JPH0873579A - Polyester resin, production thereof, paint, and adhesive - Google Patents
Polyester resin, production thereof, paint, and adhesiveInfo
- Publication number
- JPH0873579A JPH0873579A JP20852994A JP20852994A JPH0873579A JP H0873579 A JPH0873579 A JP H0873579A JP 20852994 A JP20852994 A JP 20852994A JP 20852994 A JP20852994 A JP 20852994A JP H0873579 A JPH0873579 A JP H0873579A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- weight
- molecular weight
- acid
- parts
- 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.)
- Granted
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリエチレンテレフタ
レート（ＰＥＴ）フィルムなどのポリエステルフィルム
への接着性に優れ、塗料、接着剤等に有用なポリエステ
ル樹脂、その製造法、塗料及び接着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin having excellent adhesiveness to a polyester film such as a polyethylene terephthalate (PET) film, which is useful for paints, adhesives and the like, a process for producing the same, paints and adhesives.
【０００２】[0002]
【従来の技術】従来、ポリエチレンテレフタレート（Ｐ
ＥＴ）フィルムなどのコーティング用樹脂材料として
は、高分子量飽和ポリエステル樹脂が用いられることが
多い。これは、樹脂構造がＰＥＴに近いため、他の樹脂
系に比較して接着性に優れていることによる。2. Description of the Related Art Conventionally, polyethylene terephthalate (P
High molecular weight saturated polyester resin is often used as a resin material for coating such as ET) film. This is because the resin structure is close to that of PET, and therefore the adhesiveness is superior to other resin systems.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
の高分子量飽和ポリエステル樹脂においても、ＰＥＴフ
ィルムへの接着性、接着後の耐水性など、物性の向上が
さらに求められている。高分子量飽和ポリエステル樹脂
は、単独で又はポリイソシアネート、アミノ樹脂などの
硬化剤と組み合わせて用いられることが多いが、高分子
量直鎖構造のポリエステル樹脂では、接着点となる官能
基が分子鎖の両末端のみで少なく、接着性に劣る場合が
ある。一方、官能基を増やすため分岐構造とする場合、
高分子量化が困難となり、また低分子量化した場合は、
強度、可とう性などが低下し、何れも実用化し難い。However, these high-molecular-weight saturated polyester resins are also required to have improved physical properties such as adhesion to a PET film and water resistance after adhesion. The high molecular weight saturated polyester resin is often used alone or in combination with a curing agent such as polyisocyanate and amino resin.However, in the polyester resin having a high molecular weight linear structure, the functional group serving as an adhesion point has both molecular chains. It may be inferior in adhesiveness because it has few ends only. On the other hand, when a branched structure is used to increase the number of functional groups,
If it becomes difficult to increase the molecular weight, and if the molecular weight decreases,
Strength, flexibility, etc. are reduced, and it is difficult to put them into practical use.
【０００４】これらを解決するものとして、特開昭６３
−９８９７０号公報には、数平均分子量１０，０００以
上の直鎖ポリエステル樹脂をジメチロールプロピオン酸
を用いて解重合することにより接着点となる極性基を樹
脂分子鎖中に導入して、接着性を向上させた分岐ポリエ
ステル樹脂を得る方法が記載されている。この分岐ポリ
エステル樹脂は、合成初期から３価以上の多官能モノマ
ーを配合した場合に比べ、直鎖構造が多く残るため可と
う性に優れ、接着点となるカルボキシル基がポリエステ
ル分子主鎖に導入されるため接着性に優れている。しか
しながら、接着性向上のために、多くの３価以上の多官
能モノマー（例えばジメチロールプロピオン酸）を導入
しようとすると、解重合による分子量低下が大きく、強
度、可とう性など他の特性の低下が著しいという欠点が
ある。As a means for solving these problems, Japanese Patent Laid-Open No. Sho 63 has been proposed.
In JP-98970, a polar group serving as an adhesion point is introduced into a resin molecular chain by depolymerizing a linear polyester resin having a number average molecular weight of 10,000 or more using dimethylolpropionic acid, to thereby improve adhesiveness. A method for obtaining a branched polyester resin having improved This branched polyester resin is superior in flexibility because it has many linear structures as compared with the case where a polyfunctional monomer having a valence of 3 or more is blended from the initial stage of synthesis, and a carboxyl group serving as an adhesion point is introduced into the main chain of the polyester molecule. Therefore, it has excellent adhesiveness. However, when many polyfunctional monomers having a valence of 3 or more (for example, dimethylolpropionic acid) are introduced to improve the adhesiveness, the molecular weight is largely decreased by depolymerization, and other properties such as strength and flexibility are deteriorated. Has the drawback that it is remarkable.
【０００５】一方、強度、耐水性などは、ポリエステル
樹脂の分子量が高い方が一般に優れている。ジメチロー
ルプロピオン酸などの３価以上の多官能モノマーを合成
初期から配合してポリエステル樹脂を合成する場合、高
分子量化するために反応を進めると、合成途中にゲル化
し易くなる。また、得られたポリエステル樹脂は、分子
量分散度が広くなりすぎ、高分子量部分が多いと同時
に、低分子量オリゴマーなどが多く含まれるため、耐水
性などの性能低下の原因となりやすい。本発明は、接着
性が良好でかつ、強度、耐水性等の物性に優れた塗料、
接着剤などの材料用として有用なポリエステル樹脂、そ
の製造法、塗料及び接着剤を提供するものである。On the other hand, the higher the molecular weight of the polyester resin, the better the strength and water resistance. When a polyester resin is synthesized by incorporating a polyfunctional monomer having a valence of 3 or more such as dimethylolpropionic acid from the initial stage of the synthesis, if the reaction is advanced to increase the molecular weight, gelation tends to occur during the synthesis. Further, the obtained polyester resin has an excessively wide molecular weight dispersity, has a large amount of high molecular weight portions, and at the same time contains a large amount of low molecular weight oligomers, and therefore tends to cause performance deterioration such as water resistance. The present invention is a coating having good adhesiveness and excellent physical properties such as strength and water resistance,
The present invention provides a polyester resin useful as a material such as an adhesive, a method for producing the same, a paint and an adhesive.
【０００６】[0006]
【課題を解決するための手段】すなわち本発明は、芳香
族ジカルボン酸類及び／又は脂肪族ジカルボン酸類を酸
成分とし、ジアルコール類をアルコール成分として合成
された数平均分子量６，０００以上の直鎖ポリエステル
樹脂１００重量部を、３価以上のヒドロキシカルボン酸
０．２〜１０重量部により解重合して分岐ポリエステル
樹脂を製造し、次いで減圧重縮合反応により重量平均分
子量２０，０００以上に高分子量化することを特徴とす
るポリエステル樹脂の製造法、これにより得られるポリ
エステル樹脂、このポリエステル樹脂を含有してなる塗
料並びに接着剤に関する。That is, the present invention is directed to a linear chain having a number average molecular weight of 6,000 or more synthesized by using aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids as acid components and dialcohols as alcohol components. 100 parts by weight of a polyester resin is depolymerized with 0.2 to 10 parts by weight of a hydroxycarboxylic acid having a valence of 3 or more to produce a branched polyester resin, which is then polymerized to a weight average molecular weight of 20,000 or more by a reduced pressure polycondensation reaction. The present invention relates to a method for producing a polyester resin, a polyester resin obtained by the method, and a paint and an adhesive containing the polyester resin.
【０００７】前記直鎖ポリエステル樹脂の合成に用いら
れる酸成分である芳香族ジカルボン酸類としては、テレ
フタル酸、イソフタル酸、フタル酸、ナフタリンジカル
ボン酸、それらの低級アルキルエステル、酸無水物等が
挙げられ、これらの一種以上を使用することができる。
また脂肪族ジカルボン酸類としては、アジピン酸、セバ
シン酸、アゼライン酸、コハク酸、フマル酸、マレイン
酸、ハイミック酸、１，６−シクロヘキサンジカルボン
酸等があり、これらの低級アルキルエステル、酸無水物
等を用いても良く、これらの一種以上を使用することも
できる。上記芳香族ジカルボン酸類と脂肪族ジカルボン
酸類は、その用途により任意の割合で併用しても良い。Examples of aromatic dicarboxylic acids which are acid components used in the synthesis of the linear polyester resin include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, lower alkyl esters thereof, acid anhydrides and the like. , One or more of these can be used.
Further, examples of the aliphatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid, succinic acid, fumaric acid, maleic acid, hymic acid, 1,6-cyclohexanedicarboxylic acid, etc., and lower alkyl esters thereof, acid anhydrides, etc. Can be used, and one or more of these can also be used. The above-mentioned aromatic dicarboxylic acids and aliphatic dicarboxylic acids may be used in an optional ratio depending on the application.
【０００８】前記直鎖ポリエステル樹脂の合成に用いら
れるアルコール成分であるジアルコール類としては、エ
チレングリコール、プロピレングリコール、１，２−プ
ロパンジオール、１，３−プロパンジオール、１，３−
ブタンジオール、１，４−ブタンジオール、ネオペンチ
ルグリコール、１，５−ペンタンジオール、１，６−ヘ
キサンジオール、３−メチルペンタンジオール、ジエチ
レングリコール、１，４−シクロヘキサンジメタノー
ル、３−メチル１，５−ペンタンジオール、２−メチル
−１，３−プロパンジオール、２，２−ジエチル−１，
３−プロパンジオール、２−ブチル−２−エチル−１，
３−プロパンジオール、キシリレングリコール、水添ビ
スフェノールＡ、ビスフェノールＡ又はこれらのエチレ
ンオキサイド若しくはプロピレンオキサイド付加物等が
あり、これらの１種以上を用いることができる。Examples of dialcohols which are alcohol components used in the synthesis of the linear polyester resin include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol and 1,3-
Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5 -Pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,
3-propanediol, 2-butyl-2-ethyl-1,
There are 3-propanediol, xylylene glycol, hydrogenated bisphenol A, bisphenol A, and ethylene oxide or propylene oxide adducts thereof, and one or more of them can be used.
【０００９】前記直鎖ポリエステル樹脂の製造は、まず
上記の酸成分とアルコール成分を、好ましくは水酸基数
／カルボキシル基数＝１／１〜３／１となるように配合
して用い、必要に応じて、ジブチル錫オキシド、酢酸
鉛、酢酸カルシウム、Ｎーブチルチタネート等の触媒の
存在下に２００〜３００℃にてエステル化又はエステル
交換反応を行ったのち、さらに、必要に応じて、三酸化
アンチモン、酸化ゲルマニウム、Ｎーブチルチタネート
のような触媒の存在下に、好ましくは１３００Ｐａ以
下、特に好ましくは１３０Ｐａ以下の減圧下で、好まし
くは２００〜３００℃、特に好ましくは２３０〜２８０
℃で重縮合反応を行うことができる。この製造におい
て、得られる直鎖ポリエステル樹脂は、数平均分子量
６，０００以上、好ましくは数平均分子量１５，０００
以上に調整される。ここで、数平均分子量が６，０００
未満では、その後の解重合により得られる分岐樹脂の分
子量が低くなりすぎ、再度減圧重縮合し高分子量化する
際に、高分子量化する以前にゲル化する。なお、数平均
分子量の上限は特に制限されないが、通常３０，０００
以下である。In the production of the straight-chain polyester resin, the above-mentioned acid component and alcohol component are first mixed and used so that the number of hydroxyl groups / the number of carboxyl groups = 1/1 to 3/1 is used, and if necessary, , Dibutyltin oxide, lead acetate, calcium acetate, N-butyl titanate, etc., after esterification or transesterification reaction at 200 to 300 ° C., and, if necessary, antimony trioxide, In the presence of a catalyst such as germanium oxide or N-butyl titanate, preferably under reduced pressure of 1300 Pa or less, particularly preferably 130 Pa or less, preferably 200 to 300 ° C., particularly preferably 230 to 280.
The polycondensation reaction can be carried out at ° C. In this production, the obtained linear polyester resin has a number average molecular weight of 6,000 or more, preferably 15,000.
Adjusted above. Here, the number average molecular weight is 6,000.
When the amount is less than 1, the molecular weight of the branched resin obtained by the subsequent depolymerization becomes too low, and when the polycondensation is carried out again under reduced pressure to increase the molecular weight, gelation occurs before the molecular weight increases. The upper limit of the number average molecular weight is not particularly limited, but is usually 30,000.
It is the following.
【００１０】得られた直鎖ポリエステル樹脂を解重合し
て分岐ポリエステル樹脂とするのに用いられる３価以上
のヒドロキシカルボン酸とは、水酸基とカルボキシル基
を各々少なくとも１つ、合計で３つ以上有するものであ
り、ジメチロールプロピオン酸が好ましいものとして挙
げられ、これらを１種以上用いることができる。また、
必要に応じて、他の多価アルコール、例えば、トリメチ
ロールエタン、トリメチロールプロパン、グリセリン、
ペンタエリスリトール等のように水酸基を３つ以上有す
るアルコールや、前述のジアルコールなどを併用するこ
とも可能である。これらのヒドロキシカルボン酸は、前
記の直鎖ポリエステル樹脂１００重量部に対して、０．
２〜１０重量部、好ましくは０．５〜５重量部、特に好
ましくは０．５〜３重量部の割合で用いられる。１０重
量部を超えるとゲル化の可能性が高くなり、高分子量化
が困難であり、０．２重量部未満では接着性向上の効果
が不十分である。The trivalent or higher hydroxycarboxylic acid used for depolymerizing the obtained linear polyester resin to form a branched polyester resin has at least one hydroxyl group and at least one carboxyl group, and a total of three or more. Among them, dimethylolpropionic acid is preferred, and one or more of them can be used. Also,
If desired, other polyhydric alcohols, such as trimethylolethane, trimethylolpropane, glycerin,
It is also possible to use an alcohol having three or more hydroxyl groups such as pentaerythritol and the above-mentioned dialcohol in combination. These hydroxycarboxylic acids are added in an amount of 0.
It is used in a proportion of 2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight. If it exceeds 10 parts by weight, the possibility of gelation becomes high and it is difficult to obtain a high molecular weight. If it is less than 0.2 part by weight, the effect of improving the adhesiveness is insufficient.
【００１１】分岐ポリエステル樹脂の製造は、得られた
直鎖ポリエステル樹脂１００重量部に対して、上記の３
価以上のヒドロキシカルボン酸成分を０．２〜１０重量
部配合し、常圧下、好ましくは２００〜３００℃、特に
好ましくは２１０〜２５０℃で解重合する。ここで得ら
れる分岐ポリエステル樹脂の数平均分子量は、２，００
０以上であることが好ましい。なお、数平均分子量の上
限は特に制限されないが、通常３０，０００以下であ
る。The production of the branched polyester resin is carried out according to the above 3 steps with respect to 100 parts by weight of the obtained linear polyester resin.
0.2 to 10 parts by weight of a hydroxycarboxylic acid component having a valency or more is blended and depolymerized under normal pressure, preferably at 200 to 300 ° C, particularly preferably at 210 to 250 ° C. The number average molecular weight of the branched polyester resin obtained here is 2,000.
It is preferably 0 or more. The upper limit of the number average molecular weight is not particularly limited, but is usually 30,000 or less.
【００１２】次いで、得られた分岐ポリエステル樹脂
に、必要に応じて、三酸化アンチモン、酸化ゲルマニウ
ム、Ｎーブチルチタネートのような触媒を新たに添加
し、好ましくは１３００〜１３０Ｐａ、特に好ましくは
６００〜４００Ｐａの減圧下で、好ましくは１８０〜２
８０℃、特に好ましくは２００〜２６０℃で重縮合反応
を行うことにより、目的のポリエステル樹脂を得ること
ができる。こうして得られるポリエステル樹脂は、重量
平均分子量２０，０００以上に調整する。重量平均分子
量が２０，０００未満では、強度、耐水性等に劣る。な
お、重量平均分子量の上限は特に制限されないが、樹脂
がゲル化する限度まで高分子量化した方が、強度、耐水
性は良好である。通常、重量平均分子量は１００，００
０以下とされる。また、分子量分散度（重量平均分子量
／数平均分子量）は、３〜１５であることが好ましい。
３未満では高分子量部分が少なく、塗膜物性に劣る傾向
にあり、１５を超えると合成中にゲル化し易い。Next, if necessary, a catalyst such as antimony trioxide, germanium oxide or N-butyl titanate is newly added to the obtained branched polyester resin, preferably 1300 to 130 Pa, and particularly preferably 600 to 130 Pa. Under reduced pressure of 400 Pa, preferably 180-2
By carrying out the polycondensation reaction at 80 ° C., particularly preferably 200 to 260 ° C., the target polyester resin can be obtained. The polyester resin thus obtained is adjusted to have a weight average molecular weight of 20,000 or more. When the weight average molecular weight is less than 20,000, strength and water resistance are poor. The upper limit of the weight average molecular weight is not particularly limited, but the higher the molecular weight up to the gelation limit of the resin, the better the strength and water resistance. Usually, the weight average molecular weight is 100,000.
It is set to 0 or less. The molecular weight dispersity (weight average molecular weight / number average molecular weight) is preferably 3 to 15.
When it is less than 3, the high molecular weight portion is small and the physical properties of the coating film tend to be inferior, and when it exceeds 15, gelation tends to occur during synthesis.
【００１３】なお、こうして得られた高分子量ポリエス
テル樹脂は、分子量、酸価、水酸基価などの調整のた
め、安息香酸、メチル安息香酸、パラターシャリ−ブチ
ル安息香酸、イソデカン酸、シクロヘキサン酸、イソオ
クタン酸等の一塩基酸、ラウリン酸、ミリスチン酸、パ
ルミチン酸、ステアリン酸等の各種高級脂肪酸、無水ト
リメリット酸などの多塩基酸、先に示した脂肪族ジカル
ボン酸、芳香族ジカルボン酸などのカルボン酸類、ラウ
リルアルコール、アリルアルコールなどの一価脂肪族ア
ルコール、グリセリン、トリメチロールエタン、トリメ
チロールプロパン、ペンタエリスリトール等の多価脂肪
族アルコール、先に示したジアルコールなどのアルコー
ル類、先に示したジメチロールプロピオン酸等のヒドロ
キシカルボン酸類などで再度解重合することも可能であ
る。The high molecular weight polyester resin thus obtained is used for adjusting the molecular weight, acid value, hydroxyl value, etc., of benzoic acid, methylbenzoic acid, paratertiary-butylbenzoic acid, isodecanoic acid, cyclohexanoic acid, isooctanoic acid, etc. Monobasic acids, lauric acid, myristic acid, palmitic acid, various higher fatty acids such as stearic acid, polybasic acids such as trimellitic anhydride, aliphatic dicarboxylic acids shown above, carboxylic acids such as aromatic dicarboxylic acids, Monohydric aliphatic alcohols such as lauryl alcohol and allyl alcohol, polyhydric aliphatic alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol, alcohols such as the dialcohols described above, and dimethylol described above. Hydroxycarboxylic acids such as propionic acid In it is possible to depolymerize again.
【００１４】この際、解重合に用いる上記の解重合成分
の量は、高分子量ポリエステル樹脂１００重量部に対し
て、好ましくは０．０２〜５重量部、特に好ましくは
０．１〜１重量部で用いられる。解重合成分量が５重量
部を超えると分子量の低下が大きく、強度などの性能が
低下する傾向にあり、０．０２重量部未満では再度の解
重合による、酸価、水酸基価などの調整効果が少ない。
この解重合は、常圧下、２１０〜２５０℃で行うことが
好ましい。再度解重合して得られるポリエステル樹脂
は、重量平均分子量２０，０００以上であることが好ま
しい。重量平均分子量が２０，０００未満では、先に示
したように強度、耐水性に劣る傾向にある。At this time, the amount of the above depolymerization component used for depolymerization is preferably 0.02 to 5 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the high molecular weight polyester resin. Used in. When the amount of the depolymerization component exceeds 5 parts by weight, the molecular weight largely decreases, and the performance such as strength tends to decrease. When the amount is less than 0.02 part by weight, the effect of adjusting the acid value, the hydroxyl value, etc. by re-depolymerization. Less is.
This depolymerization is preferably carried out at 210 to 250 ° C. under normal pressure. The polyester resin obtained by depolymerization again preferably has a weight average molecular weight of 20,000 or more. When the weight average molecular weight is less than 20,000, the strength and water resistance tend to be poor as described above.
【００１５】こうして得られる本発明のポリエステル樹
脂は、直鎖高分子量ポリエステル樹脂を３価以上のヒド
ロキシカルボン酸成分で解重合し、ポリエステル分子鎖
中に分岐成分を導入することで、接着点となる官能基、
特にカルボキシル基が分子鎖の中間に多数導入できるた
め、接着性に優れ、さらに、解重合後、再度減圧重縮合
することにより、低分子量のオリゴマーが少なく、分子
量分散度が小さく、かつ、高分子量の分岐ポリエステル
樹脂となるため、解重合直後の低分子量の分岐ポリエス
テル樹脂又は分岐成分を合成初期から配合し合成した高
分子量ポリエステル樹脂に比べ、強度、耐水性などに優
れている。なお、本発明において「数平均分子量」「重
量平均分子量」とは、ゲルパーミエーションクロマトグ
ラフィーを利用し、標準ポリスチレンの検量線を使用し
て算出したものである。The polyester resin of the present invention thus obtained becomes an adhesive point by depolymerizing a linear high molecular weight polyester resin with a trivalent or higher valent hydroxycarboxylic acid component and introducing a branched component into the polyester molecular chain. Functional group,
In particular, a large number of carboxyl groups can be introduced in the middle of the molecular chain, so it has excellent adhesiveness. Furthermore, after depolymerization, polycondensation under reduced pressure reduces the number of low-molecular weight oligomers, the molecular weight dispersity is low, and the high molecular weight is high. Therefore, it is excellent in strength and water resistance as compared with a low molecular weight branched polyester resin immediately after depolymerization or a high molecular weight polyester resin synthesized by mixing a branching component from the initial stage of synthesis. In the present invention, the "number average molecular weight" and "weight average molecular weight" are calculated by using gel permeation chromatography and using a calibration curve of standard polystyrene.
【００１６】本発明により得られるポリエステル樹脂
は、必要に応じて、その他のポリエステル樹脂、エポキ
シ樹脂、フェノール樹脂、アクリル樹脂等の他の樹脂を
本発明の効果を損なわない程度に混合したり、芳香族炭
化水素、脂肪族炭化水素、エステル類、ケトン類等の溶
剤で希釈することができる。本発明により得られるポリ
エステル樹脂は、単独で又はメラミン、尿素、ベンゾグ
アナミン等のアミノ化合物とホルムアルデヒドとを反応
させて得られるアミノ樹脂、該アミノ樹脂をメタノー
ル、エタノール、プロパノール、ブタノール等の低級ア
ルコールでエーテル化して得られるエーテル化アミノ樹
脂等のアミノ系樹脂、若しくはポリイソシアネートなど
の硬化剤と組み合わせて、使用することができる。得ら
れたポリエステル樹脂を塗料や接着剤とする際には、さ
らに必要に応じて顔料、可塑剤、着色剤、ｐートルエン
スルホン酸、ドデシルベンゼンスルホン酸、ジノニルナ
フタレンスルホン酸、ジノニルナフタレンジスルホン酸
等の酸触媒又はそのブロック体を添加することもでき
る。The polyester resin obtained by the present invention may be mixed with other resins such as polyester resin, epoxy resin, phenol resin, acrylic resin, etc. to the extent that the effects of the present invention are not impaired, and aromatic resins may be used. It can be diluted with a solvent such as a group hydrocarbon, an aliphatic hydrocarbon, an ester or a ketone. The polyester resin obtained by the present invention is an amino resin obtained alone or by reacting an amino compound such as melamine, urea or benzoguanamine with formaldehyde, and the amino resin is ether with a lower alcohol such as methanol, ethanol, propanol or butanol. It can be used in combination with an amino resin such as an etherified amino resin obtained by polymerization, or a curing agent such as polyisocyanate. When the obtained polyester resin is used as a coating material or an adhesive, a pigment, a plasticizer, a colorant, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfone may be added, if necessary. An acid catalyst such as an acid or a block thereof can be added.
【００１７】[0017]
【実施例】次に実施例により本発明を詳述する。以下、
数平均分子量及び重量平均分子量は、日立６３５型ＨＬ
Ｃ装置（(株)日立製作所製）及びカラムとしてゲルパッ
ク（GELPACK）Ｒ４４０、Ｒ４５０、Ｒ４００Ｍ（商品
名、いずれも日立化成工業(株)製）を直列に連結して使
用し、溶離剤としてテトラヒドロフランを使用し、クロ
マトグラムを得た後、標準ポリスチレンを基準にして算
出した。EXAMPLES The present invention will be described in detail with reference to examples. Less than,
For the number average molecular weight and weight average molecular weight, Hitachi 635 Model HL
A C device (manufactured by Hitachi, Ltd.) and a column, GELPACK R440, R450, and R400M (trade names, all manufactured by Hitachi Chemical Co., Ltd.) are connected in series, and tetrahydrofuran is used as an eluent. Used and after obtaining a chromatogram, it was calculated based on standard polystyrene.
【００１８】実施例１ （Ａ）：テレフタル酸１６６重量部（１．０モル）、イ
ソフタル酸８３重量部（０．５モル）、アジピン酸２１
９重量部（１．５モル）、エチレングリコール１２４重
量部（２．０モル）、ネオペンチルグリコール１２５重
量部（１．２モル）及びジブチル錫ジオキシド０．１重
量部を不活性ガス存在下、２５０℃でエステル化反応に
付し、生成する水を除去し、酸価１．０のポリエステル
樹脂中間体（ａ）を得た。 （Ｂ）：（Ａ）で得られたポリエステル樹脂中間体
（ａ）５００重量部に、三酸化アンチモン０．１重量
部、トリエチルホスフェート０．２重量部を加えて、１
００Ｐａの減圧下に、２８０℃で重縮合反応を行い、数
平均分子量２３，０００の高分子量直鎖ポリエステル樹
脂（ｂ）を得た。 （Ｃ）：（Ｂ）で得られた直鎖ポリエステル樹脂（ｂ）
５００重量部に、ジメチロールプロピオン酸１０重量部
を、２６０℃で添加後、１時間保温し、解重合反応を行
い、数平均分子量７，０００、重量平均分子量２０，０
００の分岐ポリエステル樹脂（ｃ−１）を得た。 （Ｄ）：（Ｃ）で得られた分岐ポリエステル樹脂（ｃ−
１）を、再度５００Ｐａの減圧下に、２４０℃で重縮合
反応を行い、数平均分子量１６，０００、重量平均分子
量７０，０００のポリエステル樹脂を得た。Example 1 (A): terephthalic acid 166 parts by weight (1.0 mol), isophthalic acid 83 parts by weight (0.5 mol), adipic acid 21
9 parts by weight (1.5 moles), 124 parts by weight (2.0 moles) of ethylene glycol, 125 parts by weight (1.2 moles) of neopentyl glycol and 0.1 part by weight of dibutyltin dioxide were added in the presence of an inert gas. An esterification reaction was carried out at 250 ° C. to remove the produced water to obtain a polyester resin intermediate (a) having an acid value of 1.0. (B): To 500 parts by weight of the polyester resin intermediate (a) obtained in (A), 0.1 parts by weight of antimony trioxide and 0.2 parts by weight of triethyl phosphate were added, and 1
A polycondensation reaction was performed at 280 ° C. under a reduced pressure of 00 Pa to obtain a high molecular weight linear polyester resin (b) having a number average molecular weight of 23,000. (C): Linear polyester resin (b) obtained in (B)
To 500 parts by weight, 10 parts by weight of dimethylolpropionic acid was added at 260 ° C., and then kept at the temperature for 1 hour to carry out a depolymerization reaction to obtain a number average molecular weight of 7,000 and a weight average molecular weight of 20,0.
00 branched polyester resin (c-1) was obtained. (D): Branched polyester resin (c- obtained in (C)
1) was again subjected to a polycondensation reaction at 240 ° C. under a reduced pressure of 500 Pa to obtain a polyester resin having a number average molecular weight of 16,000 and a weight average molecular weight of 70,000.
【００１９】実施例２ 実施例１の（Ｃ）において、解重合に用いたジメチロー
ルプロピオン酸を２５重量部とした以外は、実施例１と
同様に操作し、数平均分子量３，５００、重量平均分子
量１５，０００の分岐型ポリエステル樹脂（ｃ−２）を
得た。さらに、（ｃ−２）を用いて実施例１の（Ｄ）と
同様に操作し、数平均分子量１４，０００、重量平均分
子量６５，０００のポリエステル樹脂を得た。 実施例３ 実施例１の（Ｃ）において、解重合に用いたジメチロー
ルプロピオン酸を３重量部とした以外は、実施例１と同
様に操作し、数平均分子量１１，０００、重量平均分子
量３０，０００の分岐ポリエステル樹脂（ｃ−３）を得
た。さらに、（ｃ−３）を用いて実施例１の（Ｄ）と同
様に操作し、数平均分子量２０，０００、重量平均分子
量７５，０００のポリエステル樹脂を得た。Example 2 The procedure of Example 1 was repeated except that the amount of dimethylolpropionic acid used in the depolymerization was changed to 25 parts by weight in (C) of Example 1, and the number average molecular weight was 3,500 and the weight was 3,500. A branched polyester resin (c-2) having an average molecular weight of 15,000 was obtained. Further, using (c-2), the same operation as in (D) of Example 1 was carried out to obtain a polyester resin having a number average molecular weight of 14,000 and a weight average molecular weight of 65,000. Example 3 The procedure of Example 1 (C) was repeated except that the dimethylolpropionic acid used for depolymerization was changed to 3 parts by weight, and the number average molecular weight was 11,000 and the weight average molecular weight was 30. 1,000 branched polyester resins (c-3) were obtained. Further, using (c-3), the same operation as in (D) of Example 1 was carried out to obtain a polyester resin having a number average molecular weight of 20,000 and a weight average molecular weight of 75,000.
【００２０】実施例４ 実施例１の（Ｃ）において、解重合に用いたジメチロー
ルプロピオン酸を４０重量部とした以外は、実施例１と
同様に操作し、数平均分子量２，２００、重量平均分子
量１０，０００の分岐ポリエステル樹脂（ｃ−４）を得
た。さらに、（ｃ−４）を用いて実施例１の（Ｄ）と同
様に操作し、数平均分子量１２，０００、重量平均分子
量６０，０００のポリエステル樹脂を得た。 実施例５ 実施例１で得られたポリエステル樹脂５００重量部に、
ジメチロールプロピオン酸１重量部を、２６０℃で添加
後、１時間保温し解重合反応を行い、数平均分子量１
２，０００、重量平均分子量５０，０００のポリエステ
ル樹脂を得た。Example 4 The procedure of Example 1 was repeated except that the amount of dimethylolpropionic acid used for depolymerization was changed to 40 parts by weight in (C) of Example 1, and the number average molecular weight was 2,200 and the weight was 2,200. A branched polyester resin (c-4) having an average molecular weight of 10,000 was obtained. Further, using (c-4), the same operation as in (D) of Example 1 was carried out to obtain a polyester resin having a number average molecular weight of 12,000 and a weight average molecular weight of 60,000. Example 5 To 500 parts by weight of the polyester resin obtained in Example 1,
After adding 1 part by weight of dimethylolpropionic acid at 260 ° C., the mixture was kept warm for 1 hour to carry out a depolymerization reaction to give a number average molecular weight of 1
A polyester resin having a weight average molecular weight of 2,000 and a weight average molecular weight of 50,000 was obtained.
【００２１】比較例１ 実施例１で（Ｃ）において得られた、分岐ポリエステル
樹脂（ｃ−１）。 比較例２ 実施例２で（Ｃ）において得られた、分岐ポリエステル
樹脂（ｃ−２）。 比較例３ 実施例３で（Ｃ）において得られた、分岐ポリエステル
樹脂（ｃ−３）。 比較例４ 実施例４で（Ｃ）において得られた、分岐ポリエステル
樹脂（ｃ−４）。 比較例５ 実施例１で（Ｂ）で得られた直鎖ポリエステル樹脂
（ｂ）。Comparative Example 1 Branched polyester resin (c-1) obtained in (C) in Example 1. Comparative Example 2 The branched polyester resin (c-2) obtained in (C) in Example 2. Comparative Example 3 The branched polyester resin (c-3) obtained in (C) in Example 3. Comparative Example 4 The branched polyester resin (c-4) obtained in (C) in Example 4. Comparative Example 5 Linear polyester resin (b) obtained in (B) in Example 1.
【００２２】比較例６ 実施例１の（Ｃ）において得られた分岐ポリエステル樹
脂（ｃー１）を、再度１００Ｐａの減圧下に、２８０℃
で重縮合反応を行ったが、短時間で樹脂がゲル化し、目
標の樹脂が得られなかった。 比較例７ 実施例２の（Ｃ）において得られた分岐ポリエステル樹
脂（ｃー１）を、再度１００Ｐａの減圧下に、２８０℃
で重縮合反応を行った結果、短時間で樹脂がゲル化し、
目標の樹脂が得られなかった。Comparative Example 6 The branched polyester resin (c-1) obtained in (C) of Example 1 was again subjected to a reduced pressure of 100 Pa at 280 ° C.
The polycondensation reaction was carried out in 1. However, the resin gelled in a short time and the target resin could not be obtained. Comparative Example 7 The branched polyester resin (c-1) obtained in (C) of Example 2 was again subjected to a reduced pressure of 100 Pa at 280 ° C.
As a result of polycondensation reaction with, the resin gelled in a short time,
The target resin was not obtained.
【００２３】各実施例及び比較例に得られた樹脂をそれ
ぞれトルエン／メチルエチルケトン＝５０／５０（重量
比）により、加熱残分４０重量％の樹脂液に調製した。
こうして得た樹脂液を下記の配合によりクリアエナメル
とし試験を行った。実施例又は比較例のポリエステル樹
脂（加熱残分４０重量％）１００重量部、コロネートＬ
（日本ポリウレタン(株)製ポリイソシアネート）５重量
部を配合し、トルエン／メチルエチルケトン＝５０／５
０（重量比）により希釈し、加熱残分１５重量％（接着
性試験用）及び加熱残分３０重量％（フィルム強度、耐
水性試験用）のクリアエナメルを得た。The resin obtained in each of the examples and comparative examples was prepared into a resin liquid having a heating residue of 40% by weight with toluene / methylethylketone = 50/50 (weight ratio).
The resin liquid thus obtained was tested as clear enamel with the following formulation. 100 parts by weight of polyester resin (residual heating 40% by weight) of Example or Comparative Example, Coronate L
(Polyisocyanate manufactured by Nippon Polyurethane Co., Ltd.) 5 parts by weight was mixed, and toluene / methyl ethyl ketone = 50/5.
Diluted with 0 (weight ratio) to obtain a clear enamel having a heating residue of 15% by weight (for adhesion test) and a heating residue of 30% by weight (for film strength and water resistance test).
【００２４】得られたクリアエナメルを用いて、下記の
試験を行った。 １．接着性試験 基材：ポリエステル（ＰＥＴ）フィルム（１２μｍ） 塗布：固形分６ｇ／ｍ2、アプリケータ塗布 乾燥：８０℃、２０秒 接着：上記、ポリエステルクリアエナメルを塗布したフ
ィルムに未塗布フィルムをヒートロールで１００℃、５
kg／cm2の条件で１分間転圧し接着した。 接着性試験方法：引張り試験機（(株)島津製作所製オー
トグラフ）を用いて、２０℃でＴ剥離試験（引っ張り速
度５０mm／分）を行った。結果は、接着力（Ｎ／ｍ）で
示した。The following tests were conducted using the obtained clear enamel. 1. Adhesion test Substrate: Polyester (PET) film (12 μm) Application: Solid content 6 g / m 2 , applicator application Drying: 80 ° C., 20 seconds Adhesion: Heat the uncoated film to the above polyester clear enamel coated film Roll at 100 ℃, 5
Adhesion was performed by rolling under a condition of kg / cm 2 for 1 minute. Adhesion test method: A T-peel test (pulling speed: 50 mm / min) was performed at 20 ° C. using a tensile tester (Autograph manufactured by Shimadzu Corporation). The results are shown in adhesive strength (N / m).
【００２５】２．フィルム引張り試験、耐水性試験 基材：ブリキ板 塗布：アプリケータ塗布（乾燥膜厚２５μｍ） 乾燥：１００℃で５時間。ついで１５０℃で１２時間。 フィルム引張り試験方法：上記のクリアエナメルを塗
布、乾燥したブリキ板から水銀アマルガム法により単離
したフィルムを、引張り試験機（(株)島津製作所製オー
トグラフ）を用いて、２０℃で引張り試験（引張り速度
５０mm／分）を行った。結果は、破断強度（Ｎ／ｍ2）
及び破断伸び率（％）で示した。 耐水性試験：上記のクリアエナメルを塗布乾燥したブリ
キ板を、沸水中に２時間浸漬後、ブリスターの発生、密
着性（ＪＩＳＫ５４００に示された碁盤目テープ法で、
すきま間隔１mmで試験）を評価した。2. Film tensile test, water resistance test Substrate: Tin plate Coating: Applicator coating (dry film thickness 25 μm) Drying: 100 ° C. for 5 hours. Then at 150 ° C for 12 hours. Film tensile test method: A film isolated by a mercury amalgam method from a tin plate coated with the above-mentioned clear enamel and dried, was subjected to a tensile test at 20 ° C. using a tensile tester (Autograph manufactured by Shimadzu Corporation) ( A pulling speed of 50 mm / min) was performed. The result is the breaking strength (N / m 2 ).
And the elongation at break (%). Water resistance test: A tin plate coated with the above-mentioned clear enamel and dried was immersed in boiling water for 2 hours, and then blister generation and adhesion (by the cross-cut tape method shown in JIS K5400,
The test was evaluated at a clearance of 1 mm.
【００２６】上記による試験結果を表１に示す。The test results according to the above are shown in Table 1.
【表１】 [Table 1]
【００２７】得られた実施例１〜５のポリエステル樹脂
は、ＰＥＴフィルムへの接着性に優れていると同時に、
強度、耐水性が良好である。これに対して、比較例１〜
４は、実施例１〜５のポリエステル樹脂を得る際の、ジ
メチロールプロピオン酸による解重合により得られた分
岐ポリエステル樹脂を再度高分子量化せずに使用した場
合であるが、接着性は、比較例５の直鎖ポリエステル樹
脂に比べ良好であるものの、各々の分岐ポリエステル樹
脂を高分子量化した、実施例１〜５のポリエステルに比
べ、強度、耐水性に劣っている。比較例６及び７は、解
重合後の減圧重縮合による高分子量化を比較的に低真空
度、高温下に実施した例であるが、終点制御が困難であ
り、樹脂のゲル化を招いている。The obtained polyester resins of Examples 1 to 5 have excellent adhesiveness to a PET film, and at the same time,
Good strength and water resistance. On the other hand, Comparative Examples 1 to 1
4 is a case where the branched polyester resin obtained by depolymerization with dimethylolpropionic acid when obtaining the polyester resins of Examples 1 to 5 was used without being made into a high molecular weight again, but the adhesiveness was compared. Although it is better than the linear polyester resin of Example 5, it is inferior in strength and water resistance to the polyesters of Examples 1 to 5 in which each branched polyester resin has a high molecular weight. Comparative Examples 6 and 7 are examples in which high molecular weight polymerization by decompression polycondensation after depolymerization was carried out at a relatively low vacuum and high temperature, but it was difficult to control the end point, which caused gelation of the resin. There is.
【００２８】[0028]
【発明の効果】本発明によれば、ポリエステルフィルム
などへの接着性に優れているだけでなく、強度、耐水性
にも優れ、塗料用、接着剤用などとして有用なポリエス
テル樹脂を得ることができる。According to the present invention, it is possible to obtain a polyester resin which is not only excellent in adhesion to a polyester film and the like, but also excellent in strength and water resistance and which is useful for paints and adhesives. it can.
Claims (8)
ジカルボン酸類を酸成分とし、ジアルコール類をアルコ
ール成分として合成された数平均分子量６０００以上の
直鎖ポリエステル樹脂１００重量部を、３価以上のヒド
ロキシカルボン酸０．２〜１０重量部により解重合して
分岐ポリエステル樹脂を製造し、次いで減圧重縮合反応
により重量平均分子量２０，０００以上に高分子量化す
ることを特徴とするポリエステル樹脂の製造法。1. 100 parts by weight of a linear polyester resin having a number average molecular weight of 6000 or more synthesized using an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid as an acid component and a dialcohol as an alcohol component is trivalent or more. A method for producing a polyester resin, which comprises depolymerizing with 0.2 to 10 parts by weight of a hydroxycarboxylic acid to produce a branched polyester resin, and then reducing the molecular weight to a molecular weight of 20,000 or more by polycondensation under reduced pressure. .
０，０００以上のポリエステル樹脂を、カルボン酸類、
アルコール類及び／又はヒドロキシカルボン酸類で再度
解重合することを特徴とするポリエステル樹脂の製造
法。2. The weight average molecular weight 2 obtained in claim 1.
50,000 or more polyester resins, carboxylic acids,
A method for producing a polyester resin, which comprises depolymerizing again with alcohols and / or hydroxycarboxylic acids.
ルボン酸が、ジメチロールプロピオン酸である請求項１
又は２記載のポリエステル樹脂の製造法。3. The hydroxycarboxylic acid having a valence of 3 or more used for depolymerization is dimethylolpropionic acid.
Or the method for producing a polyester resin according to 2.
ルボン酸の量が、直鎖ポリエステル樹脂１００重量部に
対して０．５〜５．０重量部である請求項１、２又は３
記載のポリエステル樹脂の製造法。4. The amount of hydroxycarboxylic acid having a valence of 3 or more used for depolymerization is 0.5 to 5.0 parts by weight based on 100 parts by weight of the linear polyester resin.
A method for producing the described polyester resin.
ルボン酸の量が、直鎖ポリエステル樹脂１００重量部に
対して０．５〜３．０重量部である請求項１、２又は３
記載のポリエステル樹脂の製造法。5. The amount of trivalent or higher valent hydroxycarboxylic acid used for depolymerization is 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the linear polyester resin.
A method for producing the described polyester resin.
により得られるポリエステル樹脂。6. A polyester resin obtained by the method according to claim 1.
してなる塗料。7. A paint comprising the polyester resin according to claim 6.
してなる接着剤。8. An adhesive containing the polyester resin according to claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20852994A JP3424857B2 (en) | 1994-09-01 | 1994-09-01 | Polyester resin, its production method, paint and adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20852994A JP3424857B2 (en) | 1994-09-01 | 1994-09-01 | Polyester resin, its production method, paint and adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0873579A true JPH0873579A (en) | 1996-03-19 |
| JP3424857B2 JP3424857B2 (en) | 2003-07-07 |
Family
ID=16557700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20852994A Expired - Lifetime JP3424857B2 (en) | 1994-09-01 | 1994-09-01 | Polyester resin, its production method, paint and adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3424857B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001288403A (en) * | 2000-02-01 | 2001-10-16 | Unitika Ltd | Water-base coating composition |
| JP2007191656A (en) * | 2006-01-23 | 2007-08-02 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same |
| JP2007320976A (en) * | 2006-05-30 | 2007-12-13 | Nitto Denko Corp | Flame-retardant adhesive sheet |
| JP2009007544A (en) * | 2007-05-29 | 2009-01-15 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009242713A (en) * | 2008-03-31 | 2009-10-22 | Unitika Ltd | Polyester resin pellet and method of manufacturing the same, and aqueous dispersion of polyester resin |
-
1994
- 1994-09-01 JP JP20852994A patent/JP3424857B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001288403A (en) * | 2000-02-01 | 2001-10-16 | Unitika Ltd | Water-base coating composition |
| JP2007191656A (en) * | 2006-01-23 | 2007-08-02 | Nitto Denko Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using the same |
| JP2007320976A (en) * | 2006-05-30 | 2007-12-13 | Nitto Denko Corp | Flame-retardant adhesive sheet |
| JP2009007544A (en) * | 2007-05-29 | 2009-01-15 | Toyo Ink Mfg Co Ltd | Polyester resin and pressure-sensitive adhesive composition |
| JP2009242713A (en) * | 2008-03-31 | 2009-10-22 | Unitika Ltd | Polyester resin pellet and method of manufacturing the same, and aqueous dispersion of polyester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3424857B2 (en) | 2003-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4071578A (en) | One-coat polyester-based coating and method of making same | |
| JPS61236865A (en) | Coating material composition for coating coil | |
| JPH073203A (en) | Radical-curable coating composition and method of coating base wood therewith | |
| JPS5949260B2 (en) | Polyester resin composition for powder coatings | |
| JPS5935928B2 (en) | Sulfonka polyarylether sulfone diyushino | |
| EP0134691A2 (en) | Compositions curable at ambient or slightly elevated temperatures comprising a polyhxdroxy compound together with a specified epoxide/carboxylic anhydride crosslinking system | |
| US6218448B1 (en) | Mixtures or pastes based on cellulose and the use thereof in coatings | |
| JP2858895B2 (en) | Polyesters containing acryloyl groups | |
| US5068125A (en) | Process for the production of coatings based on unsaturated polyester resins by hardening under infra-red radiation | |
| JP3424857B2 (en) | Polyester resin, its production method, paint and adhesive | |
| US4668763A (en) | Polyesters containing side chains and the use thereof | |
| 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 | |
| US4379895A (en) | Acid-capped polyester resins | |
| JP2510513B2 (en) | Hydroxyl polyester liquid at room temperature having an OH-value of 10-100 and process for its preparation | |
| US4113898A (en) | Method of applying powder coatings of unsaturated branched hydroxyester resins | |
| JP2666496B2 (en) | Manufacturing method of polyester resin for coating | |
| JP3601560B2 (en) | Polyester resin manufacturing method and paint manufacturing method | |
| US3275710A (en) | Air-drying linear polyester resins | |
| US4365046A (en) | Process to control the curing reaction between a copolyester resin and an epoxide compound, and a composition formed for that process | |
| EP0351024A2 (en) | Process for the preparation of polyesters | |
| JP3546978B2 (en) | Method for producing modified polyester resin | |
| JP2667896B2 (en) | Polyester and resin composition for paint | |
| JPS6226677B2 (en) | ||
| USRE32029E (en) | Process to control the curing reaction between a copolyester resin and an epoxide compound, and a composition formed for that process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20090502 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100502 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100502 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110502 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 8 Free format text: PAYMENT UNTIL: 20110502 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120502 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130502 Year of fee payment: 10 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130502 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |