JP3590469B2 - Flame retardant resin composition - Google Patents
Flame retardant resin composition Download PDFInfo
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- JP3590469B2 JP3590469B2 JP06071096A JP6071096A JP3590469B2 JP 3590469 B2 JP3590469 B2 JP 3590469B2 JP 06071096 A JP06071096 A JP 06071096A JP 6071096 A JP6071096 A JP 6071096A JP 3590469 B2 JP3590469 B2 JP 3590469B2
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- 0 CC(C)(*c1c(C=C)cccc1C)P*=C Chemical compound CC(C)(*c1c(C=C)cccc1C)P*=C 0.000 description 2
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Description
【0001】
【発明の属する技術分野】
本発明は、新規な難燃性樹脂組成物に関する。更に詳しくは、樹脂混練及び射出成形の加工性が良好であり、高度な難燃性を有し、外観及び機械的特性の良好な成形品が得られる非ハロゲン系の難燃性ポリエステル樹脂組成物に関する。
【0002】
【従来の技術】
ポリブチレンテレフタレートを始めとするポリエステル樹脂は、優れた機械的特性、耐熱性、耐薬品性等を有するため、電気・電子分野、自動車分野等の用途の成形品として広く使用されている。
【0003】
これらの中で難燃性が要求される用途は多く、主にハロゲン化合物、アンチモン化合物を難燃剤、難燃助剤に使用して難燃性を付与した樹脂が供されている。
【0004】
しかし、ハロゲン系難燃剤は、分解生成物が電気部品である金属を腐食する場合があり、また一部のハロゲン系難燃剤は環境への影響が問題となったことから、非ハロゲン系の難燃性樹脂が求められている。
【0005】
非ハロゲン系の難燃剤として、燐化合物があり、トリフェニルホスフェート等の低分子のリン酸エステルが従来からよく使用されている。ところで、ポリブチレンテレフタレート等のポリエステル樹脂は、比較的加工温度が高く、低分子量の燐酸エステルの場合ブリードアウトや耐熱性の問題があった。このため、特開平5ー1079号公報では、分子量の高い耐熱性の燐酸エステルが提示されている。
【0006】
しかしながら、本発明者らが検討したところ、これらの耐熱性の燐酸エステルをポリエステル樹脂に使用した場合ブリードアウトや耐熱性の問題は改善されるものの、高度な難燃性を得るには燐酸エステル及びメラミン化合物等の併用剤を比較的多量に配合する必要がある。このため樹脂混練の加工性、射出成形の加工性が問題となり、また成形品の機械特性等の物性が満足なものとはならなかった。更に、特にガラス繊維を配合する場合、ポリエステル樹脂100重量部に対し、ガラス繊維を20重量部程度迄の比較的少量配合したものについては燐酸エステル及び併用剤のメラミン化合物を比較的多量に配合しても充分な難燃性を得ることが困難であった。
【0007】
【発明が解決すべき課題】
本発明の課題は、高度な難燃性を有し、外観及び機械的特性の良好な成形品が得られ、樹脂混練、射出成形の加工性が良好な非ハロゲン系の難燃性ポリエステル樹脂組成物を提供することである。さらにガラス繊維を配合する場合、配合量が比較的少量から多量迄の広い範囲で難燃性の樹脂組成物とすることである。
【0008】
【課題を解決する手段】
本発明者らは、上記の課題を解決するため鋭意検討した結果、特定の燐酸エステルに、併用剤として働く特定の化合物を適量組み合わせて使用することにより、高度な難燃性とし、しかも機械的特性が良好で、樹脂混練、射出成形の加工性が問題とならないものにできることを見出し、本発明に到達した。
【0009】
即ち、本発明によれば、(A)ポリエステル樹脂100重量部、(B)式(I)で表されるリン酸エステル5〜60重量部、(C)ノボラック型フェノール樹脂3〜40重量部及び(D)ガラス繊維0〜50重量部よりなる樹脂組成物であって、一般式(1)で表わされる化合物とシアヌール酸またはイソシアヌール酸からなる塩1〜100重量部を含むものを除く難燃性樹脂組成物が提供される。
【0010】
【化3】
(式中、Xは結合手または−C(CH3)2−を、nは0または1を示す。)
【0011】
【化4】
(ただし上式においてR 1 、R 2 、R 3 、R 4 、は同一または相異なる水素、アリール基、アルキル基、アラルキル基、シクロアルキル基、または−CONH 2 である。また、Rは上式中の−NR 1 R 2 または−NR 3 R 4 と同一の基、またはこれらと独立に水素、アリール基、アルキル基、アラルキル基、シクロアルキル基、−NH 2 および−CONH 2 からなる群から選ばれた基である。)
【0012】
本発明で用いられるポリエステル樹脂(A)は、ポリブチレンテレフタレート、ポリブチレンテレフタレートとポリオキシテトラメチレングリコールとからなるポリエステルエラストマー、ポリブチレンナフタンジカルボキシレート、ポリシクロヘキサンジメタノールテレフタレート等が例示される。また、これらのポリマーに共重合成分が少量共重合された共重合ポリマーでも良い。
【0013】
この中で、ポリブチレンテレフタレート、これにイソフタル酸、ナフタレンジカルボン酸等を少量共重合した共重合ポリマー、ポリブチレンテレフタレートとポリオキシテトラメチレングリコールとからなるポリエステルエラストマー、及びこれにイソフタル酸、ナフタレンジカルボン酸等を少量共重合した共重合ポリマーが特に好ましい。
【0014】
本発明で用いられる燐酸エステル(B)は、式(I)で表される化合物である。
【0015】
【化5】
(式中、Xは結合手または-C(CH3)2-を、nは0または1を示す。)
【0016】
燐酸エステル(B)としては、式(II)、式(III)または式(IV)で表わされる化合物が例示される。
【0017】
【化6】
【0018】
燐酸エステルの添加量は、ポリエステル樹脂(A)100重量部に対して5〜50重量部、好ましくは5〜40重量部である。添加量が5重量部未満の場合難燃性が充分でなく、50重量部以上の場合成形品の機械的特性が低くなるため好ましくない。
【0019】
本発明で用いられるノボラック型フェノール樹脂(C)は、熱可塑性のフェノール樹脂であり、ヘキサメチレンテトラミン等の硬化剤を添加していないものである。フェノール、ホルムアルデヒドより得られる純フェノール樹脂、または変性フェノール樹脂が用いられる。
【0020】
ノボラック型フェノール樹脂の添加量は、ポリエステル樹脂(A)100重量部に対して3〜40重量部、好ましくは5〜30重量部である。添加量が3重量部未満の場合難燃性が充分でなく、40重量部以上の場合成形品の機械的特性が低くなるため好ましくない。
【0021】
本発明で用いられるガラス繊維(D)は、特に限定されないが、無アルカリガラス繊維が好ましく用いられる。
【0022】
ガラス繊維の添加量は、ポリエステル樹脂(A)100重量部に対して0〜50重量部、好ましくは0〜40重量部である。
【0023】
本発明で用いられるテトラゾール化合物は、5,5'−ビステトラゾール2−アンモニウム、5,5'−ビステトラゾール2−アミノグアニジン、5,5'−ビステトラゾールピペラジンが例示される。
【0024】
テトラゾール化合物の添加量は、ポリエステル樹脂100重量部に対して5〜100重量部、好ましくは5〜50重量部である。添加量が5重量部未満の場合、これらの化合物の添加による難燃性への効果が充分でなく、100重量部以上の場合成形品の機械特性が低くなるため好ましくない。
【0025】
本発明で用いられる弗素樹脂(F)は、ポリテトラフルオロエチレン、テトラフルオロエチレン/エチレン共重合体等が例示される。
【0026】
弗素樹脂の添加量は、ポリエステル樹脂100重量部に対して0.01〜2重量部である。添加量が0.01重量部未満の場合弗素樹脂の添加による難燃性への効果が充分でなく、2重量部以上の場合成形加工性の点から好ましくない。
【0027】
本発明の難燃性樹脂組成物は、本発明の目的を損なわない範囲で、ガラス繊維以外の強化充填剤、酸化防止剤、熱安定剤、各種エラストマーの如き衝撃改良剤、核剤、可塑剤、離型剤、酸化チタンやカーボンブラックの如き顔料、染料等の通常使用される添加剤をさらに添加しても良い。
【0028】
本発明の難燃性樹脂組成物の製造は通常の方法で行われる。例えば、ポリエステル樹脂、燐酸エステル、ノボラック型フェノール樹脂、ガラス繊維をエクストルーダーを用いて溶融混練する方法があげられる。
【0029】
本発明の難燃性樹脂組成物は、通常の射出成形、押出成形等で成形することができる。
【0030】
【発明の効果】
本発明の難燃性樹脂組成物は、非ハロゲン系の難燃性樹脂組成物であって、高度な難燃性を有すると共に、成形品の外観、機械的特性が良好であり、しかも樹脂混練加工性、射出成形加工性が良好であることから、その工業的価値は極めて大きい。
【0031】
【実施例】
以下、実施例により本発明をさらに詳述する。なお、実施例中「部」とは「重量部」を示す。固有粘度はオルトクロロフェノール溶媒を用いて35℃で測定した。
【0032】
[実施例1]
固有粘度0.90のポリブチレンテレフタレート57部、式(II)で表わされる燐酸エステル20部、ノボラック型フェノール樹脂(住友デュレズ(株)PRー53195)8部、及びガラス繊維15部を押出機(ラボプラストミル)を使用し250℃で混練しスレッドを押出してカッターによりチップ化した。押出し加工性はスレッド切れがほとんど起こらず安定なものであった。
【0033】
得られたチップを120℃で4時間乾燥後、溶融温度250℃、金型温度80℃の条件で、燃焼試験片、引張試験片を射出成形した。
【0034】
【表1】
【0035】
この試験片を用い、垂直燃焼試験(UL94、1/16インチ)及び引張試験(ASTM D−638)を実施した。結果は表1に示した通りである。
【0036】
燃焼試験の結果はUL94 V−0相当で高い難燃性を示した。
【0037】
【化7】
【0038】
[比較例1]
固有粘度0.98のポリブチレンテレフタレート60部、式(II)で表わされる燐酸エステル20部、メラミンシアヌレート15部、及びガラス繊維15部を実施例1と同様に押出してチップ化した。押出し加工性は、スレッド切れがしばしば生じ、実施例1と比較して不安定なものであった。
【0039】
さらに、実施例1と同様にして、成形、燃焼試験、引張試験を実施した。結果を表1に示した。
【0040】
燃焼試験の結果は、UL94 V−2相当であり、実施例1と比較し劣るものであった。また、引張特性も実施例1と比較し劣るものであった。
【0041】
[実施例2、4〜6、比較例2、参考例1]
ポリブチレンテレフタレートの量、配合剤の種類、量を表1のようにする以外は、実施例1と同様にして行った。結果を表1に示した。
【0042】
[実施例7]
ポリブチレンテレフタレート30重量%及び平均分子量が2000のポリオキシテトラメチレングリコール70重量%からなり、融点190℃、固有粘度1.30のポリエステルエラストマー73部、式(II)で表わされる燐酸エステル15部、ノボラック型フェノール樹脂(PRー53195)12部を押出機(ラボプラストミル)を使用し230℃で混練し実施例1と同様にしてチップ化した。
【0043】
得られたチップを120℃で4時間乾燥後、溶融温度230℃、金型温度80℃の条件で、燃焼試験片を射出成形した。
【0044】
この試験片を用い、垂直燃焼試験(UL94に準拠、試料片厚み1/16インチ)を実施した。結果は表1に示した通りである。
【0045】
燃焼試験の結果は、UL94 V−0相当で優れた難燃性を示した。
【0046】
[比較例3]
ポリエステルエラストマーの量、配合剤の種類、量を表1のようにする以外は、実施例5と同様にして行った。結果を表1に示した。
【0047】
燃焼試験の結果は、UL94 V−2相当であり、実施例5と比較し劣るものであった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel flame-retardant resin composition. More specifically, a non-halogen flame-retardant polyester resin composition having good processability of resin kneading and injection molding, having high flame retardancy, and obtaining a molded article having good appearance and mechanical properties. About.
[0002]
[Prior art]
BACKGROUND ART Polybutylene terephthalate and other polyester resins have excellent mechanical properties, heat resistance, chemical resistance, and the like, and are therefore widely used as molded articles for applications in the electric / electronic fields, automotive fields, and the like.
[0003]
Among these, there are many applications that require flame retardancy, and resins provided with flame retardancy mainly by using halogen compounds and antimony compounds as flame retardants and flame retardant auxiliaries are provided.
[0004]
However, halogen-based flame retardants may cause the decomposition products to corrode metals that are electrical components, and some halogen-based flame retardants have a problem with the environment. There is a need for a flammable resin.
[0005]
As a non-halogen flame retardant, there is a phosphorus compound, and a low molecular phosphate such as triphenyl phosphate has been often used. By the way, polyester resins such as polybutylene terephthalate have a relatively high processing temperature, and in the case of low molecular weight phosphate esters, there are problems of bleed out and heat resistance. For this reason, JP-A-5-1079 discloses a heat-resistant phosphate ester having a high molecular weight.
[0006]
However, the present inventors have studied that, when these heat-resistant phosphate esters are used for polyester resin, bleed-out and heat resistance problems are improved, but to obtain high flame retardancy, phosphate esters and It is necessary to add a relatively large amount of a concomitant drug such as a melamine compound. For this reason, the workability of resin kneading and the workability of injection molding become problems, and the physical properties such as the mechanical properties of the molded product were not satisfactory. Furthermore, particularly when glass fiber is blended, a relatively small amount of glass fiber blended up to about 20 parts by weight with respect to 100 parts by weight of polyester resin is blended with a phosphate ester and a melamine compound as a concomitant agent in a relatively large amount. However, it was difficult to obtain sufficient flame retardancy.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a non-halogen flame-retardant polyester resin composition having high flame retardancy, obtaining a molded article having good appearance and mechanical properties, and having good workability in resin kneading and injection molding. It is to provide things. Further, when glass fiber is blended, the flame retardant resin composition is used in a wide range from a relatively small amount to a large amount.
[0008]
[Means to solve the problem]
The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, by using a specific compound that works as a concomitant agent in an appropriate amount in combination with a specific phosphate, a high degree of flame retardancy, and mechanical The present inventors have found that they have good properties and can be processed without any problem in resin kneading and injection molding processability, and have reached the present invention.
[0009]
That is, according to the present invention, (A) 100 parts by weight of a polyester resin, (B) 5 to 60 parts by weight of a phosphate ester represented by the formula (I), (C) 3 to 40 parts by weight of a novolak type phenol resin, (D) Flame retardancy excluding a resin composition comprising 0 to 50 parts by weight of glass fiber , comprising 1 to 100 parts by weight of a salt represented by the compound represented by the general formula (1) and cyanuric acid or isocyanuric acid A resin composition is provided.
[0010]
[Formula 3]
(In the formula, X represents a bond or —C (CH 3 ) 2 —, and n represents 0 or 1.)
[0011]
Embedded image
(However, in the above formula, R 1 , R 2 , R 3 , and R 4 are the same or different and are hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH 2 . Selected from the group consisting of hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, —NH 2, and —CONH 2 independently of the same group as —NR 1 R 2 or —NR 3 R 4 Group.)
[0012]
Examples of the polyester resin (A) used in the present invention include polybutylene terephthalate, polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol, polybutylene naphthane dicarboxylate, and polycyclohexane dimethanol terephthalate. Further, a copolymer obtained by copolymerizing a small amount of a copolymer component with these polymers may be used.
[0013]
Among them, polybutylene terephthalate, a copolymer obtained by copolymerizing a small amount of isophthalic acid, naphthalenedicarboxylic acid, etc., a polyester elastomer composed of polybutylene terephthalate and polyoxytetramethylene glycol, and isophthalic acid, naphthalenedicarboxylic acid A copolymer obtained by copolymerizing a small amount of the above is particularly preferred.
[0014]
The phosphate (B) used in the present invention is a compound represented by the formula (I).
[0015]
[Of 5]
(In the formula, X represents a bond or —C (CH 3 ) 2 —, and n represents 0 or 1.)
[0016]
Examples of the phosphate (B) include compounds represented by the formula (II), the formula (III) or the formula (IV).
[0017]
[Omitted]
[0018]
The addition amount of the phosphoric acid ester is 5 to 50 parts by weight, preferably 5 to 40 parts by weight based on 100 parts by weight of the polyester resin (A). If the added amount is less than 5 parts by weight, the flame retardancy is not sufficient, and if it is more than 50 parts by weight, the mechanical properties of the molded product are undesirably lowered.
[0019]
The novolak-type phenol resin (C) used in the present invention is a thermoplastic phenol resin to which no curing agent such as hexamethylenetetramine is added. A pure phenol resin obtained from phenol or formaldehyde, or a modified phenol resin is used.
[0020]
The amount of the novolak-type phenol resin to be added is 3 to 40 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polyester resin (A). If the addition amount is less than 3 parts by weight, the flame retardancy is not sufficient, and if it is more than 40 parts by weight, the mechanical properties of the molded product are undesirably lowered.
[0021]
The glass fiber (D) used in the present invention is not particularly limited, but non-alkali glass fiber is preferably used.
[0022]
The amount of glass fiber added is 0 to 50 parts by weight, preferably 0 to 40 parts by weight, based on 100 parts by weight of the polyester resin (A).
[0023]
Examples of the tetrazole compound used in the present invention include 5,5′-bistetrazole 2-ammonium, 5,5′-bistetrazole 2-aminoguanidine, and 5,5′-bistetrazole piperazine.
[0024]
Amount of Te Torazoru compounds, 5 to 100 parts by weight per 100 parts by weight of the polyester resin, preferably from 5 to 50 parts by weight. If the added amount is less than 5 parts by weight, the effect of the addition of these compounds on the flame retardancy is not sufficient, and if the added amount is more than 100 parts by weight, the mechanical properties of the molded article are undesirably lowered.
[0025]
Examples of the fluorine resin (F) used in the present invention include polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer.
[0026]
The addition amount of the fluorine resin is 0.01 to 2 parts by weight based on 100 parts by weight of the polyester resin. When the addition amount is less than 0.01 part by weight, the effect of the addition of the fluororesin on the flame retardancy is not sufficient, and when the addition amount is 2 parts by weight or more, it is not preferable from the viewpoint of moldability.
[0027]
The flame-retardant resin composition of the present invention includes a reinforcing filler other than glass fiber, an antioxidant, a heat stabilizer, an impact modifier such as various elastomers, a nucleating agent, and a plasticizer, as long as the object of the present invention is not impaired. Further, commonly used additives such as a release agent, a pigment such as titanium oxide and carbon black, and a dye may be further added.
[0028]
The production of the flame-retardant resin composition of the present invention is performed by a usual method. For example, a method of melt-kneading a polyester resin, a phosphoric ester, a novolak-type phenol resin, and a glass fiber using an extruder can be used.
[0029]
The flame-retardant resin composition of the present invention can be molded by ordinary injection molding, extrusion molding or the like.
[0030]
【The invention's effect】
The flame-retardant resin composition of the present invention is a non-halogen flame-retardant resin composition, has a high degree of flame retardancy, has good appearance and mechanical properties of a molded product, and has resin kneading. Because of good workability and injection molding workability, its industrial value is extremely large.
[0031]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "parts" means "parts by weight". Intrinsic viscosity was measured at 35 ° C. using an orthochlorophenol solvent.
[0032]
[Example 1]
57 parts of polybutylene terephthalate having an intrinsic viscosity of 0.90, 20 parts of a phosphoric ester represented by the formula (II), 8 parts of a novolak type phenol resin (PR-53195, Sumitomo Durez Co., Ltd.), and 15 parts of glass fiber were extruded with an extruder ( The mixture was kneaded at 250 ° C. using a Labo Plast Mill, and the threads were extruded to form chips with a cutter. The extrusion processability was stable with almost no thread breakage.
[0033]
After drying the obtained chip at 120 ° C. for 4 hours, a combustion test piece and a tensile test piece were injection molded under the conditions of a melting temperature of 250 ° C. and a mold temperature of 80 ° C.
[0034]
[Table 1]
[0035]
Using this test piece, a vertical combustion test (UL94, 1/16 inch) and a tensile test (ASTM D-638) were performed. The results are as shown in Table 1.
[0036]
The result of the combustion test showed high flame retardancy equivalent to UL94 V-0.
[0037]
[Omitted]
[0038]
[Comparative Example 1]
As in Example 1, 60 parts of polybutylene terephthalate having an intrinsic viscosity of 0.98, 20 parts of the phosphoric ester represented by the formula (II), 15 parts of melamine cyanurate, and 15 parts of glass fiber were extruded into chips. The extrudability was unstable as compared to Example 1, often with thread breakage.
[0039]
Further, a molding, a combustion test, and a tensile test were performed in the same manner as in Example 1. The results are shown in Table 1.
[0040]
The result of the combustion test was equivalent to UL94 V-2, which was inferior to Example 1. Further, the tensile properties were inferior to those of Example 1.
[0041]
[Examples 2 , 4 to 6, Comparative Example 2 , Reference Example 1 ]
The procedure was performed in the same manner as in Example 1 except that the amount of polybutylene terephthalate, the type and the amount of the compounding agent were as shown in Table 1. The results are shown in Table 1.
[0042]
[Example 7]
30 parts by weight of polybutylene terephthalate and 70 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 2,000, 73 parts of a polyester elastomer having a melting point of 190 ° C. and an intrinsic viscosity of 1.30, 15 parts of a phosphoric ester represented by the formula (II), 12 parts of a novolak type phenol resin (PR-53195) was kneaded at 230 ° C. using an extruder (Laboplast mill) to form chips in the same manner as in Example 1.
[0043]
After drying the obtained chip at 120 ° C. for 4 hours, a combustion test piece was injection molded under the conditions of a melting temperature of 230 ° C. and a mold temperature of 80 ° C.
[0044]
Using this test piece, a vertical combustion test (based on UL94, sample thickness 1/16 inch) was performed. The results are as shown in Table 1.
[0045]
The result of the combustion test showed excellent flame retardancy equivalent to UL94 V-0.
[0046]
[Comparative Example 3]
The procedure was performed in the same manner as in Example 5 except that the amount of the polyester elastomer, the type and the amount of the compounding agent were as shown in Table 1. The results are shown in Table 1.
[0047]
The result of the combustion test was equivalent to UL94 V-2, which was inferior to Example 5.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06071096A JP3590469B2 (en) | 1996-03-18 | 1996-03-18 | Flame retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06071096A JP3590469B2 (en) | 1996-03-18 | 1996-03-18 | Flame retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09249800A JPH09249800A (en) | 1997-09-22 |
| JP3590469B2 true JP3590469B2 (en) | 2004-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06071096A Expired - Fee Related JP3590469B2 (en) | 1996-03-18 | 1996-03-18 | Flame retardant resin composition |
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| Country | Link |
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| JP (1) | JP3590469B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60024278T2 (en) * | 1999-02-19 | 2006-08-03 | Akzo Nobel N.V. | PHOSPHORUS, FLAME-RESISTANT THERMOPLASTIC POLYESTER COMPOSITIONS |
| US6312824B1 (en) * | 1999-08-27 | 2001-11-06 | E. I. Du Pont De Nemours And Company | Copolyester elastomer compositions and fusion bonded articles |
| JP2002030204A (en) * | 2000-05-09 | 2002-01-31 | Du Pont Toray Co Ltd | Flame retardant polyester elastomer resin composition |
| JP2002060596A (en) * | 2000-06-05 | 2002-02-26 | Du Pont Toray Co Ltd | Flame retardant polyester elastomer resin composition |
| WO2012165206A1 (en) * | 2011-05-31 | 2012-12-06 | 東洋紡株式会社 | Resin composition for sealing electric/electronic component, method for manufacturing electric/electronic component, and electric/electronic component sealed body |
| JP2018090724A (en) * | 2016-12-06 | 2018-06-14 | 三井化学株式会社 | Resin composition and molded article |
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1996
- 1996-03-18 JP JP06071096A patent/JP3590469B2/en not_active Expired - Fee Related
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| JPH09249800A (en) | 1997-09-22 |
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