JPH02255760A - Resin composition having high specific gravity - Google Patents
Resin composition having high specific gravityInfo
- Publication number
- JPH02255760A JPH02255760A JP7952289A JP7952289A JPH02255760A JP H02255760 A JPH02255760 A JP H02255760A JP 7952289 A JP7952289 A JP 7952289A JP 7952289 A JP7952289 A JP 7952289A JP H02255760 A JPH02255760 A JP H02255760A
- Authority
- JP
- Japan
- Prior art keywords
- specific gravity
- resin composition
- high specific
- metal powder
- resin
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 230000005484 gravity Effects 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004918 carbon fiber reinforced polymer Substances 0.000 abstract description 19
- 239000004677 Nylon Substances 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- 229920001778 nylon Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- XHWQYYPUYFYELO-UHFFFAOYSA-N ditridecyl phosphite Chemical compound CCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCC XHWQYYPUYFYELO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920006380 polyphenylene oxide Polymers 0.000 description 6
- 239000012756 surface treatment agent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- -1 Methyl-1- butyl Chemical group 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 1
- SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101000994880 Homo sapiens Inorganic pyrophosphatase 2, mitochondrial Proteins 0.000 description 1
- 102100034415 Inorganic pyrophosphatase 2, mitochondrial Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高比重樹脂組成物に係り、特に、炭素繊維−樹
脂複合材料からなる部材の質量体の原料として好適な高
比重樹脂組成物に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a high specific gravity resin composition, and particularly relates to a high specific gravity resin composition suitable as a raw material for a mass body of a member made of a carbon fiber-resin composite material. .
［従来の技術］
炭素繊維−樹脂複合材料（以下、ＣＦＲＰと称す）は、
軽量で比強度が大きく、耐食性や耐衝撃性に優れる等の
利点を有しているため、航空・宇宙材料やスポーツ・レ
ジャー用品等、幅広い分野で利用されている。しかしな
がら、ゴルフクラブヘッドに代表されるように、用途に
よってはＣＦＲＰの軽量である点が欠点となるものもあ
る。このような場合には、ＣＦＲＰからなる部材（以下
、ＣＦＲＰ部材と称す）に質量体を内包させて、ＣＦＲ
Ｐの他の利点は活かしつつ重量化を図っている。[Prior art] Carbon fiber-resin composite material (hereinafter referred to as CFRP) is
Because it has the advantages of being lightweight, having a high specific strength, and having excellent corrosion resistance and impact resistance, it is used in a wide range of fields such as aerospace materials and sports and leisure goods. However, the light weight of CFRP may be a disadvantage in some applications, as exemplified by golf club heads. In such a case, a mass body is included in a member made of CFRP (hereinafter referred to as a CFRP member), and the CFR
The weight is reduced while taking advantage of the other advantages of P.
質量体の原料としては、従来よりポリアミド系樹脂に金
属粉を分散させてなる高比重樹脂組成物が用いられてお
り、ポリアミド系樹脂に分散させる金属粉の表面は、防
錆、成形時の流動性の確保および成形品の強度保持を目
的として、シラン系カップリング剤により表面処理を施
している。As a raw material for the mass body, a high-density resin composition made by dispersing metal powder in polyamide resin has traditionally been used. In order to ensure the properties and maintain the strength of the molded product, the surface is treated with a silane coupling agent.
ＣＦＲＰ部材に質量体を内包させることによりこのＣＦ
ＲＰ部材の重量化を図る場合、ゴルフクラブヘッドのよ
うに高速移動体であって耐衝撃性が要求される部材にあ
っては、質量体についても耐衝撃性が要求されるととも
に、衝撃によりＣＦＲＰと質量体とが剥離しないよう、
ＣＦＲＰと質量体との間には高い接着性が要求される。By incorporating a mass body into the CFRP member, this CF
When trying to increase the weight of the RP member, in the case of a member such as a golf club head that moves at high speed and requires impact resistance, the mass body must also have impact resistance, and the impact may cause the CFRP to To prevent separation between the body and the mass body,
High adhesiveness is required between the CFRP and the mass body.
［発明が解決しようとする課題］
しかしながら、従来より用いられている質量体では、耐
衝撃性については実用−Ｌ十分な特性（例えばゴルフク
ラブヘッドの場合、シャルピー衝撃強度（ノツチなし７
）で１４ ｋｇ−ｃｍ／ ｃｄ以」二）が得られている
が、ＣＦＲＰとの接着性については、実用」二十分な特
性（例えばゴルフクラブへ・ソドの場合、圧縮剪断接着
強度で安全率を加味して１００ｋｇ／ｃＩ＃以上）を得
るためには、接着表面の細心なサンディング等、接着工
程で手間がかかるという問題があった。このため、高速
移動体であって耐衝撃性が要求されるＣＦＲＰ部材の重
量化を図るにあたっては、耐衝撃性に優れるとともに、
簡易な接着作業によりＣＦＲＰと高い接着強度で接着す
る質ｍ体の開発が望まれている。[Problems to be Solved by the Invention] However, the mass bodies conventionally used have sufficient impact resistance for practical use (for example, in the case of golf club heads, Charpy impact strength (notched 7
), but the adhesion with CFRP is said to be sufficient for practical use (for example, in the case of golf clubs and blades, it is safe due to the compressive shear adhesive strength). In order to obtain a bonding rate of 100 kg/cI# or more), there was a problem in that the bonding process required careful sanding of the bonding surface, which required time and effort. For this reason, when trying to increase the weight of a CFRP member that is a high-speed moving body and requires impact resistance, it is necessary to
It is desired to develop a material that can be bonded to CFRP with high adhesive strength through simple bonding operations.
したかて本発明の目的は、耐衝撃性に優れるとともに簡
易な接着作業によりＣＦＲＰと高い接着強度で接着する
質量体の原料として好適な、高比重樹脂組成物を提供す
ることにある。Therefore, an object of the present invention is to provide a high specific gravity resin composition that has excellent impact resistance and is suitable as a raw material for a mass body that can be bonded to CFRP with high adhesive strength through a simple bonding operation.
［課題を解決するための手段］
本発明は上記目的を達成するためになされたもので、本
発明の高比重樹脂組成物は、チタネート系カップリング
剤により表面処理された金属粉と、ポリアミド系樹脂と
を含み、前記金属粉と前記ポリアミド系樹脂との総量に
対する前記金属粉の配合割合が２５〜５０ｖｏ１％であ
ることを特徴とするものである。[Means for Solving the Problems] The present invention has been made to achieve the above object, and the high specific gravity resin composition of the present invention comprises a metal powder surface-treated with a titanate coupling agent and a polyamide-based resin, and the blending ratio of the metal powder to the total amount of the metal powder and the polyamide resin is 25 to 50 vol%.
本発明に用いるチタネート系カップリング剤は、下記一
般式
％式％
（ただし、Ｒ１は炭素数１〜１２個の有機基（不飽和結
合やエーテル結合を含んでいてもよい）であり、Ｒ１は
炭素数５〜１６個の有機基であり、Ｒ１とＲ２は同一で
あっても異なっていてもよい）で表されろ６配位タイプ
のチタネート系カップリング剤であることが好ましい。The titanate coupling agent used in the present invention has the following general formula % (where R1 is an organic group having 1 to 12 carbon atoms (which may contain an unsaturated bond or an ether bond), and R1 is It is preferably a hexacoordination type titanate coupling agent, which is an organic group having 5 to 16 carbon atoms, and R1 and R2 may be the same or different.
このようなチタネート系カップリング剤としては、下記
構造式（Ｉ）で表されるテトラオクチルビス（ジトリデ
シルホスファイト）チタネート、下記構造式（ＩＩ）で
表されるテトラ（２，２−ジアリルオキシメチル−１−
ブチル）ビス（ジトリデシルホスファイト）チタネート
、下記構造式（ＩＩＩ）で表されるテトライソプロピル
ビス（ジオクチルホスファイト）チタネート等が挙げら
れる。Examples of such titanate-based coupling agents include tetraoctylbis(ditridecylphosphite) titanate represented by the following structural formula (I), and tetra(2,2-diallyloxy) represented by the following structural formula (II). Methyl-1-
butyl) bis(ditridecyl phosphite) titanate, tetraisopropyl bis(dioctyl phosphite) titanate represented by the following structural formula (III), and the like.
（Ｃ，に−０１Ｔｉ（Ｐ（０−Ｃ＋５Ｈ２７）ｚ ＯＨ
コ、 ・・・ （Ｉ）・・・（ｎ）
上記６配位タイプのチタネート系カップリング剤により
表面処理を施す金属粉としては、Ｆｅ、Ｚｎ、Ｓｎ、Ｐ
ｂＳＣｕ等の金属単体またはその酸化物の粉末、あるい
はこれら金属単体またはその酸化物からなる合金の粉末
を用いることができ、経済性を考慮すると鉄（Ｆｅ）粉
が最も好ましい。(C, ni-01Ti(P(0-C+5H27)z OH
(I)...(n) The metal powders to be surface treated with the above six-coordination type titanate coupling agent include Fe, Zn, Sn, and P.
Powders of metals such as bSCu or their oxides, or powders of alloys made of these metals or their oxides can be used, and iron (Fe) powder is most preferred in terms of economy.
金属粉の粒径は、０．１〜３００μｍであることが好ま
しく、特に０． １〜７５μｍであることが好ましい。The particle size of the metal powder is preferably 0.1 to 300 μm, particularly 0.1 to 300 μm. It is preferable that it is 1-75 micrometers.
金属粉の粒径が０．１μｍより小さいと成形時の流動性
が低下するため、また３００μｍを超えると得られた高
比重樹脂組成物を原料とする成形品の耐衝撃性が低下す
るとともに成形機を傷つけるため、ともに実用上好まし
くない。If the particle size of the metal powder is smaller than 0.1 μm, the fluidity during molding will decrease, and if it exceeds 300 μm, the impact resistance of the molded product made from the obtained high specific gravity resin composition will decrease and the molding will be difficult. Both are undesirable from a practical standpoint as they damage the machine.
金属粉の表面処理を行うにあたっては、チタネート系カ
ップリング剤の使用量を、金属粉に対して０．１〜３．
０ｗｔ％とすることが好ましく、特に０．２〜２．
Ｏｖｔ％とすることが好ましい。チタネート系カップリ
ング剤の使用量が、０． １ｗｔ％未満であると、得ら
れた高比重樹脂組成物を原料とする成形品とＣＦＲＰと
の接着性が低下するため、また３、 ０ｗｔ％を超える
と、得られた高比重樹脂組成物を原料とする成形品の耐
衝撃性が低下するため、ともに実用」二好ましくない。When performing surface treatment on metal powder, the amount of titanate coupling agent to be used is 0.1 to 3.
It is preferable to set it as 0wt%, especially 0.2-2.
It is preferable to set it as Ovt%. The amount of titanate coupling agent used is 0. If it is less than 1 wt%, the adhesion between the molded product made from the obtained high specific gravity resin composition and CFRP will decrease, and if it exceeds 3.0 wt%, the obtained high specific gravity resin composition will be Both are undesirable in practical use because the impact resistance of the molded product used as the raw material is reduced.
なお、前述した６配位タイプのチタネート系カップリン
グ剤に限らず、他のチタネート系カップリング剤、例え
ばイソプロピルトリ（Ｎ−アミノエチルアミノエチル）
チタネート等の４配位タイプのチタネート系カップリン
グ剤を用いて金属粉の表面処理を施しても、従来の高比
重樹脂組成物を原料とする成形品よりＣＦＲＰとの接着
性に優れた成形品となりうる高比重樹脂組成物を得るこ
とができるが、この場合には６配位タイプのチタネート
系カップリング剤を用いた場合と同程度の耐衝撃性を与
えることが困難である。In addition to the above-mentioned 6-coordination type titanate coupling agent, other titanate coupling agents such as isopropyl tri(N-aminoethylaminoethyl)
Molded products with superior adhesion to CFRP than molded products made from conventional high-density resin compositions, even when metal powder is surface-treated using a 4-coordination type titanate coupling agent such as titanate. However, in this case, it is difficult to provide impact resistance comparable to that obtained using a hexacoordination type titanate coupling agent.
金属粉の表面処理をチタネート系カップリング剤を用い
て行うにあたっては、チタネート系カップリング剤をメ
タノールやベンゼン、トルエン、キシレン等の有機溶媒
に溶解させ、常温下あるいは加熱下で金属粉をこの溶液
に浸漬させた後、有機溶媒を除去して金属粉を乾燥させ
る湿式法により行うことができる。また、ヘンシェルミ
キサースーパーミキサー等を用いた乾式の混合法により
行ってもよい。When surface-treating metal powder using a titanate coupling agent, the titanate coupling agent is dissolved in an organic solvent such as methanol, benzene, toluene, or xylene, and the metal powder is dissolved in this solution at room temperature or under heating. This can be carried out by a wet method in which the metal powder is immersed in water, the organic solvent is removed, and the metal powder is dried. Alternatively, a dry mixing method using a Henschel mixer super mixer or the like may be used.
本発明の高比重樹脂組成物は、上述のようにして表面処
理を施した金属粉と、ナイロン６−ＡＢＳアロイ樹脂、
ナイロン６−ポリフェニレンオキシド（Ｐ Ｐ Ｏ）ア
ロイ樹脂等のポリアミド系樹脂とを必須成分として含有
する。さらに、必要に応じて流動パラフィン、天然パラ
フィン、ワックス等の炭化水素系滑剤や、高級脂肪酸、
脂肪酸アミド等の脂肪酸系滑剤、脂肪酸の低級アルコー
ル、ポリグリコール等のアルコール系滑剤、ステアリン
酸カルシウム、ステアリン酸バリウム等の金属石鹸、シ
リコンオイルあるいは変性シリコン等の滑剤を含有させ
てもよい。The high specific gravity resin composition of the present invention comprises metal powder subjected to the surface treatment as described above, nylon 6-ABS alloy resin,
Contains polyamide resin such as nylon 6-polyphenylene oxide (PPO) alloy resin as an essential component. Furthermore, if necessary, hydrocarbon lubricants such as liquid paraffin, natural paraffin, and wax, higher fatty acids,
A lubricant such as fatty acid lubricant such as fatty acid amide, lower alcohol of fatty acid, alcohol lubricant such as polyglycol, metal soap such as calcium stearate or barium stearate, silicone oil or modified silicone may be contained.
チタネート系カップリング剤により表面処理を施した金
属粉とポリアミド系樹脂とを配合するにあたっては、上
記金属粉とポリアミド系樹脂との総量に対する前記金属
粉の配合割合を２５〜５０ｖｏ１％とする。金属粉の配
合割合が２５ｖｏ１％未満では、ＣＦＲＰとの十分な接
着強度を有する成形品を得ることが困難であるため、ま
た５０ｖｏ［％を超えると、成形時に十分な流動性を得
ることが困難となるため、ともに実用上好ましくない。When blending the metal powder surface-treated with a titanate coupling agent and the polyamide resin, the blending ratio of the metal powder to the total amount of the metal powder and polyamide resin is set to 25 to 50 vol%. If the blending ratio of metal powder is less than 25vo[%], it is difficult to obtain a molded product with sufficient adhesive strength with CFRP, and if it exceeds 50vo[%], it is difficult to obtain sufficient fluidity during molding. Therefore, both are unfavorable from a practical standpoint.
なお滑剤を用いる場合には、チタネート系カップリング
剤により表面処理を施した金属粉とポリアミド系樹脂と
の総量に対する滑剤の配合割合を５ｖ０１％以下とする
ことが好ましい。滑剤の配合割合が５ｖ０１％を超える
と、得られた高比重樹脂組成物を原料とする成形品のＣ
ＦＲＰに対する接着性が低下するため、実用上好ましく
ない。In addition, when using a lubricant, it is preferable that the blending ratio of the lubricant to the total amount of the metal powder surface-treated with a titanate coupling agent and the polyamide resin is 5v01% or less. If the blending ratio of the lubricant exceeds 5v01%, the C of the molded product made from the obtained high specific gravity resin composition
This is not preferred from a practical standpoint since the adhesion to FRP decreases.
本発明の高比重樹脂組成物を用いた成形品は、前述した
チタネート系カップリング剤により表面処理を施した金
属粉、ポリアミド系樹脂および必要に応じて滑剤を配合
した混合物を、押出し法、加圧ニーダ−法等の従来公知
の方法により混練造粒し、押出し成形法、射出成形法、
圧縮成形法、ロール成形法等の従来公知の方法により成
形加工することにより得ることができる。A molded article using the high specific gravity resin composition of the present invention can be produced by extrusion or processing using a mixture of metal powder surface-treated with the titanate coupling agent mentioned above, a polyamide resin, and a lubricant if necessary. Kneading and granulating by a conventionally known method such as a pressure kneader method, extrusion molding method, injection molding method,
It can be obtained by molding using conventionally known methods such as compression molding and roll molding.
このようにして得た高比重樹脂組成物の成形品を、炭素
繊維強化エポキシ樹脂、炭素繊維強化不飽和ポリエステ
ル樹脂等のＣＦＲＰに内包させるにあたっては、−液性
エポキシ樹脂、二液性エポキシ樹脂、フェノール樹脂等
の従来公知の接着剤を用いることができ、これにより簡
易な接着作業でも実用上十分な接着強度をトｊ与するこ
とができる。In order to encapsulate the molded article of the high specific gravity resin composition thus obtained in CFRP such as carbon fiber reinforced epoxy resin, carbon fiber reinforced unsaturated polyester resin, -liquid epoxy resin, two-component epoxy resin, A conventionally known adhesive such as a phenol resin can be used, and thereby a practically sufficient adhesive strength can be imparted even in a simple bonding operation.
［実施例］ 以下、本発明の実施例について説明する。[Example] Examples of the present invention will be described below.
実施例１
まず、表面処理剤としてチタネート系カップリング剤で
あるテトラオクチルビス（ジトリデシルホスファイト）
チタネート（商品名：ＫＲ−４６８１味の素棟製）を用
い、このチタネート系カップリング剤０．７重量部を２
０重量部のメタノールに溶解させた溶液に、最大粒径が
７５μｍ以下のアトマイズ鉄粉（商品名：アトメル３０
０Ｍ−２００、■神戸製鋼所製）１００重量部を常温下
に浸漬して、このアトマイズ鉄粉に表面処理を施した。Example 1 First, tetraoctyl bis(ditridecyl phosphite), which is a titanate coupling agent, was used as a surface treatment agent.
Using titanate (product name: KR-4681 manufactured by Ajinomoto Building), 0.7 parts by weight of this titanate-based coupling agent was added to 2
Add atomized iron powder (product name: Atmel 30) with a maximum particle size of 75 μm or less to a solution dissolved in 0 parts by weight of methanol.
The atomized iron powder was surface-treated by immersing 100 parts by weight of 0M-200 (manufactured by Kobe Steel, Ltd.) at room temperature.
次いで、表面処理を施したアトマイズ鉄粉の配合割合が
４６゜４ ｖｏ１％となるように、このアトマイズ鉄粉
とポリアミド系樹脂であるナイロン６−ＡＢＳアロイ樹
脂（商品名：トヨラック５Ｘ−０１、東し特製）とを配
合し、さらに脂肪酸アミド系滑剤（商品名：スリパック
スし、日本化成■製）を、表面処理を施したアトマイズ
鉄粉とナイロン６−ＡＢＳアロイ樹脂との総量に対して
３゜５ ｖｏ１％添加し、得られた高比重樹脂組成物を
一軸混練押出機を用いて２２０〜２３０℃で混練造粒し
て、密度が３．９２である高比重樹脂組成物のベレット
を得た。Next, the atomized iron powder and nylon 6-ABS alloy resin, which is a polyamide resin (trade name: Toyolac 5X-01, Toyo Lac 5X-01, Furthermore, a fatty acid amide-based lubricant (product name: Slipax, manufactured by Nippon Kasei ■) is added to the surface-treated atomized iron powder and nylon 6-ABS alloy resin at a rate of 3° relative to the total amount of the atomized iron powder and nylon 6-ABS alloy resin. The high specific gravity resin composition obtained by adding 5 vol. .
この後、得られたペレトを射出成形により加工して、大
きさが４０Ｘ４０Ｘ５＋ｕａである接着試験用成形品と
、大きさが１２０Ｘ１５Ｘ３゜２＋＋ｍである衝撃試験
用成形品とを作製し、接着性および耐衝撃性の評価試験
を行った。Thereafter, the obtained pellets were processed by injection molding to produce a molded article for adhesion test with a size of 40×40×5+ua and a molded article for impact test with a size of 120×15×3°2++ m, and the adhesive and resistance properties were evaluated. An impact evaluation test was conducted.
接着性の評価試験は、接着試験用成形品および、ＣＦＲ
Ｐであるカーボンクロス強化エポキシ樹脂積層板を、そ
れぞれ２５Ｘ３０Ｘ５ａｎの大きさに切り出して、−液
性エポキシ樹脂（商品名：アラルダイトＸＤ９１１、チ
バガイキー社製）を接着剤として用いて両者をそのまま
接着し、ＪＩＳＫ６８５２の方法に基づいて圧縮剪断接
着強度を測定することにより行った。また耐衝撃性の評
価試験は、衝撃試験用成形品を１２０Ｘ１０Ｘ３゜２■
の大きさに切り出し、ＪＩＳ Ｋ７１１１の方法に基
づいてシャルピー衝撃強度（ノツチなし）を測定するこ
とにより行った。The adhesion evaluation test was conducted using molded products for adhesion testing and CFR
Each of the carbon cloth reinforced epoxy resin laminates (P) was cut out to a size of 25x30x5an, and the two were bonded together using liquid epoxy resin (product name: Araldite This was done by measuring the compressive shear adhesive strength based on the method of . In addition, in the impact resistance evaluation test, the impact test molded product was
The sample was cut out to a size of , and the Charpy impact strength (without notches) was measured based on the method of JIS K7111.
各試験の結果は、圧縮剪断接着強度が１３８ｋｇ／ｃＩ
＃、シャルピー衝撃強度（ノツチなし）が２０゜９ｋｇ
−ｃｌｌ／ｃ！＃であり、本実施例で得た高比重樹脂組
成物の成形品は、簡易な接着作業によりＣＦＲＰと高い
接着強度で接着するとともに、耐衝撃性にも優れている
ことが確認された。The results of each test showed that the compressive shear adhesive strength was 138 kg/cI.
#, Charpy impact strength (without notch) is 20°9kg
-cll/c! #, and it was confirmed that the molded article of the high specific gravity resin composition obtained in this example adhered to CFRP with high adhesive strength through a simple bonding operation, and also had excellent impact resistance.
実施例２
表面処理剤としてテトラ（２，２−ジアリルオキシメチ
ル−１−ブチル）ビス（ジトリデシル）ホスファイトチ
タネート（商品名：ＫＲ−５５、味の素■製）を用い、
表面処理を施したアトマイズ鉄粉（最大粒径７５μｍ以
下、商品名：アトメル３００Ｍ−２００、■神戸製鋼新
製）の配合割合を、このアトマイズ鉄粉とナイロン６−
ＡＢＳアロイ樹脂（商品名：トヨラック５Ｘ−０１、東
し■製）との総量に対して４６．８ ｖｏ１％とじた以
外は実施例１と同様にして高比重樹脂組成物を得た後、
実施例１と同様にして、密度が３゜９４である成形品を
得た。Example 2 Using tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate (trade name: KR-55, manufactured by Ajinomoto ■) as a surface treatment agent,
The blending ratio of surface-treated atomized iron powder (maximum particle size 75 μm or less, product name: Atmel 300M-200, ■Kobe Steel New Co., Ltd.) was adjusted between this atomized iron powder and nylon 6-
A high specific gravity resin composition was obtained in the same manner as in Example 1, except that 46.8 vol.
A molded article having a density of 3°94 was obtained in the same manner as in Example 1.
得られた高比重樹脂組成物の成形品の接着強および耐衝
撃性の評価試験を実施例１と同様にして行ったところ、
圧縮剪断接着強度は１０８ｋｇ／ｃｄ、シャルピー衝撃
強度（ノツチなし）は１６．６ｋｇ・ｃｍ／ｃｄであり
、本実施例で得られた高比重樹脂組成物の成形品は、簡
易な接着作業によりＣＦＲＰと高い接着強度で接着する
とともに、実用上十分な耐衝撃性を有していることが確
認された。比較例１
表面処理剤として、シラン系カップリング剤であるγ−
ウレイドプロピルトリエトキシシラン（商品名：Ａ−１
１６０、日本ユニカー仲製）を用い、表面処理を施した
アトマイズ鉄粉（最大粒径７５μｍ以下、商品名：アト
メル３００Ｍ−２００、■神戸製鋼新製）の配合割合を
、このアトマイズ鉄粉とナイロン６−ＡＢＳアロイ樹脂
（商品名：トヨラック５Ｘ−０１、東し■製）との総量
に対して４６． １ ｖｏ１％とじた以外は実施例１と
同様にして、密度が３．９１である高比重樹脂組成物の
成形品を得た。Evaluation tests for the adhesive strength and impact resistance of the molded product of the obtained high specific gravity resin composition were conducted in the same manner as in Example 1.
The compressive shear adhesive strength was 108 kg/cd, and the Charpy impact strength (without notch) was 16.6 kg cm/cd. It was confirmed that it adhered with high adhesive strength and had sufficient impact resistance for practical use. Comparative Example 1 γ- which is a silane coupling agent was used as a surface treatment agent.
Ureidopropyltriethoxysilane (Product name: A-1
160, manufactured by Nippon Unicar Nakama), and the surface-treated atomized iron powder (maximum particle size 75 μm or less, product name: Atmel 300M-200, ■Kobe Steel New Co., Ltd.) was mixed with the atomized iron powder and nylon. 6-ABS alloy resin (product name: TOYOLAC 5X-01, manufactured by Toshi ■) 46. A molded article of a high specific gravity resin composition having a density of 3.91 was obtained in the same manner as in Example 1, except that 1 vol.
得られた高比重樹脂組成物の成形品の接着性および耐衝
撃性の評価試験を実施例１と同様にして行ったところ、
圧縮剪断接着強度は７８ｋｇ／ｃｄ、シャルピー衝撃強
度（ノツチなし）は１９．１ｋｇφｃｍ ／ｃ−であり
、本比較例で得られた高比重樹脂組成物の成形品は、耐
衝撃性については実用上十分な特性を有していることが
確認されたが、接着性については実施例１で得られた高
比重樹脂組成物の成形品に比べて下回っていることが確
認された。Evaluation tests for the adhesion and impact resistance of the molded product of the obtained high specific gravity resin composition were conducted in the same manner as in Example 1.
The compressive shear adhesive strength was 78 kg/cd, and the Charpy impact strength (without notch) was 19.1 kgφcm/c-, and the molded product of the high specific gravity resin composition obtained in this comparative example had impact resistance that was not practical in terms of impact resistance. Although it was confirmed that the product had sufficient properties, it was confirmed that the adhesiveness was lower than that of the molded product of the high specific gravity resin composition obtained in Example 1.
実施例３
ポリアミド系樹脂として、ナイロン６−ポリフェニレン
オキシド（ＰＰＯ）アロイ樹脂（商品名：ＰＰＡ２６３
、東し■製）を用いた以外は実施例１と同様にして、密
度が４．００である高比重樹脂組成物の成形品を得た。Example 3 Nylon 6-polyphenylene oxide (PPO) alloy resin (trade name: PPA263) was used as a polyamide resin.
A molded article of a high specific gravity resin composition having a density of 4.00 was obtained in the same manner as in Example 1 except that a molded article (manufactured by Toshi Corporation, Inc.) was used.
得られた高比重樹脂組成物の成形品の接着性および耐衝
撃性の評価試験を実施例１と同様にして行ったところ、
圧縮剪断接着強度は１４４ ｋｇ／ ｃｄ。Evaluation tests for the adhesion and impact resistance of the molded product of the obtained high specific gravity resin composition were conducted in the same manner as in Example 1.
Compression shear adhesive strength is 144 kg/cd.
シャルピー衝撃強度（ノツチなし）は１６．０ｋｇ・ａ
ｍ ／ｃｄであり、本実施例で得られた高比重樹脂組成
物の成形品は、簡易な接着作業によりＣＦＲＰと高い接
着強度で接着するとともに、実用上十分な耐衝撃性を有
していることが確認された。Charpy impact strength (without notch) is 16.0 kg・a
m / cd, and the molded product of the high specific gravity resin composition obtained in this example can be bonded to CFRP with high adhesive strength by a simple bonding operation, and has impact resistance sufficient for practical use. This was confirmed.
比較例２
表面処理剤として、シラン系カップリング剤であるγ−
ウレイドプロピルトリエトキシシラン（商品名：Ａ−１
１６０、日本ユニカー仲製）を用い、表面処理を施した
アトマイズ鉄粉（最大粒径７５μｍ以下、商品名：アト
メル３００Ｍ−２００、■神戸製鋼新製）の配合割合を
、このアトマイズ鉄粉とナイロン６−ポリフェニレンオ
キシド（Ｐ Ｐ Ｏ）アロイ樹脂（商品名： ＰＰＡ２
６３、東し■製）との総量に対して４５．３ｖｏ１％と
じた以外は実施例３と同様にして、密度が４．００であ
る高比重樹脂組成物の成形品を得た。Comparative Example 2 As a surface treatment agent, γ- which is a silane coupling agent was used as a surface treatment agent.
Ureidopropyltriethoxysilane (Product name: A-1
160, manufactured by Nippon Unicar Nakama), and the surface-treated atomized iron powder (maximum particle size 75 μm or less, product name: Atmel 300M-200, ■Kobe Steel New Co., Ltd.) was mixed with the atomized iron powder and nylon. 6-Polyphenylene oxide (PPO) alloy resin (product name: PPA2
A molded article of a high specific gravity resin composition having a density of 4.00 was obtained in the same manner as in Example 3, except that 45.3 vol.
得られた高比重樹脂組成物の成形品の接着性および耐衝
撃性の評価試験を実施例３と同様にして行ったところ、
圧縮剪断接着強度は３９ｋｇ／ｃｄ。Evaluation tests for the adhesion and impact resistance of the molded product of the obtained high specific gravity resin composition were conducted in the same manner as in Example 3.
Compression shear adhesive strength is 39 kg/cd.
シャルピー衝撃強度（ノツチなし）は１３．３ｋｇ・ｃ
ｍ／ｃｄであり、本比較例で得られた高比重樹脂組成物
の成形品は、実施例３で得られた高比重樹脂組成物の成
形品に比べて、接着性および耐衝撃性ともに大きく下回
っていることが確認された。Charpy impact strength (without notch) is 13.3 kg・c
m/cd, and the molded article of the high specific gravity resin composition obtained in this comparative example has greater adhesion and impact resistance than the molded article of the high specific gravity resin composition obtained in Example 3. It was confirmed that it was below.
なお、実施例１．２．３および比較例１．２で得られた
各高比重樹脂組成物の成形品について、用いた表面処理
剤、金属粉およびポリアミド系樹脂の種類ならびに配合
割合、成形品の密度、圧縮剪断接着強度の測定結果およ
びシャルピー衝撃強度（ノツチなし）の測定結果を一覧
にして、表−１に示す。Regarding the molded products of each high specific gravity resin composition obtained in Example 1.2.3 and Comparative Example 1.2, the surface treatment agent used, the type and blending ratio of metal powder and polyamide resin, and the molded product Table 1 shows the measurement results of the density, compression shear adhesive strength, and Charpy impact strength (without notches).
（以下、余白）
［発明の効果］
以上説明したように、本発明の高比重樹脂組成物は、こ
れを成形品とした場合、簡易な接着作業でもＣＦＲＰと
高い接着強度で接着するとともに、実用上十分な耐衝撃
性を有している。(Hereinafter, blank space) [Effects of the Invention] As explained above, when the high specific gravity resin composition of the present invention is made into a molded product, it can be bonded to CFRP with high adhesive strength even in a simple bonding operation, and can be used in practical applications. It also has sufficient impact resistance.
したがって、本発明の高比重樹脂組成物を、高速移動体
であって耐衝撃性が要求される炭素繊維−樹脂複合材料
部材の質量体の原料として用いることにより、このよう
な部材の信頼性を容易に向上させることが可能となる。Therefore, by using the high specific gravity resin composition of the present invention as a raw material for the mass body of a carbon fiber-resin composite material member that is a high-speed moving body and requires impact resistance, the reliability of such a member can be improved. This can be easily improved.
Claims (1)
た金属粉と、ポリアミド系樹脂とを含み、前記金属粉と
前記ポリアミド系樹脂との総量に対する前記金属粉の配
合割合が２５〜５０ｖｏｌ％であることを特徴とする高
比重樹脂組成物。(1) Contains metal powder surface-treated with a titanate coupling agent and a polyamide resin, and the blending ratio of the metal powder to the total amount of the metal powder and the polyamide resin is 25 to 50 vol%. A high specific gravity resin composition characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7952289A JPH02255760A (en) | 1989-03-30 | 1989-03-30 | Resin composition having high specific gravity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7952289A JPH02255760A (en) | 1989-03-30 | 1989-03-30 | Resin composition having high specific gravity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02255760A true JPH02255760A (en) | 1990-10-16 |
Family
ID=13692316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7952289A Pending JPH02255760A (en) | 1989-03-30 | 1989-03-30 | Resin composition having high specific gravity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02255760A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062489A (en) * | 2003-11-14 | 2012-03-29 | Wild River Consulting Group Llc | Metal polymer composite, method for its extrusion and shaped article made therefrom |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179538A (en) * | 1983-03-30 | 1984-10-12 | Maruki Kagaku Kogyo Kk | Thermoplastic resin composition having high specific gravity |
-
1989
- 1989-03-30 JP JP7952289A patent/JPH02255760A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59179538A (en) * | 1983-03-30 | 1984-10-12 | Maruki Kagaku Kogyo Kk | Thermoplastic resin composition having high specific gravity |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012062489A (en) * | 2003-11-14 | 2012-03-29 | Wild River Consulting Group Llc | Metal polymer composite, method for its extrusion and shaped article made therefrom |
| JP2015145509A (en) * | 2003-11-14 | 2015-08-13 | ワイルド リバー コンサルティング グループ リミテッド ライアビリティー カンパニー | Metal polymer composite, method for its extrusion and shaped article made therefrom |
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