JPH05214121A - Polyester-based thermosetting resin film - Google Patents
Polyester-based thermosetting resin filmInfo
- Publication number
- JPH05214121A JPH05214121A JP4754992A JP4754992A JPH05214121A JP H05214121 A JPH05214121 A JP H05214121A JP 4754992 A JP4754992 A JP 4754992A JP 4754992 A JP4754992 A JP 4754992A JP H05214121 A JPH05214121 A JP H05214121A
- Authority
- JP
- Japan
- Prior art keywords
- film
- thermosetting resin
- polyester
- resin film
- blend
- 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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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、可撓性、寸法安定性、
防融性、耐薬品性に優れたポリエステル系熱硬化性樹脂
フィルムに関するものである。更に詳しくは可撓性に乏
しく、脆いという問題のある熱硬化性樹脂組成物を硬化
させて得られるフイルムについて、ポリエステル系樹脂
の組成や硬化剤等の組合せ、硬化条件によりフイルムに
可撓性を持たせ、実用に供し得る熱硬化性樹脂フイルム
に関するものである。FIELD OF THE INVENTION The present invention provides flexibility, dimensional stability,
The present invention relates to a polyester thermosetting resin film having excellent anti-fusing property and chemical resistance. More specifically, regarding a film obtained by curing a thermosetting resin composition having poor flexibility and brittleness, flexibility of the film can be obtained depending on the combination of the composition of the polyester resin, the curing agent, and the curing conditions. The present invention relates to a thermosetting resin film which can be used and put to practical use.
【０００２】[0002]
【従来の技術】従来、モーター用絶縁フィルムやフレキ
シブルプリント基板等の寸法安定性、防融性、耐薬品性
を要求される分野では、一般の衣料用、産業資材用ポリ
エステルやポリアミド等の熱可塑性樹脂フィルムではこ
れらの性能が十分でなく、使用条件に制限があった。ま
た、ポリエーテルエーテルケトンやポリイミド等の高耐
熱性樹脂ではコストが高かったり、フィルム成形性がよ
くなかったりする等の問題があった。2. Description of the Related Art Conventionally, thermoplastic resin such as polyester and polyamide for general clothing and industrial materials has been used in the fields where dimensional stability, melting resistance and chemical resistance of insulating films for motors and flexible printed circuit boards are required. The resin film is not sufficient in these performances, and there is a limitation in use conditions. Further, high heat resistant resins such as polyetheretherketone and polyimide have problems such as high cost and poor film formability.
【０００３】熱硬化性樹脂等の架橋型の樹脂は、一般に
安価で寸法安定性、防融性、耐薬品性もよいが、可撓性
に乏しく脆いといった問題があった。Crosslinking resins such as thermosetting resins are generally inexpensive and have good dimensional stability, melting resistance and chemical resistance, but have the problem of poor flexibility and brittleness.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記のよう
な欠点を解消し、安価で寸法安定性、防融性、耐薬品性
にも優れ、しかも、可撓性、強度共に満足し得るポリエ
ステル系熱硬化性樹脂フィルムを提供するものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks, is inexpensive, is excellent in dimensional stability, antifussion property and chemical resistance, and is satisfactory in flexibility and strength. A polyester thermosetting resin film is provided.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、このよう
な状況に対して、上記のごとき問題のない熱硬化性樹脂
フィルムについて鋭意研究を重ねた結果、芳香族成分と
脂肪族成分を適度に含有しているポリエステル系樹脂を
その硬化剤により架橋させることにより得られる熱硬化
性樹脂フィルムが可撓性を有し、かつ、寸法安定性、防
融性、耐薬品性についても満足し得るものであることを
見いだし本発明に到達した。すなわち、本発明の要旨は
次のとおりである。Means for Solving the Problems Under these circumstances, the present inventors have conducted earnest studies on a thermosetting resin film having no problem as described above, and as a result, have identified aromatic components and aliphatic components. The thermosetting resin film obtained by cross-linking the polyester resin contained in a proper amount with the curing agent has flexibility, and also satisfies the dimensional stability, the fusion resistance and the chemical resistance. They have found that they have something to gain, and have arrived at the present invention. That is, the gist of the present invention is as follows.
【０００６】ポリエステル系樹脂とその硬化剤からな
り、破断強度が５Kgf/mm2 以上、２００℃における乾熱
収縮率が１．０％以下、破断伸度が２．０％以上で３０
０℃以上の防融性を有し、８０℃の５％水酸化ナトリウ
ム水溶液強度保持率が９０％以上の可撓性を有するポリ
エステル系熱硬化性樹脂フイルムに関する。It is composed of polyester resin and its curing agent and has a breaking strength of 5 kgf / mm 2 or more, a dry heat shrinkage ratio at 200 ° C. of 1.0% or less, and an elongation at break of 2.0% or more of 30.
The present invention relates to a polyester thermosetting resin film having a melting resistance of 0 ° C. or higher and a flexibility of maintaining a strength of a 5% sodium hydroxide aqueous solution at 80 ° C. of 90% or higher.
【０００７】本発明のフィルムは、破断強度が５Kgf/mm
2 以上必要である。これ以下のものはフィルムの強度が
弱く実用に適さない。また、２００℃における乾熱収縮
率が１．０％以下であることが必要で、これより収縮率
が大きくなると寸法安定性が必要な所では使用できな
い。The film of the present invention has a breaking strength of 5 Kgf / mm.
2 or more is required. Films of less than this are not suitable for practical use because the strength of the film is weak. Further, the dry heat shrinkage at 200 ° C. is required to be 1.0% or less, and if the shrinkage is higher than this, it cannot be used in a place where dimensional stability is required.
【０００８】本発明のフィルムは、破断伸度が２．０％
以上必要である。これ以下のものはフィルムの可撓性に
乏しく、フィルムを折り曲げると破断してしまい、実用
に適さない。The film of the present invention has a breaking elongation of 2.0%.
The above is necessary. Films less than this are not suitable for practical use because the film is poor in flexibility and breaks when the film is bent.
【０００９】本発明のいう防融性とは、フィルムに高温
の物体が接触して、接触した部分のフィルムが溶融、収
縮して孔があいてしまうことがない性質である。通常の
ポリエステルフィルムでは、ポリエステルの融点以上の
温度の物体が接触すると簡単に孔があいてしまうが、本
発明のフィルムはフィルムを構成する分子が架橋されて
いるので３００℃以上の物体が接触しても溶融すること
なく、したがって孔もあかないのである。The anti-fusing property referred to in the present invention is a property in which a high temperature object does not come into contact with the film and the film in the contacted part is not melted and shrunk to form a hole. In a normal polyester film, when an object having a temperature higher than the melting point of polyester comes into contact with the film, holes are easily formed. However, it does not melt and therefore has no holes.
【００１０】本発明のフィルムは８０℃の５％水酸化ナ
トリウム（以下NaOHと記す）水溶液に１時間浸漬したと
きの強度保持率が９０％以上であり、その他に酸や有機
溶剤に対しても優れた耐薬品性を有している。The film of the present invention has a strength retention of 90% or more when immersed in a 5% sodium hydroxide (hereinafter referred to as NaOH) aqueous solution at 80 ° C. for 1 hour, and also with respect to acids and organic solvents. Has excellent chemical resistance.
【００１１】本発明のフィルムは、ポリエステル系樹脂
とその硬化剤、硬化触媒、その他添加剤等から成る樹脂
組成物をフィルム状に成形し、これを硬化させればよい
のであるが、工業的に有利に得るという点から次の方法
が好ましい。すなわち、熱硬化性樹脂組成物を粉末状に
粉砕し、これを基材上に均一に散布した後、この基材を
熱硬化性樹脂組成物が溶融流動し、かつ実質的に硬化反
応が可能な温度以上で熱処理することにより熱硬化性樹
脂組成物を溶融させるとともに架橋させてフィルム状と
し、基材とフィルムを分離して熱硬化性樹脂フィルムを
得る方法による。The film of the present invention can be obtained by molding a resin composition comprising a polyester resin and its curing agent, curing catalyst, other additives, etc. into a film and curing it. The following method is preferable from the viewpoint of obtaining the advantage. That is, the thermosetting resin composition is pulverized into a powder, and the powder is evenly dispersed on the base material. Then, the thermosetting resin composition melts and flows on the base material, and the curing reaction is substantially possible. It is a method of obtaining a thermosetting resin film by melting the thermosetting resin composition and crosslinking it to form a film by heat treatment at a temperature not lower than that, and separating the film from the substrate.
【００１２】実際には、熱硬化性樹脂組成物の粉砕は５
０メッシュ以下にするのがよく、より好ましくは１４５
メッシュ以下にするのがよい。これより大きくなるとフ
ィルム表面が粗くなり平滑性が損なわれる。粉砕には、
十分に冷却固化した熱硬化性樹脂組成物をボールミルで
粉砕するのが均一な粉体が得られるので好ましい。In practice, the crushing of the thermosetting resin composition is 5
0 mesh or less is preferable, and 145 is more preferable.
It is better to have a mesh or less. If it is larger than this, the film surface becomes rough and smoothness is impaired. For crushing,
It is preferable to pulverize the thermosetting resin composition that has been sufficiently cooled and solidified with a ball mill because a uniform powder can be obtained.
【００１３】次に、熱硬化性樹脂組成物の基材上への散
布は、粉砕した熱硬化性樹脂組成物の粉体を金属または
樹脂等の基材上に均一に散布すればよいのであるが、よ
り好ましくは粉砕した熱硬化性樹脂組成物の粉体に静電
気を帯電させ、これを金属製の板上に散布し、静電気の
作用で粉体を板の表面に吸着させる方法が簡便かつ均一
に行える。しかも静電気による吸着であるので、任意の
形状のものに、任意の厚さで熱硬化性樹脂組成物の粉体
を吸着させることができ、従って任意の形状の熱硬化性
フィルムを製造することができる。また、基材上に分散
させる熱硬化性樹脂組成物の量を加減することにより容
易にフィルムの厚さを制御できる。なお、金属製の板の
表面はフィルムの分離性をよくするためにフッ素系また
はシリコン系の離型剤で処理しておくのが好ましい。Next, the application of the thermosetting resin composition onto the substrate may be carried out by uniformly applying the pulverized powder of the thermosetting resin composition onto the substrate such as metal or resin. However, more preferably, a method of charging the powder of the crushed thermosetting resin composition with static electricity, spraying this on a metal plate, and adsorbing the powder to the surface of the plate by the action of static electricity is simple and easy. Can be done uniformly. Moreover, since it is adsorbed by static electricity, it is possible to adsorb the powder of the thermosetting resin composition to an arbitrary shape with an arbitrary thickness, and thus it is possible to produce a thermosetting film having an arbitrary shape. it can. Further, the thickness of the film can be easily controlled by adjusting the amount of the thermosetting resin composition dispersed on the substrate. The surface of the metal plate is preferably treated with a fluorine-based or silicon-based release agent in order to improve the separability of the film.
【００１４】熱処理については、恒温の炉の中で行い、
熱硬化性樹脂組成物が溶融流動し、かつ実質的に硬化反
応が可能な温度以上で行う。しかし、必要以上に高温で
長時間行うとフィルムが脆くなり、可撓性が得られなく
なる。The heat treatment is carried out in a constant temperature oven,
It is carried out at a temperature at which the thermosetting resin composition melts and flows and a curing reaction can be substantially performed. However, if the film is heated at an unnecessarily high temperature for a long time, the film becomes brittle and flexibility cannot be obtained.
【００１５】また、フィルムの基材からの分離は、熱硬
化したフィルムを基材からはがすことにより簡単に分離
できる。The film can be easily separated from the substrate by peeling the thermoset film from the substrate.
【００１６】本発明において、その特性を発揮するため
の熱硬化性樹脂組成物において、ポリエステル樹脂の組
成としては、ジカルボン酸成分としてテレフタル酸、イ
ソフタル酸等の芳香族ジカルボン酸を主体とし、ジオー
ル成分としてエチレングリコール、ネオペンチルグリコ
ール等の脂肪族ジオールを主体とするものがよく、これ
らにアジピン酸やアゼライン酸等の脂肪族ジカルボン
酸、トリメリット酸やピロメリット酸等の三価以上のカ
ルボン酸、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−ル等の三価以上のアルコール
等を少量含んでいるものは溶融流動性、架橋反応性が向
上するのでより好ましい。In the present invention, in the thermosetting resin composition for exhibiting its characteristics, the composition of the polyester resin is mainly composed of an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid as a dicarboxylic acid component, and a diol component. As ethylene glycol, those mainly composed of an aliphatic diol such as neopentyl glycol are often used, and an aliphatic dicarboxylic acid such as adipic acid or azelaic acid, a trivalent or higher carboxylic acid such as trimellitic acid or pyromellitic acid, Those containing a small amount of trihydric or higher alcohol such as trimethylolethane, trimethylolpropane, and pentaerythritol are more preferable because the melt fluidity and the crosslinking reactivity are improved.
【００１７】また、ポリエステル樹脂の平均重合度は５
〜５０の範囲のものが好ましい。これより低いものはフ
ィルムにしたとき十分な強度が得られず、これより高い
ものは粉砕が困難になる。次に硬化剤としては、ポリエ
ステルの末端基が−ＯＨ型のものはイソシアナート化合
物やメラミン樹脂、例えばε−カプロラクタムブロック
イソシアナートやメチル化メラミン等が好ましい。末端
基が−ＣＯＯＨ型のものはエポキシ樹脂やトリグリシジ
ルイソシアヌレート等が好ましい。The average degree of polymerization of the polyester resin is 5
The thing of the range of -50 is preferable. If it is lower than this, sufficient strength cannot be obtained when formed into a film, and if it is higher than this, it becomes difficult to grind. Next, as the curing agent, when the terminal group of polyester is -OH type, an isocyanate compound or a melamine resin, such as ε-caprolactam block isocyanate or methylated melamine, is preferable. An epoxy resin, triglycidyl isocyanurate, or the like having a terminal group of -COOH type is preferable.
【００１８】[0018]
【実施例】次に実施例によって本発明を具体的に説明す
る。なお、実施例中の特性値の測定法は次の通りであ
る。 強伸度 東洋ボールドウィン社製テンシロンＵＴＭ−４−１００
型を用い、１cm×１０cmのフィルム片を１０cm/minの速
度にて引張試験を行い、フィルムが破断した点の破断強
度 (Kgf/mm2)、破断伸度（％）を求めた。 熱収縮率 ２００℃の熱風乾燥機中に１０分間放置した後のフィル
ムの収縮率（％）を測定した。 可撓性 フィルムを折り曲げて破断するかどうかをみた。破断し
ないものを○、破断したものを×とした。 平滑性 フィルム表面の平滑度合を目視にて判定した。平滑なも
のを○、粗いものを×とした。 耐アルカリ性 フィルムを８０℃の５％NaOH水溶液中に６０分間浸漬し
て、破断強度の保持率を測定した。保持率が９０％以上
のものを○、９０％以下のものを×とした。 防融性 フィルムに火の着いたタバコを接触させ孔があくかどう
かをみた。孔のあかなかったものを○、あいたものを×
とした。EXAMPLES The present invention will be described in detail with reference to examples. In addition, the measuring method of the characteristic value in an Example is as follows. High elongation Tensilon UTM-4-100 manufactured by Toyo Baldwin
Using a mold, a 1 cm × 10 cm film piece was subjected to a tensile test at a speed of 10 cm / min to determine the breaking strength (Kgf / mm 2 ) and the breaking elongation (%) at the point where the film was broken. Heat Shrinkage The shrinkage (%) of the film after standing for 10 minutes in a hot air dryer at 200 ° C. was measured. The flexible film was bent to see if it broke. Those that did not break were rated as O, and those that did break were rated as X. Smoothness The smoothness of the film surface was visually evaluated. The smooth one was marked with ◯ and the rough one was marked with x. The alkali resistance film was immersed in a 5% NaOH aqueous solution at 80 ° C. for 60 minutes, and the breaking strength retention rate was measured. Those with a retention rate of 90% or more were evaluated as O, and those with a retention rate of 90% or less were evaluated as X. The fusible film was contacted with a lit cigarette to see if it had holes. ○ those with no holes, × with holes
And
【００１９】実施例１ 平均重合度が２５、末端水酸基価が５５０geq ／１０6g
で、ジカルボン酸成分としてテレフタル酸、ジオ−ル成
分としてエチレングリコール４０mol ％、ネオペンチル
グリコール６０mol ％から成る共重合ポリエステル樹脂
８５重量部、ε−カプロラクタムブロックイソシアナー
ト１５重量部、硬化促進剤（オクチル錫マレエート）
０．３重量部、流展剤（ＢＡＳＦ社製アクロナル４Ｆ）
１重量部をヘンシェルミキサー（三井三池製作所製ＦＭ
２０Ｂ型）でドライブレンドした後、コニーダー（ブッ
ス社製ＰＲ−４６型）を用いて１００℃で溶融混練し、
冷却固化後ボールミルにて粉砕し、１４５メッシュの金
網で分離して粉体を得た。この粉体を塗装用の静電塗装
機を用いて、鋼板上に膜厚が７５μm になるように散布
した。この鋼板を１９０℃で２０分熱風乾燥機中で熱処
理した。なお、鋼板の表面はあらかじめゴミ、油脂等を
洗浄し、フッ素系離型剤（ダイキン社製ダイフリー）を
塗布した。熱処理した鋼板を空気中で室温まで冷却した
後、鋼板からフィルムをはがして熱硬化性樹脂フィルム
を得た。得られたフィルムの物性を表１に示す。Example 1 An average degree of polymerization of 25 and a terminal hydroxyl value of 550 geq / 10 6 g
Then, 85 parts by weight of a copolyester resin comprising terephthalic acid as a dicarboxylic acid component, 40 mol% of ethylene glycol and 60 mol% of neopentyl glycol as a diol component, 15 parts by weight of ε-caprolactam block isocyanate, a curing accelerator (octyl tin Maleate)
0.3 parts by weight, leveling agent (Acronal 4F manufactured by BASF)
1 part by weight of a Henschel mixer (Mitsui Miike Seisakusho FM
20B type), after dry blending, melt kneading at 100 ° C. using a co-kneader (PR-46 type manufactured by Buss),
After cooling and solidification, it was pulverized with a ball mill and separated with a wire mesh of 145 mesh to obtain a powder. This powder was sprayed on a steel plate using an electrostatic coating machine for coating so that the film thickness was 75 μm. This steel sheet was heat-treated at 190 ° C. for 20 minutes in a hot air dryer. It should be noted that the surface of the steel sheet was washed with dust, oils and fats in advance, and a fluorine-based release agent (Die-free manufactured by Daikin) was applied. After the heat-treated steel sheet was cooled in air to room temperature, the film was peeled off from the steel sheet to obtain a thermosetting resin film. Table 1 shows the physical properties of the obtained film.
【００２０】実施例２ 膜厚を５０μm にした以外は実施例１と同様に行った。
得られたフィルムの物性を表１に示す。Example 2 Example 2 was repeated except that the film thickness was 50 μm.
Table 1 shows the physical properties of the obtained film.
【００２１】実施例３ 平均重合度が５０、末端酸価が１１１９geq/１０6gで、
ジカルボン酸成分としてテレフタル酸８９mol ％、イソ
フタル酸５mol ％、三価のカルボン酸としてトリメリッ
ト酸６mol ％、ジオ−ル成分としてエチレングリコール
６０mol ％、ネオペンチルグリコール４０mol ％から成
る共重合ポリエステル樹脂８９重量部、トリグリシジル
イソシアヌレ−ト１１重量部、流展剤（ＢＡＳＦ社製ア
クロナル４Ｆ）１重量部を用い実施例１と同様にして行
った。得られたフィルムの物性を表１に示す。Example 3 The average degree of polymerization was 50, the terminal acid value was 1119 geq / 10 6 g,
89 parts by weight of a copolymerized polyester resin comprising 89 mol% of terephthalic acid as a dicarboxylic acid component, 5 mol% of isophthalic acid, 6 mol% of trimellitic acid as a trivalent carboxylic acid, 60 mol% of ethylene glycol as a diol component, and 40 mol% of neopentyl glycol. , 11 parts by weight of triglycidyl isocyanurate, and 1 part by weight of a leveling agent (Acronal 4F manufactured by BASF) were used in the same manner as in Example 1. Table 1 shows the physical properties of the obtained film.
【００２２】比較例１ 熱処理を２５０℃で６０分行った以外は実施例１と同様
にして行った。得られたフィルムの物性を表１に示す。
高温で長時間の熱処理を行ったため、フィルムが脆くな
り破断強度、破断伸度が低下し、可撓性が得られなくな
った。Comparative Example 1 Example 1 was repeated except that the heat treatment was carried out at 250 ° C. for 60 minutes. Table 1 shows the physical properties of the obtained film.
Since the heat treatment was performed at a high temperature for a long time, the film became brittle, the breaking strength and the breaking elongation decreased, and the flexibility could not be obtained.
【００２３】比較例２ 熱処理を２５０℃で６０分行った以外は実施例２と同様
にして行った。得られたフィルムの物性を表１に示す。
比較例１と同様に、可撓性のないフィルムとなった。Comparative Example 2 Example 2 was repeated except that the heat treatment was carried out at 250 ° C. for 60 minutes. Table 1 shows the physical properties of the obtained film.
As in Comparative Example 1, the film became inflexible.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明は、安価で寸法安定性、防融性、
耐薬品性にも優れ、しかも、可撓性、強度共に満足し得
る熱硬化性樹脂フィルムが得られる。INDUSTRIAL APPLICABILITY The present invention is inexpensive and has dimensional stability, fusion resistance, and
A thermosetting resin film having excellent chemical resistance and satisfying both flexibility and strength can be obtained.
Claims (1)
り、破断強度が５Kgf/mm2 以上、２００℃における乾熱
収縮率が１．０％以下、破断伸度が２．０％以上で３０
０℃以上の防融性を有し、８０℃の５％水酸化ナトリウ
ム水溶液強度保持率が９０％以上の可撓性を有するポリ
エステル系熱硬化性樹脂フイルム。1. A polyester resin and a curing agent therefor, which has a breaking strength of 5 kgf / mm 2 or more, a dry heat shrinkage ratio at 200 ° C. of 1.0% or less, and an elongation at break of 2.0% or more.
A polyester thermosetting resin film having a melting resistance of 0 ° C. or higher and a flexibility of maintaining a strength of a 5% sodium hydroxide aqueous solution at 80 ° C. of 90% or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4754992A JPH05214121A (en) | 1992-02-03 | 1992-02-03 | Polyester-based thermosetting resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4754992A JPH05214121A (en) | 1992-02-03 | 1992-02-03 | Polyester-based thermosetting resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214121A true JPH05214121A (en) | 1993-08-24 |
Family
ID=12778241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4754992A Pending JPH05214121A (en) | 1992-02-03 | 1992-02-03 | Polyester-based thermosetting resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05214121A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002252458A (en) * | 2001-02-26 | 2002-09-06 | Mitsubishi Polyester Film Copp | Polyester film used for manufacturing multilayer printed wiring board |
| CN109232869A (en) * | 2018-09-13 | 2019-01-18 | 腾龙特种树脂(厦门)有限公司 | A kind of PETG modified copolyester |
-
1992
- 1992-02-03 JP JP4754992A patent/JPH05214121A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002252458A (en) * | 2001-02-26 | 2002-09-06 | Mitsubishi Polyester Film Copp | Polyester film used for manufacturing multilayer printed wiring board |
| CN109232869A (en) * | 2018-09-13 | 2019-01-18 | 腾龙特种树脂(厦门)有限公司 | A kind of PETG modified copolyester |
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