JP2007182470A - Flame-retardant polyester resin and film comprising the same - Google Patents
Flame-retardant polyester resin and film comprising the same Download PDFInfo
- Publication number
- JP2007182470A JP2007182470A JP2006000442A JP2006000442A JP2007182470A JP 2007182470 A JP2007182470 A JP 2007182470A JP 2006000442 A JP2006000442 A JP 2006000442A JP 2006000442 A JP2006000442 A JP 2006000442A JP 2007182470 A JP2007182470 A JP 2007182470A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- polyester resin
- film
- retardant polyester
- mol
- 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
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は難燃性ポリエステル樹脂に関する。さらに詳しくは、ハロゲンフリーでありながら優れた難燃性を呈するポリエチレン−２，６−ナフタレート樹脂に関するものである。 The present invention relates to a flame retardant polyester resin. More specifically, the present invention relates to a polyethylene-2,6-naphthalate resin that is halogen-free and exhibits excellent flame retardancy.
飽和ポリエステル樹脂、特にポリアルキレンナフタレートは、その優れた電気絶縁性や耐水性などの特微を生かして電気部品などの成形用材料として利用されている。
これらの用途における樹脂の難燃化は、従来ハロゲン系難燃剤を添加する方法が主として採用されている。しかし、このハロゲン系難燃剤を含有するポリエステル樹脂は、燃焼時にダイオキシンを発生する等の理由で、環境を配慮した難燃剤が望まれている。
Saturated polyester resins, particularly polyalkylene naphthalates, are utilized as molding materials for electrical parts, taking advantage of their excellent electrical insulation and water resistance.
Conventionally, a method of adding a halogen-based flame retardant has been mainly employed to make the resin flame-retardant in these applications. However, the polyester resin containing the halogen-based flame retardant is desired to be an environment-friendly flame retardant for reasons such as generating dioxins upon combustion.
このため、ハイドロタルサイト系難燃剤等のノンハロゲン系難燃剤が提案されている（特許文献１）。しかし、これらの難燃剤は、十分な難燃性を発現させるためにはその添加量を多くする必要があり、得られる成形品の機械的特性の低下を招いたり、ポリエステル樹脂中から難燃剤がブリードアウトしたりするという問題がある。 For this reason, non-halogen flame retardants such as hydrotalcite flame retardants have been proposed (Patent Document 1). However, it is necessary to increase the amount of these flame retardants in order to exhibit sufficient flame retardancy, which leads to a decrease in the mechanical properties of the resulting molded product, and the flame retardants from the polyester resin. There is a problem of bleeding out.
一方、ポリエステル樹脂に化学的に結合させる反応型難燃剤は、従来、種々提案されている。例えば、特許文献２〜３には、不飽和ポリエステルの不飽和結合の一部に特定のリン化合物を付加させてなるリン含有不飽和ポリエステルが提案されている。しかしながら、全部の不飽和結合に該リン化合物を結合させることは困難であり、残存する不飽和結合に起因して耐熱性が不十分となり、例えば酸化劣化が起こりやすくなり、その結果、フィルムや成型体で通常行われるリサイクル工程を通過すると、難燃性や物性が損なわれるという問題がある。 On the other hand, various reactive flame retardants that are chemically bonded to a polyester resin have been proposed. For example, Patent Documents 2 to 3 propose phosphorus-containing unsaturated polyesters obtained by adding a specific phosphorus compound to a part of unsaturated bonds of unsaturated polyesters. However, it is difficult to bond the phosphorus compound to all unsaturated bonds, resulting in insufficient heat resistance due to residual unsaturated bonds, for example, oxidative degradation is likely to occur, resulting in film or molding There is a problem that flame retardancy and physical properties are impaired when passing through a recycling process normally performed on the body.
また、電気部品などの材料として用いる場合、例えばフレキシブルプリントサーキット等の電気部材用途では、はんだ付け工程など高温での熱処理を経るため、はんだに接する際の成形品の変形を小さくすることや、成形加工時に生じるデラミ（層間剥離による白化現象）などの抑制も求められていた。 In addition, when used as a material for electrical parts, for example, in electrical member applications such as flexible printed circuits, heat treatment at high temperature such as a soldering process is performed, so that deformation of the molded product when contacting with solder is reduced, or molding is performed. There has also been a demand for suppression of delamination (whitening phenomenon due to delamination) that occurs during processing.
本発明の目的は、優れた難燃性を耐久性良く有し、難燃剤のブリードアウトが少なく、ハンダ加工性などの高温での加工性や耐デラミ性にも優れたポリエチレン−２，６−ナフタレート樹脂からなる難燃性ポリエステル樹脂およびそれを用いたフィルムを提供することにある。 An object of the present invention is polyethylene-2,6-, which has excellent flame retardancy with good durability, has little bleed out of the flame retardant, and is excellent in solderability and other high-temperature processability and delamination resistance. An object of the present invention is to provide a flame retardant polyester resin made of naphthalate resin and a film using the same.
本発明者は上記目的を達成するために鋭意研究した結果、ポリエチレン−２，６−ナフタレート樹脂に特定のリン化合物を共重合するとき、上記目的を達成できることを見出し、本発明に到達した。 As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved when a specific phosphorus compound is copolymerized with a polyethylene-2,6-naphthalate resin, and has reached the present invention.
かくして本発明によれば、エチレン−２，６−ナフタレートを主たる繰返し単位とし、下記一般式（１）
本発明によれば、優れた難燃性を耐久性良く有し、難燃剤のブリードアウトが少なく、ハンダ加工性などの高温での加工性や耐デラミ性にも優れたエチレン−２，６−ナフタレートを主たる繰返し単位とする難燃性ポリエステル樹脂が提供されることから、フィルムなどの成形体として好適に利用することができ、特にフレキシブルプリントサーキット等の電気部材用のベースフィルムとして好適に利用することができる。 According to the present invention, ethylene-2,6- has excellent flame retardancy with good durability, less flame retardant bleed-out, and excellent workability at high temperatures such as solderability and delamination resistance. Since a flame-retardant polyester resin having naphthalate as a main repeating unit is provided, it can be suitably used as a molded article such as a film, and particularly suitably used as a base film for an electric member such as a flexible printed circuit. be able to.
先ず、本発明で用いられるポリエステル樹脂は、エチレン−２，６−ナフタレートを主たる繰返し単位とするものであり、好ましくは全繰返し単位の８０モル％以上、さらに９０モル％以上、特に９５モル％以上がエチレン−２，６−ナフタレート単位を主たる繰返し単位とするポリエステルが好ましい。かかるポリエステルであることによって、ハンダなどの高温での加工性を高度に発現でき、さらに難燃剤による耐デラミ性向上効果もより顕著に発現される。 First, the polyester resin used in the present invention has ethylene-2,6-naphthalate as a main repeating unit, preferably 80 mol% or more, more preferably 90 mol% or more, particularly 95 mol% or more of all repeating units. Is preferably a polyester having ethylene-2,6-naphthalate units as the main repeating unit. By using such a polyester, processability at a high temperature such as solder can be expressed to a high degree, and the effect of improving the delamination resistance by the flame retardant is also more remarkably exhibited.
かかる飽和ポリエステルの固有粘度（重量比が６／４のフェノール／トリクロロエタン混合溶媒を用いて温度３５℃で測定）は、小さすぎると機械的特性が不十分になる場合があり、逆に大きすぎると成形が難しくなる場合があるので０．４０〜０．９０ｄｌ／ｇの範囲が適当である。なお、本発明の目的を阻害しない範囲内で、従来公知の各種添加剤を含有していてもよく、例えば有機または無機の滑剤粒子、着色剤、帯電防止剤、酸化防止剤、紫外線吸収剤、潤滑剤充填材、補強材などをあげることができる。 If the intrinsic viscosity of the saturated polyester (measured at a temperature of 35 ° C. using a phenol / trichloroethane mixed solvent having a weight ratio of 6/4) is too small, the mechanical properties may be insufficient. Since molding may be difficult, a range of 0.40 to 0.90 dl / g is appropriate. In addition, within the range not inhibiting the purpose of the present invention, it may contain various conventionally known additives such as organic or inorganic lubricant particles, colorants, antistatic agents, antioxidants, ultraviolet absorbers, Lubricant fillers, reinforcing materials and the like can be mentioned.
本発明の難燃性ポリエステル樹脂は、上記の飽和ポリエステルに前記一般式（１）で表されるホスホネート化合物を、リン元素含有量として０．１〜４モル％、好ましくは０．２〜３．５モル％、特に好ましくは０．３〜３モル％の範囲で共重合している必要がある。この共重合量が下限未満の場合には本発明の目的を達成するのに十分な難燃性を発現するに至らず、逆に上限を超える場合には、ゲル化が生じ得られるポリエステルの反応性が損なわれ、得られる成形体の物性が損なわれる。 In the flame-retardant polyester resin of the present invention, the phosphonate compound represented by the general formula (1) is added to the above saturated polyester in an amount of 0.1 to 4 mol%, preferably 0.2 to 3. mol. Copolymerization is required in the range of 5 mol%, particularly preferably in the range of 0.3 to 3 mol%. If this amount of copolymerization is less than the lower limit, the flame retardancy sufficient to achieve the object of the present invention will not be expressed, and conversely if it exceeds the upper limit, gelation may occur. Property is impaired, and the physical properties of the resulting molded article are impaired.
前記一般式（１）で表されるホスホネート化合物のＲ１およびＲ２は炭素数２以上のアルキレン基であって、直鎖状であっても分岐状であってもよい。アルキレン基としては、炭素数２〜１８、好ましくは炭素数２〜８のアルキレン基であり、具体的にはエチレン基、プロピレン基、ブチレン基、イソプロレン基、ｔ−ブチレン基、ｓｅｃ−ブチレン基等を例示することができる。また、シクロアルキレン基としては、炭素数３〜１８、好ましくは炭素数３〜８のシクロアルキレン基であり、具体的には、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基等を例示することができる。なお、式中のＲ１とＲ２は、それぞれが同一の基であっても異なる基であってもよい。 R 1 and R 2 of the phosphonate compound represented by the general formula (1) are alkylene groups having 2 or more carbon atoms, and may be linear or branched. The alkylene group is an alkylene group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Specifically, an ethylene group, a propylene group, a butylene group, an isopropylene group, a t-butylene group, a sec-butylene group, etc. Can be illustrated. The cycloalkylene group is a cycloalkylene group having 3 to 18 carbon atoms, preferably 3 to 8 carbon atoms. Specific examples include a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Can do. In the formula, R 1 and R 2 may be the same group or different groups.
上記一般式（１）において、ｍおよびｎは整数であって互いに同一であっても異なっていてもよく、ｍ＋ｎの範囲は３〜１０の範囲である。３未満であると、耐加水分解性に劣ったり、鯛デラミ性の向上効果が乏しく、一方上限を超えるとがＲ基の熱安定性に劣るようになる。好ましいｍ＋ｎの範囲は４〜８であり、特に好ましい範囲は４〜７である。 In the general formula (1), m and n are integers which may be the same as or different from each other, and the range of m + n is 3 to 10. If it is less than 3, the hydrolysis resistance is poor, or the effect of improving the delamination property is poor, while if it exceeds the upper limit, the thermal stability of the R group becomes poor. A preferable range of m + n is 4 to 8, and a particularly preferable range is 4 to 7.
前記一般式（１）で表されるホスホネート化合物の具体例としては、例えば下記の表１に召されるような化合物が挙げられる。
なお本発明において、前記したホスホネート化合物は、１種に限定されず、２種以上を併用してもかまわない。
上記一般式（１）で示されるホスホネート化合物は、公知の方法により製造することができる。すなわち、ヒドロキシメチルリン酸に所望のジオールをエステル化反応することで得ることができる。
In the present invention, the phosphonate compound described above is not limited to one type, and two or more types may be used in combination.
The phosphonate compound represented by the general formula (1) can be produced by a known method. That is, it can be obtained by esterifying a desired diol with hydroxymethyl phosphoric acid.
以上で説明した本発明の難燃性ポリエステル樹脂は、その製造方法について特に限定されず、任意の方法により製造することができる。例えば、ポリエステル樹脂の重合の任意の段階で添加すればよく、例えば、ポリエステルの重縮合反応終了前に前記一般式（１）で示されるホスホネート化合物を添加してもよいし、別の方法としては、真空吸引可能なベント機構を有する二軸混練押出機にポリエステル樹脂および前記一般式（１）で示されるホスホネート化合物を添加供給し、溶融押し出しすればよい。 The flame-retardant polyester resin of the present invention described above is not particularly limited with respect to its production method, and can be produced by any method. For example, it may be added at any stage of the polymerization of the polyester resin. For example, the phosphonate compound represented by the general formula (1) may be added before the completion of the polycondensation reaction of the polyester. The polyester resin and the phosphonate compound represented by the general formula (1) may be added and supplied to a twin-screw kneading extruder having a vent mechanism capable of vacuum suction, followed by melt extrusion.
このようにして得られた難燃性ポリエステル樹脂は、一旦ペレット状に成形した後に再度溶融して、あるいはペレット状に成形することなく連続して種々の成形品に成形することができる。例えば、押出成形、射出成形、ブロー成形、発泡成形、紡糸成形、フィルム製膜などにより、板状、シート状、フィルム状、糸状等の任意の形状に成形することができ、特にフィルムに好適に使用できる。得られた成形品は、工業機材、自動車・車両、電気・電子部品等の各種分野に使用することができる。 The flame retardant polyester resin thus obtained can be once molded into a pellet and then melted again or continuously into various molded articles without being molded into a pellet. For example, it can be molded into any shape such as plate, sheet, film, and thread by extrusion molding, injection molding, blow molding, foam molding, spinning molding, film formation, etc. Can be used. The obtained molded product can be used in various fields such as industrial equipment, automobiles / vehicles, electric / electronic parts and the like.
これらの成形で用いられる成形機は特に限定されないが、例えば、通常の射出成形機や、いわゆる射出圧縮成形機、二軸スクリュー押出機、一軸スクリュー押出機、ベント付き二軸スクリュー押出機、ベント付き一軸スクリュー押出機などが好ましく用いられる。 The molding machine used in these moldings is not particularly limited. For example, a normal injection molding machine, a so-called injection compression molding machine, a twin screw extruder, a single screw extruder, a twin screw extruder with a vent, a vent A single screw extruder or the like is preferably used.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。なお、本発明における各種特性は、以下の測定方法にしたがった。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In addition, the various characteristics in this invention followed the following measuring methods.
（１）固有粘度
フェノール／トリクロロエタン＝６／４（重量比）を溶媒に用いて３５℃恒温下オストワルト型粘度計を用いて測定した。
(1) Intrinsic viscosity Phenol / trichloroethane = 6/4 (weight ratio) was used as a solvent and measured using an Ostwald viscometer at a constant temperature of 35 ° C.
（２）難燃性
試料を１７５℃で４時間乾燥した後、成型温度３００℃、プレス圧力３０ＭＰａ、成型時間１分間の条件でメルトプレスして未延伸シートを得た。この未延伸シートを１５０℃で長手方向および幅方向にそれぞれ３．８倍に同時二軸延伸し、次いで２１０℃で１５秒間熱固定処理を行い、厚さが７５μｍのフィルムとなし、ＵＬ−９４規格にしたがって、ＶＴＭを評価した。このとき、同時に消炎するまでの時間も測定した。
(2) Flame retardance The sample was dried at 175 ° C. for 4 hours and then melt-pressed under conditions of a molding temperature of 300 ° C., a press pressure of 30 MPa, and a molding time of 1 minute to obtain an unstretched sheet. This unstretched sheet was simultaneously biaxially stretched 3.8 times in the longitudinal direction and the width direction at 150 ° C., and then heat-fixed at 210 ° C. for 15 seconds to form a film having a thickness of 75 μm. UL-94 VTM was evaluated according to the standard. At this time, the time until extinction was simultaneously measured.
（３）ヤング率
上記（２）の難燃性の試験と同様にして得たサンプルフィルムを試料幅１０ｍｍ、長さ１５ｃｍに切り試料片を得た。この試料片を、チャック間１００ｍｍにして引張速度１０ｍｍ／分、チャート速度５００ｍｍ／分でインストロンタイプの万能引張試験装置にて引張り、得られる加重−伸び曲線の立ち上がり部の接線よりヤング率を測定した。
(3) Young's modulus A sample film obtained in the same manner as the flame retardancy test in (2) above was cut into a sample width of 10 mm and a length of 15 cm to obtain a sample piece. This sample piece was pulled with an Instron type universal tensile tester at a pulling speed of 10 mm / min and a chart speed of 500 mm / min with a chuck spacing of 100 mm, and the Young's modulus was measured from the tangent of the rising part of the obtained load-elongation curve. did.
（４）耐久難燃性
上記（２）の難燃性の試験と同様にして得た未延伸シートを１０メッシュに破砕し、粉砕したポリマーと未延伸シートに成形する前の同組成の難燃性ポリエステル樹脂ペレットとを、６：４の重量比で配合し、１７５℃で４時間乾燥した後、上記の難燃性評価方法と同様にしてＶＴＭを評価した。このとき、同時に消炎するまでの時間も測定した。
(4) Durable flame retardancy The unstretched sheet obtained in the same manner as the flame retardancy test of (2) above was crushed into 10 mesh, and the flame retardant of the same composition before forming into a crushed polymer and unstretched sheet After blending the curable polyester resin pellets at a weight ratio of 6: 4 and drying at 175 ° C. for 4 hours, VTM was evaluated in the same manner as in the flame retardancy evaluation method described above. At this time, the time until extinction was simultaneously measured.
（５）耐デラミ性
上記（２）の難燃性の試験と同様にして得たサンプルフィルムを８０×８０ｍｍの大きさに切り出し、折目ができるように手で軽く２つに折りながら、平坦な一対の金属板で挟んだ後、プレス機により所定の圧力Ｐ１（ＭＰａ）で２０秒間プレスした。プレス後、プレスを開放し、次いで、２つ折りのフィルムサンプルを手で元の状態に戻し、前記金属板に挟んで圧力Ｐ１（ＭＰａ）で２０秒間プレスした。その後、フィルムサンプルを取り出し、折目にあらわれた白化部分の長さ（ｍｍ）を顕微鏡で測定する。それぞれ新しいフィルムサンプルを使用し、プレス圧Ｐ１＝０．１，０．３，０．５（ＭＰａ）について測定を繰り返す。各プレス圧における白化部分の長さ（ｍｍ）の合計の平均値が折目の全長（８０ｍｍ）に占める割合をもって折目デラミネーション白化率とし、この値をフィルムのデラミネ−ション（層間剥離）の起こり易さを示す指標として使用する。この折目デラミネーション白化率の値が小さいほど耐デラミネーションが良好と判断した。
(5) Delamination resistance A sample film obtained in the same manner as the flame retardancy test in (2) above is cut into a size of 80 × 80 mm, and folded flat by hand so that a crease can be made. After being sandwiched between a pair of metal plates, it was pressed with a press machine at a predetermined pressure P1 (MPa) for 20 seconds. After pressing, the press was released, and then the half-folded film sample was returned to the original state by hand and sandwiched between the metal plates and pressed at a pressure P1 (MPa) for 20 seconds. Thereafter, the film sample is taken out, and the length (mm) of the whitened portion appearing in the fold is measured with a microscope. Each new film sample is used, and the measurement is repeated for the press pressure P1 = 0.1, 0.3, 0.5 (MPa). The ratio of the total length (mm) of the whitened portion at each press pressure to the total length (80 mm) of the fold is taken as the fold delamination whitening rate, and this value is the delamination (delamination) of the film. It is used as an index indicating the likelihood of occurrence. The smaller the value of the fold delamination whitening rate, the better the delamination resistance.
（６）ハンダ加工性：
得られたポリエステル樹脂を３００℃でダイ型より押し出し、厚さ３ｍｍの注型板を得た。これらの注型板から長さ１２５ｍｍ×幅１３ｍｍ×厚さ３ｍｍの試験板を切り出し、温度を２６０℃にしたはんだを１ｍｍ径で無加圧下５秒接触させ、下記の基準に従って評価した。○と△が合格である。
○： 凹深が０．２ｍｍ以下
△： 凹深が０．２ｍｍ超０．５ｍｍ以下
×： 凹深が０．５ｍｍ超
(6) Solder processability:
The obtained polyester resin was extruded from a die mold at 300 ° C. to obtain a cast plate having a thickness of 3 mm. A test plate having a length of 125 mm, a width of 13 mm and a thickness of 3 mm was cut out from these cast plates, and a solder having a temperature of 260 ° C. was brought into contact with a 1 mm diameter for 5 seconds under no pressure, and evaluated according to the following criteria. ○ and △ are acceptable.
○: Recess depth is 0.2 mm or less Δ: Recess depth is more than 0.2 mm and 0.5 mm or less ×: Recess depth is more than 0.5 mm
（７）ポリマー中のリン元素量：
ポリマーチップ中のリン元素量はサンプルを加熱溶融して円形ディスクを作成し、リガク社製蛍光Ｘ線測定装置３２７０を用いて測定した。
(7) Amount of phosphorus element in polymer:
The amount of phosphorus element in the polymer chip was measured by using a fluorescent X-ray measuring device 3270 manufactured by Rigaku Corp. by heating and melting the sample to form a circular disk.
（８）ブリードアウト性
上記ヤング率の測定で作成した二軸配向フィルムを、１３０℃に飽和湿熱保持したエスペック（株）製プレッシャクッカーＴＰＣ−４１２Ｍに仕込み、５０時間処理したのち、フィルムサンプルを取り出し、試験片表面をクロロホルムで洗浄し、洗浄液中に含まれる難燃剤量を定量し、樹脂組成物の重量を基準として、ブリードアウト量とした。なお、測定値が０．０１重量％より小さいものは、０．０１重量％未満と表示した。
(8) Bleed-out property The biaxially oriented film prepared by measuring the above Young's modulus was charged into an ESPEC CORP. Pressure cooker TPC-412M maintained at 130 ° C. and saturated wet heat, treated for 50 hours, and then a film sample was taken out. The surface of the test piece was washed with chloroform, the amount of the flame retardant contained in the cleaning liquid was quantified, and the amount of bleed out was determined based on the weight of the resin composition. In addition, when the measured value was less than 0.01% by weight, it was indicated as less than 0.01% by weight.
［実施例１］
２，６−ナフタレンジカルボン酸ジメチル（以下、ＮＤＣＭという）１００モル（２４．４ｋｇ）、エチレングリコール（以下、ＥＧという）１８０モル（１１．２ｋｇ）、酢酸マンガン四水和物０．０３モルを反応器に仕込み、窒素雰囲気下で２４０℃まで昇温してエステル交換反応を行った。メタノールの留出量が理論量に対して９０％以上に達した後、ＮＤＣＭ１００モルに対して三酸化二アンチモン０．０２モルとジオキシエチレントリオキシエチレンヒドロキシメチルホスホネート（ＣＢＷ社製、商品名：Ｗｏｆａｐｌｅｘｘ３３、ｍ＋ｎ＝５）をポリステルの繰返し単位を基準として、３モル％添加し、２６０℃で３０分間保持した。その後、昇温と減圧を徐々に行い、最終的に３００℃、０．１ｋＰａ以下で重合を行った。適度な溶融粘度になった時点で、反応を終了して固有粘度０．６３のポリエチレンナフタレート樹脂を得た。
[Example 1]
Reaction of 100 mol (24.4 kg) of dimethyl 2,6-naphthalenedicarboxylate (hereinafter referred to as NDCM), 180 mol (11.2 kg) of ethylene glycol (hereinafter referred to as EG), and 0.03 mol of manganese acetate tetrahydrate The vessel was charged and the ester exchange reaction was performed by raising the temperature to 240 ° C. in a nitrogen atmosphere. After the distillation amount of methanol reaches 90% or more with respect to the theoretical amount, 0.02 mol of diantimony trioxide and dioxyethylene trioxyethylene hydroxymethylphosphonate (trade name: CBW Co., Ltd.) with respect to 100 mol of NDCM Wofaplexx33, m + n = 5) was added at 3 mol% based on the repeating unit of polyester, and kept at 260 ° C. for 30 minutes. Thereafter, the temperature was increased and the pressure was gradually reduced, and polymerization was finally performed at 300 ° C. and 0.1 kPa or less. When the melt viscosity reached an appropriate level, the reaction was terminated to obtain a polyethylene naphthalate resin having an intrinsic viscosity of 0.63.
このようにして得られた樹脂組成物を１７５℃で４時間乾燥した後、成型温度３００℃、プレス圧力３０ＭＰａ、成型時間１分間の条件でメルトプレスして、厚さ３５０μｍの未延伸シートを得た。この未延伸シートを１５０℃で長手方向および幅方向にそれぞれ３．８倍に同時二軸延伸し、次いで２１０℃で１５秒間熱固定処理を行い、厚さが２５μｍのフィルムとした。
得られた樹脂組成物およびそれを用いたフィルムの特性を表２に示す。
The resin composition thus obtained was dried at 175 ° C. for 4 hours, and then melt-pressed under conditions of a molding temperature of 300 ° C., a press pressure of 30 MPa, and a molding time of 1 minute to obtain an unstretched sheet having a thickness of 350 μm. It was. This unstretched sheet was simultaneously biaxially stretched 3.8 times in the longitudinal direction and the width direction at 150 ° C., and then heat-set at 210 ° C. for 15 seconds to obtain a film having a thickness of 25 μm.
Table 2 shows properties of the obtained resin composition and a film using the resin composition.
［実施例２〜３、比較例１および２］
ホスホネート化合物の種類および共重合量を表２に示すとおり変更した以外は実施例１と同様な操作を繰り返した。得られた樹脂組成物およびそれを用いたフィルムの特性を表２に示す。
[Examples 2-3, Comparative Examples 1 and 2]
The same operation as in Example 1 was repeated except that the type and copolymerization amount of the phosphonate compound were changed as shown in Table 2. Table 2 shows properties of the obtained resin composition and a film using the resin composition.
［比較例３］
ホスホネート化合物の代わりに、トリメチルホスフェートを添加した以外は実施例１と同様な操作を繰り返したが、樹脂の粘度が上がらず、樹脂を得ることができなかった。
[Comparative Example 3]
The same operation as in Example 1 was repeated except that trimethyl phosphate was added instead of the phosphonate compound, but the viscosity of the resin did not increase and the resin could not be obtained.
［比較例４］
ホスホネート化合物の代わりに、ビスオキシエチレンヒドロキシメチルホスホネート（ｍ＋ｎ＝２）を添加した以外は実施例１と同様な操作を繰り返した。得られた樹脂組成物およびそれを用いたフィルムの特性を表２に示す。
[Comparative Example 4]
The same operation as in Example 1 was repeated except that bisoxyethylene hydroxymethylphosphonate (m + n = 2) was added instead of the phosphonate compound. Table 2 shows properties of the obtained resin composition and a film using the resin composition.
［比較例５］
酸成分として、２，６−ナフタレンジカルボン酸ジメチルの代わりにテレフタル酸ジメチルを用いた以外は実施例１と同様な操作を繰り返した。得られた樹脂組成物およびそれを用いたフィルムの特性を表２に示す。
[Comparative Example 5]
The same operation as in Example 1 was repeated except that dimethyl terephthalate was used in place of dimethyl 2,6-naphthalenedicarboxylate as the acid component. Table 2 shows properties of the obtained resin composition and a film using the resin composition.
上記表２中の、Ａはジオキシエチレントリオキシエチレンヒドロキシメチルホスホネート（ｍ＋ｎ＝５）、Ｂはオキシエチレンテトラオキシエチレンヒドロキシメチルホスホネート（ｍ＋ｎ＝５）、Ｃはトリメチルフォスフェート、Ｄはビスオキシエチレンヒドロキシメチルホスホネート（ｍ＋ｎ＝２）を示す。 In Table 2, A is dioxyethylene trioxyethylene hydroxymethyl phosphonate (m + n = 5), B is oxyethylene tetraoxyethylene hydroxymethyl phosphonate (m + n = 5), C is trimethyl phosphate, D is bisoxyethylene Hydroxymethylphosphonate (m + n = 2) is shown.
本発明の難燃性ポリエステル樹脂は、優れた難燃性を耐久性良く有しながらも、ブリードアウトが少なく、ハンダ加工性などの高温での加工性や耐デラミ性も有することから、種々の成形品の材料、例えば電気部品などの成形用材料に好適である。特に、フレキシブルプリントサーキット等の電気部材用途に用いるフィルムとして好適に利用できる。 Since the flame-retardant polyester resin of the present invention has excellent flame retardancy and durability, there are few bleed-outs, high-temperature processability such as solderability, and delamination resistance. It is suitable for molding materials such as molding materials such as electric parts. In particular, it can be suitably used as a film used for electric member applications such as flexible printed circuits.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006000442A JP4824410B2 (en) | 2006-01-05 | 2006-01-05 | Flame retardant polyester resin and film comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006000442A JP4824410B2 (en) | 2006-01-05 | 2006-01-05 | Flame retardant polyester resin and film comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007182470A true JP2007182470A (en) | 2007-07-19 |
| JP4824410B2 JP4824410B2 (en) | 2011-11-30 |
Family
ID=38338832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006000442A Expired - Fee Related JP4824410B2 (en) | 2006-01-05 | 2006-01-05 | Flame retardant polyester resin and film comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4824410B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918145A (en) * | 1972-06-12 | 1974-02-18 | ||
| JPS62187726A (en) * | 1986-02-13 | 1987-08-17 | Toray Ind Inc | Production of poplyester for high-speed spinning |
| WO2002086209A1 (en) * | 2001-04-16 | 2002-10-31 | Kaneka Corporation | Polyester fibers |
| JP2005255914A (en) * | 2004-03-12 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Liquid crystal polyester excellent in adhesion to metal |
-
2006
- 2006-01-05 JP JP2006000442A patent/JP4824410B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4918145A (en) * | 1972-06-12 | 1974-02-18 | ||
| JPS62187726A (en) * | 1986-02-13 | 1987-08-17 | Toray Ind Inc | Production of poplyester for high-speed spinning |
| WO2002086209A1 (en) * | 2001-04-16 | 2002-10-31 | Kaneka Corporation | Polyester fibers |
| JP2005255914A (en) * | 2004-03-12 | 2005-09-22 | National Institute Of Advanced Industrial & Technology | Liquid crystal polyester excellent in adhesion to metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4824410B2 (en) | 2011-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101520133B1 (en) | Polybutylene terephthalate resin composition and thin molded article | |
| EP1609820B1 (en) | Injection-molded object | |
| DE112007002973T5 (en) | polybutylene terephthalate resin | |
| KR20160079783A (en) | Flame-retardant biaxially-oriented polyester film, and flame-retardant polyester film layered body and flexible circuit board comprising same | |
| KR101796269B1 (en) | Phosphorus-containing thermoplastic polyester and phosphorus-containing heat-shrinkable tube made therefrom | |
| JP2010046914A (en) | Laminate and method of manufacturing the same | |
| JP4438968B2 (en) | Polyester resin | |
| JP4824410B2 (en) | Flame retardant polyester resin and film comprising the same | |
| JP5005161B2 (en) | Polyphenylene ether resin sheet | |
| JP4716585B2 (en) | Resin composition sheet | |
| JP5860366B2 (en) | Resin composition containing copolymerized polyester resin | |
| JP5379033B2 (en) | Oriented polyester film and method for producing the same | |
| KR102360899B1 (en) | Flame retardant polyester film | |
| JP2004091583A (en) | Flame-retardant polybutylene terephthalate resin composition and molding | |
| JP2006274068A (en) | Liquid crystalline resin composition and molded product of the same | |
| JP5596457B2 (en) | Flame retardant polyester resin composition and molded article using the same | |
| JP2938299B2 (en) | Aromatic polyester, process for producing the same, and molding resin composition using the same | |
| JP2005126716A (en) | Uni- or bi-axially oriented flame retardant polyester film | |
| CN114163783B (en) | Low-warpage high-CTI halogen-free flame-retardant reinforced PBT material and preparation method thereof | |
| JP5894453B2 (en) | Copolyester resin | |
| JP7220864B2 (en) | Thermally conductive insulating composition, thermally conductive insulating molded article, and method for producing the same | |
| JPH02212525A (en) | Polyester film | |
| JP2016108459A (en) | Polyester resin composition and polyester film | |
| TW202405050A (en) | Liquid crystal polyester resin, liquid crystal polyester resin composition, and molded product comprising same | |
| JP3215286B2 (en) | Flame retardant polyethylene terephthalate resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081110 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20110711 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20110711 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110810 |
|
| 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: 20110816 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110908 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140916 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |