JP2006131807A - Modified latex, and product containing hydrogenated natural polyisoprenoid or its modification - Google Patents
Modified latex, and product containing hydrogenated natural polyisoprenoid or its modification Download PDFInfo
- Publication number
- JP2006131807A JP2006131807A JP2004324229A JP2004324229A JP2006131807A JP 2006131807 A JP2006131807 A JP 2006131807A JP 2004324229 A JP2004324229 A JP 2004324229A JP 2004324229 A JP2004324229 A JP 2004324229A JP 2006131807 A JP2006131807 A JP 2006131807A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- modified
- natural
- natural polyisoprenoid
- polyisoprenoid
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、天然ポリイソプレノイドラテックスをラテックス状態のまま水素添加して構造変性し、飽和度を高めた高分子体とした変性ラテックスと、前記変性ラテックスを用いて調製又は作製された天然ポリイソプレノイド水素添加物又はその変性体含有製品に関する。 The present invention relates to a modified latex in which a natural polyisoprenoid latex is hydrogenated in the latex state to form a polymer having a modified structure and a high degree of saturation, and a natural polyisoprenoid hydrogen prepared or produced using the modified latex The present invention relates to an additive or a modified product containing the additive.
天然ポリイソプレノイドはヘベアブラジリエンシス種（ヘベア種ゴムノキ）の樹木から採取される天然ゴムに代表される、ある種の植物やキノコが生合成により作り出すイソプレン単位（Ｃ5Ｈ8）で構成される重合体の総称である。天然ポリイソプレノイドは、ヘベア種ゴムノキのほか、インドゴムノキ、トチュウ、チチタケなどのラクタリウス（Lactarius）属キノコ等の多くの植物やキノコから産生されることが知られている。しかし、天然ゴム以外の天然ポリイソプレノイドはほとんど工業的に利用されていない。これは、ゴムとして利用するには、多くのポリイソプレノイドの立体構造が天然ゴムほど規則的でないこと、重合度が小さく分子量が十分大きくないこと、多量に産出させることが経済的に難しいことなどの理由による。 Natural polyisoprenoids are composed of isoprene units (C 5 H 8 ) produced by biosynthesis by certain plants and mushrooms, typified by natural rubber extracted from trees of Hevea brasiliensis species (Hevea rubber tree). Is a general term for polymers. Natural polyisoprenoids are known to be produced from many plants and mushrooms such as Lactarius genus mushrooms such as Indian rubber tree, eucommia and chichitake, in addition to Hevea rubber tree. However, natural polyisoprenoids other than natural rubber are hardly used industrially. This is because, for use as rubber, the three-dimensional structure of many polyisoprenoids is not as regular as natural rubber, the degree of polymerization is small and the molecular weight is not sufficiently large, and it is economically difficult to produce a large amount. Depending on the reason.
一方、天然ゴムは、その栽培方法、品質の安定化など長年の研究と努力により、安定に、しかも安価に供給されるようになっており、タイヤをはじめとする種々のゴム製品に用いられている最も汎用的なゴム材料である。この天然ゴムは、ゴム弾性や強度に優れるが、耐油性、耐薬品性、耐熱性、耐候性に劣る特徴がある。このため、優れたエコマテリアルであるにもかかわらず、用途は限られ、いわゆる高性能、多機能材料としては使用されない。 Natural rubber, on the other hand, has come to be supplied stably and inexpensively through years of research and efforts such as cultivation methods and quality stabilization, and is used in various rubber products including tires. It is the most versatile rubber material. This natural rubber is excellent in rubber elasticity and strength, but is inferior in oil resistance, chemical resistance, heat resistance and weather resistance. For this reason, although it is an excellent eco-material, its application is limited and it is not used as a so-called high-performance, multifunctional material.
また、天然ポリイソプレノイドラテックスは、樹木からラテックス状態で採取され、手袋、カテーテル、コンドームなどの浸漬製品や、水系塗料及びコーティング剤の原料として利用されている。しかし、これらのラテックス製品においても、耐熱性、耐候性等が十分でなく、これらの特性の向上が求められている。 Natural polyisoprenoid latex is collected from trees in a latex state and used as a raw material for immersion products such as gloves, catheters and condoms, water-based paints and coating agents. However, these latex products also have insufficient heat resistance, weather resistance, etc., and improvement of these properties is required.
ジャーナル オブ アプライド ポリマー サイエンス（Journal of Applied Polymer Science）、第６６巻、第１６４７頁〜第１６５２頁（１９９７年）には、天然ゴムを有機溶媒中、ロジウム錯体触媒の存在下、１００℃の温度で水素と反応させて、天然ゴムの水素添加物を得る方法が記載されている。しかし、この文献における研究は水素化反応の速度論的研究とポリマーの熱的物性の研究にとどまっている。 Journal of Applied Polymer Science, Vol. 66, pp. 1647 to 1652 (1997) describes natural rubber in an organic solvent at a temperature of 100 ° C. in the presence of a rhodium complex catalyst. A method is described for reacting with hydrogen to obtain hydrogenated natural rubber. However, research in this document is limited to kinetic studies of hydrogenation reactions and thermal properties of polymers.
本発明の目的は、天然ポリイソプレノイドラテックスを原料として製造でき、高い耐熱性及び耐候性を備えた製品を得る上で有用な変性ラテックスと、該変性ラテックスより得られる製品を提供することにある。 An object of the present invention is to provide a modified latex that can be produced using a natural polyisoprenoid latex as a raw material and is useful in obtaining a product having high heat resistance and weather resistance, and a product obtained from the modified latex.
本発明者らは、上記目的を達成するため鋭意検討を重ねた結果、天然ポリイソプレノイドラテックスをラテックス状態のまま水素添加して得られる変性ラテックスから得られる製品が高い耐熱性及び耐候性を有することを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have found that a product obtained from a modified latex obtained by hydrogenating natural polyisoprenoid latex in a latex state has high heat resistance and weather resistance. The present invention has been completed.
すなわち、本発明は、天然ポリイソプレノイドラテックスを水素添加して得られる変性ラテックスを提供する。 That is, the present invention provides a modified latex obtained by hydrogenating natural polyisoprenoid latex.
この変性ラテックスには、天然ポリイソプレノイドラテックスを、水素化触媒の存在下、水素と反応させて得られる変性ラテックスが含まれる。変性ラテックス中の天然ポリイソプレノイド水素添加物の水素添加率は５０％以上であるのが好ましい。天然ポリイソプレノイドラテックスとして、へベア種ゴムノキ、インドゴムノキ、トチュウ又はラクタリウス（Lactarius）属キノコ由来のラテックスを使用できる。 This modified latex includes a modified latex obtained by reacting natural polyisoprenoid latex with hydrogen in the presence of a hydrogenation catalyst. The hydrogenation rate of the natural polyisoprenoid hydrogenated product in the modified latex is preferably 50% or more. As the natural polyisoprenoid latex, latex derived from Hevea rubber tree, Indian rubber tree, Eucommia or Lactarius genus mushroom can be used.
本発明は、また、前記変性ラテックスを用いて調製又は作製された天然ポリイソプレノイド水素添加物又はその変性体含有製品を提供する。 The present invention also provides a natural polyisoprenoid hydrogenated product or a modified product-containing product prepared or produced using the modified latex.
本発明の変性ラテックスより得られる天然ポリイソプレノイド水素添加物含有製品は、高い耐熱性と耐候性を備える。また、耐薬品性、耐寒性、機械的特性等の点でも優れている。さらに、植物由来の原料を用いるため、資源、環境の面でも好ましい。 The natural polyisoprenoid hydrogenated product-containing product obtained from the modified latex of the present invention has high heat resistance and weather resistance. It is also excellent in terms of chemical resistance, cold resistance, mechanical properties and the like. Furthermore, since plant-derived raw materials are used, it is preferable in terms of resources and the environment.
本発明の変性ラテックスは天然ポリイソプレノイドラテックスをラテックス状態（水性乳濁液状態）のまま水素添加して得られる。天然ポリイソプレノイドラテックスとしては、イソプレン単位（Ｃ5Ｈ8）を構成単位とする重合体のラテックスであれば特に限定されないが、代表的な例として、ヘベア種ゴムノキ、インドゴムノキ、トチュウ等の植物由来のポリイソプレノイドラテックス、チチタケなどのラクタリウス（Lactarius）属キノコ等のキノコ由来のポリイソプレノイドラテックスが挙げられる。天然ポリイソプレノイドラテックスとしては、植物やキノコから採取したものをそのまま用いてもよく、また、それを適当な濃度にまで希釈又は濃縮したもの、脱蛋白処理等の適宜な処理を施したものを用いてもよい。 The modified latex of the present invention can be obtained by hydrogenating natural polyisoprenoid latex in a latex state (aqueous emulsion state). The natural polyisoprenoid latex is not particularly limited as long as it is a latex of a polymer having an isoprene unit (C 5 H 8 ) as a structural unit, but representative examples include plant derived from Hevea rubber tree, Indian rubber tree, eucommia and the like. And polyisoprenoid latex derived from mushrooms such as Lactarius genus mushrooms such as Tichitake. As natural polyisoprenoid latex, those collected from plants and mushrooms may be used as they are, or those obtained by diluting or concentrating them to an appropriate concentration, or those subjected to appropriate treatment such as deproteinization treatment are used. May be.
天然ポリイソプレノイドラテックスの水素添加反応は、例えば、天然ポリイソプレノイドラテックスを、水素化触媒の存在下、水素と反応させることにより行われる。反応で使用する水素化触媒としては、炭素−炭素二重結合の水素添加に一般に用いられる均一系又は不均一系触媒を用いることができる。均一系触媒としては、例えば、ＲｈＣｌ（ＰＰｈ3）3等のロジウム錯体触媒などの金属錯体触媒（特に、周期表第８族、第９族又は第１０族金属元素を含む錯体触媒）；カルボン酸ニッケル−トリアルキルアルミニウム、塩化パラジウム、酢酸パラジウムなどの金属塩或いは金属を含むイオン性化合物（特に、周期表第８族、第９族又は第１０族金属元素を含む金属塩）などが挙げられる。また、不均一系触媒としては、例えば、Ｐｄ／ＣａＣＯ3、Ｐｄ／Ｃ等のパラジウム触媒などの固体触媒（特に、周期表第８族、第９族又は第１０族金属元素を含む触媒活性成分を担体に担持した触媒）などが用いられる。触媒の使用量は、触媒の種類等によっても異なるが、一般には、原料として用いる天然ポリイソプレノイドラテックス中の天然ポリイソプレノイドに対して０．０１〜３０重量％、好ましくは０．１〜２０重量％程度である。 The hydrogenation reaction of natural polyisoprenoid latex is performed, for example, by reacting natural polyisoprenoid latex with hydrogen in the presence of a hydrogenation catalyst. As the hydrogenation catalyst used in the reaction, a homogeneous or heterogeneous catalyst generally used for hydrogenation of carbon-carbon double bonds can be used. Examples of the homogeneous catalyst include a metal complex catalyst such as a rhodium complex catalyst such as RhCl (PPh 3 ) 3 (particularly a complex catalyst containing a Group 8, 9 or 10 metal element of the periodic table); a carboxylic acid Examples thereof include metal salts such as nickel-trialkylaluminum, palladium chloride and palladium acetate, or ionic compounds containing metals (particularly metal salts containing Group 8, Group 9 or Group 10 metal elements of the periodic table). Further, as the heterogeneous catalyst, for example, a solid catalyst such as a palladium catalyst such as Pd / CaCO 3 , Pd / C, etc. (particularly, a catalytically active component containing a periodic table group 8, group 9, or group 10 metal element) And the like are used. The amount of the catalyst used varies depending on the type of catalyst, but generally 0.01 to 30% by weight, preferably 0.1 to 20% by weight, based on the natural polyisoprenoid in the natural polyisoprenoid latex used as a raw material. Degree.
触媒として塩化パラジウム等の金属塩を用いる場合、触媒の可溶化のため、塩化ナトリウムなどの塩を系内に添加してもよい。なお、触媒として塩化パラジウム等の金属塩を用いた場合には、該金属塩は反応系中で還元されて、高い触媒活性を有する金属超微粒子が生成する。 When a metal salt such as palladium chloride is used as the catalyst, a salt such as sodium chloride may be added to the system in order to solubilize the catalyst. When a metal salt such as palladium chloride is used as the catalyst, the metal salt is reduced in the reaction system to produce ultrafine metal particles having high catalytic activity.
反応温度は、触媒の種類等によって異なるが、例えば、前記金属錯体触媒などを用いる場合には、例えば０〜１００℃、好ましくは１０〜７０℃程度の範囲から選択できる。また、塩化パラジウム等の金属塩などを用いる場合には、例えば０〜１００℃、好ましくは１０〜６０℃程度である。反応温度が高すぎると、ラテックスが凝固しやすくなるとともに、分子切断（低分子量化）などの副反応が多く進行し、所望の特性（機械的強度や熱的特性）が得られにくくなる。また、反応温度が低すぎると反応速度が低下し、生産性の点で不利である。 The reaction temperature varies depending on the type of catalyst and the like. For example, when the metal complex catalyst or the like is used, it can be selected from the range of, for example, 0 to 100 ° C., preferably about 10 to 70 ° C. Moreover, when using metal salts, such as palladium chloride, it is 0-100 degreeC, for example, Preferably it is about 10-60 degreeC. If the reaction temperature is too high, the latex tends to coagulate, and side reactions such as molecular cutting (lower molecular weight) proceed frequently, making it difficult to obtain desired properties (mechanical strength and thermal properties). Moreover, when reaction temperature is too low, reaction rate will fall and it is disadvantageous at the point of productivity.
反応圧力としては、反応効率、操作性、装置のコスト等を考慮して適宜選択でき、触媒の種類や反応温度等によっても異なるが、例えば前記金属錯体触媒などを用いる場合には、通常０．１〜１５ＭＰａ、好ましくは２〜１０ＭＰａである。また、塩化パラジウム等の金属塩などを用いる場合には、通常大気圧〜１５ＭＰａ、好ましくは大気圧〜１０ＭＰａである。反応時間は、反応温度や反応圧力に応じて適宜選択できる。 The reaction pressure can be appropriately selected in consideration of reaction efficiency, operability, cost of the apparatus, and the like, and varies depending on the type of catalyst, reaction temperature, and the like. 1-15 MPa, preferably 2-10 MPa. When a metal salt such as palladium chloride is used, the pressure is usually atmospheric pressure to 15 MPa, preferably atmospheric pressure to 10 MPa. The reaction time can be appropriately selected according to the reaction temperature and reaction pressure.
反応は、水素の存在下又は水素の流通下で行われ、反応方式は、バッチ式、セミバッチ式、連続式等の何れの方式も採用できる。反応終了後、反応混合液から濾過等の手段で触媒を除去することにより変性ラテックスを得ることができる。なお、塩化パラジウム等の金属塩を触媒として用いた場合には、反応終了後、反応混合液を酸素又は空気の存在下で撹拌したり、或いは反応混合液に適当な酸化剤（例えば、過酸化水素等）を添加すると、系内で一旦還元されて生成した金属が酸化されて凝集し、粒径が大きくなり、濾過等による除去が容易になる。 The reaction is carried out in the presence of hydrogen or under the flow of hydrogen, and any reaction system such as a batch system, a semi-batch system, or a continuous system can be adopted. After completion of the reaction, a modified latex can be obtained by removing the catalyst from the reaction mixture by means such as filtration. When a metal salt such as palladium chloride is used as a catalyst, the reaction mixture is stirred in the presence of oxygen or air after completion of the reaction, or an appropriate oxidizing agent (for example, peroxidation) is added to the reaction mixture. When hydrogen or the like is added, the metal once reduced and formed in the system is oxidized and aggregated, the particle size becomes large, and removal by filtration or the like becomes easy.
こうして得られる変性ラテックス中の天然ポリイソプレノイド水素添加物の水素添加率は、好ましくは５０％以上、さらに好ましくは７０％以上、特に好ましくは９０％以上（中でも９５％以上）である。水素添加率が高いほど、耐熱性、耐老化性、耐候性、耐摩耗性、ＳＥＴ性に優れた製品を得ることができる。なお、水素添加率ｒは原料である天然ポリイソプレノイド中の炭素−炭素二重結合の水素添加された割合［ｒ＝（Ｄ0−Ｄ）／Ｄ0×１００（％）；Ｄ0は天然ポリイソプレノイド中の炭素−炭素二重結合の量（ｍｏｌ／ｇ）、Ｄは反応後の水素添加物中の炭素−炭素二重結合の量（ｍｏｌ／ｇ）である］を示す。本明細書では、天然ポリイソプレノイド中の炭素−炭素二重結合の量Ｄ0は、便宜上、イソプレンのホモポリマーと仮定した場合の値を採用する。反応後の水素添加物中の炭素−炭素二重結合の量Ｄは、1Ｈ−ＮＭＲ又はヨウ素価測定により求めることができる。なお、水素添加された部位は、通常エチレン−プロピレン交互共重合構造を有している。天然ポリイソプレノイド水素添加物としては、主鎖の少なくとも５０％以上（好ましくは７０％以上、特に９０％以上、とりわけ９５％以上）がエチレン−プロピレン交互共重合構造となっているのが望ましい。 The hydrogenation rate of the natural polyisoprenoid hydrogenated product in the modified latex thus obtained is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more (particularly 95% or more). The higher the hydrogenation rate, the more excellent the heat resistance, aging resistance, weather resistance, wear resistance, and SET properties can be obtained. Incidentally, the carbon of the hydrogenation ratio r natural polyisoprenoid in isoprenoid which is the raw material - percentage of hydrogenated carbon double bond [r = (D 0 -D) / D 0 × 100 (%); D 0 is native polypeptide The amount of carbon-carbon double bonds in the isoprenoid (mol / g), D is the amount of carbon-carbon double bonds (mol / g) in the hydrogenated product after the reaction]. In the present specification, for the sake of convenience, a value assuming a homopolymer of isoprene is adopted as the amount D 0 of carbon-carbon double bonds in the natural polyisoprenoid. The amount D of carbon-carbon double bonds in the hydrogenated product after the reaction can be determined by 1 H-NMR or iodine value measurement. The hydrogenated site usually has an ethylene-propylene alternating copolymer structure. As the natural polyisoprenoid hydrogenated product, it is desirable that at least 50% or more (preferably 70% or more, particularly 90% or more, especially 95% or more) of the main chain has an ethylene-propylene alternating copolymer structure.
天然ポリイソプレノイド水素添加物の重量平均分子量は、例えば２０万以上、好ましくは４０万以上、さらに好ましくは６０万以上である。重量平均分子量が小さすぎると、物理的強度及びクリープ特性が低下し、好ましくない。重量平均分子量の上限については特に制限はないが、例えば３００万程度である。なお、前述のように、水素添加反応の反応温度が高すぎると、重量平均分子量が小さくなる。 The weight average molecular weight of the natural polyisoprenoid hydrogenated product is, for example, 200,000 or more, preferably 400,000 or more, and more preferably 600,000 or more. If the weight average molecular weight is too small, the physical strength and creep properties are lowered, which is not preferable. Although there is no restriction | limiting in particular about the upper limit of a weight average molecular weight, For example, it is about 3 million. As described above, when the reaction temperature of the hydrogenation reaction is too high, the weight average molecular weight decreases.
天然ポリイソプレノイド水素添加物の分子量分布［Ｍｗ（重量平均分子量）／Ｍｎ（数平均分子量）］は、例えば２．０以上、好ましくは２．３以上、さらに好ましくは２．６以上である。分子量分布が小さすぎると、加工性が低下し、好ましくない。分子量分布の上限については特に制限はないが、例えば７．０程度である。なお、水素添加反応の反応温度が高すぎると、高分子量側のポリマーが切断されやすくなり、分子量分布が小さくなる。 The molecular weight distribution [Mw (weight average molecular weight) / Mn (number average molecular weight)] of the natural polyisoprenoid hydrogenated product is, for example, 2.0 or more, preferably 2.3 or more, and more preferably 2.6 or more. If the molecular weight distribution is too small, the processability is lowered, which is not preferable. Although there is no restriction | limiting in particular about the upper limit of molecular weight distribution, For example, it is about 7.0. If the reaction temperature of the hydrogenation reaction is too high, the polymer on the high molecular weight side is easily cleaved, and the molecular weight distribution becomes small.
本発明の天然ポリイソプレノイド水素添加物又はその変性体含有製品は、こうして得られた変性ラテックスを用いて調製又は作製されている。例えば、前記変性ラテックス又はその変性体（グラフト変性体、エポキシ変性体、カルボキシル化変性体、架橋体等）に、着色剤（顔料、染料）、可塑剤、分散剤、増粘剤、防かび剤、紫外線吸収剤、酸化防止剤、充填剤、粘着付与樹脂等の添加剤を添加することにより、ラテックス型塗料（水系塗料）、下塗り剤、コーティング剤、シーリング剤、接着剤などを調製することができる。また、前記変性ラテックスに、必要に応じて、素練り促進剤、軟化剤・可塑剤、架橋用配合剤、老化防止剤、発泡剤、カップリング剤、加工助剤、着色剤、充填剤、補強剤などの各種配合剤を添加、配合し、成形加工（特に、架橋を伴った成形加工）に付すことにより種々の製品を製造できる。 The natural polyisoprenoid hydrogenated product or modified product-containing product of the present invention is prepared or produced using the modified latex thus obtained. For example, the modified latex or modified products thereof (graft modified products, epoxy modified products, carboxylated modified products, cross-linked products, etc.), colorants (pigments, dyes), plasticizers, dispersants, thickeners, fungicides By adding additives such as UV absorbers, antioxidants, fillers, and tackifying resins, latex paints (water-based paints), primer, coating agents, sealing agents, adhesives, etc. can be prepared. it can. In addition, the modified latex is optionally mixed with a peptizer, softener / plasticizer, crosslinking compounding agent, anti-aging agent, foaming agent, coupling agent, processing aid, colorant, filler, reinforcement. Various products can be produced by adding and blending various compounding agents such as an agent, and subjecting to molding processing (particularly, molding processing with crosslinking).
素練り促進剤としては、例えば、芳香族ジスルフィド系化合物、芳香族メルカプタン金属塩系化合物などが挙げられる。軟化剤・可塑剤には、鉱物油系軟化剤、植物油系軟化剤、合成軟化剤などが含まれる。 Examples of the peptizer include aromatic disulfide compounds and aromatic mercaptan metal salt compounds. The softener / plasticizer includes mineral oil softener, vegetable oil softener, synthetic softener and the like.
架橋用配合剤には、架橋剤、加硫促進剤、加硫促進助剤、スコーチリターダ等が使用される。架橋剤としては、硫黄や不溶性硫黄（加硫剤）、ジクミルペルオキシド等の過酸化物（パーオキサイド）、オキシムなどが挙げられる。架橋剤の使用量は、天然ポリイソプレノイド水素添加物１００重量部に対して、例えば０．３〜５重量部程度である。加硫促進剤としては、例えば、グアニジン系化合物、チウラム系化合物、ジチオカルバミン酸塩系化合物、チアゾール系化合物、スルフェンアミド系化合物などが挙げられる。加硫促進剤の使用量は、天然ポリイソプレノイド水素添加物１００重量部に対して、例えば０．２〜５重量部程度である。加硫促進助剤としては、例えば、酸化亜鉛（亜鉛華）などが挙げられる。加硫促進助剤の使用量は、天然ポリイソプレノイド水素添加物１００重量部に対して、例えば１〜１０重量部程度である。スコーチリターダとしては、例えば、無水フタル酸、Ｎ−シクロヘキシルチオフタルイミドなどが挙げられる。 As the crosslinking compounding agent, a crosslinking agent, a vulcanization accelerator, a vulcanization acceleration aid, a scooter retarder, and the like are used. Examples of the crosslinking agent include sulfur, insoluble sulfur (vulcanizing agent), peroxides such as dicumyl peroxide, and oxime. The usage-amount of a crosslinking agent is about 0.3-5 weight part with respect to 100 weight part of natural polyisoprenoid hydrogenation products, for example. Examples of the vulcanization accelerator include guanidine compounds, thiuram compounds, dithiocarbamate compounds, thiazole compounds, sulfenamide compounds, and the like. The usage-amount of a vulcanization accelerator is about 0.2-5 weight part with respect to 100 weight part of natural polyisoprenoid hydrogenation products, for example. Examples of the vulcanization acceleration aid include zinc oxide (zinc white). The usage-amount of a vulcanization | cure acceleration | stimulation adjuvant is about 1-10 weight part with respect to 100 weight part of natural polyisoprenoid hydrogenation products, for example. Examples of the scooter retarder include phthalic anhydride and N-cyclohexylthiophthalimide.
老化防止剤としては、アミン系老化防止剤、フェノール系老化防止剤、硫黄系二次老化防止剤、リン系二次老化防止剤、トリブチルチオウレア、ワックスなどが挙げられる。発泡剤には、無機発泡剤及び有機発泡剤が含まれる。カップリング剤としては、白色充填剤用カップリング剤、カーボンブラック用カップリング剤などが用いられる。加工助剤としては、パラフィン、炭化水素樹脂、ステアリン酸等の高級脂肪酸、ステアリン酸アミド等の高級脂肪酸アミド、ステアリン酸ブチル等の高級脂肪酸エステル、ステアリルアルコールなどの高級脂肪族アルコール、グリセリン脂肪酸エステル等の脂肪酸と多価アルコールの部分エステル、ステアリン酸亜鉛等の高級脂肪酸金属塩などの滑剤；クマロン樹脂、フェノール樹脂・テルペン系樹脂、石油系炭化水素樹脂、ロジン誘導体等の粘着付与剤などが挙げられる。加工助剤の使用量は、天然ポリイソプレノイド水素添加物１００重量部に対して、例えば０．１〜１０重量部程度である。 Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based secondary anti-aging agents, phosphorus-based secondary anti-aging agents, tributylthiourea, and waxes. The foaming agent includes an inorganic foaming agent and an organic foaming agent. As the coupling agent, a white filler coupling agent, a carbon black coupling agent, or the like is used. As processing aids, paraffins, hydrocarbon resins, higher fatty acids such as stearic acid, higher fatty acid amides such as stearic acid amide, higher fatty acid esters such as butyl stearate, higher fatty alcohols such as stearyl alcohol, glycerin fatty acid esters, etc. Lubricants such as partial esters of fatty acids and polyhydric alcohols, higher fatty acid metal salts such as zinc stearate; tackifiers such as coumarone resins, phenolic / terpene resins, petroleum hydrocarbon resins, rosin derivatives, etc. . The amount of the processing aid used is, for example, about 0.1 to 10 parts by weight with respect to 100 parts by weight of the natural polyisoprenoid hydrogenated product.
着色剤としては、無機顔料、有機顔料が使用される。また、充填剤としては、カーボンブラック、シリカなどの補強性充填剤；補強用短繊維；クレー・タルク類、炭酸塩類、アルミナ水和物、硫酸バリウムなどの非補強性充填剤；導電性物質などの機能性充填剤などが挙げられる。充填剤の使用量は、天然ポリイソプレノイド水素添加物１００重量部に対して、例えば１〜２００重量部、好ましくは５〜１００重量部程度である。 As the colorant, inorganic pigments and organic pigments are used. Further, as fillers, reinforcing fillers such as carbon black and silica; reinforcing short fibers; non-reinforcing fillers such as clay, talc, carbonates, alumina hydrate, and barium sulfate; conductive materials, etc. And functional fillers. The usage-amount of a filler is 1-200 weight part with respect to 100 weight part of natural polyisoprenoid hydrogenated products, Preferably it is about 5-100 weight part.
前記成形加工としては、特に制限はなく、ラテックスを原料として成形品を作製する際に通常行われる方法を採用できる。ラテックスを用いる代表的な成形加工として、浸漬法による皮膜成形が挙げられる。浸漬法による皮膜成形は、例えば、前記変性ラテックスに、架橋剤、加硫促進剤、加硫促進助剤等を配合して変性ラテックス組成物を調製し、これに、アノード浸漬法により、内面に凝固液を均一に付着させた型を浸漬して皮膜を形成した後、適当な温度で加熱加硫することにより行われる。このような皮膜成形により得られる製品（浸漬製品）として、例えば、ゴム手袋、カテーテル、コンドーム、指サックなどが挙げられる。 There is no restriction | limiting in particular as said shaping | molding process, The method normally performed when producing a molded article from latex as a raw material is employable. As a typical molding process using latex, there is a film molding by dipping method. Film formation by the dipping method is performed, for example, by preparing a modified latex composition by blending the modified latex with a crosslinking agent, a vulcanization accelerator, a vulcanization acceleration aid, and the like on the inner surface by an anode dipping method. The film is formed by immersing a mold to which the coagulation liquid is uniformly attached, and then heated and vulcanized at an appropriate temperature. Examples of products (immersion products) obtained by such film forming include rubber gloves, catheters, condoms, finger sacks, and the like.
こうして得られた本発明の天然ポリイソプレノイド水素添加物又はその変性体含有製品は、天然ゴム製品と比較して、特に耐熱性及び耐候性に優れる。また、機械的特性、耐寒性、加工性、疲労耐久性、耐薬品性等にも優れている。 The natural polyisoprenoid hydrogenated product or modified product-containing product of the present invention thus obtained is particularly excellent in heat resistance and weather resistance as compared with natural rubber products. It also has excellent mechanical properties, cold resistance, workability, fatigue durability, chemical resistance, and the like.
以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。なお、ポリマーの平均分子量及び分子量分布の測定は、ゲル浸透クロマトグラフィー装置（ＧＰＣ）を用い、以下の条件で行った。
検出器：示差屈折計（ＲＩ）
注入液：サンプルの０．１重量％テトラヒドロフラン溶液
溶離液：テトラヒドロフラン
定量 ：標準ポリスチレン換算
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. The average molecular weight and molecular weight distribution of the polymer were measured using a gel permeation chromatography apparatus (GPC) under the following conditions.
Detector: Differential refractometer (RI)
Injection solution: 0.1% by weight tetrahydrofuran solution of the sample Eluent: Tetrahydrofuran Determination: Standard polystyrene conversion
実施例１
塩化パラジウム０．３ｇ、塩化ナトリウム０．５ｇ及び水１０ｇをビーカーに入れ、完全に溶解するまで撹拌混合して触媒水溶液を調製した。内容積２００ｍｌのオートクレーブに、脱蛋白天然ゴムラテックス（固形ゴム分６０重量％）５０ｇと上記の触媒水溶液を入れ、容器内部を水素置換した後、水素により加圧し（１０ａｔｍ＝１．０１ＭＰａ）、撹拌しながら３０℃で２４時間反応させた。容器内を除圧し、開放系のまま空気雰囲気下で引き続き１２時間撹拌した。反応混合液を濾過して触媒を除去した。
得られた水素化天然ゴムラテックス（変性ラテックス）１６６．７重量部に、ボールミルで粉砕した硫黄１重量部、亜鉛華０．５重量部、及び加硫促進剤［商品名「ノクセラーＢＺ」、大内新興化学工業（株）製］１重量部を添加してゴムラテックス組成物を調製した。このゴムラテックス組成物に、アノード浸漬法により、凝固液（３０重量％硝酸カルシウム水溶液）を均一に付着させた５０℃に加温した陶器製板を浸漬し、直ちに引き上げ、１００℃で３０分間オーブン中で加熱加硫して加硫シート（厚さ：１００μｍ）を得た。
なお、上記水素化天然ゴムラテックス中の高分子体（水素化天然ゴム）の水素添加率は９５％であり、重量平均分子量（Ｍｗ）は１００万、分子量分布（Ｍｗ／Ｍｎ）は３．２であった。
Example 1
A catalyst aqueous solution was prepared by adding 0.3 g of palladium chloride, 0.5 g of sodium chloride and 10 g of water into a beaker and stirring and mixing until completely dissolved. In an autoclave with an internal volume of 200 ml, 50 g of deproteinized natural rubber latex (solid rubber content 60% by weight) and the above catalyst aqueous solution were placed, and the inside of the container was replaced with hydrogen, and then pressurized with hydrogen (10 atm = 1.01 MPa) and stirred. The reaction was carried out at 30 ° C. for 24 hours. The inside of the container was depressurized and stirred for 12 hours in an open atmosphere in an open atmosphere. The reaction mixture was filtered to remove the catalyst.
To 166.7 parts by weight of the obtained hydrogenated natural rubber latex (modified latex), 1 part by weight of sulfur pulverized by a ball mill, 0.5 part by weight of zinc white, and a vulcanization accelerator [trade name “Noxeller BZ”, large Uchisei Chemical Co., Ltd.] 1 part by weight was added to prepare a rubber latex composition. In this rubber latex composition, a ceramic plate heated to 50 ° C. with a coagulating liquid (30% by weight calcium nitrate aqueous solution) uniformly attached was immersed by the anode dipping method, immediately pulled up, and then oven-treated at 100 ° C. for 30 minutes. A vulcanized sheet (thickness: 100 μm) was obtained by heat vulcanization in the medium.
The hydrogenation rate of the polymer (hydrogenated natural rubber) in the hydrogenated natural rubber latex is 95%, the weight average molecular weight (Mw) is 1,000,000, and the molecular weight distribution (Mw / Mn) is 3.2. Met.
実施例２
実施例１において、反応時間を４８時間とした以外は実施例１と同様の操作を行って、水素化天然ゴムラテックス（変性ラテックス）を得た。得られた水素化天然ゴムラテックス１６６．７重量部に、ボールミルで粉砕した硫黄１重量部、亜鉛華０．５重量部、及び加硫促進剤［商品名「ノクセラーＢＺ」、大内新興化学工業（株）製］１重量部を添加してゴムラテックス組成物を調製した。このゴムラテックス組成物に、アノード浸漬法により、凝固液（３０重量％硝酸カルシウム水溶液）を均一に付着させた５０℃に加温した陶器製板を浸漬し、直ちに引き上げ、１００℃で３０分間オーブン中で加熱加硫して加硫シート（厚さ：１００μｍ）を得た。
なお、上記水素化天然ゴムラテックス中の高分子体（水素化天然ゴム）の水素添加率は９９％であり、重量平均分子量（Ｍｗ）は９０万、分子量分布（Ｍｗ／Ｍｎ）は３．０であった。
Example 2
A hydrogenated natural rubber latex (modified latex) was obtained in the same manner as in Example 1 except that the reaction time was 48 hours in Example 1. 166.7 parts by weight of the resulting hydrogenated natural rubber latex, 1 part by weight of sulfur pulverized by a ball mill, 0.5 part by weight of zinc white, and a vulcanization accelerator [trade name “Noxeller BZ”, Ouchi Shinsei Chemical Industries, Ltd. [Made by Co., Ltd.] 1 part by weight was added to prepare a rubber latex composition. In this rubber latex composition, a ceramic plate heated to 50 ° C. with a coagulating liquid (30% by weight calcium nitrate aqueous solution) uniformly attached was immersed by the anode dipping method, immediately pulled up, and then oven-treated at 100 ° C. for 30 minutes. A vulcanized sheet (thickness: 100 μm) was obtained by heat vulcanization in the medium.
The hydrogenation rate of the polymer (hydrogenated natural rubber) in the hydrogenated natural rubber latex is 99%, the weight average molecular weight (Mw) is 900,000, and the molecular weight distribution (Mw / Mn) is 3.0. Met.
比較例１
脱蛋白天然ゴムラテックス（固形ゴム分６０重量％）１６６．７重量部に、ボールミルで粉砕した硫黄１重量部、亜鉛華０．５重量部、及び加硫促進剤［商品名「ノクセラーＢＺ」、大内新興化学工業（株）製］１重量部を添加してゴムラテックス組成物を調製した。このゴムラテックス組成物に、アノード浸漬法により、凝固液（３０重量％硝酸カルシウム水溶液）を均一に付着させた５０℃に加温した陶器製板を浸漬し、直ちに引き上げ、１００℃で３０分間オーブン中で加熱加硫して加硫シート（厚さ：１００μｍ）を得た。
なお、上記脱蛋白天然ゴムラテックス中の天然ゴムの重量平均分子量（Ｍｗ）は１２０万、分子量分布（Ｍｗ／Ｍｎ）は５．７である。
Comparative Example 1
166.7 parts by weight of deproteinized natural rubber latex (solid rubber content 60% by weight), 1 part by weight of sulfur pulverized by a ball mill, 0.5 part by weight of zinc white, and a vulcanization accelerator [trade name “Noxeller BZ”, [Ouchi Shinsei Chemical Co., Ltd.] 1 part by weight was added to prepare a rubber latex composition. In this rubber latex composition, a ceramic plate heated to 50 ° C. with a coagulating liquid (30% by weight calcium nitrate aqueous solution) uniformly attached was immersed by the anode dipping method, immediately pulled up, and then oven-treated at 100 ° C. for 30 minutes. A vulcanized sheet (thickness: 100 μm) was obtained by heat vulcanization in the medium.
In addition, the weight average molecular weight (Mw) of the natural rubber in the deproteinized natural rubber latex is 1.2 million, and the molecular weight distribution (Mw / Mn) is 5.7.
物性評価試験
実施例及び比較例で得られたシートにつき、耐熱性試験及び耐候性試験を行った。その結果を表１に示す。
Physical property evaluation test A heat resistance test and a weather resistance test were performed on the sheets obtained in Examples and Comparative Examples. The results are shown in Table 1.
（耐熱性試験）
シートを１号ダンベル（１０ｍｍ幅短冊状；ＪＩＳ）で打ち抜き、１００℃で９６時間ギアオーブン中で熱老化後、シート表面の状態を調べ、以下の基準で耐熱性を評価した。
○：変化無し
△：表面が若干粘着性を帯びている
×：表面の粘着性が著しい
(Heat resistance test)
The sheet was punched out with a No. 1 dumbbell (10 mm wide strip; JIS), thermally aged at 100 ° C. for 96 hours in a gear oven, the state of the sheet surface was examined, and heat resistance was evaluated according to the following criteria.
○: No change △: The surface is slightly sticky ×: The surface is extremely sticky
（耐候性試験）
ＪＩＳ Ｋ ６２５９に準拠し、シートを１号ダンベル（１０ｍｍ幅短冊状）で打ち抜き、５０％伸長させ、専用ホルダーに固定し、４０℃、オゾン濃度５０ｐｐｈｍの雰囲気下に９６時間置き、オゾンクラックを調べた。
○：変化無し
△：細かな亀裂が少量発生した
×：大きな亀裂が多数発生した
(Weather resistance test)
In accordance with JIS K 6259, the sheet is punched out with a dumbbell No. 1 (10 mm wide strip), stretched 50%, fixed to a dedicated holder, placed in an atmosphere of 40 ° C. and ozone concentration 50 pphm for 96 hours to check for ozone cracks It was.
○: No change △: A small amount of fine cracks occurred ×: Many large cracks occurred
Claims (5)
A natural polyisoprenoid hydrogenated product or a modified product-containing product prepared or produced using the modified latex according to any one of claims 1 to 4.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004324229A JP5030377B2 (en) | 2004-11-08 | 2004-11-08 | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same |
| US10/582,000 US8207386B2 (en) | 2003-12-08 | 2004-12-01 | Rubber-like articles and rubber-like material-containing articles |
| CN2004800363673A CN1890267B (en) | 2003-12-08 | 2004-12-01 | Rubbery product or rubbery substance containing product |
| PCT/JP2004/018237 WO2005056612A1 (en) | 2003-12-08 | 2004-12-01 | Rubbery product or rubbery substance containing product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004324229A JP5030377B2 (en) | 2004-11-08 | 2004-11-08 | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006131807A true JP2006131807A (en) | 2006-05-25 |
| JP5030377B2 JP5030377B2 (en) | 2012-09-19 |
Family
ID=36725641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004324229A Active JP5030377B2 (en) | 2003-12-08 | 2004-11-08 | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5030377B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257417A (en) * | 2005-03-18 | 2006-09-28 | Lanxess Inc | Organic solvent-free hydrogenation of diene-based polymer |
| JP2006257416A (en) * | 2005-03-18 | 2006-09-28 | Lanxess Inc | Hydrogenation of diene-based polymer latex |
| JP2007169385A (en) * | 2005-12-20 | 2007-07-05 | Sumitomo Rubber Ind Ltd | Tire rubber composition and tire having sidewall using the same |
| JP2007277343A (en) * | 2006-04-04 | 2007-10-25 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2008184572A (en) * | 2007-01-31 | 2008-08-14 | Bridgestone Corp | Production method of modified hydrogenated natural rubber, modified hydrogenated natural rubber, rubber composition and pneumatic tire |
| JP2009221306A (en) * | 2008-03-14 | 2009-10-01 | Hitachi Zosen Corp | Biopolymer originating in eucommia ulmoides |
| JP2013076038A (en) * | 2011-09-30 | 2013-04-25 | Bridgestone Corp | Modified natural rubber latex and method of producing the same, as well as modified natural rubber, rubber composition, and tire |
| JP2014231490A (en) * | 2013-05-28 | 2014-12-11 | 日立造船株式会社 | Antibacterial composition and method for producing the same |
| JP2016089017A (en) * | 2014-11-04 | 2016-05-23 | 株式会社レヂテックス | High strength polyisoprene having flexibility, polyisoprene composition and manufacturing method therefor |
| JP2018104483A (en) * | 2016-12-22 | 2018-07-05 | 株式会社レヂテックス | Manufacturing method of hydrogenated natural rubber latex |
| WO2019208028A1 (en) * | 2018-04-27 | 2019-10-31 | 日立造船株式会社 | Composition for resin molding and molded resin object obtained using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5917033B2 (en) * | 1977-07-08 | 1984-04-19 | 三菱電機株式会社 | Elevator entrance/exit device |
| JPS59161415A (en) * | 1983-02-22 | 1984-09-12 | ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− | Hydrogenation of carbon-carbon double bond in unsaturated polymer |
| JPH0220505A (en) * | 1988-06-23 | 1990-01-24 | Hormoz Azizian | Deuteration of polymer |
-
2004
- 2004-11-08 JP JP2004324229A patent/JP5030377B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5917033B2 (en) * | 1977-07-08 | 1984-04-19 | 三菱電機株式会社 | Elevator entrance/exit device |
| JPS59161415A (en) * | 1983-02-22 | 1984-09-12 | ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− | Hydrogenation of carbon-carbon double bond in unsaturated polymer |
| JPH0220505A (en) * | 1988-06-23 | 1990-01-24 | Hormoz Azizian | Deuteration of polymer |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006257417A (en) * | 2005-03-18 | 2006-09-28 | Lanxess Inc | Organic solvent-free hydrogenation of diene-based polymer |
| JP2006257416A (en) * | 2005-03-18 | 2006-09-28 | Lanxess Inc | Hydrogenation of diene-based polymer latex |
| JP2007169385A (en) * | 2005-12-20 | 2007-07-05 | Sumitomo Rubber Ind Ltd | Tire rubber composition and tire having sidewall using the same |
| JP2007277343A (en) * | 2006-04-04 | 2007-10-25 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| JP2008184572A (en) * | 2007-01-31 | 2008-08-14 | Bridgestone Corp | Production method of modified hydrogenated natural rubber, modified hydrogenated natural rubber, rubber composition and pneumatic tire |
| JP2009221306A (en) * | 2008-03-14 | 2009-10-01 | Hitachi Zosen Corp | Biopolymer originating in eucommia ulmoides |
| JP2013076038A (en) * | 2011-09-30 | 2013-04-25 | Bridgestone Corp | Modified natural rubber latex and method of producing the same, as well as modified natural rubber, rubber composition, and tire |
| JP2014231490A (en) * | 2013-05-28 | 2014-12-11 | 日立造船株式会社 | Antibacterial composition and method for producing the same |
| JP2016089017A (en) * | 2014-11-04 | 2016-05-23 | 株式会社レヂテックス | High strength polyisoprene having flexibility, polyisoprene composition and manufacturing method therefor |
| JP2018104483A (en) * | 2016-12-22 | 2018-07-05 | 株式会社レヂテックス | Manufacturing method of hydrogenated natural rubber latex |
| WO2019208028A1 (en) * | 2018-04-27 | 2019-10-31 | 日立造船株式会社 | Composition for resin molding and molded resin object obtained using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5030377B2 (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101003648B (en) | Microgel-containing vulcanizable composition based on hydrogenated nitrile rubber | |
| EP2986647B1 (en) | Oil extended functionalized styrene-butadiene copolymer | |
| JP5030377B2 (en) | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same | |
| TWI503330B (en) | Nitrile rubbers and their preparation in organic solvents | |
| KR20150022836A (en) | High-mooney ndbr having mooney jump | |
| EP2177374A1 (en) | Rubber mixtures with functionalised diene rubbers and micro gels, a method for producing and using the same | |
| JP4208037B2 (en) | Rubber composition for belt and rubber belt | |
| JP6641487B2 (en) | Hydrogenated nitrile-butadiene-PEG acrylate copolymer | |
| JP6224429B2 (en) | Rubber composition for tire and pneumatic tire | |
| JP3855480B2 (en) | Novel vinyl cis-butadiene rubber production method and vinyl cis-butadiene rubber composition | |
| EP3412708A1 (en) | Polymer latex production method | |
| JP4895600B2 (en) | Rubber composition for tire and tire having sidewall using the same | |
| CN109988368A (en) | A kind of dynamic-vulcanization thermoplastic sizing material and preparation method thereof | |
| JPS60158225A (en) | Rubber containing rosin acid ester | |
| JP4748933B2 (en) | Rubber-like elastic body and its manufacturing method | |
| JPH09249716A (en) | Plasticizer | |
| JP6074160B2 (en) | Rubber composition and tire manufacturing method | |
| US20230203282A1 (en) | Polybutadiene composition, production method therefor, rubber composition, tire, and rubber belt | |
| JP6875051B2 (en) | Improved rubber composition and its use | |
| Chuayjujit et al. | Preparation of thermoplastic elastomer from epoxidised natural rubber and polystyrene | |
| JP2006249299A (en) | Vinyl-cis-polybutadiene rubber | |
| JP2007119743A (en) | Process for production of vinyl-cis-polybutadiene composition | |
| JP2017132958A (en) | Rubber composition and tire | |
| CN116710493A (en) | Chloroprene polymer, chloroprene polymer latex, method for producing chloroprene polymer latex, composite composition, and vulcanized molded article | |
| BE840097R (en) | SYNTHETIC RUBBER PREPARATION PROCESS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070829 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101012 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101210 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20101210 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20111206 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120305 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20120427 |
|
| 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: 20120626 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120626 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5030377 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150706 Year of fee payment: 3 |