JP2006273992A - Resin composition for welding and method for welding resin - Google Patents

Resin composition for welding and method for welding resin Download PDF

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JP2006273992A
JP2006273992A JP2005094257A JP2005094257A JP2006273992A JP 2006273992 A JP2006273992 A JP 2006273992A JP 2005094257 A JP2005094257 A JP 2005094257A JP 2005094257 A JP2005094257 A JP 2005094257A JP 2006273992 A JP2006273992 A JP 2006273992A
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welding
resin composition
resin
polycarbonate
polycarbonate resin
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Nobuaki Shirakawa
信明 白川
Shigeru Okita
茂 沖田
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Toray Industries Inc
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Toray Industries Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1603—Laser beams characterised by the type of electromagnetic radiation
    • B29C65/1612—Infrared [IR] radiation, e.g. by infrared lasers
    • B29C65/1616—Near infrared radiation [NIR], e.g. by YAG lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1635—Laser beams characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. laser transmission welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1629—Laser beams characterised by the way of heating the interface
    • B29C65/1654—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined
    • B29C65/1658—Laser beams characterised by the way of heating the interface scanning at least one of the parts to be joined scanning once, e.g. contour laser welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • B29C65/1677—Laser beams making use of an absorber or impact modifier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/82—Testing the joint
    • B29C65/8207—Testing the joint by mechanical methods
    • B29C65/8215—Tensile tests
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112—Single lapped joints
    • B29C66/1122—Single lap to lap joints, i.e. overlap joints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43—Joining a relatively small portion of the surface of said articles

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Electromagnetism (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for welding comprising a polyamide resin, a polycarbonate resin and a filler, excellent in weld strength while maintaining mechanical properties, heat resistance, dimensional stability, etc., possessed by conventional polyamide resin, and provide a method for welding the resin composition with a polycarbonate resin composition. <P>SOLUTION: The resin composition for welding comprising 100 pts.wt. polyamide resin (A), 10-90 pts.wt. polycarbonate resin (B) and 10-90 pts.wt. filler (C) is prepared as one of adherends constituting a weld-bonding part, and it is weld-bonded to the polycarbonate resin composition as the counter material. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ポリアミド樹脂とポリカーボネート樹脂と充填剤からなる溶着用樹脂組成物、および本樹脂組成物とポリカーボネート樹脂組成物との溶着方法に関するものである。特に、溶着加工において優れた溶着強度を有し、複雑な形状の部品、例えばヘッドランプ、電装品ケースなどの自動車関連部品、電動工具棟の筐体、その他容器類などの意匠性を要求される製品製造に適した溶着用樹脂組成物および溶着方法に関するものである。   The present invention relates to a welding resin composition comprising a polyamide resin, a polycarbonate resin, and a filler, and a method for welding the present resin composition and a polycarbonate resin composition. In particular, it has excellent welding strength in welding processing, and it requires complex design parts such as automobile-related parts such as headlamps and electrical component cases, housings for power tool buildings, and other containers. The present invention relates to a welding resin composition suitable for product manufacture and a welding method.

ポリアミド樹脂は結晶性の樹脂であり、その優れた機械的特性、耐熱性、耐薬品性を有しており、自動車や電気部品材料として広く使用されている。また、ガラス繊維や無機フィラーを配合することにより、強度や寸法安定性が向上するため、これらを配合した状態でも広く使用されている。一方、ポリカーボネート樹脂は非晶性の透明樹脂であり、衝撃強さ、耐熱性そして寸法安定性等に優れており、同様に自動車や電気部品、外装用途などに適した部材として広く用いられている。昨今、例えばヘッドランプなどの透明部材及び非透明部材からなる部品、および意匠性が要求される外装部品に、これら２つの樹脂組成物を接合させ用いるケースが増加している。   A polyamide resin is a crystalline resin, and has excellent mechanical properties, heat resistance, and chemical resistance, and is widely used as a material for automobiles and electric parts. Moreover, since the strength and dimensional stability are improved by blending glass fibers and inorganic fillers, they are widely used even in the blended state. Polycarbonate resin, on the other hand, is an amorphous transparent resin that has excellent impact strength, heat resistance, dimensional stability, etc., and is also widely used as a member suitable for automobiles, electrical parts, exterior applications, etc. . Recently, for example, cases in which these two resin compositions are bonded to a component made of a transparent member and a non-transparent member, such as a headlamp, and an exterior component requiring a design property are increasing.

このような接合においては、接着剤を用いたり、噛合構造を用いたり、部材を構成する樹脂自身を熱等で流動化させて接合したり（溶着）する方法が挙げられる。しかし、接着剤を用いる方法は作業が繁雑であり、噛合構造を用いる方法は液体に接触する用途に向かない。溶着法は簡便な方法であるが、具体的には溶融温度、分子極性などのポリアミド樹脂とポリカーボネート樹脂の特性の相違などに起因し両樹脂組成物間の接合強度は低く、近年部品の大型化、複雑化に伴い、より高い溶着強度が要求されるようになってきたところ、溶着部分の強度が不十分であるために使用が制限されるのが現状であった。また、溶着強度を上げる為には樹脂組成物中のポリマー比率を上げざるを得ず、この為特に高温下で成形体の寸法安定性が劣る欠点を有し、本件に起因し接合部の破壊が生じるなど実用に耐えないケースが多く報告されている。   Examples of such joining include methods of using an adhesive, using a meshing structure, and joining (welding) by fluidizing the resin constituting the member with heat or the like. However, the method using an adhesive is complicated, and the method using a meshing structure is not suitable for an application in contact with a liquid. Although the welding method is a simple method, specifically, the bonding strength between the two resin compositions is low due to differences in the properties of the polyamide resin and the polycarbonate resin, such as the melting temperature and molecular polarity. However, as the welding process becomes more complex, higher welding strength has been demanded. However, since the strength of the welding part is insufficient, the use of the welding part is limited. Also, in order to increase the welding strength, the polymer ratio in the resin composition must be increased, and this has the disadvantage that the dimensional stability of the molded product is inferior, especially at high temperatures. Many cases have been reported that cannot withstand practical use such as

特許文献１では、ポリカーボネート樹脂をレンズに、ポリカーボネート系材料をボディに用い、車両灯具用部材をレーザー溶着工法により一体化しているが、レーザー光照射方向を斜めにする事でボディにおけるストレスクラック発生抑制を図ったものであり、材料レベルでの溶着強度向上に関しては言及されていない。   In Patent Document 1, polycarbonate resin is used for the lens, polycarbonate-based material is used for the body, and the vehicle lamp member is integrated by the laser welding method, but the occurrence of stress cracks in the body is suppressed by making the laser light irradiation direction oblique. However, there is no mention of improving the welding strength at the material level.

特許文献２では、非相溶性の２つの樹脂成形部品を溶着する際、接合部分のみ両樹脂からなるアロイ成分となるよう設計し、溶着強度向上が図られている。但し、接合部分のみ樹脂アロイ状物とする為設計上の制約があり、適用可能な形状品が限定されるデメリットを有する。具体例として明示されている組み合わせとしてはＡＢＳとポリカーボネートのみであり、又材料レベルでの改質検討についても具体的に言及されていない。   In Patent Document 2, when two incompatible resin molded parts are welded, only the joint portion is designed to be an alloy component made of both resins, thereby improving the welding strength. However, since only the joint portion is made of a resin alloy, there is a design limitation, and there is a demerit that an applicable shape product is limited. The combination specified as a specific example is only ABS and polycarbonate, and there is no specific mention of modification studies at the material level.

特許文献３では異種プラスチック材料同士を溶着させる手段として、接合面に両方の材料と相溶性のあるラミネートフィルムを介在する事で溶着する方法を示している。但し、フィルムを介在させねばならず、成形品同士での溶着が出来ない事から溶着時の生産性の面で好ましくなく、またコスト増にも繋がる。
特開２００２−２９２７４１号公報 特開平１０−２８６８８４号公報 特開昭５９−７６２１８号公報 In Patent Document 3, as a means for welding different kinds of plastic materials, a method of welding by interposing a laminated film compatible with both materials on the joint surface is shown. However, it is not preferable in terms of productivity at the time of welding because it is necessary to interpose a film and welding between molded products is not possible, and this also leads to an increase in cost.
JP 2002-292741 A Japanese Patent Laid-Open No. 10-286884 JP 59-76218

本発明は上述した従来のポリアミド樹脂およびポリカーボネート樹脂の持つ機械的性質、耐熱性などを維持し溶着強度に優れる、ポリアミド樹脂とポリカーボネート樹脂および充填剤からなる溶着用樹脂組成物、および本樹脂組成物とポリカーボネート樹脂組成物との溶着接合方法の提供を課題とする。   The present invention provides a welding resin composition comprising a polyamide resin, a polycarbonate resin, and a filler, which maintains the mechanical properties and heat resistance of the conventional polyamide resin and polycarbonate resin described above, and is excellent in welding strength, and the present resin composition. It is an object of the present invention to provide a method for welding and bonding a polycarbonate resin composition.

上述の課題を解決すべく鋭意検討した結果、ポリアミド樹脂、ポリカーボネート樹脂、充填材を特定比率で配合した樹脂組成物と、ポリカーボネート樹脂からなる樹脂組成物を用いて溶着する事により達成されることを見出し、本発明に到達した。   As a result of diligent investigations to solve the above-mentioned problems, it is achieved by welding using a resin composition composed of a polyamide resin, a polycarbonate resin and a filler in a specific ratio and a polycarbonate resin. The headline, the present invention has been reached.

すなわち本発明は、溶着用樹脂組成物
（１）ポリアミド樹脂（Ａ）１００重量部に対しポリカーボネート樹脂（Ｂ）１０〜９０重量部と充填材（Ｃ）１０〜９０重量部を含有する溶着用樹脂組成物、
（２）前記ポリアミド樹脂（Ａ）がナイロン６、ナイロン６６、ナイロン６６／６Ｉ／６コポリマーのいずれかである（１）の溶着用樹脂組成物、
（３）前記ポリカーボネート樹脂（Ｂ）が芳香族ポリカーボネートである（１）または（２）の溶着用樹脂組成物、
（４）前記充填材（Ｃ）がガラス繊維、炭素繊維、ワラステナイト、カオリン、マイカ、クレー、酸化チタン、ガラスフレーク、ガラスビーズの群から選ばれる１種または２種以上である（１）〜（３）のいずれかの溶着用樹脂組成物、
（５）（１）〜（４）のいずれかの溶着用樹脂組成物とポリカーボネート樹脂組成物とを溶着することを特徴とする樹脂溶着方法、
（６）前記ポリカーボネート樹脂組成物が芳香族ポリカーボネートである（６）の樹脂溶着方法、
（７）溶着方法がレーザー溶着法または２色射出成形法による溶着接合であることを特徴とする、（５）または（６）の樹脂溶着方法、
（８）溶着用樹脂組成物をレーザー光線吸収側、ポリカーボネート樹脂組成物をレーザー光線透過側としてレーザー溶着することを特徴とする、（７）の樹脂溶着方法、
（９）溶着用樹脂組成物を２色射出成形時の一次成形体、ポリカーボネート樹脂組成物を二次成形体として２色射出成形法により溶着することを特徴とする、（７）の樹脂溶着方法、
を提供するものである。 That is, the present invention provides a welding resin containing 10 to 90 parts by weight of the polycarbonate resin (B) and 10 to 90 parts by weight of the filler (C) with respect to 100 parts by weight of the welding resin composition (1) polyamide resin (A). Composition,
(2) The welding resin composition according to (1), wherein the polyamide resin (A) is any one of nylon 6, nylon 66, and nylon 66 / 6I / 6 copolymer,
(3) The welding resin composition according to (1) or (2), wherein the polycarbonate resin (B) is an aromatic polycarbonate,
(4) The filler (C) is one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, clay, titanium oxide, glass flake, and glass beads (1) to (1) to (3) any one of the welding resin compositions,
(5) A resin welding method characterized by welding the welding resin composition of any one of (1) to (4) and a polycarbonate resin composition,
(6) The resin welding method according to (6), wherein the polycarbonate resin composition is an aromatic polycarbonate,
(7) The resin welding method according to (5) or (6), wherein the welding method is laser welding or welding by a two-color injection molding method,
(8) The resin welding method according to (7), wherein the welding resin composition is used as a laser beam absorption side, and the polycarbonate resin composition is used as a laser beam transmission side.
(9) The resin welding method according to (7), wherein the welding resin composition is welded by a two-color injection molding method as a primary molded body at the time of two-color injection molding and the polycarbonate resin composition is a secondary molded body. ,
Is to provide.

本発明によれば、以下に説明する通り成形製品表面外観、寸法安定性、耐熱性が均衡して優れた、ポリアミド樹脂とポリカーボネート樹脂および充填剤からなる溶着用樹脂組成物を得る事が出来る。加えて、本樹脂組成物とポリカーボネート樹脂組成物とを溶着接合した場合には、強度において顕著に優れた接合性を得る事が出来る。   According to the present invention, it is possible to obtain a welding resin composition comprising a polyamide resin, a polycarbonate resin, and a filler, which is excellent in balance between the appearance of a molded product surface, dimensional stability, and heat resistance as described below. In addition, when the present resin composition and the polycarbonate resin composition are welded and joined, it is possible to obtain bondability that is remarkably excellent in strength.

以下に本発明の好ましい実施形態を説明する。文中の「重量」とは「質量」を意味する。   Hereinafter, preferred embodiments of the present invention will be described. “Weight” in the text means “mass”.

本発明の溶着用樹脂組成物に用いられるポリアミド樹脂（Ａ）として、具体的には、ポリカプロアミド（ナイロン６）、ポリヘキサメチレンアジパミド（ナイロン６６）、ポリテトラメチレンアジパミド（ナイロン４６）、ポリヘキサメチレンセバカミド（ナイロン６１０）、ポリヘキサメチレンドデカミド（ナイロン６１２）、ポリウンデカミド（ナイロン１１）、ポリドデカミド（ナイロン１２）、ポリヘキサメチレンアジパミド／ポリヘキサメチレンテレフタルアミドコポリマー（ナイロン６６／６Ｔ）、ポリヘキサメチレンアジパミド／ポリヘキサメチレンテレフタルアミド／ポリヘキサメチレンイソフタルアミドコポリマー（ナイロン６６／６Ｔ／６Ｉ）、ポリヘキサメチレンテレフタルアミド／ポリヘキサメチレンイソフタルアミドコポリマー（ナイロン６Ｔ／６Ｉ）、ポリヘキサメチレンアジパミド／ポリヘキサメチレンイソフタルアミドコポリマー（ナイロン６６／６Ｉ）、ポリヘキサメチレンアジパミド／ポリヘキサメチレンイソフタルアミド／ポリカプロアミドコポリマー（ナイロン６６／６Ｉ／６）、ポリキシリレンアジパミド（ナイロンＸＤ６）、およびこれらの混合物、ないし共重合体などが挙げられる。これらは特に限定されるものではないが、中でもナイロン６、ナイロン６６、ナイロン６６／６Ｉ／６コポリマーが好ましい。また、ナイロン６６／６Ｉ／６コポリマーは成形品の外観が優れているという点において意匠性の面から好ましい。   Specific examples of the polyamide resin (A) used in the welding resin composition of the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon). 46), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamide (nylon 11), polydodecamide (nylon 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer ( Nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide Copolymer (nylon 6T / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyxylylene adipamide (nylon XD6), and mixtures or copolymers thereof. These are not particularly limited, but among these, nylon 6, nylon 66, and nylon 66 / 6I / 6 copolymer are preferable. Nylon 66 / 6I / 6 copolymer is preferable from the viewpoint of design in that the appearance of the molded product is excellent.

本発明の溶着用樹脂組成物に用いられるポリアミド樹脂（Ａ）の相対粘度（９８％硫酸法）は、靱性あるいは成形性において充分であれば特に制限されないが、好ましくは１．９〜３．５である。１．９未満では、溶着接合部の耐久性が充分でない可能性があり、３．５を超えると流動性が優れないため外観に優れた成形品が得られ難くなる。   The relative viscosity (98% sulfuric acid method) of the polyamide resin (A) used in the welding resin composition of the present invention is not particularly limited as long as it is sufficient in toughness or moldability, but preferably 1.9 to 3.5. It is. If it is less than 1.9, the durability of the welded joint may not be sufficient, and if it exceeds 3.5, the fluidity is not excellent, so that it is difficult to obtain a molded product having an excellent appearance.

一方、本発明の溶着用樹脂組成物に用いられるポリカーボネート樹脂（Ｂ）、または溶着相手材であるポリカーボネート樹脂組成物に用いられるポリカーボネート樹脂としては、種々のジヒドロキシアリール化合物とホスゲンとの反応によって得られるもの（ホスゲン法）、あるいはジヒドロキシアリール化合物とジフェニルカーボネートとのエステル交換反応によって得られるもの（エステル交換法）が挙げられる。ここで、ポリカーボネート の原料となるジヒドロキシアリール化合物としては、ビス（４−ヒドロキシフェニル）メタン、１，１′−ビス（４−ヒドロキシフェニル）エタン、２，２′−ビス（４−ヒドロキシフェニル）プロパン、２，２′−ビス（４−ヒドロキシフェニル）ブタン、２，２′−ビス（４−ヒドロキシフェニル）オクタン、２，２′−ビス（４−ヒドロキシフェニル）フェニルメタン、２，２′−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２′−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）プロパン、２，２′−ビス（４−ヒドロキシ−３−ブロモフェニル）プロパン、２，２′−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパン、１，１′−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１′−ビス（４−ヒドロキシフェニル）シクロヘキサン、４，４′−ジヒドロキシジフェニルエーテル、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルエーテル、４，４′−ジヒドロキシフェニルスルフィド、４，４′−ジヒドロキシ−３，３′−ジメチルフェニルスルフィド、４，４′−ジヒドロキシ−３，３′−ジメチルフェニルスルホキシド、４，４′−ジヒドロキシフェニルスルホキシド、４，４′−ジヒドロキシフェニルスルホン、４，４′−ジヒドロキシ−３，３′−ジメチルフェニルスルホン、１，１′−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、１，１′−ビス（４−ヒドロキシフェニル）−３，３−ジメチルシクロヘキサン、１，１′−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロペンタン、ヒドロキノン、レゾルシンなどが挙げられ、これらは、１種または２種以上で用いられる。中でも好ましくは芳香族ポリカーボネートであり、より好ましくは代表的な芳香族ポリカーボネートである、２，２′−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）とホスゲンとの反応によって得られるポリカーボネートである
ポリカーボネート樹脂（Ｂ）の粘度平均分子量は、ポリアミド樹脂（Ａ）での分散性の観点から、好ましくは１５，０００〜４０，０００、さらに好ましくは１７，０００〜３５，０００である。ポリカーボネート樹脂（Ｂ）の粘度平均分子量が１５，０００未満または４０，０００を超える場合、アロイ状になりにくく好ましくない。 On the other hand, the polycarbonate resin (B) used in the welding resin composition of the present invention, or the polycarbonate resin used in the polycarbonate resin composition that is a welding partner, can be obtained by reaction of various dihydroxyaryl compounds with phosgene. And those obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate (a transesterification method). Here, the dihydroxyaryl compound used as a raw material for polycarbonate includes bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, and 2,2′-bis (4-hydroxyphenyl) propane. 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, 2,2'-bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methylphenyl) propane, 2,2′-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2′-bis (4-hydroxy-3-bromophenyl) propane, 2,2'-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclo Pentane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-dihydroxyphenyl sulfide, 4, 4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfone, 4, 4'-dihydroxy-3,3'-dimethylphenylsulfone, 1,1'-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl) -3 , 3-Dimethylcyclohexane, 1,1'-bis (4-hydroxy Eniru) -3,3,5-trimethyl-cyclopentane, hydroquinone, resorcinol and the like, which are used alone or in combination of two or more. Among them, preferred is an aromatic polycarbonate, and more preferred is a typical aromatic polycarbonate, which is a polycarbonate obtained by reaction of 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene. From the viewpoint of dispersibility in the polyamide resin (A), the viscosity average molecular weight of the resin (B) is preferably 15,000 to 40,000, more preferably 17,000 to 35,000. When the viscosity average molecular weight of the polycarbonate resin (B) is less than 15,000 or exceeds 40,000, it is difficult to form an alloy, which is not preferable.

溶着用樹脂組成物中におけるポリカーボネート樹脂（Ｂ）の含有量は前記ポリアミド樹脂（Ａ）１００重量部に対して、好ましく１０〜９０重量部である。更に好ましくは３０〜７０重量部である。１０重量部未満では溶着相手材のポリカーボネート樹脂組成物との溶着強度が充分ではなく、９０重量部を超えると特にレーザー溶着の際にクラックが発生し易くなり好ましくない。   The content of the polycarbonate resin (B) in the welding resin composition is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the polyamide resin (A). More preferably, it is 30-70 weight part. If it is less than 10 parts by weight, the welding strength with the polycarbonate resin composition as a welding partner is not sufficient, and if it exceeds 90 parts by weight, cracks are likely to occur particularly during laser welding, which is not preferable.

溶着用樹脂組成物の溶着相手材であるポリカーボネート樹脂組成物に用いられるポリカーボネート樹脂は、ポリカーボネート樹脂（Ｂ）と同一のものでも異なるものでも構わないが、溶着強度の観点からは粘度平均分子量が好ましくは１５，０００〜４０，０００、より好ましくは１７，０００〜３５，０００の範囲内の異なるポリカーボネート樹脂、またはポリカーボネート樹脂（Ｂ）と同一であることが好ましい。   The polycarbonate resin used in the polycarbonate resin composition, which is a welding partner of the welding resin composition, may be the same as or different from the polycarbonate resin (B), but from the viewpoint of the welding strength, the viscosity average molecular weight is preferable. Is preferably the same as a different polycarbonate resin or polycarbonate resin (B) in the range of 15,000 to 40,000, more preferably 17,000 to 35,000.

本発明の溶着用樹脂組成物には充填材（Ｃ）を好ましく含有することができる。かかる充填材（Ｃ）としては繊維状充填材、非繊維状充填材いずれの態様としても用いることができる。強度が要求される場合においては、繊維状充填材を用いる事が好ましい。繊維状充填材としては、例えばガラス繊維、炭素繊維、チタン酸カリウィスカ、酸化亜鉛ウィスカ、硼酸アルミウィスカ、アラミド繊維、アルミナ繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石コウ繊維、金属繊維などが挙げられる。特に好ましくはガラス繊維、炭素繊維である。一方、成形体の異方性低減を図る為には非繊維状充填材を用いる事が好ましい。非繊維状充填材としては、例えばワラステナイト、ゼオライト、セリサイト、カオリン、マイカ、クレー、パイロフィライト、ベントナイト、アスベスト、タルク、アルミナシリケートなどの珪酸塩、アルミナ、酸化珪素、酸化マグネシウム、酸化ジルコニウム、酸化チタン、酸化鉄などの金属酸化物、炭酸カルシウム、炭酸マグネシウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウムなどの水酸化物、ミルドガラスファイバー、ガラスフレーク、ガラスビーズ、セラミックビーズ、窒化ホウ素、炭化珪素などが挙げられ、これらは中空であってもよい。特に好ましくは、ワラステナイト、カオリン、マイカ、クレー、酸化チタン、ガラスフレーク、ガラスビーズである。なお、これら繊維状、非繊維状充填材は１種または２種以上の併用のいずれの態様でも使用可能である。また、これら充填材をイソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物、エポキシ化合物などのカップリング剤をポリアミド樹脂への配合時同時に配合し、もしくは予め充填材に処理して配合することは、より優れた機械的特性や外観性を得る意味において好ましい。充填材（Ｃ）の含有量は前記ポリアミド樹脂（Ａ）１００重量部に対して、好ましく１０〜９０重量部であり、更に好ましくは１０〜３０重量部である。１０重量部未満では補強効果は充分ではなく、９０重量部を超えると溶着強度の低下や成形品とした際の表面外観低下が生じる。   The filler resin composition of the present invention can preferably contain a filler (C). The filler (C) can be used as either a fibrous filler or a non-fibrous filler. When strength is required, it is preferable to use a fibrous filler. Examples of the fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, and metal fiber. Can be mentioned. Particularly preferred are glass fiber and carbon fiber. On the other hand, in order to reduce the anisotropy of the molded body, it is preferable to use a non-fibrous filler. Non-fibrous fillers include, for example, silicates such as wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide , Metal oxides such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide , Milled glass fibers, glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide and the like, which may be hollow. Particularly preferred are wollastonite, kaolin, mica, clay, titanium oxide, glass flakes and glass beads. These fibrous and non-fibrous fillers can be used in any form of one kind or a combination of two or more kinds. In addition, these fillers are combined with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound at the same time as the compounding with the polyamide resin, or are previously processed into the filler. Is preferable in terms of obtaining better mechanical properties and appearance. The content of the filler (C) is preferably 10 to 90 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A). If the amount is less than 10 parts by weight, the reinforcing effect is not sufficient. If the amount exceeds 90 parts by weight, the welding strength is lowered and the surface appearance of the molded product is lowered.

本発明の溶着用樹脂組成物および溶着用樹脂組成物の溶着相手材として用いるポリカーボネート樹脂組成物においては、発明の目的を損なわない範囲で、要求される特性に応じて添加剤、結晶核剤、耐熱剤や紫外線吸収剤などの安定剤、難燃剤、帯電防止剤、可塑剤、滑剤、着色剤、カップリング剤などを含有しても構わない。   In the welding resin composition of the present invention and the polycarbonate resin composition used as a welding partner material of the welding resin composition, the additive, crystal nucleating agent, You may contain stabilizers, such as a heat resistant agent and a ultraviolet absorber, a flame retardant, an antistatic agent, a plasticizer, a lubricant, a coloring agent, a coupling agent.

なお、溶着用樹脂組成物およびポリカーボネート樹脂組成物を調整する方法は特定の方法に限定されない。効率的な例として、上記両樹脂組成物の構成単位である各原料を、単軸あるいは２軸押出機などの公知の機器に供給して溶融混練する方法などを挙げることができる。   In addition, the method of adjusting the welding resin composition and the polycarbonate resin composition is not limited to a specific method. As an efficient example, there can be mentioned a method in which each raw material, which is a constituent unit of both resin compositions, is supplied to a known apparatus such as a single screw or twin screw extruder and melt kneaded.

本発明の溶着用樹脂組成物成形体およびポリカーボネート樹脂組成物成形体は、射出成形、押出成形などにより成形することができるが、より実用に即した複雑形状成形体を得るには射出成形が好ましい。   The fusion-bonding resin composition molded body and the polycarbonate resin composition molded body of the present invention can be molded by injection molding, extrusion molding, or the like, but injection molding is preferred to obtain a more complex shaped molded body that is more practical. .

本発明の溶着用樹脂組成物とポリカーボネート樹脂組成物を接合する場合、外観等の特性においても良好である溶着接合法により好ましく接合することができる。溶着接合法としては、例えば、振動溶着法、オービタル溶着法、超音波溶着法、レーザー溶着法、熱板溶着法、スピン溶着法、２色成形溶着法、高周波溶着法などが挙げられるが、好ましくは、レーザー溶着法、２色成形溶着法である。   When joining the welding resin composition of this invention and a polycarbonate resin composition, it can join preferably by the welding joining method which is favorable also in characteristics, such as an external appearance. Examples of the welding method include vibration welding method, orbital welding method, ultrasonic welding method, laser welding method, hot plate welding method, spin welding method, two-color molding welding method, high frequency welding method, etc. Is a laser welding method or a two-color molding welding method.

レーザー溶着法は、重ね合わせた樹脂成形体にレーザー光を照射し、照射した一方を透過させてもう一方で吸収させ溶融、融着させる工法であり、三次元接合が可能、非接触加工、バリ発生が無いなどの利点を利用して、幅広い分野に広がりつつある工法である。当工法において、レーザー光線透過側成形体に適用する樹脂材料においては、レーザー光線を透過する特徴が必須となり、照射したレーザー光線のエネルギーを１００％とした場合、そのレーザー光線透過側成形体の裏側に透過して出てくるエネルギーは、１０％以上は必要であることが本発明者らの検討結果から判明している。１０％未満のレーザー光線透過率の成形体をレーザー光線透過側成形体に用いた場合、レーザー光線入射表面で溶融、発煙するなどの不具合を生じる可能性が十分に考えられる。本発明の溶着方法の場合、本発明の溶着用樹脂組成物の溶着相手材であるポリカーボネート樹脂組成物は非晶性であり透明性が高い事から、照射したレーザー光線のエネルギーが樹脂部分で吸収、減衰する程度は低い。一方、溶着用樹脂組成物は、ポリアミド樹脂（Ａ）とポリカーボネート樹脂（Ｂ）との屈折率差、および充填材の含有によりレーザー光の透過性が損なわれる。以上の事から、本発明の溶着方法の場合、レーザー光線吸収側成形体を本発明の溶着用樹脂組成物、レーザー光線透過側成形体をポリカーボネート樹脂組成物とする事が望ましい。   The laser welding method is a method of irradiating laser beams to the laminated resin moldings, transmitting one irradiated beam and absorbing the other, melting and fusing it. Three-dimensional bonding is possible, non-contact processing, burring It is a construction method that is spreading in a wide range of fields, taking advantage of the absence of occurrence. In this construction method, in the resin material applied to the laser beam transmission side molded body, the characteristic of transmitting the laser beam is essential, and when the energy of the irradiated laser beam is 100%, it is transmitted to the back side of the laser beam transmission side molded body. From the examination results of the present inventors, it has been found that the energy to be output needs to be 10% or more. When a molded article having a laser beam transmittance of less than 10% is used as the molded article on the laser beam transmission side, there is a sufficient possibility that defects such as melting and smoke generation may occur on the laser beam incident surface. In the case of the welding method of the present invention, the polycarbonate resin composition that is the welding partner of the welding resin composition of the present invention is amorphous and highly transparent, so the energy of the irradiated laser beam is absorbed by the resin part, The degree of attenuation is low. On the other hand, in the welding resin composition, the transmittance of the laser beam is impaired by the difference in refractive index between the polyamide resin (A) and the polycarbonate resin (B) and the inclusion of the filler. From the above, in the case of the welding method of the present invention, it is desirable that the laser beam absorption side molded body is the welding resin composition of the present invention and the laser beam transmission side molded body is the polycarbonate resin composition.

２色成形溶着法の場合、一次材より二次材の溶融温度が高い方が、溶着部で一次材成形体が再溶融し二次材と相溶する為、溶着強度は高い事が知られている。本発明の溶着接合用部材の場合、本発明の溶着用樹脂組成物を一次材、ポリカーボネート樹脂組成物を二次材として用いると上記の状態となる為望ましい。   In the case of the two-color molding welding method, it is known that when the melting temperature of the secondary material is higher than that of the primary material, the primary material molding is remelted at the welded part and is compatible with the secondary material, so the welding strength is higher ing. In the case of the member for welding and bonding according to the present invention, it is preferable to use the welding resin composition of the present invention as a primary material and the polycarbonate resin composition as a secondary material because the above-mentioned state is obtained.

以下、本発明の最良の実施形態を、発明者が調整、特性評価した際の結果を例にとって、図面も参照しながら説明する。   Hereinafter, the best embodiment of the present invention will be described with reference to the drawings, taking as an example the results of adjustment and characteristic evaluation by the inventor.

[溶着用樹脂組成物]
使用したポリアミド樹脂（Ａ）は、いずれも市販の東レ社製ポリマーを用いた。
ナイロン６：東レ社製ＣＭ１００１
ナイロン６６：東レ社製ＣＭ３００１
また、使用したナイロン６６／６Ｉ／６コポリマーの重合概要は次のとおりである。すなわち、ヘキサメチレンジアミンとアジピン酸の等モル塩、ヘキサメチレンジアミンとイソフタル酸の等モル塩、ε−カプロラクタムをそれぞれ８０：５：１５の重量比で投入し、投入した全原料と同量の純水を加え、重合缶内を十分窒素置換した後、撹拌しながら加温を開始した。缶内圧力は最大１．９６ＭＰａ（Ｇ）に調整しながら最終到達温度は２７０℃とし、水浴中に吐出したポリマーをストランドカッターでペレタイズした。また、ナイロン６６／６Ｉコポリマーの重合概要は次のとおりである。すなわち、ヘキサメチレンジアミンとアジピン酸の当モル塩、ヘキサメチレンジアミンとイソフタル酸の当モル塩、およびε−カプロラクタムをそれぞれ８０：２０の重量比で投入し、投入した全原料と同量の純水を加え、重合缶内を充分窒素置換した後、撹拌しながら加温を開始した。缶内圧力は最大１．９６ＭＰａ（Ｇ）に調節しながら最終到達温度は２７０℃とし、水浴中に吐出したポリマーをストランドカッターでペレタイズした。 [Resin composition for welding]
As the polyamide resin (A) used, a commercially available polymer manufactured by Toray Industries, Inc. was used.
Nylon 6: Toray Industries, Inc. CM1001
Nylon 66: CM3001 manufactured by Toray Industries, Inc.
The polymerization outline of the nylon 66 / 6I / 6 copolymer used is as follows. That is, equimolar salts of hexamethylene diamine and adipic acid, equimolar salts of hexamethylene diamine and isophthalic acid, and ε-caprolactam were introduced at a weight ratio of 80: 5: 15, respectively, and the same amount of pure material as the total amount of raw materials charged. Water was added and the inside of the polymerization vessel was sufficiently substituted with nitrogen, and then heating was started with stirring. The final pressure was 270 ° C. while adjusting the maximum pressure in the can to 1.96 MPa (G), and the polymer discharged into the water bath was pelletized with a strand cutter. The outline of polymerization of nylon 66 / 6I copolymer is as follows. That is, equimolar salts of hexamethylene diamine and adipic acid, equimolar salts of hexamethylene diamine and isophthalic acid, and ε-caprolactam were added at a weight ratio of 80:20, respectively, and the same amount of pure water as the total amount of raw materials charged. Was added, and the inside of the polymerization can was sufficiently purged with nitrogen, and then heating was started with stirring. The final pressure was 270 ° C. while adjusting the maximum pressure in the can to 1.96 MPa (G), and the polymer discharged into the water bath was pelletized with a strand cutter.

今回使用したポリカーボネート樹脂（Ｂ）としては、市販の出光石油化学社製ポリマーであるタフロンＡ１９００（芳香族標準タイプ、粘度平均分子量：１９，０００）を用いた。   As the polycarbonate resin (B) used this time, Taflon A1900 (standard aromatic type, viscosity average molecular weight: 19,000), which is a commercially available polymer manufactured by Idemitsu Petrochemical Co., Ltd., was used.

樹脂組成物を調整する際の溶融混練は、全て日本製鋼所製ＴＥＸ３０型２軸押出機を用いて行った。構成単位である各原料をシリンダー温度：２８０〜３００℃、スクリュー回転数：２５０〜２８０min-1に設定した押出機へ表１、２に示す各割合で供給し、ついで、サイドフィーダーから同じく表１、２に示す各割合にて充填材を供給し、押出されたストランドをペレタイザーにかけサンプルペレットを得た。 All the melt-kneading for adjusting the resin composition was performed using a TEX30 twin-screw extruder manufactured by Nippon Steel Works. Each raw material which is a structural unit is supplied to the extruder set at a cylinder temperature of 280 to 300 ° C. and a screw rotation speed of 250 to 280 min −1 at each ratio shown in Tables 1 and 2, and then from the side feeder, the same Table 1 is used. The filler was supplied at each ratio shown in 2, and the extruded strand was applied to a pelletizer to obtain sample pellets.

今回評価に用いた充填材（Ｃ）は以下のものである。
繊維状充填材（ＧＦ）：日本電気硝子社製 Ｔ２８９
非繊維状充填材（ワラステナイト）：ＮＹＣＯ社製 ナイヤード ３２５。 The filler (C) used for evaluation this time is as follows.
Fibrous filler (GF): T289 manufactured by Nippon Electric Glass Co., Ltd.
Non-fibrous filler (Wollastonite): Nyyard 325 manufactured by NYCO.

[ポリカーボネート樹脂組成物]
溶着用樹脂組成物と溶着させるポリカーボネート樹脂組成物としては、ポリカーボネート樹脂（Ｂ）と同じ、出光石油化学社製ポリマーであるタフロンＡ１９００（芳香族標準タイプ）を使用した。 [Polycarbonate resin composition]
As the polycarbonate resin composition to be welded to the welding resin composition, Taflon A1900 (aromatic standard type) which is a polymer manufactured by Idemitsu Petrochemical Co., Ltd., the same as the polycarbonate resin (B) was used.

溶着性、強度の評価は、次の方法により行った。   The weldability and strength were evaluated by the following methods.

[レーザー溶着性評価]
図１は切削前のレーザー溶着用試験片成形体の形状を示す（ａ）平面図（ｂ）側面図である。試験片は、図１のレーザー光線透過性評価試験片１の厚さDが３ｍｍ成形品から切削加工してなる、幅Ｗが２４ｍｍ、長さＬが７０ｍｍ、厚みＤは３ｍｍのレーザー溶着用試験片４を用いた。 [Laser weldability evaluation]
FIG. 1: is the (a) top view (b) side view which shows the shape of the test piece molded object of the laser welding before cutting. The test piece is a laser welding test piece having a width W of 24 mm, a length L of 70 mm, and a thickness D of 3 mm, which is obtained by cutting a laser beam transmission evaluation test piece 1 of FIG. 4 was used.

図２はレーザー溶着用試験片切削品の形状を示す（ａ）平面図（ｂ）側面図である。（ａ）は上記切削加工後の試験片４の平面図であり、（ｂ）はその側面図である。   FIG. 2: is a (a) top view (b) side view which shows the shape of the laser welding test piece cutting goods. (A) is a top view of the test piece 4 after the said cutting process, (b) is the side view.

レーザー溶着機は、ライスター社のＭＯＤＵＬＡＳ Ｃを用いた。該溶着機は半導体レーザー使用の機器であり、レーザー光の波長は９４０ｎｍの近赤外線である。最大出力が３５Ｗ、焦点距離Ｌが３８ｍｍ、焦点径Ｄが０．６ｍｍである。   As the laser welding machine, MODULAS C manufactured by Leister was used. The welding machine is a device using a semiconductor laser, and the wavelength of the laser beam is near infrared at 940 nm. The maximum output is 35 W, the focal length L is 38 mm, and the focal diameter D is 0.6 mm.

図３はレーザー溶着方法の概略を示す概略図である。レーザー溶着方法は図３に示すように、レーザー光線を透過させる材料を用いたレーザー光線透過側試験片８を上部に、下部にはレーザー光線を吸収させる材料を用いたレーザー光線吸収側試験片９を置き、重ね合わせ、上部よりレーザー光線を照射する。レーザー照射はレーザー溶着軌道７に沿って行い、レーザー溶着条件は、出力１５〜３５Ｗ範囲および、レーザー走査速度１〜８０ｍｍ／ｓｅｃの範囲で最も良好な溶着強度が得られる条件で行った。尚、焦点距離は３８ｍｍ、焦点径は０．６ｍｍ固定で実施した。   FIG. 3 is a schematic view showing an outline of the laser welding method. As shown in FIG. 3, the laser welding method is such that a laser beam transmission side test piece 8 using a material that transmits a laser beam is placed on the upper side, and a laser beam absorption side test piece 9 that uses a material that absorbs the laser beam is placed on the lower side. Combine and irradiate with laser beam from the top. The laser irradiation was performed along the laser welding track 7 and the laser welding conditions were performed under the conditions that the best welding strength was obtained in the range of 15 to 35 W output and the laser scanning speed of 1 to 80 mm / sec. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm.

[レーザー溶着強度測定]
図４はレーザー溶着強度測定用試験片を示す（ａ）平面図（ｂ）側面図である。（ａ）は上記方法でレーザー溶着したレーザー溶着強度測定用試験片１０の平面図であり、（ｂ）は同試験片の側面図である。試験片厚みは透過側と吸収側が同じになるようにセットする。レーザー溶着強度測定用試験片１０は図４に示したレーザー溶着試験片であるレーザー光線透過側試験片８とレーザー光線吸収側試験片９とが、重ね合わせ長さＬを３０ｍｍとし、溶着距離Ｙは２０ｍｍとして、重ね合わせて溶着部１１で溶着したものである。溶着強度測定には一般的な引張試験器（ＡＧ−５００Ｂ）を用い、該試験片の両端を固定し、溶着部位には引張剪断応力が発生するように引張試験を行った。強度測定時の引張速度は１ｍｍ／ｍｉｎ、スパンは４０ｍｍである。溶着強度は溶着部位が破断したときの応力とした。尚、レーザー光線透過試料へはポリカーボネート樹脂組成部を用い、レーザー光線吸収側試料へは、ポリアミド樹脂、ポリカーボネート樹脂および充填材を表中記載の割合で混合、調整した樹脂組成物１００重量部に対し、カーボンブラックを０．４部添加,ブレンドし成形した材料を用いた。成形は東芝機械ＩＳ８０型射出成形機を用いて実施、図１記載の成形品を得た。溶着用樹脂組成物の成形条件はシリンダー温度：２６０〜２９０℃、金型温度：８０℃、射出−冷却時間：１０−１０秒、射出速度：７０％、射出圧力：充填下限圧力＋０．９８ＭＰａ（Ｇ）とした。ポリカーボネート樹脂組成物に関しては、いずれもシリンダー温度：３００℃、金型温度：８０℃、射出−冷却時間：２０−２０秒、射出速度：７０％、射出圧力：充填下限圧力＋０．９８ＭＰａ（Ｇ）とした。いずれの樹脂組成物も成形前には予備乾燥を実施し、溶着用樹脂組成物は除湿乾燥機を用い８０℃で４時間、ポリカーボネート樹脂組成物は１２０℃の熱風乾燥機中で４時間乾燥を実施した。また、それぞれ成形後２０時間以上、常温下デシケータ中にて保管後に切削加工、溶着を行い、更に２０時間以上常温下デシケータ中で保管した後に強度測定実施した。溶着特性測定は、上記の方法で溶着した試験片を用い、ＡＳＴＭ Ｄ６３８に準じ実施した。溶着強度は溶着部位が破断したときの応力とした。 [Laser welding strength measurement]
FIG. 4 is a (a) plan view and (b) side view showing a test piece for measuring laser welding strength. (A) is a top view of the test piece 10 for laser welding strength measurement laser-welded by the said method, (b) is a side view of the test piece. The specimen thickness is set so that the transmission side and the absorption side are the same. The test piece 10 for measuring the laser welding strength is a laser beam transmission side test piece 8 and a laser beam absorption side test piece 9 which are the laser welding test pieces shown in FIG. 4, and the overlapping length L is 30 mm, and the welding distance Y is 20 mm. As shown in FIG. A general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welding site. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, a polycarbonate resin composition part is used for a laser beam transmission sample, and a carbon resin is mixed with 100 parts by weight of a resin composition in which a polyamide resin, a polycarbonate resin, and a filler are mixed and adjusted in a ratio shown in the table for a laser beam absorption side sample. A material prepared by adding 0.4 part of black and blending was used. Molding was carried out using a Toshiba Machine IS80 type injection molding machine to obtain the molded product shown in FIG. The molding conditions of the welding resin composition are as follows: cylinder temperature: 260 to 290 ° C., mold temperature: 80 ° C., injection-cooling time: 10-10 seconds, injection speed: 70%, injection pressure: filling lower limit pressure + 0.98 MPa ( G). Regarding the polycarbonate resin composition, cylinder temperature: 300 ° C., mold temperature: 80 ° C., injection-cooling time: 20-20 seconds, injection speed: 70%, injection pressure: filling lower limit pressure + 0.98 MPa (G) It was. Each resin composition is pre-dried before molding, the welding resin composition is dried at 80 ° C. for 4 hours using a dehumidifying dryer, and the polycarbonate resin composition is dried for 4 hours in a 120 ° C. hot air dryer. Carried out. Further, after each molding, the cutting and welding were performed after storage in a desiccator at room temperature for 20 hours or more, and the strength was measured after further storage in the desiccator at room temperature for 20 hours or more. The welding characteristics were measured according to ASTM D638 using the test piece welded by the above method. The welding strength was the stress when the welded site was broken.

［二色成形溶着性の評価］
図５は２色成形溶着性評価用いた試験片の概略図である。ＪＩＳＫ７１１３で規定された１号引張り試験片を中央で左右対系となるよう２分割した、図５に示す形状の試験片を一次成形品として成形した。成形は東芝機械ＩＳ８０型射出成形機を用いて実施した。一次成形品としては溶着用樹脂組成物（Ａ）を用い、条件はシリンダー温度：２６０〜２９０℃、金型温度：８０℃、射出−冷却時間：１０−１０秒、射出速度：７０％、射出圧力：充填下限圧力＋０．９８ＭＰａ（Ｇ）とした。また、金型は上記半ダンベル形状となるよう独自に作成した金型を用いた。次に、一次成形品をＪＩＳＫ７１１３で規定された１号引張り試験片成形用の金型に、二次材が流入した際接する面が図５の１２部となるようセットし、二次材としてポリカーボネート樹脂組成物を射出、２材を成形溶着させた。二次材成形条件に関しては、いずれもシリンダー温度：３００℃、金型温度：８０℃、射出−冷却時間：２０−２０秒、射出速度：７０％、射出圧力：充填下限圧力＋０．９８ＭＰａ（Ｇ）とした。いずれの樹脂組成物も成形前には予備乾燥を実施し、溶着用樹脂組成物は除湿乾燥機を用い８０℃で４時間、ポリカーボネート樹脂組成物は１２０℃の熱風乾燥機中で４時間乾燥を実施した。
[二次成形溶着強度測定]
また、二次材成形後２０時間以上、常温下デシケータ中にて保管後に強度測定実施した。溶着特性測定は、上記の方法で溶着成形した１号引張り試験片を用い、ＡＳＴＭ Ｄ６３８に準じ実施した。溶着強度は溶着部位が破断したときの応力とした。
［外観評価］
溶着用樹脂組成物（Ａ）につき、以下の基準により成形品外観を評価した。
◎：表面の転写良好であり、極めて外観良好である状態
○：上記と下記×の中間であり、外観良好な状態
×：表面の転写良好ではなく、外観が悪い状態
[実施例１〜１２]
以上の手法により具体的に評価した際の結果を説明する。なお、本発明は実施例の記載に限定されるものではない。 [Evaluation of two-color molding weldability]
FIG. 5 is a schematic view of a test piece used for two-color molding weldability evaluation. A test piece having a shape shown in FIG. 5 was formed as a primary molded product, in which a No. 1 tensile test piece defined in JISK7113 was divided into two at the center so as to form a left-right paired system. Molding was performed using a Toshiba Machine IS80 type injection molding machine. The welding resin composition (A) is used as the primary molded product, and the conditions are cylinder temperature: 260-290 ° C., mold temperature: 80 ° C., injection-cooling time: 10-10 seconds, injection speed: 70%, injection Pressure: Filling lower limit pressure + 0.98 MPa (G). Moreover, the metal mold | die produced uniquely so that it might become the said half dumbbell shape was used. Next, the primary molded product is set in a mold for molding No. 1 tensile test piece defined in JIS K7113 so that the surface to be contacted when the secondary material flows is 12 parts in FIG. 5, and polycarbonate is used as the secondary material. The resin composition was injected and two materials were molded and welded. Regarding the secondary material molding conditions, cylinder temperature: 300 ° C., mold temperature: 80 ° C., injection-cooling time: 20-20 seconds, injection speed: 70%, injection pressure: filling lower limit pressure + 0.98 MPa (G ). Each resin composition is pre-dried before molding, the welding resin composition is dried at 80 ° C. for 4 hours using a dehumidifying dryer, and the polycarbonate resin composition is dried for 4 hours in a 120 ° C. hot air dryer. Carried out.
[Measurement of secondary forming weld strength]
In addition, the strength was measured after storage in a desiccator at room temperature for 20 hours or more after forming the secondary material. Measurement of welding characteristics was carried out in accordance with ASTM D638 using No. 1 tensile test pieces welded and molded by the above method. The welding strength was the stress when the welded site was broken.
[Appearance evaluation]
About the resin composition (A) for welding, the external appearance of the molded product was evaluated according to the following criteria.
◎: Excellent surface transfer and very good appearance ○: Intermediate between the above and the following ×, Appearance good state ×: Surface transfer is not good and appearance is poor
[Examples 1 to 12]
The results when specifically evaluated by the above method will be described. In addition, this invention is not limited to description of an Example.

表１は今回発明の最適の形態にて評価実施した際の結果を示したものである。表１に示す配合にて溶着用樹脂組成物を得、上記各方法により溶着評価を実施した。結果は表中に示すとおりである。ナイロン樹脂の相違により若干の差違は生じるものの、いずれも実用価値の高いものであった。なお、溶着用樹脂組成物外観に関してはナイロン６６／６Ｉ／６コポリマーを用いた水準（例９、１１、１２）で良好な結果が得られ、成形品表面外観が重視される用途ではこれら組成物が適しているものと考えられる。   Table 1 shows the results when the evaluation was carried out in the optimum form of the present invention. The welding resin composition was obtained by the formulation shown in Table 1, and the welding evaluation was performed by the above methods. The results are as shown in the table. Although a slight difference was caused by the difference in nylon resin, all were high in practical value. In terms of the appearance of the resin composition for welding, good results were obtained at the level using nylon 66 / 6I / 6 copolymer (Examples 9, 11, and 12). Is considered suitable.

Figure 2006273992
Figure 2006273992

[比較例１〜１２]
本発明の最良の実施形態において発現する効果を明確化する為、比較例として本発明範囲外での例につき評価実施した際の結果を示す。表２はその結果を示したものである。表中に示す配合以外は、前記実施例と同様に混練、特性評価などを行った。ここで得られた組成物は溶着強度において実施例記載の各水準比で充分なものが得られなかった。なお、ポリカーボネート樹脂配合比率の多い溶着用樹脂組成物を用いた水準（比較例２、６、１０）では、ポリカーボネート樹脂同士での溶着性の高さに起因し高い溶着強度が期待されたが、いずれも期待された強度を得る事が出来ず、特にレーザー溶着時の溶着強度が予測を大幅に下回った。レーザー照射時にポリカーボネート部位に発生するストレスクラック起因の可能性が考えられる。 [Comparative Examples 1 to 12]
In order to clarify the effect manifested in the best mode of the present invention, the results of evaluation of examples outside the scope of the present invention are shown as comparative examples. Table 2 shows the results. Except for the blending shown in the table, kneading, characteristic evaluation and the like were performed in the same manner as in the above Examples. The composition obtained here was not satisfactory in welding strength at each level ratio described in the examples. In addition, in the level (Comparative Examples 2, 6, and 10) using a welding resin composition with a high polycarbonate resin blending ratio, a high welding strength was expected due to the high welding property between polycarbonate resins. In either case, the expected strength could not be obtained, and the welding strength during laser welding was significantly lower than expected. The possibility of stress cracks occurring in the polycarbonate part during laser irradiation is considered.

Figure 2006273992
Figure 2006273992

本発明は、複雑な形状の部品、例えばヘッドランプ、電装品ケースなどの自動車関連部品、電動工具棟の筐体、その他容器類などの製造に適した溶着接合部材としての展開が期待出来るが、その応用範囲はこれらに限られるものではない。   Although the present invention can be expected to develop as a welding joint member suitable for the manufacture of parts having complicated shapes, such as automobile-related parts such as headlamps and electrical component cases, casings of electric tool buildings, and other containers, The application range is not limited to these.

切削前のレーザー溶着用試験片成形体の形状を示す（ａ）平面図（ｂ）側面図である。It is (a) top view (b) side view which shows the shape of the laser welding test piece molded object before cutting. レーザー溶着用試験片切削品の形状を示す（ａ）平面図（ｂ）側面図である。It is (a) top view (b) side view which shows the shape of the laser welding test piece cutting goods. レーザー溶着方法の概略図である。It is the schematic of a laser welding method. レーザー溶着強度測定用試験片を示す（ａ）平面図（ｂ）側面図である。It is (a) top view (b) side view which shows the test piece for laser welding strength measurement. ２色成形溶着性評価用いた試験片の概略図である。It is the schematic of the test piece used for 2 color molding weldability evaluation.

符号の説明Explanation of symbols

１ 切り出し前のレーザー溶着用試験片成形体
２ ゲート部
３ スプルーランナー部
４ レーザー溶着用試験片
５ レーザー光線照射部
６ レーザー光線
７ レーザー光の軌道
８ レーザー光線透過側試験片
９ レーザー光線吸収側試験片
１０ レーザー溶着強度測定用試験片
１１ レーザー溶着部
１２ ２色成形溶着時の溶着面 DESCRIPTION OF SYMBOLS 1 Laser welding test piece molding before cutting 2 Gate part 3 Sprue runner part 4 Laser welding test piece 5 Laser beam irradiation part 6 Laser beam 7 Laser beam orbit 8 Laser beam transmission side test piece 9 Laser beam absorption side test piece
10 Laser Welding Strength Measurement Specimen 11 Laser Welding Part 12 Welding Surface at Two-color Molding Welding

Claims (9)

ポリアミド樹脂（Ａ）１００重量部に対しポリカーボネート樹脂（Ｂ）１０〜９０重量部と充填材（Ｃ）１０〜９０重量部を含有する溶着用樹脂組成物。 A welding resin composition containing 10 to 90 parts by weight of a polycarbonate resin (B) and 10 to 90 parts by weight of a filler (C) with respect to 100 parts by weight of a polyamide resin (A). 前記ポリアミド樹脂（Ａ）がナイロン６、ナイロン６６、ナイロン６６／６Ｉ／６コポリマーのいずれかである請求項１記載の溶着用樹脂組成物。 The welding resin composition according to claim 1, wherein the polyamide resin (A) is any one of nylon 6, nylon 66, and nylon 66 / 6I / 6 copolymer. 前記ポリカーボネート樹脂（Ｂ）が芳香族ポリカーボネートである請求項１または２記載の溶着用樹脂組成物。 The welding resin composition according to claim 1 or 2, wherein the polycarbonate resin (B) is an aromatic polycarbonate. 前記充填材（Ｃ）がガラス繊維、炭素繊維、ワラステナイト、カオリン、マイカ、クレー、酸化チタン、ガラスフレーク、ガラスビーズの群から選ばれる１種または２種以上である請求項１〜３のいずれかに記載の溶着用樹脂組成物。 The filler (C) is one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, clay, titanium oxide, glass flakes, and glass beads. A welding resin composition according to claim 1. 請求項１〜４のいずれかに記載の溶着用樹脂組成物とポリカーボネート樹脂組成物とを溶着することを特徴とする樹脂溶着方法。 A resin welding method comprising welding the welding resin composition according to claim 1 and a polycarbonate resin composition. 前記ポリカーボネート樹脂組成物が芳香族ポリカーボネートである請求項５記載の樹脂溶着方法。 The resin welding method according to claim 5, wherein the polycarbonate resin composition is an aromatic polycarbonate. 溶着方法がレーザー溶着法または２色射出成形法による溶着接合であることを特徴とする、請求項５または６に記載の樹脂溶着方法。 The resin welding method according to claim 5 or 6, characterized in that the welding method is welding joining by a laser welding method or a two-color injection molding method. 溶着用樹脂組成物をレーザー光線吸収側、ポリカーボネート樹脂組成物をレーザー光線透過側としてレーザー溶着することを特徴とする、請求項７記載の樹脂溶着方法。 8. The resin welding method according to claim 7, wherein the welding resin composition is laser welded with the laser beam absorption side and the polycarbonate resin composition is laser beam transmission side. 溶着用樹脂組成物を２色射出成形時の一次成形体、ポリカーボネート樹脂組成物を二次成形体として２色射出成形法により溶着することを特徴とする、請求項７記載の樹脂溶着方法。 The resin welding method according to claim 7, wherein the welding resin composition is welded by a two-color injection molding method using a primary molded body at the time of two-color injection molding and a polycarbonate resin composition as a secondary molded body.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112882A (en) * 2005-10-19 2007-05-10 E I Du Pont De Nemours & Co Resin composition for laser welding, resin member using the same composition and method for producing the same resin member
JP2010013522A (en) * 2008-07-02 2010-01-21 Teijin Chem Ltd Polycarbonate resin composition for two-color molding
KR101507293B1 (en) 2012-09-14 2015-03-30 미쓰비시 엔지니어링-플라스틱스 코포레이션 Resin composition for laser direct structuring, resin molded article, and method for manufacturing molded resin article with plated layer
WO2019116952A1 (en) * 2017-12-12 2019-06-20 オイレス工業株式会社 Sliding bearing and method for manufacturing same
WO2019160117A1 (en) 2018-02-16 2019-08-22 三井化学株式会社 Polyamide resin composition, molded body thereof, and method for manufacturing laser-welded body

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007112882A (en) * 2005-10-19 2007-05-10 E I Du Pont De Nemours & Co Resin composition for laser welding, resin member using the same composition and method for producing the same resin member
JP4695483B2 (en) * 2005-10-19 2011-06-08 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Laser welding resin composition, resin member using the composition, and method for producing the resin member
JP2010013522A (en) * 2008-07-02 2010-01-21 Teijin Chem Ltd Polycarbonate resin composition for two-color molding
KR101507293B1 (en) 2012-09-14 2015-03-30 미쓰비시 엔지니어링-플라스틱스 코포레이션 Resin composition for laser direct structuring, resin molded article, and method for manufacturing molded resin article with plated layer
WO2019116952A1 (en) * 2017-12-12 2019-06-20 オイレス工業株式会社 Sliding bearing and method for manufacturing same
WO2019160117A1 (en) 2018-02-16 2019-08-22 三井化学株式会社 Polyamide resin composition, molded body thereof, and method for manufacturing laser-welded body
KR20200104411A (en) 2018-02-16 2020-09-03 미쯔이가가꾸가부시끼가이샤 Polyamide resin composition and its molded article, method for producing a laser welded article
US11673341B2 (en) 2018-02-16 2023-06-13 Mitsui Chemicals, Inc. Polyamide resin composition, molded body thereof, and method for manufacturing laser-welded body

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