ester bonds such as H groups, COOH groups and amino groups are contained, the molecular weight reduction and gelation due to depolymerization can be controlled to such an extent that they do not pose a practical problem.
【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。A specific example of the compound (B) used in depolymerization is HO- (CH 2 -CHOH-CH 2 O) n H.
A polyglycerin represented by the following general formula, an acrylic or olefin copolymer obtained by copolymerizing a monomer having a functional group selected from X and a functional group selected from Y, a natural polymer such as cellulose or chitosan, or a part thereof. Examples thereof include modified products, and polyglycerin compounds and copolymerized acrylic compounds are preferable.
【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。The compound (B) used for depolymerization in the present invention is preferably 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 it is less than 1% by weight, the effect due to 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】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。Number average molecular weight of 5,000 used in the present invention
As the carboxylic acid component of the polyester resin (A) of 100,000, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid,
Aromatic dicarboxylic acids such as 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid and 4,4′-diphenyletherdicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer Aliphatic dibasic acids such as acids, alicyclic dibasic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid are mentioned, and terephthalic acid, isophthalic acid, adipic acid and sebacic acid are particularly preferable. .
【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。The glycol component is ethylene glycol, propylene glycol, 1,3-propanediol, 1,
4-butanediol, 1,3-butanediol, 1,2
-Butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentylglycol, diethyleneglycol , Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexane dimethanol, neopentyl hydroxypivalate, bisphenol A ethylene oxide adduct and propylene oxide adduct Products, ethylene oxide adducts of hydrogenated bisphenol A and propylene oxide adducts, 1,9
-Nonanediol, 2-methyloctanediol, 1,
10-dodecanediol, 2-butyl-2-ethyl-
1,3-propanediol, tricyclodecane dimethanol and the like, among them, ethylene glycol,
Neopentyl glycol, cyclohexane dimethano-
Le, neopentyl hydroxypivalate ester, 2-
Butyl-2-ethyl-1,3 propanediol and tricyclodecane dimethanol are preferred. In addition, polyethers such as polytetramethylene glycol, polypropylene glycol and polyethylene glycol are also included.
【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１０，０００〜４０，０
００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５，０
００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。Polyester resin (A) used in the present invention
Having a number average molecular weight of 5,000 to 100,000, preferably a number average molecular weight of 10,000 to 400,000.
Use 00. Since the molecular weight of the modified polyester resin obtained by depolymerization in the present invention is lower than the original molecular weight, the number average molecular weight of the polyester resin (A) is 5,0.
If it is less than 00, the mechanical properties are poor. When the number average molecular weight of the polyester resin (A) exceeds 100,000,
Melt viscosity becomes too high and depolymerization does not proceed uniformly.
【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。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 is carried out in a molten state at a temperature at which a transesterification reaction or an amidation reaction occurs, in view of reaction efficiency. desirable. Examples of the apparatus used for denaturation include a kneader, an extruder and a reaction kettle. The modification may be carried out continuously or separately from the polyester polymerization reaction. A catalyst for a transesterification reaction or an amidation reaction which is usually used in the depolymerization reaction may be used.
【００１３】[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。[Function] The modification of the polyester resin of the present invention focuses on the ester bond present at a high concentration in the polyester resin,
A polyester resin is depolymerized 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 for depolymerization is not good is utilized, the decrease in the molecular weight of the polyester resin is small, and gelation does not occur during depolymerization.
【００１４】[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。The present invention will be specifically illustrated by the following 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, tetrabutyl titanate.
07 parts were charged into an autoclave, a transesterification reaction was carried out at 180 to 210 ° C. for 4 hours, and then the reaction system was heated to 20
The pressure was reduced to 5 mmHg over minutes, and the temperature was raised to 270 ° C. during this period. Furthermore, the polycondensation reaction was carried out at 270 ° C. for 100 minutes, and finally the pressure reached a degree of reduced pressure of 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 added 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 polyester resin before modification were analyzed by gel permeation chromatography in a tetrahydrofuran (THF) solution, and the acid value (equivalent / ton) of the resin was 1/10 N KOH ethanol. It was determined by analysis by titration in solution. Moreover, the composition analysis of the polyester resin before and after modification was performed by NMR. Furthermore, the polyester resin (1) was mixed with methyl ethyl ketone / toluene = 1 /
One solution was dissolved at 80 ° C. so that the solid content concentration was 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 beginning of dissolution, but neither layer separation nor precipitation was observed. Table 1 shows the results.
【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−４０
Ｓ」）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。Furthermore, a melamine resin (Sumimar M-40 manufactured by Sumitomo Chemical Co., Ltd.
S)) was added so that the solid content weight ratio was 100: 20, and 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 that the thickness after drying was 10 μm, and dried at 150 ° C. for 2 minutes. The curability of the obtained coating film was evaluated by rubbing xylene. Table 3 shows the results.
【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。Examples 2 to 4 As in Example 1, but instead of the polyglycerin (PGL-10) used in Example 1, polyglycerin (PGL-20) having a molecular weight of 1,500 is shown in Table 1. The modified polyester resin (2) was obtained by using in proportion. Table 1 shows the analytical values before and after denaturation
Shown in Similarly, modified polyester resins (3) and (4) were obtained from the polyglycerin shown in Table 1.
【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５
ｍｍＨｇまで減圧し２７０℃まで昇温した時点でゲル化
した。Comparative Example 1 The polyglycerin used in Example 1 was added after the transesterification reaction of Example 1 was completed, and then the polycondensation reaction was carried out under the same conditions as in Example 1. 5 minutes over 20 minutes
Gelation occurred when the pressure was reduced to mmHg and the temperature was raised to 270 ° C.
【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。Comparative Example 2 The transesterification reaction was carried out in the same manner as in Example 1, then the polycondensation reaction was started, and when the molecular weight was 3,800, the polycondensation reaction was terminated, and polyglycerin was used as in Example 1. Denatured. Table 1 shows the analysis results of the modified polyester resin obtained.
【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。Comparative Examples 3 to 4 As in Example 1, except that the polyglycerin (PGL-10) used in Example 1 was replaced by diglycerin having a molecular weight of 166,
Depolymerization was performed using triglycerin having a molecular weight of 240. Table 1 shows the analysis results of the obtained polyester resin.
【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。Comparative Example 5 A solution of the polyester resin (molecular weight: 23,000, acid value: 12 equivalent / ton) before addition of polyglycerin in Example 1 in a methyl ethyl ketone / toluene = 1/1 solid content concentration of 20% was used. The polyglycerin used in 2 was added at room temperature so that the weight ratio of the polyester resin to the polyglycerin was 75:25. The resulting solution separated into two layers after 1 day.
【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＝５０／５
０／１００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。Examples 5 to 7 Polyester resin having an acid value of 8 equivalents per ton of resin and a molecular weight of 25,000 (composition: terephthalic acid / isophthalic acid /
2-methyl-1,3-propylene glycol = 50/5
(0/100 molar ratio) and copolymer resin-1 shown in Table 2 were used for modification by a twin-screw extruder at a mixing temperature of 225 ° C. and a mixing time of 5 minutes. Table 2 shows the analysis results of the obtained modified polyester resin (5). Similarly, a copolymer resin-
Table 2 shows the analysis results of modified polyester resins (6) and (7) using 2 and copolymer resin-3. Further, as in Example 1, the preservability of a 20% solid content solution of methylethylketone / toluene = 1/1 was observed by leaving it at 4 ° C. for 1 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】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。Comparative Examples 6 to 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 only a primary OH group was present at the end of the molecule, and in Comparative Example 7, the compound used was a tertiary carboxylic acid. Only exists. The methyl ethyl ketone / toluene solution of the resin obtained in Comparative Example 7 undergoes layer separation after one day.
【００２３】[0023]
【表１】 [Table 1]
【００２４】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The ratio (wt%) of the modifier (B) represents the weight% of the modifier in the modified polyester. The abbreviations in the table are as follows. T: terephthalic acid I: isophthalic acid EG: ethylene glycol NPG: neopentyl glycol
【００２５】[0025]
【表２】 [Table 2]
【００２６】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)The abbreviations in the table are as follows. Copolymer resin-1: Styrene / methacryl 2-hydroxyethyl methacrylate (50/40/10 mole ratio) Copolymer resin-2: Styrene / methacrylic acid / acrylic acid (50/40/10 mole 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】[0027]
【表３】 [Table 3]
【００２８】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Curability: The coating film was rubbed with a waste cloth impregnated with xylene, and the number of rubbing until the steel sheet was seen was measured. ◯: 50 times or more; Δ: 50 to 10 times; ×: 10 times or less
【００２９】[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。By modifying the polyester resin of the present invention, it is possible to introduce a high concentration of a hydroxyl group, a carboxyl group or an amino group into the polyester resin, and
Since the poor compatibility between the polyester resin and the modifier is used, the decrease in molecular weight is small and gelation does not occur.
Claims (1)
０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３００〜１５，０
００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。 Ｘ：１級ＯＨ基、２級ＯＨ基、１級ＣＯＯＨ基、２級Ｃ
ＯＯＨ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Ｃ
ＯＯＨ基、３級アミノ基 （ただし、ＸとＹとは異なる。）1. A number average molecular weight of 5,000 to 100,000.
No. 0 polyester resin (A) having 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 having a number average molecular weight of 300 to 15,0.
A method for producing a modified polyester resin, which comprises depolymerizing the compound (B) which is 00. X: primary OH group, secondary OH group, primary COOH group, secondary C
OOH group, primary amino group, secondary amino group Y: secondary OH group, tertiary OH group, secondary COOH group, tertiary C
OOH 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 true JPH09136948A (en) | 1997-05-27 |
| JP3546978B2 JP3546978B2 (en) | 2004-07-28 |
Family
ID=17862162
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| 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 |
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| Country | Link |
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| JP (1) | JP3546978B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348363A (en) * | 2001-03-19 | 2002-12-04 | Toyobo Co Ltd | Biodegradable polyester |
| JP2002348366A (en) * | 2001-03-19 | 2002-12-04 | Toyobo Co Ltd | Manufacturing method of biodegradable polyester |
| 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
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348363A (en) * | 2001-03-19 | 2002-12-04 | Toyobo Co Ltd | Biodegradable polyester |
| JP2002348366A (en) * | 2001-03-19 | 2002-12-04 | Toyobo Co Ltd | Manufacturing method of biodegradable polyester |
| WO2020230692A1 (en) | 2019-05-15 | 2020-11-19 | 東洋紡株式会社 | Modified copolymer polyester resin and aqueous dispersion thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3546978B2 (en) | 2004-07-28 |
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