JP3301816B2 - Polyester-based composite molded article and production method thereof - Google Patents
Polyester-based composite molded article and production method thereofInfo
- Publication number
- JP3301816B2 JP3301816B2 JP10738593A JP10738593A JP3301816B2 JP 3301816 B2 JP3301816 B2 JP 3301816B2 JP 10738593 A JP10738593 A JP 10738593A JP 10738593 A JP10738593 A JP 10738593A JP 3301816 B2 JP3301816 B2 JP 3301816B2
- Authority
- JP
- Japan
- Prior art keywords
- resin material
- resin
- molded article
- composite molded
- carbon atoms
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は気密性及び密着性に優れ
た複合成形品及びその製造法に関し、自動車や電気・電
子分野の各種機器部品に好適な複合成形品を提供するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite molded product excellent in airtightness and adhesion and a method for producing the same, and provides a composite molded product suitable for various equipment parts in the fields of automobiles and electric and electronic fields.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】結晶性
熱可塑性樹脂であるポリエチレンテレフタレート（ＰＥ
Ｔ樹脂）、ポリブチレンテレフタレート（ＰＢＴ樹脂）
等は機械的性質、電気的性質、その他物理的・化学的特
性に優れ、かつ、加工性が良好であるがゆえにエンジニ
アリングプラスチックとして自動車、電気・電子部品等
の広汎な用途に使用されている。しかしながら近年、自
動車、電気・電子部品には多種の特性が求められてお
り、その特性付与手法の１つとして異質材料を組み合わ
せた２体成形部品が開発されている。一般に２種の材料
を一体的に成形する方法としては、樹脂の一次側成形品
上に異材質樹脂を二次成形してその界面を融着固定させ
る二重成形法により部分的に異なる特性を有する複合成
形品を得ることが知られているが、高結晶性熱可塑性ポ
リエステルを多重成形に使用した複合成形品では一次側
の樹脂と二次側の樹脂の界面の融着が不充分であり、外
力によって剥離しやすく、又、そり変形等を生じ易く、
使用上一体成形品としての機能を満足しないことが多
い。両樹脂の界面の融着強度を補う目的で一次側成形品
にアンダーカットや貫通孔を設ける等メカニカルなアン
カー効果を有する形状構造を設けたり、一次成形品に接
着剤を塗布する等の工夫が見られるが、形状が複雑化し
たり、工程が煩雑化して経済的にも不利であり、又、生
産効率の面でも望ましくない。特にポリブチレンテレフ
タレートやポリプロピレンテレフタレート又はポリエチ
レンテレフタレートは高い結晶性を有するために、これ
を二重成形法により成形し、樹脂間の界面の融着強度の
高い複合成形品を簡単な方法で経済的に効率良く生産す
るのは至難であった。2. Description of the Related Art Polyethylene terephthalate (PE) which is a crystalline thermoplastic resin
T resin), polybutylene terephthalate (PBT resin)
Are used as engineering plastics in a wide range of applications such as automobiles, electric and electronic parts, etc. because of their excellent mechanical properties, electrical properties, and other physical and chemical properties and good workability. However, in recent years, various kinds of characteristics are required for automobiles and electric / electronic parts, and a two-part molded part combining different materials has been developed as one of the characteristics imparting methods. Generally, as a method of integrally molding two kinds of materials, partially different characteristics are obtained by a dual molding method in which a dissimilar resin is secondarily molded on a primary molded article of the resin and the interface is fused and fixed. Although it is known to obtain a composite molded product having a composite molded product using a highly crystalline thermoplastic polyester for multiple molding, fusion at the interface between the resin on the primary side and the resin on the secondary side is insufficient. , Easy to peel off by external force, easy to warp, etc.
In many cases, the function as an integrally molded product is not satisfied. In order to compensate for the fusion strength at the interface between the two resins, the primary molded product must be provided with a mechanical structure that has a mechanical anchor effect, such as by providing undercuts or through holes, or by applying an adhesive to the primary molded product. As can be seen, the shape becomes complicated and the process becomes complicated, which is economically disadvantageous, and is also undesirable in terms of production efficiency. In particular, since polybutylene terephthalate, polypropylene terephthalate, or polyethylene terephthalate has high crystallinity, it is molded by a double molding method, and a composite molded product having a high fusion strength at the interface between resins can be economically produced by a simple method. It was very difficult to produce efficiently.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、ポリアル
キレンテレフタレート系樹脂の優れた機械的性質、化学
的性質、熱的性質等を有する一体成形品で、特にアンカ
ー形状の付与や接着剤等を用いることなく簡単な多重成
形法により樹脂間の融着強度の高い複合成形品を経済的
に効率良く得るべく鋭意検討した結果、本発明に到達し
た。即ち本発明は下記（Ｉ）又は（II）で示される樹脂
材料(A) と下記(III) で示される樹脂材料(B) とを多重
成形法により一体的に成形してなる気密性及び密着性の
高い複合成形品及びその製造法である。 （Ｉ）ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）を主体とし１〜40モル％の他のジカルボ
ン酸化合物或いは低分子量ジヒドロキシ化合物から導入
されるコモノマーユニットを含有する共重合体（但し、
液晶性ポリエステルを除く） （II）上記（Ｉ）の共重合体にポリアルキレンテレフタ
レート（アルキレン基の炭素数２〜４）を全量に対して
１〜95重量％混合したブレンド物 (III)ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）又はこれを主体とし40モル％以下の他の
ジカルボン酸化合物或いは低分子量ジヒドロキシ化合物
から導入されるコモノマーユニットを含有する重合体
（但し、液晶性ポリエステルを除く） 以下、本発明の一体成形品の構成材料及びその成形法に
ついて詳しく説明する。DISCLOSURE OF THE INVENTION The present inventors have developed a polyalkylene terephthalate resin which is an integrally molded product having excellent mechanical properties, chemical properties, thermal properties, etc. As a result of intensive studies to economically and efficiently obtain a composite molded product having a high fusion strength between resins by a simple multiple molding method without using any method, the present invention has been achieved. That is, the present invention provides airtightness and adhesion obtained by integrally molding a resin material (A) represented by the following (I) or (II) and a resin material (B) represented by the following (III) by a multiple molding method. This is a composite molded article having high properties and a method for producing the same. (I) 1 to 40 mol% of other dicarboxy mainly composed of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms)
Introduced from acid compounds or low molecular weight dihydroxy compounds
A copolymer containing a comonomer unit (provided that
(II) A blend of the copolymer of (I) and 1-95% by weight of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) with respect to the total amount. (III) Polyalkylene Terephthalate (alkylene group having 2 to 4 carbon atoms) or other main component containing up to 40 mol%
Dicarboxylic acid compound or low molecular weight dihydroxy compound
(Excluding Liquid Crystalline Polyester) Containing Comonomer Units Introduced from the following, the constituent materials of the integrally molded article of the present invention and the molding method thereof will be described in detail.
【０００４】本発明の複合成形品に有効な樹脂材料(A)
の一つを構成する（Ｉ）は、ポリアルキレンテレフタレ
ート（アルキレン基の炭素数２〜４）を主体とし１〜40
モル％の他のコモノマーユニットを含有する共重合体で
あり、具体的にはテレフタル酸又はそのエステル形成誘
導体と炭素数２〜４のアルキレングリコール又はそのエ
ステル形成誘導体を重縮合反応して得られるポリアルキ
レンテレフタレートを主体とするものであり、例えばポ
リエチレンテレフタレート、ポリプロピレンテレフタレ
ート又はポリブチレンテレフタレートを主成分とし、こ
れに１〜40モル％の他のコモノマーユニットを導入した
共重合体が挙げられる。かかる共重合体を構成する第三
成分（コモノマー）としては、イソフタル酸、ナフタレ
ンジカルボン酸、ジフェニルジカルボン酸、ジフェニル
エーテルジカルボン酸、ジフェニルエタンジカルボン
酸、シクロヘキサンジカルボン酸、アジピン酸、セバシ
ン酸、ドデカン二酸の如き公知のジカルボン酸及びこれ
らのアルキル、アルコキシ又はハロゲン置換体等が挙げ
られる。また、これらのジカルボン酸化合物は、エステ
ル形成可能な誘導体、例えばジメチルエステルの如き低
級アルコールエステルの形で重縮合に使用しコモノマー
成分として導入することも可能である。又、共重合体を
構成するための第三成分として使用されるジヒドロキシ
化合物の例を示せば、エチレングリコール、1,3 −プロ
パンジオール、1,4 −ブタンジオール、ネオペンチルグ
リコール、ハイドロキノン、レゾルシン、ジヒドロキシ
フェニル、ナフタレンジオール、ジヒドロキシジフェニ
ルエーテル、シクロヘキサンジオール、2,2 −ビス（４
−ヒドロキシフェニル）プロパン、ジエトキシ化ビスフ
ェノールＡの如き比較的低分子量のジヒドロキシ化合
物、及びこれらのアルキル、アルコキシ又はハロゲン置
換体等である。これらのコモノマー成分は２種以上混合
して導入したものであってもよい。本発明では、上記の
如き化合物をコモノマー成分として、重縮合により生成
する熱可塑性ポリエステル共重合体を単独又は２種以上
混合して本発明の樹脂材料(A) として使用することがで
きる。本発明における一体成形品を構成するポリアルキ
レンテレフタレートを主体とする樹脂材料(A) は本来の
エンジニアリングプラスチックとしての特性を有し且つ
気密性及び密着性に優れた特性を兼備する材料であるた
め、共重合成分の含有量は１〜40モル％の範囲であり、
好ましくは３〜35モル％の範囲である。またかかる樹脂
材料(A) は、一般には一次成形品として使用し、この上
に二次材料(B) を成形融着するので、その界面の融着強
度を得るためには二次成形において樹脂材料(B) によっ
てその表面（界面）部が一時的に溶融することが必要と
なり、その融点も考慮する必要がある。そのため樹脂材
料(A) の融点は 250℃以下、好ましくは 240℃以下であ
ることが望ましい。樹脂材料(A) の融点が高すぎると、
二次成形における樹脂材料(B) の成形樹脂温度を更に高
くする必要が生じ、その熱分解等を生じ易く、又、粘度
低下等により成形性を害し、好ましくない。又、樹脂材
料(A) の融点が低過ぎると、二次成形時に一次材料の変
形を生じ易く、好ましくない。樹脂材料(A) の融点はこ
れに使用するポリアルキレンテレフタレート系樹脂の種
類、共重合成分の種類と量等により調製される。この見
地から特に好ましいのはポリエチレンテレフタレート、
ポリプロピレンテレフタレート又はポリブチレンテレフ
タレートを主体とし、３〜35モル％共重合成分を有する
共重合体である。又、本発明の複合成形品に有効な樹脂
材料(A) として、前記（Ｉ）の共重合体にポリアルキレ
ンテレフタレート（アルキレン基の炭素数２〜４）を全
量に対して１〜95重量％混合したブレンド物（II）も挙
げられる。ブレンドされるポリブチレンテレフタレー
ト、ポリプロピレンテレフタレートあるいはポリエチレ
ンテレフタレートの混合量は、成形品の気密性及び融着
性の付与及び混合物の融点の観点から（II）全量に対し
て95重量％以下、好ましくは90重量％以下が好ましい。Resin material (A) effective for the composite molded article of the present invention
(I) constituting one of the above is mainly composed of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) and 1 to 40
A copolymer containing at least one mol% of another comonomer unit, specifically, a poly (ethylene glycol) obtained by a polycondensation reaction between terephthalic acid or an ester-forming derivative thereof and an alkylene glycol having 2 to 4 carbon atoms or an ester-forming derivative thereof. It is mainly composed of alkylene terephthalate, and includes, for example, a copolymer containing polyethylene terephthalate, polypropylene terephthalate or polybutylene terephthalate as a main component, into which 1 to 40 mol% of another comonomer unit is introduced. The third component (comonomer) constituting such a copolymer includes isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecanediacid. Examples of such known dicarboxylic acids and their alkyl, alkoxy or halogen-substituted products. These dicarboxylic acid compounds can also be used as a comonomer component in the form of a derivative capable of forming an ester, for example, a lower alcohol ester such as dimethyl ester, for polycondensation. Examples of the dihydroxy compound used as the third component for constituting the copolymer include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, hydroquinone, resorcinol, Dihydroxyphenyl, naphthalene diol, dihydroxydiphenyl ether, cyclohexanediol, 2,2-bis (4
-Hydroxyphenyl) propane, relatively low molecular weight dihydroxy compounds such as diethoxylated bisphenol A, and alkyl, alkoxy or halogen substituted products thereof. These comonomer components may be introduced by mixing two or more kinds. In the present invention, the above-mentioned compound can be used as a comonomer component, and a thermoplastic polyester copolymer produced by polycondensation can be used alone or as a mixture of two or more kinds as the resin material (A) of the present invention. The resin material mainly composed of polyalkylene terephthalate constituting the integrally molded product in the present invention (A) is a material having characteristics as an original engineering plastic and having both excellent airtightness and excellent adhesiveness, The content of the copolymer component is in the range of 1 to 40 mol%,
Preferably it is in the range of 3-35 mol%. Further, such a resin material (A) is generally used as a primary molded product, and the secondary material (B) is molded and fused thereon, so that in order to obtain the fusion strength at the interface, the resin material is used in the secondary molding. Depending on the material (B), its surface (interface) needs to be temporarily melted, and its melting point also needs to be considered. Therefore, the melting point of the resin material (A) is desirably 250 ° C or lower, preferably 240 ° C or lower. If the melting point of the resin material (A) is too high,
In the secondary molding, it is necessary to further raise the molding resin temperature of the resin material (B), which tends to cause thermal decomposition and the like, and also impairs the moldability due to a decrease in viscosity, which is not preferable. On the other hand, if the melting point of the resin material (A) is too low, the primary material tends to be deformed during the secondary molding, which is not preferable. The melting point of the resin material (A) is adjusted according to the type of the polyalkylene terephthalate resin used, the type and amount of the copolymer component, and the like. Particularly preferred from this point of view are polyethylene terephthalate,
A copolymer mainly composed of polypropylene terephthalate or polybutylene terephthalate and having a copolymer component of 3 to 35 mol%. Further, as a resin material (A) effective for the composite molded article of the present invention, poly (alkylene terephthalate (alkylene group having 2 to 4 carbon atoms) is added to the copolymer (I) in an amount of 1 to 95% by weight based on the total amount. Mixed blends (II) are also mentioned. The mixing amount of polybutylene terephthalate, polypropylene terephthalate or polyethylene terephthalate to be blended is 95% by weight or less, preferably 90% by weight, based on the total amount of (II) from the viewpoint of imparting airtightness and fusibility of the molded article and melting point of the mixture. % By weight or less is preferred.
【０００５】更に本発明の成形品を構成する樹脂材料
(A) としては、目的とする性質を付与するため、前記の
（Ｉ）又は（II）で示される樹脂以外に、補助的に少量
の他の熱可塑性樹脂を配合してもよい。かかる補助的熱
可塑性樹脂としては、例えばポリオレフィン系重合体、
ポリアミド系重合体、ポリカーボネート系重合体、ポリ
アリレート系重合体、主成分以外のポリエステル系重合
体（例えば完全芳香族ポリエステル）、スチレン系重合
体（例えばＡＳ又はＡＢＳ樹脂）、ポリフェニレンオキ
サイド系重合体、アクリレート系重合体、ポリアセター
ル、ポリスルホン、ポリエーテルスルホン、ポリエーテ
ルイミド、ポリエーテルケトン、ポリアリーレンサルフ
ァイド系重合体、フッ素樹脂、オレフィン系熱可塑性エ
ラストマー（例えばＥＰＤＭ又はアイオノマー）、スチ
レン系熱可塑性エラストマー（例えばＳＢＳ又はＳＥＢ
Ｓ）、ウレタン系熱可塑性エラストマー、ポリエステル
系熱可塑性エラストマー、ポリアミド系熱可塑性エラス
トマー、ポリエーテル系熱可塑性エラストマー、或いは
これらの変性体などを挙げることができ、これらの熱可
塑性樹脂は２種以上混合して使用することもできるが、
このような他の熱可塑性樹脂を補助的に配合する場合も
上述の如く、その配合物の剛性、融点等に配慮する必要
がある。又、本発明の成形品を構成する樹脂材料(A) に
は無機充填剤を配合することが出来る。かかる充填剤
は、機械的強度、耐熱性、寸法安定性、電気的性質等の
性能に優れた性質を得るためには配合することが好まし
く、特に剛性を高める目的で有効である。これは目的に
応じて繊維状、粉粒状又は板状の充填剤が用いられる。
繊維状充填剤としては、ガラス繊維、アスベスト繊維、
カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジ
ルコニア繊維、窒化硼素繊維、窒化硅素繊維、硼素繊
維、チタン酸カリ繊維、更にステンレス、アルミニウ
ム、チタン、銅、真鍮等の金属の繊維状物などの無機質
繊維状物質が挙げられる。特に代表的な繊維状充填剤は
ガラス繊維である。尚、ポリアミド、フッ素樹脂、アク
リル樹脂などの高融点有機質繊維状物質も使用すること
ができる。一方、粉粒状充填剤としては、カーボンブラ
ック、シリカ、石英粉末、ガラスビーズ、ガラス粉、硅
酸カルシウム、硅酸アルミニウム、カオリン、タルク、
クレー、硅藻土、ウォラストナイトの如き硅酸塩、酸化
鉄、酸化チタン、アルミナの如き金属の酸化物、炭酸カ
ルシウム、炭酸マグネシウムの如き金属の炭酸塩、硫酸
カルシウム、硫酸バリウムの如き金属の硫酸塩、その他
炭化硅素、窒化硅素、窒化硼素、各種金属粉末等が挙げ
られる。又、板状充填剤としては、マイカ、ガラスフレ
ーク、各種金属箔等が挙げられる。これらの無機充填剤
は１種又は２種以上併用することができる。繊維状充填
剤、特にガラス繊維又はカーボン繊維と、粒状又は板状
充填剤の併用は特に機械的強度と寸法精度、電気的性質
等を兼備する上で好ましい組み合わせである。無機充填
剤の添加量は樹脂材料(A) 全量に対し40重量％以下であ
る。これより多いと成形加工性や靭性を害し好ましくな
い。特に好ましくは30重量％以下である。Further, a resin material constituting the molded article of the present invention
As (A), a small amount of another thermoplastic resin may be supplemented in addition to the resin represented by (I) or (II) in order to impart desired properties. As such an auxiliary thermoplastic resin, for example, a polyolefin-based polymer,
Polyamide-based polymer, polycarbonate-based polymer, polyarylate-based polymer, polyester polymer other than the main component (for example, completely aromatic polyester), styrene-based polymer (for example, AS or ABS resin), polyphenylene oxide-based polymer, Acrylate-based polymers, polyacetals, polysulfones, polyethersulfones, polyetherimides, polyetherketones, polyarylenesulfide-based polymers, fluororesins, olefin-based thermoplastic elastomers (eg, EPDM or ionomer), styrene-based thermoplastic elastomers (eg, SBS or SEB
S), a urethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyether-based thermoplastic elastomer, or a modified product thereof, and the like. Two or more kinds of these thermoplastic resins are mixed. You can also use
As described above, it is necessary to consider the rigidity, melting point, and the like of the compound even when such other thermoplastic resin is compounded supplementarily. The resin material (A) constituting the molded article of the present invention may contain an inorganic filler. Such a filler is preferably blended in order to obtain excellent properties such as mechanical strength, heat resistance, dimensional stability, and electrical properties, and is particularly effective for increasing rigidity. For this purpose, a fibrous, powdery or plate-like filler is used depending on the purpose.
As the fibrous filler, glass fiber, asbestos fiber,
Inorganic substances such as carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass Fibrous substances. Particularly typical fibrous fillers are glass fibers. In addition, a high melting point organic fibrous substance such as polyamide, fluororesin, and acrylic resin can also be used. On the other hand, as powdery fillers, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc,
Clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron oxide, titanium oxide and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, metals such as calcium sulfate and barium sulfate Sulfates, other silicon carbide, silicon nitride, boron nitride, various metal powders, and the like. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These inorganic fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly a glass fiber or a carbon fiber, and a granular or plate-like filler is a preferable combination, particularly in terms of having both mechanical strength, dimensional accuracy, electrical properties and the like. The amount of the inorganic filler added is 40% by weight or less based on the total amount of the resin material (A). If it is more than this, the moldability and toughness are impaired, which is not preferable. Particularly preferably, it is at most 30% by weight.
【０００６】次に複合成形品の他部分を形成するための
樹脂材料(B) を構成する(III) は、主としてポリエチレ
ンテレフタレート、ポリプロピレンテレフタレート、ポ
リブチレンテレフタレート等のポリエステル樹脂、又は
これらを主成分とし、これに40モル％以下の他のコモノ
マーユニットを導入した重合体である。かかる共重合体
を構成する第三成分（コモノマー）としては、前記樹脂
材料(A) で記載したものと同様のジカルボン酸化合物、
ジヒドロキシ化合物が挙げられ、コモノマー成分は２種
以上混合して導入したものであってもよい。本発明で
は、上記の如き化合物をコモノマー成分として、重縮合
により生成する熱可塑性ポリエステル共重合体を単独又
は２種以上混合して本発明の樹脂材料(B) として使用す
ることができる。本発明における一体成形品を構成する
樹脂材料(B) は本来エンジニアリングプラスチックとし
ての特性を有するための材料であるため、共重合成分の
含有量は多くとも、40モル％以下であり、好ましくは35
モル％以下である。又、これを曲げ弾性率で示せば少な
くとも15000kgf/cm2以上、好ましくは18000kgf/cm2以上
であることが望ましい。又、本発明の成形品を構成する
樹脂材料(B) としては、前記の(III) で示される樹脂以
外に熱可塑性樹脂および／又は種々の充填剤を配合して
もよい。かかる配合する熱可塑性樹脂および充填剤とし
ては前記樹脂材料(A) で用いるものと同様のものが例示
される。[0006] Next, (III) constituting the resin material (B) for forming the other part of the composite molded article is mainly a polyester resin such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, or a resin containing these as a main component. a polymer obtained by introducing 40 mol% or less of other comonomer units thereto. As the third component (comonomer) constituting such a copolymer, the same dicarboxylic acid compound as described in the resin material (A),
A dihydroxy compound may be used, and the comonomer component may be a mixture of two or more components. In the present invention, the above-described compound can be used as a comonomer component, and a thermoplastic polyester copolymer produced by polycondensation can be used alone or as a mixture of two or more kinds as the resin material (B) of the present invention. Since the resin material (B) constituting the integrally molded article in the present invention is a material originally having properties as an engineering plastic, the content of the copolymer component is at most 40 mol% or less, preferably 35 mol% or less.
Mol% or less. If this is expressed in terms of flexural modulus, it is desirably at least 15000 kgf / cm 2 or more, preferably 18000 kgf / cm 2 or more. In addition, as the resin material (B) constituting the molded article of the present invention, a thermoplastic resin and / or various fillers may be blended in addition to the resin represented by the above (III). Examples of the thermoplastic resin and filler to be compounded are the same as those used in the resin material (A).
【０００７】尚、本発明において使用する樹脂材料(A)
及び(B) は何れか一方又は両方にその目的に応じ所望の
特性を付与するため、一般に熱可塑性樹脂に添加される
上記以外の公知の物質、すなわち、酸化防止剤、紫外線
吸収剤等の各種安定剤、帯電防止剤、難燃剤、難燃助
剤、染料や顔料等の着色剤、潤滑剤、可塑剤及び結晶化
促進剤、結晶核剤、離型剤等を配合することも勿論可能
である。The resin material (A) used in the present invention
And (B) are known substances other than the above, which are generally added to a thermoplastic resin in order to impart desired properties to one or both of them, that is, various kinds of substances such as antioxidants and ultraviolet absorbers. It is of course possible to incorporate stabilizers, antistatic agents, flame retardants, flame retardant aids, coloring agents such as dyes and pigments, lubricants, plasticizers and crystallization accelerators, crystal nucleating agents, mold release agents, etc. is there.
【０００８】本発明の複合成形品は、上記(A) 、(B) ２
種の樹脂材料を使用して、いわゆる多重成形法により成
形される。成形方法としては射出成形、圧縮成形その他
の成形法が適用されるが一般には射出成形が好ましい。
樹脂材料(A) 又は(B) の何れか一方を予め成形して一次
成形品とし、次いでこれに他の樹脂材料を成形して融着
し一体化するもので、成形品の形状構造或いは目的とす
る用途により何れを一次側成形品としてもよいが、一般
には樹脂材料(A) で一次成形し、次いで樹脂材料(B) を
二次成形する方が成形品の形崩れや成形時又は成形後に
おける変形を防止する上で好ましい。この場合、強固に
融着させるためには、二次成形において、樹脂材料(B)
の樹脂温度によって一次成形品の表層（界面）部が溶融
することが必要であり、このため二次成形における樹脂
温度は少なくとも一次成形品の樹脂材料(A) の融点以上
の温度とする必要があり、二次成形における接触時の二
次材料の樹脂温度を一次材料の融点より10〜120 ℃、好
ましくは30〜100 ℃高くして二次成形を行うことが好ま
しい。しかし、二次材料の樹脂温度が高すぎると二次材
料の分解変質をまねく場合があり、これを避けるため一
次成形品の樹脂材料(A) の融点が高過ぎるものは好まし
くなく、一般には前述の通り、一次材料の融点が 250℃
以下、好ましくは 240℃以下であって、これは一次成形
品を構成する樹脂材料(A) のポリアルキレンテレフタレ
ート系樹脂の共重合成分及びその導入量、補助的成分及
びその配合量等によって調節することができるが、かか
る調整は材料自体の剛性にも影響するため、その兼ね合
いによって樹脂材料構成は選択される。[0008] The composite molded article of the present invention comprises the above (A) and (B) 2
It is molded by a so-called multiple molding method using various kinds of resin materials. As a molding method, injection molding, compression molding and other molding methods are applied, but injection molding is generally preferred.
Either resin material (A) or (B) is molded in advance to form a primary molded product, and then another resin material is molded, fused and integrated, and the shape and structure of the molded product or purpose Any of the primary side molded products may be used depending on the application.However, it is generally better to perform primary molding with the resin material (A) and then secondary mold the resin material (B) when the molded product loses its shape or during molding or during molding. It is preferable in order to prevent deformation later. In this case, in order to perform strong fusion, in the secondary molding, the resin material (B)
It is necessary that the surface layer (interface) of the primary molded article is melted by the resin temperature of the primary molded article. Therefore, the resin temperature in the secondary molding must be at least a melting point of the resin material (A) of the primary molded article. Yes, it is preferable to perform the secondary molding by raising the resin temperature of the secondary material at the time of contact in the secondary molding by 10 to 120 ° C., preferably 30 to 100 ° C. above the melting point of the primary material. However, if the resin temperature of the secondary material is too high, the secondary material may be decomposed and deteriorated.To avoid this, it is not preferable that the resin material (A) of the primary molded product has a melting point that is too high. As shown, the melting point of the primary material is 250 ° C
The temperature is preferably 240 ° C. or lower, which is controlled by the copolymerization component of the polyalkylene terephthalate-based resin of the resin material (A) constituting the primary molded product and its introduction amount, auxiliary components and its blending amount, etc. However, since such adjustment also affects the rigidity of the material itself, the resin material configuration is selected depending on the balance.
【０００９】[0009]
【実施例】本発明者は、ポリエステルの最適な組み合わ
せを見出すため、異なる特性のポリエステルを選択し、
それらの組み合わせにより発揮される密着強度について
の実験を行った。次にその実験例を説明する。先ず、樹
脂材料(A) を用い、一次成形品として80mm角、厚さ２mm
の平板を成形した。次にこの平板を80mm角、厚さ４mmの
金型キャビティーに装着し、樹脂材料(B) を二次材とし
てその樹脂温度を変えて、二次成形を行い平板状の複合
成形品を成形し、界面の剥離強度を測定した。尚、剥離
強度の測定は、複合成形品を巾10mmに切断し、その一端
の接合界面を一定の長さだけナイフで強制剥離し、その
各々を引張り試験機の固定具にセットし引張り、剥離を
生じる最大荷重を剥離強度とした。又、本発明者は各ポ
リエステルの組み合わせにより発揮される気密性につい
ての実験も行った。次にその実験例を説明する。検査方
法は、平板状の複合成形品を 130℃の雰囲気中に60分間
さらした後、それを０℃の水中に60分間浸漬し、水中か
ら取り出して常温で15分間放置する加熱・冷却サイクル
を50回繰り返し、次いで浸透性の高いインクに浸漬し、
インクが乾いた後接着面を破壊してインクの進入状況を
目視観察した。EXAMPLES In order to find the best combination of polyesters, the present inventors have selected polyesters with different properties,
An experiment was conducted on the adhesion strength exhibited by these combinations. Next, an experimental example will be described. First, using resin material (A), 80mm square, 2mm thick as primary molded product
Was molded. Next, this flat plate is mounted in a mold cavity of 80 mm square and 4 mm thick, and the resin material (B) is used as a secondary material and the resin temperature is changed to perform secondary molding to form a flat composite molded product. Then, the peel strength at the interface was measured. The peel strength was measured by cutting a composite molded product to a width of 10 mm, forcibly peeling off the joint interface at one end by a fixed length with a knife, setting each of them on a fixture of a tensile tester, pulling and peeling. The maximum load that caused the pressure was defined as the peel strength. The inventor also conducted an experiment on the airtightness exhibited by the combination of each polyester. Next, an experimental example will be described. The inspection method is as follows: After exposing a flat composite molded article to an atmosphere of 130 ° C for 60 minutes, immersing it in water of 0 ° C for 60 minutes, taking it out of the water and leaving it at room temperature for 15 minutes, a heating and cooling cycle Repeat 50 times, then immerse in highly permeable ink,
After the ink had dried, the adhesive surface was broken and the state of penetration of the ink was visually observed.
【００１０】以下に本発明の実施例を示すが本発明はこ
れに限定されるものではない。 実施例１ 樹脂材料(A) としてＤＭＩ（ジメチルイソフタレート）
を約 12.5mol％を共重合することにより変性した変性Ｐ
ＢＴ（融点 205℃）(A-1) を一次成形し、ＰＢＴ樹脂
（融点 225℃）(B-1) を二次材としてその樹脂温度を変
えて二次成形を行い、平板状の複合成形品を成形し、そ
の剥離強度と気密性の評価を行った。結果を表１に示
す。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. Example 1 DMI (dimethyl isophthalate) was used as the resin material (A).
Is modified by copolymerizing about 12.5 mol% of
Primary molding of BT (melting point 205 ° C) (A-1), secondary molding using PBT resin (melting point 225 ° C) (B-1) as a secondary material and changing the resin temperature, flat composite molding The product was molded and its peel strength and airtightness were evaluated. Table 1 shows the results.
【００１１】実施例２ 樹脂材料(A) として、ＤＭＩ変性ＰＢＴ（融点205 ℃）
(A-1) を一次成形し、樹脂材料(B) として同じＤＭＩ変
性ＰＢＴ(A-1) を、その樹脂温度を変えて二次成形し、
実施例１と同様の評価を行った。結果を表１に示す。Example 2 As a resin material (A), DMI-modified PBT (melting point 205 ° C.)
(A-1) is first molded, and the same DMI-modified PBT (A-1) as the resin material (B) is secondarily molded by changing its resin temperature,
The same evaluation as in Example 1 was performed. Table 1 shows the results.
【００１２】実施例３ 樹脂材料(A) としてＤＭＩを約５ mol％共重合すること
により変性したＤＭＩ変性ＰＢＴ（融点 215℃）(A-2)
を一次成形し、樹脂材料(B) として、ＰＥＴ樹脂(B-2)
をその樹脂温度を変えて二次成形し、実施例１と同様の
評価を行った。結果を表１に示す。Example 3 DMI modified PBT modified by copolymerizing about 5 mol% of DMI as resin material (A) (melting point: 215 ° C.) (A-2)
Is primarily molded, and as the resin material (B), PET resin (B-2)
Was subjected to secondary molding while changing the resin temperature, and the same evaluation as in Example 1 was performed. Table 1 shows the results.
【００１３】実施例４ 樹脂材料(A) としてエチレングリコールを約17.5mol ％
共重合することにより変性した変性ＰＢＴ（融点 205
℃）(A-3) を一次成形し樹脂材料(B) としてＰＢＴ樹脂
(B-1) をその樹脂温度を変えて二次成形し実施例１と同
様の評価を行った。結果を表１に示す。Example 4 About 17.5 mol% of ethylene glycol as the resin material (A)
Modified PBT modified by copolymerization (melting point 205
℃) (A-3) as primary resin and PBT resin as resin material (B)
(B-1) was subjected to secondary molding by changing the resin temperature, and the same evaluation as in Example 1 was performed. Table 1 shows the results.
【００１４】比較例１ ＰＢＴ樹脂（融点 257℃）(B-1) を一次成形し、ついで
同じＰＢＴ樹脂(B-1)をその樹脂温度を変えて二次成形
し、実施例２と同様の評価を行った。結果を表１に示
す。Comparative Example 1 PBT resin (melting point: 257 ° C.) (B-1) was first molded, and then the same PBT resin (B-1) was secondarily molded by changing the resin temperature. An evaluation was performed. Table 1 shows the results.
【００１５】比較例２ ＰＥＴ樹脂（融点257 ℃）(B-2) を一次成形し、次いで
同じＰＥＴ樹脂(B-2)をその樹脂温度を変えて二次成形
し、実施例１と同様の評価を行った。結果を表１に示
す。Comparative Example 2 PET resin (melting point: 257 ° C.) (B-2) was first molded, and then the same PET resin (B-2) was secondarily molded by changing its resin temperature. An evaluation was performed. Table 1 shows the results.
【００１６】[0016]
【表１】 [Table 1]
【００１７】実施例５ 樹脂材料(A) として、ＤＭＩ変性ＰＢＴ（融点 205℃）
(A-1) （70重量％）とガラス繊維（30重量％）よりなる
組成物(a-1) 、樹脂材料(B) としてＰＢＴ樹脂（融点 2
25℃）(B-2) （70重量％）とガラス繊維（30重量％) よ
り成る組成物(b-1) を使用して複合成形品を成形し実施
例１と同様の評価を行った。結果を表２に示す。Example 5 As a resin material (A), DMI-modified PBT (melting point 205 ° C.)
(A-1) A composition (a-1) composed of (70% by weight) and glass fiber (30% by weight), and a PBT resin (melting point 2) as a resin material (B).
A composite molded article was molded using the composition (b-1) composed of (B-2) (70% by weight) and glass fiber (30% by weight) and evaluated in the same manner as in Example 1. . Table 2 shows the results.
【００１８】実施例６ 樹脂材料(A) 及び樹脂材料(B) として実施例５と同じ組
成物(a-1) を使用して複合成形品を成形し、同様の評価
を行った。結果を表２に示す。Example 6 A composite molded article was molded using the same composition (a-1) as in Example 5 as the resin material (A) and the resin material (B), and the same evaluation was performed. Table 2 shows the results.
【００１９】実施例７ 樹脂材料(A) としてＤＭＩ変性ＰＢＴ（融点215 ℃）(A
-2) （70重量％）とガラス繊維（30重量％）より成る組
成物(a-2) 、樹脂材料(B) としてＰＥＴ樹脂（融点 257
℃）(B-2) （70重量％）とガラス繊維（30重量％）より
成る組成物(b-2) を使用して、複合成形品を成形し実施
例５と同様の評価を行った。結果を表２に示す。Example 7 As a resin material (A), DMI-modified PBT (melting point: 215 ° C.) (A
-2) Composition (a-2) consisting of (70% by weight) and glass fiber (30% by weight), and PET resin (melting point 257) as resin material (B)
° C) (B-2) A composite molded article was molded using the composition (b-2) consisting of (70% by weight) and glass fiber (30% by weight), and was evaluated in the same manner as in Example 5. . Table 2 shows the results.
【００２０】実施例８ 樹脂材料(A) としてエチレングリコール変性ＰＢＴ（融
点 205℃）(A-3) （70重量％）とガラス繊維（30重量
％）より成る組成物(a-3) 、樹脂材料(B) として、ＰＢ
Ｔ樹脂（融点 225℃）(B-1) （70重量％）とガラス繊維
（30重量％）より成る組成物(b-1) を使用して複合成形
品を成形し実施例５と同様の評価を行った。結果を表２
に示す。Example 8 As a resin material (A), a composition (a-3) comprising ethylene glycol-modified PBT (melting point: 205 ° C.) (A-3) (70% by weight) and glass fiber (30% by weight), resin PB as material (B)
A composite molded article was formed using a composition (b-1) composed of T resin (melting point: 225 ° C.) (B-1) (70% by weight) and glass fiber (30% by weight). An evaluation was performed. Table 2 shows the results
Shown in
【００２１】実施例９ 樹脂材料(A) としてＤＭＩ変性ＰＢＴ（融点 205℃）(A
-1) を使用し、そして樹脂材料(B) としてＰＢＴ樹脂
（融点 225℃）(B-1) （70重量％）とガラス繊維（30重
量％）より成る組成物(b-1) を使用して複合成形品を成
形し実施例５と同様の評価を行った。結果を表２に示
す。Example 9 As a resin material (A), DMI-modified PBT (melting point 205 ° C.) (A
-1) and a composition (b-1) consisting of PBT resin (melting point: 225 ° C.) (B-1) (70% by weight) and glass fiber (30% by weight) as the resin material (B) Then, a composite molded article was formed, and the same evaluation as in Example 5 was performed. Table 2 shows the results.
【００２２】実施例10 樹脂材料(A) としてＤＭＩ変性ＰＢＴ（融点 205℃）(A
-1) （30重量％）、ＰＢＴ樹脂（融点 225℃）(B-1)
（40重量％）とガラス繊維（30重量％）より成る組成物
（組成物の融点 215℃）(b-3) を一次成形し、樹脂材料
(B) としてＰＢＴ樹脂（融点 225℃）(B-1) （70重量
％）とガラス繊維（30重量％）より成る組成物(b-1) を
使用して、複合成形品を成形し実施例５と同様の評価を
行った。結果を表２に示す。Example 10 As a resin material (A), DMI-modified PBT (melting point 205 ° C.) (A
-1) (30% by weight), PBT resin (melting point 225 ° C) (B-1)
(B-3) (b-3) is primarily molded from a composition (40% by weight) and glass fiber (30% by weight) (melting point of the composition: 215 ° C)
Using PBT resin (melting point 225 ° C) (B-1) (70% by weight) and glass fiber (30% by weight) composition (b-1) as (B), molding a composite molded article The same evaluation as in Example 5 was performed. Table 2 shows the results.
【００２３】比較例３ ＰＢＴ樹脂（融点 225℃）(B-1) （70重量％）とガラス
繊維（30重量％）より成る組成物(b-1) を一次成形し、
ついで同じ組成物(b-1) を二次成形し実施例５と同様の
評価を行った。結果を表２に示す。Comparative Example 3 A composition (b-1) composed of PBT resin (melting point: 225 ° C.) (B-1) (70% by weight) and glass fiber (30% by weight) was first molded,
Subsequently, the same composition (b-1) was subjected to secondary molding, and the same evaluation as in Example 5 was performed. Table 2 shows the results.
【００２４】比較例４ ＰＥＴ樹脂（融点 257℃）(B-2) （70重量％）とガラス
繊維（30重量％）より成る組成物(b-2) を一次成形し、
ついで同じ組成物(b-2) を二次成形し、実施例５と同様
の評価を行った。結果を表２に示す。Comparative Example 4 A composition (b-2) composed of PET resin (melting point: 257 ° C.) (B-2) (70% by weight) and glass fiber (30% by weight) was first molded,
Subsequently, the same composition (b-2) was subjected to secondary molding, and the same evaluation as in Example 5 was performed. Table 2 shows the results.
【００２５】比較例５ ＰＢＴ樹脂（融点 225℃）(B-1) を一次成形し、ついで
ＰＢＴ樹脂(B-1) （70重量％）とガラス繊維（30重量
％）より成る組成物(b-1) を二次成形し、実施例５と同
様の評価を行った。結果を表２に示す。Comparative Example 5 PBT resin (melting point: 225 ° C.) (B-1) was first molded, and then a composition (b) comprising PBT resin (B-1) (70% by weight) and glass fiber (30% by weight) -1) was subjected to secondary molding, and the same evaluations as in Example 5 were performed. Table 2 shows the results.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【発明の効果】多重成形法によって複合成形品を作製す
るにあたってＰＢＴ樹脂を使用する場合、二次成形時の
樹脂温度が 260℃以下では実用的な樹脂間の密着強度及
び気密性は期待されず、さらにＰＥＴ樹脂を使用する場
合では、 290℃の二次樹脂材料温度でさえも充分な樹脂
間の密着性及び気密性が得られていない。しかしながら
本発明によれば前記の如き特定の樹脂材料(A) 、(B) を
使用することにより樹脂の熱分解の恐れのない通常の成
形樹脂温度条件下でアンカー形状を設けたり、接着剤を
使用することなく、従来の二重成形法では得られない強
固な界面密着強度及び気密性を有する複合成形品を簡単
に経済的に効率よく生産することができる。According to the present invention, when a PBT resin is used in producing a composite molded product by the multiple molding method, practical resin adhesion strength and airtightness are not expected at a resin temperature of 260 ° C. or less during secondary molding. Further, when a PET resin is used, even at a temperature of the secondary resin material of 290 ° C., sufficient adhesiveness and airtightness between the resins are not obtained. However, according to the present invention, the use of the specific resin materials (A) and (B) as described above provides an anchor shape under normal molding resin temperature conditions where there is no risk of thermal decomposition of the resin, or provides an adhesive. Without using it, it is possible to easily and economically efficiently produce a composite molded article having a strong interfacial adhesion strength and airtightness that cannot be obtained by the conventional double molding method.
【００２８】しかも本発明の複合成形品はポリエステル
系エンジニアリングプラスチックの優れた熱安定性、物
理的性質、機械的性質等を備え、特に薬品、溶剤、潤滑
剤、洗剤等に対する化学安定性を有する成形品としてか
かる特性の要求される自動車分野や電気・電子分野の多
くの用途に好適である。Moreover, the composite molded article of the present invention has excellent thermal stability, physical properties, mechanical properties, etc. of polyester engineering plastics, and especially has a chemical stability to chemicals, solvents, lubricants, detergents, etc. It is suitable for many uses in the automotive field and electric / electronic field where such characteristics are required as a product.
Claims (6)
料(A) と下記(III)で示される樹脂材料(B) とを多重成
形法により一体的に成形してなる気密性及び密着性の高
い複合成形品。 （Ｉ）ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）を主体とし１〜40モル％の他のジカルボ
ン酸化合物或いは低分子量ジヒドロキシ化合物から導入
されるコモノマーユニットを含有する共重合体（但し、
液晶性ポリエステルを除く） （II）上記（Ｉ）の共重合体にポリアルキレンテレフタ
レート（アルキレン基の炭素数２〜４）を全量に対して
１〜95重量％混合したブレンド物 (III)ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）又はこれを主体とし40モル％以下の他の
ジカルボン酸化合物或いは低分子量ジヒドロキシ化合物
から導入されるコモノマーユニットを含有する重合体
（但し、液晶性ポリエステルを除く）An airtightness obtained by integrally molding a resin material (A) represented by the following (I) or (II) and a resin material (B) represented by the following (III) by a multiple molding method. Composite molded product with high adhesion. (I) 1 to 40 mol% of other dicarboxy mainly composed of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms)
Introduced from acid compounds or low molecular weight dihydroxy compounds
A copolymer containing a comonomer unit (provided that
(II) A blend of the copolymer of (I) and 1-95% by weight of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) with respect to the total amount. (III) Polyalkylene Terephthalate (alkylene group having 2 to 4 carbon atoms) or other main component containing up to 40 mol%
Dicarboxylic acid compound or low molecular weight dihydroxy compound
Polymer containing comonomer unit introduced from (excluding liquid crystalline polyester)
求項１記載の複合成形品。2. The composite molded article according to claim 1, wherein the resin material (A) has a melting point of 250 ° C. or less.
(A) の全量に対し、１〜40重量％含有する組成物である
請求項１又は２記載の複合成形品。3. The resin material (A) comprises an inorganic filler and a resin material.
3. The composite molded article according to claim 1, which is a composition containing 1 to 40% by weight based on the total amount of (A).
(B) の全量に対し、１〜40重量％含有する組成物である
請求項１〜３の何れか１項記載の複合成形品。4. The resin material (B) comprises an inorganic filler and a resin material.
The composite molded article according to any one of claims 1 to 3, which is a composition containing 1 to 40% by weight based on the total amount of (B).
料(A) を射出成形して一次成形品を形成し、この一次成
形品に更に下記(III) で示される樹脂材料(B) を二次的
に射出成形して両者を融着し一体化することを特徴とす
る気密性及び密着性に優れた複合成形品の製造法。 （Ｉ）ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）を主体とし１〜40モル％の他のジカルボ
ン酸化合物或いは低分子量ジヒドロキシ化合物から導入
されるコモノマーユニットを含有する共重合体（但し、
液晶性ポリエステルを除く） （II）上記（Ｉ）の共重合体にポリアルキレンテレフタ
レート（アルキレン基の炭素数２〜４）を全量に対して
１〜95重量％混合したブレンド物 (III)ポリアルキレンテレフタレート（アルキレン基の
炭素数２〜４）又はこれを主体とし40モル％以下の他の
ジカルボン酸化合物或いは低分子量ジヒドロキシ化合物
から導入されるコモノマーユニットを含有する重合体
（但し、液晶性ポリエステルを除く）5. A resin article (A) represented by the following (I) or (II) is injection-molded to form a primary molded product, and the resin material (B) represented by the following (III) is further added to the primary molded article. ), By injection molding and fusing them together to form a composite molded article having excellent airtightness and adhesion. (I) 1 to 40 mol% of other dicarboxy mainly composed of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms)
Introduced from acid compounds or low molecular weight dihydroxy compounds
A copolymer containing a comonomer unit (provided that
(II) A blend of the copolymer of (I) and 1-95% by weight of polyalkylene terephthalate (alkylene group having 2 to 4 carbon atoms) with respect to the total amount. (III) Polyalkylene Terephthalate (alkylene group having 2 to 4 carbon atoms) or other main component containing up to 40 mol%
Dicarboxylic acid compound or low molecular weight dihydroxy compound
Polymer containing comonomer unit introduced from (excluding liquid crystalline polyester)
の樹脂温度が樹脂材料(A) の融点より10℃以上高い請求
項５記載の複合成形品の製造法。6. The method according to claim 5, wherein the resin temperature at the time of secondary injection molding of the resin material (B) is higher than the melting point of the resin material (A) by 10 ° C. or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10738593A JP3301816B2 (en) | 1993-04-08 | 1993-04-08 | Polyester-based composite molded article and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10738593A JP3301816B2 (en) | 1993-04-08 | 1993-04-08 | Polyester-based composite molded article and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06293044A JPH06293044A (en) | 1994-10-21 |
| JP3301816B2 true JP3301816B2 (en) | 2002-07-15 |
Family
ID=14457792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10738593A Expired - Lifetime JP3301816B2 (en) | 1993-04-08 | 1993-04-08 | Polyester-based composite molded article and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3301816B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3315594B2 (en) * | 1996-06-28 | 2002-08-19 | ポリプラスチックス株式会社 | Polyester-based composite molded article and production method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02220821A (en) * | 1989-02-22 | 1990-09-04 | Toppan Printing Co Ltd | Multi-layered molded product |
| JPH089187B2 (en) * | 1990-09-10 | 1996-01-31 | ポリプラスチックス株式会社 | Polyester composite molded article and method for producing the same |
-
1993
- 1993-04-08 JP JP10738593A patent/JP3301816B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06293044A (en) | 1994-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5354532A (en) | Methods for molding composite polyester articles having rigid and flexible regions | |
| JP4024437B2 (en) | Insert molded product | |
| WO2008075776A1 (en) | Polybutylene terephthalate resin composition | |
| JP2001026656A (en) | Preparation of molded article by welding | |
| JP3301816B2 (en) | Polyester-based composite molded article and production method thereof | |
| KR950009155B1 (en) | Polyester resin compositions | |
| JP6953716B2 (en) | Composite molded body and its manufacturing method | |
| KR920004813B1 (en) | Thermoplastic polyester resin compositions | |
| JPH11320606A (en) | Polyacetal composite molded product and manufacture thereof | |
| JPH07126496A (en) | Polyester resin composition and molded product therefrom | |
| JP3325102B2 (en) | Polyester-based composite molded article and method for producing the same | |
| JP2000263586A (en) | Insert molded article | |
| JP3014594B2 (en) | Composite resin molded article for enclosure and production method | |
| JP3315594B2 (en) | Polyester-based composite molded article and production method thereof | |
| JP3269763B2 (en) | Polyester-based composite molded article and production method thereof | |
| JPH11320605A (en) | Composite molded product and manufacture thereof | |
| JP3315570B2 (en) | Manufacturing method of polyester-based composite molded products | |
| JP3274886B2 (en) | Crystalline polyarylene sulfide resin composite molded article and method for producing the same | |
| JP3250865B2 (en) | Polyester resin molded product | |
| JPH03247436A (en) | Hollow molded item of polyarylene sulfide resin and preparation thereof | |
| JP3311566B2 (en) | Composite molded article and method for producing the same | |
| EP0332429A2 (en) | Thermoplastic polyester resin composition | |
| JPH09208810A (en) | Polyester resin composition | |
| JP2002234991A (en) | Resin composition for composite molded product | |
| JPH10235678A (en) | Polyester composite molding and its manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090426 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090426 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100426 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110426 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120426 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130426 Year of fee payment: 11 |