WO2003037968A1 - Molded crystalline thermoplastic resin - Google Patents

Molded crystalline thermoplastic resin Download PDF

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Publication number
WO2003037968A1
WO2003037968A1 PCT/JP2002/011233 JP0211233W WO03037968A1 WO 2003037968 A1 WO2003037968 A1 WO 2003037968A1 JP 0211233 W JP0211233 W JP 0211233W WO 03037968 A1 WO03037968 A1 WO 03037968A1
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Prior art keywords
thermoplastic resin
crystalline thermoplastic
crosslinking
molded article
resistance
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PCT/JP2002/011233
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French (fr)
Japanese (ja)
Inventor
Tsutomu Tamura
Tomohide Nakagawa
Original Assignee
Toyo Boseki Kabushiki Kaisha
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Priority to JP2003540242A priority Critical patent/JP4174721B2/en
Publication of WO2003037968A1 publication Critical patent/WO2003037968A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking

Definitions

  • the present invention provides a cross-linked structure that has significantly improved heat resistance properties such as high-temperature creep resistance, arc resistance, and solder resistance while maintaining excellent strength and impact resistance of a molded article made of a crystalline thermoplastic resin.
  • the present invention relates to a crystalline thermoplastic resin molded article.
  • thermoplastic resin molded articles have been used in a wide range of applications as engineering plastics because of their excellent mechanical properties, impact resistance, and chemical resistance.
  • a crystalline thermoplastic resin molded article to which an inorganic reinforcing material represented by glass fiber is added significantly improves rigidity, strength, heat resistance and the like.
  • the heat resistance of the polyamide resin highly cross-linked by the peroxide and the cross-linking aid is improved, but the fluidity is significantly reduced, and it becomes difficult to form a thin molded product, and the elongation at break is increased. This is not preferred because the degree of reduction is low and the toughness is extremely low.
  • the present invention is based on the background of the problems of the prior art, and is resistant to arc resistance ⁇ ⁇ ⁇ high temperature and short-time heat resistance higher than the melting point necessary for solder resistance, and creep resistance at high temperatures near the melting point. It is an object of the present invention to produce a crosslinked crystalline thermoplastic resin molded article which is excellent in quality and retains the impact resistance and toughness inherently possessed by the crystalline thermoplastic resin molded article at low cost. Disclosure of the invention
  • the present invention provides: (1) a molded article obtained by irradiating a molded article obtained mainly from a composition containing a crystalline thermoplastic resin with an electron beam, at least a surface layer of which is cross-linked; A crystalline thermoplastic resin molded article having a degree of crosslinking higher than the degree of crosslinking of the inner layer part and the lower layer part. (2) The crystalline thermoplastic resin molded article as described in (1) above, wherein the degree of crosslinking of the surface layer of the molded article is 70% or more.
  • the composition mainly containing a crystalline thermoplastic resin is a polyamide resin composition containing (A) a polyamide resin, (B) a crosslinking aid, and (C) a hindered phenol-based heat stabilizer.
  • the crystalline thermoplastic resin molded article according to the above-mentioned item (1) which is a polyamide resin composition containing a type-olefin resin.
  • the present invention will be described specifically.
  • the crosslinked crystalline thermoplastic resin molded article according to the present invention is a crystal obtained by molding a composition containing at least (A) a crystalline thermoplastic resin, (B) a crosslinking aid, and (C) a heat stabilizer. It can be obtained by irradiating a thermoplastic resin molded article with an electron beam.
  • the crystalline thermoplastic resin as the component (A) is not particularly limited as long as it is crystalline, Since heat resistance is required, a crystalline thermoplastic resin having a melting point of 160 ° C. or more is preferable.
  • Particularly preferred crystalline thermoplastic resins include polyamide resins, polyester resins, and polyphenylene sulfide resins.
  • the polyamide resin used in the present invention has an acid amide bond (one CON H—) in the molecule, and specifically includes: one-strand prolactam, 6-aminocaproic acid, ⁇ -enantholactam, Polymers, copolymers or blends obtained from 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, sodium pyrrolidone, ⁇ -piperidone, and the like. Hexamethylene diamine, nonamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, metaxylylene diamine and other diamines and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc.
  • the polyamide resin having a number average molecular weight of 7,000 to 30,000 is preferably used. When the number average molecular weight is less than 7,000, evening funnel is undesirably reduced. On the other hand, if it exceeds 30,000, the fluidity decreases, which is not preferable.
  • the polyester resin used in the present invention includes resins alone or blends such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-1,6-naphthalate (PEN), and polymer alloys. Examples include, but are not limited to: The number average molecular weight of these polyester resins is preferably from 6,000 to 30,000.
  • polyphenylene sulfide resin (PPS) used in the present invention any of a linear type, a branched type and a partially crosslinked type can be used.
  • the (B) crosslinking aid used in the present invention promotes crosslinking of the crystalline thermoplastic resin upon irradiation with an electron beam, and specifically includes triaryl cyanurate (TAC) and triallyl isocyanurate.
  • TAC triaryl cyanurate
  • TMAIC trimethylaryl isocyanurate
  • TMPTA trimethylolpropane trimethacrylate
  • TCEICA hydroxoxytyl isocyanuric acrylate
  • MPBM ⁇ , ⁇ '-m-phenylenebismaleimide
  • These or crosslinking assistants can be used alone or in combination of two or more.
  • the compounding amount of the crosslinking aid is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the total of the crystalline thermoplastic resin composition excluding the crosslinking aid and the heat stabilizer. If the amount is less than 0.01 part by weight, the crosslinking does not proceed and the degree of bridge is reduced. If the amount exceeds 10 parts by weight, not only does the efficiency as a crosslinking aid deteriorate, but also the physical properties of the crystalline thermoplastic resin-based resin are deteriorated, which is not preferable.
  • the (C) heat stabilizer used in the present invention is the thermal degradation of a compound having relatively low heat stability such as a crosslinking aid when kneading a crystalline thermoplastic resin with a crosslinking aid and other compounding agents.
  • the purpose of the present invention is to use a hindered phenol-based heat stabilizer in the present invention.
  • BHT 2,6-di-t-butyl 4-methylphenol
  • tetrakis-l- [methylene-l- (3 ', 5' di-t-l-butyl 4-hydroxyphenyl) propionate ] Methane (ilganox 1010)
  • triethylene glycol-bis- [3- (3-t-butyl-4-hydroxy-15-methylphenyl) propionate] (ilganox 245), and the like, but are not limited thereto. Not something.
  • These heat stabilizers can be used alone or in combination of two or more.
  • the amount of the heat stabilizer is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the crystalline thermoplastic resin composition excluding the crosslinking assistant and the heat stabilizer. . If the amount is less than 0.05 part by weight, the effect as a heat stabilizer is not obtained. If the amount is more than 5 parts by weight, the efficiency as a heat stabilizer is poor, and it is not economical.
  • the composition molded into the molded article of the present invention has improved impact resistance and toughness, and has improved electron beam properties.
  • a crosslinked olefin resin containing a functional group that reacts with the crystalline thermoplastic resin may be further blended as a component (D) in order to promote crosslinking.
  • the cross-linked olefin-based resin specifically includes various polyethylene resins, an ethylene / propylene copolymer, an ethylene / propylene / zene copolymer, an ethylene / butene-11 copolymer, an ethylene / octene-11 copolymer, Ethylene Z And propylene / ⁇ -olefin copolymers such as propylene / butene copolymer and propylene / octene copolymer.
  • the present invention is not limited to these.
  • (D) crosslinked type olefin-based resins need to be provided with ( ⁇ ) a functional group that reacts with the crystalline thermoplastic resin.
  • a functional group that reacts with the crystalline thermoplastic resin include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxadrine group, an amino group and an isocyanate group. The most responsive and particularly preferred. The content of these functional groups is usually 0.05 to 10% by weight.
  • the amount of the (D) crosslinked olefin resin is from 1 to 40% by weight, preferably from 3 to 30% by weight, based on the weight of the crystalline thermoplastic resin excluding the crosslinking aid and the heat stabilizer. If it is less than 1% by weight, the effect of improving impact resistance is not obtained, and if it exceeds 40% by weight, the elastic modulus is remarkably lowered and the heat resistance is also lowered, which is not preferable.
  • Phenol-based antioxidants, phosphorus-based antioxidants, flame retardants, release agents, lubricants, antistatic agents, pigments, dyes, etc. may be added as agents, and the reinforcing inorganic substances are glass fibers, carbon, and the like.
  • Fibrous reinforcement such as fiber, ceramic fiber, and various whiskers. Examples include powdered inorganic reinforcing materials such as silica, alumina, talc, kaolin, quartz, powdered glass, myriki, and graphite. These reinforcing inorganic substances may be treated with a silane coupling agent as a surface treatment agent.
  • the crystalline thermoplastic resin molded article of the present invention comprises at least ( ⁇ ) a crystalline thermoplastic resin, ( ⁇ ) a crosslinking assistant, and (C) a heat stabilizer other than the above ( ⁇ ) depending on the application depending on the application.
  • the dose of electron beam irradiation obtained by irradiating a crystalline thermoplastic resin molded product obtained by molding a crystalline thermoplastic resin-based composition containing a thermoplastic resin, a reinforcing inorganic substance, a flame retardant, etc. with an electron beam is crystalline. Although it varies depending on the type of the thermoplastic thermoplastic resin composition and the shape of the molded product, it is generally 50 to 400 kGy, and in particular, the desired molded product can be obtained. The lowest dose is preferred.
  • the crystalline thermoplastic resin-based molded article is post-crosslinked, it is possible to produce a thinly molded article having a high degree of crosslinking, which is difficult to obtain by the peroxide cross-linking method, and the molded article has a high temperature creep resistance near the melting point. The properties are extremely excellent.
  • the degree of crosslinking at the surface layer portion of the molded body directly exposed to the electron beam is preferably 70% or more.
  • the degree of crosslinking of the inner layer may be 0.
  • the degree of crosslinking of the surface layer of the crosslinked crystalline thermoplastic resin molded product is extremely important.
  • the surface layer of the compact has a degree of cross-linking of 70% or more, so it has excellent arc resistance and withstands a lead-free solder bath of 300 ° C or more.
  • a molded article having heat resistance of 0 seconds or more is obtained.
  • the degree of crosslinking of the inner layer portion and the back surface of the molded article gradually decreases, so that the impact strength and toughness of the entire molded article can maintain the excellent properties inherent to the crystalline thermoplastic resin.
  • the crosslinked crystalline thermoplastic resin molded article according to the present invention is excellent even in a thin molded article because the high-temperature material properties are improved by crosslinking and the degree of crosslinking between the surface layer portion, the inner layer portion, and the back surface of the molded article is changed. It has made it possible to achieve both arc resistance and anti-skid properties as well as conflicting properties such as high impact resistance and toughness.
  • the crosslinking degree and Izod impact strength in the present invention are values measured by the following methods.
  • solder resistance When immersed for 30 seconds in a lead-free solder bath at 350 ° C for 30 seconds, the material that does not melt or deform is solder resistant: ⁇ , melting or deformation No solder resistance: X
  • Polyamide resins include NY-6 (Polycapramid: Toyobo Nylon T-840, manufactured by Toyobo Co., Ltd.), NY-66 (polyhexamethylene dizipamide: CN3001N, manufactured by Toray Industries, Inc.), and polyester resins.
  • PBT polybutylene terephthalate: N-1000, manufactured by Mitsubishi Rayon Co., Ltd.
  • TAIC triaryl isocyanurate
  • TMAIC trimethyl aryl isocyanurate
  • BHT Kawaguchi Chemical Co., Ltd.
  • FT- 710 Asahi Glass Fiber Co., Ltd.
  • Flame retardant PDBS80, Gray Lakes Chemical Co., Ltd.
  • Flame retardant aid antimony trioxide: Nippon Seiko Co., Ltd.), modified with maleic acid EPR (Tahuma-MH5020: Three Using Chemical Co., Ltd.).
  • each of the raw materials was weighed at the ratio shown in Table 1, mixed in a tumbler, and kneaded with a twin-screw extruder at a temperature of 270 to obtain a pellet.
  • a 2 mm flat plate was formed from the obtained pellet with an injection molding machine, and used as an evaluation sample.
  • the cylinder temperature of the injection molding machine was 270 and the mold temperature was 80 ° C.
  • the flat plate of the evaluation sample was irradiated with an electron beam from one direction by an electron beam irradiation device.
  • the irradiation dose at this time was 120 kGy.
  • the entire crosslinked crystalline thermoplastic resin molded article of the present invention has a high degree of crosslinking, has a particularly high degree of crosslinking in the surface layer, and has a low degree of crosslinking in the inner layer and the lower layer.
  • the high degree of cross-linking of the entire sample improves high-temperature material properties such as creep characteristics at high temperatures, as well as high arc resistance and melting even after a high-temperature solder bath treatment of 350 or 30 seconds. No deformation of the molded product or deformation occurred, indicating that extremely excellent soldering resistance was obtained.
  • the degree of cross-linking of the inner layer portion and the lower layer portion is relatively low, impact strength, toughness, and the like can maintain the physical properties inherent to the polyamide and polyester moldings. The invention's effect
  • the crosslinked crystalline thermoplastic resin molded article of the present invention has a high degree of cross-linking in the surface layer and a low degree of cross-linking in the inner layer and the lower layer, and thus has both high heat resistance and toughness.
  • Such a molded article can provide excellent creep resistance and arc resistance in electric and electronic-related parts such as various switch parts. Also, the solder resistance of the thinned electronic parts can be remarkably improved. On the other hand, it can also be used for applications that come into direct contact with fire, such as automobile ashtrays, so that the use of crystalline thermoplastic resin-based molded products will be significantly expanded, contributing to the industrial world.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

A crosslinked crystalline thermoplastic resin molding which not only withstands short-term heating at a temperature not lower than the melting point, such heat resistance being necessary for soldering resistance, but has satisfactory creep resistance at high temperatures around the melting point and retains the impact resistance and toughness inherent in the crystalline thermoplastic resin molding. It can be produced at low cost. The crystalline thermoplastic resin molding is one obtained by irradiating a molding of a composition consisting mainly of a crystalline thermoplastic resin with electron beams to crosslink the resin in at least a surface layer of the molding, and is characterized in that the degree of crosslinking in the surface layer is higher than in an inner layer and lower layer.

Description

明 細 書 結晶性熱可塑性樹脂成形体 技術分野  Description Crystalline thermoplastic resin molding Technical field
本発明は結晶性熱可塑性樹脂からなる成形体の優れた強度、 耐衝撃性を保持 しつつ、 高温での耐クリープ特性、 耐アーク性ゃ耐ハンダ性等の耐熱特性が著 しく向上した架橋した結晶性熱可塑性樹脂成形体に関するものである。 背景技術  The present invention provides a cross-linked structure that has significantly improved heat resistance properties such as high-temperature creep resistance, arc resistance, and solder resistance while maintaining excellent strength and impact resistance of a molded article made of a crystalline thermoplastic resin. The present invention relates to a crystalline thermoplastic resin molded article. Background art
従来より、 結晶性熱可塑性樹脂成形体は、 機械的特性、 耐衝撃性、 および耐 薬品性等が優れているため、 ェンジニヤリングプラスチックとして広範な用途 分野で用いられている。 なかでもガラス繊維を代表とする無機強化材を添加し た結晶性熱可塑性樹脂成形体は剛性、 強度、 耐熱性等が大幅に向上することが 知られている。  Conventionally, crystalline thermoplastic resin molded articles have been used in a wide range of applications as engineering plastics because of their excellent mechanical properties, impact resistance, and chemical resistance. Among them, it is known that a crystalline thermoplastic resin molded article to which an inorganic reinforcing material represented by glass fiber is added significantly improves rigidity, strength, heat resistance and the like.
しかしながら、 最近ェンジニヤリングプラスチックに要求される特性が益々 高度になり、 例えば高温での耐クリープ特性やコロナ放電 （アーク） が起きた 場合に材料の劣化や溶融が起こりにくい、 優れた耐アーク性を持つ材料や、 鉛 の毒性を嫌つて鉛を含有しない鉛フリ一ハンダの高温ハンダ浴に耐える高温耐 熱材料等の高度な性能や特殊な機能を持つ材料が求められている。  However, recently, the properties required of engineering plastics have become increasingly sophisticated. For example, creep resistance at high temperatures and excellent arc resistance, in which the material is unlikely to degrade or melt when corona discharge (arc) occurs, are required. Materials with advanced performance and special functions, such as high-temperature heat-resistant materials that can withstand the high-temperature solder bath of lead-free solder that does not contain lead because of its toxicity, are required.
このような高度な要求を満たすため、 結晶性熱可塑性樹脂であるポリアミド 系樹脂に、 ペルォキシドと架橋助剤を配合し、 加熱により架橋することによつ て耐熱性を高める検討が行われている （例えば特開 2 0 0 1—4 0 2 0 6号公 報） 。  In order to satisfy such advanced requirements, studies are being made to increase the heat resistance by blending peroxide and a crosslinking aid with a polyamide-based resin, which is a crystalline thermoplastic resin, and crosslinking by heating. (For example, Japanese Unexamined Patent Publication No. 2001-406206).
しかしながら、 高温での耐クリープ性、 '耐アーク性ゃ耐ハンダ性等の耐熱性 を高めるためには高度な架橋結晶性熱可塑性樹脂が必要である。 前記方法によ ると、 ペルォキシドと架橋助剤によって高度に架橋されたポリアミド系樹脂の 耐熱特性は向上するが、 流動性が著しく低下し、 肉薄な成形体の成形が困難と なると共に、 破断伸度が低下しタフネスが著しく低くなるので好ましくない。 本発明は従来技術の課題を背景になされたものであり、 耐アーク性ゃ耐ハン ダ性に必要な融点以上の高温短時間の耐熱性に耐えるとともに、 融点近傍の高 温での耐クリープ特性も良好でかつ結晶性熱可塑性樹脂成形体が本来持ってい る耐衝撃性やタフネスを保持している架橋した結晶性熱可塑性樹脂成形体を安 価に製造することを課題とするものである。 発明の開示 However, in order to improve the heat resistance such as creep resistance at high temperature, 'arc resistance ゃ solder resistance, etc., a highly crosslinked crystalline thermoplastic resin is required. According to the above method, the heat resistance of the polyamide resin highly cross-linked by the peroxide and the cross-linking aid is improved, but the fluidity is significantly reduced, and it becomes difficult to form a thin molded product, and the elongation at break is increased. This is not preferred because the degree of reduction is low and the toughness is extremely low. The present invention is based on the background of the problems of the prior art, and is resistant to arc resistance ア ー ク high temperature and short-time heat resistance higher than the melting point necessary for solder resistance, and creep resistance at high temperatures near the melting point. It is an object of the present invention to produce a crosslinked crystalline thermoplastic resin molded article which is excellent in quality and retains the impact resistance and toughness inherently possessed by the crystalline thermoplastic resin molded article at low cost. Disclosure of the invention
本発明者らは上記課題を解決するために鋭意研究した結果、 遂に本発明を 完成するに到った。 即ち本発明は、 ①主として結晶性熱可塑性樹脂を含有する 組成物から得られる成形体を電子線照射することによって、 少なくとも表層部 が架橋された成形体であって、 該成形体表層部の架橋度が内層部および下層部 の架橋度より高いことを特徴とする結晶性熱可塑性樹脂成形体。 ②成形体表層 部の架橋度が 7 0 %以上である前記①記載の結晶性熱可塑性樹脂成形体。 ③主 として結晶性熱可塑性樹脂を含有する組成物が (A)ポリアミド樹脂、 （B) 架橋 助剤および （C) ヒンダードフエノール系熱安定剤を含有するポリアミド系樹 脂組成物である前記①記載の結晶性熱可塑性樹脂成形体。 ④主として結晶性熱 可塑性樹脂を含有する組成物が （A) ポリアミド樹脂、 （B) 架橋助剤、 （C) ヒンダードフエノール系熱安定剤および （D) ポリアミド樹脂と反応する官能 基を有する架橋型ォレフィン系樹脂を含有するポリアミド系樹脂組成物である 前記①記載の結晶性熱可塑性樹脂成形体。 ⑤電子線照射によって架橋された主 としてポリアミド樹脂を主体とした成形体であって、 3 5 0 °Cのハンダ浴で 3 0秒以上のハンダ耐熱性を有することを特徴とする架橋ポリアミド系成形体で ある。 以下本発明を具体的に説明する。  The present inventors have conducted intensive studies to solve the above problems, and as a result, have finally completed the present invention. That is, the present invention provides: (1) a molded article obtained by irradiating a molded article obtained mainly from a composition containing a crystalline thermoplastic resin with an electron beam, at least a surface layer of which is cross-linked; A crystalline thermoplastic resin molded article having a degree of crosslinking higher than the degree of crosslinking of the inner layer part and the lower layer part. (2) The crystalline thermoplastic resin molded article as described in (1) above, wherein the degree of crosslinking of the surface layer of the molded article is 70% or more. (3) The composition mainly containing a crystalline thermoplastic resin is a polyamide resin composition containing (A) a polyamide resin, (B) a crosslinking aid, and (C) a hindered phenol-based heat stabilizer. The molded article of the crystalline thermoplastic resin described in the above.が Cross-linking having a functional group that reacts mainly with (A) polyamide resin, (B) cross-linking aid, (C) hindered phenolic heat stabilizer and (D) polyamide resin The crystalline thermoplastic resin molded article according to the above-mentioned item (1), which is a polyamide resin composition containing a type-olefin resin.架橋 A crosslinked polyamide-based molded article mainly composed of a polyamide resin crosslinked by electron beam irradiation, characterized by having a solder heat resistance of at least 30 seconds in a 350 ° C solder bath. Body. Hereinafter, the present invention will be described specifically.
本発明による架橋した結晶性熱可塑性樹脂成形体は少なくとも (A)結晶性熱可 塑性樹脂、 （B)架橋助剤および (C)熱安定剤を含有する組成物を成形して得られ る結晶性熱可塑性樹脂成形体に電子線照射することによって得られる。  The crosslinked crystalline thermoplastic resin molded article according to the present invention is a crystal obtained by molding a composition containing at least (A) a crystalline thermoplastic resin, (B) a crosslinking aid, and (C) a heat stabilizer. It can be obtained by irradiating a thermoplastic resin molded article with an electron beam.
前記 (A)成分である結晶性熱可塑性樹脂は結晶性であれば特に制限はないが、 耐熱性が必要なため、 融点が 1 6 0 °C以上の結晶性熱可塑性樹脂が好ましい。 特に好ましい結晶性熱可塑性樹脂はポリアミド樹脂、 ポリエステル樹脂および ポリフエ二レンサルフアイド樹脂等が挙げられる。 The crystalline thermoplastic resin as the component (A) is not particularly limited as long as it is crystalline, Since heat resistance is required, a crystalline thermoplastic resin having a melting point of 160 ° C. or more is preferable. Particularly preferred crystalline thermoplastic resins include polyamide resins, polyester resins, and polyphenylene sulfide resins.
本発明で用いられる前記ポリアミド樹脂とは分子中に酸アミド結合 （一 CON H— ) を有するものであり、 具体的には £一力プロラクタム、 6—アミノカプ ロン酸、 ω—ェナントラクタム、 7—ァミノヘプタン酸、 1 1—アミノウンデ カン酸、 9—アミノノナン酸、 ひ一ピロリドン、 α—ピぺリドンなどから得ら れる重合体または共重合体もしくはブレンド物。 へキサメチレンジァミン、 ノ ナメチレンジァミン、 ゥンデカメチレンジァミン、 ドデカメチレンジァミン、 メタキシリレンジァミンなどのジァミンとテレフタル酸、 イソフタル酸、 アジ ピン酸、 セバシン酸などのジカルポン酸とを重縮合して得られる重合体または 共重合体もしくはブレンド物等を例示することが出来るが、 これらに限定され るものではない。 本発明において上記ポリアミド樹脂の数平均分子量は 7,000 〜30，000のものが好ましく用いられる。 数平均分子量が 7,000未満では夕フネ スが低下して好ましくない。 また 30,000を超えると流動性が低下し好ましくな い。  The polyamide resin used in the present invention has an acid amide bond (one CON H—) in the molecule, and specifically includes: one-strand prolactam, 6-aminocaproic acid, ω-enantholactam, Polymers, copolymers or blends obtained from 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, sodium pyrrolidone, α-piperidone, and the like. Hexamethylene diamine, nonamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, metaxylylene diamine and other diamines and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc. Examples thereof include a polymer, a copolymer or a blend obtained by polycondensation with dicarponic acid, but are not limited thereto. In the present invention, the polyamide resin having a number average molecular weight of 7,000 to 30,000 is preferably used. When the number average molecular weight is less than 7,000, evening funnel is undesirably reduced. On the other hand, if it exceeds 30,000, the fluidity decreases, which is not preferable.
本発明で用いられる前記ポリエステル樹脂とは、 ポリエチレンテレフ夕レー ト （P E T) 、 ポリプチレンテレフタレート （P B T) およびポリエチレン一 2 , 6—ナフタレート （P E N) などの樹脂単独やブレンド物、 またはポリマ ーァロイ等を挙げることが出来るがこれらに限定されるものではない。 これら のポリエステル樹脂の数平均分子量は 6,000〜30，000のものが好ましく用いら れる。  The polyester resin used in the present invention includes resins alone or blends such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-1,6-naphthalate (PEN), and polymer alloys. Examples include, but are not limited to: The number average molecular weight of these polyester resins is preferably from 6,000 to 30,000.
本発明で用いられる前記ポリフエ二レンサルファイド樹脂 （P P S ) はリニ ヤータイプ、 分岐タイプぉよび一部架橋夕イブのいずれも使用することができ る。  As the polyphenylene sulfide resin (PPS) used in the present invention, any of a linear type, a branched type and a partially crosslinked type can be used.
本発明で用いられる前記 （B)架橋助剤とは電子線照射時に結晶性熱可塑性樹 脂の架橋を促進させるもので、 具体的にはトリァリルシアヌレート （TAC) 、 トリアリルイソシァヌレー卜 (TAIC) 、 トリメチルァリルイソシァヌレート (TMAIC) 、 トリメチロールプロパントリメタクリレート （TMPTA) 、 トリ スハイドロォキシェチルイソシァヌリックァクリレート (THEICA) 、 Ν,Ν'— m—フエ二レンビスマレイミド （MPBM) 等の多官能性化合物を例示すること が出来るが、 これらに限定されるものではない。 これらか架橋助剤は一種類ま たは二種類以上を併用することもできる。 架橋助剤の配合量は、 架橋助剤と熱 安定剤を除いた結晶性熱可塑性樹脂系組成物の合計 100重量部に対し 0.01〜： 10 重量部、 好ましくは 0.03〜5重量部である。 0.01重量部未満では架橋が進まず架 橋度が低くなる。 また 10重量部を超えると架橋助剤としての効率が悪くなるば かりか、'結晶性熱可塑性樹脂系樹脂の物性を低下させるので好ましくない。 The (B) crosslinking aid used in the present invention promotes crosslinking of the crystalline thermoplastic resin upon irradiation with an electron beam, and specifically includes triaryl cyanurate (TAC) and triallyl isocyanurate. (TAIC), trimethylaryl isocyanurate (TMAIC), trimethylolpropane trimethacrylate (TMPTA), Examples thereof include polyfunctional compounds such as hydroxoxytyl isocyanuric acrylate (THEICA) and Ν, Ν'-m-phenylenebismaleimide (MPBM), but are not limited thereto. Not something. These or crosslinking assistants can be used alone or in combination of two or more. The compounding amount of the crosslinking aid is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the total of the crystalline thermoplastic resin composition excluding the crosslinking aid and the heat stabilizer. If the amount is less than 0.01 part by weight, the crosslinking does not proceed and the degree of bridge is reduced. If the amount exceeds 10 parts by weight, not only does the efficiency as a crosslinking aid deteriorate, but also the physical properties of the crystalline thermoplastic resin-based resin are deteriorated, which is not preferable.
本発明で用いられる前記 （C)熱安定剤とは結晶性熱可塑性樹脂と架橋助剤お よび他の配合剤を混練するときに架橋助剤等の比較的熱安定性の悪い化合物の 熱劣化を防止することを主目的に配合するもので、 本発明においてはヒンダ一 ドフエノール系の熱安定剤が好ましい。 具体的には 2、 6—ジ一 t一ブチル 4メ チルフエノール （BHT) 、 テ卜ラキス一[メチレン一 3— (3'、 5' ージ一 t一プチ ルー 4—ヒドロキシフエニル）プロピオネート]メタン (ィルガノックス 1010)、 ト リエチレングリコール一ビス一 [3— (3— t—プチルー 4ーヒドロキシ一 5—メチ ルフエニル)プロピオネート] ( ィルガノックス 245)等を例示することが出来る が、 これらに限定されるものではない。 これらの熱安定剤は一種類または二種 類以上を併用することが出来る。 熱安定剤の配合量は、 架橋助剤と熱安定剤を 除いた結晶性熱可塑性樹脂系組成物の合計 100重量部に対し 0.05〜5重量部、 好 ましくは 0.1〜3重量部である。 0.05重量部未満では熱安定剤としての効果がな く、 5重量部を超えると熱安定剤としての効率が悪く、 経済的でないので好ま しくない。  The (C) heat stabilizer used in the present invention is the thermal degradation of a compound having relatively low heat stability such as a crosslinking aid when kneading a crystalline thermoplastic resin with a crosslinking aid and other compounding agents. The purpose of the present invention is to use a hindered phenol-based heat stabilizer in the present invention. Specifically, 2,6-di-t-butyl 4-methylphenol (BHT), tetrakis-l- [methylene-l- (3 ', 5' di-t-l-butyl 4-hydroxyphenyl) propionate ] Methane (ilganox 1010), triethylene glycol-bis- [3- (3-t-butyl-4-hydroxy-15-methylphenyl) propionate] (ilganox 245), and the like, but are not limited thereto. Not something. These heat stabilizers can be used alone or in combination of two or more. The amount of the heat stabilizer is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total of the crystalline thermoplastic resin composition excluding the crosslinking assistant and the heat stabilizer. . If the amount is less than 0.05 part by weight, the effect as a heat stabilizer is not obtained. If the amount is more than 5 parts by weight, the efficiency as a heat stabilizer is poor, and it is not economical.
本発明成形体に成形される組成物には、 （A)結晶性熱可塑性樹脂、 （B)架橋助 剤および (C)熱安定剤の他に、 耐衝撃性やタフネスを改良すると共に電子線照射 による架橋の際、 架橋を促進させるために、 （D)成分として、 結晶性熱可塑性樹 脂と反応する官能基を含有する架橋型ォレフィン系樹脂をさらに配合してもよ レ 。 前記架橋型ォレフイン系樹脂は、 具体的に各種ポリエチレン樹脂、 ェチレ ン /プロピレン共重合体、 エチレン Zプロピレン Zジェン共重合体、 エチレン /ブテン一 1共重合体、 エチレン/ォクテン一 1共重合体、 エチレン Zへキセ ンー 1共重合体、 等のエチレン / α—才レフイン共重合体、 プロピレン/ブテ ン共重合体、 プロピレン/ォクテン共重合体等のプロピレン Ζ α—才レフィン 共重合体等を挙げることが出来るが、 これらに限定されるものではない。 In addition to (A) the crystalline thermoplastic resin, (B) the crosslinking aid and (C) the heat stabilizer, the composition molded into the molded article of the present invention has improved impact resistance and toughness, and has improved electron beam properties. At the time of crosslinking by irradiation, a crosslinked olefin resin containing a functional group that reacts with the crystalline thermoplastic resin may be further blended as a component (D) in order to promote crosslinking. The cross-linked olefin-based resin specifically includes various polyethylene resins, an ethylene / propylene copolymer, an ethylene / propylene / zene copolymer, an ethylene / butene-11 copolymer, an ethylene / octene-11 copolymer, Ethylene Z And propylene / α-olefin copolymers such as propylene / butene copolymer and propylene / octene copolymer. However, the present invention is not limited to these.
これら前記 (D)架橋型ォレフイン系樹脂は、 (Α) 結晶性熱可塑性樹脂と反応す る官能基を付与することが必要である。 結晶性熱可塑性樹脂と反応する官能基 とは具体的にカルボン酸基、 酸無水物基、 エポキシ基、 ォキサドリン基、 アミ ノ基イソシァネート基等が例示されるが、 これらの中でも酸無水物基が最も反 応性が高く、 特に好ましい。 これらの官能基の含有量は通常 0.05〜10重量％で ある。  These (D) crosslinked type olefin-based resins need to be provided with (す) a functional group that reacts with the crystalline thermoplastic resin. Specific examples of the functional group that reacts with the crystalline thermoplastic resin include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxadrine group, an amino group and an isocyanate group. The most responsive and particularly preferred. The content of these functional groups is usually 0.05 to 10% by weight.
前記 (D)架橋型ォレフイン系樹脂の配合量は架橋助剤と熱安定剤を除いた結 晶性熱可塑性樹脂に対し 1〜4 0重量％、 好ましくは 3〜3 0重量％である。 1重量％未満では耐衝撃性の改良効果がなく、 また 4 0重量％を超えると弾性 率が著しく低下すると共に耐熱性も低下し好ましくない。  The amount of the (D) crosslinked olefin resin is from 1 to 40% by weight, preferably from 3 to 30% by weight, based on the weight of the crystalline thermoplastic resin excluding the crosslinking aid and the heat stabilizer. If it is less than 1% by weight, the effect of improving impact resistance is not obtained, and if it exceeds 40% by weight, the elastic modulus is remarkably lowered and the heat resistance is also lowered, which is not preferable.
また、 前記組成物以外に、 通常の結晶性熱可塑性樹脂組成物に用いられる強 化用無機物類、 耐候性改良剤であるカーボンブラックや銅酸化物および/または ハロゲン化アルカリ金属、 光または熱安定剤としてフエノール系酸化防止剤や リン系酸化防止剤、 難燃剤、 離型剤、 滑材、 帯電防止剤、 顔料、 染料等を配合 してもよく、 前記強化用無機物類とはガラス繊維、 炭素繊維、 セラミックス繊 維、 各種ウイスカ一等の繊維状強化材。 シリカ、 アルミナ、 タルク、 カオリン 、 石英、 粉状ガラス、 マイ力、 グラフアイト、 等の粉末状の無機強化材が挙げ られる。 またこれら強化用無機物類は表面処理剤としてシランカップリング剤 を処理しても良い。  In addition to the above-mentioned composition, inorganic substances for strengthening used in ordinary crystalline thermoplastic resin compositions, carbon black and copper oxide and / or alkali metal halide as weather resistance improvers, light or heat stability Phenol-based antioxidants, phosphorus-based antioxidants, flame retardants, release agents, lubricants, antistatic agents, pigments, dyes, etc. may be added as agents, and the reinforcing inorganic substances are glass fibers, carbon, and the like. Fibrous reinforcement such as fiber, ceramic fiber, and various whiskers. Examples include powdered inorganic reinforcing materials such as silica, alumina, talc, kaolin, quartz, powdered glass, myriki, and graphite. These reinforcing inorganic substances may be treated with a silane coupling agent as a surface treatment agent.
本発明結晶性熱可塑性樹脂成形体は、 少なくとも (Α)結晶性熱可塑性樹脂、 （Β )架橋助剤および (C)熱安定剤の基本組成に用途に応じて、 前記 (Α)以外の熱可塑 性樹脂、 強化用無機物類や難燃剤等を配合した結晶性熱可塑性樹脂系組成物を 成形した結晶性熱可塑性樹脂成形体に電子線を照射することによって得られる 電子線照射の線量は結晶性熱可塑性樹脂系組成物の種類やその成形体の形状 によっても異なるが、 一般に 5 0〜4 0 0 k Gy、 特には目的の成形体が得られ る最小の線量が好ましい。 The crystalline thermoplastic resin molded article of the present invention comprises at least (Α) a crystalline thermoplastic resin, (Β) a crosslinking assistant, and (C) a heat stabilizer other than the above (Α) depending on the application depending on the application. The dose of electron beam irradiation obtained by irradiating a crystalline thermoplastic resin molded product obtained by molding a crystalline thermoplastic resin-based composition containing a thermoplastic resin, a reinforcing inorganic substance, a flame retardant, etc. with an electron beam is crystalline. Although it varies depending on the type of the thermoplastic thermoplastic resin composition and the shape of the molded product, it is generally 50 to 400 kGy, and in particular, the desired molded product can be obtained. The lowest dose is preferred.
本発明は結晶性熱可塑性樹脂系成形体を後架橋するため、 ペルォキシド架橋 法では得られにくい肉薄成形体の高架橋度成形体の製造も可能であり、 その成 形体は融点近傍における高温の耐クリープ性が極めて優れている。  In the present invention, since the crystalline thermoplastic resin-based molded article is post-crosslinked, it is possible to produce a thinly molded article having a high degree of crosslinking, which is difficult to obtain by the peroxide cross-linking method, and the molded article has a high temperature creep resistance near the melting point. The properties are extremely excellent.
また本発明の架橋した結晶性熱可塑性樹脂成形体は電子線が直接あたる成形 体表面から約 0.5mm程度の表層部は極めて高い架橋度が得られ、 内層部や裏面 では架橋度が徐々に低下する傾斜的架橋度をもつ成形体が得られる。 本発明に おいては電子線が直接当たる成形体表層部の架橋度は 7 0 %以上であることが 好ましい。 なお本発明においては内層部の架橋度は 0であってもよい。  In the crosslinked crystalline thermoplastic resin molded article of the present invention, a very high degree of crosslinking is obtained in the surface layer of about 0.5 mm from the surface of the molded article directly hit by the electron beam, and the degree of crosslinking gradually decreases in the inner layer and the backside. A molded article having a graded degree of crosslinking is obtained. In the present invention, the degree of cross-linking at the surface layer portion of the molded body directly exposed to the electron beam is preferably 70% or more. In the present invention, the degree of crosslinking of the inner layer may be 0.
成形体の表面特性によって耐アーク性ゃ耐ハンダ特性が変化するため、 架橋 された結晶性熱可塑性樹脂成形体の表層部の架橋度が極めて重要となる。 特に 成形体の表層部が 7 0 %以上の架橋度を持つことによって、 優れた耐アーク性 や鉛フリーの 300°C以上のハンダ浴にも耐え、 特に 3 5 0 °Cのハンダ浴で 3 0 秒以上の耐熱性のある成形体が得られる。  Since the arc resistance and the solder resistance change depending on the surface properties of the molded product, the degree of crosslinking of the surface layer of the crosslinked crystalline thermoplastic resin molded product is extremely important. In particular, the surface layer of the compact has a degree of cross-linking of 70% or more, so it has excellent arc resistance and withstands a lead-free solder bath of 300 ° C or more. A molded article having heat resistance of 0 seconds or more is obtained.
一方成形体の内層部や裏面の架橋度が徐々に低下することにより、 成形体全 体の衝撃強度やタフネスは結晶性熱可塑性樹脂が本来有する優れた特性を維持 することが出来るようになる。  On the other hand, the degree of crosslinking of the inner layer portion and the back surface of the molded article gradually decreases, so that the impact strength and toughness of the entire molded article can maintain the excellent properties inherent to the crystalline thermoplastic resin.
本発明による架橋した結晶性熱可塑性樹脂成形体は肉薄の成形体でも架橋によ り高温材料特性が向上すると共に成形体の表層部と内層部および裏面との架橋 度が変化することにより、 優れた耐アーク性ゃ耐八ンダ特性と高い耐衝撃性や タフネスという相反する特性を両立させることが可能となった。 実施例 The crosslinked crystalline thermoplastic resin molded article according to the present invention is excellent even in a thin molded article because the high-temperature material properties are improved by crosslinking and the degree of crosslinking between the surface layer portion, the inner layer portion, and the back surface of the molded article is changed. It has made it possible to achieve both arc resistance and anti-skid properties as well as conflicting properties such as high impact resistance and toughness. Example
次に実施例および比較例を用いて本発明を具体的に説明するが、 本発明は これらに限定されるものではない。  Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
なお、 本発明における架橋度およびアイゾット衝撃強度は、 以下の方法で測 定した値である。  The crosslinking degree and Izod impact strength in the present invention are values measured by the following methods.
( 1 ) 架橋橋度：電子線照射した試料の架橋度の評価は蟻酸溶液中に 2 4時間 浸漬した後、 真空乾燥機で溶剤を取り除き、 下記の式 （I ) でゲル分率 （％) を測定して、 架橋度とした。 (1) Degree of crosslinking: The degree of crosslinking of the sample irradiated with electron beam was evaluated by immersing it in a formic acid solution for 24 hours, removing the solvent with a vacuum dryer, and using the following formula (I) to determine the gel fraction (%). Was measured to determine the degree of crosslinking.
ゲル分率 (％)=溶剤浸漬後の試料乾燥重量 xioo/溶剤浸漬前の試料乾燥重量 Gel fraction (%) = sample dry weight after solvent immersion xioo / sample dry weight before solvent immersion
( I )  (I)
( 2 ) アイゾット衝撃強度： ASTMD- 2 5 6に準じて測定した。  (2) Izod impact strength: Measured according to ASTM D-256.
( 3 ) 耐ハンダ特性： 3 5 0 °Cの鉛を含有しないハンダ浴中に 3 0秒間浸漬し た時、 材料の溶融や変形がないものを、 耐ハンダ性あり ：〇とし、 溶融または 変形があるものを、 耐ハンダ性なし： Xとした。  (3) Solder resistance: When immersed for 30 seconds in a lead-free solder bath at 350 ° C for 30 seconds, the material that does not melt or deform is solder resistant: 〇, melting or deformation No solder resistance: X
(実施例 1〜8、 比較例 1〜3 ) (Examples 1 to 8, Comparative Examples 1 to 3)
実施例、 比較例に用いた各種原料は以下のとおりである。 Various raw materials used in Examples and Comparative Examples are as follows.
ポリアミド樹脂としては NY-6 (ポリ力プラミド：東洋紡績 （株） 製 東洋紡 ナイロン T- 8 4 0 ) 、 NY-66 (ポリへキサメチレンジアジパミド：東レ (株) 製 CN3001N) 、 ポリエステル樹脂として： PBT (ポリブチレンテレフタレ一 ト：三菱レーヨン （株） 製 N-1000) 、 架橋助剤としてトリァリルイソシァヌ レート （TAIC： 日本化成 （株） 製） 、 およびトリメチルァリルイソシァヌレ ート （TMAIC : 日本化成 （株） 製） 、 熱安定剤として 2 , 6—ジー t一ブチル 4メチルフエノール (BHT：川口化学工業 (株) 製） 、 他の添加剤としてガラ ス繊維 （FT-710：旭ガラスファイバー （株） 製） 、 難燃剤 （PDBS80，グレー トレイクスケミカル （株） 製） 難燃助剤 （3酸化アンチモン： 日本精鉱 （株） 製） 、 改質材としてマレイン酸変性 EPR (タフマ- MH5020：三井化学 （株） 製） を用いた。  Polyamide resins include NY-6 (Polycapramid: Toyobo Nylon T-840, manufactured by Toyobo Co., Ltd.), NY-66 (polyhexamethylene dizipamide: CN3001N, manufactured by Toray Industries, Inc.), and polyester resins. : PBT (polybutylene terephthalate: N-1000, manufactured by Mitsubishi Rayon Co., Ltd.), triaryl isocyanurate (TAIC: manufactured by Nippon Kasei Co., Ltd.) as a cross-linking aid, and trimethyl aryl isocyanurate (TMAIC: Nippon Kasei Co., Ltd.), 2,6-di-tert-butyl 4-methylphenol (BHT: Kawaguchi Chemical Co., Ltd.) as a heat stabilizer, and glass fiber (FT- 710: Asahi Glass Fiber Co., Ltd.), Flame retardant (PDBS80, Gray Lakes Chemical Co., Ltd.) Flame retardant aid (antimony trioxide: Nippon Seiko Co., Ltd.), modified with maleic acid EPR (Tahuma-MH5020: Three Using Chemical Co., Ltd.).
まず、 表 1に示す割合で前記各原料を計量し、 タンブラ一で混合した後、 2 軸押出機で 2 7 0 の温度で混練してペレツトを得た。 得られたペレツトを射 出成形機で 2 mmの平板を成形し、 評価サンプルとした。 射出成形機のシリン ダー温度は 2 7 0 、 金型温度は 8 0 °Cであった。  First, each of the raw materials was weighed at the ratio shown in Table 1, mixed in a tumbler, and kneaded with a twin-screw extruder at a temperature of 270 to obtain a pellet. A 2 mm flat plate was formed from the obtained pellet with an injection molding machine, and used as an evaluation sample. The cylinder temperature of the injection molding machine was 270 and the mold temperature was 80 ° C.
評価サンプルの平板は電子線照射装置で一方向から電子線を照射した。 この 時の照射線量は 1 2 0 kGyであった。  The flat plate of the evaluation sample was irradiated with an electron beam from one direction by an electron beam irradiation device. The irradiation dose at this time was 120 kGy.
各評価サンプルは試料全体のゲル分率を測定すると共に電子線が直接当たる 試料表面から 0.5mmの深さまでを表層部とし、 0.5〜2.0nmiの深さを内層 +下 層部として、 それぞれの部分に切削し、 区別してゲル分率を測定した それぞれ得られた評価結果を表 1に示す。For each evaluation sample, measure the gel fraction of the entire sample, and make the surface layer 0.5 mm deep from the sample surface directly hit by the electron beam. As a layer part, each part was cut, and the gel fraction was measured separately. Table 1 shows the evaluation results obtained.
Figure imgf000010_0001
表 1から明らかなように、 本発明の架橋結晶性熱可塑性樹脂成形体全体に高 い架橋度を持つと共に表層部では特に高い架橋度を持ち、 内層部や下層部では 架橋度が低くなる。 試料全体の高い架橋度は高温でのクリープ特性等の高温材 料特性を向上させるとともに、 高度な耐アーク性や、 3 5 0 、 3 0秒と言う 高温のハンダ浴の処理をしても溶融や成形体の変形が起こらず、 極めて優れた 耐ハンダ特性が得られていることが判る。 また内層部や下層部の架橋度が比較 的低いため、 衝撃強度やタフネス等はポリアミドおよびポリエステル系成形体 が本来持つ物性を維持することが出来る。 発明の効果
Figure imgf000010_0001
As is clear from Table 1, the entire crosslinked crystalline thermoplastic resin molded article of the present invention has a high degree of crosslinking, has a particularly high degree of crosslinking in the surface layer, and has a low degree of crosslinking in the inner layer and the lower layer. The high degree of cross-linking of the entire sample improves high-temperature material properties such as creep characteristics at high temperatures, as well as high arc resistance and melting even after a high-temperature solder bath treatment of 350 or 30 seconds. No deformation of the molded product or deformation occurred, indicating that extremely excellent soldering resistance was obtained. In addition, since the degree of cross-linking of the inner layer portion and the lower layer portion is relatively low, impact strength, toughness, and the like can maintain the physical properties inherent to the polyamide and polyester moldings. The invention's effect
本発明の架橋した結晶性熱可塑性樹脂成形体は、 表層部分に高い架橋度を持 ち、 内層部や下層部での架橋度が低いので高い耐熱性とタフネスを兼ね備えて いる。 このような成形体は各種のスィツチ部品等の電気、電子関連部品で優れ た耐クリープ性ゃ耐アーク性が得られる。 また薄肉化した電子部品の耐ハンダ 特性を著しく改良することが出来る。 一方自動車の灰皿等の直接火気と接触す る用途でも使用することができるので、 結晶性熱可塑性樹脂系成形体の用途を 著しく拡大し、 産業界に寄与すること大である。  The crosslinked crystalline thermoplastic resin molded article of the present invention has a high degree of cross-linking in the surface layer and a low degree of cross-linking in the inner layer and the lower layer, and thus has both high heat resistance and toughness. Such a molded article can provide excellent creep resistance and arc resistance in electric and electronic-related parts such as various switch parts. Also, the solder resistance of the thinned electronic parts can be remarkably improved. On the other hand, it can also be used for applications that come into direct contact with fire, such as automobile ashtrays, so that the use of crystalline thermoplastic resin-based molded products will be significantly expanded, contributing to the industrial world.

Claims

請 求 の 範 囲 The scope of the claims
1 . 主として結晶性熱可塑性榭脂を含有する組成物から得られる成形体を電 子線照射することによって、 少なくとも表層部が架橋された成形体であつて 、 該成形体表層部の架橋度が内層部および下層部の架橋度より高いことを特 徴とする結晶性熱可塑性樹脂成形体。 1. By irradiating a molded product obtained mainly from a composition containing a crystalline thermoplastic resin with an electron beam, at least a surface layer portion of the molded product is crosslinked, and the degree of crosslinking of the surface layer portion of the molded product is reduced. A crystalline thermoplastic resin molded article characterized by having a higher degree of cross-linking of an inner layer portion and a lower layer portion.
2 . 成形体表層部の架橋度が 7 0 %以上である請求項 1記載の結晶性熱可塑 性樹脂成形体。 2. The crystalline thermoplastic resin molded article according to claim 1, wherein the degree of crosslinking of the surface layer portion of the molded article is 70% or more.
3 . 主として結晶性熱可塑性樹脂を含有する組成物が (A)ポリアミド樹脂、 （B )架橋助剤および （C) ヒンダードフエノール系熱安定剤を含有するポリアミ ド系樹脂組成物である請求項 1記載の結晶性熱可塑性樹脂成形体。 3. The composition mainly comprising a crystalline thermoplastic resin is a polyamide resin composition comprising (A) a polyamide resin, (B) a crosslinking aid and (C) a hindered phenolic heat stabilizer. 2. The crystalline thermoplastic resin molded article according to 1.
4 . 主として結晶性熱可塑性樹脂を含有する組成物が （A) ポリアミド樹脂 、 (B) 架橋助剤、 （C) ヒンダードフエノール系熱安定剤および （D) ポリ アミド樹脂と反応する官能基を有する架橋型ォレフィン系樹脂を含有するポ リアミド系樹脂組成物である請求項 1記載の結晶性熱可塑性樹脂成形体。 4. A composition mainly containing a crystalline thermoplastic resin has a functional group that reacts with (A) a polyamide resin, (B) a crosslinking aid, (C) a hindered phenolic heat stabilizer, and (D) a polyamide resin. 2. The crystalline thermoplastic resin molded article according to claim 1, which is a polyamide resin composition containing a crosslinked olefin resin.
5 . 電子線照射によって架橋された主としてポリアミド樹脂を主体とした成 形体であって、 3 5 0 °C'のハンダ浴で 3 0秒以上のハンダ耐熱性を有するこ とを特徴とする架橋ポリアミド系成形体。 5. A cross-linked polyamide mainly formed of a polyamide resin cross-linked by electron beam irradiation and having a solder heat resistance of at least 30 seconds in a 350 ° C 'solder bath. Molded body.
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JP2005330314A (en) * 2004-05-18 2005-12-02 Toyobo Co Ltd Heat-resistant polyamide film and mold release film for electronic component and copper-clad laminate
JP2011225880A (en) * 2010-04-22 2011-11-10 Evonik Degussa Gmbh Process for production of cross-linked organic polymer
US8476377B2 (en) 2005-12-23 2013-07-02 EMS—Patent AG Crosslinkable polyamide molding compounds and molded parts produced therewith
EP2070973A4 (en) * 2006-10-02 2016-02-17 Sumitomo Elec Fine Polymer Inc Transparent resin molded article, optical lens, and optical film
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