JP2004155959A - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- JP2004155959A JP2004155959A JP2002324246A JP2002324246A JP2004155959A JP 2004155959 A JP2004155959 A JP 2004155959A JP 2002324246 A JP2002324246 A JP 2002324246A JP 2002324246 A JP2002324246 A JP 2002324246A JP 2004155959 A JP2004155959 A JP 2004155959A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber
- petroleum
- process oil
- parts
- 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
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明はゴム組成物に関し、更に詳しくは特定の石油系プロセス油を配合することによって低燃費性、グリップ性および耐熱老化性を両立させかつ加工性及び安全性にも優れたゴム組成物に関する。
【０００２】
【従来の技術】
従来ゴム組成物に配合する軟化剤として、例えば特許文献１に記載のように、典型的には芳香族炭化水素含有量（アロマ分）が約３０〜５５％、ナフラン系炭化水素（ナフラン分）及びパラフィン系炭化水素（パラフィン分）含量が約４０〜６５％の、所謂アロマ油が使用されている。然るに、近年に至って、アロマ油中の多環芳香族成分量が環境的に問題があるとの声があがっている。
【０００３】
【特許文献１】
特許公報第２９４８６５９号
【０００４】
【発明が解決しようとする課題】
石油系プロセスオイルは極めて多種類の低分子炭化水素化合物との混合物であり、その性質は、アロマティク、ナフテニック及びパラフィニック成分の構成比率、各成分分子のミクロな形状（側鎖や環状成分の割合等）、分子量等を総合したオイルの構造によって決まる。このオイルの構造が、ゴムとオイルの親和性、伸長下あるいは動的条件下でのゴムの分子挙動、コンパウンド中のオイル流動性、マイグレーション等を支配し、その結果がゴムの未加硫、加硫物性に反映していると考えるが、その詳細な機構については解明されていない。
【０００５】
一般に芳香族炭化水素含有量ＣＡが大きいと、親和性は強くなり、動的条件下でのｔａｎδは増加する。プロセスオイルはゴム製品の製造時の省エネ、ゴム粘度の低下による加工生産性の向上などのために使用するものであるが、その他にも製品の品質特性、特に例えばタイヤ製品の燃費性、グリップ性にも影響を与える。
【０００６】
ｔａｎδを下げて、燃費性を向上させるには、芳香族炭化水素含有量ＣＡ（％）の少ないナフテニック又はパラフィニック成分比率の高いオイルが、逆に、ｔａｎδを上げてグリップ性をよくするには、ＣＡ％の多いアロマティックオイルが適していることがよく知られている。このように低燃費性とグリップ性とを両立させる石油系プロセスオイルは未だ見出されていない。
【０００７】
従って、本発明は前述のような石油系プロセスオイルを配合する場合の問題点を排除して、ゴム組成物の加硫物性、特に低燃費性、グリップ性及び耐熱老化性を両立させることを目的とする。
【０００８】
【課題を解決するための手段】
本発明の第一の態様に従えば、少なくとも１種のジエン系ゴム１００重量部に、芳香族炭化水素含量ＣＡが２０〜３５重量％、ガラス転移温度Ｔｇが−５５℃〜−３０℃、動粘度（１００℃）が２０〜５０ｍｍ２／ｇでかつ多環芳香族成分量（ＰＣＡ）が石油系プロセスオイル中の３重量％以下である石油系プロセスオイル１〜１５０重量部を配合してなるゴム組成物が提供される。
【０００９】
本発明の第二の態様に従えば、ガラス転移温度Ｔｇが−５５℃以上のスチレン−ブタジエン共重合体ゴム（ＳＢＲ）を少なくとも一種含むジエン系ゴム１００重量部に、芳香族炭化水素含量ＣＡが２０〜３５重量％、Ｔｇが−５５℃〜−３０℃、動粘度（１００℃）が２０〜５０ｍｍ２／ｇでかつ多環芳香族成分量（ＰＣＡ）が石油系プロセスオイル中の３重量％以下である石油系プロセスオイル５〜８０重量部と芳香族系、ロジン系及びクマロン系から選ばれる少なくとも一種の軟化点８０〜１３０℃の樹脂２〜３０重量部を配合してなるゴム組成物が提供される。
【００１０】
本発明の第三の態様に従えば、少なくとも１種のジエン系ゴム１００重量部に、芳香族炭化水素含有量（ＣＡ）が２０〜３５重量％、ガラス転移温度Ｔｇが−５５℃〜−３０℃、動粘度（１００℃）が２０〜５０ｍｍ２／ｇでかつ多環芳香族成分量（ＰＣＡ）３重量％以下の石油系プロセスオイルと、重量平均分子量が２００〜１０，０００のノボラック型アルキルフェノール樹脂との混合物で、該プロセスオイルと該樹脂との重量割合が２５〜９５重量％／５〜７５重量％である混合物１０〜３０重量部を配合してなるゴム組成物が提供される。
【００１１】
【発明の実施の形態】
本発明のゴム組成物に配合される石油系プロセスオイルは、プロセスオイル中の芳香族炭化水素含量ＣＡが２０〜３５重量％、好ましくは２５〜３５重量％、ガラス転移温度Ｔｇ（ＤＳＣ：示差熱走査型熱量計で測定）が−５５℃〜−３０℃、好ましくは−４５℃〜−３５℃である。ここでＣＡは環分析法（ｎ−ｄ−Ｍ法）（ＡＳＴＭ Ｄ３２３８）で測定することができる。動粘度（１００℃）が２０〜５０ｍｍ２／ｇ、好ましくは２５〜５０ｍｍ２／ｇである。また、多環芳香族成分量（ＰＣＡ）が３重量％以下である。ここでＰＣＡは多環芳香族などの２環以上が融合した芳香族化合物で、ＤＭＳＯ抽出物質としてＩＰ３４６／９２法で測定することができる。
【００１２】
本発明において使用する石油系プロセスオイルのＣＡが２０重量％未満ではグリップ性能の指標であるｔａｎδ（０℃）が低下するので好ましくなく、逆に３５重量％を超えると低燃費性の指標であるｔａｎδ（６０℃）が増加（燃費性悪化）するので好ましくない。Ｔｇが−５５℃より低いとグリップ性能、耐熱老化性が低下するので好ましくなく、逆に−３０℃より高いと低燃費性が悪化するので好ましくない。動粘度（１００℃）が２０ｍｍ２／ｇ未満ではグリップ性能が低下するので好ましくなく、逆に５０ｍｍ２／ｇを超えると輸送時の高温加温が必要になり、使用コストの増大を招くので好ましくない。更にＰＣＡが３重量％を超えると環境・安全性の潜在的問題があるので好ましくない。
【００１３】
本発明の第一の態様に係るゴム組成物では、少なくとも一種のジエン系ゴム１００重量部に、前記石油系プロセスオイル１〜１５０重量部、好ましくは３〜１００重量部を配合する。このゴム組成物は、石油系プロセスオイルのＴｇを−５５℃〜−３０℃とすることによってジエン系原料ゴムとの相溶性、ブリード性及び低燃費性、グリップ性の問題を解決することができ、更にＣＡ（％）を２０〜３５重量％とすることによって低燃費性とグリップ性を両立させ、又、動粘度（１００℃）を２０〜５０ｍｍ２／ｇとすることによってグリップ性の更なる向上と耐熱老化性を確保することができる。
【００１４】
本発明の第一の態様に係るゴム組成物に用いることのできるジエン系ゴムとしては、従来からゴム組成物に一般的に配合されている任意のジエン系ゴム、例えば天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）などをその用途に応じて単独又は任意のブレンドとして用いることができる。
【００１５】
本発明の第一の態様に係るゴム組成物には前記した必須成分に加えて、カーボンブラックやシリカなどの補強剤、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる配合物は一般的な方法で混練、加硫して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も本発明の目的に反しない限り、従来の一般的な配合量とすることができる。かかるゴム組成物の用途には特に限定はないが、例えばベルト・ホース等の工業用品、タイヤなどに使用するのに好適である。
【００１６】
本発明の第二の態様に係るゴム組成物では、ガラス転移温度Ｔｇが−５５℃以上のスチレンブタジエン共重合体（ＳＢＲ）を少なくとも一種類含むジエン系ゴム１００重量部に、前記石油系プロセスオイル５〜８０重量部、好ましくは１０〜７０重量部並びに軟化点が８０〜１３０℃、好ましくは８０〜１２０℃の芳香族系、ロジン系及び／又はクマロン系の樹脂２〜３０重量部、好ましくは２〜１５重量部を配合する。石油系プロセスオイルの配合量が少な過ぎるとゴムの加工性が悪化するので好ましくなく、逆に多過ぎると低燃費性が悪化するので好ましくない。また樹脂の軟化点が低過ぎる場合にはグリップ性能が低下するので好ましくなく、逆に高過ぎると軟化効果が小さくなり、加工性が悪化するので好ましくない。更に樹脂の配合量が少な過ぎると軟化効果が小さくなり、加工性が悪化するので好ましくなく、逆に多過ぎると低燃費性が悪化するので好ましくない。
【００１７】
前記芳香族系、ロジン系及び／又はクマロン系樹脂としては、例えばＣ９ 樹脂、ガムロジン、ウッドロジン、トールロジン等のロジン系樹脂、さらにはロジンエステル系樹脂等の変性樹脂、クマロン−インデン樹脂などをあげることができ、これらは例えば三井石油製ペトロジン、安原油脂（株）製の各種ロジンエステウ樹脂神戸油化学工業（株）製クマロン１００などとして市販されている。
【００１８】
本発明の第二の態様に係るゴム組成物に前記ＳＢＲと併用することのできるジエン系ゴムとしては、従来からゴム組成物に一般的に配合されている任意のジエン系ゴム、例えば天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、他のスチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）などをその用途に応じて単独又は任意のブレンドとして用いることができる。
【００１９】
本発明の第二の態様に係るゴム組成物には前記した必須成分に加えて、カーボンブラックやシリカなどの補強剤、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる配合物は一般的な方法で混練、加硫して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も本発明の目的に反しない限り、従来の一般的な配合量とすることができる。かかるゴム組成物の用途には特に限定はないが、例えばタイヤトレッド用、ベルト類、ホース類などのゴム製工業用品などに使用するのに好適である。
【００２０】
本発明の第三の態様に係るゴム組成物では、少なくとも一種のジエン系ゴム１００重量部に、前記石油系プロセスオイルと重量平均分子量が２００〜１０，０００、好ましくは２５０〜５０００のノボラック型アルキルフェノール樹脂との混合物で、前記石油系プロセスオイルとノボラック製アルキルフェノール樹脂との重量割合が（２５〜９５重量％）／（５〜７５重量％）である混合物１０〜３０重量部を軟化剤として配合する。
【００２１】
本発明の第三の態様によれば、前記石油系プロセスオイルと共に、分子量２００〜１０，０００、好ましくは２５０〜５，０００のノボラック型アルキルフェノールを配合することにより、所望のゴムコンパウンド性能を得ることができることを見出した。ノボラック型アルキルフェノールの分子量が２００未満では低伸長域でのモジュラスの増大効果が認められず、逆に分子量が１０，０００を超えると、高伸長域での軟化効果が小さく、またゴムの混合加工性が悪化する傾向にあるので、好ましくない。前記石油系プロセスオイルとの配合量は、両者の合計量に対しノボラック型アルキルフェノールが５〜７５重量％、好ましくは１０〜５０重量％の範囲である。ノボラック型アルキルフェノールの配合量が５重量％未満ではモジュラス増加効果を発現できず、また７５重量％を超えると、加工性が悪化するだけでなくコストアップとなり、タイヤ用ゴムとしては好ましくない。軟化剤の配合量はジエン系ゴム１００重量部に対し、１０〜３０重量部である。この配合量が少なすぎるとゴムの加工性が悪化するので好ましくなく、逆に多過ぎると低燃費性が低下するので好ましくない。
【００２２】
本発明の第三の態様に係るゴム組成物に用いることのできるジエン系ゴムとしては、従来からゴム組成物に一般的に配合されている任意のジエン系ゴム、例えば天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、ブチルゴム（ＩＩＲ）などをその用途に応じて単独又は任意のブレンドとして用いることができる。
【００２３】
本発明の第三の態様に係るゴム組成物には前記した必須成分に加えて、カーボンブラックやシリカなどの補強剤、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑性剤などのタイヤ用、その他一般ゴム用に一般的に配合されている各種添加剤を配合することができ、かかる配合物は一般的な方法で混練、加硫して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も本発明の目的に反しない限り、従来の一般的な配合量とすることができる。かかるゴム組成物の用途には特に限定はないが、例えばタイヤ用カーカス部材、タイヤ用トレッド、ベルト、ホース類などに使用するのに好適である。
【００２４】
【実施例】
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことは言うまでもない。なお、以下の例中「％」は特にことわりのない限り「重量％」を示す。
【００２５】
実施例１〜４及び比較例１〜３
表Ｉに示す配合（重量部）に従って、加硫促進剤及び硫黄以外のゴム及び配合剤を１．７リットルのバンバリーミキサーで５分間混練し、次にこの配合物に加硫促進剤及び硫黄を８インチの試験用練りロール機で４分間混練してゴム組成物を得た。これらのゴム組成物を１５０℃で３０分間プレスして、目的とする試験片を調製し、各種試験を行い、その物性を測定した。その結果を表Ｉに示す。
【００２６】
物性の測定方法は以下の通りであった。
１）ｔａｎδ（０℃及び６０℃）：粘弾性スペクトロメーター（上島製作所（株）製伸長型粘弾性測定機）を用い、温度０℃及び６０℃、歪率１０±２％、周波数２０Ｈｚの条件で測定した。
２）ΔＨｓ：高分子計器（株）製 ＪＩＳ Ａ型硬さ計を用いてＪＩＳ Ｋ−６３０１に準じて測定した。比較例を基準にして値の増減を示している。
３）引張り強度（老化後）（Ｍｐａ）：ＪＩＳ Ｋ−６３０１に準じて、空気加熱老化試験（１００℃、２４時間）を行った後に引張り試験を実施した。
【００２７】
【表１】
表Ｉの脚注
＊１：ＲＳＳ＃１
＊２：Ｎ３３０（東海カーボン（株）製シースト３）
＊３：ノクセラー６Ｃ（大内新興化学製）
＊４：ＣＡ４４％、Ｔｇ＝−３２℃、動粘度（１００℃）＝２７ｍｍ２／ｓｅｃ、ＰＣＡ＝１０．５％
＊５：ＣＡ４％、Ｔｇ＝−９３℃、動粘度（１００℃）＝２ｍｍ２／ｓｅｃ、ＰＣＡ＝０．８％
＊６：ＣＡ３０％、Ｔｇ＝−６０℃、動粘度（１００℃）＝５２ｍｍ２／ｓｅｃ、ＰＣＡ＝２．８％
＊７：ＣＡ２７％、Ｔｇ＝−４０℃、動粘度（１００℃）＝４７ｍｍ２／ｓｅｃ、ＰＣＡ＝２．８％
＊８：Ｎ−ｔｅｒｔ−Ｂｕｔｙｌ−２−ｂｅｎｚｏｔｈｉａｚｏｌｙｌ−ｓｕｌｆｅｎａｍｉｄｅ（大内新興化学（株）製）
【００２９】
実施例５〜６及び比較例４〜１０
表ＩＩに示す配合（重量部）に従って、加硫促進剤及び硫黄以外のゴム及び配合剤を１．７リットルのバンバリーミキサーで５分間混練し、次にこの配合物に加硫促進剤及び硫黄を８インチの試験用練りロール機で４分間混練してゴム組成物を得た。これらのゴム組成物を１５０℃で３０分間プレスして、目的とする試験片を調製し、各種試験を行い、その物性を測定した。なお物性の測定法は前述の通りである。結果を表ＩＩに示す。
【００３０】
【表２】
表 ＩＩ の脚注
＊１：ＳＢＲ：Ｓｔ＝２３．５％、Ｖｎ＝１０％、Ｔｇ＝−５５℃の乳化重合ＳＢＲ
＊２：Ｎ３３０（東海カーボン（株）製シースト３）
＊３：ノクセラー６Ｃ（大内新興化学（株））
＊４：Ｃａ＝４４％、Ｔｇ＝−３２℃、動粘度（１００℃）＝２７ｍｍ２／ｓｅｃ ，ＰＣＡ値＝１０．５％
＊５：Ｃａ＝４％、Ｔｇ＝−９３℃、動粘度（１００℃）＝２ｍｍ２／ｓｅｃ ，ＰＣＡ値＝０．８％
＊６：Ｃａ＝３０％、Ｔｇ＝−６０℃、動粘度（１００℃）＝５２ｍｍ２／ｓｅｃ ，ＰＣＡ値＝２．８％
＊７：Ｃａ＝２７％、Ｔｇ＝−４０℃、動粘度（１００℃）＝４７ｍｍ２／ｓｅｃ ，ＰＣＡ値＝２．８％
＊８：ノクセラーＮＳ（大内新興化学（株））
【００３２】
実施例７〜１０及び比較例１１〜１４
表ＩＩＩに示す配合（重量部）に従って、加硫促進剤及び硫黄以外のゴム及び配合剤を１．７リットルのバンバリーミキサーで５分間混練し、次にこの配合物に加硫促進剤及び硫黄を８インチの試験用練りロール機で４分間混練してゴム組成物を得た。これらのゴム組成物を１５０℃で３０分間プレスして、目的とする試験片を調製し、各種試験を行いその物性を測定した。その結果を表ＩＩＩに示す。
【００３３】
なお物性はｔａｎδ（６０℃）及びΔＨｓは前述の通りであり、耐摩耗性は岩本製作所製ランボーン摩耗試験機（測定条件：荷重＝３．０ｋｇ、砥石の表面速度＝４０ｍ／ｍｉｎ 、スリップ率２５％、試験時間＝５分間、落砂量＝２０ｇ／ｍｉｎ ）で測定し、測定温度は室温で、体積減量（ｃｃ）を調べ、比較例１１の値を１００として指数表示した。この値が大きいほど耐摩耗性に優れている。
【００３４】
【表３】
表 ＩＩＩ の脚注
＊１：Ｓｔ＝３３％、Ｖｎ＝１４％、Ｔｇ＝−３６℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（アロマ）＊１６
＊２：Ｓｔ＝３３％、Ｖｎ＝１４％、Ｔｇ＝−３６℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（パラフィン）＊１７
＊３：Ｓｔ＝３３％、Ｖｎ＝１４％、Ｔｇ＝−３６℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（オイル）＊１８
＊４：Ｓｔ＝２５％、Ｖｎ＝１６％、Ｔｇ＝−５１℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（アロマ）＊１６
＊５：Ｓｔ＝２５％、Ｖｎ＝１６％、Ｔｇ＝−５１℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（パラフィン）＊１７
＊６：Ｓｔ＝２５％、Ｖｎ＝１６％、Ｔｇ＝−５１℃の乳化重合ＳＢＲ、３７．５ｐｈｒ油展（オイル）＊１８
＊７：日本ゼオン（株）製Ｎｉｐｏｌ１２２０
＊８：昭和キャボット（株）製ショウブラックＮ２２０
＊９：フレキシス（株）製サントフレックス６ＰＰＤ
＊１０：昭和シェル石油（株）製デゾレックス３号
＊１１：昭和シェル石油（株）製マシン油２２
＊１２：アロマ系オイル（ＣＡ＝２７％、Ｔｇ＝−４０℃、動粘度（１００℃）＝４７ｍｍ２／ｓｅｃ ）
＊１３：ヤスハラケミカル（株）製ハイロジン 軟化点：９５℃
＊１４：大内新興化学工業（株）製クマロン樹脂 軟化点：９０℃
＊１５：大内新興化学工業（株）製ノクセラーＣＺ−Ｇ
＊１６：昭和シェル石油（株）製デゾレックス３号
＊１７：昭和シェル石油（株）製マシン油２２
＊１８：アロマ系オイル（ＣＡ＝２７％、Ｔｇ＝−４０℃、動粘度（１００℃）＝４７ｍｍ２／ｓｅｃ ）
【００３６】
【発明の効果】
本発明者らはプロセスオイルのＴｇが−５５〜−３０℃でかつＣＡ＝２０〜３５重量％、動粘度（１００℃）＝２０〜５０ｍｍ２／ｇの範囲のオイルはｔａｎδ（６０℃）を下げ、ｔａｎδ（０℃）を上げて、燃費性とグリップ性を両立することを見出した。また、市販のアロマオイルはＣＡ＝４０〜４５重量％の範囲のものが一般的であるが、最近アロマオイル中に含まれている多環芳香族成分（ＰＣＡ）が健康阻害、環境汚染などの問題を生じることが懸念されている。ＰＣＡ値を低下させるためには、オイル中に占める全芳香族成分（アロマ成分）の比率を低くすることが必要であるが、単にこれのみでは結果としてＣＡ成分比率が減ることによる、グリップ性能の低下、耐熱老化性の低下などゴム製品の品質低下を招く。然るに本発明に従えば、プロセスオイルのＴｇ、芳香族含有量（ＣＡ％）、動粘度をある特定範囲に確保することにより、グリップ性能を低下させないで、低燃費性を維持することが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a rubber composition, and more particularly, to a rubber composition having a low fuel consumption, a good gripping property and a good heat aging resistance, and excellent in processability and safety by blending a specific petroleum-based process oil.
[0002]
[Prior art]
As a softening agent to be added to a conventional rubber composition, for example, as described in Patent Document 1, typically, an aromatic hydrocarbon content (aroma content) is about 30 to 55%, and a nafuran-based hydrocarbon (nafuran content) A so-called aroma oil having a paraffinic hydrocarbon (paraffin content) content of about 40 to 65% is used. However, in recent years, there have been voices saying that the amount of polycyclic aromatic components in aroma oil is environmentally problematic.
[0003]
[Patent Document 1]
Patent Publication No. 2948659
[Problems to be solved by the invention]
Petroleum-based process oils are mixtures with a very wide variety of low-molecular hydrocarbon compounds, and their properties include the composition ratio of aromatic, naphthenic and paraffinic components, the microscopic shape of each component molecule (side chains and cyclic components). Ratio, etc.), and molecular weight, etc., depending on the structure of the oil. The structure of the oil governs the affinity of the rubber with the oil, the molecular behavior of the rubber under elongation or dynamic conditions, the fluidity of the oil in the compound, migration, and the like. It is thought to be reflected in sulphate properties, but the detailed mechanism has not been elucidated.
[0005]
In general the aromatic hydrocarbon content C A is large, the affinity becomes stronger, increases tanδ under dynamic conditions. Process oil is used to save energy during the production of rubber products and to improve processing productivity due to a reduction in rubber viscosity, but it also has other quality characteristics of products, especially fuel efficiency and grip of tire products. Also affect.
[0006]
In order to reduce tan δ and improve fuel efficiency, oil having a low naphthenic or paraffinic component ratio with a low aromatic hydrocarbon content C A (%) increases tan δ to improve grip. It is well known that aromatic oils with high C A % are suitable. Thus, a petroleum-based process oil that achieves both low fuel consumption and grip properties has not been found yet.
[0007]
Accordingly, an object of the present invention is to eliminate the above-mentioned problems when compounding a petroleum-based process oil, and to achieve both vulcanization properties, particularly low fuel consumption, gripping properties, and heat aging resistance of a rubber composition. And
[0008]
[Means for Solving the Problems]
According to the first aspect of the present invention, 100 parts by weight of at least one diene rubber has an aromatic hydrocarbon content C A of 20 to 35% by weight, a glass transition temperature Tg of −55 ° C. to −30 ° C., 1 to 150 parts by weight of a petroleum-based process oil having a kinematic viscosity (100 ° C.) of 20 to 50 mm 2 / g and a polycyclic aromatic component amount (PCA) of 3% by weight or less in the petroleum-based process oil is blended. Provided is a rubber composition.
[0009]
According to a second aspect of the present invention, the glass transition temperature Tg is above -55 ° C. Styrene - 100 parts by weight of the diene rubber containing at least one kind butadiene copolymer rubber (SBR), aromatic hydrocarbon content C A Is 20 to 35% by weight, Tg is −55 ° C. to −30 ° C., kinematic viscosity (100 ° C.) is 20 to 50 mm 2 / g, and polycyclic aromatic component amount (PCA) is 3% by weight in petroleum-based process oil. % Of a petroleum process oil having a softening point of 80 to 130 ° C. selected from aromatic, rosin, and cumarone resins. Is provided.
[0010]
According to the third aspect of the present invention, 100 parts by weight of at least one diene rubber has an aromatic hydrocarbon content (C A ) of 20 to 35% by weight and a glass transition temperature Tg of −55 ° C. to −55%. Petroleum process oil having a kinematic viscosity (100 ° C.) of 20 to 50 mm 2 / g and a polycyclic aromatic component amount (PCA) of 3% by weight or less, and a novolak type having a weight average molecular weight of 200 to 10,000 at 30 ° C. The present invention provides a rubber composition comprising 10 to 30 parts by weight of a mixture of an alkylphenol resin and 25 to 95% by weight / 5 to 75% by weight of a mixture of the process oil and the resin.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Petroleum process oil to be blended in the rubber composition of the present invention, the aromatic hydrocarbon content C A in the process oil 20 to 35% by weight, preferably 25 to 35 wt%, the glass transition temperature Tg (DSC: Differential (Measured by a thermal scanning calorimeter) is -55C to -30C, preferably -45C to -35C. Wherein C A can be measured by the ring analysis (n-d-M method) (ASTM D3238). Kinematic viscosity (100 ° C.) is 20 to 50 mm 2 / g, preferably 25-50 mm 2 / g. The polycyclic aromatic component amount (PCA) is 3% by weight or less. Here, PCA is an aromatic compound in which two or more rings such as polycyclic aromatics are fused, and can be measured as a DMSO extractable substance by the IP346 / 92 method.
[0012]
It is not preferable because the C A petroleum based process oil is less than 20 wt% used as an indicator of grip performance tan [delta (0 ° C.) is reduced in the present invention, in fuel economy index exceeds 35 wt% in the reverse A certain tan δ (60 ° C.) is not preferred because it increases (fuel efficiency deteriorates). If the Tg is lower than -55 ° C, the grip performance and heat aging resistance decrease, which is not preferable. Since kinematic viscosity (100 ° C.) grip performance decreases less than 20 mm 2 / g is not preferable, contrary to 50 mm 2 / g than the high-temperature heating is required during transport, so causing an increase of the use cost preferably Absent. Further, if PCA exceeds 3% by weight, there is a potential problem of environment and safety, which is not preferable.
[0013]
In the rubber composition according to the first embodiment of the present invention, 1 to 150 parts by weight, preferably 3 to 100 parts by weight of the petroleum-based process oil is mixed with 100 parts by weight of at least one diene rubber. This rubber composition can solve the problems of compatibility with the diene-based raw rubber, bleeding property, low fuel consumption, and grip property by setting the Tg of the petroleum-based process oil to -55 ° C to -30 ° C. Further, by setting the C A (%) to 20 to 35% by weight, both low fuel consumption and grip can be achieved, and by setting the kinematic viscosity (100 ° C.) to 20 to 50 mm 2 / g, the grip can be further improved. Further improvement and heat aging resistance can be secured.
[0014]
Examples of the diene rubber that can be used in the rubber composition according to the first aspect of the present invention include any diene rubber conventionally compounded generally in a rubber composition, such as natural rubber (NR), Butadiene rubber (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), butyl rubber (IIR) and the like can be used alone or as an arbitrary blend depending on the application.
[0015]
The rubber composition according to the first embodiment of the present invention, in addition to the essential components described above, a reinforcing agent such as carbon black or silica, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, various oils, an antioxidant Various additives commonly used for tires and other general rubbers, such as plasticizers, can be compounded. Such a compound is kneaded and vulcanized by a general method to obtain a composition, Can be used for vulcanization or crosslinking. The compounding amounts of these additives can also be conventional general compounding amounts, as long as they do not contradict the object of the present invention. Although the use of such a rubber composition is not particularly limited, it is suitable for use in, for example, industrial articles such as belts and hoses and tires.
[0016]
In the rubber composition according to the second aspect of the present invention, the petroleum-based process oil is added to 100 parts by weight of a diene-based rubber containing at least one styrene-butadiene copolymer (SBR) having a glass transition temperature Tg of −55 ° C. or higher. 5 to 80 parts by weight, preferably 10 to 70 parts by weight, and 2 to 30 parts by weight of an aromatic, rosin and / or coumarone resin having a softening point of 80 to 130 ° C, preferably 80 to 120 ° C, preferably 2 to 15 parts by weight are blended. If the blending amount of the petroleum-based process oil is too small, the processability of the rubber is deteriorated, which is not preferable. On the other hand, if the softening point of the resin is too low, the gripping performance is deteriorated, which is not preferable. Further, if the amount of the resin is too small, the softening effect is reduced, and the processability is deteriorated, which is not preferable. On the contrary, if the amount is too large, the fuel efficiency is deteriorated.
[0017]
The aromatic, examples of rosin-based and / or coumarone-based resins, for example, C 9 resins, gum rosin, wood rosin, rosin-based resins such as tall rosin, further modified resins, coumarone such rosin ester resin - the like indene resin These are commercially available as, for example, Petrozine manufactured by Mitsui Oil, various rosin esteu resin manufactured by Yasuhara Yushi Co., Ltd., and Coumalon 100 manufactured by Kobe Oil Chemical Industry Co., Ltd.
[0018]
As the diene rubber that can be used in combination with the SBR in the rubber composition according to the second aspect of the present invention, any diene rubber conventionally blended generally in rubber compositions, for example, natural rubber ( NR), various butadiene rubbers (BR), other styrene-butadiene copolymer rubbers (SBR), polyisoprene rubbers (IR), butyl rubbers (IIR) and the like can be used alone or as an arbitrary blend depending on the application. it can.
[0019]
The rubber composition according to the second aspect of the present invention, in addition to the essential components described above, a reinforcing agent such as carbon black or silica, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, various oils, an antioxidant Various additives commonly used for tires and other general rubbers, such as plasticizers, can be compounded. Such a compound is kneaded and vulcanized by a general method to obtain a composition, Can be used for vulcanization or crosslinking. The compounding amounts of these additives can also be conventional general compounding amounts, as long as they do not contradict the object of the present invention. The use of the rubber composition is not particularly limited, but it is suitable for use in, for example, rubber industrial products such as tire treads, belts and hoses.
[0020]
In the rubber composition according to the third aspect of the present invention, the petroleum-based process oil and a novolak-type alkylphenol having a weight average molecular weight of 200 to 10,000, preferably 250 to 5,000 are added to 100 parts by weight of at least one diene rubber. 10-30 parts by weight of a mixture of a resin and a mixture of the petroleum-based process oil and the novolak alkylphenol resin in a weight ratio of (25-95% by weight) / (5-75% by weight) is blended as a softening agent. .
[0021]
According to the third aspect of the present invention, a desired rubber compound performance can be obtained by blending the petroleum-based process oil with a novolak-type alkylphenol having a molecular weight of 200 to 10,000, preferably 250 to 5,000. I can do it. If the molecular weight of the novolak-type alkylphenol is less than 200, no effect of increasing the modulus in the low elongation region is observed, while if the molecular weight exceeds 10,000, the softening effect in the high elongation region is small, and the mixing processability of rubber is low. Tend to worsen, which is not preferable. The amount of the novolak-type alkylphenol is in the range of 5 to 75% by weight, preferably 10 to 50% by weight, based on the total amount of the two components. If the amount of the novolak type alkylphenol is less than 5% by weight, the effect of increasing the modulus cannot be exhibited, and if it exceeds 75% by weight, not only the workability is deteriorated but also the cost is increased, which is not preferable as a rubber for tires. The compounding amount of the softener is 10 to 30 parts by weight based on 100 parts by weight of the diene rubber. If the amount is too small, the processability of the rubber deteriorates, which is not preferable. On the other hand, if the amount is too large, the fuel economy is lowered, which is not preferable.
[0022]
Examples of the diene rubber that can be used in the rubber composition according to the third aspect of the present invention include any diene rubber conventionally compounded generally in rubber compositions, such as natural rubber (NR), Butadiene rubber (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), butyl rubber (IIR) and the like can be used alone or as an arbitrary blend depending on the application.
[0023]
The rubber composition according to the third aspect of the present invention, in addition to the essential components described above, a reinforcing agent such as carbon black or silica, a vulcanizing or crosslinking agent, a vulcanizing or crosslinking accelerator, various oils, an antioxidant Various additives commonly used for tires and other general rubbers, such as plasticizers, can be compounded. Such a compound is kneaded and vulcanized by a general method to obtain a composition, Can be used for vulcanization or crosslinking. The compounding amounts of these additives can also be conventional general compounding amounts, as long as they do not contradict the object of the present invention. Although the use of the rubber composition is not particularly limited, it is suitable for use in, for example, carcass members for tires, treads for tires, belts, hoses and the like.
[0024]
【Example】
Hereinafter, the present invention will be further described with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. In the following examples, "%" indicates "% by weight" unless otherwise specified.
[0025]
Examples 1-4 and Comparative Examples 1-3
According to the composition (parts by weight) shown in Table I, the vulcanization accelerator and the rubber other than sulfur and the compounding agent were kneaded with a 1.7 liter Banbury mixer for 5 minutes, and then the vulcanization accelerator and sulfur were added to the composition. The mixture was kneaded with an 8-inch test kneading roll machine for 4 minutes to obtain a rubber composition. These rubber compositions were pressed at 150 ° C. for 30 minutes to prepare target test pieces, various tests were performed, and the physical properties were measured. The results are shown in Table I.
[0026]
The measuring methods of the physical properties were as follows.
1) tan δ (0 ° C. and 60 ° C.): Using a viscoelastic spectrometer (extended viscoelasticity measuring device manufactured by Kamishima Seisakusho Co., Ltd.) at a temperature of 0 ° C. and 60 ° C., a strain rate of 10 ± 2% and a frequency of 20 Hz Was measured.
2) ΔHs: Measured according to JIS K-6301 using a JIS A type hardness tester manufactured by Kobunshi Keiki Co., Ltd. The increase and decrease of the values are shown based on the comparative example.
3) Tensile strength (after aging) (Mpa): According to JIS K-6301, an air heating aging test (100 ° C., 24 hours) was performed, and then a tensile test was performed.
[0027]
[Table 1]
Table I footnotes
* 1 : RSS # 1
* 2 : N330 (Seast 3 manufactured by Tokai Carbon Co., Ltd.)
* 3 : Noxeller 6C (Ouchi Shinko Chemical)
* 4: C A 44%, Tg = -32 ℃, kinematic viscosity (100 ℃) = 27mm 2 /sec,PCA=10.5%
* 5: C A 4%, Tg = -93 ℃, kinematic viscosity (100 ℃) = 2mm 2 /sec,PCA=0.8%
* 6: C A 30%, Tg = -60 ℃, kinematic viscosity (100 ℃) = 52mm 2 /sec,PCA=2.8%
* 7: C A 27%, Tg = -40 ℃, kinematic viscosity (100 ℃) = 47mm 2 /sec,PCA=2.8%
* 8 : N-tert-Butyl-2-benzothiazolyl-sulfenamide (Ouchi Shinko Chemical Co., Ltd.)
[0029]
Examples 5 to 6 and Comparative Examples 4 to 10
According to the formulation (parts by weight) shown in Table II, the vulcanization accelerator and rubber other than sulfur and the compounding agent were kneaded with a 1.7 liter Banbury mixer for 5 minutes, and then the vulcanization accelerator and sulfur were added to the mixture. The mixture was kneaded with an 8-inch test kneading roll machine for 4 minutes to obtain a rubber composition. These rubber compositions were pressed at 150 ° C. for 30 minutes to prepare target test pieces, various tests were performed, and the physical properties were measured. The methods for measuring physical properties are as described above. The results are shown in Table II.
[0030]
[Table 2]
Table II footnotes
* 1 : SBR: emulsion polymerization SBR at St = 23.5%, Vn = 10%, Tg = −55 ° C.
* 2 : N330 (Seast 3 manufactured by Tokai Carbon Co., Ltd.)
* 3 : Noxeller 6C (Ouchi Shinko Chemical Co., Ltd.)
* 4 : Ca = 44%, Tg = −32 ° C., kinematic viscosity (100 ° C.) = 27 mm 2 / sec, PCA value = 10.5%
* 5 : Ca = 4%, Tg = −93 ° C., kinematic viscosity (100 ° C.) = 2 mm 2 / sec, PCA value = 0.8%
* 6 : Ca = 30%, Tg = −60 ° C., kinematic viscosity (100 ° C.) = 52 mm 2 / sec, PCA value = 2.8%
* 7 : Ca = 27%, Tg = −40 ° C., kinematic viscosity (100 ° C.) = 47 mm 2 / sec, PCA value = 2.8%
* 8 : Noxeller NS (Ouchi Shinko Chemical Co., Ltd.)
[0032]
Examples 7 to 10 and Comparative Examples 11 to 14
According to the formulation (parts by weight) shown in Table III, the vulcanization accelerator and the rubber other than sulfur and the compounding agent were kneaded with a 1.7 liter Banbury mixer for 5 minutes, and then the vulcanization accelerator and sulfur were added to this compound. The mixture was kneaded with an 8-inch test kneading roll machine for 4 minutes to obtain a rubber composition. These rubber compositions were pressed at 150 ° C. for 30 minutes to prepare target test pieces, which were subjected to various tests to measure their physical properties. The results are shown in Table III.
[0033]
The physical properties were tan δ (60 ° C.) and ΔHs were as described above, and the wear resistance was a Lambourn abrasion tester manufactured by Iwamoto Seisakusho (measurement conditions: load = 3.0 kg, surface speed of the grindstone = 40 m / min, slip ratio 25). %, Test time = 5 minutes, sandfall = 20 g / min), the measurement temperature was room temperature, and the volume loss (cc) was examined. The larger the value, the better the wear resistance.
[0034]
[Table 3]
Table III footnotes
* 1 : Emulsion polymerization SBR at St = 33%, Vn = 14%, Tg = −36 ° C., 37.5 phr oil extension (aroma) * 16
* 2 : Emulsion polymerization SBR at St = 33%, Vn = 14%, Tg = -36 ° C, 37.5 phr oil extension (paraffin) * 17
* 3 : Emulsion polymerization SBR at St = 33%, Vn = 14%, Tg = -36 ° C, 37.5 phr oil extension (oil) * 18
* 4 : Emulsion polymerization SBR at St = 25%, Vn = 16%, Tg = -51 ° C., 37.5 phr oil extension (aroma) * 16
* 5 : Emulsion polymerization SBR at St = 25%, Vn = 16%, Tg = -51 ° C., 37.5 phr oil extension (paraffin) * 17
* 6 : Emulsion polymerization SBR at St = 25%, Vn = 16%, Tg = −51 ° C., 37.5 phr oil extension (oil) * 18
* 7 : Nipol 1220 manufactured by Zeon Corporation
* 8 : Show black N220 manufactured by Showa Cabot Co., Ltd.
* 9 : Santoflex 6PPD manufactured by Flexis Corporation
* 10 : Desolex No. 3 manufactured by Showa Shell Sekiyu KK
* 11 : Machine oil 22 manufactured by Showa Shell Sekiyu KK
* 12 : Aroma oil (C A = 27%, Tg = −40 ° C., kinematic viscosity (100 ° C.) = 47 mm 2 / sec)
* 13 : Hyrosin manufactured by Yashara Chemical Co., Ltd. Softening point: 95 ° C
* 14 : Coumaron resin manufactured by Ouchi Shinko Chemical Co., Ltd. Softening point: 90 ° C
* 15 : Noxeller CZ-G manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
* 16 : Desolex No. 3 manufactured by Showa Shell Sekiyu KK
* 17 : Machine oil 22 manufactured by Showa Shell Sekiyu KK
* 18 : Aroma oil (C A = 27%, Tg = −40 ° C., kinematic viscosity (100 ° C.) = 47 mm 2 / sec)
[0036]
【The invention's effect】
The present inventors have Tg of process oil in the -55 to-30 ° C. and C A = 20 to 35 wt%, a kinematic viscosity (100 ℃) = 20~50mm 2 / g range of the oil is tan [delta (60 ° C.) And increased tan δ (0 ° C.) to find both fuel economy and grip. Further, a commercially available aromatic oil is those C A = 40 to 45 wt% of the range is a general, recent polycyclic aromatic components contained in the aromatic oil (PCA) health inhibitor, environmental pollution, etc. There is a concern that this may cause problems. In order to reduce the PCA value, it is necessary to lower the ratio of the total aromatic component occupying in oil (aroma component), solely according to with only the C A component ratio decreases that as a result this, grip performance Quality of rubber products, such as heat resistance and heat aging resistance. However, according to the present invention, it is possible to maintain low fuel consumption without lowering grip performance by securing the Tg, aromatic content (C A %), and kinematic viscosity of the process oil in specific ranges. It is.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002324246A JP3720016B2 (en) | 2002-11-07 | 2002-11-07 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002324246A JP3720016B2 (en) | 2002-11-07 | 2002-11-07 | Rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004155959A true JP2004155959A (en) | 2004-06-03 |
| JP3720016B2 JP3720016B2 (en) | 2005-11-24 |
Family
ID=32803891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002324246A Expired - Lifetime JP3720016B2 (en) | 2002-11-07 | 2002-11-07 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3720016B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009102506A (en) * | 2007-10-23 | 2009-05-14 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire and pneumatic tire |
| KR20120004407A (en) | 2009-03-27 | 2012-01-12 | 제이엑스 닛코닛세키에너지주식회사 | Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same |
| KR20120004408A (en) | 2009-03-27 | 2012-01-12 | 제이엑스 닛코닛세키에너지주식회사 | Rubber compounding oil and method for producing same |
| WO2013140823A1 (en) | 2012-03-21 | 2013-09-26 | Ｊｘ日鉱日石エネルギー株式会社 | Highly aromatic base oil and method for producing highly aromatic base oil |
| US10160847B2 (en) | 2010-11-26 | 2018-12-25 | Compagnie Generale Des Etablissments Michelin | Tyre tread |
-
2002
- 2002-11-07 JP JP2002324246A patent/JP3720016B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009102506A (en) * | 2007-10-23 | 2009-05-14 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire and pneumatic tire |
| KR20120004407A (en) | 2009-03-27 | 2012-01-12 | 제이엑스 닛코닛세키에너지주식회사 | Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same |
| KR20120004408A (en) | 2009-03-27 | 2012-01-12 | 제이엑스 닛코닛세키에너지주식회사 | Rubber compounding oil and method for producing same |
| TWI472569B (en) * | 2009-03-27 | 2015-02-11 | Nippon Oil Corp | Rubber blend oil and aromatic base oil, and the like |
| US10160847B2 (en) | 2010-11-26 | 2018-12-25 | Compagnie Generale Des Etablissments Michelin | Tyre tread |
| WO2013140823A1 (en) | 2012-03-21 | 2013-09-26 | Ｊｘ日鉱日石エネルギー株式会社 | Highly aromatic base oil and method for producing highly aromatic base oil |
| US9476006B2 (en) | 2012-03-21 | 2016-10-25 | Jx Nippon Oil & Energy Corporation | Highly aromatic base oil and method for producing highly aromatic base oil |
| US9988583B2 (en) | 2012-03-21 | 2018-06-05 | Jx Nippon Oil & Energy Corporation | Highly aromatic base oil and method for producing highly aromatic base oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3720016B2 (en) | 2005-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5529008B2 (en) | Rubber composition for tire and tire | |
| JP4275388B2 (en) | Tread rubber composition and tire | |
| JP2008019334A (en) | Rubber composition for tire tread | |
| JP2005298804A (en) | Rubber composition and pneumatic tire obtained using the same | |
| JP2007106799A (en) | Rubber composition for tire | |
| JP5205876B2 (en) | Rubber composition for tire tread | |
| JP2005146115A (en) | Tire tread rubber composition | |
| EP1460103B1 (en) | Rubber composition | |
| JP2007246573A (en) | Rubber composition for tire tread | |
| JP2008169298A (en) | Rubber composition and pneumatic tire using same | |
| JP2008297445A (en) | Rubber composition for tire tread | |
| JPH0827313A (en) | Rubber composition for tire tread | |
| JP4102075B2 (en) | Rubber softener, rubber composition using the same, and oil-extended rubber | |
| JP3720016B2 (en) | Rubber composition | |
| JP2008297449A (en) | Rubber composition for tire tread | |
| JP3400887B2 (en) | Rubber composition for tire tread | |
| JP2001294711A (en) | Rubber composition | |
| JP2008169280A (en) | Rubber composition for tire tread and pneumatic tire using the same | |
| JPWO2003031511A1 (en) | Rubber composition | |
| JP3544717B2 (en) | Tread rubber composition for tire | |
| JP2007246622A (en) | Rubber composition | |
| JP2009173797A (en) | Method for producing rubber composition for tire tread | |
| JPH10182881A (en) | Rubber composition | |
| JP5205716B2 (en) | Silica-containing rubber composition | |
| JP2006241315A (en) | Rubber composition for pneumatic tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050426 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050510 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050711 |
|
| 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: 20050809 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050906 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 3720016 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080916 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090916 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090916 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100916 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100916 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110916 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110916 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110916 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120916 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120916 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120916 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120916 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130916 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |