JP2014005361A - Polyphenylene sulfide resin/polyamide 46 resin composite material - Google Patents
Polyphenylene sulfide resin/polyamide 46 resin composite material Download PDFInfo
- Publication number
- JP2014005361A JP2014005361A JP2012141754A JP2012141754A JP2014005361A JP 2014005361 A JP2014005361 A JP 2014005361A JP 2012141754 A JP2012141754 A JP 2012141754A JP 2012141754 A JP2012141754 A JP 2012141754A JP 2014005361 A JP2014005361 A JP 2014005361A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- pps resin
- pps
- fine powder
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 331
- 229920005989 resin Polymers 0.000 title claims abstract description 331
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 215
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 215
- 229920003189 Nylon 4,6 Polymers 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000000805 composite resin Substances 0.000 title claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 86
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000004898 kneading Methods 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- 239000008188 pellet Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 13
- 238000001746 injection moulding Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract 2
- 230000002787 reinforcement Effects 0.000 abstract 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002245 particle Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000009864 tensile test Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- 238000007561 laser diffraction method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 238000000790 scattering method Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000003484 crystal nucleating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000012758 reinforcing additive Substances 0.000 description 3
- 230000002051 biphasic effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001330 spinodal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000907661 Pieris rapae Species 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229920003465 Stanyl® TW341-J Polymers 0.000 description 1
- 229920013629 Torelina Polymers 0.000 description 1
- 239000004742 Torelina™ Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、単独使用または他の樹脂のベース樹脂としても使用され、薄肉製品でポリフェニレンサルファイド樹脂（以下、単に『ＰＰＳ樹脂』という）と同等以上の耐熱性、耐薬品性、延性、靭性が必要な自動車部品、家電部品及び製品、同じくＰＰＳ樹脂部品として、強化材、添加剤等で補強や新たな機能を付与するためのベース樹脂として使用されるＰＰＳ樹脂とポリアミド４６樹脂（以下、単に『ＰＡ４６樹脂』という）との複合材料であるＰＰＳ樹脂／ＰＡ４６樹脂複合材料に関するものである。 The present invention can be used alone or as a base resin for other resins and needs to have heat resistance, chemical resistance, ductility and toughness equivalent to or better than polyphenylene sulfide resin (hereinafter simply referred to as “PPS resin”) for thin-walled products. PPS resin and polyamide 46 resin (hereinafter simply referred to as “PA46”) used as a base resin for reinforcing or adding new functions with reinforcing materials, additives, etc. PPS resin / PA46 resin composite material which is a composite material.
この種の複合材料の技術として特許文献１に記載の技術がある。特許文献１は、少なくとも２成分の樹脂からなり、かつ、ＰＰＳ樹脂を１種以上含むＰＰＳ樹脂組成物であり、該ＰＰＳ樹脂組成物が構造周期０．０１〜１μｍの両相連続構造または粒子間距離０．０１〜１μｍの分散構造を有し、優れた機械特性、低バリ性を有する成形材料を開示している。 There exists a technique of patent document 1 as a technique of this kind of composite material. Patent Document 1 is a PPS resin composition comprising at least two component resins and containing one or more PPS resins, and the PPS resin composition has a biphasic continuous structure or interparticle structure with a structural period of 0.01 to 1 μm. Disclosed is a molding material having a dispersed structure with a distance of 0.01 to 1 μm and having excellent mechanical properties and low burr.
また、特許文献２には、スチレン系単量体及び／またはアクリル系単量体を用いて合成された少なくとも１種以上の熱可塑性樹脂、ポリアミド系樹脂、単体での熱伝導率が１．５Ｗ／ｍ・Ｋ以上でかつ電気絶縁性を示す高熱伝導性無機化合物からなり、熱可塑性樹脂／ポリアミド系樹脂の体積比が１５／８５〜７５／２５の割合であり、高熱伝導性無機化合物／｛熱可塑性樹脂＋ポリアミド系樹脂｝の体積比が１０／９０〜７５／２５であり、高熱伝導性無機化合物が熱可塑性樹脂の相中に存在している比率が熱可塑性樹脂の体積分率×０．４以下であり、更に、少なくともポリアミド系樹脂が連続相構造を形成しており、汎用樹脂の機械的特性及び成形加工性等の諸特性を実用上保持し、熱伝導性に優れた無機物含有熱可塑性樹脂組成物を開示している。 Patent Document 2 discloses that at least one thermoplastic resin synthesized from a styrene monomer and / or an acrylic monomer, a polyamide resin, and a single substance have a thermal conductivity of 1.5 W. / M · K or higher and a high thermal conductivity inorganic compound exhibiting electrical insulation, and the volume ratio of thermoplastic resin / polyamide resin is 15/85 to 75/25, and the high thermal conductivity inorganic compound / { The volume ratio of thermoplastic resin + polyamide resin} is 10/90 to 75/25, and the ratio of the high thermal conductivity inorganic compound in the phase of the thermoplastic resin is the volume fraction of the thermoplastic resin × 0. .4 or less, and at least the polyamide-based resin forms a continuous phase structure, and practically retains various properties such as mechanical properties and molding processability of general-purpose resins, and contains an inorganic substance excellent in thermal conductivity Thermoplastic resin composition Shows.
そして、特許文献３には、ポリアミド樹脂とポリフェニレンエーテルの樹脂混合物に、熱伝導性充填材粒子が分散されたもので、良好な成形性とともに耐水性に優れ、しかも、高熱伝導性を有する熱伝導性樹脂組成物を開示している。 In Patent Document 3, heat conductive filler particles are dispersed in a resin mixture of a polyamide resin and a polyphenylene ether, which has excellent moldability and water resistance, and also has high heat conductivity. A functional resin composition is disclosed.
更に、特許文献４には、ポリフェニレンスルフィド樹脂１００重量部に対し、ＢＥＴ比表面積が１４０ｍ2／ｇ以上のアルミナ粒子０．０１〜１０重量部を配合してなり、成形時の流動性を損なうことなく機械的強度、結晶化特性が著しく改良されたポリフェニレンスルフィド樹脂組成物を開示している。 Further, in Patent Document 4, 0.01 to 10 parts by weight of alumina particles having a BET specific surface area of 140 m 2 / g or more are blended with 100 parts by weight of the polyphenylene sulfide resin, thereby impairing fluidity during molding. And a polyphenylene sulfide resin composition with significantly improved mechanical strength and crystallization characteristics.
このように、特許文献１は、ＰＰＳ樹脂の靭性を改良する技術に関するものであり、従来から他の熱可塑性樹脂を配合する方法が検討されてきたが、単純に配合するのみでは、ＰＰＳ樹脂との相性が悪く、十分な効果が得られていなかった。ここではアロイにおいて優れた規則性を有する組織とすることで、優れた靭性を確保する技術として、特に、溶融混練により相溶化させた樹脂を、吐出後氷水中などで急冷し、スピノーダル分解による構造生成物を構造周期０．０１〜１μｍに固定化することで両相連続構造に構造制御して、優れた靭性を確保する方法が記載されている。ここで、ＰＰＳ樹脂とのポリマーアロイさせる樹脂は、スピノーダル分解可能な樹脂が好ましい。比較例では、ＰＰＳ樹脂とＰＡ４６樹脂を７／３で混合させた例が記載されている。
しかし、この特許文献１の技術では、実用状態の射出成形においては、急冷効果が損なわれ、靭性が確保できない可能性が想定される。また、本技術では、構造周期０．０１〜１μｍに固定化することで両相連続構造に構造制御するものであるから、射出成形をすると、製品の厚さによって、この構造を採ることは困難となるので、ある程度の大きさになっても引張伸び率を維持できるようにする必要があった。
As described above, Patent Document 1 relates to a technique for improving the toughness of a PPS resin. Conventionally, methods for blending other thermoplastic resins have been studied. The compatibility was poor, and sufficient effects were not obtained. Here, as a technology to ensure excellent toughness by forming a structure having excellent regularity in the alloy, in particular, a resin compatibilized by melt kneading is rapidly cooled in ice water after discharge, and a structure by spinodal decomposition A method is described in which the product is fixed to a structural period of 0.01 to 1 μm to control the structure to a biphasic continuous structure to ensure excellent toughness. Here, the resin alloyed with the PPS resin is preferably a resin capable of spinodal decomposition. In the comparative example, an example in which PPS resin and PA46 resin are mixed at 7/3 is described.
However, in the technique of Patent Document 1, it is assumed that in the injection molding in a practical state, the rapid cooling effect is impaired and the toughness cannot be ensured. In addition, in this technology, since the structure is controlled to a two-phase continuous structure by fixing the structure period to 0.01 to 1 μm, it is difficult to adopt this structure depending on the thickness of the product when injection molding is performed. Therefore, it has been necessary to maintain the tensile elongation even when the size becomes a certain size.
また、特許文献２では、スチレン系樹脂とポリアミド系樹脂、熱伝導フィラーでポリアミド系樹脂を海構造とし、その中に熱伝導フィラーが集中的に存在する形態であるが、スチレン系(アクリル）樹脂が入っており、ＰＰＳ樹脂に比較して耐熱性を高くすることができなかった。
そして、特許文献３では、ポリフェニレンエーテル（ＰＰＥ）とポリアミド６６(ＰＡ６６；６６ナイロン)と海島構造で海部をＰＡ６６としている。ＰＡ６６中に熱伝導フィラーであるアルミナ粒子が多く存在している。この特許文献３の実施物では流動性は良くならなかった。
In Patent Document 2, a styrene resin, a polyamide resin, and a heat conductive filler are used to form a sea structure of the polyamide resin, and the heat conductive filler is concentrated in the styrene resin (acrylic resin). The heat resistance could not be increased as compared with the PPS resin.
And in patent document 3, the sea part is made into PA66 by polyphenylene ether (PPE), polyamide 66 (PA66; 66 nylon), and a sea island structure. A lot of alumina particles, which are heat conductive fillers, are present in PA66. In the embodiment of Patent Document 3, the fluidity was not improved.
更に、特許文献４では、ＰＰＳ樹脂の流動性を損なうことなく、機械的強度、結晶化特性を向上させ、ＰＰＳ樹脂にＢＥＴ比表面積が１４０ｍ2／ｇ以上のアルミナ粒子をＰＰＳ樹脂１００重量部に対して１重量部をヘンシェルミキサーでドライブレンドした後、２軸押出機で溶融混練後ペレタイズして得られたペレットを、射出成形したサンプルでＰＰＳ樹脂と比較すると流動性が低下することもなく、引張、曲げ、衝撃強度の機械的特性が向上し、また、降温結晶化温度も高くなり結晶化特性が向上し、著しく特性が改良され、特に、アルミナはγ-アルミナで５〜１０ｎｍのものが特に効果が大きい。アルミナはアロイ材としてではなく、ＰＰＳ樹脂に対して使用している。殊に、ＰＰＳ樹脂にアルミナ微粉を入れると物性が向上すると記載されているが、アロイ材を入れると物性が一義的に向上するものではなく、アロイ材の効果は相性の問題である。 Further, in Patent Document 4, mechanical strength and crystallization characteristics are improved without impairing the fluidity of the PPS resin, and alumina particles having a BET specific surface area of 140 m 2 / g or more are added to 100 parts by weight of the PPS resin. On the other hand, pellets obtained by dry blending 1 part by weight with a Henschel mixer, melt-kneading with a twin-screw extruder and pelletizing are not reduced in fluidity when compared with PPS resin in an injection molded sample, The mechanical properties of tensile, bending, and impact strength are improved, the temperature of crystallization is lowered, the crystallization properties are improved, and the properties are remarkably improved. In particular, alumina is γ-alumina having 5 to 10 nm. Especially effective. Alumina is not used as an alloy material but for PPS resin. In particular, it is described that the physical properties are improved when alumina fine powder is added to the PPS resin, but the physical properties are not uniquely improved when the alloy material is added, and the effect of the alloy material is a problem of compatibility.
このように、射出成型で薄肉製品として成形可能なＰＰＳ樹脂と同等以上の耐熱性、延性、靭性、耐薬品性が確保されるためには、ベース樹脂にそのベース樹脂と物性の似たものを添加すると、相溶性が増すと云われていた。そこで発明者らは、実験を繰り返し、ＰＰＳ樹脂をベース樹脂とし、他の材料を混ぜ合わせ、流動性の向上及び引張伸び率の向上を図るため、混ぜ合わせる材料としてＰＰＳ樹脂より流動性の良いＰＡ４６樹脂を前提に進めてきた。しかし、実験結果は、ただ単に混ぜ合わせても引張伸び率が向上せず、そればかりか反対に低下したのが現状である。 In this way, in order to ensure heat resistance, ductility, toughness, and chemical resistance equal to or better than PPS resin that can be molded as a thin product by injection molding, the base resin should have similar properties to the base resin. The addition was said to increase compatibility. Accordingly, the inventors have repeated experiments, and in order to improve the fluidity and the tensile elongation rate by using PPS resin as the base resin and mixing other materials, the PA46 has better fluidity than PPS resin as the mixing material. We have been proceeding on the premise of resin. However, the experimental result is that the tensile elongation does not improve even if it is simply mixed, but it is decreased on the contrary.
そこで、本発明は、単独使用または他の樹脂のベース樹脂としても使用され、薄肉製品が射出成型でき、ＰＰＳ樹脂並みの耐熱性、耐薬品性、延性、靭性が必要な自動車部品、家電部品及び製品として、また、強化材、添加剤等で補強や新たな機能を付与するためのベース樹脂としても使用できるＰＰＳ樹脂／ＰＡ４６樹脂複合材料及びその製造方法の提供を課題とするものである。 Accordingly, the present invention can be used alone or as a base resin for other resins, and can be used for injection molding of thin-walled products, and it requires automobile parts, home appliance parts and PPS resin that require heat resistance, chemical resistance, ductility, and toughness. It is an object of the present invention to provide a PPS resin / PA46 resin composite material that can be used as a product and as a base resin for reinforcing or adding new functions with reinforcing materials, additives, and the like, and a method for producing the same.
請求項１に係る発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、ＰＰＳ樹脂(ポリフェニレンサルファイド樹脂)とＰＡ４６樹脂(ポリアミド４６樹脂)を溶融混練して作製した海島構造を有するポリマーアロイであって、前記ＰＰＳ樹脂が海島構造の海部となり、前記海部の前記ＰＰＳ樹脂側に中位径１００ｎｍ未満の微粉体が配されているものである。 The PPS resin / PA46 resin composite material of the invention according to claim 1 is a polymer alloy having a sea-island structure prepared by melt-kneading a PPS resin (polyphenylene sulfide resin) and a PA46 resin (polyamide 46 resin). The resin becomes a sea part having a sea-island structure, and fine powder having a median diameter of less than 100 nm is arranged on the PPS resin side of the sea part.
ここで本発明の説明において、ＪＩＳ Ｚ ８９０１「試験用粉体及び試験用粒子」の本文及び解説の用語の定義によれば、「中位径」とは、粉体の粒径分布において、ある粒子径より大きい個数（または質量）が、全粉体のそれの５０％を占めるときの粒子径（直径）、即ち、オーバサイズ５０％の粒径であり、通常、メディアン径または５０％粒子径といいＤ５０と表わされる。定義的には、平均粒子径と中位径で粒子群のサイズを表現されるが、ここでは、商品説明の表示、レーザ回折・散乱法によって測定した値である。そして、この「レーザ回折・散乱法によって測定した中位径」とは、レーザ回折式粒度分布測定装置を用いてレーザ回折・散乱法によって得られた粒度分布において積算重量部が５０％となる粒子径（Ｄ50）をいう。なお、上記数値は、厳格なものでなく概ねの値であり、当然、測定等による誤差を含む概略値であり、数割の誤差を否定するものではない。この意味で、平均粒子径と中位径は殆ど同じである。 Here, in the description of the present invention, according to the definition of the terminology in the text and the explanation of JIS Z 8901 “Test Powder and Test Particles”, “median diameter” is the particle size distribution of the powder. The particle diameter (diameter) when the number (or mass) larger than the particle diameter occupies 50% of that of the whole powder, that is, the particle diameter of 50% oversize, usually the median diameter or 50% particle diameter It is expressed as D50. By definition, the size of the particle group is expressed by the average particle diameter and the median diameter, but here, it is a value measured by the display of the product description and the laser diffraction / scattering method. The “median diameter measured by the laser diffraction / scattering method” is a particle whose cumulative weight part is 50% in the particle size distribution obtained by the laser diffraction / scattering method using a laser diffraction particle size distribution measuring apparatus. This refers to the diameter (D 50 ). Note that the above numerical values are not strict, but are approximate values, and are naturally approximate values including errors due to measurement and the like, and do not deny errors of several percent. In this sense, the average particle diameter and the median diameter are almost the same.
請求項２に係る発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の微粉体は、前記ＰＰＳ樹脂１００に対して１重量部乃至９重量部配されているものである。 The fine powder of the PPS resin / PA46 resin composite material of the invention according to claim 2 is disposed in an amount of 1 to 9 parts by weight with respect to the PPS resin 100.
請求項３に係る発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の前記微粉体は、中位径３０〜５０ｎｍの範囲内のアルミナとしたものである。
ここで、中位径３０〜５０ｎｍの範囲内の微粉体をアルミナとしたものでは、特に、アロイ化が安定して行われる。
The fine powder of the PPS resin / PA46 resin composite material of the invention according to claim 3 is an alumina having a median diameter of 30 to 50 nm.
Here, when the fine powder having a median diameter in the range of 30 to 50 nm is made of alumina, alloying is particularly stably performed.
請求項４に係る発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の製造方法は、ＰＰＳ樹脂中に、中位径１００ｎｍ未満の微粉体を配合量で前記ＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部配合して、溶融押出により微粉体添加ＰＰＳ樹脂のペレットを作製し、次いで、前記微粉体添加ＰＰＳ樹脂ペレットとＰＡ４６樹脂を溶融押出して複合化するものである。 In the method for producing a PPS resin / PA46 resin composite material according to the fourth aspect of the present invention, a fine powder having a median diameter of less than 100 nm is blended in the PPS resin in an amount of 1 to 9 parts by weight with respect to 100 parts by weight of the PPS resin. The fine powder-added PPS resin pellets are prepared by melting and extruding, and then the fine powder-added PPS resin pellets and the PA46 resin are melt-extruded to form a composite.
請求項５に係る発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の製造方法の前記微粉体は、中位径３０〜５０ｎｍの範囲内のアルミナとしたものである。
ここで、中位径３０〜５０ｎｍの範囲内の微粉体をアルミナとしたものでは、特に、アロイ化が安定して行われる。
The fine powder of the method for producing a PPS resin / PA46 resin composite material of the invention according to claim 5 is alumina having a median diameter of 30 to 50 nm.
Here, when the fine powder having a median diameter in the range of 30 to 50 nm is made of alumina, alloying is particularly stably performed.
請求項１のＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、ＰＰＳ樹脂(ポリフェニレンサルファイド樹脂)とＰＡ４６樹脂樹脂(ポリアミド４６樹脂)を溶融混練して作製した海島構造を有するポリマーアロイであって、前記ＰＰＳ樹脂が海島構造の海部となり、前記海部の前記ＰＰＳ樹脂側に中位径１００ｎｍ未満の微粉体が配されているものである。
ＰＰＳ樹脂とＰＡ４６樹脂のポリマーアロイのＰＰＳ樹脂側に１００ｎｍ未満の微粉末を集中的に配すると、流動性と引張伸び率が良好なＰＰＳ樹脂／ＰＡ４６樹脂複合材料となる。このＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、薄肉製品の射出成型ができ、耐熱性、耐薬品性、延性、靭性が必要な部品、例えば、自動車部品、家電部品に使用できる。また、強化材、添加剤等での補強や新たな機能を付与するためのベース樹脂としても使用ができる。
The PPS resin / PA46 resin composite material according to claim 1 is a polymer alloy having a sea-island structure prepared by melt-kneading PPS resin (polyphenylene sulfide resin) and PA46 resin resin (polyamide 46 resin), wherein the PPS resin is It becomes a sea part of a sea-island structure, and fine powder having a median diameter of less than 100 nm is arranged on the PPS resin side of the sea part.
When fine powders of less than 100 nm are concentrated on the PPS resin side of the polymer alloy of PPS resin and PA46 resin, a PPS resin / PA46 resin composite material having good fluidity and tensile elongation is obtained. This PPS resin / PA46 resin composite material can be used for injection molding of thin-walled products, and can be used for parts that require heat resistance, chemical resistance, ductility, and toughness, such as automobile parts and household appliance parts. Further, it can be used as a base resin for reinforcing with a reinforcing material, an additive or the like or for providing a new function.
請求項２のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の微粉体は、前記ＰＰＳ樹脂１００に対して１重量部乃至９重量部配されているものである。
１００ｎｍ未満の微粉体の配合量を前記ＰＰＳ樹脂１００に対して１重量乃至９重量部の範囲内とすることで、ＰＡ４６樹脂とアロイ化したときＰＰＳ樹脂単体のときに比べて引張強度の低下を招くことなく流動性が向上したＰＰＳ樹脂／ＰＡ４６樹脂複合材料が得られる。
The fine powder of the PPS resin / PA46 resin composite material according to claim 2 is disposed in an amount of 1 to 9 parts by weight with respect to the PPS resin 100.
By making the blending amount of the fine powder less than 100 nm within the range of 1 to 9 parts by weight with respect to the PPS resin 100, when alloyed with the PA46 resin, the tensile strength is reduced as compared with the case of the single PPS resin. A PPS resin / PA46 resin composite material with improved fluidity without incurring is obtained.
請求項３のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の前記微粉体は、中位径３０〜５０ｎｍの範囲内のアルミナとしたものであるから、より安定した複合化が可能となる。 Since the fine powder of the PPS resin / PA46 resin composite material according to claim 3 is alumina having a median diameter of 30 to 50 nm, more stable composite is possible.
請求項４のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の製造方法は、ＰＰＳ樹脂中に、中位径１００ｎｍ未満の微粉体を配合量で前記ＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部配合して溶融押出により微粉体添加ＰＰＳ樹脂のペレットを作製し、次いで、前記微粉体添加ＰＰＳ樹脂ペレットとＰＡ４６樹脂を溶融押出して複合化するものである。この様な製造方法によってＰＰＳ樹脂単体のときに比べて引張強度の低下を招くことなく流動性が向上したＰＰＳ樹脂／ＰＡ４６樹脂複合材料を作製出来る。 5. The method for producing a PPS resin / PA46 resin composite material according to claim 4, wherein a fine powder having a median diameter of less than 100 nm is blended in the PPS resin in an amount of 1 to 9 parts by weight with respect to 100 parts by weight of the PPS resin. Then, a fine powder-added PPS resin pellet is prepared by melt extrusion, and then the fine powder-added PPS resin pellet and PA46 resin are melt-extruded to form a composite. By such a production method, a PPS resin / PA46 resin composite material having improved fluidity can be produced without causing a decrease in tensile strength as compared with the case of a single PPS resin.
請求項５のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の製造方法の前記微粉体は、中位径３０〜５０ｎｍの範囲内のアルミナとしたものであるから、より安定した複合化が可能となる。 Since the fine powder of the method for producing a PPS resin / PA46 resin composite material according to claim 5 is alumina having a median diameter of 30 to 50 nm, more stable composite is possible.
以下、本発明の実施例について説明する。なお、実施例において、図示の同一記号及び同一符号は、同一または相当する機能部分であるから、ここではその重複する説明を省略する。 Examples of the present invention will be described below. Note that, in the embodiments, the same reference numerals and the same reference numerals are the same or corresponding functional parts, and therefore, redundant description thereof is omitted here.
まず、各比較例及び本発明の実施例と共にＰＰＳ樹脂として、東レ株式会社製のトレリナＡ９００(商品名)を使用した。また、ＰＡ４６樹脂（ＤＳＭエンジニアリングプラスチックス株式会社）のスタニールＴＷ３４１Ｊ(商品名)を使用した。
そして、比較例３乃至比較例４、及び実施例では、ＰＰＳ樹脂／ＰＡ４６樹脂を７０／３０の重量部とした。そして、比較例４では、微粉体である粒子径が中位径１００ｎｍのアルミナ(大明化学工業株式会社、タイミクロンＴＭ−ＤＡ(商品名)をＰＰＳ樹脂７０重量部に対し１重量部添加し、比較例５及び実施例では、微粉体である粒子径が中位径３３ｎｍのアルミナ(シーアイ化成株式会社、ナノテック(商品名)をＰＡ４６樹脂３０重量部またはＰＰＳ樹脂７０重量部に対し１重量部を添加した。
First, TORELINA A900 (trade name) manufactured by Toray Industries, Inc. was used as a PPS resin together with each comparative example and the examples of the present invention. Further, Stanyl TW341J (trade name) of PA46 resin (DSM Engineering Plastics Co., Ltd.) was used.
And in the comparative example 3 thru | or the comparative example 4 and the Example, PPS resin / PA46 resin was 70 weight part weight. In Comparative Example 4, 1 part by weight of alumina (Daiming Chemical Industry Co., Ltd., Tymicron TM-DA (trade name) having a median diameter of 100 nm as a fine powder is added to 70 parts by weight of PPS resin, In Comparative Example 5 and Examples, alumina (Cai Kasei Co., Ltd., Nanotech (trade name)) having a median diameter of 33 nm as a fine powder was added in an amount of 1 part by weight to 30 parts by weight of PA46 resin or 70 parts by weight of PPS resin. Added.
なお、ＪＩＳ Ｚ ８９０１「試験用粉体及び試験用粒子」の本文及び解説の用語の定義によれば、「中位径」とは、粉体の粒径分布において、ある粒子径より大きい個数（または質量）が、全粉体のそれの５０％を占めるときの粒子径（直径）、即ち、オーバサイズ５０％の粒径であり、通常、メディアン径または５０％粒子径といいＤ５０と表わされる。定義的には、平均粒子径と中位径で粒子群のサイズを表現されるが、ここでは、レーザ回折・散乱法によって測定した値である。
そして、この「レーザ回折・散乱法によって測定した中位径」とは、レーザ回折式粒度分布測定装置を用いてレーザ回折・散乱法によって得られた粒度分布において積算重量部が５０％となる粒子径（Ｄ50）をいう。なお、上記数値は、厳格なものでなく概ねの値であり、当然、測定等による誤差を含む概略値であり、数割の誤差を否定するものではない。この意味で、平均粒子径と中位径は殆ど同じである。
In addition, according to the definitions of terms in the text and explanation of JIS Z 8901 “Test Powder and Test Particles”, “median diameter” means the number larger than a certain particle diameter ( Or (mass) is the particle diameter (diameter) when 50% of that of the total powder, that is, the particle size of 50% oversize, usually referred to as the median diameter or 50% particle diameter, expressed as D50. . By definition, the size of the particle group is expressed by the average particle diameter and the median diameter, but here, it is a value measured by a laser diffraction / scattering method.
The “median diameter measured by the laser diffraction / scattering method” is a particle whose cumulative weight part is 50% in the particle size distribution obtained by the laser diffraction / scattering method using a laser diffraction particle size distribution measuring apparatus. This refers to the diameter (D 50 ). Note that the above numerical values are not strict, but are approximate values, and are naturally approximate values including errors due to measurement and the like, and do not deny errors of several percent. In this sense, the average particle diameter and the median diameter are almost the same.
比較例及び本発明の実施例をまとめると、比較例１はＰＰＳ樹脂のみ、比較例２はＰＡ４６樹脂のみ、比較例３はＰＰＳ樹脂／ＰＡ４６樹脂を７０／３０の重量部とし、微粉体を混入していない。比較例４はＰＰＳ樹脂／ＰＡ４６樹脂を７０／３０の重量部とし、ここに微粉体である中位径１００ｎｍのアルミナをＰＰＳ樹脂７０重量部に対して１重量部添加した。比較例５はＰＰＳ樹脂／ＰＡ４６樹脂を７０／３０の重量部とし、ここに微粉体である中位径３３ｎｍのアルミナをＰＡ４６樹脂３０重量部に対して１重量部添加したものである。実施例はＰＰＳ樹脂／ＰＡ４６樹脂を７０／３０の重量部とし、ここに微粉体である中位径３３ｎｍのアルミナをＰＰＳ樹脂７０重量部に対して１重量部添加したものである。ここで、ＰＡ４６樹脂は吸水率が高く、寸法精度が悪いので、ＰＰＳ樹脂をベース樹脂とする。 To summarize the comparative examples and the examples of the present invention, Comparative Example 1 contains only PPS resin, Comparative Example 2 contains only PA46 resin, Comparative Example 3 contains 70/30 parts by weight of PPS resin / PA46 resin, and contains fine powder. Not done. In Comparative Example 4, 70 parts by weight of PPS resin / PA46 resin was added, and 1 part by weight of alumina having a median diameter of 100 nm as a fine powder was added to 70 parts by weight of PPS resin. In Comparative Example 5, 70 parts by weight of PPS resin / PA46 resin was added, and 1 part by weight of alumina having a median diameter of 33 nm as a fine powder was added to 30 parts by weight of PA46 resin. In the example, PPS resin / PA46 resin was 70/30 parts by weight, and 1 part by weight of alumina having a median diameter of 33 nm as a fine powder was added to 70 parts by weight of PPS resin. Here, since PA46 resin has a high water absorption rate and poor dimensional accuracy, PPS resin is used as a base resin.
次に、比較例及び本発明の実施例の製造方法について説明する。
まず、比較例及び本発明の実施例の成形材料は２軸混練押出機(株式会社テクノベル製)を使用し、スクリュー径がφ１５ｍｍ、回転数３００ｒｐｍ、温度３２０℃の条件にて混練及び押出によりペレットとして作製した。このペレットを射出成形機(株式会社ソディックプラスチック製)にて射出することで流動長の測定と、引張試験用板材（厚みｔ＝０.８ｍｍ、幅Ｗ＝７ｍｍ）を成形した。流動長は、流動長の厚みをｔ＝０.８ｍｍとし、樹脂温度３２０℃、金型温度１３０℃、圧力１００ＭＰａのときのスパイラルフローにて測定した。そして引張試験は、引張試験用板材から引張試験用板材の長さ方向中央部に幅５ｍｍとなるようにＲ１０ｍｍのくびれ部を切削加工によって引張試験用ダンベルを作製し、このダンベルを２３℃の温度で引張試験機(株式会社島津製作所製)にて引張速度５ｍｍ／分で引張り、破断時の強度とそのときの伸びを測定した。なお、引張試験用板材は樹脂温度３２０℃、金型温度３０℃にて射出成形した後、１５０℃で６０分アニール処理を施したものを使用した。
Next, the manufacturing method of a comparative example and the Example of this invention is demonstrated.
First, the molding material of the comparative example and the example of the present invention was a pellet by kneading and extrusion using a twin screw kneading extruder (manufactured by Technobel Co., Ltd.) under the conditions of a screw diameter of φ15 mm, a rotation speed of 300 rpm, and a temperature of 320 ° C. As produced. The pellets were injected with an injection molding machine (manufactured by Sodick Plastic Co., Ltd.) to measure the flow length and form a tensile test plate (thickness t = 0.8 mm, width W = 7 mm). The flow length was measured by a spiral flow when the thickness of the flow length was t = 0.8 mm, the resin temperature was 320 ° C., the mold temperature was 130 ° C., and the pressure was 100 MPa. In the tensile test, a tensile test dumbbell was produced by cutting a constricted portion of R10 mm from the tensile test plate material to a width of 5 mm at the center in the length direction of the tensile test plate material. Then, the sample was pulled with a tensile tester (manufactured by Shimadzu Corporation) at a pulling speed of 5 mm / min, and the strength at break and the elongation at that time were measured. Note that the tensile test plate material was injection molded at a resin temperature of 320 ° C. and a mold temperature of 30 ° C. and then annealed at 150 ° C. for 60 minutes.
比較例１はＰＰＳ樹脂のみ、比較例２はＰＡ４６樹脂のみの特性であるから、その説明を省略する。
製造方法１の比較例４では、ステップＳ１０でホッパーからＰＰＳ樹脂を供給し、ステップＳ１１でホッパーからＰＡ４６樹脂を供給し、それらを一体化して７０／３０の重量部となるように押出機の投入口に供給し、ステップＳ１２でＰＰＳ樹脂７０重量部に対し微粉体Ａとしてのアルミナを１重量部サイドフィーダーにて押出機に供給する。そしてスクリュー内で混練されることで、ステップＳ１３でＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が７０／３０の重量部で、ＰＰＳ樹脂側にＰＰＳ樹脂７０重量部に対してアルミナが１重量部添加されて、ＰＰＳ樹脂／ＰＡ４６樹脂複合材料としては、ＰＰＳ樹脂とＰＡ４６樹脂の総量１００重量部に対し微粉体Ａとしてのアルミナを１重量部含有するコンパウンドとなる。そして、このコンパウンドされた試料をステップＳ１４でカットしてペレットを形成する。
比較例３では、ステップＳ１２の混練したＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が７０／３０重量部で、微粉体Ａとしてのアルミナを添加する工程が省略されている。
Since Comparative Example 1 has characteristics of only PPS resin and Comparative Example 2 has characteristics of only PA46 resin, the description thereof is omitted.
In Comparative Example 4 of Production Method 1, PPS resin is supplied from the hopper in step S10, PA46 resin is supplied from the hopper in step S11, and the extruder is charged so that they are integrated to 70/30 parts by weight. In step S12, alumina as fine powder A is supplied to the extruder by 1 part by weight side feeder with respect to 70 parts by weight of PPS resin. Then, by kneading in the screw, 1 part by weight of alumina is added to the PPS resin side with 70 parts by weight of the PPS resin at a blending ratio of PPS resin / PA46 resin of 70/30 in step S13. The PPS resin / PA46 resin composite material is a compound containing 1 part by weight of alumina as fine powder A with respect to 100 parts by weight of the total amount of PPS resin and PA46 resin. Then, the compounded sample is cut in step S14 to form a pellet.
In Comparative Example 3, the blending ratio of the kneaded PPS resin / PA46 resin in Step S12 is 70/30 parts by weight, and the step of adding alumina as the fine powder A is omitted.
また、製造方法２の比較例５は、ステップＳ２０でホッパーからＰＡ４６樹脂を押出機の投入口に供給し、ステップＳ２１でＰＡ４６樹脂を３０重量部としたとき微粉体Ａとしてのアルミナが１重量部添加となるように計算して微粉体Ａとしてのアルミナをサイドフィーダーにて押出機に供給する。そして、押出機で混練することでステップＳ２２のＰＡ４６樹脂に微粉体Ａとしてのアルミナが添加された中間コンパウンドを得る。次に、この中間コンパウンドをステップＳ２３でペレット状とし、ステップＳ２４のＰＰＳ樹脂とともに押出機の投入口に供給し押出機で混練する。このときステップＳ２４のＰＰＳ樹脂は、ＰＰＳ樹脂／ＰＡ４６樹脂の重量比が７０／３０重量部となるように調整して供給される。そしてステップＳ２５でＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が７０／３０重量部で、ＰＡ４６樹脂側にＰＡ４６樹脂３０重量部に対してアルミナが１重量部添加されて、ＰＰＳ樹脂／ＰＡ４６樹脂複合材料としては、ＰＰＳ樹脂とＰＡ４６樹脂の総量１００重量部に対し微粉体Ａとしてのアルミナを１重量部含有するコンパウンドとなる。そして、得られたコンパウンドをステップＳ２６でカットし試料のペレットを形成する。 In Comparative Example 5 of the production method 2, PA46 resin is supplied from the hopper to the inlet of the extruder in step S20, and 1 part by weight of alumina as the fine powder A is 30 parts by weight of PA46 resin in step S21. It calculates so that it may become addition, and the alumina as the fine powder A is supplied to an extruder with a side feeder. And the intermediate compound by which the alumina as the fine powder A was added to PA46 resin of step S22 by kneading with an extruder is obtained. Next, this intermediate compound is formed into a pellet in step S23, and is supplied to the inlet of the extruder together with the PPS resin in step S24 and kneaded by the extruder. At this time, the PPS resin in step S24 is supplied by adjusting so that the weight ratio of PPS resin / PA46 resin is 70/30 parts by weight. In step S25, the blending ratio of PPS resin / PA46 resin is 70/30 parts by weight, and 1 part by weight of alumina is added to the PA46 resin side with respect to 30 parts by weight of PA46 resin. As a PPS resin / PA46 resin composite material, , A compound containing 1 part by weight of alumina as fine powder A with respect to 100 parts by weight of the total amount of PPS resin and PA46 resin. Then, the obtained compound is cut in step S26 to form a sample pellet.
そして、製造方法３の実施例は、ステップＳ３０でホッパーからＰＰＳ樹脂を押出機の投入口に供給し、ステップＳ３１でＰＰＳ樹脂を７０重量部としたとき微粉体Ａとしてのアルミナが１重量部添加となるように計算して微粉体としてのアルミナをサイドフィーダーにて押出機に供給する。そして、押出機で混練することでステップＳ３２のＰＰＳ樹脂に微粉体Ａとしてのアルミナが添加された中間コンパウンドを得る。次に、この中間コンパウンドをステップＳ３３でペレット状とし、ステップＳ３４のＰＡ４６樹脂とともに押出機の投入口に供給し押出機で混練する。このときステップＳ３４のＰＰＳ樹脂は、ＰＰＳ樹脂／ＰＡ４６樹脂の重量比が７０／３０重量部となるように調整して供給される。そしてステップＳ３５でＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が７０／３０重量部で、ＰＰＳ樹脂側にＰＰＳ樹脂７０重量部に対してアルミナが１重量部添加されて、ＰＰＳ樹脂／ＰＡ４６樹脂複合材料としては、ＰＰＳ樹脂とＰＡ４６樹脂の総量１００重量部に対し微粉体Ａとしてのアルミナを１重量部含有するコンパウンドとなる。そして、得られたコンパウンドをステップＳ３６でカットし試料のペレットを形成する。 In the embodiment of manufacturing method 3, PPS resin is supplied from the hopper to the inlet of the extruder in step S30, and 1 part by weight of alumina as fine powder A is added when 70 parts by weight of PPS resin is added in step S31. Alumina as a fine powder is supplied to the extruder through a side feeder. And the intermediate compound by which the alumina as the fine powder A was added to the PPS resin of step S32 is obtained by kneading with an extruder. Next, this intermediate compound is formed into a pellet in step S33, and is supplied to the charging port of the extruder together with the PA46 resin in step S34 and kneaded by the extruder. At this time, the PPS resin in step S34 is supplied by adjusting so that the weight ratio of PPS resin / PA46 resin is 70/30 parts by weight. In step S35, the blending ratio of PPS resin / PA46 resin is 70/30 parts by weight, and 1 part by weight of alumina is added to the PPS resin side with respect to 70 parts by weight of PPS resin. As a PPS resin / PA46 resin composite material, , A compound containing 1 part by weight of alumina as fine powder A with respect to 100 parts by weight of the total amount of PPS resin and PA46 resin. Then, the obtained compound is cut in step S36 to form a sample pellet.
比較例１乃至比較例５及び実施例を表にまとめると、次のようである。 It is as follows when the comparative example 1 thru | or the comparative example 5 and an Example are put together in a table | surface.
図４は、比較例１乃至比較例５及び実施例の流動長を示すものであり、比較例１のＰＰＳ樹脂は比較例２のＰＡ４６樹脂に比べて流動性が１／２以下と悪いことが分かる。これに対し、ＰＰＳ樹脂にＰＡ４６樹脂を複合化した比較例３乃至比較例５及び実施例は、流動性が向上し、流動特性の改良が得られている。したがって、ＰＰＳ樹脂を単独で使用したときに比べてＰＡ４６樹脂を複合化することで流動性が増して成形性が向上するため薄肉での成形が出来、製品の薄肉化が可能となる。 FIG. 4 shows the flow lengths of Comparative Examples 1 to 5 and Examples, and the PPS resin of Comparative Example 1 has a poor fluidity of 1/2 or less compared to the PA46 resin of Comparative Example 2. I understand. In contrast, Comparative Examples 3 to 5 and Examples in which PA46 resin is combined with PPS resin have improved fluidity and improved flow characteristics. Therefore, compared with the case where the PPS resin is used alone, the PA46 resin is compounded, so that the fluidity is increased and the moldability is improved, so that it is possible to mold with a thin wall and to reduce the thickness of the product.
図５に示す引張強度の結果から比較例１のＰＰＳ樹脂と比較例２のＰＡ４６樹脂の引張強度は略同等の結果であることから、ＰＰＳ樹脂とＰＡ４６樹脂の複合化によっても同等の強度を示すことが期待できるが、この点については、複合化した比較例３乃至比較例５及び実施例の結果が略同等の強度を示していることで確認された。ここで比較例３乃至比較例５及び実施例は重量部で７０／３０重量部で複合化しているが、ＰＡ４６樹脂の比率が５０重量部まで多くなるとと流動性や引張強度の低下を招くことになる。 From the results of the tensile strength shown in FIG. 5, the PPS resin of Comparative Example 1 and the PA46 resin of Comparative Example 2 have substantially the same tensile strength, and therefore the same strength is exhibited even when the PPS resin and PA46 resin are combined. Although this can be expected, this was confirmed by the fact that the composite results of Comparative Examples 3 to 5 and Examples showed substantially the same strength. Here, Comparative Examples 3 to 5 and Examples are combined in 70/30 parts by weight by weight, but when the ratio of PA46 resin increases to 50 parts by weight, fluidity and tensile strength are reduced. become.
そして、引張伸び率は、図６に示すように、比較例２のＰＡ４６樹脂及び実施例が他より２〜３倍以上伸び率がよいことが確認される。ここで引張伸び率は、引張試験において引張試験によって破断したときのチャック間距離に対する引張前のチャック間距離（本試験では２００ｍｍ）の比率で求められる値であり、引張伸び率が大きいほど破断するまでの伸びが大きいといえる。 As shown in FIG. 6, it is confirmed that the PA46 resin and the example of Comparative Example 2 have a tensile elongation of 2 to 3 times or more better than others. Here, the tensile elongation is a value determined by the ratio of the distance between chucks before tension (200 mm in this test) to the distance between chucks when fractured by a tensile test in a tensile test. It can be said that the growth up to is large.
以上の測定結果から、ＰＰＳ樹脂と同等の引張強度を有し、成形品の肉厚を薄肉化するためにはＰＰＳ樹脂にＰＡ４６樹脂を複合化させることで可能となる。しかし、ＰＰＳ樹脂と同等の引張強度を有し、破断時の伸びをＰＰＳ樹脂より大きくＰＡ４６樹脂に近づけるためには本発明の実施例のように１００ｎｍ未満の微粉体をＰＰＳ樹脂側に配する必要がある。
次に、ＰＰＳ樹脂／ＰＡ４６樹脂複合樹脂中での微粉体の存在状況について説明する。
From the above measurement results, it is possible to have a tensile strength equivalent to that of the PPS resin and to reduce the thickness of the molded product by combining the PA46 resin with the PPS resin. However, it has the same tensile strength as PPS resin, and in order to make elongation at break larger than PPS resin closer to PA46 resin, it is necessary to arrange fine powder of less than 100 nm on the PPS resin side as in the embodiment of the present invention. There is.
Next, the presence of fine powder in the PPS resin / PA46 resin composite resin will be described.
本実施例のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の断面を走査型電子顕微鏡(ＳＥＭ)で観測すると、図７の写真のようになっている。写真は目盛１０個の間隔が５μｍである。ここで、ＰＰＳ樹脂で形成される図７のＳＥＭ写真の灰色部分を海原の海部Ｂと呼び、また、斑点がある黒色系の略円形状はＰＡ４６樹脂であり、海部Ｂに存在するから島部Ｃと呼ぶ。
白い細かい点がアルミナのナノ粒子であり、中位径３３ｎｍの微粉体Ａである。この中位径３３ｎｍの微粉体Ａは、ＰＰＳ樹脂で形成される図７のＳＥＭ写真で海部Ｂのみに集中して分散されているが、ＰＰＳ樹脂で形成される図７のＳＥＭ写真で孔状の斑点がある黒色系の略円形状の島部Ｃには分散されていない。即ち、島部Ｃが受け入れを拒否しているかの如く形成されている。この孔状の斑点がある黒色系の略円形状の島部ＣはＰＡ４６樹脂である。
When the cross section of the PPS resin / PA46 resin composite material of this example is observed with a scanning electron microscope (SEM), it is as shown in the photograph of FIG. In the photograph, the interval of 10 graduations is 5 μm. Here, the gray part of the SEM photograph of FIG. 7 formed of PPS resin is called the sea part B of the sea, and the black, substantially circular shape with spots is the PA46 resin, and the island part because it exists in the sea part B. Call it C.
White fine dots are alumina nanoparticles and fine powder A having a median diameter of 33 nm. The fine powder A having a median diameter of 33 nm is concentrated and dispersed only in the sea part B in the SEM photograph of FIG. 7 formed of PPS resin, but in the SEM photograph of FIG. It is not dispersed in the black, substantially circular island portion C having spots. That is, it is formed as if the island C refuses to accept. The black, substantially circular island C having the hole-like spots is PA46 resin.
ここで、図７の島部Ｃの面積は、本実施例のＰＰＳ樹脂／ＰＡ４６樹脂複合材料のペレットを形成する樹脂の流れ方向に対して垂直の断面を採ったときに生ずるものである。本実施例のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の射出成型等による成形品の樹脂の流れ方向に沿って断面を形成したときには、図８のような形態となる。
島部Ｃの大きさは、平均直径で示されるが、平均直径１μｍ〜３０μｍの範囲である。この平均直径とは、各島部Ｃを円と見做した算術平均（相加平均）であり、まず、図７の写真の島部Ｃの縦長と横長の平均、即ち、[（縦長＋横長）／２]で計算した単純平均の直径距離を各々の島部Ｃで算出し、その各々の島部Ｃの積分値を島部Ｃの数で除したものである。
Here, the area of the island portion C in FIG. 7 occurs when a cross section perpendicular to the flow direction of the resin forming the PPS resin / PA46 resin composite material pellets of this example is taken. When the cross section is formed along the flow direction of the resin of the molded product by injection molding or the like of the PPS resin / PA46 resin composite material of this embodiment, the form is as shown in FIG.
Although the magnitude | size of the island part C is shown by an average diameter, it is the range of an average diameter of 1 micrometer-30 micrometers. The average diameter is an arithmetic average (arithmetic average) in which each island C is regarded as a circle. First, the average of the vertical and horizontal lengths of the island C in the photograph of FIG. ) / 2] is calculated for each island C, and the integral value of each island C is divided by the number of islands C.
また、ＰＡ４６樹脂からなる島部Ｃと島部Ｃとの間隔は、平均距離が１０μ以下となっている。この島部Ｃと島部Ｃとの間隔は、図８の両端矢印の直線のように、図７の断面の写真ばかりでなく、樹脂の流れ方向の断面からも測定できる。
このとき本発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、ＰＰＳ樹脂中に中位径１００ｎｍ未満の微粉体Ａを混練して形成したペレットを基準にしている。図７の写真では、島部Ｃと島部Ｃとの間隔が密であるが、その成形品では、島部Ｃと島部Ｃとの間隔が粗くなっていることが確認される。何れも、島部Ｃには白い細かい点のアルミナの微粉体Ａが殆ど存在していない。なお、図８の成形品の写真では、白い細かい点のアルミナの微粉体Ａが島部Ｃにも数個存在するように写っているが、これは切断の際に微粉体Ａが移動したものと推定されるが、その事実関係は不明である。しかし、ＰＰＳ樹脂のように集中して分布した状態にないことは明らかである。
The distance between the island portion C and the island portion C made of PA46 resin has an average distance of 10 μm or less. The distance between the island portion C and the island portion C can be measured not only from the photograph of the cross section of FIG. 7 but also from the cross section in the resin flow direction as shown by the straight line of the double-ended arrow in FIG.
At this time, the PPS resin / PA46 resin composite material of the present invention is based on pellets formed by kneading fine powder A having a median diameter of less than 100 nm in the PPS resin. In the photograph of FIG. 7, the distance between the island part C and the island part C is close, but in the molded product, it is confirmed that the distance between the island part C and the island part C is rough. In any case, the fine powder A of alumina with fine white spots is hardly present in the island portion C. In the photograph of the molded product in FIG. 8, it is shown that there are several white fine alumina powders A on the islands C. This is a result of the fine powders A moving during cutting. The fact is unclear. However, it is clear that the PPS resin is not concentrated and distributed.
図９の写真は、図８の成形品の写真におけるアルミナの微粉体Ａが島部Ｃにも数個存在するかの如く写っているので、更に１０倍走査型電子顕微鏡の倍率を上げて確認したものである。この写真の結果からは、ＰＰＳ樹脂に微粉体Ａが存在しているが、ＰＡ４６樹脂には微粉体Ａが存在していないと確認できる。
なお、図１０の写真は、成形品の板成物の表面の写真である。右下に１０μｍのスケールが表示されているが、この光学顕微鏡では、表層にも海部Ｂと島部Ｃが形成されているのが確認できる程度である。
The photograph in FIG. 9 is shown as if there are several alumina fine powders A in the island part C in the photograph of the molded product in FIG. 8, so confirm by further increasing the magnification of the 10 × scanning electron microscope. It is a thing. From the result of this photograph, it can be confirmed that the fine powder A exists in the PPS resin, but the fine powder A does not exist in the PA46 resin.
In addition, the photograph of FIG. 10 is a photograph of the surface of the plate product of a molded product. A scale of 10 μm is displayed in the lower right, but with this optical microscope, it is only possible to confirm that the sea part B and the island part C are also formed on the surface layer.
即ち、図７の写真を説明のために概念的に図示すると、図１１及び図１２に示すようになる。図１１は本発明の実施の形態のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の試料として形成したペレットの断面写真に相当する概念図であり、図１２は図７のペレットの断面写真とは異なる状態を示す概念図である。
ＰＰＳ樹脂で形成される海原の海部Ｂは、全体に広がっている。略円形状はＰＡ４６樹脂であり、海部Ｂに存在する島部Ｃとなっている。ここで、黒い細かい点が微粉体Ａである。この微粉体Ａは、図７の写真の概念図の図１１に示すように、ＰＰＳ樹脂で形成される海部Ｂのみに集中して分散されている。
微粉体Ａが全体に分散するものであれば、図１２のように、略円形状の島部Ｃにも分散さるべきであるが、図７のＳＥＭ写真で確認されるように、図１２のようにはなっていない。即ち、微粉体ＡはＰＰＳ樹脂で形成される海原の海部Ｂに集中して存在している。この現象は、予め微粉体ＡをＰＰＳ樹脂に含有させた後、ＰＡ４６樹脂と複合化する製造方法によるものである。つまり微粉体ＡはＰＰＳ樹脂とＰＡ４６樹脂を複合化しても事前に含有しているＰＰＳ樹脂中に留まり、ＰＡ４６樹脂中への移行が起こらないからである。
That is, if the photograph of FIG. 7 is conceptually illustrated for explanation, it is as shown in FIGS. FIG. 11 is a conceptual diagram corresponding to a cross-sectional photograph of a pellet formed as a sample of the PPS resin / PA46 resin composite material according to the embodiment of the present invention, and FIG. 12 shows a state different from the cross-sectional photograph of the pellet of FIG. It is a conceptual diagram.
The sea part B of the sea formed with PPS resin spreads throughout. The substantially circular shape is PA46 resin, which is an island C existing in the sea B. Here, the fine black dots are the fine powder A. As shown in FIG. 11 of the conceptual diagram of the photograph of FIG. 7, the fine powder A is concentrated and dispersed only in the sea part B formed of PPS resin.
If the fine powder A is dispersed throughout, it should be dispersed in the substantially circular island C as shown in FIG. 12, but as confirmed by the SEM photograph in FIG. It's not like that. That is, the fine powder A is concentrated in the sea part B of the sea formed of PPS resin. This phenomenon is due to the manufacturing method in which the fine powder A is previously contained in the PPS resin and then combined with the PA46 resin. That is, even if the fine powder A is combined with the PPS resin and the PA46 resin, the fine powder A remains in the PPS resin contained in advance and does not migrate into the PA46 resin.
上記実施例では、ＰＰＳ樹脂とＰＡ４６樹脂の重量比率を７０／３０重量部としてのデータを添付しているが、発明者らの実験によると、６０／４０〜８０／２０重量部の範囲内であれば実用的にＰＰＳ樹脂単独よりも特性がよいと評価できることを確認した。そして５０／５０重量部ではかえって強度低下を招くことも確認できている。つまりＰＡ４６樹脂に対するＰＰＳ樹脂の重量比率が５０％を超えるとＰＰＳ樹脂と同等の引張強度を有したまま、流動性と引張伸び率を向上させることができるが、重量部以下ではＰＡ４６樹脂量が多くなりすぎて複合化のバランスが崩れ強度低下を招き、また重量部を超えるとＰＰＳ樹脂の特性が強くなり過ぎて特性の向上が図れなくなる。
このようにＰＡ４６樹脂に対するＰＰＳ樹脂の重量比率が５０％を越えて８０％以下の範囲内のとき、薄肉製品が射出成型でき、ＰＰＳ樹脂並みの耐熱性であり、延性、靭性に富む安定した材料となる。
In the above examples, data with the weight ratio of PPS resin and PA46 resin as 70/30 parts by weight is attached, but according to the experiments by the inventors, within the range of 60/40 to 80/20 parts by weight. It has been confirmed that if it is present, it can be evaluated that the characteristics are practically better than the PPS resin alone. It has also been confirmed that 50/50 parts by weight causes a decrease in strength. In other words, if the weight ratio of the PPS resin to the PA46 resin exceeds 50%, the fluidity and the tensile elongation can be improved while maintaining the same tensile strength as the PPS resin. If the amount of the PPS resin exceeds the weight, the properties of the PPS resin become too strong and the properties cannot be improved.
Thus, when the weight ratio of the PPS resin to the PA46 resin is in the range of more than 50% and not more than 80%, a thin product can be injection-molded, and it has a heat resistance comparable to that of the PPS resin, and is a stable material rich in ductility and toughness. It becomes.
また、ＰＰＳ樹脂７０重量部に対し、中位径３３ｎｍの微粉体を１重量部混練した事例を示したが、発明者らの実験によると、混練する量はＰＰＳ樹脂の配合量によって決定され最小はＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が８０／２０重量部のとき、１重量部（ＰＰＳ樹脂１００重量部に対して１重量部）であり、最大はＰＰＳ樹脂／ＰＡ４６樹脂の配合割合が６０／４０重量部のときで５重量部（ＰＰＳ樹脂１００重量部に対して９重量部）であることが確認された。 In addition, an example in which 1 part by weight of a fine powder having a median diameter of 33 nm was kneaded with 70 parts by weight of PPS resin. According to experiments by the inventors, the amount to be kneaded is determined by the blending amount of the PPS resin and is minimum. When the blending ratio of PPS resin / PA46 resin is 80/20 parts by weight, it is 1 part by weight (1 part by weight with respect to 100 parts by weight of PPS resin), and the maximum blending ratio of PPS resin / PA46 resin is 60 / It was confirmed that it was 5 parts by weight (9 parts by weight with respect to 100 parts by weight of PPS resin) at 40 parts by weight.
ＰＰＳ樹脂に配する微粉体Ａは、ＰＰＳ樹脂の結晶化を促進させるための結晶核剤として働かせるためにＰＰＳ樹脂中に含有させている。つまりＰＰＳ樹脂とＰＡ４６樹脂は結晶化に差があるが、ＰＰＳ樹脂に微粉体Ａを含有させることでＰＰＳ樹脂の結晶化を制御してＰＡ４６樹脂の結晶化に同期させることができ両樹脂の特性を併せ持った複合材料とすることが可能となる。ここで、微粉体Ａの配合量が少ないと結晶核剤としての働きが少なく所望の特性が得ることが困難となり、微粉体Ａの配合量が多いと異物として働き、返って特性の低下を招くことになる。したがって、中位径１００ｎｍ未満の微粉体であればＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部の微粉体Ａは異物として作用せずに結晶化を促進させることができる。 The fine powder A distributed in the PPS resin is contained in the PPS resin in order to function as a crystal nucleating agent for promoting crystallization of the PPS resin. In other words, there is a difference in crystallization between PPS resin and PA46 resin, but by adding fine powder A to PPS resin, crystallization of PPS resin can be controlled and synchronized with crystallization of PA46 resin. It becomes possible to make a composite material having both. Here, when the blending amount of the fine powder A is small, the function as a crystal nucleating agent is small and it is difficult to obtain desired characteristics, and when the blending amount of the fine powder A is large, it acts as a foreign substance and causes a decrease in characteristics. It will be. Therefore, if the fine powder has a median diameter of less than 100 nm, 1 to 9 parts by weight of fine powder A with respect to 100 parts by weight of the PPS resin can promote crystallization without acting as a foreign substance.
ここで微粉体Ａは結晶核剤となりえる微粉体であれば特に限定されるものではないが、中位径３０〜５０ｎｍの範囲内のアルミナとしたものでは、特に、複合化（アロイ化）が安定して行われることが確認された。そして、アルミナの持つ熱伝導性等の特性によってＰＰＳ樹脂／ＰＡ４６樹脂複合材料自体の熱伝導性等の向上も見込まれる。
また、この微粉体Ａは、表面処理した粒体とすることもできる。特に、微粉体Ａの表面にコーティングした材料とすると、コーティング材料に多種多様のものが使用でき、そして、コーティング材料の変化及びその芯材の選択の自由度が高くなる。
Here, the fine powder A is not particularly limited as long as it is a fine powder that can be a crystal nucleating agent. However, in the case of alumina having a median diameter of 30 to 50 nm, the composite (alloying) is particularly important. It was confirmed that it was performed stably. And the improvement of the thermal conductivity etc. of PPS resin / PA46 resin composite material itself is also anticipated with the characteristics, such as thermal conductivity which an alumina has.
The fine powder A can also be a surface-treated granule. In particular, when the material is coated on the surface of the fine powder A, a wide variety of coating materials can be used, and the degree of freedom in changing the coating material and selecting the core material is increased.
本実施例のＰＰＳ樹脂／ＰＡ４６樹脂複合材料のＰＡ４６樹脂からなる島部Ｃと島部Ｃとの間隔は、平均距離が１０μ以下としたものである。
ここで、本発明の説明において、平均距離とは、算術平均（相加平均）であり、島部Ｃと島部Ｃとの相互間隔の距離の積分値を島部Ｃと島部Ｃとの相互間隔の数で除したものである。勿論、発明者らの確認によると、試料用のペレットでは、実施例のＰＰＳ樹脂／ＰＡ４６樹脂複合材料のＰＡ４６樹脂からなる島部Ｃと島部Ｃとの間隔は、１０μ以下としても殆ど問題はない。但し、それを用いて製品の成形を行うと、そのばらつきのために、１０μを超える場合が出てくる。そこで、特定を明確にするため、島部Ｃと島部Ｃとの間隔を１０μ以下と特定したものである。
The distance between the island portion C and the island portion C made of the PA46 resin of the PPS resin / PA46 resin composite material of this example is such that the average distance is 10 μm or less.
Here, in the description of the present invention, the average distance is an arithmetic average (arithmetic average), and an integrated value of the distance between the island part C and the island part C is calculated as an integral value between the island part C and the island part C. Divided by the number of mutual intervals. Of course, according to the confirmation by the inventors, in the pellet for the sample, there is almost no problem even if the distance between the island part C and the island part C made of PA46 resin of the PPS resin / PA46 resin composite material of the example is 10 μm or less. Absent. However, when a product is molded using the same, there are cases where it exceeds 10 μm due to the variation. Therefore, in order to clarify the specification, the interval between the island part C and the island part C is specified as 10 μm or less.
このように、本発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の製造方法は、ＰＰＳ樹脂／ＰＡ４６樹脂複合材料中のＰＰＳ樹脂の体積がＰＡ４６樹脂の体積より大きく、ＰＰＳ樹脂とＰＡ４６樹脂の重量比率を６０／４０〜８０／２０重量部の範囲内とし、先にＰＰＳ樹脂と中位径１００ｎｍ以下の微粉体ＡをＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部を混練し、次いで、ＰＡ４６樹脂を加えて混練し、得られた材料の構造として海島構造を有している。そして、海部ＢとなるＰＰＳ樹脂側に微粉末Ａが集中して存在し、また、ＰＡ４６樹脂からなる島部Ｃの大きさは平均直径が１μ〜３０μとしたものである。 Thus, in the method for producing the PPS resin / PA46 resin composite material of the present invention, the volume of the PPS resin in the PPS resin / PA46 resin composite material is larger than the volume of the PA46 resin, and the weight ratio of the PPS resin to the PA46 resin is set to 60. First, the PPS resin and the fine powder A having a median diameter of 100 nm or less are kneaded with 1 to 9 parts by weight with respect to 100 parts by weight of the PPS resin. A resin is added and kneaded, and the resulting material has a sea-island structure. The fine powder A is concentrated on the PPS resin side serving as the sea part B, and the size of the island part C made of the PA46 resin has an average diameter of 1 to 30 μm.
特に、発明者らは、ＰＰＳ樹脂とＰＡ４６樹脂を混ぜ合わせ、５０ｎｍ以下の微粉末ＡをＰＰＳ樹脂側に集中的に添加すると、引張強度の低下を抑えて、得られた材料の引張伸び率が向上することを確認した。したがって、このＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、薄肉製品の射出成型ができ、ＰＰＳ樹脂並みの耐熱性、耐薬品性、延性、靭性が必要な部品、例えば、自動車部品、家電部品、また、同じくＰＰＳ樹脂であるが、強化材、添加剤等で補強や新たな機能を付与するためのベース樹脂としても使用できる。 In particular, when the inventors mixed PPS resin and PA46 resin and concentratedly added fine powder A of 50 nm or less to the PPS resin side, the tensile elongation of the obtained material was reduced while suppressing the decrease in tensile strength. Confirmed to improve. Therefore, this PPS resin / PA46 resin composite material can be used for injection molding of thin-walled products, and parts that require heat resistance, chemical resistance, ductility, and toughness similar to PPS resins, such as automobile parts, home appliance parts, Although it is a PPS resin, it can also be used as a base resin for reinforcing or adding a new function with a reinforcing material or additive.
上記実施例では、ＰＰＳ樹脂／ＰＡ４６樹脂複合材料中のＰＰＳ樹脂の体積がＰＡ４６樹脂の体積より大きい関係があり、ＰＰＳ樹脂とＰＡ４６樹脂の重量比率を６０／４０〜８０／２０重量部の範囲内とし、先にＰＰＳ樹脂と中位径１００ｎｍ未満の微粉体ＡをＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部を混練し、次いで、ＰＡ４６樹脂を加えて混練し、得られた材料の構造として海島構造を有しており、海部ＢとなるＰＰＳ樹脂側に微粉末Ａが集中して存在し、また、ＰＡ４６樹脂からなる島部Ｃの大きさは平均直径が１μ〜３０μとしたものであるが、図７の実施例の形態を維持できた構造であればよい。 In the above examples, the volume of the PPS resin in the PPS resin / PA46 resin composite material is larger than the volume of the PA46 resin, and the weight ratio of the PPS resin to the PA46 resin is in the range of 60/40 to 80/20 parts by weight. First, the PPS resin and fine powder A having a median diameter of less than 100 nm are kneaded with 1 to 9 parts by weight with respect to 100 parts by weight of the PPS resin, and then the PA46 resin is added and kneaded to obtain the obtained material. As a structure of the sea part, the fine powder A is concentrated on the PPS resin side which becomes the sea part B, and the size of the island part C made of PA46 resin has an average diameter of 1 μ to 30 μ. However, any structure that can maintain the form of the embodiment of FIG.
即ち、本発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、体積比でＰＰＳ樹脂＞ＰＡ４６樹脂の関係があり、ＰＰＳ樹脂とＰＡ４６樹脂の重量比率を６０／４０〜８０／２０重量部の範囲内とし、それらＰＰＳ樹脂に対して中位径１００ｎｍ未満の微粉体をＰＰＳ樹脂１００重量部に対して１重量部乃至９重量部を混練し、得られた材料の構造として海島構造を有しており、前記海部ＢとなるＰＰＳ樹脂側に微粉末Ａが集中して存在し、また、前記ＰＡ４６樹脂からなる島部Ｃの大きさは平均直径が１μ〜３０μとした実施例とすることができる。 That is, the PPS resin / PA46 resin composite material of the present invention has a volume ratio of PPS resin> PA46 resin, and the weight ratio of the PPS resin to the PA46 resin is in the range of 60/40 to 80/20 parts by weight. A fine powder having a median diameter of less than 100 nm with respect to the PPS resin is kneaded with 1 to 9 parts by weight with respect to 100 parts by weight of the PPS resin, and the resulting material has a sea-island structure, The fine powder A is concentrated on the PPS resin side that becomes the sea part B, and the size of the island part C made of the PA46 resin can be set to an average diameter of 1 to 30 μm.
特に、発明者らは、ＰＰＳ樹脂とＰＡ４６樹脂を混ぜ合わせ、５０ｎｍ以下の微粉末ＡをＰＰＳ樹脂に集中的に添加すると引張伸び率が向上する事実を確認し、流動性と引張伸び率が良好なＰＰＳ樹脂／ＰＡ４６樹脂複合材料を得た。ＰＰＳ樹脂／ＰＡ４６樹脂複合材料は、薄肉製品の射出成型ができ、ＰＰＳ樹脂並みの耐熱性、耐薬品性、延性、靭性が必要な部品、例えば、自動車部品、家電部品、また、同じくＰＰＳ樹脂であるが、強化材、添加剤等で補強や新たな機能を付与するためのベース樹脂としても使用ができる。 In particular, the inventors confirmed that the tensile elongation is improved by mixing PPS resin and PA46 resin and adding fine powder A of 50 nm or less intensively to the PPS resin, and the fluidity and tensile elongation are good. PPS resin / PA46 resin composite material was obtained. PPS resin / PA46 resin composite material can be used for injection molding of thin-walled products, and parts that require heat resistance, chemical resistance, ductility, and toughness similar to PPS resin, such as automobile parts, home appliance parts, and PPS resin. However, it can be used as a base resin for reinforcing or adding a new function with a reinforcing material or additive.
微粉体Ａは結晶核剤の効果を有する材料が使用できるが、本発明を実施する場合には、微粉体Ａは、表面処理した粒体とすることによって如何なる材料とすることもできる。特に、微粉体Ａの表面にコーティングした材料では、コーティング材料に多種多様のものが使用でき、また、コーティング材料の変化及びその芯材の選択の自由度が高くなり、本発明のＰＰＳ樹脂／ＰＡ４６樹脂複合材料の比重も任意に設定できる。また、ナノバルーン等を使用することもできる。
また、ＰＰＳ樹脂が海部Ｂを構成しているから接合性がよく、他の樹脂のベース樹脂としても使用可能であり、薄肉製品でＰＰＳ樹脂と同等以上の耐熱性、耐薬品性、延性、靭性が必要な自動車部品、家電部品及び製品、同じくＰＰＳ樹脂部品として、強化材、添加剤等で補強や新たな機能を付与するためのベース樹脂として使用されるＰＰＳ樹脂とＰＡ４６樹脂の複合材料となる。
As the fine powder A, a material having the effect of a crystal nucleating agent can be used. However, when the present invention is carried out, the fine powder A can be any material by forming a surface-treated granule. In particular, in the material coated on the surface of the fine powder A, a wide variety of coating materials can be used, and the degree of freedom in changing the coating material and the core material is increased. The specific gravity of the resin composite material can also be set arbitrarily. A nanoballoon or the like can also be used.
In addition, PPS resin constitutes sea part B, so it has good bondability and can be used as a base resin for other resins. It is a thin-walled product with heat resistance, chemical resistance, ductility, and toughness equivalent to or better than PPS resin. Is a composite material of PPS resin and PA46 resin that is used as a base resin for reinforcing or adding new functions with reinforcing materials, additives, etc. .
Ａ 微粉体
Ｂ 海部
Ｃ 島部
A Fine powder B Sea part C Island part
Claims (5)
前記ＰＰＳ樹脂が海島構造の海部となり、前記海部の前記ＰＰＳ樹脂側に中位径１００ｎｍ未満の微粉体が配されていることを特徴とするＰＰＳ樹脂／ＰＡ４６樹脂複合材料。 A polymer alloy having a sea-island structure prepared by melt-kneading PPS resin (polyphenylene sulfide resin) and PA46 resin (polyamide 46 resin),
The PPS resin / PA46 resin composite material, wherein the PPS resin becomes a sea part having a sea-island structure, and fine powder having a median diameter of less than 100 nm is arranged on the PPS resin side of the sea part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012141754A JP5916532B2 (en) | 2012-06-25 | 2012-06-25 | Polyphenylene sulfide resin / polyamide 46 resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012141754A JP5916532B2 (en) | 2012-06-25 | 2012-06-25 | Polyphenylene sulfide resin / polyamide 46 resin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014005361A true JP2014005361A (en) | 2014-01-16 |
| JP5916532B2 JP5916532B2 (en) | 2016-05-11 |
Family
ID=50103391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012141754A Active JP5916532B2 (en) | 2012-06-25 | 2012-06-25 | Polyphenylene sulfide resin / polyamide 46 resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5916532B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130112611A (en) * | 2012-04-04 | 2013-10-14 | 삼성전자주식회사 | Data receiver device and testing method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551532A (en) * | 1991-01-14 | 1993-03-02 | Kureha Chem Ind Co Ltd | Composition consisting of polyarylene sulfide and polyamide |
| JPH0959511A (en) * | 1995-08-18 | 1997-03-04 | Tokai Rubber Ind Ltd | Thermally conductive resin composition |
| JP2001302918A (en) * | 1999-10-12 | 2001-10-31 | Toray Ind Inc | Resin structure and its use |
| JP2003113307A (en) * | 2001-07-31 | 2003-04-18 | Toray Ind Inc | Polyphenylene sulfide resin composition and method for producing the same |
| JP2005139347A (en) * | 2003-11-07 | 2005-06-02 | Toray Ind Inc | Thermoplastic resin composition and method for producing the same |
| JP2009263476A (en) * | 2008-04-24 | 2009-11-12 | Otsuka Chem Co Ltd | Highly heat conductive resin composition |
-
2012
- 2012-06-25 JP JP2012141754A patent/JP5916532B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551532A (en) * | 1991-01-14 | 1993-03-02 | Kureha Chem Ind Co Ltd | Composition consisting of polyarylene sulfide and polyamide |
| JPH0959511A (en) * | 1995-08-18 | 1997-03-04 | Tokai Rubber Ind Ltd | Thermally conductive resin composition |
| JP2001302918A (en) * | 1999-10-12 | 2001-10-31 | Toray Ind Inc | Resin structure and its use |
| JP2003113307A (en) * | 2001-07-31 | 2003-04-18 | Toray Ind Inc | Polyphenylene sulfide resin composition and method for producing the same |
| JP2005139347A (en) * | 2003-11-07 | 2005-06-02 | Toray Ind Inc | Thermoplastic resin composition and method for producing the same |
| JP2009263476A (en) * | 2008-04-24 | 2009-11-12 | Otsuka Chem Co Ltd | Highly heat conductive resin composition |
Non-Patent Citations (1)
| Title |
|---|
| 林小太郎, 中津美智代, 近藤幸江, 小高忠男, 森坂鶴江: "ポリマーアロイの研究開発 PPSとPAの溶融混練アロイの研究 (第3報) SEMによる構造解析", 福井県工業技術センター研究報告書, vol. No.9(1992), JPN6015045179, November 1993 (1993-11-01), JP, pages 46 - 50, ISSN: 0003289552 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130112611A (en) * | 2012-04-04 | 2013-10-14 | 삼성전자주식회사 | Data receiver device and testing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5916532B2 (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101309738B1 (en) | Polymer/conductive filler composite with high electrical conductivity and the preparation method thereof | |
| JP6319287B2 (en) | Resin composition for high dielectric constant material, molded product containing the same, and coloring masterbatch | |
| KR20100075878A (en) | Heat-processable thermally conductive polymer composition | |
| JPWO2012050083A1 (en) | High thermal conductive resin molding and method for producing the same | |
| JP2008088377A (en) | Polyamide resin composition for breaker box body and breaker box body | |
| JP6527010B2 (en) | Thermally conductive resin molding and method for producing the same | |
| JPWO2009044884A1 (en) | Glass-containing molding pellets and method for producing the same | |
| JP2006097006A (en) | Method for producing electrically conductive resin composition and application thereof | |
| WO2019079471A1 (en) | Thermally conductive polymer based filament | |
| JP2008024924A (en) | Binding band | |
| CN104968727B (en) | Electronic apparatus | |
| JP5359825B2 (en) | Thermally conductive resin composition | |
| JP2008007753A (en) | Polyamide resin composition and molded product thereof | |
| JP2009155359A (en) | Thermoplastic resin molding | |
| JP5916532B2 (en) | Polyphenylene sulfide resin / polyamide 46 resin composite material | |
| JP2016017086A (en) | Electrically insulating thermally conductive resin composition and method for producing the same | |
| JP2007016221A (en) | Resin material for molding and molded product | |
| KR20170112980A (en) | Electro-conductive polymer composite and resin composition having improved impact strength and method for preparing the same | |
| KR101380841B1 (en) | Method for preparing the molded parts of heat resistant and thermally conductive polymer compositions and the molded parts of heat resistant and thermally conductive polymer compositions prepared by the same method | |
| CN108070158A (en) | A kind of PP composite material of low post-shrinkage ratio and preparation method thereof | |
| JP5981759B2 (en) | Method for producing thermoplastic resin composition | |
| JP2013203869A (en) | Polyamide resin composition | |
| JP2017200986A (en) | Thermoplastic resin composition, molded article, and method for producing molded article | |
| US20170287585A1 (en) | Electroconductive Resin Composite and Electroconductive Resin Composition Having Excellent Impact Strength, and Method of Producing the Same | |
| JP2019014163A (en) | Injection molded article and production method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20141204 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20151021 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151110 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160405 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160405 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5916532 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |